EA002673B1 - Method for preparing cement, concrete based thereon and concrete and reinforced concrete articles and cast structures of said concrete - Google Patents

Abstract

1. A process for manufacturing of cement, forming a quickly soluble and interacting cementitious material with high early strength after mixing with a liquid by sintering of a cement raw mix in the clinker burning kiln, using solid, and/or liquid and/or gaseous fuel and/or other source of energy, said mix comprising main oxides in the mineral forms from the group: calcium oxide, silicium oxide, aluminium oxide, iron oxides, main small constituents from the group: magnesium oxide, sulfur trioxide, potassium oxide, sodium oxide, the remaining small constituents-impurities, and chemical compounds, being returned in said kiln with a dust, caught from stack gases, forming portland cement clinker, containing at least three clinker minerals from the group: tricalcium silicate (3CaOxSiO2), dicalcium silicate (2CaOxSiO2), tricalcium silicate (3CaOxA12O3), calcium aluminoferrite [2CaOx(A12O3)xx(Fe2O3)1-x], 1>x>0, with subsequent cooling and grinding of clinker obtained, characterized in that a promotor of mineral formation is further fed to said raw mix or to said partly burnt material, said promotor is a mineral-oxide additive comprising at least two clinker minerals from groups I: tricalcium silicate (3CaOxSiO2), dicalcium silicate (2CaOxSiO2), tricalcium silicate (3CaOxA12O3), calcium aluminoferrite [2CaOx(A12O3)xx(Fe2O3)1- x], 2/3>=x>=1/3 and/or II: mayenite (12CaOx7Al2O3), calcium monoaluminate (CaOxA12O3), dicalcium and monocalcium ferrites (2CaOxFe2O3, CaOxFe2O3) and/or III: alkaline, sulfate and halogenide derivatives of minerals of said groups and/or IV: calcium sulfoaluminate (4CaOx3Al2O3xSO3), calcium sulphate (CaSO4) and/or mixtures and derivatives thereof and/or V: aluminates and/or silicates and/or ferrites of alkaline metals; VI: mixes and/or compounds of minerals from said groups therebetween and/or with free calcium oxide, such mixes and/or compounds have mechanical and/or chemical genesis having been obtained in the forms of clinker and/or agglomerate and/or slag and/or deposit and/or suspension, wherein the promoter composition and obtained in its presence promoted clinker is chosen, corrected and sustained by criterion of the promotor basicity level (PBL), which exceeding the basicity level of clinker euthectic melt (BLEM), said melt composition disposing in a domain of portland cement clinker on the phase diagram of the system CaO - Al2O3 - SiO2 - Fe2O3 with temperature of crystallization at 1338 degree C, leaving out all impurities from considerations, said promotor basicity level as well as basicity level of promoted clinker (BLPC), obtained by using said promotor, is designed by calculated electronegativity values of chemical compounds in said promotor composition and in said promoted clinker composition compared to the similar calculated the clinker euthectic melt basicity level. 2. A process according to claim 1, characterized in that said promotor basicity level (PBL) and said basicity level of promoted clinker (BLPC) are chosen, corrected and sustained in the ranges correspondingly in about 1.005-1.07 and in about 1.0003-1.04 times larger compared to said basicity level of clinker euthectic melt (BLEM). 3. A process according to any claims 1 or 2, characterized in that the burning of promoted clinker is carried out at presence of an mineralizer, containing the accessory components from the group: mineral salts, minerals, oxides, impurities, including said small constituents, and also chemical compounds and oxides, returning in a said kiln with a dust, caught from stack gases, and the composition of said mineralizer and its content in a burning material are selected by calculations on criterion by basicity level of promoted and mineralized clinker (BLPMC), which exceeding the basicity level of control clinker (BLCC), burnt without using the promotor and mineralizer additives, said both basicity levels calculating with consideration of basicity levels of impurities on elecronegativity values of chemical combinations and/or oxides in impurities. 4. A process according to claim 3, characterized in that a complex mineralizer is used as said mineralizer for said clinker burning kiln, using powder coal, said complex mineralizer further comprises the high-basicity-part, namely calcium part in the form of powder-like materials from the group: lime, calcium carbonates, limestone, dolomite, mix thereof, and the low-basicity-part, namely low calcium, preferentially aluminosilicate content part consisting of powder or granular or slurry materials from group: ash and slage of power coals; granulated or crushed or groud metallurgical slags; chemical combinations from a dust caught from air, used for clinker cooling; ash of the mentioned powder coal for clinker burning, said ash is added to a burning material in a sintering zone of said kiln, and said additive parts of said mineralizer are used together on criterion of total basicity and had total content up to ab. 22% by weight of said raw mix of selected composition calculated as promoted and mineralized clinker. 5. A process according to any of Claims 1-4, characterized in that the values of basicity levels of said promotor (PBL), of said promoted clinker (BLPC), of said clinker euthectic melt (BLEM), and as well as the values of basicity level of said mineralizer (BLM), of said promoted and mineralized clinker (BLPMC) and of said control clinker (BLCC) are chosen, corrected, sustained and designed by representation of basicity levels values of chemical combinations, namely minerals, oxides, mineral salts, halogenides, other said materials, included in mentioned compositions, as a decreasing general series of the sums of values, which are inverse to the algebraic sums of electronegativity values of atoms, included in each of said chemical combinations. 6. A process according to any of claims 1, 2 and 5, characterized in that the levels of said relative basicity of said promotor Bprom and of said promoted clinker Bpc are chosen, corrected and sustained by the fixed values which are equal to the products of the value of relative basicity clinker melt level Beumelt which is accepted as 1 to relative basicity coefficients Kp of said promotor and for said promoted clinker, and selection of mineral composition for said promotor and said promoted clinker is carried out by calculated values of the sums Σ of products of chemical combinations relative basicity values Bpmin, included in promotor composition, to the weight part of each of mentioned chemical combination Npmin in said promotor, in the form Σprom (BpminNpmin) as well as for said promoted clinker in the form Σpc (BpcminNpcmin), where Bpcmin are chemical combinations relative basicity values in the composition of said promoted clinker, Npcmin are weight parts of mentioned chemical combinations in said promoted clinker, said sums are equated to the said fixed values, according to the following formulae: where: B - calculated values of relative basicity, expressed in conventional units (in abbreviated form designated as c.u.), and equal to the algebraic sums of inverse electronegativity levels of chemical elements by Linus Pauling scale in chemical combinations, namely in minerals and/or oxides, i.e. for the components of the all said materials, in this case for said promotor and said clinker euthectic melt - without taking in calculations mentioned small constituents - impurities, dividing by a constant, equal to 2.24; Boxide - said values for oxides in said clinker euthectic melt composition; N - weight or stoichiometric coefficients, expressed accordingly in weight percents for components of said promotor, said promoted and control clinkers, said mineralizers and in molar parts for said melt components; Noxide - said stoichiometric coefficients for oxides, included in chemical composition of clinker melt; Beumelt - in this case is constant equal to 2.24 in units, inversal to units of electronegativity by Linus Pauling scale, and in this application assumed as 1 or 100 conventional units in mathematical expressions, including molar parts for said melt components and weight percents for components accordingly, Kp has been chosen in the range from minimum (K<1>p), equal ab. to 1.0003, and up to maximum (K<max>p), equal ab. to 1.07. 7. A process according to any of claims 3 and 4, characterized in that the calculated value of relative basicity of said promoted and mineralized clinker Bmc is chosen, corrected and sustained by the fixed value which is equal to the product of the value of relative basicity of the said control clinker Bcc and of calculated value of relative basicity coefficient Km for mineralized clinker, and selection of mineral composition of the last is carried out by calculated value of the sum Σmc of products of relative basicities of chemical combinations Bmcmin, included in composition of mineralized clinker, to the weight part of each of mentioned chemical combination Nmcmin in said mineralized clinker in the form Σmc (BmcminNmcmin), said sum is equated to the said fixed value, according to the following formulae: where: Bcc - current value of relative basicity of said control clinker, calculated as the sum Σcc of products of relative basicity values of including chemical combinations Bccmin without small constituents to their weight parts Nccmin in the form Σcc (BccminNccmin), Km has been chosen in the range from minimum (K<1>m), equal ab. to 1.01, and up to maximum (K<max>m), equal ab. to 1.07. 8. A process according to any of claims 1, 2, 5 and 6, characterized in that the calculated value of relative basicity of said promotor, promoted clinker, promoted and mineralized clinker and control clinker are chosen, corrected and sustained having taken into calculations only chemical combinations and/or oxides which contents in said materials exceeds ab.0.5 weight percent (Wt. %). 9. A process according to any of claims 1-8, characterized i

Description

The invention relates to the field of building materials and products, and in particular to methods of manufacturing cement, concrete based on it and concrete and reinforced concrete products and monolithic structures made of concrete.

A method is known from the prior art for the manufacture of cement by calcining, before sintering in a clinker kiln, a cement raw material mixture comprising, in mineral forms, the main oxides from the group calcium oxide, silicon oxide, aluminum oxide, iron oxide, the main minor constituents from the group magnesium oxide, sulfur trioxide, oxide potassium, sodium oxide, the remaining small components are impurities, with the formation of the product of firing of the specified cement raw mix Portland cement clinker, including three or more clinker minerals from g groups: three-calcium silicate (3СаО-8Ю ₂ ), two-calcium silicate (2СаО-8Ю ₂ ), three-calcium aluminate (3СаО-Л1 ₂ О ₃ ), calcium aluminoferrite [2СаО- (А1 ₂ Оz) _х (Ве ₂ О ₃ ) _{1- x} ], 2/3>x> 1/3 (in industrial clinkers, these minerals, including impurities, on offer

Turnboma, 1897, is also called, respectively, alite, white, highly basic calcium aluminate and celite, and according to the proposal of V.N. it is used below in a purely chemical sense to indicate the activity of a mineral in acid-base interactions), followed by cooling of the clinker and grinding it [1]. The main disadvantages of the method are the low productivity of the furnaces, the low grinding capacity of the clinker, leading to low productivity of cement mills, and the low hydraulic activity of the clinker, which also manifests itself in the delayed hardening of cement in the initial period of 1-3 days. These shortcomings are caused by the high level of activation energy calculated by the S. Arrhenius equation (more than 1880 kJ / mol) and the long induction period of the reaction of the formation of the most important clinker mineral - tricalcium silicate (alite) - in the calcined material in the sintering zone of clinker kilns, and the longer this period, the lower the hydration rate of this mineral and the lower the strength of the cement stone after grinding the clinker and mixing the resulting cement with water.

The importance of the activation energy and the duration of the induction period of alite formation for the technological process of cement production was first noticed by V. Kurdowski (Poland), who in the early 60s of the XX century even discovered two induction periods of alite formation, namely, two delays in the appearance of alite in the sintered mixtures with a duration of 10 to 30 minutes with periods of acceleration of the process after each delay [2] with a total duration of delays of up to 50 minutes and a total duration of reactions to completion of mineral formation, in 2-3 times beyond the total duration of the specified delays. Costs of approximately 1/3 of the firing time in vain cannot but adversely affect the performance of clinker kilns. In a discussion at the VI International Congress on Cement Chemistry (Moscow, 1974), V. Kurdovsky pointed to this circumstance as a reason that increases fuel consumption for firing and reduces the quality of clinker. Indeed, by that time it was established [3] that, as a result of finer grinding of the raw mix and the introduction of mineralizers into it during the transition from two-stage alite formation to one-stage with one induction period, instead of two, the quality of clinker and cement made from it increases. So one of the main tasks of chemistry and technology of cement arose - the complete elimination of induction periods of alite formation during sintering of Portland cement clinker.

Fine grinding of the raw material mixture can increase its reactivity, reduce the activation energy of the alite formation process and increase the hydraulic activity of cement, that is, the strength of standard samples made from cement-sand mortar, tested at 28 days after water storage, by about 5 MPa [ 4]. However, fine grinding of the raw material mixture does not manage to eliminate the presence of at least one induction period of alite formation, therefore, the mentioned fine grinding of raw materials has almost no effect on the performance of clinker kilns.

The introduction of mineralizing additives in the raw material mixture or in the calcined material in order to accelerate mineral formation during sintering of clinker is experienced in the cement industry around the world. As a mineralizer, salts of strong acids — chlorides, fluorides, sulfates, and also salts of other acids containing fluorine, for example, silicofluorides — are introduced mainly [5]. In their presence, during production tests, they reduce fuel consumption for clinker burning by about 2-3%, increase the productivity of clinker kilns by 3-5%, increase the clinker grindability, and finally increase the initial strength by 2-3 MPa (i.e., strength indicators at 1- and 3-day-old age) of manufactured cement. The main reasons for these positive effects are a decrease in the activation energy of the formation of tricalcium silicate (alite) by 3-5% and energy consumption for decarbonization of the calcareous (carbonate) component of the raw material mixture [6], as well as modification of the main clinker phases by impurity ions, which accelerates their hydration after cement mixing with water and, accordingly, increases the strength characteristics of cement [7]. However, of the many cement plants in the world, only about 1% of enterprises that can not do without it, constantly use mineralizers, including two in Russia - the Angarsk cement plant and the Voskresenskaya group of cement plants out of a total of 54 Russian enterprises. At the mentioned enterprises, calcium fluoride and calcium sulfate, the latter in the form of phosphogypsum, are respectively introduced into the raw material mixture. And only two more Russian cement plants use mineralizers occasionally. The reasons for the reluctance of the technical management of cement plants in our country and around the world to use mineralizers, despite these advantages, are not limited to the complexity of engineering work associated with the need to maintain a constant mineralizer content in the raw material mixture and clinker, and to take into account changes in the composition of dust collected from the waste gases of the furnace and returned to the latter, more closely monitor the operation of baking heat exchangers, filters, etc. The disadvantages of mineralizers are well known to all Who ever participated in their industrial tests. They consist of: 1) a quick change and thinning of the coating layer in a clinker kiln (a skull formed from the calcined material on the refractory lining and protecting the lining and furnace body from thermochemical corrosion by high-temperature melts) after starting work with the mineralizer in view of the decrease in the viscosity of the melt in the sintering zone and to enhance the formation of rings narrowing the working volume of the furnace on the coating due to the acceleration of crystallization and solidification of the mineralized melt. The instability of the coating requires caution from personnel and restraining the performance of the furnace, so as not to damage its body and at the same time not to release a poor-quality product; 2) if necessary, when using mineralizers, the initial decrease in the value of the coefficient of saturation with lime of the raw material mixture; the reason is that mineralizers having an acid character change the crystal chemical structure of clinker melts in their surface layers at the boundaries with solid and gas phases in the direction of decreasing the allowable maximum of lime in them. If the content of lime in the raw mix is not reduced, either it will not be assimilated and an unburnt clinker will be released, or it is necessary to burn the material before sublimating a part of the mineralizer, spending even more fuel than in control modes without a mineralizer. In this case, gumming can occur, burnout lining up to burnout of the furnace body in the zone of solid-phase reactions and in the sintering zone, which was repeatedly observed, in particular, at domestic cement plants in the 60s and 70s, when they tried to use mineralizers on technological lines with rotary kilns with a diameter of more than 3.5 m; a forced decrease in this regard in clinker and cement obtained by grinding it, the content of the main active clinker mineral of tricalcium silicate 3СаО-81О ₂ - alite can lead to a decrease in the strength characteristics of cement; 3) in changing the mode of movement of the material in a rotary kiln, until an unfavorable shuttle mode of movement of the layer of calcined material appears, in contrast to the usual mode, in which the segment of the calcined material continuously rises along the inner surface of the lining, carried away by the coating, and pours down its own slope; in shuttle mode, the aforementioned segment of the calcined material swings, then crawling along the coating to the horizontal level drawn through the center of the furnace cross-section, then sliding as a whole without mixing to the bottom of the furnace cross-section, with a sharp acceleration of the sloping fraction of the calcined material along the furnace axis , covering the layer of the latter, by burning this fraction to eliminate excess free lime in it and burning the rest of the layer of calcined material. This leads to the presence in the clinker of both burnt and unburnt granules of the material and, as a rule, to a decrease in the quality of average samples of clinker with their correct selection and to a deterioration in the quality of cement, especially in connection with false setting and lower strength in the later stages of hardening (7-28 days), which is also accompanied by an increase in shrinkage, a decrease in the level of water tightness and durability of concrete based on cement from the specified clinker, especially air resistance (strength relief during concrete hardening in air) and is frost-resistant spines (with repeated cycles of freezing / thawing). In addition, when using sulfate mineralizers, undesirable changes in the mineralogical composition of clinker are observed, in particular, preservation of the 12CaO-7A1 ₂ O ₃ mayenite mineral in the finished clinker, which, in the absence of a mineralizer, is observed only in semi-calcined material at the beginning of the sintering zone of furnaces, as well as alkali-containing minerals - aluminates and calcium silicates, characterized not only by reduced hydraulic activity, but also contributing to false setting, increased hygroscopicity, clumping, cement pipes and silos. All these disadvantages complicate both the production and use of cement in the presence of mineralizers. They caused a cautious attitude of cement industry workers around the world to the use of mineralizers, despite the successes achieved by using the latter in individual cement plants.

To characterize the current state of the art, we also note that the process of formation of the most important Portland cement clinker mineral - the aforementioned tricalcium silicate, or alite (abbreviated designation C ₃ 8), proceeds with the participation of all the other main clinker minerals - dicalcium silicate in the calcined cement raw material mixture (Belita, С ₂ 8), tricalcium aluminate (С ₃ А), calcium aluminoferrite [2СаО- (А1 ₂ О ₃ ) _х · (Its ₂ О ₃ ) _1-х ], 2/3>х> 1/3, abbreviated C ₂ (a, E), and the marginal az - C ₁₂ A _7, C ₂ E, SE [8] and their alkali, sulfate, fluoride, and other derivatives. [9]. Here and below, in the description of the invention, the abbreviated notation used in cement chemistry is used: A1 ₂ O ₃ = A; CaO = C; Her ₂ O ₃ = E; E ^- (fluoride ion) = G; H ₂ O = H; K ₂ O = K; MdO = M; Na ₂ O = Ν; P ₂ O ₅ = P; the sum of alkali metal oxides in terms of sodium oxide ^ 2О + 0,658К2О = К ₂ О = К; 81O2 = 8; 8O3 = y; T1O ₂ = T, and the coefficient of the oxide becomes subscript. So, Ca ₃ 81O ₅ =

3CaO-81O ₂ = C ₃ 8, etc .; in addition, the loss on ignition is abbreviated as ppt and the insoluble residue is n.o. Other abbreviations are introduced as they are used. At the suggestion of V.N. Young, M, U, Ν, K are called the main small components of the cement raw material mixture and clinker, since these impurities most significantly affect the processes of firing and grinding of clinker and hardening of cement, and P ₂ O ₅ , L _{1 2} O , BaO, 8gO, N1O, CoO, Mn ₂ O ₃ , T1O ₂ , Cr ₂ O ₃ , CuO, MoO ₂ , C1 ₂ , E are called secondary, or other small components, since usually their content in the clinker and, accordingly, their effect on the properties of the latter are small. However, in practice, numerous exceptions are noted from the rule on the insignificance of the influence of minor minor components on the properties of clinker and cement, and in some cases they need to be taken into account.

The process of alitogenesis during sintering of Portland cement clinker in the presence of a liquid phase without taking into account small components is described, as was recently established [8], by the following reaction system:

С ₂ 8 + 7 С ₃ А θ 9 С ₃ 8 + С1 ₂ А ₇ , (1)

C1 ₂ A ₇ + 9 C O 7 SzA. (2)

С ₂ 8 + 7 С ₄ АЕ о 6 С ₃ 8 - С ₁₂ А ₇ + 3 С ₂ Р + 4 CE, (3)

C1 ₂ A ₇ + 3 C ₂ D + 4 CE + 3 C o 7 C ₄ AE. (4)

The final minerals in the clinker are C ₃ 8, C ₂ 8, C ₃ A and C ₄ AE, otherwise referred to as C2 (A, E), to characterize a variable ratio in the latter of oxides Ca, A1,

Her. The remaining phases - C ₁₂ A ₇ , C ₂ E, CE, C are present in the calcined material temporarily, and if stored in the finished clinker, in particular, during underburning, they worsen, as you know, the construction and technical properties of cement, distracting the oxides bound in them from a beneficial role in the composition of basic minerals. It is because of non-participation in the main technical functions of the clinker that these phases were called marginal [8].

The above reactions, as shown in [8], are cyclically conjugated. Specifically, this means that, distinguishing among them the reactions according to equations (1, 2) as the first pair, the reactions according to equations (3, 4) as the second pair, the conjugation of reactions inside these pairs and between them is determined by the fact that one or more products of each of these reactions is a reagent for at least one of the remaining reactions, as well as the fact that the first reactions (1, 3) in each pair are exothermic, and the second reactions (2, 4) in each pair are endothermic, and, therefore, they can carry out mutual energy exchange both within pairs and between pairs.

The conjugation of reactions determines the fulfillment by all minerals participating in them, in addition to the function of the reagents in the reactions of alite formation, also of catalytic functions, and tricalcium silicate, accordingly, plays an autocatalytic role in them, but the main catalysts of the process are heterogeneous mineral nuclei - surface microphases [10]. Mineralizers, also considered as catalysts for mineral formation [10–12], especially alite formation, accelerate the formation of surface microphases, the concept of which was introduced in [13], and the significance for alite formation was established in [10]. The indicated microphases, approximately coinciding in composition with the final minerals, are characterized by high concentrations of ion vacancies in the crystal lattices [10, 13]. To increase the rate of formation and enhance the positive role of the mentioned microphases, complex mineralizers are recommended to be introduced into the cement raw material mixture together with its glandular component [10], since the first contact of the mineralizer with this main source of common clinker melt accelerates the process of homogenization of the latter with the mineralizer by reducing the average length diffusion paths of the constituent ions of the mineralizer inside the conglomerate of particles of the cement raw material mixture, within which the average chemical composition is about clinker formation approximately corresponds to the average chemical composition of the raw mix (the diameter of such a conglomerate is 20-30 times larger than the average particle size of the raw mix [14]).

Taking into account the feasibility of reducing the average length of the pathways for the diffusion of reagents, a method was proposed that is closest to the proposed invention in terms of cement production for the manufacture of cement forming a rapidly soluble and interacting cementitious material with high early strength after mixing with a liquid by sintering in a clinker kiln using solid and / or liquid and / or gaseous fuel or other energy source of a cement raw material mixture, including mineral the main oxides from the group of calcium oxide, silicon oxide, alumina, iron oxide, the main minor components from the group of magnesium oxide, sulfur trioxide, potassium oxide, sodium oxide, the remaining minor components are impurities, as well as chemical compounds returned to the specified furnace with dust trapped from the exhaust gases, with the formation of Portland cement clinker, including three or more clinker minerals from the group: tricalcium silicate (3СаО-81О ₂ ), dicalcium silicate (2СаО-81О ₂ ), tricalcium aluminate (3СаО-Л1 ₂ О ₃ ), aluminoferrite calcium [2CaO- (A1 ₂ O ₃ ) _x · (Fe ₂ O ₃ ) 1- _x ], 1>x> 0, followed by cooling and grinding of clinker [15]. However, the production according to this method of high-quality alite cements, comprising 55-65% C ₃ 8, at cement plants causes an increase in the specific fuel consumption for clinker burning and the specific energy consumption for cement grinding [1, 4, 7, 9, 12, 15].

The alleged invention in the manufacture of clinker is free from these disadvantages. It lies in the fact that in the method of manufacturing cement, forming a rapidly soluble and interacting cementitious material with high early strength after mixing with a liquid, by sintering in a clinker kiln using solid, and / or liquid, and / or gaseous fuel or other energy source cement raw mix, including in mineral forms the main oxides from the group calcium oxide, silicon oxide, aluminum oxide, iron oxide, the main small components from the group magnesium oxide, trioxide sulfur, potassium oxide, sodium oxide, the remaining small components are impurities, as well as chemical compounds returned to the specified furnace with dust trapped from the exhaust gases, with the formation of Portland cement clinker containing three or more clinker minerals from the group of three-calcium silicate (3СаОЯ1О ₂ ) , dicalcium silicate (2СаОЯ1О ₂ ), tricalcium aluminate (3СаО ^ Л1 ₂ О ₃ ), calcium aluminoferrite [2СаО <Л1 ₂ О ₃ ) _х · (Pe ₂ О ₃ ) g _- х], 1>х> 0, followed by by cooling and grinding clinker, into the cement raw material mixture fed to the firing or into the firing th material additionally introduced promoter mineral, which is a mineral oxide additive comprising two or more of clinker minerals of the groups I: trohkaltsievy silicate (3SaOYa1O _2), dicalcium silicate (2SaOYa1O ₂₎ trohkaltsievy aluminate (3SaO ^ A1 ₂ O _3), alumina ferrite calcium [2CaO <AkO3) x · (Γ ^ ΘβΕ-χ], 2/3>x> 1/3, and / or II: mayenite (12СаО7Л1 ₂ О ₃ ), calcium monoaluminate (CaО ^ Л1 ₂ О ₃ ), dicalcium and monocalcium ferrites (2CaOPe ₂ O ₃ , CaOPe ₂ O ₃ ), and / or III: alkaline, sulfate and halide derivatives of minerals of the indicated groups, and / or IV : calcium sulfoaluminate (4СаОЭЛ1 ₂ О ₃ ЯО ₃ ), calcium sulfate (Са8О ₄ ), and / or their mixtures and derivatives, and / or V: aluminates, and / or silicates, and / or ferrites of alkali metals, VI: mixtures of minerals among these groups, with each other and / or with free calcium oxide, mechanical and / or obtained together in the form of clinker or sinter, or slag, or precipitate, or suspension, the composition of the promoter and the promoted clinker obtained in its presence is selected, corrected, and support by the criterion of basicity exceeding the basicity of the eutectic blade molecular melt composition region Portland cement clinker in the phase diagram of CaO - A1 ₂ O ₃ - occupies 8 ₂ - Fe ₂ O _3, excluding minor constituents crystallizing at 1338 ° C, and as a base for action promoter basicity and promoted clinker obtained in the presence of promoter, use the calculated values of the electronegativity of chemical compounds in the compositions of the specified promoter, the promoted clinker, in comparison with a similarly calculated measure of the basicity of the eutectic clinker melt.

In an embodiment of the invention, the values of the basicity measure of said promoter and the promoted clinker are selected, adjusted and maintained within approximately 1.005-1.07 and 1,0003-1.04 times, respectively, higher than the values of the basicity measure of said eutectic clinker melt.

In another embodiment of the invention, the fired clinker is fired in the presence of a mineralizer containing additionally introduced components from the group of mineral salts, minerals, oxides and including the mentioned minor components, as well as chemical compounds returned to the said furnace with dust trapped from the exhaust gases, and the content of the mineralizer in the calcined material and the composition of the mineralizer are selected according to the criterion of basicity of the mineralized clinker calcined in his presence, exceeding the basicity l control clinker, fired without a promoter and without additionally introduced components of the mineralizer, taking into account the indicated small components in the calculated basicity of both of the mentioned clinkers, and the calculated values of the electronegativity of the compounds included in them are used as a basis for measuring the basicity of the latter.

In a further embodiment of the invention, when using solid fuel, a complex mineralizer is used as the specified mineralizer, further comprising a highly basic, namely calcareous part, in the form of powdered materials from the group of lime, calcium carbonate, limestone, dolomite, mixtures thereof, and a low basic, namely aluminosilicate part , in the form of powdered or granular or sludge-like materials from the group of ash and slag from steam coal, granular or crushed or ground metallurgical slag, and also chemical compounds from dust trapped from the air used to cool the clinker and / or the ash of said solid fuel that adheres to the calcined material in the sintering zone of the clinker kiln, in a total amount of up to about 22% by weight of said cement raw material in terms of clinker.

In an embodiment of the invention, the basicity values of said promoter, promoted clinker, eutectic clinker melt, as well as the mineralizer, mineralized clinker and control clinker are selected, corrected, maintained and calculated with the basicity values of chemical compounds, namely minerals, oxides, mineral salts, halides included in the composition of these materials, in the form of a decreasing base series of sums of quantities inverse to algebraic sums of electronegativity values included in them atoms.

In another embodiment of the invention, the values of the calculated relative basicity of the promoter B _rgot and the promoted clinker B _pc are selected, adjusted and maintained according to fixed values equal to the products of the basicity of the eutectic clinker melt B _eite11 and the calculated values of the basicity coefficient K _{p of the} indicated promoter and the promoted clinker, and the selection the mineralogical composition of the promoter and the promoted clinker is carried out according to the calculated values of the sums Σ of the products of the basicity of the compound d In _mercury , which are part of the promoter, and the mass fractions of the mentioned compounds K _mercury in the promoter, in the form Σ ^^ (In _mer 1 _P N _mer 1 _M ) and similarly to the products of the basicity of the compounds In _mer , included in the promoter clinker, and the values of the mass fractions of the mentioned compounds S _rst in the promoted clinker, in the form Σ ^ (In _rst1P S _rstt ), equivalent to the indicated fixed values, in accordance with the following formulas:

Vrgot Kr X In this _message to Kr X 2 _espe ] 1 (ΒοχίάεΝοχϊάβ)?

Vrgoth ⁼ ΣρΓοηι (WrttIrtt); (6)

Vrs ⁼ Cr X VeiteI ⁼ Cr X X ^ eteI (ΒοχίάβΝοχίάβ) :( 7)

Врс ⁼ Σρο (ΒροπύηΝροπύη), (8) where В is the calculated relative basicity expressed in arbitrary units (abbreviated below) and equal to the algebraic sum of the inverse values of the electronegativity of chemical elements according to L. Pauling in chemical compounds, namely in minerals and / or oxides - components of these materials, including for the promoter and eutectic clinker melt - excluding small components, divided by a constant value equal to 2.24, while

In _about hm _e - the specified value for the oxides included in the chemical composition of the eutectic clinker melt;

N - mass and stoichiometric coefficients for the components of the indicated promoter and clinker - in mass percent, for the specified melt - in mole fractions, while

Ν _οχ ^ - the indicated stoichiometric coefficients for oxides included in the chemical composition of the eutectic clinker melt; wherein

In _ei, t is a constant value equal to 2.24 in the inverse Pauling units and taken as 1 or 100 conventional units in mathematical expressions, including the amounts of chemical elements and their compounds, respectively, in mole fractions or in wt.%, And in these formulas taken equal to 100 conv. units, and the values of K _p are selected in the range from the minimum (K ¹ p), equal to about 1,0003, to the maximum (K ^max p), equal to about 1.07.

In a further embodiment of the invention, the value of the calculated relative basicity of the indicated mineralized clinker Wc is selected, adjusted and maintained at a fixed value equal to the product of the basicity of the control clinker Bcc obtained from the calcined material in the absence of a promoter and additionally introduced mineralizer and the calculated value of the basicity coefficient Kt of the specified mineralized clinker and the selection of the mineralogical composition of the specified mineralized clinker is carried out by the calculated value of the sum Σ ^ of the products of the basicity values of the compounds In _tst1P , which are part of the mineralized clinker taking into account small components, and the values of the mass fractions of the mentioned compounds Ν ^^ _η in the mineralized clinker, in the form Σсс (Wst ^ tst), equivalent to the specified fixed value , in accordance with the following formulas:

As with _t ^- K _t X Weight - Κ _η1 X Hee (B _{Ssp1 (MTP} ^ _n M _n) + (9) _tf = Σ _ηκ (VtsttNtstsh), (10)

In _ss = Σοο (VststIstst), (11) where In _ss is the current value of the relative basicity of the specified control clinker, calculated as the sum of Σ ^ products of the basicity values of _{S of} compounds that are part of the control clinker and include clinker minerals and small components, and the values of the mass fractions of the mentioned compounds X _cst1n in the control clinker, in the form Σ ^ (Β ^ ηΝ ^ η), while the values of the basicity coefficient of the specified mineralized clinker are selected in the range from the minimum (K * _t ) of about 1.01 to ma maximum (K ^max _t ), equal to about 1.10.

In an embodiment of the invention, the basicity values of said promoter, promoter, and control clinker are selected, adjusted, and maintained taking into account the constituent minerals and / or oxides, the content of which in said materials exceeds about 0.5 wt.%.

In another embodiment of the invention, the value of the initial content of the specified promoter ^ rgot / ss in the absence or ^ _Go t / ts in the presence of an additionally introduced mineralizer, in wt.% Clinker, is selected and calculated according to a given value of Bpc of the basicity of the promoted clinker, the value of Bcc of the basicity of the control clinker, calculated excluding small components, and the largest current or specified basicity said promoter B * _WGPA, and in the presence of a mineralizer further administered - similarly, with respect to the predetermined values The basicity _are mineralized clinker according to the formulas:

where In ^t1p _pc - the minimum specified value of the basicity of the promoted clinker, conv. units;

In ^tach _pc - the maximum specified value of the basicity value of the promoted clinker, conv. units;

In ^t1n _tc - the minimum specified value of the basicity of mineralized clinker, conv. units;

In ^tach _tc - maximum setpoint

In a further embodiment of the invention, a mixture of lime and aluminosilicate raw components containing compounds including coloring oxides of iron, manganese, chromium only in the mineral forms included in these raw materials is used as a cement raw material mixture in the preparation of decorative Portland cement clinker.

In an embodiment of the invention, white compositions containing not more than about 1 wt% of the sum of iron, manganese and chromium compounds in terms of the oxides of these metals in a promoted white clinker are used as the cement raw material mixture, the specified promoter and the specified complex mineralizer in the preparation of the white Portland cement clinker.

In another embodiment of the invention, as a raw material cement mixture and said promoter, when preparing a colored Portland cement clinker, colored compositions are used in which the calculated basicity of said promoter is controlled within the specified limits by the color intensity of the coloring minerals.

In a further embodiment of the invention, substances from the group of alkali and / or alkaline earth metal fluoride are used as the salt part of said mineralizer; sulfate of alkali and / or alkaline earth metals; alkali and / or alkaline earth metal chloride; alkaline and / or alkaline earth silicofluoride; mixtures of these substances; materials containing by-products or wastes, including these substances or mixtures thereof.

In an embodiment of the invention, by-product and / or secondary products from the group of slags and / or sludges from the ferrous and non-ferrous metallurgy, the chemical industry, ash and slag from steam coal, as well as tailings from enrichment plants, burned rocks, spent molding materials, and analogues of these are used as components of the cement raw material mixture materials.

In another embodiment of the invention, the material in the form of a powder or an aqueous suspension is used as the indicated promoter, including dicalcium silicate (2CaO-8U ₂ ), an alkaline derivative of the latter (K ₂ O-23CaO-1181O ₂ ), an alkali metal silicate (br ₂ O-p81O ₂ ) at η / t 2.8-4.8, lime in anhydrous or hydrated forms, with the following ratio of components, wt.%: Dicalcium silicate (2СаО-81О ₂ ) 30-65

Alkaline derivative of dicalcium silicate (K ₂ O-23SaO-118Yu ₂ ) 10-30

Alkali metal silicate (shK ₂ O-p8Yu ₂ ) 0.5-25

Lime (CaO) in anhydrous or hydrated forms 0.05-40

Impurities The rest of the basicity value of mineralized clinker, conv. . units, the current values of basicity promoter _WGPA V * selected in the range of about (1,005-107) In _eite1 values of basicity promoter clinker or mineralized clinker - within the above ranges between their minimum and maximum values.

In a further embodiment of the invention, the material in the form of a powder is used as the indicated promoter, comprising, as a tricalcium silicate of variable composition, a component of the composition [(3.3-3.5) CaO-81O ₂ ], idiomorphic alite, dicalcium silicate (2CaO-81O ₂ ) , as calcium aluminoferrite, a component of the composition [(4.8-7) CaO- (0.7-0.9) A1 ₂ O ₃ · Its ₂ O ₃ - (0.5-1.5) 81O ₂ ] and free calcium oxide (CaO) in the following ratio of components, wt.%:

The component of the composition [(3.3-3.5) CaO ^ 81O ₂ ] in the form of a phase idiomorphic to alite 50-85

Dicalcium silicate (2СаО ^ 81О ₂ ) 0.05-28

The component of the composition [(4.8-7) CaO · (0.7-0.9) A1 ₂ O ₃ Its ₂ O ₃ <0.5-1.5) _{8 10 2} ] 8-30

Free calcium oxide (CaO) 0.1-18

Mix the rest

In an embodiment of the invention, the material in the form of a powder is used as the indicated promoter, including tricalcium silicate (3CaOYO ₂ ), dicalcium silicate (2CaOYO ₂ O), tricalcium aluminate (3C. OOA _{1 2} O ₃ ). tetracalcium aluminoferrite (4СаО ^ А1 ₂ О ₃ дее ₂ О ₃ ), mayenite (12СаОДА1 ₂ О ₃ ), calcium monoaluminate (CaО ^ А1 ₂ О ₃ ), calcium ferrites (2СаО \ Its ₂ О ₃ , CaOWе ₂ О ₃ ), calcium sulfoaluminate (4СаОАА1 ₂ О ₃ ЯО ₃ ), calcium sulfate (Са8О ₄ ) and calcium oxide (CaО), aluminates and ferrites of alkali metals [B (A1, E) О ₂ ] in the following ratio, wt.%:

Tricalcium silicate (3СаО ^ 81О ₂ ) 55-80

Dicalcium silicate (2СаО ^ 81О ₂ ) 10-13

Tricalcium aluminate (3СаОА1 ₂ О ₃ ) 4-15

Four-calcium aluminoferrite (4CaOA1 ₂ O ₃ Te ₂ O ₃ ) 10-18

Mayenite (12СаО7А1 ₂ О ₃ ) 1-3

Calcium monoaluminate (CaO ^ A1 ₂ O ₃ ) 1-1.5

Calcium ferrites (2СаОТе ₂ О ₃ , CaО · Re ₂ О ₃ ) 1-1.5

Calcium sulfoaluminate (4СаОЗА1 ₂ О ₃ ЯО ₃ ) 5-10

Calcium Sulphate (Ca8O ₄ ) 1.5-3.5

Aluminates and ferrites of alkali metals [K (A1, Her) O ₂ ] 0.1-1.5

Calcium Oxide (CaO) 0.1-5

Mix the rest

In another embodiment of the invention, materials from the groups are used as the indicated promoter: I — including dicalcium silicate (2CaOO1O ₂ ), and / or an alkaline derivative of the latter (K ₂ O ^ 23CaOCH181O ₂ ), and / or alkali metal silicate (br ₂ O ^ and 81O ₂ ) at s / t 2.84.8, and / or lime, and / or II — comprising, as a three-calcium silicate of variable composition, a component of the composition [(3.3-3.5) CaOJAU ₂ ], idiomorphic alite, dicalcium silicate (2CaOiOiu ₂ ), as calcium aluminoferrite, a component of the composition [(4.8-7) CaOf0.7-0.9) A1 ₂ O ₃ · Its ₂ O ₃ f0.5-1.5) 8U ₂ ] and free oxide calcium ( CaO), and / or III - including tricalcium silicate (3СаОЯ1О ₂ ), dicalcium silicate (2СаОЯ1О ₂ ), tricalcium aluminate (3СаО ^ A1 ₂ О ₃ ), calcium aluminoferrite (4СаО ^ A1 ₂ О ₃ тее ₂ О ₃ ), (12СаО ^ 7А1 ₂ О ₃ ), calcium monoaluminate (CaОА1 ₂ О ₃ ), calcium ferrites (2СаОДЕ ₂ О ₃ , СаOWе ₂ О ₃ ), calcium sulfoaluminate (4СаОЭА1 ₂ О ₃ ЯО ₃ ), calcium sulfate (Ca8О ₄ ), aluminates and ferrites of alkali metals [B (A1, Her) O ₂ ], calcium oxide (CaO), IV - including materials from these groups or their components in a mixture with additionally introduced by mixing or joint about grinding with a sulfate-calcium ingredient, mainly gypsum, in an amount - in terms of 8O ₃ - 0.59 wt.% of the remaining ingredients of the promoter.

In a further embodiment of the invention, the sintering ability of said raw material mixture is maintained by controlling the content of fluxes in it according to the sum of minerals: tricalcium aluminate (3СаОА1 ₂ О ₃ ) and calcium aluminoferrite [2СаО <А1 ₂ О ₃ ) _х фее ₂ О ₃ ) _1-х ], 1 >x> 0, or about 2.65A1 ₂ O ₃ + 1.34Ee ₂ O ₃ in the form of oxides, at a level of not less than about 12 and 8 wt.% in terms of ordinary and white Portland cement clinkers, respectively.

In an embodiment of the invention, said promoter is first introduced into the calcined material in an amount of about 0.1-0.8 parts by weight. per 1 part by weight the calculated initial content, when the operating mode of the clinker kiln is changed, fixed by changing the value of any characteristic indicator, for example, by the temperature increase in the sintering zone of the specified kiln, the power of the latter is increased, adapting the firing regime of the indicated promoted clinker taking into account the response time to the action of the addition of the indicated promoter by waiting for the return of the mentioned characteristic indicator to approximately the initial value, then in parallel increase the supply of the specified motor and furnace power, and the maximum amount of the introduced promoter adapted to these firing conditions of the specified clinker is selected up to an order of magnitude in excess of the initial quantity according to the criteria of maximum cement strength obtained on the basis of the specified promoted clinker, and in particular within 0.7-3 , 5 wt.% Of the specified promoted clinker according to the criterion of maximum strength of the specified cement under standard conditions at 1-3 days of age or in the range of 0.3-1.5 wt.% Of the specified promoted clinker according to the criterion for the maximum strength of the specified cement under standard conditions at 28 days of age.

In another embodiment of the invention, the promotion of mineral formation during firing of the indicated promoted clinker is carried out repeatedly using the above minerals and / or mixtures thereof with calcium oxide as components of the specified promoter, of which at least one or more components are preliminarily obtained by sintering or melting, also carried out using the aforementioned mineral formation promoter.

In a further embodiment of the invention, the promotion of mineral formation during firing of said promoted clinker is combined with hybridization of the structure of crystal lattices and hybridization of stoichiometric ratios in solid solutions of clinker minerals of said promoted clinker, in which at least one polymorphic modification and / or one stoichiometric ratio of the components of the solid solution, at least one mineral in the composition of the specified promoter is chosen different from the corresponding According to the criteria of hybrid polymorphic modification and / or hybrid stoichiometric ratio of the components of the solid solution, at least one of the minerals of the indicated promoted clinker consider any statistically significant mismatches with similar characteristics recorded in minerals of the same name in the specified control clinker.

In an embodiment of the invention, said promoter is first introduced in an amount of about 0.010.7% by weight of said promoted clinker to increase the temperature of the calcined material in the sintering zone of said furnace compared to a control level without a promoter by about 25-50 ° C., then increase the furnace’s feed, adapting the firing mode of the indicated promoted clinker, taking into account the response time to the action of the additive of the indicated promoter, until the mentioned temperature level returns to the control level, then the filing of the decree is increased of the current promoter, they again increase the furnace power by repeating these operations iteratively, and the maximum amount of input of the specified promoter, adapted to the given conditions of mineral formation promotion during firing of the specified clinker, is selected up to an order of magnitude in excess of the initial amount according to the equilibrium criterion of the composition of the indicated promoted clinker, and as an equilibrium criterion, the content in the last magnetic fraction is used when firing an ordinary promoted clinker, not exceeding approximately 15 wt.%, and when firing white promoted clinker - the content in the latter of mayenite (12СаО-7А1 ₂ О ₃ ), and / or alkaline forms of tricalcium aluminate, or alkaline calcium aluminates (В ₂ О-8СаО-А1 ₂ О ₃ ), where B = Na, K, in an amount not exceeding a total of about 3 wt.%.

In another embodiment, as a criterion for the optimal content of said promoter in the calcined material using the appearance cellular microstructure phase of tricalcium silicate (3SaO occupies _8-2) - alite into clinker of said promoter.

In a further embodiment, as the criterion of optimal content of said promoter in the calcined material using clusters crystal phase content of tricalcium silicate (3SaO occupies _8-2) alite into clinker microstructure of said promoter in an amount of not more than 25 wt.% The above-mentioned phase.

In an embodiment of the invention, in the indicated promoted clinker, the stoichiometric composition of the tricalcium silicate phase (3CaO-8U ₂ ) - alite is controlled within the molar ratio CaO / 8U ₂ 2.8-3.2 by means of sybate regulation within the indicated limits of the content of the indicated promoter and the basicity coefficient of the indicated promoter and mineralizer, as well as the basicity of the mineral of the same name in the specified promoter.

In another embodiment of the invention, in said promoted clinker, the calculated content of tricalcium silicate is increased to about 70-80 wt.% Against about 5565% in said control clinker by increasing the content of said promoter in the calcined material to the maximum amount according to the reduction criterion in said promoted clinker of the total content marginal phases - mayenite (12CaO-7A1 ₂ O ₃ ), its analogues and alkaline derivatives, as well as dicalcium and monocalcium ferrites (2CaO-Pe ₂ O ₃ , CaO-Pe ₂ O ₃ ) - up to about 1 wt. % and less.

In a further embodiment of the invention, said promoted clinker is fired to obtain submicrocrystalline X-ray amorphous tricalcium silicate in the alite composition in the amount of 10-50% of the total mass of alite, maintaining the content of the indicated promoter at the maximum level according to the strength criterion of 28-day-old samples, standardly made from cement, obtained based on said promoted clinker.

In an embodiment of the invention, the tricalcium silicate in the indicated promoted clinker is refined by increasing the content of the indicated promoter in the calcined material to a maximum amount of about 0.6-3.5 wt.% In terms of clinker according to the criterion for the content of tricalcium silicate impurities - magnesium compounds in terms of oxide (MdO), approximately 2-10 times lower than the initial content of MdO in the specified raw material mixture, equal to about 1-7 wt.% in terms of clinker.

In another embodiment of the invention, the average content of alkali metal compounds in the indicated promoted clinker in terms of NbO equivalent - the sum of oxides NbO + 0.658K ₂ O - is reduced by increasing the content and basicity of the indicated promoter within the specified limits in the calcined material according to the criteria of average and temporary the maximum content of the specified amount of oxides in the specified promoted clinker at levels of about 50-92 and about 40-85 wt.% the corresponding amounts in the specified control clinker.

In a further embodiment of the invention, the average chromate content in said promoted clinker in terms of hexavalent chromium is reduced by increasing, within the indicated limits, the content and basicity of said promoter in the calcined material according to the criteria of average and temporary maxima of the chromate content in said promoted clinker at levels of about 2025 and about 12- 20 wt.% Chromates in the specified control clinker in terms of hexavalent chromium.

In an embodiment of the invention, the optimal degree of calcination of said promoted clinker is determined by the content in the last crystalline free lime not exceeding about 1-1.5 wt.% With a total content of free lime up to about 3 wt.%.

In another embodiment of the invention, the supply of the specified promoter in the cement raw material mixture is carried out by mixing it with the last or one of its components during its preparation, or by grinding it, or by adding the specified promoter to the ground raw mixture before it enters the clinker kiln and / or by introducing the specified promoter in the cement raw material mixture in the process of firing the latter.

In a further embodiment of the invention, the introduction of said promoter and mineralizer is carried out jointly or separately, or one of the components of said promoter and / or mineralizer is administered separately from their remaining components.

In an embodiment of the invention, the mixing of the cement raw material mixture or one of its components with the specified promoter is carried out by means of grinding, or pneumatic, or paddle, or vortex mixers, the raw mill or additional grinding device being used as the former, and the cylinder-conical vessel being used as the latter. with an oblique tangential input of the cement raw material mixture, forming a vortex spiraling tapering downward, along the vertical axis of which the indicated promo is served from above torus.

In another embodiment of the invention, said promoter is used in powder form or in the form of a suspension with a specific surface area of the powder or solid phase of the suspension of at least 150 m ² / kg, preferably in the range of 250-1800 m ² / kg.

In a further embodiment of the invention, said promoter or part thereof is pre-mixed with dust collected from the exhaust gases of a clinker kiln.

In an embodiment of the invention, the average content in the promoted clinker of hard-to-grind clinker dust, namely, a fine fraction with granule sizes of less than 0.1 mm, including predominantly tricalcium silicate (3CaO-8YU ₂ ) —alit surrounded by a dark-colored shell of calcium aluminoferrite [2CaO (A1 ₂ O ₃ ) _x - (Re ₂ O ₃ ) 1- _x ]. 1>x> 0. and calcium ferrites (2CaO-Fe ₂ O ₃ , CaO-Fe ₂ O ₃ ), reduced to a level of about 5 wt.% Or less by increasing the content of the promoter to a maximum level in the specified range and / or by choosing the alumina modulus of the promoted clinker is in the range of about 1.15-1.7. mainly 1.35-1.55.

In another embodiment of the invention, the average content in the indicated promoted clinker of a fine fraction with granule sizes of about 0.3-2 mm is increased to a level of about 50-100 wt.% When the content of clinker dust fraction less than 0.1 mm is not more than about 0.1-5 wt. % by increasing the content of the specified promoter to a maximum level within the specified limits when choosing the value of the alumina module of the specified clinker, that is, the ratio by weight of A1 ₂ O ₃ / Fe ₂ O ₃ in the range of about 0.01-1.15.

In a further embodiment of the invention, the resistance of said promoted clinker to grinding is reduced according to the criterion of the average microhardness to about 10-25 MPa by increasing the content of said promoter to a maximum level within the specified limits and / or by choosing the value of the alumina module of said clinker, i.e., the ratio by mass A1 ₂ O ₃ / Fe ₂ O ₃ in the range of about 0.9-2. mainly 1.35-1.8.

In an embodiment of the invention, a gypsum component is additionally introduced into said cement based on said promoted clinker by means of joint and / or separate grinding with subsequent mixing, as materials from the groups: I - natural gypsum one of the group - gypsum stone, natural two-gypsum, natural anhydrite; II - a gypsum-containing by-product of the chemical industry, one of the group - phosphogypsum, borogypsum, titanogypsum, citrogypsum, fluorohydrite; III - the product of desulfurization with calcium carbonate or with the knowledge of sulfur-containing waste gases of the furnaces during the combustion of energy fuels - coal or fuel oil; IV is a mixture of natural gypsum and gypsum-containing industrial by-product in a mass ratio of from about 1: 3 to about 3: 1, with a gypsum component in the specified cement of about 1-4.5 wt.% In terms of sulfur trioxide (8O ₃ ).

In another embodiment of the invention, the product of the interaction of titanogypsum with kaolin or kaolin clay in the presence of free sulfuric acid, which is an impurity in titanogypsum, is added to the specified cement by co-and / or separate grinding, followed by mixing, under conditions of mixing titanogypsum with kaolin at a temperature of 60-550 ° With, and in May. the ratio of titanogypsum / kaolin is regulated in the range from 1: 0.2 to 1: 2, introducing the resulting product into cement in an amount of 1-7 wt.% of the clinker part of the latter.

In a further embodiment of the invention, an ordinary Portland cement clinker and / or Portland cement, respectively, are additionally added to said cement during grinding and / or mixing, based on the latter, at a weight ratio of said promoted and ordinary clinker and / or cement based on them from about 5: 1 to about 1 :5.

In an embodiment of the invention, when grinding said cement, an additional grinding aid is added in an amount of about 0.05-0.5 wt.% Of said cement.

In another embodiment of the invention, surfactants from the group are used as an intensifier for grinding said cement: amino alcohols and their compositions with hardening accelerators; technical lignosulfonates and their compositions with electrolytes or surface-inactive substances from the group: salts of alkaline-earth and / or alkali metals of the condensation product of naphthalene sulfonic acid with formaldehyde; salts of alkaline earth and / or alkali metals of the condensation product of melamine-containing resins with formaldehyde; complex salts of alkaline earth metals and sulfuric and / or nitric and / or formic and / or acetic acids with low molecular weight C ₃ -C ₅ monosaccharides; paired mixtures of these materials in a mass ratio of from about 4: 1 to about 1: 4 in an amount of 0.05-0.5 wt.% the specified cement.

In a further embodiment of the invention, active silica is additionally introduced into said cement during grinding and / or mixing in the form of materials from the groups: I — crushed, or granular, or ground silicate block in an amount of about 0.2-20 wt.% Of said cement or II - silica fume in powder or granular forms: a secondary product of silicon production and / or dust trapped from the exhaust gases of ferroalloy production furnaces, in an amount of 0.2-10 wt.% Of the specified cement, and the granular form of silica fume taken with the addition of a plasticizing component, previously introduced during granulation in an amount of 0.01-0.2%, calculated on the weight of the specified cement.

In an embodiment of the invention, an active mineral additive and / or a filler, respectively, in the form of fragments of the initial or crushed form or in pre-ground form in an amount of about 1-85 wt.% Of said cement are additionally added to said cement by co-and / or separate grinding with subsequent mixing.

In another embodiment of the invention, an expanding component is additionally introduced into said cement by co-and / or separate grinding, followed by mixing, including artificially made and / or natural materials and / or products of their grinding from the groups: I - aluminous clinker or alumina slag; II - sulfoaluminate clinker or other material, including calcium sulfoaluminates; III - sulfoferrite clinker or other material, including calcium sulfoferrites; IV hyperalitic clinker or products of its grinding; V - metallurgical slag, comprising more than 10 wt.% A1 ₂ About ₃ in the form of calcium aluminates; VI - rocks, including more than 4.5 wt.% Water-soluble A1 ₂ O ₃ ; VII mixtures of any of these materials, including at least 20% of each of them, while the content of the expanding component in the specified cement is maintained in the range from 2.5 to 50 wt.%.

In a further embodiment of the invention, as promoter component of artificial origin, namely aluminous clinker or slag, sulfoaluminate, or sulfoferrite, or hyperalitic clinker, or other products, including calcium minerals of the same name, take promoted materials, and specifically obtained by introducing promoters of the same named minerals into mixtures of starting or sintering or melting materials, with a calculated promoter basicity of about 1.01-1.07 times the calculation the basicity of the mixtures mentioned.

In an embodiment of the invention, when grinding into said cement, a fibrous component of inorganic and / or organic origin is additionally introduced in an amount of about 0.2-2 wt.% Of said cement.

In another embodiment of the invention, a water-reducing component is additionally added to said cement during grinding and / or by mixing in an amount of about 0.1-2.5 wt.% Of the clinker part of said cement.

In a further embodiment of the invention, materials from the group of a salt of alkaline-earth and / or alkali metals of the condensation product of naphthalenesulfonic acid with formaldehyde are used as a water-reducing component of said cement; a salt of alkaline earth and / or alkali metals of the condensation product of melamine-containing resins with formaldehyde; technical lignosulfonate of alkaline earth and / or alkali metals, conventional or modified with phenol-formaldehyde resin; complex salts of alkaline earth metals and sulfuric and / or nitric and / or formic and / or acetic acids with low molecular weight C ₃ -C ₅ monosaccharides; paired mixtures of these materials in a mass ratio of from about 4: 1 to about 1: 4.

In an embodiment of the invention, a water-holding additive consisting of cellulose polyesters is additionally added to said cement during grinding and / or by mixing in an amount equal to about 0.01-1.5 wt.% Of the total mass of clinker minerals - tricalcium silicate (3CaO-81O ₂ ) and tricalcium aluminate (3CaO-L1 ₂ O ₃ ) - as part of the specified cement.

In another embodiment of the invention, materials from the group: methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxyacetyl cellulose, sulfocellulose or their paired mixtures in a ratio of about 4: 1 to 1: 4 by weight are used as a water-retaining additive to said cement.

The essence of the alleged invention in terms of the manufacture of cement is to eliminate the induction periods of the processes of mineral formation, mainly alite formation during sintering of Portland cement clinker containing at least two minerals from the group C ₃ 8, C ₂ 8, C ₃ L, C ₂ (L, P), and the conversion of these processes from catalytic to autocatalytic by burning said clinker in the presence of a promoter additive that stabilizes the formation and growth of clinker minerals, namely microphases of new mations in the contact surfaces of the melt / minerals, including minerals of these and / or C1 ₂ A _7, CO, C ₂ R, SR, C ₄ l of ₃ 5 ', C 5', alkali, sulfate and halide derivatives thereof, aluminates, silicates, alkali metal ferrites, as well as calcium oxide and compositions of the indicated minerals with it, at calculated basicity levels of the promoter and clinker, calcined in the presence of the promoter and called below in accordance with the usual chemical nomenclature - promoted clinker (in tables P-clinker), exceeding the basicity of the specified eute clinker melt in a 1,0003-1,07 times.

The reason for the indicated name of the introduced additive and the basis of the physicochemical mechanism of its action are explained below. It is known from crystallization theory that crystallization seeds should contribute to the elimination of the induction period, however, industrial tests of cement additives, including ground clinker and introduced into the fired cement raw material mixture, showed that the productivity of the clinker kiln increased only by the amount of added additive of the finished product, and the quality of the cement rose slightly [16]. Since the furnace’s raw material productivity has practically not increased, there is no reason to believe that the induction period of alitogenesis has decreased. Therefore, in this work, the seed of cement does not actually play its intended role. Indeed, the idea of seeds too simplifies the phenomena occurring in a multicomponent, sometimes liquating clinker melt, from which the minerals do not crystallize, as from the mother liquor in the case of coincidence of the chemical compositions of the melt and the product, but are formed as a result of a group of the mentioned conjugated reactions (1--4 ) In such a situation, the leading factor is the degree of supersaturation with respect to the forming crystalline phases in two media: a) microzones of the melt adjacent to solid surfaces - substrates, which are likely nucleation sites; b) the solid surface microphases mentioned above and which are the composition of the forming nuclei of the products of the above reactions. Moreover, for a nonequilibrium process, the rule about a positive basicity gradient in the zones of contact of the clinker melt with the microphases of the surface of clinker minerals, the catalytic effect of which on the increase in the content of the latter is intensified by the addition of a promoter, must be observed. In fact, there can be two induction periods of alitogenesis, as mentioned above, precisely because of the presence of two interconnected, catalytically active heterogeneous media mentioned above and subject to supersaturation, and not only because of the “false equilibrium” created by the reaction product films that block the initial reagents . According to old ideas, these films, consisting of alite, are formed on the surfaces of belite and free calcium oxide, the main reagents from which alite is formed, after which the reaction stops, since there are no free surfaces of the starting reagents (the moment of suspension of the reaction, as if corresponding to chemical equilibrium, actually far from it, therefore it is called the moment of "false balance"). After the enlargement of primary alite crystals (recrystallization), these alite films become permeable as a result of the opening of channels between enlarged crystals, which takes time, during which the reaction does not proceed. This period can play the role of the second induction period [4, 15]. However, with such an explanation, it should be expected that the induction periods of mineral formation are unavoidable. This is the case in the methods known from the prior art, therefore, the explanation of these periods by the emergence of films from reaction products has long been universally recognized. In fact, the induction periods of alitogenesis are eliminated by the practical implementation of the method of manufacturing cement according to the invention as a result of the implementation of the above-mentioned “rule of positive gradient”, as it is abbreviated below.

The present invention allows to eliminate both one and two induction periods of mineral formation during firing of clinker in the presence of a promoter by creating conditions for supersaturation with respect to the main clinker minerals: a) in the surface zones of primary melts at the stage of the so-called solid-phase reactions; b) in the near-surface zones of the general clinker melt after its formation at the stage of liquid-phase reactions; c) in said surface microphases at both of these stages. Under conditions of local supersaturation of melts near the surface of the reagents, the promoter stabilizes the microphase nuclei. The spatial combination of the active zones in both media ensures the stability of the crystallization courtyards of clinker minerals and creates opportunities for the rapid formation and growth of crystals of the latter without induction periods with a more intense release of crystallization heat than is known from the prior art. This is the main feature of the proposed technical solution. It should be noted that the formation of a clinker melt with partial melting of the calcined material is accompanied by a significant endothermic effect. The opposite, exothermic effect of the promoted crystallization leads to the release of an amount of heat, which often overlaps the energy consumption for melting, and the technical effects of the present invention described below depend on the degree of overlap of the last effect of the first clinker firing under the given specific conditions. The stabilization of clinker mineral embryos is considered as a heterophasic supersaturation of surface microphases. The indicated role of the promoter additive is ensured by the calculated level of its basicity - 1,0003-1,07 - higher relative to the eutectic clinker melt and when technologically caused by the combination in both media, liquid and solid, of the active reaction zones, while maintaining a local positive basicity gradient, in the local melt layer on the surface of the main reagents in mineral formation reactions, namely, microphases, which, according to [10], perform the function of the main catalysts for mineral formation in a heterogeneous system asplavy - solid phase "in the areas of spatial contacts of solid and liquid components together in the thermodynamic system under consideration. It is of interest that in the calorimetric bomb the presence of the promoter according to the invention actually reduces the energy consumption for clinker burning by 5-7%, which is not observed in the presence of mineralizers, as well as when replacing a portion of the alite in the clinker with whiteite, i.e. with a decrease in the clinker saturation coefficient with lime. The reason for this is the presence of induction periods of alitogenesis in all cases when the promoter is absent.

As you know, a promoter is a substance whose addition to a catalyst increases the activity, selectivity and stability of the latter [17]. The promoter according to the present invention performs precisely the indicated functions with respect to mineral formation catalysts — surface microphases and basic clinker minerals C ₂ 8, C ₃ A, C ₂ (A, P), and also with respect to the autocatalyst - C ₃ 8. Therefore, the designation proposed in the present invention additives by the term "promoter" is quite strict from the standpoint of the chemistry of catalysis.

A basicity at the level of 1.0003-1.07 relative to the basicity of the specified melt determines the supersaturation of the latter with respect to clinker minerals, is a fundamental difference between the present invention and the prior art, and this very difference ultimately eliminates induction (induction) periods ( period) mineral formation during clinker firing and provides all the main technical effects of the invention. In this case, an accurate assessment of the basicity value, which cannot, in accordance with the usual practice of chemistry and cement technology, be based on the levels of molar ratios C / 8, C / A and C / P in the main clinker phases, is a prerequisite. Recent relations do not allow taking into account the basicities: a) non-calcium mineral impurities; b) calcium phases, including such impurities. And most importantly, the molar ratios shown are weakly related to the reactivity of minerals during their formation during sintering, and the successful use of these molar ratios as measures of the basicity of clinker minerals in chemistry and cement technology is mainly due to their relationships with the rate of interaction of clinker minerals with water and with hydraulic activity of cement. The reactivity of the relative basicity (b, shown in parentheses) of oxides, halides and minerals, components during the formation of minerals from ionized and / or radicalized melts, which, as is known, includes clinker melts, is due to their electron affinity [7, 9] , or the relative ability to acquire / return a negative charge, characterized by such a well-known property of atoms and ions as electronegativity [18].

The idea of the basicity of chemical compounds, in particular, clinker minerals, as a reciprocal of electronegativity (EO), calculated according to the above methodology as the reciprocal of the algebraic sum of the EO of atoms in each compound - oxide, a halogen molecule - based on the EO scale developed by L. Pauling [19], i.e. as an inverse linear combination of the values of the EO of atoms, was put forward in [20]. It is based on the well-known position of the acid / base theory of G.N. Lewis: the base is a donor of electron pairs, and the less its affinity for an electron, the higher the basicity. It is this condition that is fulfilled when determining basicity as the reciprocal of the EO. Interatomic interactions are not taken into account in this calculation procedure, but for the selection of the composition of the mineralizer, as was done in [20], as well as the promoter and clinker according to the invention, the accuracy of formulas (5-17) is sufficient. A similar approach — the calculation of the target characteristics of chemical compounds or minerals — Fermi levels, electrical conductivity, chemical bond energy, ionic degree of ion-covalent bonds as functions of a linear combination of the characteristics of constituent atoms — is used in many fields of physical chemistry, in particular, in the theory of molecular orbitals as linear combinations of atomic orbitals or in the geometric theory of valency.

The meaning of formulas (5-17) and the designations of the quantities included in them becomes more clear from the examples of the invention.

The basicity of the mentioned eutectic clinker melt (ECR) is constant (eop81), equal to 2.24 srvc. units based on the values of the inverse EO calculated by Pauling and calculated from the data on the oxides, based on the composition of the ECR (wt.%): CaO 54.8; 8ΐΘ ₂ 6.0; A1 ₂ O ₃ 22.7; Re ₂ O _{3 is} 16.5, which corresponds to the composition in molar fractions of Co, 697Ao, 159%, O7z8o, O71 [12, 20]. In the present invention, the specified constant for ease of calculation is taken equal to 100 srvc. units in formulas where the proportions of chemical compounds are expressed in wt.%, and equal to 1 srvc. units in formulas where the fractions of chemical compounds are expressed in molar fractions, as presented above in alternative expressions of the composition of the ECR.

Based on the values of the EA by Pauling, the following decreasing series of significant interest for the present invention was calculated [20]:

K ₂ O (1.46)> Ma ₂ O (1.37)> L1 ₂ O (1.32)> BaO (1.12)> 8O (1.09)> CaO (1.07)> M _Y O (1.04)> C ₃ A (1.02)> ECR (1.00) = C ₃ 8 (1.00) = C ₄ AR (1.00)>> C ₂ P (0.99 ) = C ₁₂ A ₇ (0.99)> C ₂ 8 (0.97) £ CA (0.97)> C ₁₂ A ₇ £ (0.96)> CP (0.95)>> 3 (CA ) C 8 (0.94) »ReO (0.91) = ΝίΟ (0.91) = CoO (0.91) = MW ₂ O ₃ (0.91)>

> A1 ₂ O ₃ (0.90) = ΙΪ ₂ Ο ₃ (0.90) = Cr ₂ O ₃ (0.90)> CuO (0.88)> Pe ₂ O ₃ (0.86)>

> MoO ₂ (0.85)> 8O ₂ (0.83)> MnO ₂ (0.81) ^ TH ₂ (0.81)> P ₂ O ₅ (0.79)>

> Mn ₂ O ₇ (0.76)> 8 O ₃ (0.75)> C1 ₂ (0.70)> P ₂ (0.56).

(eighteen)

In bold letters, the most common oxides in the cement raw material mixture, as well as the main minerals of Portland cement clinker, are highlighted. It can be seen from the above series that the basicity of Portland cement clinkers when calculating the basicity as the product of the basicity values of clinker minerals (b,) and the content of the latter in clinkers (p (), wt.%, Can practically not exceed 100 conventional units when the basicity of the ECR is also 100 srvc. In the absence of supersaturation, the reason for the ineffectiveness of using conventional ground Portland cement clinker or Portland cement as a seed for mineral formation during clinker roasting, since gypsum (C 8), as can be seen from series (18), reduces the basicity of cement compared to ground clinker.

Designing the composition of the promoter, clinker, mineralizer according to basicity levels corresponding to the conditions of supersaturation of clinker melt, or, what is the same, surface microphases calculated according to the method described in this description of the invention, namely based on a series of (18) using formulas (5- 17), in connection with the peculiarities of using the promoter and mineralizer in various technological conditions of cement production, corresponding to the variants of the invention, is explained in the examples of the invention. From these examples it can be seen that it is the fulfillment of the conditions for the supersaturation of the melt and the specified microphases specified in the present invention that allows to obtain technical effects of the invention.

Compliance with the calculated values of the basicity of the promoter in technological embodiments of the invention allows to exclude the induction period of alite formation during roasting of the promoted clinker, to radically reduce the loss of energy released during the passage of solid-phase exothermic reactions, as well as exothermic reactions (1) and (3) occurring in the presence of melts, and due to thermal gain, it is in the high-temperature region (above 1200-1350 ° C) and, accordingly, the resulting exergy effect that ain technical effects of the present IMAGE taenia listed below, while achieving are unexpected in relation to the prior art. From the stated general considerations, it is obvious that the smaller the loss to the environment, the higher the degree of use of the additional thermal effect of the fast promoted crystallization of minerals in the calcined material. Therefore, the technical effects mentioned are the higher, the larger the dimensions of the furnace, the greater its productivity and the higher the level of energy intensity of its working volume. Therefore, small wet process furnaces are the least efficient, and large dry process furnaces are most effective for implementing the present invention. It should be noted that with respect to mineralizers the situation is the opposite: their surface activity in primary melts, which creates small fuel savings due to the acceleration of the formation of the melt and its impregnation of the calcined material, is practically independent of heat loss to the environment, but it clearly improves with quick and uniform heating a layer of material in the furnace. Consequently, mineralizers are more efficient on production lines with small furnaces of small capacity. These simple considerations are confirmed by industry practice. That is why the combined use of a promoter and a mineralizer is a universal technological technique, the most effective for any sizes of clinker kilns and technological lines of the modern cement industry.

The exact equality of the calculated basicity of the promoter and the basicity of the eutectic clinker melt is unacceptable, since it would mean the absence of supersaturation for alite formation, and therefore cannot contribute to the elimination of the induction period of alitogenesis. The calculated basicity of the medium is higher than 1.07, which corresponds to the calculated basicity of free lime in the series (18), is created only by the presence of alkali metal compounds that reduce the solubility of lime and inhibit alite formation at the final stage of the process, therefore, increasing the basicity of the promoter and catalytic media in excess of 1.07 is impractical . For the mineralizer, in cases where segregation allows the concentration of highly alkaline zones of the mineralized melt with an appropriate degree of averaging of the calcined material near the acidic microparticles of the latter, namely, microparticles with a high proportion of coarse-grained 81O2, slowly entering mineralization processes, it is permissible to increase the basicity of the mineralizer, as shown by the practice of use the method according to the invention, up to 1.10.

The alite formation promoter according to the invention is a mineral oxide additive comprising two or more clinker minerals from the groups: I: tricalcium silicate (3СаО-8Ю ₂ ), dicalcium silicate (2СаО-8Ю ₂ ), tricalcium aluminate (3СаО-Л1 ₂ О ₃ ), aluminofer calcium [2CaO (L1 ₂ Oz) _x - (Fe ₂ O ₃ ) 1- _x ], 2/3>x> 1/3, and / or II: mayenite (12CaO-7L1 ₂ O ₃ ), calcium monoaluminate (CaO -L1 ₂ O _3), monocalcium and dicalcium ferrite (2CaO-Fe ₂ O _3, CaO-Fe ₂ O ₃₎ and / or III: alkaline, sulfate and halide derivatives of said groups of minerals and / or IV: sulfoalyu calcium INAT (4SaO-3L1 ₃ -8O ₂ O _3), calcium sulfate (Sa8O ₄₎ and / or mixtures thereof and derivatives thereof, and / or V: the mixture of said minerals groups between themselves and / or with the free calcium oxide mechanical and / or obtained together in the form of clinker, or sinter, or slag, or sludge, or suspension. All four of the listed physical forms of the promoter during testing showed approximately equal efficiency in the corresponding technological options in cement production. With the additional introduction of the mineralizer provided for in the embodiment of the invention, the mass ratio of the promoter and the mineralizer is established taking into account the additional presence in the latter of mineral salts formed during firing from the components of the cement raw material mixture and process fuel. For all of the listed minerals and their acid derivatives (if there are any), the calculated relative basicity of L _{1 is} lower than or equal to 1, and only for free calcium oxide, tricalcium aluminate (C ₃ L) and alkaline derivatives of the latter L is higher than 1. Promoter acting on contacts surface microphases with solid and liquid phases, smooths out the vibrations of basicity that occur due to the heterogeneity of the material being fired, stabilizing the level of the latter inside microvolumes - crystallization courtyards, which was mentioned above as a function of industrial torus. An additionally introduced mineralizer, acting on the contacts of the surface microzones of the melt with solid and liquid phases, plays the role of an additional catalyst that enhances the action of the others, and, in turn, the promoter enhances the effect of the mineralizer: a synergistic effect takes place.

In the clinker kiln that is free from the promoter, the latter is first introduced in the fraction of the calculated amount calculated by the formulas (5-17), namely in the amount of 0.1-0.8 May. hours on May 1. hours of the estimated amount, usually approximately 0.3-1.5 wt.% of the promoted clinker, in order to cause corresponding changes in the composition of the coating (increasing the basicity to an equilibrium level, accompanied by an increase in the strength and density of the coating, since the shrinkage increases the shrinkage of the coating , respectively, its density and strength increase) and the speed of movement in the kiln of the calcined material (the indicated speed increases by 5-15% due to an increase in the uniformity coefficient of the particle size distribution we burn material and a decrease in its adhesion to the coating, which causes a decrease in the degree of entrapment of the calcined material in the rotary clinker kiln on the furnace lining when it slides down under its own weight with each revolution of the furnace and, by the way, saves energy on the rotation of the furnace).

Acceleration of mineral formation in the presence of a promoter due to the lower solubility of impurities in solid phases compared with the melt reduces the possibility of impurities entering the crystals formed from the melt and reduces the concentration of impurities in the crystal lattices of the main clinker minerals (refining effect). This further leads to changes in the composition and properties of hydrated neoplasms that occur after grinding the promoted clinker and mixing with water the cement obtained from it. The experiments of the authors of the present invention, performed in the production conditions of cement enterprises and in precast concrete plants and construction sites, show that the regulation of the content of impurities in the main clinker minerals by changing the content and basicity of the promoter introduced during clinker formation changes the nature of the growth of growths - hydrosilicates, hydrosulfoaluminates and calcium hydroaluminates in a hardening cement stone. With an optimal content of impurities corresponding to an allowable maximum content and basicity of the refining promoter, the process of hydration of the clinker part of cement of a given specific surface is accelerated, the content of hydrated phases at a given point in time increases, and the coalescence of these hydrated phases is facilitated compared to a control cement made from control clinker obtained without introducing a promoter into its composition. After the content of the indicated promoter passes through the acceptable optimum due to the increasing refinement of alite and belite in the promoted clinker, all the beneficial effects of the invention begin to decline, but usually the cement strength is the most sensitive indicator for the content of the refining promoter to pass through the acceptable maximum. This is because in the hydrated phases there is a threshold concentration of impurities, below which the hydrated phases cease to grow together and ensure the solidity of the hardening cement stone. It is known, mainly from the work of V.V. Timashev et al., That the rule of pairs of intergrowths between the main three classes of hydrated phases of Portland cement - hydrosilicates, hydrosulfoaluminates and calcium hydroaluminates, from which the first and second, as well as the second and third phases grow together , i.e., hydrosilicates and hydrosulfoaluminates, as well as hydrosulfoaluminates and calcium hydroaluminates, whereas hydroaluminates do not merge with calcium hydrosilicates. The experiments of the authors of the present invention on hydration and hardening of cements from promoted clinkers confirm this rule and indicate that calcium hydrosilicates are fused with calcium hydrosulfoaluminates due to the presence of A1 ₂ O ₃ and 8O ₃ in the first impurities, and δίθ ₂ impurities in the _second . High-sulfate hydrosulfoaluminates of calcium, on the other hand, coalesce with calcium hydroaluminates, also due to impurities of 8Su ₂ and 8O ₃ in both phases. When the impurity content is below threshold levels, the growth of neoplasms even according to the rule of pairs is difficult, apparently due to the lack of local correspondences of the sizes of crystal lattices in the surface layers provided by these impurities and which are a necessary condition for intergrowth in accordance with the well-known rules of epitaxy / endotaxy of mineral crystals. The degree of hydrate accretion is less important for the initial cement strength, when the increase in hydrate quantity has a more significant effect on the cement strength due to the surface of clinker minerals in the promoted clinker that reacts more quickly with water due to the higher concentration of microdefects per unit surface of minerals in comparison with control clinker. The value of the degree of intergrowth of hydrated phases and the monolithization of the microstructure of cement stone, at which even partial coalescence of hydroaluminates with hydrosilicates is ensured (after the introduction of impurities δίθ ₂ and A1 ₂ O _3, respectively), is significantly larger for later cement hardening periods and, correspondingly, higher level values strength of cement stone at 28 days of age. This explains the fact that, as a rule, the permissible maximum content of the refining promoter when clinker is fired according to the criterion of 1-3 day cement strength (0.7-3.5 wt.% Clinker) is on average higher than according to criterion 28- daily strength of cement (0.3-1.5 wt.% clinker). When the content of the refining promoter is excessively high, a slow increase in cement strength is observed from 1-3 days to 28 days, for which there are no other technological reasons, therefore, exceeding the content of such a promoter over the indicated permissible maxima significantly reduces the beneficial effects of the present invention in terms of strength characteristics of cement. However, the hybridizing promoter has the opposite property - to increase the content of impurities in the main clinker minerals, which allows us to achieve monolithization of the structure of cement stone and with an increase in its content, the degree of fusion of these neoplasms in the cement stone increases with each other and, accordingly, the strength of cement increases, to a greater extent - late curing. The difference between the refining and hybridizing promoters is the presence in the second of microimpurities, either not observed in the raw mix and clinker at this cement manufacturing plant, or present in a concentration an order of magnitude greater than their presence in the raw mix and clinker at this manufacturing plant cement.

Based on the refining phenomenon, the mentioned feature of calculating the composition and quantity of the promoter, as well as the composition of the promoted clinker, is based: as for the composition of ECR, small components are not taken into account in the calculations of the promoter basicity, including the main small components of MgO, 8O ₃ , K ₂ O. The reason is in that, for the growth of clinker mineral crystals from surface microphases, the main framework of crystal lattices, including five chemical elements: calcium, silicon, aluminum, iron, and oxygen, is crucial. The remaining elements, at least at the very beginning of the growth of microphases, have only a screening effect, i.e. minor effect, weakly associated with the specificity of the chemistry of this element. That is why, as well as for the calculated support of the indicated “rule of a positive gradient of basicity” at the local “melt / microphase” contacts, when calculating the basicity of the promoter as compared to the ECR, small components must be omitted. The situation is different when using mineralizers: the basicity of the near-surface microzones of the clinker melt, from which the mentioned microphases originate, is significantly affected by the surface-active small components introduced by the mineralizer. This was paid attention at the very beginning of the development of the domestic cement industry, when it turned out that without taking into account impurities to the main oxides it is impossible to explain the peculiarity of the clinker microstructures obtained at domestic cement plants, especially when using mineralizers. In the 30s, V.N. Jung introduced into practice the use of the term “minor constituents” of the raw mix and clinker [21] in the sense used in the description of the present invention, with reference to the main minor constituents — MdO, 8O ₃ , Ba ₂ О, К ₂ О and other minor components, of which N.A. Toropov, Yu.M. Butt, V.V. Timashev and A.I. Boykova in the 6070s of the XX century recognized the technological significance of the following acid compounds P , C1, P, with metal compounds that are currently classified as b-elements: Τι, Cr, Mn, Co, N1, Mo, Cu, of which the first is a chemical analog g of aluminum, and the rest, with the exception of the latter, is iron, and compounds of elements - analogues of alkali and alkaline earth metals, now called 8 elements: L1, 8g, Ba. Other small components encountered, such as V, Pb, Ζη, Cb, 8b, δη, A8, Pb, Τ1, as follows from the works performed in the 80-90s of the XX century, have mainly sanitary and hygienic significance, influencing on the environmental situation around the cement enterprises and when using cement in the construction business, and have no appreciable technological significance for cement production, therefore, they are not considered in this invention as objects taken into account when calculating basicity.

Note that, as follows from formulas (12) and (13), when calculating the initial amount of introduced promoter, one needs to know the basicity and, therefore, the design mineralogical composition of the promoted clinker before it is actually obtained, and for sound design of the basicity of the promoted clinker, production experience is required introducing the method according to the invention. At the same time, on the basis of the very first production experiments with obtaining a promoted clinker, the initial estimated amount of promoter can be clarified using real values of the basicity of the promoted clinker obtained in this furnace, and the operations of adaptively selecting the optimal promoter content in the calcined material described above, already by adjusted source data. Thus, as can be seen from the above, not only the process of selecting the optimal promoter content in the material being fired, but also the process of calculating the optimal initial amount of the promoter is also adaptive with iterative approximation to the optimum.

The main technical and economic effects and features of the method according to the invention in terms of cement production are as follows (ceteris paribus compared to the prototype method, that is, without the use of a promoter):

A. Cement according to the invention is produced on the same production lines and the same main processing equipment as the control Portland cement clinker obtained by traditional technology. The production of cement according to the invention does not require mandatory changes to all, without exception, the main technological parameters of the operating modes of technological equipment. That is why the introduction of the present invention practically does not require significant capital expenditures, which is one of the fundamental advantages of this invention over the prior art, since it decisively increases the importance of these technical effects for the practice of cement production, being a guarantee of the widespread introduction of the present invention in the cement industry. The same effects achieved by traditional routes require capital expenditures comparable to those required for the construction of a new production line.

B. The characteristics of the technological process for the production of promoted clinker and the main characteristics of the cement according to the invention are changed in comparison with the production of Portland cement according to the prior art as follows.

B1. The productivity of rotary kilns during clinker firing under the conditions of a reserve on the power of devices for supplying power to the furnace, for burning fuel and draft devices, as well as a clinker cooler increases by at least 8-10%, and specific fuel consumption is reduced by at least 5%. Maximum values are 2-3 times higher than the guaranteed minimum.

B2. The resistance of the refractory lining of a rotary kiln with its normal mechanical condition and normative operation increases significantly. The maximum life of the refractory lining in the conditions of the invention for the first time is practically unlimited.

B3. Dust formation in the furnace unit and the load on the dust collecting devices are reduced by no less than 15, on average - by 30%. The observed maximum effect - the complete suppression of dust formation in the furnace and the practical transparency of the furnace atmosphere - is achievable only in furnaces with a wet production method. But the suppression of clinker dusting according to the invention is feasible with both wet and dry production methods.

B4. Clinker grinding ability when taking into account the decrease in average granule size and excluding clinker dusting increases by at least 15%, and without taking into account the decrease in average granule size, when testing a narrow particle size class of clinker (less than 1 mm after preliminary crushing) increases by at least 10 % The maximum effects, especially when receiving a promoted clinker in the form of a fine fraction with granules of 0.3-2 mm in size, in other words, grains, are 2-5 times higher, which allows to increase the productivity of cement mills by 20-50%.

B5. The hydraulic activity of clinker, or cement based on it, ground in a laboratory mill, increases, including the early strength of cement - at the age of 1-3 days. - not less than 5 MPa, and at the age of 28 days - not less than 3 MPa. The maximum effects are also 2-4 times higher and reach respectively 20-25 MPa increase in hydraulic activity of the clinker.

B6. The consumption of Portland cement obtained from this clinker in concrete without changing the strength of concrete is reduced by at least 5%. The maximum effect is 2-4 times higher.

The indicated minimum values of technical effects are achieved on almost any cement production lines. To exceed them, one sometimes has to resort to easy modernization of auxiliary equipment if it does not have a power reserve sufficient to provide the required increase in productivity. This applies to the design and arrangement of devices for feeding the furnace with a raw material mixture, for burning process fuel, draft equipment, clinker coolers, feeders. In addition, due to a significant increase in the grindability of the promoted clinker, as a rule, it is necessary to change the grinding load in cement mills.

The main elements of the unexpectedness of the invention in terms of the method of manufacturing cement in relation to the prior art are the combination of the performance increase of a clinker kiln with specific savings of process fuel and electricity with an increase in the quality of cement with significant savings in specific energy costs for grinding it and the simultaneous achievement of all these results with virtually no noticeable capital costs.

Embodiments of the method according to the invention provide increased values of these effects, as well as additional technical effects, many of which are the same or even more unexpected in relation to the prior art.

In experiments with clinker-promoted clinkers, the inventors discovered a number of previously unknown phenomena. So, it was found that the level of electrical conductivity of promoted clinkers at high temperatures is reduced by one or two orders of magnitude compared to those obtained without the use of a promoter. This phenomenon is caused by the immobilization of the active part of the clinker melt by the nuclei of clinker mineral crystals, which quickly form and grow from surface microphases in the presence of a promoter. For this reason, an increase in the promoter content in the calcined material decreases the conductivity of the latter, including during cooling of the clinker formed and in cold clinker. Unexpectedly, it was possible to use this phenomenon as an additional criterion for the maximum content of the promoter in the material being fired. As shown by experiments with a cell of two Ρΐ electrodes operating on alternating current with a frequency of 100 Hz and immersed in the calcined material with porosity of clinker grains no more than 20-22% and porosity of the layer of calcined material and clinker no more than 3538% of the measurement during normal cooling ( The “gray”) promoted clinker made it possible to establish that the presence of the promoter in optimal amounts reduces the conductivity level by about one to two orders of magnitude compared to the control clinker to no more than about 10 ^-6 Ohm ^-1 -m ^-1 . This phenomenon is observed with both types of promoters - refining and hybridizing. Similar measurements on a white promoted clinker showed a decrease in electrical conductivity by one or two orders of magnitude compared to control samples, that is, to a level of no more than about 10 ^-8 Ohm ^-1 -m ^-1 . Both series of experiments were carried out at temperatures ranging from maximum (1450 ° С) to the temperature of complete solidification of clinker at 910-1050 ° С. The most convenient for additional control of the amount of promoter in the material to be fired was a temperature in the range of 1200 ± 30 ° C, close to solidification of real eutectics in industrial clinkers. Experiments with pairs of electrodes fused into clinker granules confirmed that in the chilled clinker the difference in conductivity of the promoted and control clinkers remains. This implies the role of electrical conductivity as the most important low-temperature physical characteristic of clinker, consisting in the fact that its decrease is a measure of increasing the concentration of structural defects per unit clinker volume, which are “traps” for charge carriers below the Curie point (640-680 ° C) of positively charged electron vacancies. Thus, according to the results of the experiments of the authors of the present invention, the concentration of structural defects in conventional and white promoted clinkers, ceteris paribus, is about one to two orders of magnitude higher than that of similar control clinkers. In turn, the increased concentration of structural defects in the promoted clinker is the reason for its reduced resistance to grinding and the increased rate of its interaction with water compared to the control clinker.

The level of electrical conductivity is connected analytically or through relationships of the type of L. Onsager with a number of physicochemical characteristics of the calcined material and clinker and / or their liquid phases, such as viscosity, self-diffusion rate of individual ions and radicals, their sizes, sizes of crystallization courtyards, chemical reaction potentials mineral formation and crystallization of minerals, their activation energies and thermal effects, crystal growth rates, the content and sizes of microvolumes of liquid phases, the electric capacity of interphase boundaries and their specific surface, the amount of the liquid phase immobilized by these boundaries and the amount of free liquid phase, the associated amount of glass in the clinker, with the main characteristics of the clinker submicrostructure, such as the density of dislocations in the main phases, primarily in alite, and also with the rate of cement hydration obtained on basis of the promoted clinker.

When analyzing such dependencies, the inventors predicted, and during production experiments on the production and study of promoted clinkers, a previously unknown phenomenon of the formation of a cellular microstructure of the phase of tricalcium silicate (3CaO-81O ₂ ) -alite was discovered. Cellular microstructures are known in metal science as a result of directed crystallization of ingots from melts with alloying impurities. In promoted clinkers, the phenomenon of the formation of a cellular microstructure was detected for the first time and is due to a faster movement of the crystallization front of the alite phase at an optimal promoter content in the material to be fired compared to the diffusion of impurities in the melt away from the crystallization front, taking into account the fact that the distribution coefficient of impurities in alite compared to uterine melt is negative, that is, the content of impurities in alite is less than in the melt. When the crystallization front is ahead of the movement of impurities, but their entry into the growing phase in equivalent amounts is excluded, the impurity migrates along the crystallization front to the sites of slower growth of the new phase, in this case, alite and, accumulating in them, forms linear or two-dimensional structures - cell boundaries , Thus “integrating” in quantities that are excessive in comparison with the normal “capacity” of the crystal lattice in the alite structure along the cell boundaries. At the end of alite formation, in view of the limitation of the amount of mother material, the growth of alite crystals slows down, impurities begin to have time to “leave” in the melt from the crystallization front. Then, i.e. at the end of the process, alite acquires its usual regular monoclinic (lamellar) or trigonal (dodecahedral) cut. The result is a conglomerate of cells inside normally faceted alite crystals. In FIG. 1, which is a photograph from the surface of a polished section of a promoted clinker, taken through an optical microscope in reflected light at a magnification of 440 times, the cellular microstructure of alite phase crystals is visible (these crystals are dark faceted polygons against a light background of the clinker intermediate, in many crystals the internal cellular texture is visible , not like round belite inclusions) obtained in the promoted clinkers according to the invention with the optimal input of the promoter into the calcined material , which is a diagnostic (that is, characteristic and sufficient) symptom of clinkers obtained according to the method of the invention. This is also due to the content of alite crystal clusters in the promoted clinker (fraction of intergrown crystals), not exceeding 10%. Such a microstructure, especially in highly alkaline clinkers, significantly facilitates the grinding of the promoted clinker compared to the known one, reducing the specific energy consumption due to weakening of physical bonds along the cell boundaries inside the alite phase crystals. Thus, the involvement of impurities along the boundaries of the blocks of the mosaic submicrostructure of alite in the process of interaction with water after mixing of cement made from promoted clinker increases. This accelerates the hydration and hydrolysis of alite in the first stages of cement hardening, despite the partial release from impurities (refining) of the internal volumes of mosaic blocks in the submicrostructure of the alite phase. However, the mentioned alite cellular structure in the promoted clinker according to the invention does not occur if mineralizing components are present in the melt that accelerate the diffusion of impurities so much that they manage to diffuse from the crystallization front faster than its advancement, or, on the contrary, significantly facilitate the direct entry of the impurity into the crystal lattice of the alite phase along the entire front of crystallization. Thus, alkali, acid anions uncompensated 8o ₄ ^2-, PO ₄ ^3-, F ^-, lowering of alite solubility in the melt, accelerate its crystallization, but slow down the diffusion of impurities such as Mg ²⁴ and in the presence of a promoter promote formation of a cellular microstructure ranging with 1.5% MdO in clinker and higher. The compensation of alkali cations by the indicated acidic anions in accordance with series (18) causes, despite the rapid crystallization of alite, a significant acceleration of the diffusion of MD ²⁴ in the melt, which does not allow the formation of a cellular microstructure of alite. In principle, it is obvious that it is always possible in this way to select the compositions and ratios in the calcined material of a complex mineralizer and promoter in order to ensure the formation of a previously unknown cellular microstructure of alite crystals while maintaining their external correct faceting. Such alita crystals resemble faceted fruits of berries, in particular raspberries (cells = grains) embedded inside tabular or dodecahedral crystals, or fruits of drupes - angiosperms, where the agglomerates of grains are under a common outer shell like in pomegranate fruits. However, in practice, the necessary set of microimpurities for the selection of the composition of the complex mineralizer or promoter may not be available, which will lead to a non-cellular, albeit finely crystalline, alite structure in the clinker. At the same time, the positive technical effects of the invention described above will continue, but their values will decrease slightly. Therefore, the cellular microstructure of the alite phase, being a sufficient sign of the clinker obtained according to the invention, is not a necessary sign of such a clinker. Belite crystals in a promoted clinker can also be cellular, but, unlike alite, the content of cellular belite never reaches, according to observations, up to 100% of the belite phase. As for calcium aluminates and aluminoferrites, the presence of their cellular forms in promoted clinkers is less likely due to about an order of magnitude higher crystallization rates upon cooling of clinker, which contributes to the occlusion of impurities rather than cell formation. The question of the cellular forms of calcium aluminates and aluminoferrites in promoted clinkers, which requires careful electron microscopic studies to be solved, remains open today.

Cell sizes in alite range from 0.3-1 to 3-7 microns. The cell sizes in belite are less studied, since in practice the inventors more often had to produce alite, high alite and especially high alite, practically not containing belite, promoted clinkers. Experiments show that with an increase in the content and basicity of the promoter, the average cell size decreases, and the number of defects — cell boundaries per unit surface area of an alite crystal — increases, which leads to an increase in clinker grindability and to an acceleration of the dissolution of ground clinker particles in water. Rapid dissolution of cement in water can significantly accelerate the formation of "cement gel" (see more on this below) and increase the growth rate of cement strength in the initial period of hardening (1-3 days).

To optimize the content of the promoter in the calcined material according to the characteristics of the microstructure of clinker that does not form cellular alite, the content of clusters of crystals of the phase of tricalcium silicate (3CaO-81O ₂ ) -alite, i.e. the fraction of the grown crystals of alite in the total, is used as a criterion for the optimal amount of promoter in the calcined material its mass. With an increase in the promoter content, the fraction of single alite crystals increases, and in principle and in practice, in some cases, the complete absence of intergrown crystals (clusters) in the microstructure of the indicated promoted clinker is achievable. However, this is actually hindered by the reduced reactivity of the feed mixture. As the production experience of the inventors shows, in order to select the optimal promoter content and achieve all the positive effects of the invention, it is sufficient to limit the content of clusters in the material to be calcined in an amount of not more than 25% by weight of alite. The increase in the cluster content reduces the effect of the invention and indicates the incompleteness of the technological preparation of the sintering process and / or insufficient and / or insufficient efficiency of the introduced promoter.

When studying promoted clinkers, the inventors also discovered the phenomenon of changes in the stoichiometry of the alite phase with changes in the composition and content of the promoter in the cement raw material mixture or in the material to be calcined, namely, an increase in the molar ratio of CaO / 81O ₂ in the phase of tricalcium silicate (3CaO-81O ₂ ) - alita in the range from 2.8 to 3.2 with an increase in the content of the promoter both in the raw material mixture and in the material to be fired within (wt.% in terms of clinker) from 0.15 to 1.5 or more according to the specified limits with calculated basicity a promoter of 1.01 or more, as well as with a constant content of the promoter with an increase in the basicity of the latter in the range from 1.01 to 1.07. This method of controlling the stoichiometric composition of alite was proposed for the first time. From the prior art, in particular, the works of A.I. Boykova, T.V. Kuznetsova, A.P. Osokina et al. It is known that when changing the stoichiometry of clinker minerals, in particular, alite in clinker, achieved by regulating the cooling mode of the latter, it is possible to control the strength characteristics of cement in both early and late hardening periods. A similar effect on the strength characteristics of cement and a change in the stoichiometric composition of the alite phase, caused by the indicated variations in the composition and content of the promoter, however, the influence of the promoter on the cement strength is more significant than changes in the clinker cooling mode. In the experiments of the authors of this invention it was found that in the presence of a promoter the influence of the clinker cooling regime on the stoichiometric composition of the alite contained in it, as expected from the Onsager ratios, is less significant than in the absence of a promoter. In other words, the quality of the promoted clinker is less sensitive to the cooling mode compared to the usual clinker, which is consistent with the conclusions from thermodynamics.

Reducing the activation energy of alitogenesis in the autocatalytic process allows increasing the estimated content of tricalcium silicate in the promoted clinker according to an embodiment of the invention to about 70-80 wt.% Against about 5565% in the control clinker by increasing the promoter content in the calcined material to the maximum amount according to the reduction criterion in the promoted the clinker of the content of marginal phases C _{! 2} A ₇ , C ₂ P and CP and their alkaline derivatives up to about 1 wt.% or less with an increase in cement strength, from made from promoted clinker compared to control cement made from control clinker, with an equal specific surface area of 10-15 MPa after 1 day and 7-10 MPa after 28 days, but taking into account the increase in grindability of cement from promoted clinker and a corresponding increase the specific surface area of the last 30-40 m ² / kg as compared with the cement clinker from the control at constant energy input at the grinding of promoter and control values increase cement clinkers strength based on the promoter nnogo clinker compared with cement-based control clinker increases by 15-20 MPa and 10-15 MPa 1sutochnom in 28-day-old. The possibility of continuous industrial production of clinker and cement based on it, containing 75-80% alite with increasing productivity of rotary kilns, fuel economy and a corresponding improvement in the quality of cement, not only the strength but also the durability of concrete made from it, is an additional significant element of the surprise of this inventions compared to the prior art.

In the experiments of the inventors on the firing of promoted clinkers, a previously unknown phenomenon of the formation of a significant amount of microcrystalline X-ray amorphous alite in the composition of the latter was also found. It was found that this is due to the special completeness of the formation of cellular alite (50-100 wt.% Alite phase), as well as the formation of fine-mesh alite, in which the cell size is close to the size of the mosaic blocks in the alite submicrostructure, which is equal to, as is known [22], 0.10.3 μm. It is such an alite that represents one of the microphases mentioned above, with the difference that in this case this microphase forms from 10 to 50% of the total alite content. In this case, at a given specific surface, the cement obtained from the promoted clinker hydrates when interacting with water 15-30% faster than that obtained from the control clinker, ceteris paribus, and taking into account the high content of alite, unattainable when firing clinkers known from the prior art , the promoted clinker interacts with water even faster by 25-40%. This allows you to achieve a significant increase in the strength of cement according to the invention, especially in the early stages of hardening. At the same time, the X-ray diffraction method41 for determining the phase composition of the promoted clinker containing the mentioned submicrocrystalline alite, as well as the X-ray spectral method for determining CaO at some frequency channels, introduce a systematic error in the estimation of the composition and, accordingly, the quality of the clinker and cannot be effectively used for production control of the composition and quality clinker when firing the promoted clinker according to the invention.

If the cement raw material mixture (in wt.% In terms of clinker) impurities of magnesium compounds in terms of oxide (MdO) is approximately 3.5-7, which reduces the hydraulic activity of cement, and / or impurities of phosphorus compounds in terms of pentoxide (P ₂ O ₅ ) approximately 0.25-1, which reduces the strength of cement, especially in the early stages of hardening (1-3 days), the content of the promoter in the calcined material is increased to a maximum amount in the range of about 0.5-1.5 wt. % in terms of clinker. In this case, tricalcium silicate in a promoted clinker is freed from most of these impurities, which pass into slowly soluble clinker minerals, which significantly reduces their harmful effect on the quality of cement. In this case, the content of MdO and P ₂ O ₅ in the tricalcium silicate of the promoted clinker is reduced by an order of magnitude in comparison with their amount in the control clinker, i.e. about 5-10 times. The same is noted for C ₃ A. This can be considered as refining the most active clinker minerals under the influence of the promoter, since refining is the cleaning of materials from harmful impurities [23]. The increase in hydraulic activity of cement from refined promoted clinker compared to the control in this case is 10–20 MPa at 1 day old and 7–15 MPa at 28 days old. This is the second significant additional element of the surprise of the invention compared to the prior art.

Promotion during sintering or melting / crystallization of the minerals that make up the promoter, in other words, repeated promotion increases the useful effect of the promoter on the characteristics of the roasting process and clinker grindability and reduces the working dosage of the promoter, which limits the possible negative effect of the accidental overdose of the promoter by reducing the coalescence of structural elements cement stone on the strength of cement at 28 days of age and later.

Combination of promotion with hybridization (from Lat. 1bpb - a crossbreed; previously the term “hybridization” was used only in biology to refer to the offspring of genetically different parental forms, now it is used in different fields of science and technology to denote the combination of heterogeneous elements in a single system to produce a new element ) the crystal lattices of the main clinker minerals and the regulation of their stoichiometry in the optimal range is achieved by combining various groups of minerals that are part of the promoter, and the above five groups, with such a manner that in the promoted clinker with the same name occur and the promoter controlling mineral clinker with different forms of both the original lattice. The authors of the present invention have experimentally found that hybridization of the alite crystal lattice eliminates the aforementioned harmful effect of exceeding the maximum content of the promoter in the calcined material on the quality of cement obtained from the promoted clinker, and thereby maximize the effect of the implementation of the present invention both in terms of saving energy consumption and the quality of the cement.

The acceleration of mineral formation due to the conservation of the heat of the exothermic effect and the autocatalytic nature of the genesis of minerals causes changes in almost all characteristics of the operation mode of the clinker kiln. The main one is the increase in the temperature of the calcined material in the sintering zone of the furnace compared to the control level without a promoter. This phenomenon, as shown by the inventors, is conveniently used for iterative adaptation of the fired clinker firing mode to the characteristics of the used clinker kiln, or kiln unit consisting of two pieces of equipment - a clinker kiln and a clinker cooler. Adaptation is as follows. Given the response time of the furnace unit, after the initial introduction of the promoter, an increase in temperature in the sintering zone of the specified furnace is expected to reach an easily visually fixed value of about 25-50 ° C compared to the control mode, which is achievable with sufficient operator experience or using any pyrometer installed in furnace head. Then, the furnace power is increased, adapting the firing of the promoted clinker taking into account the response time to the action of the promoter additive, until the temperature level returns to the control level, and usually this increase in power is 3-5%. The next step is to increase the supply of the promoter, then again increase the power of the specified furnace. Repeating these operations, that is, acting by the iteration method in relation to increasing the feed of the promoter and the feed of the furnace, they increase the productivity of the furnace by introducing the maximum amount of the promoter of the calculated composition adapted to these conditions, which is selected up to an order of magnitude in excess of the specified estimated initial quantity, and the criterion for the permissible maximum content of the promoter, determined directly during the clinker firing, is to achieve equilibrium of the composition of the promoted clinker but. This corresponds to the approximate equality of the actual alite content in the clinker, determined, in particular, using optical microscopy and the calculated (potential according to Bogg or Kind [24]) alite content in the clinker.

In the presence of the indicated equality, the clinker contains no marginal phases C1 ₂ L ₇ , C ₂ P, SB, which, as is known [5, 8], worsen the construction and technical properties of cement. The results of the experiments of the inventors showed that in the presence of phases C2B and SB with magnetic permeability, almost two orders of magnitude higher than the magnetic permeability of the clinker, it is convenient to use the content in the last magnetic fractions not exceeding about 15 wt.%, and when firing white promoted clinker - the content in the latter of mayenite (12СаО-7А1 ₂ О ₃ ) and / or alkaline forms of tricalcium aluminate a (K ₂ O-8CaO-A1 ₂ O ₃ ), where R = No., K, in an amount not exceeding about 3 wt.%.

The decrease in the content of marginal phases in the material to be fired in the presence of a promoter at all stages of mineral formation and in the finished clinker is explained by the fact that, by increasing the number of promoter, they accelerate the above reactions (1, 3), and only after the response time - reactions (2, 4) , which kinetically allows the clinker sintering zone to be heated in the furnace due to autocatalytic acceleration of exothermic reactions (1, 3), which, according to the Le Chatelier principle, provides parallel acceleration of conjugated reactions (2, 4), which provide izhenie content marginal phases. By increasing the feed of the furnace with the raw material mixture after heating, this additional exothermic effect is compensated, and the temperature in the sintering zone is again increased by an additional increase in the concentration of the promoter. Thus significantly increase the productivity of the furnace. The question arises about the endothermic effect of reactions (2, 4), which, if these reactions go to the end, sooner or later reduce the indicated temperature to the initial level, is removed by the nature of the reactions (2, 4): under catalytic conditions, they occur almost without heat absorption . This is facilitated by the fact that in the presence of a promoter during stationary operation of the furnace during cooling of the clinker, due to the exhaustion of marginal phases, endothermic reactions lose their effect on the temperature in the furnace. From the foregoing, it follows that the aforementioned response time of the furnace unit “clinker refrigerator furnace” should not be more than 1-4 hours, otherwise, some of the positive effect of the invention is lost. This ultimately involves the influence of the main technical characteristics of the furnace unit on the technical and economic effect of the present invention.

Accordingly, the decrease in the number and lifetime of the promoted clinker of the marginal phases decreases, and the content of alkali metals in the latter decreases to 50-92 and 40-85 wt.% In average samples and in samples taken at the time of alkali discharge from overflowing cycles of their circulation in the furnace, compared with the amounts of these oxides in the respective samples taken during the firing of the control clinker. The reason for the decrease in alkali content in the promoted clinker is the high degree of their sublimation in the sintering zone of the furnace due to the increase in the temperature of the calcined material in it compared to the firing of the control clinker and the lower likelihood of alkali being absorbed by the calcined material from the furnace atmosphere, primarily uncompensated valencies of the marginal phases, due to the reduction the time of presence of these phases in the calcined material. In some cases, the production conditions even in the "gray" promoted clinkers I ₂ O content = №-bo _th possible to reduce to a level of 0.1-0.3%, which has a significant positive value for the stability and durability properties designs and constructions of concrete based on cements from promoted clinkers, especially in the presence of aggregates containing active silica such as opal or dolomite. If the indicated level of promoter alkali cement clinker it is advisable to mix even with ordinary cement containing more than 1% I O ₂ and especially more than 1.5% I ₂ O that is characteristic for cements powerful technological lines dry process, in particular in a number of Nordic countries.

A significant additional element of the surprise of the present invention is the reduction in the presence of a promoter of the chromate content in clinker, which is of great sanitary and hygienic importance in connection with dermatitis caused by an admixture of Cr ⁶⁺ when using cement in mortars and concrete, mainly in finishing workers having direct contact with freshly prepared mortars and concrete. In the experiments of the authors of the present invention, a decrease in the average concentration of Cr ^{6+ by} 4-5 times in average samples of promoted clinker and in

5-7 times the maximum concentration of Cr ⁶⁴ in the samples of promoted clinkers at the moments of excess alkali discharge compared to the corresponding levels of chromates in the samples taken during the firing of control clinkers. The reasons are a decrease in the content of alkalis that contribute to the conversion of trivalent chromium impurities from raw materials to hexavalent chromium in clinker, as well as the concentration of impurities, including chromates, observed during promotion in separate zones (at the intercellular boundaries), with a decrease in their average concentration on the cement surface . This corresponds to a general increase in the oxidative thermodynamic potential of the surface of the promoted clinker with an increase in the reduction potential in the impurity concentration zones, which determines the reduction of chromate impurities into harmless calcium chromites. The accelerated decrease in the content of the magnetic fraction in promoted clinkers, mentioned above, is carried out under the influence of similar factors accelerating the reaction (4), which translates especially ferromagnetic calcium ferrites, characterized by a lack of oxygen compared to the stoichiometric composition and concentrated during crystallization from melt along interblock boundaries in calcium aluminoferrites , in calcium aluminoferrites with balanced stoichiometry.

It should also be noted the positive impact of the technology of promoting clinker burning to reduce the content in clinker / cement and other most harmful forms of small components having sanitary and hygienic significance, with their translation, at least in part, into less harmful forms. So, the translation of V ⁵ 'to V ² '' ³ ' is noted. Pb impurities transfer, Sb, V, T1, 8n of alite and C ₃ A to less rapidly interacting with water calcium alyumoferrity, amplification sublimation 8e, 8b, Ag from the clinker burning process in the presence of promoters. Studies of the influence of promoter basicity on these small clinker components are ongoing.

The acceleration of mineral formation during firing of promoted clinker is the reason for the decrease in the total content of free lime in the fired material and the absence of its recrystallization. As a result, free lime in the promoted clinker is present in two forms - crystalline and submicrocrystalline, or X-ray amorphous. Mas. the ratio of these forms of CaO in a promoted clinker made of a raw material mixture of high reactivity (with an activation energy of alitization according to S. Arrhenius is less than 1200 kJ / mol, see [4] for a method of calculating the activation energy of alitization), - approximately 1: 1 . In this case, only crystalline free lime in the finished promoted clinker has a harmful effect on the uniformity of the volume change of the cement stone and the strength characteristics of the cement made. As for submicrocrystalline CaO, it is extinguished even when the promoted clinker is stored in the unmilled state in air for 12 days. Therefore, as a criterion for the degree of calcination of the promoted clinker, the inventors recommend using the content of crystalline free lime in the latter in an amount of: up to 1 wt.% Upon receipt of the promoted clinker from a raw mixture of low reactivity (with an activation energy of alite formation according to S. Arrhenius of more than 1200 kJ / mol) or up to 1.5 wt.% upon receipt of a promoted clinker from a raw material mixture of high reactivity, while the total content of free lime may be allowed in the latter case, up to 3 wt.% without harm to the technical properties of cement.

The promoted Portland cement clinker obtained according to the method according to the invention fully complies with the main world standards, surpassing the clinkers known in the prior art in a number of characteristics, primarily in milling and hydraulic activity.

The use of mineralizers in combination with a promoter does not cause any additional difficulties in accurately following the requirements for selecting the composition of the mineralizer according to the level of basicity according to the present invention. The resulting synergistic effect is described in an example embodiment of the invention. Additional mineral components present in the complex mineralizer are allowed only when selecting their basicity in the composition of the mineralizer in accordance with the described requirements.

These positive technical effects of the invention are observed regardless of the options for supplying the promoter to the cement raw material mixture, carried out by mixing it with the last or one of its components during its preparation, or during its grinding, or by adding the specified promoter to the ground raw mixture before it enters clinker kiln, or by introducing the specified promoter into the cement raw material mixture during the firing of the latter. These options are chosen in connection with the characteristics of the furnace unit and the main technological equipment for the preparation of a cement raw material mixture, usually including calcareous, aluminosilicate and ferrous components (conventional mixture) or calcareous and aluminosilicate components (decorative or white mixture) and equipment for grinding the specified raw material mixture, In an effort to maximize the degree of homogenization of the promoter with the raw mixture and / or with the calcined material.

These positive technical effects of the invention are also observed regardless of the homogenization options of the promoter with a complex mineralizer and the options of homogenization and supply of both materials or their components to the cement raw material mixture or to the calcined material, carried out jointly or separately, taking into account the desire to maximize the degree of homogenization of the promoter with complex mineralizer and with the raw mix, since this leads to a decrease in the size of the courtyards of crystallization of minerals in clinker and, ultimately, to reduce the required dosages of the promoter and mineralizer. In this case, one of the components of the complex mineralizer is introduced separately from its other components and from the promoter only in cases where the cement raw material mixture is introduced into the furnace unit not in a single intake, but in parts; in particular, this is the case when using fuel containing an ash portion and adding the latter to the calcined material in the sintering zone of the furnace. Here, in order to comply with the conditions of K _r 1.01-1.07, the calcareous part of the complex mineralizer is introduced into the calcined material in the same place where the ash part of the fuel is seated to it and in the calculated amount to comply with the required range of K _p values. Otherwise, the main technical effects of the invention are reduced to a minimum.

To increase the degree of homogenization of the promoter with the cement raw material mixture according to an embodiment of the method according to the invention, the promoter is pre-mixed with a row or with one of the components of the cement raw material mixture, often in the dry production method with the glandular component, because in fact the promoter plays the role of smoothing in case of lack of glandular component, increasing the proportion of the melt in the calcined material due to the noted increase in the temperature of the latter in the sintering zone and an increase in the proportion of the melt due to an increase in vorimosti in the latter minerals burnt material with increasing temperature. The homogenization of the feed mixture with the specified promoter is carried out using any known mixers, but mainly, as was established in industrial experiments, by means of paddle, or vortex, or grinding mixers. In this case, with the wet production method, a vortex mixer is predominantly used, in which a stream of slurry is twisted with the supply of a promoter along the central axis of the vortex. In the dry method, for the homogenization of the feed mixture with the promoter, a feed mill or an additional grinding device is mainly used. In this case, the sticking of the calcined material in the heat exchange devices does not enhance the presence of the promoter under the following restrictions imposed on its chemical composition. With the wet method, it is advisable to increase the content of aluminate phases in the composition of the promoter, and in the dry method, the silicate phases, in order to reduce the interaction of alkali metal compounds with it, which are the main cause of the formation of heat build-up in the furnaces with the wet method and baking heat exchangers - with the dry method of cement production. In this case, there are no problems associated with preliminary chemical interaction between the promoter and the raw material mixture in the stages preceding the solid-phase reactions.

To increase the degree of homogenization of the promoter with the cement raw material mixture or calcined material, the specified promoter is used in powder form or in the form of a suspension with a specific surface area of the powder or solid phase of the suspension in the dried state (drying is required for disaggregation) of at least 150 m ² / kg, mainly in the range of about 2501800 m ² / kg when measured by the method of breathability, or about at least 400 m ² / kg, mainly in the range of 650-4500 m ² / kg when measured by the Brunauer-Emmett method Teller (BET) using low temperature nitrogen adsorption.

To further increase the degree of homogenization of the promoter with the cement raw material mixture or calcined material, it is possible to pre-mix the promoter or part of it with dust trapped from the exhaust gases of a clinker kiln, although this option is less desirable compared to those described above in order to avoid a decrease in the solubility of free lime in the melts at sintering associated with a local increase in the content of alkaline compounds in surface microphases in this embodiment. However, when firing the cement raw mix in kiln units with a suspended or fluidized bed, as was established in experiments with models of the respective kiln aggregates, this variant of introducing the promoter is possible, which is used in addition to introducing the promoter also with the raw mix.

The main feature of the variants of the invention related to the introduction and homogenization of the promoter with other reagents in the composition of the calcined material in clinker kilns, which necessitates a detailed determination of these options, consists in providing and taking into account the following main point of the clinker kiln promotion technology: the first contact of the promoter with cement raw mixture or with individual components of the latter, as well as with the mineralizer with its additional introduction carry out this way m, to minimize the likelihood of the contact of the promoter in the working area of the clinker kiln with low-base particles of other reagents. Accordingly, it is advisable that the low-base particles, before working contact with the promoter, have time to at least partially react with the high-base particles of the raw mix or complex mineralizer. Otherwise, the promoter is used inefficiently and the expected result is not obtained.

When implementing a variant of the method according to the invention, as in general in the modern cement industry, a rotary kiln is usually used as a clinker kiln. It is possible to use the method according to the invention, as already mentioned, when using kilns with fired cement raw material mixture in suspension, including in the flowing layer, as well as shaft furnaces or furnaces with a conveyor burning grid using carbon fuel (oil products, coal, natural or synthetic gases) or radiation heaters or furnaces with full or partial melting of the fired material - vertical, bathtubs, cupolas and their large analogues and converters and even blast furnaces minutes, in which the clinker is at the metal slag smelting of ore. The use of fuel with oxygen enrichment, as well as the use of waste gases from underground coal gasification, waste incineration, and the like, does not interfere with the use of the invention. In practice, the method according to the invention is applicable under any known conditions for the production of Portland cement and its varieties, including stages involving solid-phase and / or liquid-phase reactions occurring during the firing of cement raw mixes.

When firing the latter in a rotary kiln using preliminary decarbonization in a baking heat exchanger or in an additionally heated decarbonizer supporting the processed material in suspended and / or granular granular states, the highly basic or calcareous part of the complex mineralizer is introduced into the furnace or into the heat exchanger or decarbonizer towards the calcined including a promoter. The physical meaning of this, according to formulas (5-17), is to improve the provision of the condition К _р л 1,0003-1,07 for primary melts at the stage of solid-phase reactions, for general clinker melt at the stage of liquid-phase reactions and for surface microphases throughout time of these two stages of the clinker formation process, since part of the alkali metal compounds, when lime or highly basic part of the complex mineralizer is fed from the hot (tail) end of the rotary kiln, sublimates, it passes into the gas phase in the form of steam and removed through the chimney, lowering the alkali metal content in the promoted clinker, which when fired with ashless fuel reduces the possible displacement of Кр to the region above 1.07. This embodiment of the invention is especially important for highly alkaline cement raw mixes and is required when firing with coal fuel, which reduces the possible temporary displacements K _p in the region below 1.0003, paralyzing the action of the promoter.

For the same purpose, when using coal dust and / or other ash-forming material as a technological fuel, the calcareous part of the complex mineralizer is introduced into the sintering zone of the furnace or into the heat exchanger or decarbonizer with an increase in the basicity of acid ash from the calcareous part of these materials almost at the moment of their contact with the bulk material to be fired, and the initial promoter content Ν _{ρΓΟΟ is} calculated from the content of the complex mineralizer without taking into account the calcareous part of the latter in in accordance with formulas (5-17), in which K _p is taken to be 1.04-1.07, for which the content of the promoter in the calcined material is maintained at about 5 ± 2 wt.% of the calcareous part of the complex mineralizer. The indicated features of calculating the composition and amount of the introduced promoter are required to put into practice the aforementioned “rule of positive gradient of basicity”, without which the technical effects of the invention are not achievable to the maximum. With a lower content of the Kp promoter, surface microphases can be below 1.0003, and with a higher content of it, difficulties can arise due to the uncontrolled occurrence of preliminary low-temperature reactions between the promoter and the raw material mixture.

When using various clinker kilns, stability of the coating, or skull, formed by the calcined material on the surface of the refractory lining of the furnace body, is important for their trouble-free operation and cost savings. Considering the temperature and basicity of the calcined material in the production of Portland cement clinker in the sintering zone in the range of 1350-1550 ° C, the refractories used contain significant amounts of MDO. The promoter in composition and content in the material is selected so that through its introduction to clean alite and white in a promoted clinker from magnesia impurities, translating them mainly into the composition of the intermediate substance, which contains

i.e., the external phase for crystals of basic minerals. The concentration of MDO in calcium aluminoferrite increases approximately twofold in comparison with the control clinker, which, as experience with the use of promotion technology of clinker burning on various furnace devices shows, sharply increases the ability of the calcined material to form a coating on a magnesium-containing lining, increases the contact strength of the coating with the lining and last service life. On the chamotte lining that does not contain MdO, but instead includes 81O ₂ in combination with A1 ₂ O ₃ , by controlling the content of the promoter while increasing the alumina module of the cement raw mix and clinker to values of 1.35-1.8, they also form a strong and stable coating for a short period of 8-12 hours, followed by strengthening within 2-3 days, with an acceptable level of alumina module to maintain the already created coating in the intervals of 1.15-1.35 and 1.8-2. The reason for the coating in the presence of a promoter of plaster on the chamotte zones of the refractory lining is an increase in the gross concentration of 81О ₂ in the flooded minerals, that is, in the clinker intermediate, due to the preservation of a part of the submicrocrystals of silicate minerals in the intermediate that did not manage to join large alite and belite crystals .

The promotion of clinker firing according to the invention makes it possible to eliminate clinker dusting even in those cases when it was not possible to eliminate it previously by any known method, including in furnaces operating according to traditional technology on unfavorable raw materials for 30-40 years with continuous clinker dusting. To this end, the content and basicity of the promoter are increased within the specified limits against the background of an increase in the value of the alumina clinker module in the range of 1.15-1.7, mainly 1.35-1.55, with a final dust fraction in the promoted clinker of not more than 5 wt.% . Clinker dust is a conglomerate of alite grains impregnated with the highly iron part of the clinker melt, separated from the general clinker melt as a result of segregation due to local overheating or local oxygen deficiency. The size of the particles of clinker dust is less than 0.5 mm, the usual color is dark to black due to the similar coloring of the minerals of the glandular part of the intermediate substance of calcium ferrites - brown, and with an admixture of MgO - black. The structure and composition of the grains of clinker dust determine its high resistance to mechanical grinding and strong abrasive effects with respect to furnace coating and refractory lining in the furnace, as well as to grinding media in cement mills, and, in addition, the very low hydraulic activity of clinker dust, despite the high content of alite in it, in view of the low dissolution / interaction rate with water containing the mentioned alite ferrite phase. One of the main reasons for eliminating clinker dusting by promotion is that, when the composition of the promoter is rationally selected, the melt crystallization centers and surface microphases have such a developed specific surface and so significant cohesion that they simultaneously adsorb the melt, increasing its viscosity, and reducing its apparent content and not allowing it to flow out of the calcined material even with local overheating and a local lack of oxygen in the furnace atmosphere. In addition, the mentioned increase in cohesion sharply increases the tendency of the calcined material to granulate and the strength of the granules, which is the main reason for the cessation of dust formation in the sintering zone of clinker kilns and in clinker refrigerators. This allows us to guarantee the content of clinker dust in the promoted clinker at a level of no more than 5%, that is, up to its practical absence, especially in case of single-pass crystallization of alite from the melt in the range of alumina module values of 1.35-1.55, and in the presence of MgO 2-3 wt.% And in the range of alumina module 1.15-1.7. This is important not only for the ecological situation at the cement plant and fuel economy, but also for the durability of the lining of clinker kilns, which wears out quickly when it comes in contact with clinker dust and liquified high-iron melt, and, most importantly, to increase the strength characteristics of cement by 15-25 MPa compared to cement from a dust-containing control clinker. In addition, the elimination of clinker dust reduces the specific consumption of grinding media in cement mills per unit mass of manufactured cement by at least 5-7%.

The promotion of clinker firing according to the invention for the first time allows one to obtain an ultrafine and evenly-sized clinker, the so-called “clinker grain” fraction of 0.5-3 mm in an amount of up to 100 wt.% Clinker by controlling the increase in the content of the promoter against the background of a decrease in the alumina module of the raw material mixture and clinker in the range from a value of 1.15 or lower, in extreme cases, to a value below 0.3, theoretically up to 0.01 in a practically non-aluminate mixture. Clinker grains, unlike clinker dust, are characterized by a microstructure of particles similar to the normal promoted clinker, differing from it only by the smaller size of alite crystals and reduced resistance to grinding, which is also facilitated by its reduced geometric dimensions, more noticeable effect of large pores on its crushing strength , as well as a lower ability of fragments to bounce under the impacts of grinding bodies, which increases the frequency of contact of fragments of the specified clinker grains with grinding bodies when grinding cement. Promoting clinker burning by reducing the resistance of the promoted clinker to grinding generally increases the productivity of cement mills by 10-25%, sometimes up to 70% compared to grinding cement based on control clinker, and when grinding promoted grains to 40-100%. This effect is the greater, the larger the diameter of the cement mill, so in laboratory mills it is much less pronounced compared with the production conditions.

A more distinct correlation is between the microhardness, determined by pressing a diamond pyramid under a fixed load into the surface of a polished thinner prepared from clinker granules, with the measurement of the print diagonal with a micrometer, and the productivity of large cement mills. At the usual level of microhardness of Portland cement clinkers known from the prior art, 35-60 MPa [4] by adjusting the composition and content of the promoter in the fired material, it is possible to reduce the microhardness of the promoted clinker to 10-25 MPa, which even without the transition to the production of the above grains allows increase the productivity of cement mills by about 20-50%.

Increasing the reactivity in the processes of mineral formation of a raw material mixture with a complex mineralizer by introducing a promoter for the first time allows to obtain, according to the invention, Portland cement of standard quality when using a cement raw material mixture based on marl crushed stone with a particle size of about 1-20 mm without preliminary grinding or after coarse grinding of a mixture of lime component, and specifically calcium carbonate, and aluminosilicate, and specifically clay component, to a fineness corresponding to about 4-35 m p.% sieve residue № 02 with cells 200 microns in size. This result is one of the elements of the surprise of the present invention compared with the prior art, which is important in the extreme situation in the country in conditions of extreme shortage of electricity. At the same time, it is advisable to supplement the clinker kiln with a device that allows the calcined, namely decarbonizable, non-ground or coarsely ground material to be suspended, such as an additional drum rotating with an angular velocity of approximately 0.9-0.98 critical, with heating of the clinker kiln off-gas suspension or an incinerator, pulled out with a smoke exhauster, and / or with additional heating, suspended part of the process fuel burned in the specified drum.

The production of Portland cement of a color other than traditional gray, in particular cream color based on a raw material mixture without an iron component, although it is known from the prior art, is practically not widespread due to the increased cost of such cement by at least 40%, due to an increase in fuel consumption for clinker burning by at least 30%. According to a variant of the method according to the invention, the cost of said non-ferrous cement obtained by introducing a promoter into a sintered raw material mixture, by increasing the content and regulating the composition of the promoter, is reduced to the level of ordinary gray Portland cement due to economy of process fuel, reduction of energy consumption for clinker firing and grinding of cement and increase in hydraulic activity of cement with the advent of the opportunity in connection with the last additional input of mineral additives cream color and other etov, as well as inorganic and organic pigments.

When implementing a variant of the method according to the invention, white compositions containing not more than about 1 wt.% Based on the promoted clinker of the sum of coloring oxides: iron, manganese and chromium are used as a cement raw material mixture, promoter, and, if necessary, complex mineralizer. Using a variant of the present invention, the quality of white Portland cement and the productivity of clinker kilns for firing white clinker are also improved. In this case, as a cement raw material mixture, a white cement raw material mixture is used, including the sum of coloring oxides Fe ₂ O ₃ + ReO + Mn ₂ O ₃ + MnO + Cr ₂ O ₃ + CrO ₃ in an amount of 0.01-1 wt.%, and as a composition of white mineral and oxide components of the indicated promoter, minerals from the group of tricalcium silicate (3CaO-81O ₂ ), dicalcium silicate (2CaO-81O ₂ ), tricalcium aluminate (3CaO-A1 ₂ O ₃ ), mayenite (12CaO-7A1 _{2 are used)} O ₃₎ and calcium oxide (CaO) in the composition or separately burnt from pure raw materials, are ca. they are removed when receiving cement for especially critical facade layers, or obtained as part of a white clinker, with a mass ratio of the mentioned components (45-75) :( 5-38) :( 7-13) :( 0.1-3) :( 0 , 1-7). By using the promoter, the grindability of white, especially high alumina clinker and the strength characteristics of cement by 10-15 MPa are significantly increased by 20–40% - in the early and subsequent hardening periods, as compared to cement known from the prior art, and also increase the performance of clinker kilns furnaces during the firing of this clinker by 15-35% with a corresponding saving in process fuel. Thus, in this case, according to the invention, maximum beneficial effects are achieved. The reason for their maximum value is due to the particularly long induction period of alitogenesis during the firing of white cement raw mixes and the more significant useful effect of reducing or eliminating this period by introducing a promoter into the raw mix or calcined material.

Colored clinker obtained by introducing coloring additives into a cement raw material mixture, in particular a green clinker obtained by introducing an additive of chromium ore into a low alkaline raw material mixture, is known in the art. Other coloring additives also contain variable valence metals. According to a variant of the method according to the invention, the color intensity of clinker is increased by increasing the basicity of the promoter within the specified limits, converting the dye metal mainly into an intermediate substance, which is the reason for the increase in the color intensity of color clinker.

To perform clinker formation promotion functions, it is necessary to release the minerals and oxides of the promoter additive from screening diffusion layers. This position, as well as the condition for combining the active zones of melts and microphases, is achieved using a variety of technological methods in numerous embodiments of the invention. One of them is the combined use of the promoter and the mineralizer, while the selection of the composition of the latter is also carried out using the criterion of basicity.

The complex mineralizer containing mineral salts, minerals and oxides, including chemical compounds from dust from clinker kilns, according to the invention is a mixture of alkaline and alkaline-earth salts of fluorides, sulfates, chlorides, silicofluorides, phosphates, and the alkaline metals are mainly used a raw mixture of potassium and sodium, and as alkaline earth metals - calcium and magnesium. Of the minerals it contains, in addition to salts of strong acids and bases, also alkaline derivatives C ₂ 8, C ₃ L, C1 ₂ L ₇ , CA, C _b5 8, C8, calcium carbonate, and also free from oxides, which are also present in the dust of clinker kilns lime. Thus, conventional clinker minerals are absent in the complex mineralizer. The composition of the latter also uses additionally introduced magnesium carbonate and dolomite, provided that the total content of MgO in the clinker does not exceed the optimum - 2.5%. The complex mineralizer in the present invention is used as a component of the mentioned primary clinker melts and the general clinker melt, which are a catalytic medium, to regulate its calculated basicity K _t in the range of about 1,0003-1,07.

To increase the efficiency of a variant of the method according to the invention, when the silicate or aluminosilicate components of the cement raw material mixture are inactive during the mineral formation, substances containing alkali and / or alkaline earth metal fluorides and / or alkaline and / or alkaline earth metal fluorides are used as the salt part of the complex mineralizer; for inactive and difficult to grind lime components of the cement raw material mixture, alkali and / or alkaline earth metal sulfates and / or alkali and / or alkaline earth metal chlorides are used; mixtures of these substances; materials containing by-products or wastes, including these substances or mixtures thereof. Alkali metal compounds in the complex mineralizer are used at a low alkali content in terms of NiO - not more than 0.8 wt.% Clinker. In other cases, alkaline earth metal compounds are used.

In view of the increased efficiency of the proposed method with a low reactivity of the raw material mixture in the embodiment of the invention more successfully than with the current level of technology, side and / or secondary products of other industries from the group of blast furnace slag, cupola slag, slag are used as components of the cement raw mix open-hearth furnace, converter slag, boiler slag, copper slag, nickel slag, ferrochrome slag, thermophosphoric slag, electric steel melting slag, nepheline slurry , burnt rock, tailings of concentration plants, spent molding material, ash-ash, ash-and-slag waste of TPP and TPP. In this case, it is possible to obtain the entire set of technical effects according to the invention at their lower level.

When grinding a promoted clinker to produce cement according to an embodiment of the invention, materials from groups I are used as an additionally introduced gypsum component of cement — natural gypsum, gypsum stone from one group, natural two-water gypsum, natural anhydrite; II - a gypsum-containing by-product of the chemical industry, one of the group phosphogypsum, bor57 gypsum, titanogypsum, citrogypsum, fluorohydrite; III - a product of desulfurization with calcium carbonate or lime of sulfur-containing exhaust gases in the energy sector from furnaces operating on coal or fuel oil; IV is a mixture of natural gypsum and a gypsum-containing industrial by-product in a mass ratio of from about 1: 3 to about 3: 1 with a gypsum component in the cement of about 1-4.5 wt.% In terms of sulfur trioxide (8O ₃ ). Since the lighterly milled promoted clinkers form more active fine cement fractions, the reactivity of the gypsum component of the cement in the ground form after mixing the cement with water is important for the strength of the cement. The faster and with a greater completeness of C ₃ A, the clinker reacts with gypsum in the liquid phase after mixing the cement with water, the higher the initial (12-24 hours) strength characteristics of the cement. Natural gypsum is not always the best material for this. In combination with a highly alkaline promoted clinker, more effective mixtures of the so-called chemical gypsum of phosphogypsum, borogypsum, titanogypsum, cytogypsum, fluorohydrite with natural gypsum in the indicated proportions are used, and with a low alkaline promoted clinker, a mixture of gypsum stone or natural two-water gypsum with more quickly soluble cement mixing with natural anhydrite or a rapidly water-soluble product of desulfurization with calcium carbonate or lime sulfur-containing exhaust gases in energy tike from fire chambers operating on coal or fuel oil (synthetic gypsum). This allows you to increase the strength of cement according to the invention compared to standard gypsum stone by 5-7 MPa at 1 and 3 days of age and 3-5 MPa at 28 days of age.

Titanogypsum is mainly ferrous sulfate stored in dumps with impurities of up to 5-10 wt.% Gypsum and up to 15 wt.% 30% aqueous solution of sulfuric acid, which is a by-product of the production of titanium dioxide from ilmenite CaT1O ₃ by decomposition of the latter sulfuric acid and step crystallization of products. When used as a component of the cement according to the invention, the obtained titanogypsum is additionally mixed with prebaked at 60-550 ° C, mainly at 200-450 ° C, kaolin or kaolin clay or other active mineral additive, including water-soluble alumina, in May before use. the ratio of iron sulfate (P) / (kaolin or an active mineral additive with water-soluble alumina) from 1: 0.2 to 1: 2, introducing the resulting product into cement in an amount of 1-7 wt.% of the clinker part of cement. In this case, kaolin or an active mineral supplement with water-soluble alumina decomposes into amorphous 81O ₂ , aluminum sulfate and impurities. The first serves as an initial reagent for the formation of calcium hydrosilicates during cement hardening, and the second - calcium hydrosulfoaluminates. Both of these hydrated minerals are freshly formed and therefore in a state of nucleation (ίη 8ΐ; · ιΙιι pa8sepb1) are particularly active artificial seeds for crystallization of the basic elements of the structure of cement stone. These seeds, as you know, increase the hydration rate of the clinker part and conventional cement, improve the coalescence of the main hydration products of the latter and, accordingly, increase its strength [25]. The increase in the strength of cement from conventional clinker with a titanium-gypsum derivative by 5-7 MPa, achieved at the age of 1-3 days, and the even greater increase in its strength by 10-15 MPa at the age of 28 days, is all the more interesting because the promoter causes on the contrary, greater growth at an early and smaller growth at a late age. In this embodiment of the invention, when using promoted clinker and a titanic gypsum derivative when grinding together with gypsum stone or in the absence of the latter, an approximately 10-20 MPa increase in the strength of the cement obtained according to the invention is achieved both in the early (1-3 days) and in the later stages of hardening (28 days and later). This is explained by the greater completeness of the reaction of the formation of ettringite during hardening of cement based on promoted clinker in view of the greater degree of opening of the surface of C ₃ A and alite in ground cement from clinker with a cellular or clusterless microstructure.

Despite a clear improvement in the grindability of promoted clinkers compared to those known from the prior art, when grinding cement in an embodiment of the method according to the invention, an additional effect is achieved by introducing a grinding intensifying additive in an amount of about 0.05-0.5 wt.% Cement. Even with the introduction of a traditional for highly active clinkers such a hydrophobic intensifier for grinding oil-based cement as a solution of higher fatty acids and higher fatty alcohols with the number of carbon atoms in the chain 16-22 (traditional abbreviation VZhK + VZhS _{! 6} -С ₂₂ ) in mineral oil in some cases, an increase in grinding ability of the crushed material reaches 25-30% or more. The choice of this universal grinding intensifier is advisable at high average relative humidity during grinding of cement (more than 75%) and its storage in silos with an average humidity of more than 80%.

At a lower average humidity, in an embodiment of the method according to the invention, even more effective grinding intensifiers — surfactants from the group of amino alcohols and their compositions with hardening accelerators — are used as cement grinding intensifier; technical lignosulfonates and their compositions with electrolytes or surfactants from the group of salts of alkaline-earth and / or alkali metals of the condensation product of naphthalene sulfonic acid, usually (β-naphthalene sulfonic acid with formaldehyde; alkaline-earth and / or alkali metal salts of the condensation product of melamine-containing resins with formaldehyde; salts of alkaline earth metals and sulfuric and / or nitric and / or formic and / or acetic acids with low molecular weight C2-C5 monosaccharides; paired mixtures of these mothers catch in a mass ratio of from about 4: 1 to about 1: 4 in the amount of 0.05-0.5 wt.% cement. The performance increase of mills using these grinding intensifiers in combination with a promoted clinker is 30-50%. This is another an essential element of the surprise of the present invention compared with the prior art.Its physical basis is a new mechanism for intensification of cement grinding associated with the use of these grinding intensifiers. Let us consider it in more detail for the complex salts mentioned in this embodiment of the method according to the invention. They are obtained by treating an aqueous solution of these monosaccharides with alkaline earth bases and acids. When grinding cement, their intensifying effect is due to the non-Rinderian physical mechanism of stepwise diffusion of intensifier molecule aggregates from one dislocation zone on the surface of the split particles of the promoted clinker to an adjacent similar zone during the contact of cement particles with grinding media and with each other. Such a diffusion process is provided by the temporary grafting of the complex salt onto coordination atomic groups of the clinker surface active zone with a calcium deficiency versus the stoichiometric composition for this clinker mineral. This calcium deficiency occurs on the surface of the particles of the promoted clinker during the grinding process, representing the loosening of the surface layer as a result of the movement of dislocations along the surface and in the thickness of the surface layer before the chemisorption of the intensifier. The diffusion of calcium cations from the inside of the crushed particles to their surface, initiated by the act of chemisorption of the intensifier, further loosens the crystal lattice of the mineral, creating nuclei of cracks. Moreover, this diffusion locally returns the stoichiometric composition to non-stoichiometric coordination groups of the active zones of the surface layer, and immediately thereafter, it also locally releases aggregates of intensifier molecules for further loosening of the lattice in other places of the surface layer. This mechanism was established by Auger spectroscopy in experiments with the participation of the inventors. It significantly increases the grinding efficiency when introducing an intensifier into cement based on the promoted clinker when grinding it. The complex salts mentioned above can increase the mill productivity when grinding cement, obtained on the basis of the promoted clinker, by 30-50% with the content of 0.1-0.2% intensifier from the mass of cement, which is approximately 2-4 times more effective in the calculation per unit mass of this intensifier compared with other known grinding intensifiers.

The peculiarity of using active silica in combination with a promoted clinker - both ground silicate block and microsilica of various genesis - lies in the fact that in a promoted clinker in combination with such mineral additives it is possible to leave an increased content of amorphous free lime, which allows 3- 7% of technological fuel for clinker burning. The increase in strength characteristics of cement from promoted clinker is not less, but more than based on clinker, known from the prior art.

With the additional introduction of an active mineral additive and / or filler corresponding to the standards in the amount of about 1-85 wt.% Cement, as usual, a reduction in the specific energy consumption of cement and its cost is achieved. An increase in the hydration activity of the promoted clinker as compared to the traditional clinker allows: a) to introduce the indicated additives at the given levels of cement strength in larger quantities; b) a less strict approach to the content in these additives of impurities such as clay and silt, as well as limestone dust, compared with the current level of technology.

A feature of the use of known expanding components in compositions with a promoted clinker is that with a higher content of free lime added to the expanding components in the latter and an increased strength of the main matrix due to the increased alite content, significant savings in the expanding component are achieved. In the example embodiment, it is seen that even with the introduction of the expanding component in an amount of 2.5%, expansion is achieved, which is practically impossible for expandable compositions known in the art in which the minimum required content of the expanding component is 8-10 wt.%. Obviously, saving the expanding component leads to a significant reduction in the cost of expanding cements based on the promoted clinker. This greatly expands the prospects for the introduction of expanding cements. This effect is further enhanced by promoting the process of mineral formation during sintering or another method of manufacturing such expanding components as sulfoaluminate, sulfoferrite and aluminous clinkers, especially in the presence of a gypsum mineralizer: the amount of expanding component used to achieve the expansion effect of a Portland cement clinker composition is only 1, 5-2 wt.%.

An additional introduction to the cement based on the promoted clinker of the fibrous component in an amount of about 0.2-2 wt.% Cement is an element of surprise: it is known in the prior art to introduce the fibrous component into cement and concrete only by mixing. To reduce the grinding of fibers into dust when co-grinding with a promoted clinker, its reduced grinding resistance at a microhardness level corresponding to 10-25 MPa and / or the use of clinker with the predominant amount of grains mentioned above allows it. In this case, during grinding of cement with the addition of a standard alkali-resistant fiberglass, it is crushed to fragments with a length of 10,300 μm, which increase the strength of the cement in the hardened state under tension and bending. This significantly increases the uniformity of the structure of concrete under external load in comparison with the prior art. The increase in the strength of composite cement with fiber is about 20% in tension and about 15% in bending, affecting also, but to a lesser extent, the compressive strengths, at lower dispersion values of these properties compared to fiber cementing materials obtained by known methods materials. This result is an essential element of the surprise of the present invention. With a higher fiber content compared to the specified maximum, a significant part of it is spent in vain, since it turns into dust, and with a lower content compared to the specified minimum, the positive effect of introducing the fiber into the cement is small.

As the fibrous component of cement in an embodiment of the method according to the invention, ordinary glass fiber or asbestos fiber or a mixture thereof is used in a ratio of from about 5: 1 to about 10: 1 by weight. With a higher asbestos fiber content of more than 2% by weight, it is difficult to pass the material through the inter-chamber partitions and the outlet grill of the cement mill.

The peculiarity of using cement introduced during grinding in combination with a clinker-promoted water-reducing component in an amount of about 0.1-2.5 wt.% Of the clinker part of cement, which reduces the water content of cementing material formed after cement is mixed with water, cement paste, mortar and concrete, is in a lower sensitivity of the resulting cement to an overdose of a water-reducing component over the specified limits due to the higher absorption capacity of the promoted blade and when milling in the presence of water-reduction component over known clinker and lower sensitivity obtained from promoted cement clinker after it mixing with water to the retarding influence of the excess component dewatering cement hydration rate of cementitious material in the composition. This can be seen in the example of such a common water-lowering component as sodium abietate, effective in combination with low-alkaline clinkers (Na ₂ O _e not more than 0.6 wt.% Clinker).

As a water-reducing component of cement, effective when the content of alkaline compounds in the promoted clinker in terms of Na ₂ O _{e is} up to 1.0%, materials from the group of alkaline earth and / or alkali metal salts of the condensation product of naphthalene sulfonic acid, usually β-naphthalene sulfonic acid with formaldehyde, are used; a salt of alkaline earth and / or alkali metals of the condensation product of melamine-containing resins with formaldehyde; industrial lignosulfonate alkaline earth and / or alkali metals modified with phenol-formaldehyde resin; complex salts of alkaline earth metals and sulfuric and / or nitric and / or formic and / or acetic acids with low molecular weight C ₂ -C ₅ monosaccharides; paired mixtures of these materials in a mass ratio of from about 4: 1 to about 1: 4. The higher the content of the promoter in the cement raw material mixture according to the invention, the usually smaller the silicate mineral crystals in the promoted clinker, the higher the initial activity of the cement and its adsorption capacity, the more effective the water-lowering effect of the said water-reducing components. The introduction of a water-reducing component in cement based on promoted clinker allows very significantly - by 5-40 MPa - to increase the strength of cement at 28 days of age while increasing the strength of cement at 1 and 2 days of age by 3-15 MPa compared to the cement according to the invention but without a water-reducing component. The greatest effect is achieved with an increased content (wt.%) In clinker of tricalcium silicate (alite) - more than 65 and a reduced content of No. ₂ O _e - less than 0.8 wt.% Clinker. At the same time, technical lignosulfonate (TLS) is less effective in comparison with other water-reducing components, while its mixtures with the rest of these substances give intermediate or closer to a more active water-reducing component.

With the additional introduction to the composition of cement obtained on the basis of promoted clinker, the addition of cellulose polyesters in an amount equal to about 0.01-1 wt.% Of the sum of the masses of clinker minerals of tricalcium silicate (3СаО-8Ю ₂ ) and tricalcium aluminate (3СаО-А1 ₂ O ₃ ) in the cement composition according to an embodiment of the invention, cementitious material compaction is achieved. This provides an increase in the water-holding capacity and density of said cementitious material, its durability and waterproofness. A feature of cementitious material in this case is its effectiveness even in the presence of marginal phases in the indicated limited amount in the promoted clinker. In combination with cement based on conventional clinker, the content of marginal phases is generally unacceptable in this case, but they are present in almost all clinkers known from the prior art, especially including alkali metal compounds in amounts exceeding in terms of No. ₂ O _e 0.45 wt .% clinker. Thus, the introduction of the additive of cellulose polyesters into the cement composition based on conventional clinker during grinding is practically impractical, and the particular effectiveness of such an additive introduced into the cement composition obtained from the promoted clinker is another element of the surprise of the present invention.

According to an embodiment of the invention, cellulose polyesters in the composition of cement use methyl cellulose or carboxymethyl cellulose or hydroxyethyl cellulose or hydroxyacetyl cellulose or sulfocellulose or their paired mixtures in a ratio of about 4: 1 to 1: 4 by weight. Oxyethyl cellulose, as shown by experiments, is especially effective for high alumina cements that are characteristic of the present invention, which is associated with the presence of silica hydrogel in the aforementioned cementing material, the final product of the complete hydrolysis of the surface layer of alite in the promoted clinker involved in the cation exchange with hydroxyethyl cellulose.

The invention becomes clearer from the following examples of its implementation.

Example 1. To obtain clinker and cement according to the proposed method as a clinker kiln, a rotary kiln with a diameter of 5.8 and a length of 185 m is used, heated with natural gas with a calorific value of about 6700 kcal / kg or about 28000 kJ / kg with an average clinker output of the control mode according to the prototype - without a promoter - 70 t / h, and for clinker with the addition of a mineralizer - hydrofluoric ore mixed with sodium silicate in the cement raw material mixture in terms of clinker, respectively 0.5 and 0.09 wt.% CaP ₂ and Να ₂ Ο · 3.58ίΟ ₂ - 72.5 t / h, or 3.5 wt.% Higher than in the control mode without mineralizer, with the following average design characteristics of the control Portland cement clinker: a) saturation coefficient lime (KN) according to V.A. Kindu, the method for calculating the SC is given, in particular, in [24], and the mentioned modules, calculated by the formulas

KN = [C - (1.65A + 0.35G)] / 2.88; (19) silicate module n = 8 / (A + P), (20) alumina module p = A / P, (21) whence KH 0.91, η 1.93, p 1.03; and b) the estimated (potential) mineralogical composition, wt.%, also according to V.A. Kindu (calculation method, see ibid.)

C ₃ 8 = 3.8 · 8ϊΟ ₂ (3ΚΗ - 2), (22) C ₂ 8 = 8.6 · 8ΐΟ ₂ (1 - KN); (23) C ₃ A = 2.65 (A - 0.64P); (24) With ₄ AR = 3.04R, (25)

where C ₃ 8 58, C ₂ 8 16; C ₃ A 5.5; With ₄ AR 16, impurities - the rest. Clinker calcined in the presence of a mineralizer, when calculated according to the same formulas, has close design characteristics: C ₃ 8 56, C ₂ 8 18, C ₃ A 2.5, C ₄ AE 15, the content of the last mineral C ₁₁ A ₇ -CaR _{2 is} calculated by the fluoride ion content in clinker in accordance with the formula (C] ι A ₇ -CaP ₂ ) = 37.04 (21-), (26) according to which the content of (C ₁₁ A ₇ -CaE ₂ ) 5.5 . According to formulas (19-21), of which the first is used here formally, mineralized clinker is characterized by the following values of KH and modules: KH 0.90, η 1.98, p 1.03.

The results of the experiments (shown in table. 1-4) include data: in table. 1 - according to the calculation of the basicity of small components in raw mixes, components of the latter, clinkers and additives introduced into the raw mix or in the calcined material - promoters and mineralizers; in table 2 - calculations of the basicity of clinkers, promoters and mineralizers for the main minerals and small components; in table 3 - according to the characteristics of average clinker samples: the content of the main oxides, the main clinker minerals, marginal phases, the two most important impurities K ₂ O and Cr ⁶⁺ in the technical and sanitary and hygienic aspects, as well as the characteristics of the micro- and submicrostructure of clinkers essential for the invention: content in pour cell crystals and clusters (in% of the total phase mass) according to the petrographic analysis based on viewing polished sections from clinker granules, as well as the content of X-ray amorphous, i.e. submicrocrystalline alite - according to the data of quantitative x-ray phase analysis using an x-ray diffractometer (in this case, the DRON-1 system); in table 4 - characteristics of the main technical effects of the implementation of the cement manufacturing method according to the invention: according to the operation mode of the furnaces, data on the quality of clinkers, including promoted, mineralized, control, as well as promoted in the presence of a mineralizer, and, in addition, the characteristic of clinker milling by microhardness of medium samples and the performance of cement mills. Details are given in the notes to the tables.

In a series of experiments, the raw material mixture from the calcareous component — limestone with humidity (here and below wt.%) Averaged 18.4, and the composition of the percentage points. 41.18, §1O ₂ 2.92; A1 ₂ O ₃ 1.10; Ge ₂ O ₃ 0.88; CaO 52.21; MdO 0.53; 8O ₃ 0.42; K ₂ O 0.09; including Na ₂ O 0.06; K ₂ O 0.05, the sum of 99.33 for the main oxides, η 2.78; p 2.03, small constituents L1 ₂ O 0.005, BaO 0.01, 8O 0.08, NO O 0.005, CoO 0, Mn ₂ O ₃ 0.014, Cr ₂ O ₃ 0.02, MoO 0.01, T1O ₂ 0.25, P ₂ O ₅ 0.23, C1 ₂ 0.005, P ₂ 0.001; aluminosilicate component - clay with a moisture content of 20.2 composition: 10.99; 81O ₂ 62.15; A1 ₂ O ₃ 14.98; Re ₂ O ₃ 7.38; CaO 0.89; MdO 0.69; 8O ₃ 0.39; K ₂ O 2.21, including Na ₂ O 1.01; K ₂ O 1.82; the sum of 99.68 on the main oxides, η 2.78; p 2.03, small constituents L1 ₂ O 0.001, BaO 0.002, 8O 0 0.001, Νΐθ 0.008, CoO 0.001, Mn ₂ O ₃ 0.01, Cr ₂ O ₃ 0.11, MoO 0.01, T1O ₂ 0.136, P ₂ O ₅ 0.03, C1 ₂ 0.01, P ₂ 0.001; the glandular component - pyrite cinder with a moisture content of 12.10% of the composition: 81O ₂ 11.17; A1 ₂ O ₃ 0.97; Re ₂ O ₃ 76.72; CaO 3.55; MdO 1.96; 8O ₃ 4.47; K ₂ O 0.63, including Nb 0.35, K ₂ O 0.43; the sum of 99.47 for the main oxides, η 0.14; p 0.12; small components of L1 ₂ O 0.001, BaO 0.08, 8O 0 0.002, M 0.037, CoO 0.03, Mn ₂ O ₃ 0.09, Cr ₂ O ₃ 0.24, MoO 0.06, T1O ₂ 0.02, Р ₂ О ₅ 0, С1 ₂ 0, Р ₂ 0, - is prepared at a ratio of the mentioned components (in parts by weight and in kg / t of clinker) 80.22: 17.88: 1.90 and 1527.3: 347, 97: 33.64 by the wet method by two-stage grinding, first in a self-grinding mill of the Hydrofol type with a diameter of 7.0 m and a length of 2.3 m, then in two tube mills with a diameter of 3 m and a length of 8.5 m, single chamber, s the filling ratio of the grinding load of 0.27. Using the correcting pools, the resulting slurry is adjusted to the required chemical composition, averaged in a horizontal pool with a capacity of 6000 m and pumped into the furnace through nutrient devices. Slurry humidity 35.6%, cone spreadability M.S. Neginsky [26] 49 mm, the chemical composition of the control sludge for the main components: p.p. 35.00; 81O ₂ 13.67; A1 ₂ O ₃ 3.58; Ge ₂ O ₃ 3.49; CaO 42.11; MdO 0.59; 8O ₃ 0.49; B ₂ O 0.48, including K ₂ O 0.37 and Nb O 0.24; the sum of 99.41, η 1.93; R 1.03, KN according to V.A. Kindu 0.91; the content of the remaining small components of L1 ₂ O 0.001, BaO 0.08, 8O 0 0.002, NO 0 0.037, CoO 0.03, Mn ₂ O ₃ 0.09, Cr ₂ O ₃ 0.24, MoO 0.06, T1O ₂ 0 , 02, P ₂ O ₅ 0, C1 ₂ 0, P ₂ 0.

An artificial draft furnace with a smoke exhaust is used, the dust trapped in the dust chamber and in the electrostatic precipitators (about 5 wt.% Clinker in the control mode) is returned from the hot end of the furnace. The average chemical compositions of the sludge and dust returned to the furnace for the main oxides (excluding alkali metal oxides and sulfur) are close, but selective pyleunos is noted: the sludge SN above the clinker NO by 0.01. The chemical composition of the control clinker (KK1 in table 1-4) for the main oxides: 81O ₂ 21.80; A1 ₂ O ₃ 5.29; Re ₂ O ₃ 5.09; CaO 65.35; MdO 0.84; 8O ₃ 0.38; B ₂ O 0.58; including K ₂ O 0.47 and Nb O 0.27; amount 99.33, η 2.10; R 1.04, KN according to V.A. Kindu 0.90; the content of the remaining small components of L1 ₂ O 0, BaO 0.07, 8O 0 0.002, N O 0.031, CoO 0.02, Mn ₂ O ₃ 0.095, Cr ₂ O ₃ 0.188, MoO 0.054, T1O ₂ 0.02, P ₂ O ₅ 0.19, C1 ₂ 0, P ₂ 0. The calculated mineralogical composition of the average samples of the control clinker (according to formulas 19-22, wt.%): C ₃ 8 58, C ₂ 8 19, C ₃ A 5,4, C ₄ AR 15.5, impurities - the rest is close to the design given above. In this and the following examples of the invention, the methods for determining the content of the main oxides are wet, the remaining small components are spectrometric according to [26].

As an additive to the complex mineralizer 1 in example 1, a mixture of crushed hydrofluoric ore, including 32% fluorspar (CaP ₂ ), quartzite (81О ₂ ) - the rest, with a silicate block of composition No.O- (3.5) 8U ₂ (brackets with a coefficient in the formula mean the average nature of the ratio of sodium and silicon oxides) in an amount of approximately 0.5 and 0.09 wt.% clinker according to the prototype, respectively. The actual average chemical composition of the additionally introduced components of the mineralizer 1 in the dry state is as follows: fluorine ore: pp 0.11; 81O ₂ 59.58; A1 ₂ O ₃ 0.34; Re ₂ About ₃ 0.13; CaO 22.97; MdO 0.21; 8O ₃ 0.63; P ₂ 15.59; K ₂ O 0.31 and Nb O 0.13; the sum of 99.89, the content of the remaining small components of L1 ₂ O 0.016, BaO 0.009, 8O 0.001, NO O 0.003, CoO 0.009, Mn ₂ O ₃ 0.011, Cr ₂ O ₃ 0.002, MoO 0.006, T1O ₂ 0.012, P ₂ O ₅ 0.034, C1 ₂ 0.003; silicate blocks:

Ν α ₂ Ο 22.32; 8ίΟ ₂ 77.02; amount of 99.34; impurities: K ₂ O 0.15, A1 ₂ O _s 0.14; Re ₂ O ₃ 0.20; CaO 0.07; MdO 0.01; 8O ₃ 0.09. The total chemical composition of the average sample of mineralizer 1: p.p. 0.09; 8/10 ₂ 62.19; A1 ₂ O _s 0.29; Re ₂ O ₃ 0.11; CaO 19.47; MdO 0.18; 8O ₃ 0.50; P ₂ 13.21; K ₂ O 0.26 and Na ₂ O 3.59; the sum is 99.89, the content of the remaining small components: L1 ₂ O 0.014, BaO 0.008, 8O = 0, NO O 0.002, CoO 0.008, MP2O3 0.009, SG2O3 0.001, MoO 0.005, T1O2 0.009, P2O5 0.029, SC 0.002. The results of calculating the basicity of small components in raw materials, raw mixes, mineralizers, as well as promoters and clinkers according to formulas (7-17) are presented in table. 1, and the total basicity of these materials, taking into account the main minerals, is given in table. 2, which also shows the results of calculating the initial number and basicity of promoters.

Obtained under the same conditions, clinker with the specified mineralizer mineralized clinker (MK-1 in tab. 1-4), with a total supply of mineralizer in the amount of 0.59 wt.% Clinker, is characterized by the following chemical composition: for the main oxides: 81О ₂ 22, thirteen; A1 ₂ O _s 5.44; Re ₂ O ₃ 5.19; CaO 65.64; MdO 0.67; 8O ₃ 0.20; K ₂ O 0.32; including K ₂ O 0.21 and Na ₂ O 0.18; amount of 99.57; η 2.08; R 1.05, KN according to V.A. Kindu: 0.88; the content of the remaining small components: L1 ₂ O = 0, BaO 0.005, 8O 0 0.001, NO 0 0.003, CoO 0.002, MP2O3 0.009, SG2O3 0.08, MoO ₂ 0.03, T1O ₂ 0.02, P ₂ O ₅ 0, 13, C1 ₂ 0, P ₂ 0.15. The values of the modular characteristics and the calculated (potential) mineralogical composition of the average sample of mineralized clinker (wt.%) In connection with the presence of low-basic calcium aluminate С ₁₁ А ₇ -САР _{2 are} calculated using the formulas

KH = [C - (0.94A + 0.35G)] / 2.88, (27) or

KN = [65.64- (0.94.5.44 + 0.35.5.19)] / (2.8-22.13) = 0.94, compare with the value of 0.88 by the formula (19);

C38 = 7.6-8 (1.5KN - 1), (28) or

C ₃ 8 = 7,6.22,13 (1,5.0,94-1) = 69,54, compare with C ₃ 8 54 by the formula (22);

C ₂ 8 according to the formula (28) 10 at KN 0.94 against 23 at KN 0.88 according to the formula (23).

SpA ₇ CaP ₂ = 1.97 (A - 0.64 G), (29) or

C ₁₁ A ₇ CaP ₂ = 1.97 (5.44 - 0.64 · 5.4) = 3.9,

With ₄ LR according to the formula (25) 15.8, impurities - the rest. As follows from the above data, the design and actual composition of the mineralized clinker, in contrast to the control, diverge, in particular, in connection with the partial replacement of C3A by the indicated fluoride derivative of mayenite. Discrepancies in the calculated (potential) mineralogical composition in two groups of the indicated formulas (19, 22-24) on the one hand and (27-29) on the other hand are common for clinkers fired in the presence of an acidic additive - fluoride, chloride, sulfate

- mineralizers, therefore, to characterize the composition of such clinkers, petrographic analysis is carried out using optical microscopes operating in transmitted light with immersion preparations and in reflected light with the preparation of the above sections [26]. The results of a quantitative petrographic analysis of the phase composition of clinker calcined with mineralizer 1, namely: alite (C ₃ 8) 62, white (C ₂ 8) 15, C ₃ A (using the methylene blue staining method according to [27]) 2.5 , С ₂ (Л, Р) 15, impurities - the rest, occupy an intermediate position in comparison with the above calculation data for both groups of these formulas. The actual content of fluoromeyenite (С ₁₁ Л ₇ -САР ₂ ), calculated by the formula (26) based on the residual fluoride ion content in the clinker, is: 37.04 (2Р ^- ) = 37.04-0.15 = 5.6 which is close to that expected under conditions of minimal sublimation, or insignificant sublimation of fluoride ion during clinker firing with p greater than 1.

From the above data it follows that for mineralized clinker, the calculated basicity, taking into account small components, is 101.1989, which corresponds to K _t 1.01, i.e. condition “b” is fulfilled, which was mentioned above when considering the essence of the invention, also fixed in formula (16) and concerning supersaturation of the clinker melt, but condition “c” - a similar supersaturation of surface microphases remains unfulfilled. To ensure it, in addition to the specified mineralizer, a mineral formation promoter is introduced.

The promoter 1 composition (wt.%): Dicalcium silicate (2СаО-8Ю ₂ ) 35, potassium derivative of dicalcium silicate (К ₂ О-23СаО1181О ₂ ) 25, lime (CaО) 40 is added in addition to the mineralizer in the form of a powder using a paddle mixer in the feed sludge immediately before feeding the sludge into the furnace. Design chemical composition of the promoter 1: 81O ₂ 30.22, CaO 65.96, K2O 3.82. Actual chemical composition of the promoter in the average sample per batch: 81O2 29.79; A12O3 0.23; Re2 Oz 0.17; CaO 64.81; MdO 0.34; 8O3 0.11; K2O 3.58 and Na ₂ O 0.02; the amount of 99.05; the content of the remaining small components: L1 ₂ O 0, BaO 0.02, 8O 0.03, O 0.287, CoO 0.119, MP2O3 0.234, SG2O3 0.16, MoO2 0.08, T1O ₂ 0.01, P ₂ O ₅ 0.01, C1 ₂ 0, P ₂ 0. Promoter 1 is obtained by treating the secondary product of slag from electrometallurgical production having the composition of wollastonite (C8) by sintering in a conveyor furnace with lime and potash (potassium carbonate) in calculated amounts taking into account the decarbonation of potash and subsequent grinding to a specific surface of 150 m ² / kg. The calculation of the basicity of promoter 1 according to its composition and the required initial amount of promoter 1 for clinker, obtained in the presence of a mineralizer, is presented in table. 1-3. The estimated initial amount of promoter 0.2% (table. 2).

The promoted clinker (PK-1 in Table 1-4) is characterized by the ratio (wt.%) Of the raw materials in the calcined raw material mixture: limestone 81.55, clay 16.66, pyrite cinder 1.79, with the actual chemical composition of the promoted clinker according to average sample for a batch: 81O ₂ 20.30; A1 ₂ O ₃ 5.30; Re ₂ O ₃ 5.16; CaO 67.12, MdO 0.56; 8O ₃ 0.34; B ₂ O 0.25; including K ₂ O 0.18 and Na ₂ O 0.15; amount of 99.11; the content of the remaining small components: L1 ₂ O 0, BaO 0.04, 8O 0.04, ΝΪΘ 0.02, CoO 0.02, Mn ₂ O ₃ 0.10, Cr ₂ O ₃ 0.11, MoO ₂ 0, 05, T1O ₂ 0.31, P ₂ O ₅ 0.20, C1 ₂ 0, P ₂ 0.

The difference in approaches to calculating the promoter content by basicity values without taking into account small components and calculating the mineralizer content, in which small components are necessary, is determined by the above-described effect of refining surface microphases and, accordingly, of the main clinker minerals in the presence of a promoter. The experiments of the authors of the present invention show that for the rapid crystallization of the main clinker minerals from surface microphases, the absolute content and basicity of small components and not even the approximate coincidence of the sets of small components in the control or mineralized clinker and promoter, which somewhat accelerates crystallization, but a local basicity gradient are not essential in the chain the surface layer of the melt / germ of minerals / surface microphases / growing microcrystals of minerals, the conservation of which o throughout the process of mineral formation in the positive interval is the driving force of the crystallization process. In the described series of experiments in Example 1, the sets of small components in the promoter / control clinker pair did not coincide completely, in other examples (see example 4) they did not affect the promotion, but when promoting, the condition of positive local gradient of basicity is satisfied .

Then, promoter 1 (0.2%) and mineralizer 1 (0.59% of clinker mass) are simultaneously introduced when clinker is fired based on the same cement raw material mixture. The ratio of the initial components of the raw material mixture: limestone: clay: cinder (wt.% And kg / t clinker) = 81.85: 16.96: 1.19 and 1572.3: 332.96: 21.17, obtained promoted mineralized clinker characterized by the following chemical and mineralogical composition according to the average sample per batch: 81O ₂ 20.38; A1 ₂ O ₃ 5.39; Re ₂ O ₃ 4.49; CaO 66.99; MdO 1.01; 8O ₃ 0.43; B ₂ O, 0.17; including K ₂ O 0.11 and Na ₂ O 0.15; amount 98.95; the content of the remaining small components: b1 ₂ O

0, BaO 0.005, 8gO 0.002, NO 0 0.002, CoO 0.001, Mn ₂ O ₃ 0.05, Cr ₂ O ₃ 0.18, MoO ₂ 0.07, T1O ₂ 0.42, P ₂ O ₅ 0.26 , C1 ₂ 0, P ₂ 0.05.

To determine the hydraulic activity of clinkers, they are preliminarily ground in laboratory and / or production cement mills with an average of 5 wt.% Calcium sulfate ingredient, in this case gypsum stone, including 98 wt.% Two-water calcium sulfate (Ca8O ₄ -2H ₂ O), argillite impurities - the rest. With the introduction of the mineralizer, the promoter and the promoter in combination with the mineralizer according to the invention, the productivity of the furnaces is increased by 3; 8.5 and 10.1 wt.% Compared with the control mode; saving in specific fuel consumption is 1.5, respectively; 5.2; 6.8 wt.%. The temperature of the furnace body, antibatically characterizing the effective thickness of the coating on the surface of the refractory lining in the furnace in the sintering zone, during firing in the presence of a promoter, is fixed at a level of about 30-35 ° C lower than in the control mode; with the introduction of the mineralizer, significant changes in this temperature are not noted. This characterizes a clear increase in the protective action of the coating and a decrease in the loss of thermal energy into the external environment in the presence of a promoter. A consistent decrease in dust return to the furnace is noted under equal operating conditions of the filters from 12 wt.% Clinker in the control mode of firing to 10%, or 1.2 times with the introduction of the mineralizer, and much more so when implementing the method according to the invention with the supply of the promoter and promoter in combination with a mineralizer - up to 6 and 5 wt.% clinker, respectively, i.e. twice and 2.5 times. This characterizes the facilitation of the operation of dust collecting devices, increasing the period of their maintenance-free operation during the implementation of the method according to the invention, as well as the important environmental significance of the latter. An approximately twofold decrease in the average granule size and an increase in the uniformity of the clinker particle size distribution with the introduction of the promoter (Table 4) with a decrease in the microhardness of clinker granules from a value of about 58 to about 35 MPa, or 1.66 times, which leads to a marked increase in the productivity of cement mills, are also observed. 2.2 x 13 m, two-chamber, working in an open cycle, when grinding the promoted clinker by 2123 wt.%. Such results of increasing the productivity of mills only by adjusting the microstructure of the clinker are not known from the prior art. The reasons for this increase in clinker grindability are, as follows from the data given in table. 3: 1) the appearance of less rigid alite cellular crystals (55-65% of the total mass of alite) in clinker, calcined in the presence of promoter 1; and 2) a more than three-fold decrease in the content of alite crystal clusters, i.e. intergrown crystallites, the separation of which when grinding the clinker has to spend additional energy. Strength indicators of the obtained cements are tested in accordance with GOST 310 in cement-sand standard solutions, from which 4 x 4 x 16 cm beam samples are formed, which are stored for 24 hours in air-wet conditions - in air at a temperature of 20 ± 3 ° С and 100% relative humidity, then placed in water of the same temperature and stored until testing. As a result, an increase in the strength of cements based on promoted clinkers at a 1-day age from 12 to 18.9-20.3 MPa, i.e. by about 50-70%, and at 28 days of age from 48.7 to 58.9-60.1 MPa, i.e. about 20-23%. All these results, achieved simultaneously, represent the main surprise of the method according to the invention in relation to the prior art.

In this series of experiments, cement strength values at 1 day and 28 day age are ultimately used as a criterion for the optimal promoter content in the material to be fired. To select the current optimum supply of the promoter to the calcined material, the criteria of the promoted clinker are used - the content of alite crystal clusters (this characteristic can be quantified in modern computerized microscopes), the proportion of cellular crystals in alite and the content of X-ray amorphous alite in the promoted clinker (Table 3). Exceeding the optimum concentration of promoter in the calcined material, as shown in the table. 3 leads to a decrease in the strength characteristics of cement based on the specified clinker, at least at 28 days of age, the strength of cement at 1 day of age does not change the further addition of the promoter and does not change in the same way given in the table. 3 structural characteristics of the promoted clinker. With the current control of production, the concentration of the promoter is noted, starting with which the increase in the supply of the promoter is ineffective for changing the indicators of the clinker structure, and this level of supply of the promoter is considered optimal.

In the next, 2 series of experiments in Example 1, carried out under the same conditions, in the composition of promoter 1A, the limits of changes in the K / 8 ratio of the silicate block component are expanded, namely, in addition to sodium, a potassium silicate block is used and the limits of the ratio of its components are expanded to p / t of 2.8 and 4.8 in the formula tK ₂ O-p8Yu ₂ , and also change the ratio of silicate block and dicalcium silicate (2CaO-81O ₂ ), with the following ratio of components of the promoter, wt.%:

Dicalcium silicate (2СаО-81О ₂ ) 30-65

Alkaline derivative of dicalcium silicate (K ₂ O-23CaO-1181O ₂ ) 10-30

Alkali metal silicate (tK. ₂ O-p8Yu ₂ ) 0.5-25

Lime (CaO) in anhydrous or hydrated forms 20-40

Mix the rest

When implementing the method according to the invention in 2 series of experiments, the strength characteristics of cements are determined in samples of laboratory grinding, which is carried out in a two-chamber mill of periodic action lined with cast iron armored plates, with the dimensions of each chamber: length 0.28 m, diameter 0.5 m, rotation speed 48 min ^-1 , drive power 1.1 kW, engine speed 930 min ^-1 , grinding load on 1 camera (with 10 kg of clinker in each chamber): balls 0 60 mm approx. 6 kg, 0 50 mm approx. 8 kg, 0 40 mm approx. 8 kg, 0 30 mm approx. 8 kg, tsilpebs 020 mm x 32 mm 25 kg, 55 kg total. Before weighing, the clinker is crushed to a fraction of 1-2 mm in a laboratory jaw crusher. According to the data given in table. 1-4, in 2 series of experiments, results are obtained that are almost similar to the above data from 1 series of experiments.

It should be noted that when replacing dicalcium silicate in the promoter with less basic minerals - rankinite (3CaO-28O ₂ ) and / or wollastonite (CaO-81O ₂ ), carried out by reducing or eliminating the addition of lime to wollastonite slag in the manufacture of the promoter, the positive effects of the method The above are sharply reduced. This can be explained by a violation of the main condition of the method according to the invention - a decrease in the level of basicity of the promoter to values that are lower than the basicity of the eutectic clinker melt.

As an analogue of promoter 1 in the form of a composition of the corresponding mineral components in 3 series of experiments, promoter 1B uses belite sludge, a by-product of the production of alumina from nepheline according to a method developed more than 50 years ago [28]. Belitic sludge at several cement plants in Russia is used as a component of a cement raw material mixture. In this case, the specified by-product is used as a substitute for a mixture of belite and its alkaline derivative from experiments of 1 and 2 series. In addition to belitic sludge, sodium silicate in the form of water glass and slaked lime are added to the promoter next May. ratio of promoter ingredients: belite sludge (amount of belite and its alkaline derivative in May. ratio of about 3: 1 in terms of dry matter): water glass (in terms of dry matter73): hydrated lime (in terms of CaO), respectively (40 -95) :( 0.5-25) :( 0.05-40). Moreover, as can be seen from the data table. 4 also obtain results approximately similar to those achieved in series 1 and 2 of the experiments.

In 4 series of experiments, the method according to the invention is carried out in accordance with series 1, while lime as a component of the promoter in the form of a dry powder is introduced in combination with dust trapped from the exhaust gases and returned from the hot end of the furnace. Given in the table. 4, the results of the experiments indicate that this technological method when implementing the method according to the invention allows to increase the quality of clinker compared to the control only by 5-7 MPa, and the productivity of the furnace by 10-15%, that is, to the same extent as in the previous series experiences.

The testing during the implementation of the method according to the invention of various methods of returning dust trapped from the furnace exhaust gases — introducing from the hot and cold ends of the furnace, feeding the trapped dust into the sludge — did not show a noticeable advantage of any of the mentioned methods. It was found that preliminary mixing of the returned dust with the promoter reduces the efficiency of the latter, which is undesirable, since it leads to the need to increase the content of the promoter in the material to be fired and, accordingly, to an uneconomical increase in the consumption of the promoter.

In the described variants of the cement manufacturing method according to the invention according to example 1, as follows from the above, positive results are achieved under the following conditions: a) the composition and content of the promoter and the promoted clinker are selected, corrected and maintained according to a basicity criterion that exceeds the basicity of the specified eutectic clinker melt without taking into account small components; b) as a basis for the measure of basicity, use the values inverse to the calculated values of the electronegativity of minerals and oxides, taken from a series of basicities (18); c) with the additional introduction of the mineralizer, the composition and content of the latter in the presence of a promoter is selected according to the basicity criterion of the promoted mineralized clinker so that the basicity level of the latter exceeds the basicity level of the control clinker when taking into account small components; d) the composition of the promoter and the promoted clinker is selected and the firing process is carried out in such a way that the basicity levels of the promoter and the promoted clinker exceed the basicity levels of the eutectic clinker melt and the control clinker by at least 1,0003 times, respectively; and a fixed value of the basicity level of the promoted mineralized clinker exceeded the basicity level of the control clinker, taking into account small components, by no less than 1.01 times. Note that the basicity levels of the promoter and the promoted clinker become equal to the above specified design values at the end of the mineral formation process, i.e. when calculating, the final equilibrium values of the basicity of the promoter and the promoted clinker are fixed. The current values of the basicity of the promoter and the promoted clinker on the surface of their particles are always higher than the final ones, since the most basic component of these materials - calcium oxide - is, as is known, the most mobile during mineral formation reactions, and at the beginning of the process it is initially contained on the surface of the particles of both materials more than at the end of the process. Thus, the current (nonequilibrium) values of the basicity gradient, which is the driving force of the crystallization process during the promotion of the mineral formation process, are significantly higher than those calculated by the calculation, but it is essential that they exceed 1 until the end of the process, which is a necessary condition for the implementation of the clinker manufacturing process according to the invention. We note additional features of the mechanisms of action of these additives revealed in the second and third series of experiments. The promoter accelerates the growth of microphase nuclei and then the crystallization of clinker minerals by accelerating the formation of nuclei in the melt, increasing the stability of the nuclei at the time of separation from the melt, their activity in combination in the solid state with collective crystallization and increasing the selectivity of the latter, promoting the integration of only the required crystal lattices into the prepared cells fragments for a given set of minerals. In other words, as a whole, the promoter accumulates, collects and builds crystals of clinker minerals from their nuclei - surface microphases. Small components do not directly participate in any of these stages of the promotion process, although they may hinder or facilitate, depending on the crystal-chemical features, the flow of the first and last stages of promotion, for which there is no generalizing vector indicator, so taking into account small components on the achieved level of development of the process mechanism does not lead. From examples of the method according to the invention it is clear that this does not preclude the use of the invention.

The mineralizer accelerates the decomposition of the starting reagents due to an increase in the rate of melt wetting of their surface, an increase in the rate of surface dissolution, intensifies the liquid-phase reactions of mineral formation due to a decrease in their activation energy, externally expressed in a decrease in the viscosity of the melt, and accelerates the precipitation of reaction products from the melt due to a decrease in the solubility of the latter, i.e. clinker minerals. In other words, on the whole, the mineralizer disperses, melts, and activates the initial reagents of the processes of mineral formation for chemical reactions to enter into chemical interactions, and then removes the products from the reaction sphere, and at each of these stages a significant influence on the course of the process of small components, the total effect of which is conveniently estimated with With the help of such a generalizing parameter as basicity, although in reality a significant additional influence, which may turn out to be decisive, is also exerted by crystal chemical features and actions of specific small components at each of these stages. These crystal-chemical features are reduced to the presence or absence of the possibility of embedding coordination groups, including small components, in the electrically charged radicals that make up clinker melts. The possibility of generalizing the situation, similar to the approach adopted by W. Gillespie in the geometric theory of valency, consists in constructing a tensor field of correspondences / discrepancies of coordination polyhedra of small components - impurities with a field of structures of the mentioned radicals, with the final construction of a compression / extension vector from a set of small components for each of names of radicals in the clinker melt. This will make it possible to supplement the resulting vector of the crystal chemical effect of impurities with a tensor value of the general level of basicity of impurities and take both quantities into account in the future. Currently, only the basicity tensor can be taken into account, which is done when calculating the basicity of the mineralizer and mineralized clinker, as well as the control clinker to evaluate the effect of the mineralizer. The application of this approach is effective for the selection of the composition of mineralizers in the presence of promoters, as shown in example 1.

Example 2. To obtain cement according to the variants of the proposed method, three rotary kilns with a diameter of 3.3 / 3.6 / 3.3 m and a length of 150 m, heated with fuel oil with a calorific value of about 8600 kcal / kg or about 36000 kJ, are used as clinker kilns / kg, or coal dust with a heat of combustion of an average of 5980 kcal / kg or about 25000 kJ / kg with clinker performance in the control mode according to the prototype - without a promoter - 26.5 t / h, with the following average characteristics:

a) raw mix, including chalk composition, wt.%: p.p. 42.29; 81O ₂ 1.61; A1 ₂ O ₃ 0.69;

Re ₂ O ₃ 0.33; CaO 54.10; MdO 0.38; 8O ₃ 0.25; the amount of 99.65, impurities - the rest, marl composition, wt.%: p.p. 34.78; 81O ₂ 17.15; A1 ₂ O ₃ 2.67; Be ₂ About ₃ 1.10; CaO 42.79; MdO 0.72; 8O ₃ 0.47; the sum of 99.68, impurities - the rest, cinder pyrite composition, wt.%: p.p.p. 0; 81O ₂ 8.18; A1 ₂ O ₃ 2.02; Re ₂ O ₃ 79.68; CaO 1.84; MdO 1.33; 8O ₃ 4.99; the amount of 98.04, impurities - the rest, in ratios,% and kg / t clinker: 10.00: 88.62: 1.38 and 187.66: 1732.5: 23.11.

b) control Portland cement clinker: chemical composition: (KK-2 in Table 1-4) for the main oxides: 23.94; A1 ₂ O ₃ 3.60; Be ₂ O ₃ 3.44; CaO 67.14; MdO 0.76; 8O ₃ 0.34; I ₂ O 0.26; including K ₂ O 0.18 and No. bO 0.14; the amount of 99.48, including p.p.p. 0.21; n 3.40; R 1.05, KN according to V.A. Kindu: 0.89; the content of the remaining small components: L1 ₂ O d 0, BaO 0.03, 8gO d 0, No. O 0.01, CoO 0.01, Mn ₂ O ₃ 0.12, Cr ₂ O ₃ 0.15, MoO ₂ 0 , 02, TU ₂ 0.09, P ₂ O ₅ 0.08, C1 ₂ 0.01, B ₂ 0. The calculated mineralogical composition of the average samples of the control clinker (according to formulas 22-25, wt.%): C ₃ 8 62 , C ₂ 8 22, C ₃ A 4.0, C ₄ AB 10.0, impurities - the rest.

Promoter 2 in a series of experiments takes the phase composition, wt.%: Mineral [(3.3-3.5) CaO · 81O ₂ ] in the form of a phase idiomorphic to alite (hyperalite [29]) 68.8, dicalcium silicate (2СаО ^ r0,7 occupies 8 _2, the mineral composition of [(4,8-7) CaO + (0.7-0.9) = A12O Re2O ₃ ^ ₃ ^ (0,5-1,5) 8YU2] - analogue calcium alyumoferrita 23.7, free calcium oxide in the form of a solid solution with dicalcium ferrite, having an approximate composition of 18СаОГе ₂ О ₃ 6.1; the sum is 99.3, the impurities are the rest. Compositions of analog minerals are established by selective chemical analysis, referred to in the Russian literature as " rational chemical analysis, according to its latest domestic modification described in [30]. The promoter is obtained by firing before sintering in a rotary kiln with a diameter of 3.6 m and a length of 51.4 m of the raw material mixture containing these components in May ratios (% and kg / t clinker) 36.65: 57.46: 5.89 and 692.5: 1131.2: 99.20 with a dust return coefficient of 2% and a productivity of about 9 t / h. The calculated characteristics of the clinker part of the promoter 2: KN according to B. A. . Kindu: 1.29; p 1.49, p 0.35. The resulting clinker is used as a promoter 2.1 after grinding in a cement mill with a diameter of 2.4 m and a length of 13 m in the ground state with a specific surface area of about 300 m ² / kg, measured by the method of breathability on a device G. S. Khodakova, as a promoter 2.2 - in the form of cement with the addition of gypsum stone (5 parts by weight per 100 parts by weight of clinker) with a specific surface of about 350 m ² / kg, as a promoter 2.3 - in the form of cement with the specified addition of gypsum stone and specific surface according to the method breathability of approximately 600 m ² / kg milled in a decree a cement mill; finally, as a promoter 2.4 use dust captured

ΊΊ bag filters from the aspiration air of the named mill during the grinding of the last cement, with a specific surface area of the specified cement dust in the range of about 1700-2000 m ² / kg. According to chemical analysis, the specified dust contains 8 parts by weight gypsum stone on May 100. including clinker component of cement.

The characteristics of promoter 2.1 are as follows: actual chemical and mineralogical composition (wt.%): Major oxides and minor constituents: 8ΐΘ ₂ 16.94; L1 ₂ O ₃ 2.96; Re ₂ O ₃ 8.45; CaO 69.00; MdO 0.98; 8O ₃ 0.61; K2O 0.21, ^ O 0.14, amount 99.3; the content of the remaining small components: b1 ₂ O a 0, BaO 0.035, 8 gO 0.0086;

0.0175, CoO 0.0175, Mn ₂ O ₃ 0.1487, Cr ₂ O ₃ 0.1663, CuO 0.07; MoO ₂ 0.0175, TU ₂ 0.105, P ₂ O ₅ 0.1139, C1 ₂ 0.01, P ₂ 0. Mineralogical composition (wt.%): Phase idiomorphic to tricalcium silicate - hyperalite (C ₃ , ₄ 8) 68.8; dicalcium silicate (C ₂ 8) 0.7; calcium aluminoferrite analogue (C ₆ L ₀ , ₈ P8) 23.8; an analogue of free calcium oxide is its solid solution with dicalcium ferrite of composition C ₁₈ P 6.1, impurities are the rest.

The calculation of the basicity of promoter 2.1 according to its composition and the calculation of the required initial amount of promoter 2.1 for clinker obtained in the presence of a promoter are presented in table. 2. The basicity of the promoter 2.1 is 100.48 conventional units, which is approximately 1.005 times higher than the basicity of ECR. The initial estimated amount of promoter is 0.55% (table. 2). Given the small components, the basicity of the promoter is higher: 104.12 conv. The following basicity values are used in the calculation:

a) hyperalite with a composition of 3.4 CaO ^ 81O ₂ , calculated taking into account the values of basicity b, from the base series (18) for CaO 1.07 conventional units and for 81O ₂ 0.83 conventional units and molecular weights of these oxides MSao 56 D and M _8Yu 2 60 D by the formula:

Bia = (3.4MsaO-LcaO ⁺ M18Yu2-L81O2) / (3.4Ms _a O + M ^ a), (30) or

Β _Ηη = (3.4 · 56 · 1.07 + 60 · 0.83) / (3.4 · 56 + 60) = 253.528 / 250.4 and 1.014 conventional units

b) an analogue of calcium aluminoferrite of the composition 6СаОД8Л1 ₂ О ₃ Te ₂ Оу8Ю ₂ , calculated also taking into account the basicity of b from the base series (18) for Л1 ₂ О ₃ 0.90 arb. and for Re ₂ About ₃ 0.86 srvc. and molecular weights of these oxides M _A1 2 _O 3 102 D and M _Re 2 _O 3 160 D according to the formula:

VAPA ⁼ (6MsaO-sao 0,8MA +] 2OZ-A12OZ ^Mre2OZ-+ Lp ⁺ _e 2OZ Mio2-b8] a2) / (+ 6Msao 0,8Md] 2Oz _{+ + Μ}. · Ε 2Ο3} + Μ8ίθ2), ( 31 ) or

Ba _{£ c} = (6 ^ 56 · 1.07 + 0.8 · 102 · 0.90 + 56 · 0.86 + 60 · 0.83) / (6 · 56 + 0.8 · 102 + 160 + 60 ) = 620.36 / 637.6ξ0.97.

Promoted clinker (PK-2 in table.

1-4) is characterized by the ratio (wt.%) Of the raw materials in the fired raw mix: chalk 18.67, marl 79.73, pyrite cinders 1.60, with the actual chemical composition of the promoted clinker in the average sample per batch: 81O ₂ 21, 90; L1 ₂ O ₃ 3.56; Re ₂ O ₃ 3.43; CaO 68.74, MdO 1.04; 8O ₃ 0.42; K ₂ O 0.14; including K ₂ O 0.09 and Na ₂ O 0.08; amount of 99.09; the content of the remaining small components: 1.aO 0, BaO 0.07, 8gO 0, Νΐ (') 0.01, CoO 0.03, Mn ₂ O ₃ 0.21, Cr ₂ O ₃ 0.22, MoO ₂ 0 03, TU ₂ 0.18, P ₂ O ₅ 0.17, C1 ₂ 0, P ₂ 0. Mineralogical composition according to the formulas (22-25), wt.%: C ₃ 8 83.0; C ₃ L 3.6; With ₄ AR 10.45, impurities - the rest. According to the petrographic analysis of the average sample, C ₃ 8 80, C ₃ L according to the staining method 4, C ₄ AR 10.5, impurities - the rest. Note that such a high alite content (80%) in the production clinker was not previously known from the prior art. The calculation and the resulting value of the basicity of the promoted clinker (Table 2) - 100,0008 and 102,469 - respectively, excluding and taking into account small components above the basic level of ECR, are approximately 1,001 and 1,025 times or higher than those calculated without accounting and taking into account small components of the level of basicity of the control clinker 99.41 and 101.374. This is a condition for achieving the technical effects presented in table. 4 and supplemented below.

When viewing polished sections under an optical microscope in reflected light, it was ascertained: a) the absence of a cellular microstructure of alite and belite; it follows that this feature - sufficient to fix the manufacture of clinker according to the proposed method, is not necessary; b) the practical absence of alite clusters, or intergrown crystals. It is known that in clinkers from mixtures in which marl is the main component, the number of alite clusters is reduced [31], but the complete absence of alite clusters in clinkers was not known from the prior art. In this case, the absence of clusters was first recorded in most samples of the promoted clinker; it also follows that this feature, sufficient to fix the manufacture of clinker according to the proposed method, is not necessary, although a reduced number of alite clusters is a necessary sign of clinker made by the proposed method. The simultaneous presence of both a cellular alite microstructure and a reduced number of alite clusters (not more than 25 wt.%) In a sample of any Portland cement clinker is considered as a necessary and sufficient diagnostic sign of the manufacture of alite by the method according to the present invention (Fig. 1).

Finally, an X-ray diffraction study of the promoted clinker revealed that: a) the amount of X-ray amorphous alite in this promoted clinker is less than in the experiments of Example 1, where the alite in the promoted clinker was characterized by a distinct cellular microstructure. This is in favor of explaining the presence of a large amount of X-ray amorphous alite in these clinkers by the presence of a fine-meshed submicrostructure of alite, in which some of the cells approximately correspond in size to the mosaic blocks in alite (0.1-0.3 μm); b) the profile of the analytical reflex on the alite powder x-ray at b = 1.76-10 ^-10 m, which has the appearance of an ordinary doublet in the control clinker in alite in the promoted clinker in this example is fixed as a triplet, whereas in hyperalite in the promoter this profile the reflex has the form of a quadruplet [32]. It is this phenomenon in this description that is called the “hybridization” of the crystal lattices of related phases in the promoter and the promoted clinker. The stoichiometry of alite in these clinkers, as follows from the data of rational chemical analysis, presented in table. 5 also changes during the promotion process, and from the above data one can see the effect of “refinement” (release from impurities) of alite and belite in the promoted clinker compared to the control clinker. Alumoferrite as an enclosing phase, when promoting, on the contrary, is enriched with impurities, which was mentioned in connection with the increase in the ability of the calcined material to form a coating during promotion. So, the concentration of MDO in calcium aluminoferrites, the first in contact with the lining of the furnace, increases, as can be seen from the table. 5, about 3 times, and Cr ₂ O ₃ about 5 times.

From the above table. 4 and 5, it also follows that the manifestation in a promoted clinker of “hybridization” of alite crystal lattices, which occupies an intermediate position between the alite of the control clinker and the alite in promoter 2.1, leads to an increase in both early strength and hydraulic activity of cement. At the same time, the composition of the promoted clinker approaches equilibrium, as evidenced by the large proximity of the composition of the promoted clinker according to the data of rational chemical analysis given in Table. 5 to the above potential composition compared with the above composition according to petrographic analysis.

A decrease in the content of floodplains from 14% in the promoted clinker 2 (PK-2) to 12% does not change the productivity of rotary kilns compared with the data presented in table. 4, but a further decrease in the number of smoothers by saving pyrite cinder - the imported component of the cement raw material mixture, leads to a decrease in the productivity of the furnaces and the hydraulic activity of cement made on the basis of the promoted clinker is closer to cement from the control clinker. This is apparently due to the difficulty in crystallization of minerals under conditions of a lack of melt and a decrease in clinker grindability, which for a given specific surface of cement leads to a decrease in the content of average fractions of particles with sizes of 5-30 μm, which determine the hydraulic activity of cement, and, in addition, increased energy costs for grinding cement. An increase in the content of floodplain over 22%, which was also tested in this series of experiments, did not lead to an increase in the quality of cement, but caused an increase in the cost of the raw mix and clinker and a slight decrease in the productivity of cement mills.

In these experiments, the estimated initial amount of the promoter when it is supplied to the sludge through a vortex feeder is 0.55 wt.% Clinker. With a decrease in the basicity of the promoter, when the content of hyperalite in the promoted clinker decreased in passive experiments to 50 wt.%, And the levels of dicalcium silicate and aluminoferrite analog increased to 25-28 and 25-30 wt.%, Respectively, regardless of the content of free calcium oxide, the initial input of the promoter, both by calculation and in practice, is increased to 0.6-0.8%. In this case, each time the feed value of the promoter is selected in the range of 0.1-0.8 wt.h. per 1 part by weight the estimated promoter content, based on the physical state of the material being fired, namely: with especially large granulometry of the control clinker (with an average granule size of 15-18 mm), with a “thick” (over 0.05 fraction of the diameter of the furnace) coating layer in the sintering zone and the presence of rings in the said zone, at the entrance and exit from it, as well as with the current content of alkali metal oxides in the clinker of more than 0.7 wt.% clinker, use the upper limit of the supply of the promoter from the specified interval, in other words, start immediately with significant input promo pa Otherwise, the process of changing the coating is delayed, the conditions for the accumulation of heat by the coating are worsened, and the furnace is put into operation with the promoter slowed down. In case of thin and dense coating in the furnace, fine particle size distribution of clinker (less than 10 mm), one should, on the contrary, start with a minimum supply of the promoter, in order to avoid particularly rapid advancement of the calcined material along the length of the furnace, which could lead to the release of clinker over free lime. The indicated rule regarding the connection of the initial supply of the promoter with the granulometry of the control clinker does not apply to the presence of clinker dusting with its characteristic features: the black color of the dusty fraction of the clinker caused by the black color of the melt surrounding the alite grains, and a clear increase in the ferromagnetic properties of this clinker containing brown granules in large granules nuclei surrounded by a dark dusty shell. In this case, regardless of the clinker facet, you should start with the maximum feed of the promoter.

Calculation of the optimal promoter content in the steady-state firing of the promoted clinker is possible only on the basis of experimental data on the specified clinker, which are absent before the start of production. Therefore, they are usually limited only to calculating the initial content of the promoter, and then correct these data by iteratively repeating the operations of stepwise increasing the content of the promoter and supplying the furnace with a cement raw material mixture. In the table. Figure 4 shows only the final results of the last stage of iteration during this series of experiments, which allowed to significantly increase the productivity of a rotary kiln. In fact, from 3 to 12 stages of iteration are encountered. As criteria for the optimum supply of the promoter, as in example 1, clinker microstructure characteristics are used for routine monitoring, for the final choice of promoter concentration in the development of technical regulations for the continuous production of promoted clinker - cement strength indicators based on the promoted clinker in standard mortar, i.e. cement -sand samples after 1- and 28-day hardening under normal conditions.

In a 2 series of experiments, a coarse raw mixture of the composition indicated in 1 series of experiments is used, with a residue on sieve No. 02 of 34.4% and sieve No. 008 of 46.7%, which is not subjected to sintering in the prior art to obtain Portland cement clinker. The content of promoter 2 is increased to 3.5-4 wt.% Clinker, firing is carried out with a decrease in furnace productivity compared to the control mode for finely ground raw materials by 12-15%, but with an increase in furnace productivity compared to firing a coarse mixture without a promoter by 25 -30%, and get a promoted clinker that meets the standards, with the following actual mineralogical composition according to petrographic analysis, wt.%: Alit 60, Belit 12, C ₃ L 4, C ₄ AE 12, C. '| ₈ E 7, impurities - the rest, with basicity in terms of 100% 100.01. However, in this case, the calculated initial content of the promoter is significantly lower than the optimal one, since the supply of the promoter has to be increased until the presence of marginal phases C _{! 2} A ₇ and its alkaline derivatives, as well as C ₂ E and CE fixed using the methods mentioned above, are eliminated . The resulting clinker is characterized by a cellular structure of alite (more than 25-30 wt.%), Increased grinding ability compared to control clinkers: from finely ground raw materials by 20-25% and from coarsely ground raw materials by 510% according to the data on the productivity of the cement mill, and strength indicators cement based on promoted clinker from coarse raw materials is equal to or 5-10% lower than cement based on control clinker from a finely ground raw material mixture, or 30-35 MPa higher than cement based on control material from coarse-ground cheese lye mixture. As mentioned, the standard Portland cement clinker cannot be obtained from the latter in a known manner, and the brown fired product of the type of romance has a hydraulic activity of about 17 MPa. In recent years, the possibility of obtaining a standard clinker from coarsely ground or non-ground raw materials under conditions of limited fuel and energy resources during periods of aggravation of the economic crisis has been of practical importance for the implementation of continuous construction in the Russian Federation.

Example 3. The experiments show that the method according to the invention is feasible not only in a rotary kiln, but also in clinker kilns of other systems. The authors of the present invention carried out the first work in this field in laboratory tube furnaces with platinum winding in an air atmosphere, and, with the exception of the productivity gain, which had to be very roughly estimated by an indirect indicator - reducing the time of assimilation of lime to a residual content of the lime in laboratory sintering of about 1- 1.5 wt.%, As well as indicators which are not amenable to modeling, of a forced-blowing regime, dust emission, housing temperatures obtained in a laboratory electric furnace x the results were approximately similar to those subsequently achieved using rotary kilns and are given in examples 1 and 2. An increase in the grindability of the product of promoted calcination in laboratory experiments is also evaluated by the decrease in microhardness of the obtained clinker sinter. Due to the lack of laboratory tests on the amount of burnt promoted clinker for standard physical and mechanical tests of cement based on it, these specs are tested after grinding by grinding in a mechanical mortar together with gypsum stone (5 wt.% Cement) in cement mortar samples of 1.41 x 1.41 x 1.41 cm, proposed in the 1920s for similar tests by G. Kühl [26]. Under such conditions, in a series of experiments in this example, the combination of promoter 2 with mineralizers is studied, including: 1) CaE ₂ , 2) CaCl ₂ , 3) Ca8O ₄ , 4) Ν α _; 8ίΕ ₆ . taken in a mixture with MDO to increase the level of basicity in excess of 100 conventional units, characteristic for ECR. In addition, check the mixtures of these mineralizers with mineral additives in the composition of the mineralizer, acting as a dispersant, 5) quartzite in the composition of fluorine ore,

6) mudstone in the composition of anhydrite, 7) silica gel in cryolite - a by-product of the production of hydrofluoric acid, as well as combinations, 8) CaP ₂ with blast furnace granulated slag (basic), 9) the same with the spent molding materials: 9-1 - with liquid glass; 9-2 with kaolin sinter; 10) the same with burnt rock; 11) the same with the dust returned to the rotary kiln in 2 series of experiments in the mode using the promoter (line 2.2 in table 4). In this series of experiments, the strength indicators are recalculated from non-standard samples of cement stone cubes with an edge of 1.41 cm to standard beam samples 4 x 4 x 16 cm according to the following nonlinear scale: cement M 400 according to GOST 310-85 in samples - cubes with an edge 1.41 cm shows a compressive strength of approximately 800 kgf / cm ² and 78.5 MPa; cement M 500 - about 1200 kgf / cm ² and 117.7 MPa, cement M 550 - about 1400 kgf / cm ² and 137.3 MPa; cement M 600 - about 1600 kG / cm ² and 157 MPa, and cement M 700 according to the technical specifications for an astringent of low water demand (TU 5744-002-00369171-97) - about 1800 kG / cm ² and 177 MPa. The results of the conversion are presented in lines 3.1-3.12 of the table. 4, where from a comparison of the data it follows that when using the method according to the invention when firing clinker in an electric furnace, the results significantly exceed the performance of the control clinker and cement based on the latter - control cement. A number of positive effects when producing cement according to the invention: reducing clinker firing time before sintering is completed, which, in a rough approximation, is the equivalent of increasing the productivity of industrial furnaces, reducing the clinker microhardness, increasing the strength characteristics of cement based on the clinker obtained both in early and late hardening periods - observe in these conditions. Dispersing additives in the composition of the mineralizer while maintaining the dosage of the latter at the level of supply of the active components (salt + magnesium oxide) reduce the effect of the mineralizer approximately in proportion to the reduction in dosage of the active components of the latter, which is reflected in the data in Table. 4. Moreover, in production furnaces under imperfect conditions for the introduction and mixing of the mineralizer, the effect of the dispersant introduced into the composition of the mineralizer, usually, on the contrary, is positive. With separate dosing of the components of the mineralizer with their subsequent mixing, maintaining the supply level of the indicated active components of the mineralizer and controlling the content of dispersing components in excess of the dosage of the active components of the mineralizer, the effect of the mineralizer is greater than without dispersing additives, even in laboratory conditions, and even more so in production conditions .

In a series of experiments of Example 3, the cement manufacturing method according to the invention is carried out in a pilot furnace with radiation heating (in this case, in vacuum with γ radiation from an particle accelerator), where it is also possible to increase the furnace productivity and product quality by the method according to the invention, which is carried out using dried and evacuated starting raw materials and promoter according to example 2. Moreover, as can be seen from the data in lines 3.14 and 3.15 in table. 4, the supply of the promoter is increased in one step to the maximum, since when forming the tape layer of the material to be calcined in this furnace on a substrate of MDO, the effects of coating, clinker granulometry and the speed of movement of the material being calcined to a much lesser extent than in a rotary kiln determine the quality of the finished product by compared with the chemical composition of the material to be fired. Of significant importance is the fact that in a radiation furnace, where the material is supplied with zero humidity, and in which the material is not mixed after firing the strip during firing, both an increase in productivity due to the acceleration of sintering visually noted through the viewing window, and an increase in the quality of cement in the presence of a promoter. Like the promoted clinker from a rotary kiln, the promoted clinker obtained in a radiation furnace, which is a sintered and then crushed strip layer, is characterized by reduced microhardness and increased hydraulic activity after testing in small samples.

Example 4. To obtain cement according to the proposed method, as a clinker kiln, a rotary kiln with a diameter of 4 and a length of 150 m is used, heated with fuel oil with a calorific value of about 8600 kcal / kg, or about 36000 kJ / kg, with an average clinker productivity in the control mode according to prototype - without promoter - 36 t / h

In a series of experiments, a raw mix of a calcareous component — limestone with humidity (here and below wt.%): An average of 23.7, the composition of percentage points 38.75, §1O ₂ 6.08; A1 ₂ O ₃ 1.65; Re ₂ O ₃ 0.67; CaO 50.22; MdO 1.08; 8O ₃ 0.43; K ₂ O 0.50; including Na ₂ O 0.18; K ₂ O 0.42, the sum of 99.36 on the main oxides, p 2.62; p 2.46, small components: L1 ₂ O 0.005, BaO 0.02, 8O 0.03, NO O 0.015, CoO 0.008, Mn ₂ O ₃ 0.084, Cr ₂ O ₃ 0.06, CuO 0.02; MoO ₂ 0.01, T1O ₂ 0.15, P ₂ O ₅ 0.23, C1 ₂ 0.005, P ₂ 0.001; aluminosilicate component - clay with a moisture content of 23.2 composition: 8.51; 81O ₂ 60.80; A1 ₂ O ₃ 16.33; Re ₂ O ₃ 5.42; CaO 2.71; MdO 1.34; 8O ₃ 0.69; K ₂ O 3.68, including Na ₂ O 1.72; K ₂ O

2.98; the sum of 99.51 on the main oxides, η 2.80; p 3.01, small parts: L1 ₂ O 0.01 0.04 BaO, 8th = 0, ΝΐΘ 0,02, 0,03 CoO, Mn ₂ O ₃ 0.01 Cr ₂ O ₃ 0.14, Cu 0.03; MoO ₂ 0.02, T1O ₂ 0.21, P ₂ O ₅ 0.01, C1 ₂ 0.001, E ₂ 0.001; the glandular component of pyrite cinder with a moisture content of 10.6 composition: 8U ₂ 8.90; A1 ₂ O ₃ 2.71; Her ₂ About ₃ 75.74; CaO 3.23; MdO 2.01; 8O _3, 6.39; P ₂ O 0.41, including Nb 0.13, K ₂ O 0.43; the sum of 99.39 on the main oxides, p 0.14; p 0.01; small components: b1 ₂ O 0.001, BaO 0.07, 8O O 0.002, NO O 0.045, CoO 0.052; Mp ₂ O ₃ 0.10, Cr ₂ O ₃ 0.21, CuO 0.06; MoO ₂ 0.04, T1O ₂ 0.03, P ₂ O ₅ 0, C1 ₂ 0, E ₂ 0, - are prepared at a ratio of the mentioned components (in parts by weight and in kg / t of clinker): 83.99: 13.76: 2.25 and 1676.6: 272.83: 38.30 by the wet method by two-stage grinding, first in a self-grinding mill of the Hydrofol type with a diameter of 7.0 m and a length of 2.3 m, then in two pipe mills with a diameter of 3.2 m and a length of 15 m, two-chamber, with a fill factor of 0.27 grinding media. The resulting sludge with the help of corrective pools (800 m ³ each) is adjusted to the required chemical composition, averaged in a horizontal pool with a capacity of 6000 m ³ and pumped into the furnace through nutrient devices. Slurry humidity: 35.6, cone spreadability M.S. Neginsky [26] 49 mm, the chemical composition of the control sludge for the main components: p.p. 33.72; 81O ₂ 13.67; A1 ₂ O ₃ 3.69; Her ₂ O ₃ 3.01; CaO 42.63; MdO 1.14; 8O ₃ 0.49; 1GO 0.79, including K ₂ O 0.74 and Na ₂ O 0.30; the sum of 99.14, p 2.04; p 1.23, according to V.A. Kindu: 0.93; the content of the remaining small components: N ₂ 0.0007, BaO 0.036; 8gO 0.0007, No. O 0.049, CoO 0.010, Mn ₂ O ₃ 0.099, Cr ₂ O ₃ 0.25, CuO 0.03; MoO ₂ 0.03, T1O ₂ 0.13, P ₂ O ₅ 0.23; C1 ₂ 0, E ₂ 0.

The furnace runs on artificial draft with a smoke exhaust, the return of dust trapped in the dust chamber and in the electrostatic precipitator (about 10 wt.% Clinker during the control mode) is carried out from the hot end of the furnace. The average chemical compositions of the sludge and dust returned to the furnace for the main oxides (with the exception of alkali metal oxides and sulfur) are close, but there is selective dust extraction, characterized in that the KN of the sludge is 0.03 higher than the KN of the clinker. The chemical composition of the control clinker (KK-4 in tab. 1-4) for the main oxides: 81O ₂ 20,99; A1 ₂ O ₃ 5.82; Her ₂ O ₃ 4.75; CaO 64.25; MdO 1.79; 8O ₃ 0.63; P ₂ O 1.08; including K ₂ O 0.84 and Nb O 0.53; amount 99.31, n 1.99; p 1.23, according to V.A. Kindu: 0.90; the content of the remaining small components: L1 ₂ O 0, BaO 0.049, 8O 0, NO 0 0.025, CoO 0.02, Mn ₂ O ₃ 0.09, Cr ₂ O ₃ 0.12, MoO ₂ 0.015, T1O ₂ 0.18 ; P ₂ O ₅ 0.19, C1 ₂ 0, E ₂ 0. The calculated mineralogical composition of the average sample of the control clinker (according to the formulas 22-25, wt.%): C ₃ 8 56, C ₂ 8 18, C ₃ A 7, 4, C ₄ AE 14.4, impurities - the rest.

The promoter is 4 compositions, wt.%: Tricalcium silicate (3СаОЯ1О ₂ ) 45-55, dicalcium silicate (2СаОЯ1О ₂ ) 10-18, tricalcium aluminate (3СаО ^ Л1 ₂ О ₃ ) 3-6, calcium aluminoferrite (4СаО ^ А1 ₂ О ₃ Her ₂ O ₃ ) 10-15, mayenite (12СаО ^ 7А1 ₂ О ₃ ) 1-6, calcium monoaluminate (CaО ^ А1 ₂ О ₃ ) 1-3, calcium ferrites (2СаОТе ₂ О ₃ , СаОТе ₂ О ₃ ) 1-3, calcium sulfoaluminate (4СаОЭА1 ₂ О ₃ ЯО ₃ ) 5-10, calcium sulfate (Са8О ₄ ) 2-4.5, aluminates and ferrites of alkali metals [B (A1, Her) O ₂ ] 0.1-1 5, calcium oxide (CaO) 0.1-5, impurities - the rest, is added in the form of a powder using a vortex mixer into the raw material sludge directly Tween before feeding sludge into the furnace. The average chemical composition of promoter 4: 81O ₂ 17.37, A1 ₂ O ₃ 11.51; Her ₂ About ₃ 5.22; CaO 61.87; MdO 0.32; 8O ₃ 2.79; 1GO 0.46; including K ₂ O 0.40 and Nb O 0.20; amount of 99.37; the content of the remaining small components: b1 ₂ O = 0, BaO 0.06, 8gO = 0, No. O 0.027, CoO 0.02; MnO 0.11, C ₂ O ₃ 0.08, CuO 0.02; MoO ₂ 0.031, T1O ₂ 0.18, P ₂ O ₅ 0.194; C1 ₂ 0, E ₂ 0. Promoter 4 is obtained by firing before sintering in the same clinker furnace the above composition using a raw material mixture consisting of limestone, clay, cinder, additional components - gypsum stone composition: 21.30; 81O ₂ 0.63, A1 ₂ O ₃ 0.19; Her ₂ About ₃ 0.08; CaO 32.60, MdO 0.22; 8O ₃ 43.20; 1GO 0.46; amount 98.68; bauxite composition: 5.86; 81O ₂ 7.34; A1 ₂ O ₃ 51.68; Her ₂ O ₃ 19.93; CaO 8.47; MdO 4.35; 8O ₂ 0.91; P ₂ O 0.56, including K ₂ O 0.26; NO 0.39, amount 99.01, on average May. ratio of approximately: 40: 3: 1: 20: 36. Firing is carried out until about 2.5-3% of free calcium oxide is retained. This allows one to simultaneously obtain tricalcium silicate in the indicated nonequilibrium promoter, on the one hand, calcium monoaluminate, calcium sulfate and sulfoaluminate, on the other hand, that is, minerals that are incompatible in the equilibrium clinker. The resulting promoter is ground to a specific surface of about 350 m ² / kg. The calculation of the basicity of promoter 4 by its composition and the required initial amount of promoter 4 for the promoted clinker are presented respectively in table. 1-4. The estimated initial amount of the promoter is 0.08% (Table 2), the actual one is 0.06, then 0.1; 0.15; 0.3 and 0.5%, which completes the iteration (Table 4).

The obtained promoted clinker (PK-4.1 in Table 1-5) is characterized by the ratio (wt.%) Of the raw materials in the calcined raw mix: limestone 85.31, clay 12.56, pyrite cinder 2.13, with the actual chemical composition of the promoted clinker the average sample per batch: 81O ₂ 19.99; A1 ₂ O ₃ 5.41; Her ₂ O ₃ 4.41; CaO 66.46; MdO 1.74; 8O ₃ 0.60; P ₂ O 0.83; including K ₂ O 0.44 and Nb O 0.39; the sum of 99.44; the content of the remaining small components: b1 ₂ O 0, BaO 0.02, 8O 0.025, No. O

0.012, CoO 0.014, Mn ₂ O ₃ 0.059, Cr ₂ O ₃ 0.03, CuO 0.01; MoO ₂ 0.03, T1O ₂ 0.20, P ₂ O ₅ 0.16, C1 ₂ 0, P ₂ 0. Estimated characteristics: Kind according to Kind 1.00; η 2.04; p 1.23; C ₃ 8 76, C ₃ A 6.8; With ₄ HR 13.4.

Clinker grains mentioned above, according to the method according to the invention, are obtained with a reduced value of the alumina module of the raw material mixture as follows. Accept the design characteristics of the promoted clinker - the aforementioned “grains” of KN in Kindou 1.05; η 1.46; p 0.65, provide for the presence in the promoter of free calcium oxide of about 1.5 wt.%, according to the values of KH and modules calculate the mineralogical composition of the promoted clinker. The ratio of these raw material components is taken: limestone 84.21, clay 10.68, pyrite cinder 5.11. Calculate the initial concentration of the promoter, as shown in the table. 2, and get the number of _mouths 0.8 wt.% Clinker, enter the promoter first in an amount of 0.06%, then 0.1; 0.15; 0.3; 0.5 and 0.8%, which completes the iteration (Tables 4, 5).

The promoted clinker in the form of grains (PK-4.2 in Table 1-5) receive the following actual chemical composition according to the average sample per batch: 81O ₂ 18.40; A1 ₂ O ₃ 4.99; Re ₂ O ₃ 7.77; CaO 65.19; MdO 1.77; 8O ₃ 0.73; K ₂ O 0.69; including K ₂ O 0.40 and Na ₂ O 0.42; the sum of 99.54, including free calcium oxide (evenly distributed) 1.6. Actual characteristics: Kind according to Kind 1.05 excluding free lime; taking into account free lime, the value of KN is 1.02; values of modules p 1.46; p 0.65 coincide with the design. The calculated mineralogical composition according to Kind: C ₃ 8 74 taking into account free lime; C ₃ A 0; With ₄ HR 23.6. Clinker particle size distribution (wt.%): Predominantly 1-1.3 mm fractions - 55, 0.5-1 mm 35 fraction, 1.3-3 mm fraction - 10. These grains are obtained practically without a dusty fraction of less than 0.1 mm and without particles larger than 3 mm by adjusting the alumina module of the calcined material and feeding the promoter. The productivity of the production of grits in a furnace with a planetary cooler is increased by 21% compared with the control clinker, by about 5% compared with the previous promotion clinker 4.1, and the productivity of cement mills with dimensions of 3 x 14 m is increased by 19 compared to the grinding of the control clinker %, and for grinding grains after overloading the mill with the addition of small balls of 0 30 mm - by 28%. This result was achieved for the first time by regulating the macrostructure and microstructure of clinker.

Observations, the results of which are presented in table. 1-5, as well as a number of experiments performed by the inventors on all possible incomplete combinations of the components of the promoter of compositions 4.1 and 4.2 show that in these promoters the components most harmoniously complement the mutual influence on the process of promoting mineral formation, although a number of incomplete compositions are also quite effective. By using the invention composite (composed of individual synthetic components are tested in the laboratory) or received in the form of clinker (sintered) promoters, including calcium sulfate in the form of anhydrite (Sa8O _4), tricalcium silicate (3SaO-81O _2), dicalcium silicate (2CaO-81O ₂ ), tricalcium aluminate (3CaO-A1 ₂ O ₃ ), four-calcium aluminoferrite (4CaO-A1 ₂ O ₃ -Ge ₂ O ₃ ), mayenite (12CaO-7A1 ₂ O ₃ ), calcium monoaluminate (CaO-A1 ₂ O ₃ ), calcium ferrites (2CaO-Ge ₂ O ₃ , CaO-Ge ₂ O ₃ ), calcium sulfoaluminate (4CaO-3 A1 ₂ O ₃ -8O ₃ ), as well as calcium oxide (CaO), with a mass ratio of these components (1.5-3.5): (55-80): (10-13): (4-15): (10-18): (1-3): (1-1.5): (1-1.5): (5-10): (0.1-7), impurities - the rest, used alone or in combination with oxide-salt components of the complex mineralizer when the basicity exceeds the basicity of the eutectic clinker melt, significantly (by 8-30%) increase the productivity of the clinker kiln compared to the prior art, significantly (by 10-70%) increase the grindability of the promoted clinker and strength character cement sticks based on the latter at 5-10 and 5-18 MPa in the early (1-3 days) and subsequent (7-28 days) hardening periods, ceteris paribus, and, in addition, increase the resistance of the refractory lining of the clinker kiln and reduce the temperature of the latter’s body, due to the improvement in the condition of the coating, reduces the dust circulation in the furnace, improves the clinker, freeing it from harmful impurities or partially reduces their content, and in this connection increases the durability of concrete and reinforced concrete products, structures and structures made on Nove cement clinker derived from the promoter. As mentioned, the promoter acts by approaching the equilibrium of the process of mineral formation during clinker burning due to a decrease in the activation energy of the formation of minerals and a decrease in the duration of the induction periods of crystallization of silicate, aluminate and aluminoferrite phases of successively increasing basicity, in this case starting from monocalcium silicate, monocalcium aluminate, mono- and dicalcium ferrites, mayenitis, calcium sulfoaluminate, part of which remains okl after crystallization is complete of calcium aluminoferrites and tricalcium silicate. Naturally, the process of promoting mineral formation begins with the low-basic phases being formed first, and then the high-basic phases are promoted, which is achieved using these promoter compositions. An exception is calcium sulfoaluminate, but the fixed composition of the latter is residual. Initially, sulfoaluminate crystallizes, as shown by x-ray phase analysis, in the form of a highly basic form (Klein-Troxell phase) of an approximate composition C ₉ A ₂ · £ ₂ , which then decomposes with the release of lime, which goes to the formation of C ₃ 8, with the formation of C ₄ A ₃ £ (Ragozin phase) as a residual mineral. The kinetic nonequilibrium of the given promoter compositions also explains the presence of both low and high basic phases in them, as mentioned above, and it is this very factor that determines the effectiveness of multistage promotion of mineral formation by similar promoters. Of course, the promotion of low aluminate clinkers does not require the presence of CA and C ₄ A ₃ · £ in the promoter, and the promotion of low aluminous clinkers does not require the presence of 70-80% C ₃ 8 in the promoter. In general, the indicated limits for changing the ratio of mineral components in the composition of the promoter are practically established. So, for example, in the presence of C ₃ 8 in the maximum amount in the composition of the promoter there will be no more C ₄ A ₃ · £, which is useful as an acid component of the promoter, effectively reducing the activation energy of crystallization of minerals at intermediate stages of clinker formation, but to a lesser extent to reduce the duration of the induction period of formation of C ₃ 8.

In this example, as in the previous ones, clinker microstructure parameters are used in the current production control to select the optimal promoter content, strength indicators of cement based on promoted clinker are used to draw up technical regulations, and, in addition, due to the presence of an increased alkali content in the raw materials in this example, the control of the content of marginal phases and their alkaline derivatives in burnt clinker is used. The determination of free calcium oxide is not a reliable characteristic of the degree of firing of the promoted clinker, since the calcium oxide in the latter is present in two forms - crystalline and X-ray amorphous, affecting the quality of clinker and cement based on it in different ways. Thus, amorphous free lime in an amount of up to 3 wt.% Clinker is completely extinguished when the clinker is stored at room temperature and humidity and is harmless to the quality of the clinker. In view of the clearly necessary differentiation of free lime by its microstructure, the determination of the total content of free calcium oxide for the same reason is difficult to automate. As for the content of calcium ferrites, its semi-quantitative evaluation control in a production environment is fully automated. Such control during firing of ordinary (gray) Portland cement clinker is carried out by the proportion of magnetic fraction in the control and promoted clinkers (see notes to table 3) as follows. Samples of clinkers with zero hygroscopic humidity are crushed and ground in a bench-top laboratory grinder and mill with non-magnetic grinding elements, or when they are not in the non-ferromagnetic mortar manually or by passing the sample through a mechanical mortar with a non-ferromagnetic cup to a specific surface of about 150 m ² / kg or more. The determination is carried out using a conventional permanent cylindrical magnet, rolling it over a clinker powder layer with a thickness of about 1 mm, throw clinker particles adhering to the magnet surface into the receiver and weigh them. Despite the approximation of the method, it is sufficient to obtain current data 3 minutes after sampling. When the content of the magnetic fraction is more than about 15 wt.%, It is concluded that there are calcium ferrites in the clinker. The described method for assessing the equilibrium of the process of mineral formation in clinker is based on the increased (about an order of magnitude) magnetic permeability of the mentioned marginal phases, which are indicators of clinker underburning, compared to the rest of the clinker minerals. An approximately linear correlation between the content of the total amount (crystalline and amorphous forms) of free lime in clinker and the proportion of the ferromagnetic fraction of more than 15 wt.% In samples comprising more than 2% of free lime was established. This method is convenient for use in the promotion of highly alkaline clinkers, since calcium ferrites in them are accompanied by alkaline ferrites that last longer during sintering in the clinker, up to the content of free lime equal to 0.5-0.8 wt.%.

The content of clinkers C12A7 and its alkaline derivatives KS ₈ A ₃ , from the crystal chemical positions being alkaline tetragonal polymorphs C3A, is controlled using IR spectroscopy according to the characteristic features of the known absorption bands of A1-O bonds in A1O ₄ tetrahedra in the anionic structure structure of these aluminate marginal phases. The direct determination of the content of marginal phases, including C1 ₂ A ₇ , is also carried out using petrographic analysis, for which purpose the clinker is ground in a mortar, shut it with water and micropreparations isolated from the atmosphere are prepared at V / C order

10, by studying these drugs in transmitted or reflected light. Around C1 ₂ L ₇ particles and their derivatives 5-10 min after mixing, characteristic gel-like spheres form from L1 (OH) 3 or L1 UN gels, which are the first hydration products of these marginal phases [27], gradually surrounded by plates of hexagonal calcium hydroaluminates visible in position "on the edge" like needles around a spherical gel core. In contrast to the IR spectrum, which is sensitive to 1-2% C1 ₂ L ₇ , the petrographic method is sensitive starting from 3% C _{! 2} L ₇ , therefore it is more suitable for high-aluminate clinkers (p> 1.4). Typically, the definition of C1 ₂ L ₇ and its derivatives is used in the implementation of the method according to the invention with a particularly high content of alite in a promoted clinker, or its analogues - about 75-80% and with a high content of free calcium oxide required in some special clinkers up to 10%, and also with the release of white clinkers.

In the presence of an X-ray diffractometer at the enterprise, the presence of an X-ray amorphous alite is determined using this apparatus by the difference between the calculated (potential) alite content based on chemical analysis data and the alite content by the graded intensity of the X-ray reflex in the diffractometer channel with b = 1.76 x 10 ^-10 m and the intensity of any second analytical reflex, and the amount of crystalline alite is set as the average for two channels, otherwise when studying promoted clinkers I get t dramatically fluctuating results. The difference between calculated according to the data of chemical analysis and the average amount of crystalline alite in the clinker over two channels of the diffractometer is taken as the content of X-ray amorphous alite in the promoted clinker. In this way, the data presented in the last column of the table are obtained. 4.

When implementing the method according to the invention with the use of promoter 4.2, the initial content of the latter in the calcined material is about 0.06% and the level of free lime in the finished clinker is more than 1.5%, the content of the magnetic fraction in the clinker is about 10%, i.e. 7-8% less than in the control clinker. As the promoter content increased to 0.7% of the clinker mass, the amount of the magnetic fraction in the latter decreased to zero with a free lime content of about 1.6%. Similarly, the amount of mayenite and its alkaline derivative from the level of 45% in the control clinker (according to petrographic analysis) as the promoter content in the calcined material increases, is reduced to almost zero, which is not fixed by any physicochemical analysis methods. In this case, the decrease in the content of the magnetic fraction and aluminate marginal phases proceeds in parallel. This is explained by an increase in the degree of completion of mineral formation reactions (1-4) as the promoter content is optimized and corresponds to an improvement in the construction and technical properties of cement based on promoted clinkers compared to control cements. The manifestation of the essential features of the promoted clinker microstructure — the cellular microstructure, the absence or low content of alite intergrowth-cluster crystals, the presence of X-ray amorphous alite, also occurs gradually as the content of promoter 4.2 in the calcined material increases: from the complete absence of the first two features and the almost complete intergrowth of alite microcrystals - before the transition to a 100% cellular microstructure of alite and belite, reaching a level of 25% of highly active X-ray amorphous alite, finally, to the zero content of the mentioned clusters. Also gradually, as the content of the promoter increases, the content of alkali metal oxides and hexavalent chromium in the promoted clinker decreases.

In the manufacture of high-alumite clinkers, a working cell with two electrodes is also used to control production to measure the electrical conductivity of the calcined material. Typically, the electrodes are made of heat-resistant steel, their surface is polished and periodically lowered into the calcined material. When firing in a furnace with radiation heating, this operation is carried out continuously by lowering the electrodes into the strip of fired material. In a furnace unit with a rotary kiln, electrodes in the form of plates are fixed in the shaft of the grate cooler at the surface of the first grate. With the supply and increase of the content of the promoter, the conductivity increases, although visually the amount of melt seems to be unchanged. Unlike thermocouples, the cell for measuring electrical conductivity on alternating current works inside the furnace unit without “overgrowing” with the material being burned, because, acting on relatively low voltages (up to 60 V), it can be cleaned by the heat effect of applying a powerful electric pulse. The criterion for the maximum content of the promoter when the number of marshes is up to 22% and alkali metal oxides is up to 1% is the electrical conductivity at a level of not more than 1 0 ^-6 Ohm ^-1 cm ^-1 . The inaccuracy of the method is due to the need to transmit a signal from the measuring cell to the circuit with low currents for conducting resistance measurements on alternating current using bridge circuits, which is complicated by interference from surrounding electrical installations. This is partially eliminated by appropriate cable insulation. The data obtained are presented in table. 5, where the data of various methods of fixing the degree of calcination of the promoted clinker according to Example 4 are compared with the promoters 4.1 and 4.2. From the above data it is seen that the electrical conductivity during firing of the above-mentioned clinker “grains” is higher than with conventional granulometry of the control clinker, and increases with increasing concentration of the promoter. The conductivity value, therefore, is an indirect indicator of the estimation of clinker granulometry during its firing and cooling, which is currently not known from the prior art for assessing the granulometric composition of sintered material, as well as a measure of the concentration of the promoter. The method of determining the electrical conductivity is used as a guideline for the production control of the fired clinker firing process. The effect of refining by the level of MdO in alite also depends on the amount of promoter feed. Low basic aluminates C ₁₂ A ₇ and K. S. ' ₈ A ₃ disappear from the promoted clinker before positive changes in other characteristics of the clinker, and therefore their presence in the promoted clinker is a sign of incomplete promotion. The exit of the C / 8 molar ratio in alite upward beyond 3 for alumina module values above 1 leads to a decrease in the hydraulic activity of cement, and a decrease in this ratio in the range of 3-2.8 has a positive effect on the hydraulic activity of cement; it is due to a decrease in the basicity of the promoter. A further decrease in the C / 8 ratio in alite to 2.7 clearly worsens the properties of the cement and even reduces the clinker grindability. A very noticeable effect on the clinker quality is exerted by the proportion of the cellular structure in alite and the content of X-ray amorphous alite. Moreover, the overdose of the promoter (compositions Nos. 8 and 9) of the rapidly determined characteristics is most sensitive to a decrease in the content of X-ray amorphous alite and an increase in the content of AlO impurities in alite, and the most reliable characteristic of an overdose of the promoter in the material to be fired is a decrease in the cement strength values in the late curing time by compared with the strength of similar clinker cement, obtained with the optimal content of the promoter in the calcined material.

More complete results of selective chemical analysis of the alite phase and other clinker minerals are given in table. 6, indicate that by increasing the content of the promoter in the material to be fired, the alite content of the promoted clinker is reduced in the presence of characteristic impurities, in particular, MdO, converting it into an intermediate clinker substance. In the alite of the promoted clinker, the content of MdO is approximately 1/6 of the total amount of this impurity in the clinker versus about 1/2 - in the alite of the control clinker, i.e., it decreases approximately threefold. The concentration of other impurities in alite is similarly changed. To a lesser extent, but a similar effect is also manifested in C ₂ 8 and C ₃ A in promoted clinkers. It is this phenomenon that is named above the effect of refining clinker minerals by promoting mineral formation in sintered clinker.

By controlling the composition of the promoter, the alite stoichiometry in the clinker is also changed within the C / 8 ratio of 2.8-3.2, more precisely 3.17 (Table 5). It was mentioned that such changes cause an increase in the hydraulic activity of cement compared to cement based on control clinker, which was previously known only by regulating the cooling mode of the clinker, and the temperature limits of the regulation did not allow the implementation of production, whereas in this case, the industrial implementation of the regulation of stoichiometry Alita through promotion existing production lines are almost ready.

The decrease in the content of alkali metal oxides and hexavalent chromium in the promoted clinkers compared to the control (see Tables 3, 5) is a characteristic feature of the promotion technology, it is observed under any promotion conditions and promoter compositions according to the invention. The degree of alkali sublimation increases especially when high alkaline dust is returned to the furnace from the hot end, so that when the content of K ₂ O in the clinker is more than 1 wt.%, The sublimation of alkaline compounds is enhanced due to the shorter residence time of the high concentration of marginal phases in the calcined material, the main absorbers of alkaline compounds holding alkali metal compounds in clinker. The closer the promoter content to the optimum, the less alkaline compounds and marginal phases remain in the promoted clinker (Table 5).

Example 5. The conditions for the implementation of the method according to example 4 using a furnace unit equipped with a coal preparation department for the possibility of using as process fuel, in addition to fuel oil, also pulverized coal containing components from short and long flame coals, with a heat of combustion of a mixture of 5980 kcal / kg, or about 25060 kJ / kg, with an ash content of about 18%. The composition of the ash, wt.%: 81O ₂ 54.57; A1 ₂ O ₃ 15.87; Re ₂ O ₃ 9.47; CaO 7.03; MdO 3.30; 8O ₃ 2.44; Specific coal consumption: 285 kg / t of control clinker is adopted in table. 7 for 100%. The furnace unit is equipped with installations for the return of dust trapped by the electrostatic precipitator from the exhaust gases, both from the loading (cold) and unloading (hot) ends of the furnace, as well as an experimental decarbonizer with the possibility of burning up to 40% of the process fuel in it and the possibility of feeding it as lime sludge from a separate vertical pool, and the raw material mixture in the form of flour, ground in a separate raw mill, heated by the exhaust gases of the furnace. To feed the product of the decarbonization product and take off the exhaust gases into the decarbonization device, the long wet process furnace is equipped with hatches with covers in the decarbonization zone, reclining in the upper position, and a spiral heat.

By supplying the promoter, changes are caused by all, without exception, performance indicators of clinker kilns, first of all, in the kilns of any systems tested by the inventors, the temperature of the calcined material in the sintering zone is increased. This is what makes it possible to increase the productivity of furnaces in the presence of a promoter: the furnaces seem to “ask” for an increase in nutrition. In this case, an immediate decrease in fuel consumption after the initial introduction of the promoter to maintain the temperature in the sintering zone at the same level is a technical error: the furnace, namely the lining, coating, and also calcined material in the presence of the initial amount of the promoter must accumulate an additional supply of thermal energy, which in the future will increase the productivity of the furnace. The time of this accumulation approximately corresponds to 4-5 times the response time of the furnace unit to control actions. In other words, before the furnace “accelerates” to increased productivity, the firing mode of the material with the promoter is more sensitive to temperature fluctuations in the sintering zone as compared to the control mode (prior art), which is consistent with the autocatalytic nature of the acceleration of mineral formation in the presence of a promoter, it is sufficient to point to a thorough stabilization of temperature conditions in the main processes of promoted catalytic synthesis in the chemical industry. Typically, an increase in temperature in the sintering zone by 25-50 ° C, caused by the initial supply of the promoter, experienced operators of clinker kilns fix visually or using pyrometers and equivalent thermocouples installed in the head or in the sintering zone of the furnace and shielded from direct radiation heating by a fuel combustion torch . The temperature in the sintering zone is the most convenient indicator of the operation of the furnace for regulating the firing regime of the promoted clinker. In order to increase the reliability of regulating the furnace operating mode during the implementation of the method according to the invention, in addition to increasing the temperature in the sintering zone, parameters from the groups are additionally used: I temperature in the decarbonization zone of the calcined material, in the heating zone, in working volumes and / or at the outlet of the furnace baking heat exchangers, exhaust gases at the cold edge of the furnace, exhaust gases at the outlet of the baking heat exchanger, clinker at the hot edge of the furnace, at the exit of the clinker refrigerator; II - current fuel consumption; III current power consumption: for a rotary kiln - for rotation of the kiln, the amperage of the main drive of the kiln, for all types of furnaces - the magnitude of the smoke suction; IV - the frequency of rotation of the smoke exhaust, for rotary kilns, the frequency of rotation of the furnace; V - vacuum: on the hot edge of the furnace, on the cold edge of the furnace, at the outlet of the baking heat exchanger, at the inlet to the exhaust fan, as well as the hydraulic resistance of the furnace; for a rotary kiln, additional vacuum in the furnace head; VI - content in the exhaust gases of the furnace and / or heat exchanger: CO ₂ , CO, O ₂ ; VII - radiation absorption: in the duct at the entrance to the bake dust collectors, in the duct at the outlet of the baking heat exchanger, as well as the density of the gas and dust flow, for example, through a nuclear densitometer: on a cold edge of the furnace, at the outlet of the baking heat exchanger; in addition, dust removal from the specified furnace, for example, by weight meters in the dust return system; VIII - amperage of fans: primary air, secondary air, with the following reactions of the furnace unit to the introduction and then an increase in the supply of the promoter to the calcined material according to the characteristic indicators from groups I, IV - increase, II, III, V, VI, VII, VIII - decrease that accompany the effects that cause opposite reactions of the furnace unit during the clinker burning process, and in addition to increasing the supply of the specified furnace with a cement raw material mixture and / or the coefficient of saturation of lime with the latter, I use All the above figures on modern kiln units included in the adaptive model of the automatic control mode of operation of furnaces. Thus, the method according to the invention is compatible with automatic control systems for the clinker firing process.

In the table. 7 presents the parameters of the adaptive choice of the operating mode of the furnace unit, including a rotary kiln and a clinker cooler, in the manufacture of the promoted clinker according to the invention in 7 stages with the introduction of a promoter without a mineralizer (lines 1-13) and in 4 stages in the presence of a mineralizer (lines 14-22 ) Various options for introducing the promoter and returning dust to the specified furnace in the absence and in the presence of a mineralizer according to the final optimal promotion modes (preliminary iterative stages are omitted) are presented in lines 23-33 of the table. 7. Finally, the option of promoting mineral formation during clinker firing using a decarbonizer in the absence and presence of a mineralizer is presented in lines 34-36 of the table. 7. The results obtained indicate that: a) during iterative stages, all operation parameters of the specified furnace change; b) increasing the productivity of the furnace during promotion is stably accompanied by a decrease in the energy consumption for the rotation of the furnace; c) the above directions of changes in the parameters of the specified furnace relate to specific values attributed to 1 kg of produced clinker, and not to integral indicators; d) the use of a promoter allows you to increase the productivity of the specified furnace by 21% while increasing the hydraulic activity of cement by 14 MPa (or 29%), and with an additional introduction of the mineralizer by 25% while increasing the hydraulic activity of cement by 22 MPa (or 46% ) Independent use of the mineralizer leads to a much smaller increase in productivity (up to 3.5%) and almost does not increase the quality of cement (by 1 MPa at 28 days of age). This indicates the feasibility of using mineralizers mainly in conjunction with promotion. In this case, the above-mentioned disadvantages characteristic of the methods of using mineralizers known from the prior art are not observed; d) various methods of returning dust to the furnace practically do not affect the efficiency of promoting mineral formation, with the exception of preliminary mixing of highly alkaline dust with a promoter, which clearly reduces the effect of the method according to the invention; f) the introduction of the promoter mitigates the negative impact of ash fuel on the quality of the cement obtained, which is very significant given the well-known global trend of replacing ash-free fuel with coal, with a lower heat of combustion; g) the greatest increase in the productivity of the furnace unit when promoting mineral formation under conditions of clinker burning on coal is observed under conditions of “neutralization” of coal ash, which sits on the material in the sintering zone, by introducing a part of the calcareous component into the sintering zone. It is to this case that the maximum level of supply of the promoter to the calcined material belongs: up to 2.5-3.5 wt.% Clinker; introducing a complex mineralizer into the furnace in an amount of up to 22 wt.% clinker, with up to half of CaO included in the feed, calculated on the weight of clinker, from the hot end of the furnace (Table 7, lines 29 and 30). Without this, the promoter introduced into the furnace heated by coal dust is ineffective; h) in addition to the productivity of the furnace, dust promotion changes most significantly during promotion: it decreases to 40-50% against the level in the control mode with optimal methods of dust return; i) the process of choosing a promotion mode through step-by-step iteration is amenable to automation using standard adaptive programs, if there are qualified sensors installed that read the parameters of the above groups, the values of which are partially presented in table. 7.

Example 6. To obtain decorative, including white cement according to the proposed method, a rotary kiln of the dry production method is used with a diameter of 3 and a length of 52.7 m, heated with natural gas with a calorific value of 9800 kcal / kg, or 7540 kcal / m ³ , that is 41060 kJ / kg or 31590 kJ / m ³ . The productivity of the furnace is 5.5 and 4.7 t / h at a gas flow rate of 362 and 435 m ³ per 1 ton of control decorative cream and white clinkers, respectively.

In a series of experiments, the release of the control decorative clinker for the production of cream-colored cement is carried out on the basis of a raw mix of chalk component of chalk with humidity (here and below wt.%) On average 11, the composition of percentage points 41.66, §1O ₂ 1.64; A1 ₂ O ₃ 0.72; Re ₂ O ₃ 0.16; CaO 54.60; MdO 0.50; 8O ₃ 0.35; B ₂ O, 0.16; including Na ₂ O 0.08; K ₂ O 0.12, the sum of 99.79 for the main oxides, p 1.85; p 4.50, small components: L1 ₂ O 0, BaO 0, 8O 0, 0 O 0, CoO 0, Mn ₂ O ₃ 0.06, Cr ₂ O ₃ 0.03, CuO 0; MoO ₂ 0, T1O ₂ 0.02; P ₂ O ₅ 0.09, C1 ₂ 0, P ₂ 0; aluminosilicate component - clay with a moisture content of 18.3 pp 13.26; §1O ₂ 45.53; A1 ₂ O ₃ 37.65; Re ₂ O ₃ 0.74; CaO 1.99; MdO 0.37; 8O ₃ 0.25; B ₂ O 0.20, including Na ₂ O 0.12; K ₂ O 0.12; the sum of 99.71 on the main oxides, p 1.19; p 50.53, small components: L1 ₂ O 0, BaO 0.01, SrO = 0, LiO 0.01, CoO 0.01, Mn ₂ O ₃ 0.01; Cr ₂ O ₃ 0.08; CuO 0.01; MoO ₂ 0, T1O ₂ 0.15, P ₂ O ₅ 0.01, C1 ₂ 0, P ₂ 0; aluminosilicate-calcium component - marl with a moisture content of 20.5: p.p.p. 34.57; §1O ₂ 17.05; A1 ₂ O ₃ 2.65; Re ₂ O ₃ 1.09; CaO 42.53; MdO 0.72; 8O ₃ 0.67; B ₂ O 0.22, including Na ₂ O 0.12, K ₂ O 0.15; the sum of 99.50 on the main oxides, p 4,56; p 2.43; small components: L1 ₂ O 0, BaO 0.01, 8O 0 0.01, NaO 0.005, CoO 0.002; Mp ₂ O ₃ 0.10, Cr ₂ O ₃ 0.11, CuO 0.002; MoO ₂ 0.001, T1O ₂ 0.10, P ₂ O ₅ 0.16; C1 ₂ 0, P ₂ 0. The raw meal obtained from these components is prepared at ratios of the mentioned components (in parts by weight and in kg / t of clinker) 54.04: 13.19: 32.77 and 951.6: 253, eleven:

646.1 by dry method by two-stage grinding, first in a hammer mill, then in a tube mill with a diameter of 2.2 m and a length of 13 m, two-chamber, with a filling factor of the grinding charge of 0.25. The specified raw flour with the help of corrective silos (100 m ³ each) is adjusted to the required chemical composition, the resulting raw material mixture is averaged in a silo (up to 250 m ³ ) and pumped to the furnace through nutrient devices. The average initial moisture content of the flour, add 99

May 100, with raw materials: 15.1, the chemical composition of the control raw mix in terms of the main components 35.58; 81O ₂ 13.91; A1 ₂ O ₃ 4.25; Re ₂ O ₃ 0.77; CaO 43.95; MdO 0.56; 8O ₂ 0.44; K ₂ O 0.19, including K ₂ O 0.13 and Na ₂ O 0.11; amount 99.65, η 3.3; p 5.6, according to V.A. Kindu: 0.96; the content of the remaining small components: b1 ₂ O 0, BaO 0.046; 8g0.0087, No. 0.0077; CoO 0.002; Mp ₂ O ₃ 0.0665; Cr ₂ O ₃ 0.0628, CuO 0.0013; MoO ₂ 0.0003, T1O ₂ 0.0636, P ₂ O ₅ 0.1023; C1 ₂ 0, P ₂ 0.

The furnace runs on artificial draft with a smoke exhaust; the return of dust trapped in the dust chamber and in the electrostatic precipitator (about 10 wt.% clinker in the control mode) is carried out from the hot end of the furnace. Clinker bleaching is carried out with water in the tray immediately after the clinker leaves the furnace edge, water vapor is removed to the atmosphere. The average chemical compositions of flour and dust returned to the furnace for the main oxides (excluding alkali metal oxides and sulfur) are close, but there is selective dust extraction: KN of sludge is higher than KN of clinker by 0.02. The chemical composition of the control clinker (KK-6.1 in Table 1-4) for the main oxides: 81О ₂ 21.88; A1 ₂ O ₃ 6.68; Re ₂ O ₃ 1.21; CaO 68.20; MdO 1.00; 8O ₃ 0.56; K ₂ O 0.22; including K ₂ O 0.18 and Na ₂ O 0.10; amount 99.74, η 2.78; p 5.52, according to V.A. Kindu: 0.94; the content of the remaining small components b1 ₂ O = 0, BaO 0.003, 8O 0.058; Νΐθ 0.058, CoO 0.001, Mn ₂ O ₃ 0.047, Cr ₂ O ₃ 0.056, MoO ₂ = 0, T1O ₂ 0.064; P ₂ O ₅ 0.08, C1 ₂ 0, P ₂ 0. The calculated mineralogical composition of the average sample of the control clinker KK 6.1 according to the formulas (22-25), wt.%: C ₃ 8 68, C ₂ 8 11, C ₃ A 15, C ₄ AR 4, impurities - the rest. The actual mineralogical composition according to the data of quantitative petrographic analysis and IR spectroscopy: alite (C ₃ 8) 62, white (C ₂ 8) 14, tricalcium aluminate (C ₃ A) 9, mayenite and its alkaline derivative (C1 ₂ A ₇ and KS ₈ a ₃₎ in the amount of 6, calcium alumina ferrite (composition in this case C ₆ a ₂ P) 1, calcium ferrites (C ₂ F + SR) 2, impurities - the rest. Values of the calculated basicity of COP ₈ A ₃ 1,05; C ₆ A ₃ P is about 1, a mixture of C ₂ P and CP 0.93. The basicity of this clinker is 99.66 (table. 2). Due to the large number of marginal phases, the strength and durability of materials based on control clinker are low (Table 3, line 6.1), therefore, despite the cream-colored eye that is pleasant to the eye, this cement is not produced on an industrial scale. The microstructure of the control clinker is characterized by the complete absence of single alite crystals (cluster content - 100%).

As a promoter, a mixture of promoters is used: No. 2.1 according to example 2, No. 3.1 according to example 3 and No. 4.2 according to example 4 of the composition according to table. 5.

line 10 in may. a ratio of 0.5: 0.5: 3 in the form of a powder with a specific surface area of about 350 m ² / g. Below this composition of the promoter is designated 6.1. The mineralogical composition of the latter (wt.%): From No. 4.2: tricalcium silicate (3CaO-81O ₂ ) 41.25, dicalcium silicate (2CaO-81O ₂ ) 0.5, tricalcium aluminate (3CaO-A12O3) 4.5, calcium aluminoferrite (4CaOA1 ₂ O ₃ -Pe ₂ O ₃ ) 9.85, mayenite (12CaO-7A1 ₂ O ₃ ) 0.75, calcium monoaluminate (CaO-A1 ₂ O ₃ ) 0.75, calcium ferrites (2CaO-Fe ₂ O ₃ , CaO-Fe ₂ O ₃ ) 0.75, calcium sulfoaluminate (4CaO-3A1 ₂ O ₃ -8O ₃ ) 3.75, calcium sulfate (Ca8O ₄ ) 1.5, aluminates and ferrites of alkali metals [K (A1, Re) O ₂ ] 2,3; calcium oxide (CaO) 5.3, impurities - the rest; from No. 2.1: dicalcium silicate (2CaO-81O ₂ ) 3.75; alkaline derivative of dicalcium silicate (K ₂ O-23CaO-1181O ₂ ) 3.75; alkali metal silicate (No. ₂ O-3,581O ₂ ) 0.6; quicklime (CaO) 4.4; from No. 3.1: a component of composition C ₃ , ₄ 8 in the form of a phase idiomorphic to alite 9.5; component of the composition [(4.8-7) CaO- (0.7-0.9)

A1 ₂ O ₃ -Pe ₂ O ₃ - (0.5-1.5) 8U ₂ ] 1, free calcium oxide in the form of a solid solution with dicalcium ferrite of composition C _{! 8} P 2. The calculated basicity of the promoter is 6.1 - 100.109 (sum of products mineral content, wt.%, and b ₁ values from the series (18)). The specified promoter is introduced into the raw meal during grinding. The average chemical composition of the promoter 6.1: 81O ₂ 16.38, A1 ₂ O ₃ 7.76; Re ₂ O ₃ 4.25; CaO 66.04; MdO 0.44; 8O ₃ 3.59; K ₂ O 0.97; including K ₂ O 1.26 and Na ₂ O 0.14; the amount of 99.43; the content of the remaining small components: b1 ₂ O a 0, BaO 0.0312; 8g; 0.0365; ΝΐΘ 0.016, CoO 0.0145; Mp ₂ O ₃ 0.095, Cr ₂ O ₃ 0.089, CuO 0.0244; MoO ₂ 0.0198, T1O ₂ 0.119, P ₂ O ₅ 0.124; C1 ₂ 0, P ₂ 0.

The calculation of the basicity of the promoter 6.1 by its composition and the required initial amount of promoter 6 for the promoted clinker 6.1 are presented in table. 1-4. The estimated initial amount of the promoter is 0.67% (table. 2). Actual - 0.67, then 0.8; 0.9 and 0.95%, which completes the iteration (Table 7 presents two stages of iteration out of four, and Table 4 shows the final result).

The obtained promoted clinker (PK-6.1 in Table 1-7) is characterized by the ratio (wt.%) Of the raw materials in the calcined raw mix: limestone 37.32, clay 6.72, marl 55.69, with the actual chemical composition of the promoted clinker according to average sample per batch: 81О ₂ 20.57; A1 ₂ O ₃ 6.66; Re ₂ O ₃ 1.12; CaO 69.00; MdO 0.95; 8O ₃ 1.04; K ₂ O 0.20; including K ₂ O 0,14 and No. 0 0,11; the sum of 99.54; the content of the remaining small components: L1 ₂ O 0, BaO 0.011, 8O 0 0.009, NO 0 0.007, CoO 0.004, Mn ₂ O ₃ 0.092, Cr ₂ O ₃ 0.079, CuO 0.003; MoO ₂ = 0, T1O ₂ 0.123, P ₂ O ₅ 0.133, C1 ₂ 0, P ₂ 0. Estimated characteristics: Kind according to Kind 1.00; η 2.64; p 5.95; C ₃ 8 78.2; C ₃ A 15.8; With ₄ AR 3.4. The actual mineralogical composition of the promoted decorative (cream) wedge101

According to the petrographic analysis, 102 kera is close to the calculated one: alite 75, no belite, tricalcium aluminate (determined by staining) 16, calcium aluminoferrite 3, impurities the rest. The content of alite clusters in the microstructure is only about 15%, a small amount of X-ray amorphous alite is present - up to 10%.

The criterion for selecting the promoter content in the calcined material during firing of the white promoted clinker according to the invention is the content in the latter of mayenite (12CaO-7L1 ₂ O ₃ ) and / or alkaline forms of tricalcium aluminate or alkaline calcium aluminates (K ₂ O-8CaO-L1 ₂ O ₃ ), where I = No., K, in an amount not exceeding a total of about 3 wt.%. Given in the table. 3, the data indicate that, at the calculated initial concentration of the promoter, the above marginal phases in the white promoted clinker are absent; therefore, as a rule, for the white promoted clinkers in the absence of additional mineralizers, the initial calculated content of the promoter is close to optimal or corresponds to it (see also the data in Table 4 for the following series of experiments).

Of particular interest is the hybridized Alite crystal lattice in this promoted clinker: according to X-ray powder diffraction analysis, the main analytical reflex at b = 1.76-10 ^-10 m is represented by a triplet (against the doublet in the control clinker, the quadruplet in the component of promoter A.3.1 and the doublet in component of the promoter A.4.2.). With an increase in the promoter content in the material being fired, the resolution of the indicated triplet in the diffractogram increases, the intensity of its peaks increases, which characterizes the intensification of the hybridization phenomenon and is accompanied by a significant increase in the hydraulic activity of the promoted clinker from 45 to 64 MPa (Table 7, lines 37-39) at an increase in the degree of hydration of alite in samples of cement paste at 28 days of age after 1 day of air-wet and 27 days of water storage at 20 ± 3 ° C from 55 to 82%, respectively (determination of the degree of hydration of alite according to x-ray analysis based on the area of the reflex at b = 1.76-10 ^-10 m). The milling capacity of this clinker according to the microhardness and productivity growth of a mill 2.2 x 13 m in size (two-chamber, with alundum lining and uralite balls) is given in Table. 4, increases by about 20-30%.

In 2 series of experiments, the release of the control white clinker for the production of white cement is carried out on the basis of a raw material mixture from the components described in the description of 1 series of experiments, but instead of marl, silica gel is taken as a silicate component, a by-product of the production of phosphoric acid with a moisture content of 20.5 composition p. p.p. 21.58; 81O ₂ 71.92; L1 ₂ O ₃ 2.51; Her ₂ About ₃ 0.52; CaO 1.03; Md O 0.64; 8O ₃ 0.15; I ₂ O>0; the sum of 98.35 on the main oxides, η 23.74; p 4.83; small components: Li ₂ O 0, BaO = 0, 8rO 0.01, ΝΪΘ = 0, CoO = 0, Mn ₂ O ₃ 0.01, Cr ₂ O ₃ 0.08, CuO 0.01; MoO ₂ = 0, T1O ₂ 0.21, P ₂ O ₅ 1.02; C1 ₂ 0, E ₂ 0.31. The raw flour obtained from these components is prepared at the ratios of the mentioned components (in parts by weight and in kg / t of clinker): 78.90: 9.41: 11.69 and 1466.1: 206.13: 256.07 dry method and burn in a furnace according to 1 series of experiments.

The chemical composition of the obtained control white clinker (KK-6.2 in table. 1-7) for the main oxides: 81O ₂ 22,21; L1 ₂ O ₃ 6.98; Her ₂ About ₃ 0.41; CaO 68.91; MdO 0.80; 8o ₃ 0.21; I ₂ O 0.16; including K ₂ O 0.13 and Nb 0.07; amount 99.68, η 3.01; R 17.02, KN according to V.L. Kindu: 0.92; the content of the remaining small components: L ₂ O = 0, BaO = 0, 8 gO 0.008; ΝΪΘ = 0, CoO = 0, Mn ₂ O ₃ 0.003, Cr ₂ O ₃ 0.012, MoO ₂ = 0, T1O ₂ 0.041; P ₂ O ₅ 0.15, C1 ₂ 0, E ₂ 0.10. The calculated mineralogical composition of the average sample of the control clinker KK 6.2 according to the formulas (22-25), wt.%: C ₃ 8 64, C ₂ 8 15, C ₃ L 18, C ₄ AE 1, impurities - the rest. The actual mineralogical composition according to the data of quantitative petrographic analysis and IR spectroscopy: alite (C ₃ 8) 62, belite (C ₂ 8) 17, tricalcium aluminate (C ₃ L) 13, fluoromayenite (ScA _7- CaE ₂ ) 3,7, calcium aluminoferrite (composition in this case, C ₆ A ₂ E) 1, impurities - the rest. The calculated basicity of ScA ₇ -CaE ₂ 0.96 from the series (18). The basicity of the white control clinker 6.2 is 99.59 (table. 4). The resulting industrial batch of control white clinker and the industrial batch of control white cement based on it are characterized by the highest indices known in the CIS countries both in terms of strength and whiteness (whiteness coefficient according to the standard 0.91). But, as shown below, the quality of the control white clinker and cement is inferior in all characteristics to the materials obtained by the method according to the invention. The microstructure of the control white clinker is characterized by the complete absence of single alite crystals (cluster content - 100%). The grindability of this clinker is low. There is also no X-ray amorphous alit. The alite hydration rate in the control white cement is also low - not higher than 66% after 28 days of storage of samples from the cement paste under the conditions described in 1 series of experiments.

As the promoter, a composition of white components is used - tricalcium silicate (3CaO-81O ₂ ), dicalcium silicate (2CaO-81O ₂ ), tricalcium aluminate

103

104 (3СаО ^ А1 ₂ О ₃ ), mayenite (12СаОГА1 ₂ О ₃ ), as well as calcium oxide (CaО), in the following ratio of components, wt.%: Tricalcium silicate (3СаО ^ 81О ₂ ) 50-85, dicalcium silicate ( 2CaO ^ 81O ₂ ) 5-30, tricalcium aluminate (3CaO · A1 ₂ O ₃ ) 7-13, mayenite (12CaOGA1 ₂ O ₃ ) 0.1-3, calcium oxide (CaO) 0.110, impurities - the rest. In this case, the composition is used in the form of ground white clinker (A.6.2.1), ground white clinker mixed with 2.5% ground gypsum stone (A.6.2.2), in the form of a mixture of sintered white clinker minerals subjected to joint grinding ( Clause 6.2.3), in the form of sludge from white clinker minerals taken in the indicated ratio, which is a mixture of intermediates for the production of clinker minerals for research purposes with a water-solid ratio of 0.48, including the stages of intermediate mixing of the intermediates with water, short-term storage (up to 1 8 h), repeated sintering and 10-12-fold repetition of these operations (A.6.2.4), finally, in the form of ground white clinker (A.6.2.5), preliminary obtained by sintering in the presence of a promoter of the composition A.6.2.2 .

Specific promoter compositions and calculated basicity values for major minerals and oxides (in terms of 100%) are as follows: A.6.2.1: C ₃ 8 50, C ₂ 8 27, C ₃ A 13, C ₁₂ A ₇ 0.1, CaO _freedom 10, _Rgot 100.06; A.6.2.2: C ₃ 8 75, C ₂ 8 5, C ₃ A 10, C12A ₇ 0.3, CaO _C wob 3, C U 2.5; In the _WG, Osh is 100.477; A.6.2.3: C ₃ 8 65, C ₂ 8 16, C ₃ A 7, C ₁₂ A ₇ 3, CaO _freedom 6, _Rgot 100,052; the promoter of P.6.2.4 of the composition — C ₃ 8 65, C ₂ 8 16, C ₃ A 7, C ₁₂ A ₇ 3, CaO _freedom 6, _Rgot 100,052 — is the hydrated form of the previous promoter with a degree of hydration of about 10% as a whole therefore, its dosage when fed into the furnace is increased compared to the calculated proportion of the hydrated product, i.e. on 10%; A.6.5: C ₃ 8 83, C ₂ 8 5, C ₃ A 8, C ₁₂ A ₇ 0.1, CaO _freedom 0.1; In the _mouth 100,0166; the last promoter in the manufacture itself is promoted, which made it possible to obtain it in a high alitic form, and is most effective. This follows from the data given in table. 4.

The calculation of the required initial number of promoters from group 6.2 for the white promoted clinkers 6.2.1-6.2.5 is presented in the table, respectively. 2, the characteristics of the operating modes of the furnaces in table. 4.

The obtained white promoted clinkers (PK-6.2.1-6.2.5) are characterized by almost the same actual chemical composition for average samples per batch (weighted average chemical composition is given): 81О ₂ 23.86; A1 ₂ O ₃ 2.82; Be ₂ About ₃ 0.37; CaO 71.58; MdO 0.84; 8O ₃ 0.17; I am ₂ O 0.11; including K ₂ O 0.10 and No. bO 0.05; with the sum of 99.75 and the average content of the remaining small components: b1 ₂ O 0, BaO d 0, 8 gO 0,01, N 0 d 0, CoO d

0, Mp ₂ O ₃ 0.004, Cr ₂ O ₃ 0.008, CuO 0.001; MoO ₂ = 0, T1O ₂ 0.028, P ₂ O ₅ 0.12, C1 ₂ 0, B ₂ 0.08. Average calculated characteristics: KN in Kind 1.00; p 7.48; p 7.62; C ₃ 8 90.7; C ₃ A 6.8; With ₄ AB 1.1. The actual mineralogical composition of the white promoted clinkers from the PK-6.2 group according to the petrographic analysis is slightly different, which is caused by the difference in the compositions and dosages of the promoters in their manufacture. The content of alite clusters in the microstructure is not more than 10%, a small amount of X-ray amorphous alite is present - up to 15%. A significant increase in the hydraulic activity of promoted white clinkers is noted in comparison with the control white clinker obtained from the same raw materials (Table 10). This increase is especially large when used as a component of the promoter of promoted clinker (A.6.2.5). It should be noted that, in contrast to the single promotion of a promoter in its manufacture, repeated and repeated promotion of the promoter does not produce significant additional effects.

Milling of white promoted clinkers according to data on microhardness and increase in productivity of a mill 2.2 x 13 m in size (two-chamber, with alundum lining and spheres from uralite), are given in table. 4, increases by about 25-33% compared with the control white clinker from the same raw materials. The absolute clarity of the clinker whiteness compared to the control clinker (88%) significantly increases to 92% for clinkers with promoters 6.2.1 and 6.2.2, 94% for clinkers with promoters 6.2.3 and 6.2.4 and up to 95% for clinker with the 6.2.5 promoter, apparently due to an increase in diffuse reflection as the average size of alite crystals in promoted clinkers decreases compared with the control. As follows from the data given in table. 4, with an increase in the basicity of the promoter, its effect increases, and the dosage decreases, which is of great practical importance. At the same time, as shown by electron microprobe data, the C / 8 ratio in alite increases from about 2.9 for clinker with the promoter 6.2.1 to 3.1 for clinker with the promoters 6.2.3 and 6.2.4, while the strength indicators cements based on these clinkers change: strength decreases at 28 days of age, and on average changes little in 1-day age. Compared to the control clinker KK-6.2, the alite of which is characterized by C / 8 3.15, all promoted clinkers are characterized by a lower C / 8 ratio and increased strength both in the early and in the late stages of hardening, with a tendency to decrease C / 8 -relations with an increase in the content of the promoter of reduced basicity and

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106 false dependence with increased basicity of the promoter. With the additional input of CaP ₂ , which was tested as a mineralizer in combination with the 6.2.5 promoter, it is highly basic, the C / 8 ratio in the alite of the promoted mineralized clinker decreases the more, the higher the supply level of the mineralizer and the promoter, and the strength characteristics of cement based on the obtained clinker, respectively increase.

In 3 series of experiments, in combination with the 6.2.5 promoter, complex mineralizers were tested, including, in addition to calcium fluoride (an average of 0.3 wt.% Clinker), also powdered lime, synthetic calcium carbonate, dolomite, and limestone, the latter being introduced from the hot end the furnaces are in a powder state, and ash coal slag was added to the raw materials to further save process fuel and crushed white synthetic metallurgical slag from converter production, comprising approximately 70% C ₁₂ A ₇ . These materials are pre-mixed with calcium fluoride, thereby improving its distribution in the feed mixture. The composition of the mineralizer is selected according to the level of basicity, combining calcium fluoride and metallurgical slag with lime, limestone or dolomite so that the calculated basicity exceeds 100 conventional units. Ash and slag is considered in the composition only for the ash part.

The results obtained in this case are not more than 1-3% in fuel economy and furnace productivity and not more than 2-4% in cement quality than those obtained in 2 series of experiments for this promoter. Apparently, the effectiveness of this promoter is too high for a noticeable manifestation of weaker additional effects from complex mineralizers, although before the start of these works it was assumed otherwise.

In 4 series of experiments, in combination with the 6.2.5 promoter, the additional introduction of chromophore additives was tested - CuO 0.45% in the form of copper sulfate and Cr ₂ O ₃ 0.8 wt.% Clinker in the form of enriched chromium ore, comprising less than 2% P ₂ O ₃ , for obtaining, according to the invention, colored promoted clinkers - blue and green. The work was undertaken before the end of the service life of the refractory lining of the furnace based on the well-known works of P.I. Bozhenova et al. In addition to introducing the promoter, the difference in this series of experiments is the introduction of an additional amount of lime so that the total basicity of the chromophore exceeds 100 conventional units. As a result, samples of the indicated color clinkers were obtained, while there were no significant changes in furnace productivity and cement quality compared with that established for this promoter in 2 series of experiments. It is of interest that, moving from promoter 6.2.5 of high basicity to promoter 6.2.2 of lower basicity, a brighter green clinker and a less bright blue are obtained, and increasing the dosage of the promoter 6.2.5 gives opposite results.

In a series of experiments, in combination with the 6.2.5 promoter, an additional introduction of mineralizers from the group was tested: sulfate, chloride, calcium silicofluoride, as well as calcium sulfate obtained by desulphurization of exhaust gases from sulfuric acid production, calcium chloride is a by-product of soda production by Solve method, sodium silicofluoride - a waste product of hydrofluoric acid. All six of these mineralizers were introduced in combination with lime to fulfill basicity conditions of more than 100 conv. units The results obtained approximately correspond to those obtained in 3 series of experiments with calcium fluoride, with a furnace productivity with gypsum 5-6% lower, and with calcium chloride - 2-3% higher compared with calcium fluoride; strength indicators of the obtained cements based on promoted clinkers with sulfate mineralizers are slightly lower and chloride ones are slightly higher compared to fluoride ones, whereas with silicofluorides with equal fluoride ion content, approximately equal values of cement strength were established in 5 and 3 series of experiments, exceeding the control by 20-23%.

Synthetic promoters 6.2.3 and 6.2.4 are made in small quantities, therefore, their total consumption in these experiments did not exceed 650 kg, and the total feed time was about 12 hours. The purity of their compositions does not predominate on the quality of clinker and cement according to the invention therefore, synthetic promoters were not used in the manufacture of gray cements.

In the 6th series of experiments, the raw materials used in the 1st series of experiments are added as additional components: 1) light blast furnace granulated slag, comprising less than 0.7% Fe ₂ O ₃ as a substitute for part of the clay; 2) belitic sludge, previously untreated from heavy glandular particles as a substitute for part of clay and marl; 3) tail of the concentration of hydrofluoric ore, comprising approximately 15% calcium fluoride, 80% 81O ₂ , the rest of the impurity, when the impurity content of Fe ₂ O _{3 is} less than 1% as a substitute for some clay; 4) burned rock composition of kaolinite, comprising about 4% carbon as a replacement for part of the clay; 5) a molding material for aluminum casting, including water glass and quartz sand, as well as an admixture of aluminum oxide, as a replacement for part of the clay. As a result of these substitutions, there was no reduction in the positive effects of the action of the promoter 6.1 compared to those achieved when used as raw materials

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108 materials only a mixture of these limestone, clay and marl or silica gel. However, with the exception of belitic sludge, the positive effects of an additional increase in furnace productivity compared to the 1st series of experiments were not achieved.

The cement obtained by grinding the white promoted clinker PK-6.2.5 is characterized by a particularly high air resistance (resistance against carbonation by carbon dioxide). After 2 years of storage of cement-sand, standardly manufactured samples of 4 x 4 x 16 cm beams under combined conditions (at a temperature of 20 ± 3 ° C - 1 day in air-wet conditions, 27 days in water, then up to 2 years in air-dry conditions at a relative humidity of 30 ± 5%) due to carbonation and shrinkage, the strength of samples from control white cement decreased by 78% compared with strength at 28 days of age, and samples from cement based on white promoted clinker PK 6.2. 5 - respectively, only 7%, which is within t chnosti assess strength characteristics. Such a high resistance of cement based on promoted clinker is due, as the experiments of the inventors show, to the refinement of alite and belite, as well as calcium aluminates in the resulting clinkers, which is “inherited” by hydrosilicates and portlandite, and also, apparently, calcium hydroaluminates in a hardening cement stone based on specified clinker. Containing fewer impurities compared to hydrated phases - hydration products of Portland cement clinkers known in the art, hydrates from promoted clinker particles are not prone to carbonation. Thus, portlandite from ordinary clinker, which was formed in micropreparations isolated from the atmosphere during the interaction of cement with 10 times as much water by weight according to the Astreeva method [27], is exposed to the atmosphere and crumbles into dust after about 2 hours. Cement portlandite based on the promoted white clinker - any of the PK.6.2 group - under the same conditions begins to corrode upon contact with the atmosphere no earlier than 2 months later, and Portlandite from PK-6.2.5 clinker - after 5 months, t. e. about 1800 times slower. This is an explanation of the mentioned increased air resistance of white cements according to the invention.

The above results allow us to conclude that the process of mineral formation promotion during roasting of alite Portland cement clinker, including the following amounts of the most active clinker minerals during cement hydration (wt.%): C ₃ 8 55-80, C ₃ A <8, slightly exceeding the upper content limit usually recommended alite (C _{3 August} 55-70) composition clinker for the production of high strength and fast-hardening Portland cement [15, first source, p.147], is very effective for increasing productivity of furnaces, grindability ti clinker and cement quality, including durability and strength.

Example 7. The conditions of the invention according to example 3 using for grinding promoted clinkers laboratory cement mill with a diameter x length (m) (0xL) 0.5 x 0.28 (2 chambers) m according to example 3.

In a series of experiments, the promoted mineralized clinker obtained according to the invention in example 1 (PMK-1) and the control clinker in example 1 (KK-1) are ground in a laboratory mill in example 3 to obtain a specific cement surface of 300 ± 10 m ² / kg together with the following gypsum components: I - natural gypsum one of the group - ΙΑ: gypsum stone, including according to petrographic analysis (in parts by weight): two-water gypsum 95, mudstone 3, bentonite 2; 1B: natural two-water gypsum 98%, impurities - the rest; ΙΒ: natural anhydrite (Ca8O ₄ ) 92%, argillite - the rest; II gypsum-containing by-product of the chemical industry is one of the ΙΙΑ group: phosphogypsum, including (wt.%): Ca (8О ₄ ) -2Н ₂ О 90, Н3РО4 (in terms of a 10% aqueous solution) 7, impurities - the rest; 11B: borogypsum, including the same components, but instead of phosphoric, boric acid, in the same proportions; 11B: titanogypsum, including (parts by weight): Re8O ₄ -4H ₂ O 70, H ₂ 8O ₄ (listed as a 10% aqueous solution) 25, impurities - the rest, processed at 220-450 ° C in wt . the ratio of 1: 2 with kaolin clay to form (parts by weight): ferric sulfate 4-hydrous 30, hydrogel 81О ₂ 50, impurities - the rest, with the original clay - up to 0.1; 11G: citrogypsum, IID: fluorohydrite; III - a product of desulfurization with calcium carbonate or lime of sulfur-containing exhaust gases of furnaces during the combustion of energy fuels - ША: coal, including (parts by weight): calcium sulfate anhydrous 80, semi-aquatic 10, two-water 3 (due to hydration during storage and transportation), impurities rest , and organic impurities and carbon - not more than 1; and 111B: fuel oil, including (parts by weight): calcium sulfate anhydrous 90, semi-aquatic 8 (due to hydration during storage and transportation), impurities - the rest, and organic impurities - not more than 0.2; IV mixture of materials: ША: or ΙΒ in a mass ratio of 1: 1; IVB1 - 3: mixture of materials and 11A in mass ratios, respectively

1: 3, 1: 1 and 3: 1; BW: a mixture of materials 1B and PV in a mass ratio of 1: 1, with the content of the gypsum component in the cement obtained, about 1-4.5 wt.% In terms of trioxide

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110 sulfur (8O ₃ ). The test results of the obtained cements, including strength indicators under normal hardening and after steaming (heat and moisture treatment) according to the regime: preliminary exposure of samples after their manufacture at a temperature of 20 ± 3 ° C for 2 hours, heating in a steaming chamber in closed forms to a temperature of 80 -85 ° C for 3 h, isothermal heating at the indicated temperature for 6 h and cooling of the samples in an open steaming chamber to an ambient temperature of 20 ± 3 ° C, are presented in table. 8, for cements based on control clinker (lines 16 and 17), the minimum and maximum values are indicated respectively.

The data presented allow us to conclude that any known calcium sulfate or gypsum components are suitable for the cement manufacturing method according to the invention. At the same time, for cements based on promoted mineralized clinker, both the strength data and other properties significantly exceed the corresponding indicators of control cements in both early and late hardening periods, practically without changing the setting time and water demand of cements. The best results are obtained when used as a gypsum component or in addition to a conventional gypsum stone, a derivative of ferrous titanogypsum sulfate mixed with sulfuric acid treated with kaolin clay.

In a 2 series of experiments, which is carried out under the same conditions as in the first, mixtures of promoted and conventional Portland cement clinkers are used, and specifically mixtures of PMK-1 and KK-1 clinkers in May. ratios 5: 1, 2: 1, 1: 1 and 1: 5 (tab. 8). The obtained results allow us to conclude that promoted clinkers in the conditions of a lack of high-alumite clinker for obtaining high-strength cements can be mixed with ordinary clinkers in the indicated ratios, namely from 5: 1 to 1: 5. With a higher content of promoted clinker in the mixtures, the results obtained differ little from the data on the promoter clinker itself, and with a lower content of promoted clinker, the positive technical effects of using the invention are reduced.

In 3 series of experiments carried out under the same conditions as the 1 and 2 series, the grinding of promoted clinkers according to the invention is carried out in the presence of intensifiers of the grinding process, which are used as: surfactants from the group: I amino alcohols: -monoethanolamine; 1B - triethanolamine; HS - a mixture of triethanolamine and calcium chloride in wt. 1: 1 ratio; 1G - a mixture of triethanolamine with sodium nitrate (also 1: 1); from group II - technical lignosulfonates: 11A sodium with a molecular weight (MM) of an average of 25,000 D; PB - calcium (imported product) with an average MM of approximately 45,000 D; PV - modified type LSTM-2 with an average MM of about 38000 D; ΙΙΓ is a mixture of the latter with sodium nitrate in May. 1: 1 ratio; IID - the same with potassium sulfate in May. 1: 1 ratio; surface-inactive substances from group III salts of alkaline-earth and / or alkali metals of the condensation product of β-naphthalene sulfonic acid with formaldehyde, and in particular: ША - the sodium salt of the condensation product of β-naphthalene sulfonic acid with formaldehyde (С-3); 111B - the same, calcium salt (imported product); from group IV - salts of alkaline earth and / or alkali metals of the condensation product of melamine-containing resins with formaldehyde, and in particular: ША - sodium salt (10-03), RUB - calcium salt (imported product); from group V — complex salts of alkaline earth metals and sulfuric and / or nitric and / or formic and / or acetic acids with low molecular weight monosaccharides C3-C5; the example shows the data for VA - nitrogen complex calcium salt with the indicated monosaccharides in an approximate ratio (in parts by weight): with C ₃ - 25, with C ₄ - 70, with C ₅ - 5; from group VI, paired mixtures of these materials in a mass ratio of from about 4: 1 to about 1: 4, and specifically: 7 ^ 1 and VIA2 - mixtures of 1B and IIIA in ratios of 4: 1 and 1: 1, respectively, and VIB1 and VIB2 - mixtures ША and VA in ratios of 4: 1 and 1: 1, respectively, while grinding intensifiers are added in the amount of approximately 0.05-0.5 wt.% Of the specified cement. The results obtained when evaluating the intensification of grinding by the increase in the specific surface of cement compared with cement ground on the basis of a mixture of clinker with gypsum stone without an additive-intensifier grinding at an electric power consumption of about 1.2 kWh / 10 kg of a sample of clinker with gypsum (Table 9) allow to conclude the following: all grinding intensifiers have a positive effect on the grinding process of both promoted and control clinkers. Thus, all grinding intensifiers are applicable when using the cement manufacturing method according to the invention. At the same time, the intensifying effect of grinding intensifier additives on the grinding of promoted clinker significantly exceeds their effect on the grinding of control clinker with a close mineralogical composition of KK-1 and PMK-1 clinkers. Obviously, the more active and defective surface of the particles of the promoted clinker with increased chemisorption energy per unit surface compared to the control clinker is

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112 The ultimate cause of this phenomenon. When evaluating the results obtained, it should be borne in mind that the increase in the specific surface of cements in a batch laboratory mill is small compared with that observed under production conditions, since in a batch mill, especially of such a small diameter, the crushed particles with an adsorbed intensifier do not leave the sphere of action of the same grinding media bodies that provide chemosorption activation energy; their repeated effects to a lesser extent affect the grinding process due to the shielding effect of the little things. The effect of grinding intensification, tested with a smaller set of grinding intensifiers, in continuous production mills, is approximately 2–3 times higher than that indicated, with a higher value of grinding intensification in a closed-cycle mill with a separator compared to an open-cycle mill. It is also noted in industrial experiments that the effects of intensification of grinding increase significantly at a higher level of specific surface area of cement compared to a level of approximately 300 m ² / kg, to which cement is ground in this series of experiments, so that the mill factor and periodic factor relatively low specific surface areas tend to equalize the results obtained among themselves. Therefore, even the small effects of intensification of grinding, recorded in this series of experiments, are of great practical importance.

In the second part of the same, 3 series of experiments, three of the indicated materials: IV, IIIA and UA, as well as a mixture of ША with UA, introducing them when grinding cement in a larger amount than to intensify grinding, are used as water-reducing components of cement according to the invention . The results of the experiments (lines 20-23, Table 9) indicate a significant increase in the strength characteristics of the cements according to the invention in these variants, and the mixture of water-lowering components exhibits a synergistic effect, manifesting itself better than the weighted average of each of the water-reducing components, administered separately. For the rest, mentioned in the claims and the text of the description, water-lowering components were obtained approximately similar results, and in their mixtures - synergistic.

In 4 series of experiments conducted under the same conditions as 1-3 series, active silica is introduced into the cement obtained on the basis of the promoted clinkers according to the invention by means of joint grinding or separate grinding followed by mixing. Joint grinding is carried out up to a specific surface of 300 ± 20 m ² / kg for the clinker component, implying the fineness of grinding cement without the addition of active silica under the same mechanical mill operation and grinding time as cement with the specified additive. For joint grinding, active silica is taken in the form of a silicate block - crushed or granular. In rows 24-28 of the table. Figure 9 compares the results of co-grinding with crushed silicate block and mixing with the ground silicate block of the promoted PMK-1 clinker. The silicate block of potassium type has the composition Kgz, ₅ . The variant under the code TA characterizes the joint grinding, the variant under the code 1B separate grinding with subsequent mixing (Table 9). The results obtained indicate that: 1) the optimum content of silicate blocks in cement from promoted clinker from 2.5 to 10 wt.% Clinker can increase the strength of cement based on promoted clinker in both early and late hardening up to about + 10%; 2) active silica increases the strength of cement based on promoted clinker both during normal hardening and during steaming; 3) the introduction of active silica through co-grinding with promoted clinker is more effective than mixing the components after co-grinding. To do this, active silica in the form of a powder is introduced into the ground mixture of the promoted clinker and gypsum component by mixing, with the code IA being referred to as powdered silica fume - a secondary product of silicon production, the code IB - to granular additive LSTM-2 (12 wt.% Powder LSTM - in calculated on a 45% aqueous solution) silica fume - dust trapped from the exhaust gases of furnaces of ferroalloy production. The test results of the cements according to the invention obtained with these additives are presented in table. 9, lines 28-29. They testify to the possibility of using silica fume in any form in the method of manufacturing cement according to the invention, but microsilica, previously granulated with a plasticizer, has a particularly favorable effect.

In the 5th series of experiments carried out under the same conditions as the 1-4th series, the grinding of promoted clinkers according to the invention is carried out together with active mineral additives and / or fillers or separately, followed by mixing. The following are used as active mineral additives:

from group I - natural pozzolans of sedimentary origin:

tripoli composition, here and below in wt.%:

p.p.p. 8.70; §1O ₂ 73.03; A1 ₂ O ₃ 7.56; Re ₂ O ₃ 3.46;

CaO 4.12; MdO 1.72; 8O ₃ 0.17; HaO 0.29; K ₂ O

0.95;

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114

1B: flask composition: 17.36; 81O ₂ 52.03; L1 ₂ O ₃ 6.25; Re ₂ O ₃ 3.54; CaO 17.31; MdO 1.67; 8O ₃ 0.05; Na ₂ O 0.25; K ₂ O 1.54;

ΙΒ: diatomaceous earth composition: 2.48; 81O ₂ 92.14; L1 ₂ O ₃ 1.01; Re ₂ O ₂ 1.22; CaO 0.96; MdO 0.21; 8O ₃ 0.89; Na ₂ O 0.89; K ₂ O 0.21;

from group ΙΙ - natural pozzolans of volcanic origin:

11L: ash composition: p.p.p. 7.42; 81O ₂ 63.38; L1 ₂ O ₃ 4.52; Re ₂ O ₃ 14.40; CaO 2.43; MdO 1.04; 8O ₃ 0.67; Na ₂ O 4.19; K ₂ O 1.95;

11B: tuff composition: p.p.p. 9.31; 81O ₂ 64.22; L1 ₂ O ₃ 11.77; Re ₂ O ₃ 1.95; CaO 6.68; MdO 0.92; 8O ₃ 1.51; impurities Na ₂ O and K ₂ O - the rest;

ΙΙΒ: composition pumice: 4.62; 81O ₂ 69.43; L1 ₂ O ₃ 12.69; Re ₂ About ₃ 2,52; CaO 6.70; MdO 0.98; 8O ₃ 0.63; impurities Na ₂ O and K ₂ O - the rest;

ΙΙΓ: routes of the composition: p.p.p. 11.43; 81O ₂ 70.07; L1 ₂ O ₃ 1.12; Re ₂ O ₃ 10.88; CaO 2.71; MdO 0.35; 8O ₃ 0.25; Na ₂ O 2.01; K ₂ O 1.18;

from group ΙΙΙ - artificial additives:

HL: blast furnace granulated slag composition: p.p.p. 0.36; 81O ₂ 31.75; L1 ₂ O ₃ 10.63; Re ₂ O ₃ 2.12; MnO 0.30; CaO 50.90; MdO 1.24; 8 (sulfide ion) 2.09; 8O ₃ 0.30;

SB: ash - ablation of a thermal power plant composition: p.p.p. 0.79; 81O ₂ 30.45; L1 ₂ O ₃ 28.25; Re ₂ About ₃ 13.01; CaO 3.23; MDO 1.59; Na ₂ O 0.74; K ₂ O 0.15; 8O ₃ 0.50; T1O ₂ 1.29;

BW: ash - slag of a thermal power plant composition: p.p.p. 1.16; 81O ₂ 49.24; L1 ₂ O ₃ 26.69; Re ₂ O ₃ 17.53; CaO 2.51; MdO 0.55; LA ₂ O footprints; K ₂ O 0.43; 8O ₃ 0.77; T1O ₂ 1.13;

ΙΙΙΓ: heat-treated kaolin at 620 ° С for 30 min of the composition: 5.20; 81O ₂ 52.89; L12O3 38.94; Fe2O3 0.99; CaO 0.96; MdO 0.23; 8O ₃ 0.54; impurities Na ₂ O and K ₂ O - the rest;

SD: heat-treated kaolin clay under the same conditions as kaolin, composition: p.p. 3.06; 81O ₂ 57.85; L1 ₂ O ₃ 31.94; Re ₂ O ₃ 3.48; CaO 1.88; MdO 1.18; 8O ₃ 0.22; impurities Na ₂ O and K ₂ O the rest;

ΙΙΙΕ: clay shale, calcined at 970 ° C for 45 min composition: p.p. 1.12; 81O ₂ 40.19; L1 ₂ O ₃ 0.75; Re ₂ O ₃ 8.02; CaO 27.23; MdO 1.89; 8O _3, 8.46; T1O ₂ 0.50; impurities Na ₂ O and K ₂ O the rest;

111Ж: burned rock taken from a representative sample of a heap above a coal mine, composition: p.p.p. 8.28; 81O ₂ 58.08; L1 ₂ O ₃ 20.57; Re ₂ O ₃ 9.01; CaO 1.02; MdO 0.31; 8O ₃ 1.08; impurities Na ₂ O and K ₂ O - the rest;

ΙΙΙ3: gliezh (clay, naturally burnt) composition: pp 1.22; 81O ₂ 73.11; L1 ₂ O ₃ 14.71; Her ₂ About ₃ 4.62; CaO 0.85; MdO 0.39; 8O ₃ 1.04; impurities Na ₂ O and K ₂ O - the rest;

analogues of these components from all three groups. The following are used as fillers:

ΙνΑ: limestone hardness on the Mohs scale 6 composition: p.p.p. 41.48; 81O ₂ 2.19; L1 ₂ O ₃ 0.59;

Her ₂ About ₃ 1.00; CaO 53.11; MdO 1.16; 8O ₂ 0.17; Na ₂ O 0.12; K ₂ O 0.18;

ΙνΒ: quartz sand composition: p.p.p. 0.23; 81O ₂ 98.07; L1 ₂ O ₃ 0.32; Her ₂ About ₃ 0.28; CaO 0.71; MdO 0.12; 8O ₃ 0.18; Na ₂ O 0.05; K ₂ O 0.04;

ΙνΒ: feldspar sand composition: p.p.p. 1.12; 81O ₂ 92.65; L1 ₂ O ₃ 1.09; Re ₂ About ₃ 0.87; CaO 1.91; MdO 0.60; 8O ₃ 0.43; Na ₂ O 0.50; K ₂ O 0.83;

ΙΥΓ: asbestos cement - production rejects, previously crushed, stale, then ground to a specific surface of about 300 m ² / kg, composition, wt.%: P.p.p. 21.60; 81O ₂ 18.60; L1 ₂ O ₃ 2.93; Her ₂ About ₃ 3.24; CaO 43.69; MdO 6.81; 8O ₃ 3.13; LA ₂ O footprints; K ₂ O footprints.

In lines 31-54 of the table. Figure 9 presents the results of comparing the joint grinding and mixing of the promoted PMK-1 clinker with active mineral additives, as well as with the fillers and properties of the obtained cements, with similar but lesser data for the control clinker KK-1 (Table 9, lines 65- 75 - all control cements, including those with active mineral additives, including active silica, and with fillers — lines 68-72, 74, 75 in Table 9). The above results allow us to conclude that all of these active mineral additives, fillers, and their analogs can be used in the composition of cement obtained according to the proposed method and in all variants according to the invention, characterized by better technical properties compared to cements of a similar material composition based on control clinker.

In the 6th series of experiments carried out under the same conditions as the 1st-5th series, the grinding of promoted clinkers according to the invention is carried out in the presence of a fibrous component. In lines 62-64 of the table. Figure 9 shows the results of comparing joint grinding and mixing of the promoted PMK-1 clinker with the fibrous component. The results obtained allow us to conclude that when co-grinding, the quality of cement, including the fibrous component for reinforcing cement stone, significantly - by 10-20% - exceeds the quality of cement without fibers, as well as the quality of cement into which the fibers are mixed by mixing. In this case, the promoted clinker during joint grinding less damages the fibers compared to the control clinker, apparently, due to the easier grinding of the first.

In the 7th series of experiments carried out under the same conditions as the 1st - 6th series, the grinding of promoted clinkers according to the invention is carried out in the presence of water-reducing components described in the 3rd series of experiments under the name "intensifiers of clinker grinding", namely in the presence of surface-inactive substances from the group группы - salt

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116 alkaline-earth and / or alkali metals of the condensation product of β-naphthalene sulfonic acid with formaldehyde, and specifically: SHL is the sodium salt of the condensation product of β-naphthalene sulfonic acid with formaldehyde (C3); SB - the same, calcium salt (imported product); from group IV - salts of alkaline earth and / or alkali metals of the condensation product of melamine-containing resins with formaldehyde, and specifically: GUL - sodium salt (10-03), IVB - calcium salt (imported product); from group V — complex salts of alkaline earth metals and sulfuric and / or nitric and / or formic and / or acetic acids with low molecular weight C ₃ -C ₅ monosaccharides; the example shows the data for VΑ - nitrogen complex calcium salt with the indicated monosaccharides in an approximate ratio (in parts by weight): with C ₃ - 25, with C ₄ - 70, with C ₅ - 5; from group VI: paired mixtures of these materials in a mass ratio of from about 4: 1 to about 1: 4, and specifically: VГΑ1 and VIА2 - mixtures of 1B and ША in ratios of 4: 1 and 1: 1, respectively, and VIБ1 and VIБ2 - mixtures of ША and VA in ratios of 4: 1 and 1: 1, respectively, while the water-reducing components are introduced into the crushed material in the amount of approximately 0.5-1.5 wt.% of the specified cement, i.e., 10-15 times more compared to with the mentioned grinding intensifiers. The results obtained when evaluating the water-lowering effect of these components to reduce the H / C values of cement-sand mortar and increase the strength characteristics of cements based on the promoted and control clinkers (Table 9) allow us to conclude the following: all water-lowering components actually reduce the water content in cement-sand standard solutions and have a positive effect on the growth process of cement strength on the basis of promoted clinker, and the positive effect of water-reducing components on the properties of cement from promoted clinker significantly exceeds their effect on the growth of cement strength from control clinker with a similar mineralogical composition of clinkers KK-1 and PMK-1.

In the 8th series of experiments carried out under the same conditions as the 1st-7th series, the grinding of promoted clinkers according to the invention is carried out in the presence of cellulose polyesters. In rows 54-57 of the table. Figure 9 presents the results of comparing co-grinding and mixing of the promoted PMK-1 clinker with cellulose polyesters. The results obtained allow us to conclude that co-milling gives better results compared to mixing, and water-retaining additives have a relatively small but positive effect on the properties of cement according to the invention, approximately the same as on the properties of cement from control clinker.

In the 9th series of experiments carried out under the same conditions as the 1st-8th series, the grinding of promoted clinkers according to the invention is carried out in the presence of expanding components. In the table. 10 shows the results of comparing joint grinding and mixing of the promoted PMK-1 clinker with expanding components. The results obtained allow us to conclude that all known expanding components can be used in the manufacture of expanding cements based on clinkers obtained by the method according to the invention. At the same time, equal expansion values of cements based on promoted clinkers are achieved at lower consumption of expanding components compared to expanding cements based on control clinkers. The saving of expensive expanding component is one of the main conditions for the competitiveness of expanding cements, an important advantage of this embodiment of the cement manufacturing method according to the invention.

It should be noted that in all the examples described above, all tested cements satisfy the standard requirement of uniformity of volume change.

Thus, the first objective of the invention is the creation of a method of manufacturing high-quality Portland cement while increasing the productivity of rotary kilns and cement mills. The above characteristics allow the use of cement obtained according to the invention as very effective, but in order to increase the strength of the mortar and concrete, it is also advisable to use special modes for preparing mixtures of their components.

Analyzing the prior art in the field of concrete production, we note that there is a known method of manufacturing concrete based on cement by mixing it with aggregates and a mixing fluid, which is used as water or electrolyte solutions, in which mixing the components of the concrete mixture - cement, aggregates and mixing fluid - they are carried out until the maximum uniformity of the concrete is achieved, estimated using the coefficient of variation of the strength characteristics of hardened concrete, the value of which according to the current page itelnym rules and regulations and standards should not exceed 7% [31]. The disadvantage of this method is the delay in determining the coefficient of variation, since the strength indicator becomes known after the standard shelf life of the samples (usually 1 day, 2 days, 3 days or 28 days). At this time, the quality of the resulting concrete can no longer be corrected if there were any violations during its manufacture.

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118 ny of technological regulations. Ultimately, this leads to an over consumption of cement in concrete due to the need for an increased margin of safety of this material compared to the minimum norm selected according to the strength values of the samples, and this, in turn, leads to a decrease in the durability of concrete and concrete and reinforced concrete made of it products and designs.

There is also a known method of manufacturing concrete based on the cement obtained by mixing it with aggregates and a mixing fluid, which is used as water or electrolyte solutions, in which the mixing of the concrete mixture components - cement, aggregates and mixing fluid is carried out with subsequent measurement of the mechanical characteristics of the mixed material, determining in it, the resonance frequency of the forced oscillations, an increase in the level of which indicates an improvement in the characteristics of the material [32]. The first disadvantage of this method is the complexity of its implementation and poor reproducibility of the results, although it is somewhat smoothed by the ease of interpretation of the latter. The second disadvantage of this method is the assessment with its help of the quality of the concrete mixture not during the mixing process, but after the fact - after the completion of the preparation of the concrete mixture.

Closest to the proposed invention is a method of manufacturing concrete based on cement by mixing it with aggregates and a mixing fluid, which is used as water or electrolyte solutions, in which mixing the components of the concrete mixture - cement, aggregates and mixing fluid - is carried out when measuring the electrical characteristics of the mixed material, determining the electric resistance and electric capacitance in it [33]. The advantages of the known method are accuracy and reproducibility, and the disadvantage, like the previous one, is the beginning of measurements after mixing is completed.

The alleged invention in the manufacture of concrete is free from this drawback. It lies in the fact that in the method of manufacturing concrete based on the specified cement, forming a rapidly soluble and interacting cementitious material with high early strength after mixing with a liquid obtained by sintering in a clinker kiln a cement raw material mixture, including in mineral forms: the main oxides from the group: calcium oxide, silicon oxide, aluminum oxide, iron oxide, the main small components from the group: magnesium oxide, sulfur trioxide, potassium oxide, sodium oxide, the remaining small components - impurities, as well as chemical compounds returned to the specified furnace with dust trapped from the furnace exhaust gases, with the formation of Portland cement clinker containing three or more clinker minerals from the group: three-calcium silicate (3СаО-81О ₂ ), two-calcium silicate (2СаО-81О ₂ ), tricalcium aluminate (3CaO-A1 ₂ O ₃ ), calcium aluminoferrite [2CaO- (A1 ₂ Oz) _x - (Ge ₂ O ₃ ) 1- _x ], 1>x> 0, followed by cooling and grinding of clinker, including mixing cement with aggregates and a liquid, which is used as water or an electrolyte solution c, and the use of the prepared concrete mixture for the manufacture of concrete by laying in the form or formwork, molding and compacting the specified mixture, with the additional introduction of the mineral formation promoter, which is a mineral-oxide additive, comprising two or more clinker minerals from the groups: I: tricalcium silicate (3СаО-81О ₂ ), dicalcium silicate (2СаО-81О ₂ ), tricalcium aluminate (3СаО-А1 ₂ О ₃ ), calcium aluminoferrite [2СаО- (А12О3) _х - (? е2О3 ) 1- ] 2/3>x> 1/3 and / or II: MAYEN (12SaO-7A1 ₂ O _3), calcium monoaluminate (CaO, A1 ₂ O _3), monocalcium and dicalcium ferrite (2CaO-Fe ₂ O _3, CaO -Re ₂ O ₃ ) and / or III: alkaline, sulfate and halide derivatives of minerals of the indicated groups and / or IV: calcium sulfoaluminate (4СаО-3А1 ₂ О ₃ -8О ₃ ), calcium sulfate (Ca8О4) and / or mixtures thereof and derivatives and / or V: aluminates and / or silicates and / or alkali metal ferrites; VI: mixtures of minerals from these groups with each other and / or with free calcium oxide, mechanical and / or obtained together in the form of clinker, or sinter, or slag, or sediment, or suspension, as well as when selecting, adjusting, maintaining the composition of the specified promoter and its presence in the resulting promoted clinker Browse basicity exceeding basicity clinker eutectic melt composition region in the phase diagram of CaO Portland cement clinker A1 ₂ O ₃ - 81O ₂ - Fe ₂ O _3, excluding minor constituents crystal generated at 1338 ° C, using the calculated electronegativity of the compounds included in them as a base for the basicity measure of the indicated promoter and the promoted clinker in comparison with the similar basicity measure of the eutectic clinker melt, the specified concrete mixture is mixed during concrete preparation until the water is distributed optimally the surface of the specified cement, estimated by approaching the maximum value and achieving the minimum growth rate of the electrical capacitance a collapsible mixture of approximately 0.0050.1 μF / m ² s, after which stirring of the mixture is stopped.

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120

In an embodiment of the invention, an addition of a water-reducing component is additionally added to the concrete mixture in an amount of about 0.2-1 wt.% Of the clinker part of the cement, moreover, material from the group of alkaline earth and / or alkali metal salts of the condensation product of β-naphthalene sulfonic acid with formaldehyde is used as a water-reducing component; a salt of alkaline earth and / or alkali metals of the condensation product of melamine-containing resins with formaldehyde; technical lignosulfonate of alkaline earth and / or alkali metals, conventional or modified with phenol-formaldehyde resin; complex salts of alkaline earth metals and sulfuric and / or nitric and / or formic and / or acetic acids with low molecular weight monosaccharides C3-C5; paired mixtures of these materials in wt. ratio from about 4: 1 to 1: 4.

In another embodiment of the invention, a pre-foamed additive of the foaming agent in the form of an aqueous solution in the amount of about 0.05-1.5 wt.% In terms of dry active substance of the total mass of clinker minerals - tricalcium silicate (3CaO-8U ₂ ) is additionally added to the concrete mixture and tricalcium aluminate (3СаО-А1 ₂ О ₃ ) - as a part of cement.

In a further embodiment of the invention, an additive of cellulose polyesters is additionally added to the cement-based concrete mixture in an amount equal to about 0.01-1 wt.% Of the sum of the masses of clinker minerals of tricalcium silicate (3CaO-81O ₂ ) and tricalcium aluminate (3CaO-A1 ₂ O ₃ ) - in the composition of cement.

The essence of the invention in the manufacture of concrete is that in the process of mixing the components of the concrete mixture, the cement-water system is modeled by a bipolar electrically conductive cell, in which the solid and liquid phases considered from a thermodynamic point of view as a single system are characterized by ion-electron conductivity, and their interphase boundary - electric capacity, gradually increasing in view of the occurrence of additional quantities of free water in the composition of the double adsorption layer, behaving like a capacitor. Therefore, the increase in the electric capacity of mortar or concrete mixtures in such a cell, lowered into these mixtures, approximately linearly depends on the increase in the content of adsorption-bound water. After the maximum growth rate of the electric capacitance of these mixtures is equal to approximately 0.8 mF / m ² s, a decrease in the growth rate of the mentioned capacitance means that the adsorption capacity of the indicated interface between the liquid and solid phases gradually approaches saturation. The saturation moment is fixed when the increase in the electric capacitance tends to zero, and then the electric capacitance begins to decrease markedly. This phenomenon is characteristic mainly for highly active cements. It means the beginning of parasitic processes using the energy of mixing mixtures to destroy the double electric layer by excess air entrainment, carbonization of prehydrates, and mainly aggregation and flocculation of components that degrade the technical properties of concrete and mortars. That is why the mixing of mortar or concrete mix is stopped during the period of minimum growth rate of the electric capacity. Measurements of the electric capacity of the concrete mixture, as well as the mortar (cement-sand) mixture during its mixing, allow us to fix this period, as proposed in the present invention, at the usual level of sensitivity of electrical equipment close to 0.1 mF / m ² s. The moment of the beginning of this period corresponds to the achievement of the optimal distribution of water on the surface of the cement, that is, the saturation state of any homogenized cement-water system - freshly made cement paste, mortar, concrete mix - adsorbed water with a minimum content of free water. The optimality of assessing the degree of mixing in this way, intuitively quite obvious, follows from the embodiments of the invention. The limit of the rate of change in the capacity of the concrete mixture (θ), to which mixing should be continued, not more than 0.1 mF / m ² s, is derived based on the experimental data of the inventors on mixing concrete mixtures based on cements, different in chemical and mineralogical composition, size water demand and dispersion. Until now, such an exact and theoretically substantiated method was not known for establishing the optimal duration of mixing mortar and concrete mixtures for a given energy intensity of the mixer to achieve the maximum degree of homogeneity. The mixing time established by this method can be related, as shown by the data of the inventors, with other physical constants of the mixed cement systems, namely cement-water suspensions, mortar and concrete mixes, such as the minimum viscosity of the cement paste included in them is maximally destroyed ( mixing) the microstructure (p _t1n ), which is at a level of not less than 1.5 Pz, etc. In principle, all such constants can be included in a single system of analytical equations. Moreover, with an increase in the electrochemical potential of cement in the aquatic environment

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122 (and cement based on promoted clinker is one of the most active binders in terms of this indicator), the effect of applying the electro-capacitive criterion for the optimal duration of mixing allows one to obtain a noticeable increase in the technical properties of mortars and concretes, since the parasitic processes occur most intensively when used for the manufacture of mortars and concrete binders with high values of electrochemical potential in aqueous suspensions.

Features of concrete obtained on the basis of cement made from promoted clinker according to the proposed method are: 1) to increase the uniformity of particle size distribution in the particle size distribution of cement due to a more uniform size distribution of the crystals of the main minerals in the promoted clinker; this facilitates the mixing of cement with water and increases the uniformity of the distribution of the latter in the concrete mix as compared to clinker-based cements known from the prior art, ceteris paribus; 2) with a lower content of fine (less than about 5 microns) and coarse (more than about 30 microns) fractions and a higher content of middle fraction (5-30 microns), providing optimal curing speed and maximum strength of concrete, the mixing time of the concrete mixture until the specified slow the growth rate of electric capacity is reduced even with increased specific surface area of cement; 3) increasing the uniformity of the distribution of bound water in the volume of concrete mix and concrete reduces the dispersion of concrete strength values in comparison with the prior art; 4) in the structure of concrete, the size of the sections of averaging the chemical and particle size distribution of the components is reduced, which helps to increase the strength of the material due to a decrease in the intensity of recrystallization processes due to a decrease in the intensity of lengthy diffusion in the concrete structure. This reduces the level of internal stresses and increases the strength of hardening concrete; 5) in increasing the uniformity of the distribution of the concentration of dissolved substances in the mixing water (liquid phase) of the concrete mixture and concrete, which also reduces the level of internal stresses and increases the strength of concrete; 6) in accelerating the dissolution and activation of hydration of tricalcium silicate (alite) in Portland cement, due to the indicated optimal characteristics of the microstructure of the clinker part of the cement, which, due to an increase in the concentration of neoplasms in concrete, increases heat release and strength; 7) in accelerating the dissolution and activation of hydration of tricalcium aluminate in Portland cement due to the aforementioned increased uniformity of distribution of mixing water (liquid phase) in concrete mix and concrete, which accelerates both the reaction of tricalcium aluminate with the gypsum component of cement, and the formation of the product of this reaction - gel-like in the first minutes after mixing trisulfate (ettringite), - the basis of the so-called "cement gel", forming a lubricant that determines the consistency, thixotropic properties of concrete impurity and ultimately concrete uniformity coefficient; 8) to increase the efficiency of using the obtained cement in concrete as a result of these phenomena, which allows to reduce the consumption rate of the obtained cement by 1 m ^{3 of} concrete. This is explained from the standpoint of the thermodynamics of irreversible processes [34] as follows: a more uniform distribution of soluble material in the volume of the liquid phase of the concrete mixture and concrete leads to a more uniform and ubiquitous heat release in the volume of the concrete mixture and concrete, reduces the unproductive loss of time on the diffusion of solute on a macro scale (diffusion paths of more than 0.5 cm) from more saturated zones to less saturated ones and to the distribution of the released heat of cement hydration over these zones, which, according to ntsipu least action nears equilibrium process in each geometrical region concrete and gives an energy gain of 10% or more. Thus accelerating the establishment of the stationary distribution of CaO concentrations occupies 8 ₂ and A1 ₂ O ₃ in said liquid phase and shortens the duration of the induction period alite hydration. At the same time, the block submicrostructure in the alite crystals of the indicated structure, due to the closer to equilibrium crystallization mechanism, the alite is more ordered, the boundaries of the blocks forming the channels through which water penetrates deep into the alite crystals are less tortuous, which also accelerates the interaction of alite in cement particles with liquid concrete phase.

The invention in terms of a method of manufacturing concrete becomes clearer from an example of its implementation.

Example 10. On the basis of Portland cement obtained according to the invention, concrete is made. Used Portland cement is obtained according to Example 1 from PMK-1 clinker (for characteristics, see row 1 of Table 9), and also for comparison - from control clinker and cement based on it according to the same example - KK-1 (for cement characteristics, see line 20 of table 9, other characteristics of the indicated clinkers and cements - see table 1-4). In addition, concrete includes the following:

- fine aggregate - sand quartz fractions 1-5 mm, containing, in wt.%: quartz

97, feldspars 2, dark-colored minerals 123

124 epidote and other impurities 1, with voidness 38% by volume;

- coarse aggregate - crushed stone granite fractions of 5-20 mm, containing, in wt.%: granite 95, quartzite 3, mica and other impurities 2, with a voidness of 42% by volume;

- drinking tap water.

All materials meet the requirements of relevant standards and specifications.

For the preparation of samples, a horizontal laboratory mixer, forced action, with a capacity of 100 l, a vibrating platform with an oscillation frequency of 50 Hz and mechanical fastening of the molds for samples - cubes 1 × 10 × 110 cm from ferrous metal with standard processing quality to the table surface is used. Tests of the samples are carried out after storage under natural conditions (100% relative humidity at a temperature of 20 ± 3 ° C). During the first days of storage under natural conditions, to prevent evaporation of moisture from the surface of the samples, the mold is covered with a cloth made of coarse canvas moistened with water. To test the samples, a standard hydraulic press with a self-aligning top plate is used. The test results lead to a standard sample size of 15x15x15 cm by multiplying the maximum compressive strength of the samples obtained by the press by a standard factor of 0.85.

The electrical capacitance of the concrete mixture, or freshly made concrete, is measured using alternating current with an experimentally selected frequency of approximately 180 Hz, using a measuring device that includes two coaxial electrodes with a dielectric gap of approximately 1 cm and a current strength of approximately 1A. The specified device is mounted on the bottom of the mixer so that the working bodies of the mixer do not touch it, but pass in the immediate vicinity (2-3 mm).

The test results in 1 series of experiments on two different concrete mixes, as follows from the data given in table. 11, lines 1 and 6 are optimums, lines 2-5 and 7-11, the remaining compositions confirm the useful effect of the method according to the invention and correspond to the above explanation of the invention. A regular dependence of the properties of concrete on the electric capacity of the concrete mixture is observed, consisting in the fact that the closer to the moment the growth of the indicated indicator stops, the mixing of the concrete mixture components is stopped, the lower the coefficient of variation of strength and the higher the strength indicators of concrete, regardless of other existing technological factors.

In an embodiment of the invention, in 2 series of experiments on the composition of the concrete mixture close to one of the mentioned compositions, similar tests are carried out with the additional introduction of the water-lowering components mentioned above into the concrete mixture. The test results (table. 11, lines 11-25) allow us to conclude that in the presence of water-lowering components introduced into the concrete mix, the above-mentioned regular dependence is preserved.

In an embodiment of the invention, in 3 series of experiments on one of the concrete mixes, similar tests are carried out with the addition of a foaming agent in the composition of the mixture. In this example, mixtures of kleukanifolny emulsion and aqueous solutions of urea and polyamide resins, the first of which contains these substances in parts by weight, are selected as a foaming agent. approximately in a ratio of 5: 5: 1 in terms of solids in the presence of, in addition, two strong electrolytes - calcium hydroxides (1.5 parts by weight), stabilizing the hydroxyl membranes on the bubbles of the foam, and sodium (0.1 wt. h), which increases the number of hydroxyl groups on the surface of the bubbles due to the increase in the ionic strength of the blowing agent solution with caustic alkali. The test results (table. 11, lines 26-28) allow us to conclude that in the presence of foam introduced into the concrete mix, the above-mentioned regular dependence is preserved. At the same time, the electric capacity of the mixture increases markedly at maximum, and the optimal mixing time increases from 3.5 minutes on average for heavy concrete mixes to 4.5-6.5 minutes for foam concrete mixes. It should be noted that other known foaming agents, for example, based on technical soaps such as alkyl sulfonates, abietates, lignosulfonates of alkali and alkaline earth metals mixed with adhesives and other stabilizers give approximately similar results.

In an embodiment of the invention, in a series of experiments on one of the mentioned compositions of the cellular concrete mixture, similar tests are carried out with the additional introduction of the water-retaining additives mentioned above and representing cellulose polyesters into the concrete mixture. The test results (Table 11, lines 29-30) allow us to conclude that in the presence of water-retaining additives, namely cellulose polyesters, introduced into the composition of the cellular concrete mixture, the above-mentioned regular dependence is preserved.

From the above data it follows that both heavy and light, in particular, cellular concrete, obtained according to the invention, i.e. by mixing the optimal duration, from a mixture of cements based on highly active promoted clinkers, during natural hardening, as well as in conditions of heat and moisture treatment for heavy

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126 tones according to the regime: holding samples at a temperature of 20 ± 3 ° C and 100% relative humidity for 2 hours, raising the temperature in the steaming chamber for 3 hours to a level of 80 ° C, isothermal heating at the indicated temperature in the steaming chamber for 6 hours, then cooling in an open steaming chamber for 2 hours to a temperature of about 25-30 ° C, for aerated concrete according to the regime: holding samples at a temperature of 20 ± 3 ° C and 100% relative humidity for 6 hours, raising the temperature in a steaming chamber 4 h to the level of 80 ° C, isothermal heating at the indicated temperature in p in a steam chamber for 6 hours, then cooling in an open steam chamber for 3 hours to a temperature of about 25-30 ° C, significantly superior in terms of strength and uniformity to concrete of the same composition obtained by the known method based on Portland cement from promoted and even more so control clinker. The latter is evidenced by the fact that the strength characteristics of concrete obtained according to the invention on the basis of cement from promoted clinker are 15-22% higher than those for concrete obtained on the basis of control Portland cement KK-1, using a technological method for determining the optimal mixing time based on indicator of the electric capacity of the concrete mixture during mixing, or 19-25% higher than the indicators of concrete obtained on the basis of the specified control Portland cement without selection duration of mixing, with the definition of the latter by means known in the art.

Thus, the second objective of the invention, the creation of a method for improving the quality of concrete made on the basis of highly active cement, forming a rapidly soluble and interacting cementitious material with high early strength after mixing with a liquid, which is used as water or a solution of electrolytes, is achieved. This also confirms the part of the invention related to the method of manufacturing concrete and reinforced concrete products and structures based on the obtained concrete.

Analyzing the state of the art in the manufacture of concrete and reinforced concrete products and monolithic structures, we note that their quality, primarily their durability, crucially depends on the concrete compaction coefficient. To increase it in excess of 0.97, which is required to guarantee water resistance and, therefore, frost resistance of products and structures [35], the thixotropy of the concrete mixture during laying, molding and compaction of products and structures is required. Portland cement, known from the prior art, during the first hour after mixing with water does not give fresh concrete the necessary thixotropy due to the lack of gel products that perform the functions of thixotropic lubrication. For their characterization, we consider in detail the physicochemical aspect of this issue. Neoplasms arising after mixing cement with water and performing the role of “lubrication” include:

1) the main initial product of hydration of alite (C ₃ 8), which is part of cement, in cement mortars and concretes at a pH of the liquid phase above 12 during the first hour of the interaction of cement with water is metastable hydrate C ₃ 8H ₂ (tricalcium hydrosilicate). It is formed by the topochemical mechanism, forms the outer layer of alite particles in the composition of cement with a thickness of up to 0.5-1 microns and the actual surface of these particles, being the first layer of lubricant. The amount of this hydrate is the higher, the more actively the alite surface interacts with the mixing liquid, in particular, the cellular structure of the alite in the cement according to the invention particularly quickly generates this hydrate. Other calcium hydrosilicates in this period after mixing, proceeding during the mixing of mortar and concrete mixtures, practically do not form; From ₃ 8H ₂ after 1 - 1.5 hours it disappears, decomposing into CH (free calcium hydroxide, part of which is a reactive amorphous phase, and the other part is portlandite, which is a crystalline form; the general name hydrolytic free lime is from the modern point of view not quite strict, since it does not arise directly as a result of hydrolysis of tricalcium alite silicate, but as a result of the decomposition of already hydrated tricalcium hydrosilicate; even in an amorphous state, it loses its ability lubricating action, since it is a binder) and the silica hydrogel approximate composition 81O (OH) _2. The latter, in turn, quickly reacting with the amorphous part of calcium hydroxide, forms in the liquid phase of the concrete mix aggregating low-basic calcium hydrosilicates, which are actually the main cement binder and are no longer related to the lubricant. In low-water concrete mixtures with a water-cement ratio (W / C) of less than 0.3, three-calcium hydrosilicate is less watered and has the composition C ₃ 8H ₁ , ₅ ;

2) the main initial product of hydration of the aluminate phase of clinker / cement (C3A) in the presence of a gypsum (calcium sulfate) component (i.e. the reaction product of C ₃ A clinker with gypsum stone C · 5 H ₂ included in the cement), with a low content caustic alkali in the composition of the cement SchA ₂ O + 0.658K ₂ O = 1 ₂ O = No. ₂ O _e <0.6 wt.% of the clinker part of the cement), when the pH of the liquid phase does not exceed 12.5-13, is ettringite C ₆ A · 5 ₃ H ₃₂ (this name refers to

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128 phase, in which there is no admixture of iron) or trisulfate (the so-called phase isomorphic to ettringite with an admixture of iron, partially replacing aluminum). Calcium hydrosulfoaluminates, calcium hydrosulfoaluminoferrites, the first of these terms are often used as a generic name for both phases. In hardening cement, ettringite and trisulfate are both present with the alumina module of the clinker part of less than 0.6-1, while the upper limit refers to clinkers with a KH above 0.97 and a MgO content of less than 2.5 wt.%, Characterized by the presence of rapidly hydrated calcium aluminoferrite . In other cases, this hydrate is predominantly ettringite, which during the first one or two hours after the cement is mixed with water exists in the form of a base gel in the aqueous layer adjacent to the surface of the cement particles and forms the basis of the “cement lubricant” in the specified liquid phase, underlain by the above-mentioned three-calcium on the clinker surface hydrosilicate, also gel. After 1-2 hours, ettringite begins to crystallize, loses its lubricating properties and acquires the character of an actual astringent. Trisulfate is characterized by a similar behavior, but it crystallizes more slowly, therefore, a gel lubricant based on it exists longer.

The amount of the by-products of the C ₃ A reaction clinker with gypsum stone that does not form the mentioned thixotropic lubricant, flowing in the liquid phase of the concrete mixture and concrete, crystalline calcium hydroaluminates of hexagonal type C ₄ AN _13-19 and C ₂ AN _8-11 (including an admixture of iron instead of part aluminum in the above case and containing less crystallization water in the above-mentioned low-water concrete mixtures), as shown by the experiments of the authors of the present invention, the higher, the lower the specific surface of the cement, lower the pH of the liquid phase (mentioning utye calcium gidrosulfoalyuminaty not formed below pH 11.5-12) and greater initial value W / C in mortars and concretes. It is also known that in this case, crystalline calcium hydroaluminates do not have astringent properties in the hardening Portland cement, because within 1 day-3 weeks they pass into inert cubic calcium hydroaluminates of the composition C3AN6 (with the replacement in this case of a part of aluminum with an admixture of iron, especially during heat and moisture treatment). The conversion of hexagonal calcium hydroaluminates to cubic proceeds with an increase in the specific volume of the solid part and the release of free water with a particularly high dissolving power, which causes disturbances in the already existing structural frame of cement stone. Thus, the experiments of the authors of the present invention in combination with information known from the prior art indicate that the coarser the cement is ground, the more water is added to the concrete in relation to the cement, so that it is easier to process and compact the concrete mixture, the lower the specific lubricant the effect of a unit of cement surface in a cement-water suspension and the less the positive effect of cement consumption on the compaction coefficient of fresh mortar and concrete during their laying, molding and compaction, as well as the distance hardening. This explains the fact known from the practice of construction business that the more time the first three specified technological operations take, the less is the possibility of obtaining high-quality mortar and concrete. Essentially, it is precisely the dependencies set forth above that are not known from the prior art that historically established significant attention is paid to the technology of concrete for molding and compacting equipment and the growth of the specific power of the latter per unit volume of the product or structure, which provides a significant increase in the quality of concrete and the products themselves and designs, including not only their durability and durability, but also bearing capacity.

The experiments of the authors of the present invention show that the effect of impurities in clinker and cement on the lubricating effect of the hydrosulfoaluminate component of “cement lubricant” in fresh mortars and concrete is more significant than on the weaker, but also more stable lubricating effect of the hydrosilicate component of this lubricant, and primarily due to the catalytic effect of alkali metal sulfates on the dissolution rate of gypsum stone in the liquid phase, which reduces the negative effect of the low specific surface of cement on the coefficient itsient sealing concrete and reinforced concrete. The high specific surface of cement reduces the specific yield of calcium hydroaluminates, the least frost-resistant and the weakest in terms of strength indicators of the hydrated phase in the products of the interaction of Portland cement with water, which, with a rational granulometric composition of cement, increases the resistance of the mortar and concrete to the external environment. If the content in cement NbO _e > 1% and the pH of the liquid phase of the mortar and concrete exceeds 13.2, then trisulfate (ettringite) is unstable, and the first hydrated phase - the reaction product C ₃ A + C 5 H ₂ is monosulfate C ₄ A 5 H ₁₈ , which was shown by the experiments of a number of researchers, including the authors of the present invention, while studying the hydration of highly alkaline (В ₂ О 0.9-1.4%) Portland cement. Monosulfate in these cases contains impurities of iron. He, as follows from these experiments, is also a gel

130 by the developer and, consequently, the third component of the "cement gel", partially or completely replacing or forming instead of ettringite-trisulfate at ultra-high pH values. However, monosulfate per unit mass produces a significantly smaller volume of gel than trisulfate, therefore its lubricating effect is less, but monosulfate gel is more plastic, less prone to cracking during deformation in the plastic state compared to ettringite gel, in particular, during immediate stripping monosulfate gel lends itself better to extrusion molding and to smoothing tools - rails, vibration rails, etc. But the monosulfate component of "cement lubricant" is more sensitive to the presence of in clinker / cement, free calcium oxide / hydroxide decomposes monosulfate to calcium hydroaluminates, which do not have lubricating properties. At the same time, the ettringite gel does not decompose with free lime from clinker; on the contrary, due to the decrease in the average length of the ettringite fibers in the presence of amorphous free lime, the lubricity of the ettringite gel increases. In this case, free calcium hydroxide arising from free lime in the clinker does not affect the lubricating effect of the hydrosilicate component of the “cement gel” (C ₃ 8H ₂ ). These features, not known from the prior art, are caused, as shown below, by the favorable technological and consumer properties of cement, which forms increased amounts of “cement lubricant”, which cement based on promoted clinker is particularly prone to.

Note that the chemical name of ettringite according to the GORAS rules is the double basic calcium-aluminum sulfate. Its structural formula is Ca ₆ A1 ₂ (OH) ₁₂ (8О ₄ ) ₃ Д6Н ₂ О reflects a greater amount of water in it in an equilibrium state than is usually given in monographs on cement chemistry, but when this hydrate is formed in a medium containing cement, as established in [36], the impurities in the cement composition noticeably reduce the equilibrium amount of water in this mineral, and the release of highly active clinker minerals from impurities with the transfer of the latter to slowly hydrated phases in promoted clinkers significantly increases gelation the surface of hydrated cement particles in mixed mortar and concrete mixtures and the content of hydrated water in ettringite - trisulfate - monosulfate. This circumstance explains the improved lubricating ability of cements based on promoted clinkers in aqueous systems and the increased thixotropic ability of the latter, shown below.

After a detailed description of the physicochemical side of the state of the issue, we consider the known methods for increasing the concrete compaction coefficient in concrete and reinforced concrete products and structures made on the basis of Portland cement, known from the prior art and not forming the necessary amount of “cement lubricant” to achieve the completeness of concrete compaction in concrete and reinforced concrete products and designs.

Known methods for manufacturing concrete and reinforced concrete products and monolithic structures include the introduction of additional gelling agents, for example, derivatives of alkyl methacrylates with the number of carbon atoms from 1 to 8, into the concrete mix [37]. The disadvantage of this method is the delay in hardening of concrete: the level of strength corresponding to setting (0.15 MPa) is achieved only 12 hours after the mixing of the concrete mixture is completed.

There are also known methods of manufacturing concrete and reinforced concrete products and prefabricated and monolithic structures, in which porous absorbents, for example, dry alumina gel, silica gel, aluminosilicate, activated carbon, etc., which are absorbed in the concrete mixture, are introduced into the concrete to increase thixotropy of concrete emit air; the latter, according to the ideas of the authors of the patents, plasticizes the concrete mixture and facilitates the laying, molding, and compaction of concrete, preventing the formation of pore piling [38]. In fact, in addition to porous absorbents for plasticizing the concrete mixture, plasticizing additives are additionally added. Only in this case, the released air is able to additionally plasticize the concrete mixture, which, of course, reduces the hardening rate of the obtained concrete. Known and methods with the introduction of powdered adsorbents with a rough surface such as calcium magnesium aluminum silicate in the amount of 30-40 wt.% Cement [39]. The disadvantage of the latter methods is technological complexity: the stability of dosing and the introduction of concrete into the air-emitting additives depends on their moisture content; stabilization of the process is possible only with the portioned introduction of packaged portions of the indicated additives in a concrete mixer in combination with plasticizers, which significantly increases the consumption of engineering labor per unit of production, increases the cost of the process, starting materials and products.

Closest to the alleged invention (prototype) is a method of manufacturing concrete and reinforced concrete products or monolithic concrete structures based on cement, forming a rapidly soluble and interacting cementitious material with high early strength after

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132 mixing with a liquid, by mixing cement with aggregates and a liquid, which is used as water or a solution of electrolytes, to obtain a concrete mixture used for the manufacture of concrete by laying in form or formwork, molding, compaction and subsequent heat and moisture treatment of the obtained concrete and reinforced concrete products or monolithic structures, in which the hydrogel-forming starch hydrolysis product is added to concrete [41]. This material is known from general and organic chemistry, as well as from cooking and plastering practice as a stable gelling agent that swells in alkaline, acidic and neutral environments. In a highly alkaline environment of the concrete mixture, the effectiveness of this gelling agent, as additional to the mentioned “cement gel”, is quite high, since it additionally lubricates the fibers and plates of the hydrosulfoaluminate component of the “cement gel”. The gel from starch hydrolysis products is also slightly sensitive to such impurities in clinker / cement as MdO, P ₂ O ₅ , K ₂ O, Xa ₂ O, which favorably characterizes the considered method according to the prototype in comparison with the previous ones. The main disadvantage of the method according to the prototype is the extreme sensitivity of starch hydrolysis products to impurities in cement due to clinker "burnout", although all the other methods described above are less characterized by the same disadvantage. It is known [8] that the most important of the impurities characteristic of unburnt clinkers and cements made from them are С1 ₂ А ₇ , С ₂ Р, СР, С and their derivatives. Calcium ferrites C2P and CP hydrate extremely slowly and do not affect the composition of primary hydrates. The role of free lime C and the product of its hydration CH - calcium hydroxide - was mentioned above. The role of C1 ₂ A ₇ boils down to the rapid formation in large quantities of “hard” concrete in the liquid phase, which does not have the lubricating and thixotropic effect of the A1O (OH) - A1 (OH) ₃ gel [26], which chemically binds hydrolyzed starch into an inert compound. In addition, the specified alumina hydrogel converts ettringite to monosulfate, and the latter decomposes, which causes a false setting of cement paste, mortar and concrete mixtures in view of the rapid separate crystallization of calcium hydroaluminates and two-water gypsum. An analysis of the experience of the Russian cement and construction industries shows that for cements without mineral and organic additives, the indicated reason for false setting, starting from the 70s of the XX century, is predominant [40]. Thus, the indicated drawback of the method according to the prototype is common to all methods of manufacturing concrete and reinforced concrete products and structures known from the prior art: not only an additional gel formed by hydrolyzed starch, but also the bulk of the “cement lubricant” described above suffers from clinker burning. This drawback is especially important in the harsh, shortened, and high-temperature regimes of heat and moisture treatment of concrete and reinforced concrete products and structures, being a widespread cause of surface cracking and even peeling of the surface layer of concrete in products and structures subjected to steaming according to the indicated modes.

The alleged invention is free from these disadvantages. It lies in the fact that in the method of manufacturing concrete and reinforced concrete products or monolithic structures from the specified concrete on the basis of the specified cement, forming a rapidly soluble and interacting cementitious material with high early strength after mixing with a liquid obtained by sintering a cement raw material mixture in a clinker kiln, including in mineral forms: the main oxides from the group calcium oxide, silicon oxide, alumina, iron oxide, the main minor components from the group oxide oxide sulphide, sulfur trioxide, potassium oxide, sodium oxide, the remaining minor components are impurities, as well as chemical compounds returned to the specified furnace with dust trapped from the furnace exhaust gases, with the formation of Portland cement clinker containing three or more clinker minerals from the tricalcium silicate group (3СаО-81О ₂ ), dicalcium silicate (2СаО-81О ₂ ), tricalcium aluminate (3СаО-А1 ₂ О ₃ ), calcium aluminoferrite [2СаО- (А1 ₂ О ₃ ) _х - (Its ₂ О ₃ ) 1- _х ] , 1>x> 0, followed by cooling and grinding of clinker, in the manufacture of the specified concrete by per mixing said cement with aggregates and a liquid, which is used as water or an electrolyte solution, using prepared concrete mix for concrete production by molding or formwork, molding and compacting said mixture, withstanding molded and compacted concrete and reinforced concrete products or monolithic structures made of concrete until the latter reaches the initial strength and with the subsequent implementation of the heat and moisture treatment of these products and the design Characterized by introducing into the supplied to the calcining cement raw meal is calcined material or mineral promoter, which is a mineral oxide additive comprising two or more of clinker from mineral groups: I: trohkaltsievy silicate (3SaO _81O-2), dicalcium silicate

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134 (2СаО ^ 81О ₂ ), tricalcium aluminate (3СаО · А1 ₂ О ₃ ), calcium aluminoferrite [2СаО <А1 ₂ О ₃ ) _х · (Бе ₂ О ₃ ) 1 _- х], 2/3>х> 1 / 3 and / or II: mayenite (12СаО · 7А12О3), calcium monoaluminate (CaО · А12О3), dicalcium and monocalcium ferrites (2СаОГе ₂ О ₃ , СаОГе ₂ О ₃ ) and / or III: alkaline, sulfate and halide derivatives of minerals of the indicated groups and / or IV: calcium sulphoaluminate ₍₂ 4SaOEA1 Og8O _3), calcium sulfate (Sa8O4) and / or mixtures thereof and derivatives and / or V: aluminates and / or silicates and / or alkali metal ferrite; VI: mixtures of minerals from these groups with each other and / or with free calcium oxide, mechanical and / or obtained together in the form of clinker, or sinter, or slag, or sediment, or suspension, as well as when selecting, adjusting, maintaining the composition of the specified promoter and its presence in the resulting promoted clinker Browse basicity exceeding basicity clinker eutectic melt composition region in the phase diagram of CaO Portland cement clinker A1 ₂ O ₃ - 81O ₂ - Fe ₂ O _3, excluding minor constituents crystal generated at 1338 ° С, using the calculated electronegativity of the compounds included in their composition as a basis for the basicity measure of the indicated promoter and promoted clinker in comparison with the similar basicity measure of the eutectic clinker melt, and, in addition, characterized by mixing of the concrete mixture during preparation the specified concrete to the optimal distribution of water on the surface of the specified cement, estimated by approaching the maximum value and the minimum grow increase capacitance stirred mixture of about 0,0050,1 uF / m ^2, after the termination of the last stirring said mixture, molding and compacting said articles and structures complete within about 15-90 minutes after reaching said minimum, and it is precisely before the appearance of the indicated products and structures of silica hydrogel in molded concrete - the decomposition product of the primary gel-like calcium hydrosilicate on the surface of clinker particles of the specified cement.

The essence of the invention in the manufacture of concrete and reinforced concrete products and monolithic structures is to increase the coefficient of compaction with equal work of compaction and other conditions being equal compared to the traditional method of manufacturing these control products and structures due to the accelerated separation of the primary gel-like hydrated phases - calcium hydrosulfoaluminates of the type mentioned trisulfate and monosulfate formed in the liquid phase adjacent to the surface of the cement particles, and the primary hydrogel hydrogel calcium ikate of composition С ₃ 8Н1, _5-2 , formed in the outer layer of the surface of alite particles (according to the topochemical mechanism [42]). Both of these hydrogels determine the thixotropy of cement paste, fresh mortar and concrete, and their number increases due to the presence of X-ray amorphous phases on the surface and in the volume of particles of the promoted clinker, in contrast to the control clinker. Gel C ₃ 8H !, _{5-2 is} thermodynamically unstable: decomposing, as mentioned above, into hydrolytic lime Ca (OH) ₂ and the “hard” silica hydrogel 81O (OH) ₂ , it loses its lubricity. According to the authors of the present invention, the moment of disintegration of the primary gel C ₃ 8H1, _5-2 , and not the start of cement setting much later, is an extremum after which the displacement of volume elements of freshly prepared cement materials is undesirable, moreover: at this point they should be such are molded and compacted so that the hydrolytic lime binds the finished structure, rather than loosens it, which occurs when the concrete mixture is moved in the presence of free, already released as growing microcrystals hydrolytic lime, the indicator of the presence of which is the presence of the simultaneously formed mentioned hydrogel of silica. It should be noted that the additional advantages of cement from promoted clinker in relation to the process of cement hydration are that the promotion, eliminating impurities from these hydrogels and the “hereditary” phases formed from them, makes it difficult to carbonate all hydrated neoplasms. So, ettringite in micropreparations with W / C of about 10 using ordinary Portland cement is carbonated and decomposes after 0.5-2 hours of contact with a CO2-containing atmosphere, and ettringite obtained by interacting with cement water from a promoted clinker remains in the same conditions stable for 3 weeks to 3 months, and in a cement stone with the usual V / C value it has not collapsed for 5 years (observations continue). Portlandite Ca (OH) 2 in a promoted cement cement stone has a hexagonal (dodecahedral) faceting observed in a conventional optical microscope, and not tabular (orthorhombic), which is typical for this hydration product in a cement stone, known from the prior art, while hexagonal ( dodecahedral faceting was previously observed only under an electron microscope in Portlandite submicrocrystals formed under conditions free of CO ₂ [43]. Like ettringite, the rate of carbonation of portlandite from cement based on promoted clinker significantly slows down135

136 Xia. The indicated morphological differences and delayed carbonatization — characteristic, even diagnostic properties of cement stone obtained on the basis of cement from promoted clinkers, are undoubtedly due to the effect of refining (releasing impurities) of silicates and calcium aluminate of the main hydrate-forming clinker minerals in the presence of a non-hybridizing promoter and concentration of impurities in the presence of the latter in slowly hydrating calcium aluminoferrites, which forms a large area for future crista llochemical studies.

The main components of the specified “cement lubricant” are protected from clinker burning and the negative influence of C ₁₂ A ₇ impurities in the unburnt clinker and cement based on it in the method according to the invention due to two main acting factors: a) acceleration of mineral formation in the manufacture of clinker, which radically reduces the likelihood the presence of marginal phases in the promoted clinker, including C ₄₂ A ₇ ; b) a lower content of impurities 81O ₂ in the hydrosulfoaluminate components of the “cement lubricant”, which greatly reduces the rate of their observed decomposition at the boundaries with the emitting silica hydrogel. In fact, under the conditions created by hydration of promoted clinkers, the first portions of silica hydrogel do not significantly affect the thixotropic properties of the cement-water suspension in concrete, while the mobility of the concrete mix on control cement reduces the very first portions of the silica hydrogel formed, which leads to to increase the consumption of water in concrete, and, as shown above, further reduces the specific lubricating effect of the "cement gel".

Returning to the separation of silica hydrogel, we note that this hydrogel, whose surface is electrostatically charged opposite to the hydrogel of ettringite (trisulfate), is added together with the first portions of the so-called hydrolytic lime that dissolve in the liquid phase in the case to the already present (formed in 2- 3 min after mixing cement with water) ettringite hydrogel (trisulfate), degrades the lubricating properties of the latter due to a decrease in the capacity of the double electric layer and destab tion of physico - chemical state trisulfatnogo or bisulfate hydrogels.

In order to ensure the early formation of a two-component hydrogel on the surface of particles, already 3-5 minutes after cement is mixed with water, alite in cement should be obtained under conditions of promotion of its formation, which decisively accelerates its interaction with water or electrolyte solutions after cement is mixed. In the future, this increases the heat during the interaction of cement with water, accelerating the hydration of alite, and favorably affects the strength of concrete, and not only its compaction coefficient and density. Similarly, an improvement in compaction and a slowdown in carbonation can explain the observed increase in the durability of cement-based concrete from promoted clinker under the influence of environmental agents, as well as the increase in water resistance and increase in the bearing capacity of precast concrete products and structures and monolithic reinforced concrete based on this cement.

A method for manufacturing reinforced concrete products and structures according to the invention is characterized by the simultaneous onset in all cement particles and the frontal nature of the alite interaction reaction with water propagating from the surface into the cement particles with a continuous phase boundary between the original alite and its hydration products; with the prior art, this reaction does not start simultaneously, part of the alite enters into it 12 to 24 hours after the cement is mixed with water and even later, up to 14 days, and the other part immediately. The simultaneous start and uniformity of the alite hydration process in concrete made by the method according to the invention reinforce the positive effect of increasing heat generation on the hardening process of concrete. During the faster process of cement hydration according to the invention, a phenomenon unknown from the prior art was discovered, namely, due to faster saturation of the liquid phase earlier than in concretes manufactured in accordance with the prior art, namely 15-90 minutes after the end of mixing the components of the concrete mixture ends the induction period of hydration and there is a noticeable thermal effect, easily distinguishable from the initial thermal effect of wetting the surface of the particles of cement water. A silica hydrogel border with an approximate composition of 81O (OH) ₂ is observed when cement is hydrated from a promoted clinker in preparations under an optical microscope in transmitted light much less frequently than when cement is hydrated from a conventional clinker. Therefore, the only reliable method for determining the moment of occurrence of the specified silica hydrogel, below for brevity denoted by the abbreviated notation: “8-H-gel”, is differential thermal analysis (DTA).

The specified 8-H-gel is detected by the exothermic effect of its recrystallization at a temperature of 325-340 ° C under the following conditions for taking a thermogram: the rate of rise of the temperature of the sample is 8-10 ° C, the mass of the sample is not

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0026Ί3

138 less than 0.4 g, atmosphere — air, etalon — corundum [44]. The indicated exoeffect was identified by keeping a sample of synthetic C ₃ 8 under a stream of water from a water supply system in a fine-mesh nylon mesh for 30 days until the lime was completely removed from the sample and the residue was examined under an optical microscope and using DTL [46]. Since the 8-H-gel in concrete is initially amorphous, in order to use X-ray analysis to detect this hydrogel, the samples have to be preheated to crystallize at 60-80 ° C for 30 min-1.5 hours. After that, the former 8-H -gel on the X-ray diffraction patterns shows a weak basic reflection of quartz at b = 0.331 nm.

The choice as a liquid in concrete instead of water of an aqueous solution of electrolytes is intended, essentially, to accelerate the hydration of alite, which is achieved by its interaction with aqueous solutions of salts from the group of potassium, sodium, aluminum or ferric sulfates in an amount of up to about 1 wt. % cement in terms of 8O ₃ .

The additional introduction of a water-lowering component, if it is not present in the cement according to the invention, in mixing water or in aqueous solutions of these salts, on the contrary, is mainly intended to be combined with hydrogels of calcium hydrosulfoaluminate and said calcium hydrosilicate, thereby increasing the strength of concrete according to the invention by about 15-18%. If there is only an ettringite hydrogel, the water-lowering component introduced into the mixing water is adsorbed by this gel and to a lesser extent affects the water demand of concrete. To enhance this effect, economically unreasonable increased dosages of introducing a water-reducing component into such concrete are required. Thus, in the method of manufacturing products and structures according to the invention, the plasticizing effect of the water-lowering components is also higher.

The invention in terms of a method of manufacturing concrete and reinforced concrete products and monolithic structures becomes clearer from the example of its implementation, set forth below.

Example 11. Conditions for implementing the method of example 10. Additionally study the mode and products of hydration of cement in concrete in samples prepared as follows. Fresh or hardened concrete is taken, grains of coarse aggregate are taken on a sieve or beaten with a geological hammer, the remaining mass is sieved through a sieve with 1 mm mesh, if necessary crushing the mass for sieving manually or on a laboratory jaw crusher. These operations are carried out for no more than 10 minutes after sampling concrete. The resulting grains are quartered, placed in a desiccator above water to avoid drying, triturated in a mechanical mortar and subjected to differential thermal analysis (DTL) on a Paulik-Erdei instrument at a heating rate of 8 deg / min, atmosphere - air, standard - corundum, thermocouple Ρί / ΡίΚΚ and after about 40 minutes they get the result - they fix the presence or absence of the mentioned exothermic effect, that is, the presence or absence of the indicated silica hydrogel. Since the prefabricated reinforced concrete production plant usually does not have a DTL device, and the methods of preserving the samples with absolute alcohol give dubious results, they usually mix concrete or cement paste with the same H / C directly near the operating DTL device. Other methods of physicochemical analysis are also used.

The test results of the physical and mechanical properties of concrete, corresponding to products made according to the invention, are presented in table. 12. Samples are kept in the laboratory room, as well as in a steaming chamber during heat-moisture treatment (TVO). In industrial conditions, the exposure time of the products before being placed in the hardening chamber differs from the period of formation of the silica hydrogel given in Table. 12, no more than 10 minutes in the direction of shortening due to the large volume of concrete in products and structures and, accordingly, a higher exothermic effect. Therefore, it is believed that the processes of molding and compaction of products and structures should be completed approximately 10-20 minutes before the appearance of the indicated silica hydrogel in concrete, fixed in laboratory samples. In practice, this is feasible if the cycle of manufacture, laying and molding of the concrete mixture in the samples and in products and structures is consistent.

Given in the table. 12 data show that the method of manufacturing concrete and reinforced concrete products after the optimal mixing mode of concrete mixtures both during hardening in natural conditions and during heat and moisture treatment really allows to obtain more durable and stable products and designs based on simple technological methods that reduce energy costs by their molding and compaction, as well as the implementation of TVO, shortening its duration due to earlier obtaining tempering strength. It should be noted that in foam concrete, the application of the method according to the invention has a lesser effect on strength than in heavy concrete, since thixotropy in the first fresh state is partially due to the plasticizing action of the foaming agent,

139

140 and not just “cement gel”, as is observed in the second when it is fresh. In other types of lightweight concrete, as shown by the experiments of the authors of the present invention, the influence of the proposed method on their strength characteristics is higher than in heavy concrete, since it manifests itself in the absence of a diluting action of a large heavy aggregate. But the increase in frost resistance (about 10%) in heavy concretes made according to the method according to the invention is less than in foam concrete (25-30%) due to the additional structures created in the walls of the foam bubbles by an additional amount of “cement gel” according to the invention.

Thus, the achievement of the third goal of the invention has been confirmed - the creation of a method for the production of concrete and reinforced concrete products and structures based on the obtained high-quality concrete, which makes it possible to use highly active cement with maximum efficiency, which forms a quickly soluble and interacting cementitious material with high early strength after mixing.

The foregoing allows us to conclude that the cement manufacturing method according to the invention, based on the introduction of a mineralization promoter during sintering of the cement raw material mixture into the last or calcined material, is a mineral oxide additive comprising clinker minerals of various groups, as well as calcium oxide, with a promoter basicity level exceeding the basicity of the eutectic clinker melt in the high-calcium part of the CaO - A1 ₂ O ₃ - Her ₂ O ₃ - 81O _{2 system} allows you to fundamentally change the mode of operation s kiln aggregates, cement mills, as well as the properties of clinker and cement obtained on the basis of elimination or a significant reduction in the duration of the induction periods of crystallization of alite and other clinker minerals during clinker formation.

So, the proposed method in terms of cement production allows to significantly increase the content of alite or its analogues in clinker up to 70-80% without increasing, and in some cases with a significant reduction in fuel consumption, which is completely unexpected for the current level of technology. At the same time, a significant increase in the productivity of furnace units (by 8-30%) is combined for the first time with a simultaneous substantial increase in product quality - an increase in the strength of cement made from clinker obtained, both at an early age (1-3 days) and in the later stages of hardening, in particular, at 28 days of age, i.e. hydraulic activity by 7–25 and 3–20 MPa, respectively, ceteris paribus, and with a significant - 10–25% increase in the productivity of cement mills due to an increase in the grindability of the promoted clinker. The synergistic combination of all these effects significantly increases the cost-effectiveness of achieving each of them, and the more so that the implementation of the method according to the invention practically does not require additional costs, except for undertaken for the introduction of the promoter.

The method according to the invention for the first time allows you to move from fixing to controlling the content of impurities in the main phases of Portland cement clinker, as well as in hydrated phases formed after mixing cement with water or an electrolyte solution. This presents additional opportunities for increasing the efficiency of the cement manufacturing method: it ensures the stability of the coating in rotary clinker kilns, significantly increases the resistance of the refractory lining of kilns, reduces the wear of grinding media and the armor lining of cement mills, and finally, has ecological value, since it reduces the content of harmful clinker and cement impurities - from alkali metal oxides to hexavalent chromium, which causes dermatitis in workers with the prior art x building complex.

Hydration of cement obtained on the basis of a promoted clinker with an optimal promoter content during its firing reveals new properties of cement stone that are unexpected for the prior art, primarily the increased resistance of its main components - calcium hydrosilicates and hydrosulfoaluminates, even calcium hydroxide (portlandite) against the effects environmental agents. By the example of hexagonal portlandite crystals observed for the first time in a cement stone from the said cement, instead of the usual tetragonal forms, an approximately 1,000-fold increase in their resistance to carbonation by carbon dioxide is shown due to a 2-5-fold lower anionic impurity background compared to the prior art and a lower density of cationic vacancies. In addition to improved ceteris paribus air, water and sulfate resistance, compared to control cements, cement clinkers from promoted clinkers are characterized in concrete and concrete and reinforced concrete products by significantly reduced shrinkage, increased resistance and the absence of violations of surface and textured layers, especially high plasticity even with an increased content of alkaline oxides in the initial clinker, improved compatibility with functional additives in cement and concrete, including expanded the range of this that allows 2-5 times to reduce the consumption of the latter, bezvysolnostyu, lack of inclination to lozhno141

142 setting, dilatancy and water separation, increased thixotropy, resistance to surface drying, which is important for concreting in hot and dry climates, and at the same time, increased frost resistance, especially at high humidity, which is essential for construction in the polar and polar regions.

In fact, mineral formation during the firing of cement clinker, occurring in the presence of promoters, proposed in the present invention, can now be justifiably called the thermochemical synthesis of Portland cement clinker. Promotion for the first time opens for research a new, promising field of chemistry and technology of cement, the beginning of work in which a number of areas of development are reflected in the present invention, which determines the significant textual volume of the patent, but the description of the latter and even the extensive claims are far from exhausting and already visible now opportunities. For example, obtaining clinker sintering as a result of promotion of clinker grains that are easy to grind on modern technological lines for clinker roasting with clinker coolers, which exclude spilling between grates, can not only significantly reduce the energy consumption for cement grinding, but for the first time it will really make it possible to use it when grinding on a mass scale cement roller mills designed for relatively “soft” materials, in their simplest and most effective forms, or “oro-mill” mills, which result a nearly 5-fold reduction in the average energy consumption for grinding of cement to now unattainable level of 5-7 kWh / t. It is possible that with the further development of this area of work, cement grinding will be completely avoided, given the speed of dissolution and the increase in chemical activity during the promotion of clinker phases such as hyperalite, free calcium oxide in solid solution with iron ferrites, refined tricalcium aluminate and its derivatives, calcium langbainite and even whitens with adjustable basicity. The energy consumption for grinding the coarse raw material mixture used in combination with an effective mineralizer in the promoted thermochemical synthesis of clinker will also significantly decrease. This will avoid a significant increase in the cost of cement for general construction purposes with the inevitable future involvement of carbonate raw materials extracted by the mine method or from underwater deposits.

On the other hand, clinkers and cements obtained according to the invention, due to the reduced content of harmful impurities, are not only particularly effective when used in combination with a number of the most valuable additives, superplasticizers and gelling agents, silica fume and active mineral additives, including crystallization components such as krents, such as processed red titanogypsum , but very promising in concrete under rational modes of mixing the components of the latter, laying, molding and compaction according to radiated mixture in concrete and reinforced concrete products and structures, which is reflected in the description of the patent. But, in addition, the resulting concretes are characterized by an increased and controlled ability to monolithization - the intergrowth of hydrates to a degree inaccessible to the existing level of technology in the field of cement and concrete technology. The development of research in this direction will allow using promotion in the future to develop hybrids of cement stone and gypsum stone, hybrids of hardening Portland cement and alumina cement, both of these binders with gypsum and lime, in the future even cement stone chemically fused with aggregates, possibly also with glass and steel reinforcement, create new structural and heat-insulating heavy and lightweight concrete, develop new types of heavy and lightweight concrete with “growing” fiber reinforcement and a chemically unified, bendable matrix for aggregates and air bubbles, new types of reinforced concrete with continuous reinforcement, finally, “malleable concrete”, compressive strength not inferior to cast iron, and bending strength of aluminum alloys, but not in thin layers or sheets, and in normal building products and structures.

From the description and examples of the invention, it follows that it is characterized by a number of elements of novelty and surprise, not arising from the prior art, and significantly exceeds the latter in terms of manufacturing methods and properties of the resulting clinker, cement based on it, as well as concrete made from it products.

The above also indicates the preparedness of the invention for industrial implementation.

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Table 1

The results of the calculation of the basicity X (B ^) _t { _n = B _{t | 11} mineralizing impurities or small components in the components of the raw material mixture, clinkers and additives introduced into the calcined material — mineralizers and promoters, conv. units (in numbers, in order, the first digit is the example number, the second digit is the experience number and the third digit is the object number)

No. p / p Components of the raw mix, clinker, additives Mas. ratio The content of the main minor components, The content of the remaining small components, in terms of the mixture, from the formula (5) = ΣΜ & Cu to ₂ o F ₂ O Mg0 8O ₃ and about Wow 8gO CaO & Geo ΝίΟ Soo Mp ₂ About _{3 2} Cr ₂ About ₃ CIO MoO ₂ Maoz P ₂ about ₅ C1 ₂ G ₂ one 2 3 4 5 6 7 8 nine 10 eleven 12 thirteen 14 fifteen sixteen 17 eighteen nineteen twenty 21 22 23 24 Example 1, a series of experiments 1 (contributions of raw materials in calculated basicity taken into account in accordance with their OLYAMI) 1.1.1 Limestone 80.92 0,0405 0,0486 0.4283. 0.3399 0.004 0.0081 0,0647 0 0 0.004 0 0.0113 0.002 0.0176 0 0.008 0 0.1861 0.004 0,0008 1,09966 ⁵ ) 1.1.2 Clay 17.88 0.3254 0.1806 0.1234 0,0697 0,0002 0,0004 0,0002 0 0 0.0014 0,0002 0.0018 0,0243 0.0197 0 0.002 0 0.0054 0.0018 0,0002 0.95331 1.1.3 Pyrite cinder 1.90 0.0082 0.0067 0,0372 0.0849 = 0 0.0015 twenty 0 2 About ¹ ) 0,0007 0,0006 0.0017 0,0004 0.0046 twenty 0.001 0 0 0 0 0.13336 1.1.4 Raw mix 100.0 0.3741 0.2359 0.5889 0.4945 0.0042 0.01 0,0649 0 twenty 0.0061 0,0008 0.0148 0,0267 0.0419 twenty 0.01 0 0.1915 0.0058 0.0010 2,18633 1.1.5 K-clinker I ² ) 100.0 0.47 0.27 0.84 0.38 twenty 0,07 0.002 0.89 ⁶ ) 0.17 ⁷ ) 0,031 0.02 0.095 0.02 0.188 twenty 0,054 0 0.19 twenty twenty 2,81134 1.1.6 Mineralizer - 100.0 0.26 3,59 0.18 0.50 0.014 0.008 0 0 0 0.002 0.008 0.009 0.009 0.001 0 0.005 0 0.0029 0.002 13.21 86,15008 additive 0.0059 0.0015 0.0212 0.0011 0.003 twenty twenty 0 0 0 twenty twenty twenty twenty twenty 0 twenty 0 twenty twenty 0,0779 0.50777 ⁸ ) 1.1.7 M - clinker I ³ ) 100.0 0.21 0.18 0.67 0.20 twenty 0.005 0.001 0.61 ⁶ ) 0,1I ⁷ ) twenty 0.002 0.009 0.02 0.08 0 0,03 0 0.13 twenty 0.15 1.7189 1.1.8 Promoter I ⁴ ) 100.0 n / a ¹⁰ . 0.02 0.34 0.11 0 0.02 0,03 twenty twenty 0.287 0.119 0.234 0.01 0.16 0 0.08 twenty 0.01 twenty twenty 1.6831 ¹¹⁵ - supplement 0.2 = 0 = 0 0.007 0.002 0 twenty twenty 0 0 0.006 0.002 0.005 twenty 0.003 0 0.002 0 twenty 0 0 0.05 1.1.9 P-clinker I ³ ) ref. ¹²⁵ 0.18 0.15 0.56 0.34 0 0.04 0.04 0.47 ⁶⁾ Oh, O5 ⁷⁵ 0.02 0.02 0.10 0.31 0.11 0 0.05 0 0.20 0 0 2,1000 1.1.10 PM clinker 1 100.0 0.11 0.15 1.01 0.43 0 0.005 0.002 0SCH ⁶⁾ 0 0.002 0.001 0.05 0.42 0.18 0 0,07 0 0.26 0 0.05 2.6270 Example 1, a series of experiments 2 1.2.1 Promoters 1A, from 100.0 n / a n / a 0.2 0.14 0 0.002 0.001 0 0 0.21 0.05 0.08 0.01 0.12 0 0.001 0 twenty 0 0.01 1.48 BEFORE 0.6 0.4 0.006 0.007 0.41 0.16 0.27 0.06 0.22 0.006 0.06 1.76 1.2.2 P-clinkers 1A, from sire. 015 0.10 0.43 0.28 0 0.02 0.02 0.1 0 0.01 0.01 0.08 0.22 0.10 0 0,03 0 0.11 0 0.01 2.03 BEFORE 0.20 0.16 0.64 0.53 0.08 0.06 0.6 " 0.08 ⁷⁵ 0.04 0.05 0.14 0.47 0.16 0,07 0.19 0,03 2.16 Example 1, a series of experiments 3 1.3.1 Promoters 1B, from 100.0 n / a n / a OD 0.05 0 0 0 0 0 0,03 0.02 0.05 0 0.02 0 0.05 0 0 0 0 2.09 before 0.8 0.45 0.01 0.01 0.40 0.2 0.32 0.05 0.45 0.12 0.06 2.24 1.3.2 P-clinkers 1B, from ref. 0.18 0.16 0.61 0.28 0 0.01 0.01 0.05 0 0.01 0.01 0.05 0.24 0.12 0 0,03 0 0.16 0 0 2.16 BEFORE 0.27 0.33 0.85 0.45 0.09 0.08 0.45 0.10 0.06 0.09 0.16 0.53 0.23 0.04 0.27 2,31 Example 1, a series of experiments 4 1.4.1 1V promoter 100.0 0.08 n / a 0.62 0.35 0 0.02 0.13 n / a n / a 0.18 0,07 0.22 0.37 0.19 0.17 0.05 0.08 0.16 0.01 twenty 2,51 1.4.2 P-clinker 1B ref. 0.52 0.68 0.82 0.61 0 0.06 0,07 0.43 ° 0.07 ⁷⁵ 0.05 0,03 0.012 0.18 0.17 0.05 0,03 0.01 0.19 twenty 0 3.77 Prima; p 2, a series of experiments 1 (raw material contributions components in basicity taken into account in accordance with their shares) 2.1.1 a piece of chalk 36.65 1 0,055 0,0293 0.1393 0.0916 0 0.0037 0.0073 0 0 0 0 0.02 0.0037 0.0037 0.0037 0 0.0037 0,0293 0 0 0.3889 2.1.2 Marl 57.46 0,1207 0.0632 0.4137 0.2701 0 0 0.0057 0 op 0 0 0.0057 0.0057 0 0 0 0 0,0230 0 0 0.9349 2.1.3 Pyrite cinder 5.89 0.013 0.0084 0,079 0.2939 twenty 0.0012 0 0 20 ¹⁵ 0,0261 0,0100 0.0062 0,0100 0,0365 0,0702 0,0752 0 0.0011 0 0 0.7432

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148

one 2 3 5 6 7 nine 10 P 12 thirteen 14 fifteen sixteen 17 eighteen nineteen twenty 21 22 23 24 2.1.4 Raw mix 100.0 0.139 0,1009 0.651 0.6556 0 0.0049 0.013 0 0 0,0266 0,0100 0,0319 0.0194 0,0402 0,0739 0,0752 0.0037 0,0534 0 0 2,067 2.1.5 K - clinker 2 100.0 0.18 0.14 0.76 0.34 0 0,03 0 0.24 ^b) 0.06 ^ 0.01 0.01 0.12 0.15 0.02 0 0.09 0 0.08 0.01 0 1.9642 2.1.6 Promoter 2 100.0 0.21 0.13 0.98 0.61 0 0,035 0.0086 n / a 0,03 '> 0.0175 0.0175 0.1487 0.105 0.1663 0,07 0.0175 0 0.1139 0 0 2,5878 2.1.7 P-clinker 2 100.0 0.09 0.08 1,04 0.42 0 0,07 0 0.32 " 0 0.01 0,03 0.21 0.22 0,03 0 0.18 0 0.17 0 0 2.4633 Prima; p 4, series of experiments 1 (contributions of raw materials to the basicity are taken into account in accordance with their shares) 4.1.1 Limestone 85.31 0.36 0.1536 0.9213 0.3668 0.0043 0.0171 0,0256 - - 0.0128 0.0068 0,0717 0.128 0,0512 0.0171 0.0085 - 0.1962 0.0085 0,0009 2,56530 4.1.2 Clay 12.56 0.3743 0.216 0.1683 0.0867 0.0013 0.005 0 - - 0.0025 0.0038 0.0013 0.0864 0.0176 0.0038 0.0025 - 0.0013 0.0001 0.0001 1,14291 4.1.3 Pyrite cinder 2.13 0.0092 0.0028 0.0428 0.136 = 0 0.0015 = 0 - - 0.001 0.0011 0.0021 0,0006 0,0005 0.0013 0,0009 - 0 0 0 0.17280 4.1.4 K-clinker4 one hundred 0.84 0.53 1.79 0.63 0 0,049 0 0.49 ^b) 0.08 ⁷⁾ 0,025 0.02 0.09 0.18 0.12 0.01 0.015 - 0.19 0 0 4,90598 4.1.5 Promoter 4, cf. one hundred 0.40 0.20 0.32 2.79 0 0.06 0 n / a 0,12 ^ό 0,027 0.02 0.11 0.18 0.08 0.02 0,031 - 0.194 0.008 0 3.93018 4.1.6 P-clinger 4.1, cf. one hundred 0.44 0.39 1.74 0.60 0 0.02 0.0025 0.22 ^b) 0.02 ^ 0.012 0.014 0.059 0.20 0,03 0.01 0,03 - 0.16 0 0 3.90647 Note 1 6, a series of experiments 1 (contributions raw material components are taken into account in accordance with their shares) 6.1.1 a piece of chalk 54.04 0,0648 0.0432 0.2702 0.1891 0 0 0.0054 - - 0 0 0,0324 0.0108 0.0162 0 0 - 0,0486 0 0 0.66844 6.1.2 Clay kaolin 13.19 0.0158 0.0158 0,0488 0,033 0 0.0013 0 - - 0.0013 0.0013 0.0013 0.02 0,0106 0.0013 0 - 0.0013 0 0 0.15493 6.1.3 Marl 32.77 0,0492 0,0393 0.2359 0.2196 0 0.0033 0.0033 - - 0.0064 0,0007 0,0328 0,0328 0,036 = 0 0,0003 - 0,0524 0 0 0.68288 6.1.4 Raw mix control (ssk 6.1) one hundred 0.1298 0,1082 0.5549 0.4417 0 0.0046 0.0087 0.0077 0.002 0.0665 0,0636 0.0628 0.0013 0,0003 0,1023 0 0 1,52607 6.1.5 Clinker cream control (KK6-1) one hundred 0.18 0.10 0.85 0.55 0 0.003 0.0058 0.65 ^b) 0.11 ⁷⁾ 0.0058 0.001 0,047 0,064 0.056 0.001 = 0 0.08 0 0 1,92070 6.1.6 Clinker white control (KK6.2) one hundred 0.13 0,07 0.80 0.21 0 = 0 0.008 0.68 ⁶⁾ 0.02 ⁷⁾ = 0 = 0 0.003 0,041 0.012 0.002 0 0.15 0 0.10 1,51061 6.1.7 Decorative promoter (P 6.1) one hundred 1.26 0.14 0.44 3,59 0 0,0312 0,0365 0.016 0.0145 0,095 0.119 0,089 0,0244 0.019 8 - 0.124 0 0 5.6939 6.1.8 Promotional cream clinker (PC 6.1) one hundred 0.14 0.11 0.95 1,04 0 0.011 0.009 0.35 ⁶⁾ 0.05 ⁷⁾ 0.007 0.004 0,092 0.123 0.0079 0.003 = 0 0.133 0 0 2,52847 6.1.9 Clinker white control (KK- 6.2) one hundred 0.13 0,07 0.80 0.21 0 = 0 0.008 0.68 ^b) 0.02 ⁷⁾ = 0 = 0 0.003 0,041 0.012 0.002 0 0.15 0 0.10 1,51061 6.1.10 Promotional white clinker (PC 6.2), average per batch one hundred 0.10 0.05 0.83 0.17 0 == 0 0.010 0.42 ⁶⁾ 0,01 ^ύ = 0 = 0 0.004 0,028 0.008 0.001 0 0.12 0 0.08 1.39262

Notes to the table. 1: 1. By the time pyrite cinders enter the mineral formation reaction, the transition of Her (11) + О ₂ from the atmosphere of Her (111) is completed. 2. Small components in the control clinker, introduced with raw materials and dust return, functionally related to the complex mineralizer. 3. Small components in clinker released in the presence of a mineralizer. 4. Small components in the promoter 1. 5. Small components in the promoted clinker 1 (short designation PK-1). 6. Here and below, it is included in the total CaO content in clinker. The calculation of basicity is not taken into account as a parasitic phase, which distracts lime from useful clinker minerals. 7. Here and below it is included in the general content of Her ₂ O ₃ in clinker with a conversion factor of May 1. o'clock Her O is obtained from 1.11 hours Her ₂ O ₃ . The basicity calculation is not taken into account as a parasitic phase that distracts iron oxide from useful clinker minerals. 8. Taking into account the content of the main oxides 81О ₂ 62.19, А ₂ О ₃

0.29, Her ₂ O ₃ 0.11, CaO 19.47. 9. The calculation is carried out according to the formula (5) using mass quantities from this row of the table. 1, the calculated basicity of the oxides was taken from series (18) as follows: Σ ΝΕ = K (K ₂ O) -E (K ₂ O) + K (Ka2O) -E (Ka2O) + K (MdO) -E (MdO) + К (8О3) -Е (8 О3) + ^ Е12О) -Е (Е12О) + ^ ВаО) -Е (ВаО) + ^ 8гО) · Е (8гО) + ^ №О) -Е (№О) + ^ CoO) -E (CoO) + K (MP2O3) -E (MP2O3) + ^ T1O2) -E (T1O2) + ^ Cr2O3) E (Cr2O3) + ^ CuO) -E (CuO) + (MoO2) - E (MoO2) + ^ MnO2) -E (MnO2) + ^ P2O5) -E (P2O5) + ^ C12) -E (C12) + Ν (Γ2) Έ (Γ2) = 0.0405x1.46 + 0.0486x1 , 37 +

0.4283x1.04 + 0.3399x0.75 + 0.004x1.32 + 0.0081x 1.12 + 0.0647x1.09 + 0x1.07 + 0x0.91 + 0.004x0.91 + 0x 0.91 + 0, 0113x0.91 + 0.002x0.90 + 0.0176x0.90 + 0x0.88 + 0.0081x0.85 + 0x0.81 + 0.1861x0.79 + 0.004x 0.70 + 0.0008x0.56 = 1, 09966. The calculations in the remaining rows of the table are also performed. 10. Not taken into account as a small component. 11. Given the contribution to the basicity of oxides A1 and Her. 12. For reference.

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150

table 2

The calculation of the content of the promoter in the raw mix in the experiments according to the formulas (5 - 17) using a number of basicities (18), D

Test No. The estimated basicity of the control clinker, In _ss , conventional units according to the actual composition of average samples The calculated basicity of mineralized clinker, In _P1C , _conventional units, in the same samples Characteristics of the promoter: basicity, In _pgop1 , _conventional units, content No. _p , wt.% The estimated basicity of the promoted clinker, In _RS , usled Estimated basicity of the promoted mineralized clinker, V _rts , conventional one 2 3 4 5 6 Example 1, a series of experiments 1 1.1 Main minerals: (Сз8) 58.16 x 1.00 + + (С ₂ 8) 16.3 x 0.97 + + (С ₃ А) 5.5 x 1.02 + + (С ₄ AR) 16.3 x 1.00 = = 96.021 , in terms of 100% In _ss = 96.021 / / 0.9626 = 99.75. Small components: (from table. 1) 2,811. Sum: B * _ss = 96.021 + +2.811 = 98.832. Main minerals: (C ₃ 8) 62x1.00 + + (C ₂ 8) 15x0.97 + + (C ₃ A) 2.5x1.02 + + (C ₄ AP) 15x1.00 + + (C _and A ₇ -SaE ₂₎ 5,5x0,96 = 99,48, in terms of 100% _at = 99.48 / 1 = 99.48. Small components (from Table 1): 1.7189. Sum: B * _tf = 99.48+ +1.7189 = 101.1989, which is more than 98.832 for KKV 101.1989 / 98.832 = = 1.024 times. Promoter: main minerals and oxides: ((2 ^ 8) 35x0.97 + + (KS ₂₃ 8ι 1) 25x0.99 + + (С) 40х 1.07 = 101.53, so that 1.015 times higher than VeiteK · S0. Small components (from Table 1): 1.6831. Sum: 101.53 + 1.68 = = 103.21, number of _companies = (100.06 99.75) / (101.53- 99.75 ) = 0.31 / / 1.78 = 0.17 = 0.2%. The main minerals: (C ₃ 8) 74x1.00 + + (C ₂ 8) 1.7x0.97 + + (C ₃ A) 5.3x1.02 + + (C ₄ AR) 15.6x1.00 = 96 , 66, in terms of 100%: In _ro = 96.66 / 0.966 = 100.06, which is more than 100 - in ECR. Small components (from Table 1): 2.1000. Sum: B * _pc = 100.06 + 2.10 = 102.106, 1.021 times the basicity of the ECR Main minerals: (C ₃ 8) 77x1.00 + + (C ₂ 8) 1.0x0.97 + + (C ₃ A) 6x1.02 + + (C ₄ AR) 14.3x1.00 + + (ScA ₇ -СаР ₂ ) 1.7 x х 0.96 = V _rts = 101.5, which is more than 100 - for ECR. Small components (from Table 1): 2.6270. Sum: B * _rto = = 101.5 + 2.6270 = = 104.127 - 104.127 / 98.832 = 1.05 times the basicity of the spacecraft, Example 1, a series of experiments 2 1.2 Same - _Rgot 100.25 - 101.66 The 100,003- _pc 100.15 * The _Sun 102.04 - 102.24 - Example 1, a series of experiments 3 1.3 In _rgot 100.18 - 101.85 In _{the RS} 100.0003 - 100.18 * The _wasps 102,16- 102,40 - Example 2, a series of experiments 1 2.1 Main minerals: (Сз8) 62x1.00 + + (С ₂ 8) 22x0.97 + + (С ₃ А) 4x1.02 + + (С ₄ АР) 10x1.00 = 97.42, calculated on 100% In _ss = 97.42 / / 0.98 = 99.41. Small components: (from table. 1) 1.9642. Sum: Β * ". = 99.41 + +1.964 = 101.374. Promoter: main minerals and oxides: (0 ^ 8) 68.8x1.014 + + (C ₂ 8) 0.7x 0.97+ + (CbAo _{> 8} P8) 23.7x0.97 + + (Ο ₈ Ρ) 6.1χ1.041 = = 99.78, in terms of 100%: 99.78 / 0.993 = = 100.48- 1.005 times DRINKED VETSCHN · Small components (from Table 1): 2.5878. Amount: 101.53 + + 2.59 = 104.12. No. _rgot = (100,0008 - - 99.41) / (100.48 - - 99.41) = 0.59 / 1.07 = 0.55 (%) The main minerals: (C ₃ 8) 80x1.00 + + (C ₃ A) 4x1.02 + + (C ₄ AR) 10.5x1.00 = 94.58, calculated on 100%: In _pc = 94, 58 / 0.945 = = 100,0008, which is more than 100 - in ECR. Small components (from Table 1): 2.4633. Sum: B * _ro = = 100,0008 + 2,463 = = 102,469, - 1,025 times more than the basicity of ECR.

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152

one ^{2 3 4 5} 6 Example 4, a series of experiments 1 4.1 Main minerals: (C ₃ 8) 56x1.00 + + (C ₂ 8) 18x0.97 + + (C ₃ A) 7.4x1.02 + + (C ₄ AR) 14.4x1.00 = 95.408, in in terms of 100% Weight = 95.408 / 0.958 = 99.59. Small components: (from table. 1) 4,906. Sum: B * _co = 99.59 + + 4.906 = 104.496. Promoter: major minerals and oxides: (C ₃ 8) 50x1 + + (C ₂ 8) 14x 0.97+ + (C ₃ A) 4.5x1.02 + + (C ₄ AR) 4.5x1 + + (C ₁₂ A ₇ ) 3.5x0.99 + + (CA) 2xO, 97 + + (ΰ _{Ι> 5} Γ) 2χΟ, 97 ^υ + + (С4А ₃ 8) 7.5x0.94 + + (С 8) 3.25x0 , 91 ²⁾ + + (KA) 1.25x1.18 ³⁾ + + (C) 2.5x1.07 = = 94.175, in terms of 100%: 94.175 / 0.885 = 106.412 - 1.064 times higher than VeshpeI · Small components (from table 1): 3.9302. Sum: 106.412 + 3.93 = = 110.342. No. _horn = (100.14 -99.59) / (106.412 - - 99.59) = 0.55 / 6.822 = = 0.08%. The main minerals: (C ₃ 8) 76x1.00 + + (C ₃ A) 6.8x1.02 + + (C ₄ AG) 13.4x1.00 = 96.336, in terms of 100%: B _ro = 96.336 / 0.962 = 100.14, which is more than 100 - for ECR. Small components (from Table 1): 3.9065. Sum: B * _pc = = 100.14 + 3.907 = = 104.047, 1.047 times the basicity of ECR. 4.2 Same Same. No. _rgot = (100.113 - 99.59) / (106.412 - 99.59) = 0.532 / 6.822 = 0.078 = 0.08%. Main minerals: (C ₃ 8) 74x1.00 + (C) 1.6x1.07 + (C ₄ AG) 23.6x1.00 = 99.312, calculated on 100%: In _pc = 99.312 / 0.992 = 100.113> Vecr = SO · Example 6, a series of experiments 1 6.1 (С ₃ 8) 62x1,00 ++ (С ₂ 8) 14x0,97 + + (С ₃ А) 9x1,02 + + (С ₁₂ А ₇ ) 4x0,99 + + (КС ₈ А ₃ ) 2x1,05 + + (С ₄ АГ) 1x1.00 + + (С ₂ Г + СГ) 2x0.93 = = 93.68, in terms of 100% _Вс = 93.68 / 0.94 = 99.66. Small components (from Table 1): 5.6939. Sum: B * ^ 99.66 + +5.694 = 105.354. Promoter: main minerals calculated and oxides: from Clause 4.2: (C ₃ 8) 41.25 x1 + + (C ₂ 8) 0.5x 0.97+ + (C ₃ A) 4.5x1.02 + + (C ₄ AG) 9.85x1 + + (C ₁₂ A ₇ ) 0.75x0.99 ++ (CA) 0.75x0.97 + + (C1 _{> 5} G) 0.75x0.97 ++ (C ₄ A ₃ 8) 3.75x0.94 + + (C 8) 5.3x0.91 + + (KA) 2.3x1.18 + + (C) 5.3x 1.07 + From Clause 2.1: + (C ₂ 8 ) 3.75 x 0.97+ + (KS ₂₃ 8c) 3.75x0.99 + + (Ν8 _{3> 5} ) 0.6 x0.95 + + (C) 4.4x1.07 + From Clause 3.1: + (C _{3. 4} 8) 9.5 x 1.014 + The main minerals: (С ₃ 8) 78,2x1,00 + + (С ₃ А) 15,8x1,02 + + (С ₄ АГ) 3,4x1,00 = = 97,716, calculated on 100%: В _р = 97.716 / 0.974 = = 100.324, which is more than 100 - on the ECR. Small components (from Table 1): 2.5285. Sum: B * _ro = 100.324 + 2.529 = = 102.853, - 1.029 times more than the basicity of the ECR.

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154

one 2 3 4 5 6 Example 6, a series of experiments 1 (continued, beginning, see the previous page) 6.1 + (^, ^ 8) 1x0.97 + + (C ₁₈ P) 2x1.041 = = 100.109; according to actual analysis: mainly oxides: (δϊθ ₂₎ 16,38x0,83 + (A1 ₂ O ₃₎ + 7,76h0,90 (Re2O ₃₎ 4,25h0,86 + (CaO) 66,04x1,07 + ( Mg0) 0.44x1.04 + (8O ₃ ) 3.59x0.75 + (K ₂ O) 1.26x 1.46 + (M1 ₂ O) 0.14x 1.37 = = 100.0787; in terms of 100%; 100.0787 / 0.9943 = 100.6524, to 1.0065 times higher in _EuTe q. Small components (from Table 1): 5.6939. Amount: 100.6524+ +5.6939 = 106.3463. No. _p1ot = (100.324 - 99.66) / (100.6524 - 99.66) = 0.664 / 0.9924 = = 0.67%. Example 6, a series of experiments 2 6.2 (Сз8) 62x1.00 + + (С ₂ 8) 17x0.97 + + (С ₃ А) 13x1,02 + + (ССА ₇ -САР ₂ ) 3,7х х0,96 + (С ₆ А ₂ Р) 1х χΙ, ΟΟ = 96.302, in terms of 100% Weight = 96.302 / 0.967 = = 99.59. Small components (from Table 1): 1.5106. Sum: Β * _No. = 99.59 + +1.5106 = 101.1. Vrgosh according to the formula (5) and in terms of 100%: A.6.2.1 = 100.06; A.6.2.2 = 100,477; A.6.2.3 = 100,052; A.6.2.4 = 100,052; A.6.2.5 = 100.0166. No. ₁ from formula (8): A.6.2.1 = (100.16 - 99.59) / / (100.06 - 99.59) = 1.2%; A.6.2.2 = (100.16 - 99.59) // (100.477-99.59) = 0.64%, A.6.2.3 = (100.16 - 99.59) // (100.052- 99.59) = 1.23 %, A.6.2.4 = the same, taking into account 10% hydrated water 1.23x1.1 = 1.35%; A.6.2.5 = (100.16 - 99.59) // (100.0166- 99.59) = 1.34%. PC average for a series of major minerals and oxides: (C ₃ 8) 80x1.00 + + (C ₃ A) 6.8 x 1.02 + + (C _b A ₂ P) 1x 1.00 = 87.94 , in terms of 100% 87.94 / 0.878 = 100.16. Small components (from Table 1): 1.3926. Sum: B * _ro = 100.16 ++ 1.39 = 101.55.

Notes: 1. The average value of basicity between C ₂ P and CP from the series (18). 2. The same, between CaO and 8O ₃ . 3. The same, between K ₂ O and L1 ₂ O ₃ .

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156

Table 3 Actual content of oxides, minerals, marginal phases, impurities, wt.%, Calculated basicity and characteristics of the clinker microstructure

No. p / p Clinker Name ¹⁵ The content of oxides,% Vrs used The main minerals.% Marginal phases ²⁾ ,% Impurities ³⁵ Microstructure 8U ₂ A1 ₂ O ₃ KegOz CaO C ₃ 8 C ₂ 8 SzA with ₄ ag S12A7 Sg? SR from Dr K ₂ O cgo I am ⁴⁵ Cl ⁵⁾ RA ⁶⁵ one 2 3 4 5 6 7 8 nine 10 and 12 thirteen 14 fifteen sixteen 17 eighteen nineteen twenty 21 Example 1, a series of experiments 1 1.1 KK-1 21.80 5.29 5.09 65.35 99.75 58 nineteen 5,4 15,5 - - - 0.40 - 0.58 40,0 - 75 - 1.2 MK-1 22.13 5.41 5.19 65.64 99.48 62 fifteen 2,5 15.0 - - - 0.29 3.9 ⁷⁾ 0.32 29.0 - 65 - 1.3 PC-1 20.30 5.30 5.16 67.12 100.06 74 1.7 5.3 15.6 - - - 0.47 ^k) - 0.21 1.8 55 twenty 12 1.4 PMK - 1 20.38 5.39 4.49 66,99 101.5 77 one 6 14.3 - - - 0.21 1.7 ⁷⁾ 0.17 2.0 65 twenty fifteen Example 1, a series of experiments 2 1.5 PC-2: from BEFORE 20.11 20.73 5.35 5.42 4.61 5.08 66.47 66.82 CM. table 2 67 71 3 nine 5.1 6.2 14.0 15.1 0.05 0.45 0.24 0.31 1,6 60- 65 fifteen 25 10 twenty Example 1, a series of experiments 3 1.6 PC-3 from BEFORE 20.16 20.85 5.12 5.62 4.80 5.13 66.38 66.92 see table 2 66 72 4 8 5 6.5 14.1 15,5 0.4 0.8 0.28 0.40 2.2 fifty 60 10 thirty 10 twenty Example 2, a series of experiments 1 2.1 KK-2 23.94 3.60 3.44 67.14 99.41 62 22 4 10 - - - 0.46 - 0.26 14.0 - 60 - 2.2 PC-2 21.90 3.56 3.43 68.74 100,001 80 0 4 10.5 - - - 0.35 - 0.14 1.8 - 0-10 fifteen Example 4, a series of experiments 1 4.1 KK-4 20,99 5.82 4.75 64.25 99.59 56 eighteen 7.4 14,4 ₊ 10) ₊ 10) 0.31 + 1,08 21.0 - one hundred - 4.2 PK-4.1 19,99 5.41 4.41 66.46 100.14 76 0 6.8 13,4 - - 0.26- 1,5 - 0.83 1.9 one hundred twenty 5-12 4.3 PC-4.2 18.40 4.99 7.77 65.19 100,113 74 0 0 23.6 - - - 1,6 - 0.69 1.8 one hundred 0 25 P Example 6, a series of experiments 1 6.1 KK-6.1 21.88 6.68 1.21 68,20 99.66 62 14 nine one 4 2 0.8 2'0 0.22 5,6 - one hundred - 6.2 PK-6.1 20.57 6.66 1.12 69.00 100.65 78,2 - 15.8 3.4 - - 0.3 - 0.20 1,5 - fifteen 10 P Example 6, a series of experiments 2 6.3 KK-6.2 22.21 6.98 0.41 68.91 99.59 62 17 12.8 1T5G - - 0.7 3.7 ²⁷ 0.16 4.2 - one hundred - 6.4 PC-6.2 average per series 23.86 2.82 0.37 71.58 100.16 80 0 7 1 ^And) 1,5 0.11 0.8 0-10 5-15

Notes: 1 Abbreviations: KK - control clinker, MK - mineralized clinker, PC - promoted clinker, PMK

- clinker, calcined in the presence of a promoter and mineralizer, numbers - numbers of experiments in example 1, including in table. 1 and 2. B - calculated basicity according to the table. 2; 2 - C ₁₂ A ₇ - according to infrared (IR) spectroscopy; С ₂ Р and СР - according to the data of selective chemical analysis (СХА) by leaching С ₂ Р soda with boiling from the alumoferritic phase of clinker, which was previously extracted using СХА; insoluble residue - SR; C - free lime according to chemical analysis (HA) by the ethyl glycerate method; other marginal phases - alkaline derivatives of C3A and C ₁₂ A ₇ - KS ₈ A ₃ and NC8A ₃ ; 3 - from impurities, only one of the main minor components is given as having important technological value K ₂ O = No. ₂ O + 0.658 K ₂ O and Cr ⁶⁺ , the last

- in mg / g clinker; 4 - the proportion of cellular crystals,% of the total mass of alite, according to optical microscopy, in reflected light, etching with ascorbic acid (2% aqueous solution); 5 - share of clusters, i.e. intergrown crystals,% of the total mass of alite according to the same data; 6 - the proportion of X-ray amorphous phases alite a total weight from the difference between the results of determination of alite according petrographic analysis and X-ray diffraction peak on analytical alite used at 1.76 x 10 ^'10 m; 7 - fluoride derivative C ₁₁ A ₇ 'CaP ₂ , 8 - part in the form of an X-ray amorphous phase, namely about 0.22% crystalline and about 0.25% X-ray amorphous lime; 9 - together with alkaline derivatives of mayenitis; 10 - together with alkaline derivatives of calcium ferrites, in particular alkaline ferrites; 11 - KS8A3 (Suzukawa phase); 12 in the form of C ₆ A ₂ R.

157

158

Table 4

Characteristics of raw materials, operating conditions of furnaces, the quality of clinker and cement based on it

N Spo Names View and Promoter ⁴ / XV, M Κθ2 Ras- Ras. Δΐ Character; oven operation ¹¹⁵ Clinker / cement Wed ¹ ^ p / p sob components ² · * number % % ⁵⁾ % % move move ° C 0xb, m AOpechkh Temperature ° C Py Permission KN P R time- micro- ΔΩ Ct K-28 . With RA and experience that m / s one) raw mix and promoter ³ · * clinker ³ · * calc. No. beg. fact Νερ. in) 7) cheese. laugh t / t class fuel Δ "> % corps 10) % In the sintering zone decarbonization zone flue gas clinker at the exit de return,% of Guardianship burning in the oven granules mm tv erdostk cf. MPa prostrate % MPa MPa one 2 4 5 3 nine 10 and 12 in 14 fifteen sixteen 17 eighteen nineteen twenty 21 22 23 24 25 26 27 28 29th 1.1 m and, g, o; KK-1 - - - 38.5 - 1,6 1.83 one hundred 0 5.8 x 185 0 1550 940 150 110 12 2.0 0.90 2.10 1,04 11.3 58.5 - 12.0 48.7 + M: SG + I8 MK-1 - - - 39.6 0.6 1,6 1.85 1,5 0 The same +3.0 1565 925 140 105 10 1.8 O ^ P 2.08 1.05 10,2 56.4 +4 15,2 47.8 + P.’S28 + КСгз $ 11 “С PK-1 0.2 0.16 0.3 38,4 1,6 1.92 -5.2 -35 +8.5 1550 940 135 95 6 1.8 0.99 1.92 1,03 5.8 40,0 +21 18.9 58.9 + P + M PMK-1 0.15 oh 1 0.2 39.9 0.5 1,6 1.94 -6.8 -thirty + 10.1 1535 935 140 90 5 1.8 0.99 2.06 1.20 5.2 35,2 +23 20.3 60.1 1.2 m + P: C ₂ 8 + K.C8 + C PC-2 0.15 od 0.3 38,0 - 1,6 1.88 -3.5 -twenty +8.2 1550 935 130 93 6 2,5 0.96 2.01 1.05 6.5 42,4 +11 17.8 55.3 0.22 0.15 0.45 38.5 - 1,6 1.93 -7.0 -thirty +12.1 1540 945 122 95 6 2,5 0.98 2.10 1,08 7.5 47.5 +18 18.6 57.3 1.3 m + P: white. sludge + PC-3 0.18 0.08 0.3 37.6 - 1.8 1.80 -3.8 -25 +18 1520 935 115 one hundred 7 2,5 0.96 2.05 1.10 4.8 42.0 +18 17.5 57.2 K.8 + C 0.24 0.20 0.4 39.1 - 2.0 1.95 -15.8 -thirty +25 1585 945 110 107 7 2,5 0.96 2.11 1.12 7.7 48.5 +20 19,2 58.1 1.4 m P: C injected with dust return PK-4 0.2 0.15 0.3 38,0 1.8 1.85 -eighteen -thirty + 20-25 1570 950 110 110 7 255 0.96 2.12 1.10 7.1 46.5 +20 17.1 55.5 2.1 m m, marl, o; KK-2 - - - 42.3 - 4.6 1.89 one hundred 0 3.3 / 3, -6 / 3.3 0 1480 920 140 110 8 1,5 0.89 3.4 1.05 10.1 62.3 0 16, D ⁷ ' 52.8 2.2 + P (ya + a & + C) ¹⁴⁾ PC-2 0.55 0.3 0.8 42.5 - 4.6 1.92 -11 ^th * -25 x150 +18 1450 900 125 95 3 2.0 1.00 3.15 1,04 3.8 29.6 +26 19.5 ^ 63.5 3.1 from The same KK-31 0.55 0 - 1.9 1.89 one hundred lab.elek- 0 1350 0.89 3.4 1.05 0.8 40.5 15 ¹⁷⁾ 51 zT PK-31 0 No. 1 1.9 1.92 Sat ¹³⁷ trail +26 1.00 3.15 1,04 26.5 22 64 3.3 Pc-32 0 Number 2 1.9 1.92 -27 +27 24.0 25 67 3? 4 PK-33 0 No. 3 1.9 1.92 -sixteen +16 32,5 nineteen 58 zT PK-34 0 Number 4 1.9 1.92 -twenty +20 31,0 twenty 60 h7 PK-35 0 Number 5 1.9 1.92 -thirteen +13 35.5 eighteen 54 s? 7 PK-36 0 Number 6 1.9 1.92 -nine +9 35.0 eighteen 55 zT PK-37 0 Number 7 1.9 1.92 -14 +14 28.5 21 62 memory PK-38 0 Number 8 1.9 1.92 -sixteen +16 30,0 eighteen 57 evil PC- 391 0 No. 91 1.9 1.92 -12 +12 33.0 21 55 ϊΐϊ PC- 392 0 No. 92 1.9 1.92 -thirteen +13 31,0 nineteen 55 ZD2 PC- 310 0 No. 10 1.9 1.92 -10 +10 34.0 eighteen 54 Of PC- 311 0 No. And 1.9 1.92 -nine +9 36.0 nineteen 54 ΪΪ4 KK-3 - - - 18.3 - 1.9 1.89 one hundred lab. 0 1420 930 330 0.89 3.4 1.05 0.08 n / a 0 17,2 56.3 Ϊ15 PC-3 0.55 0.55 0.8 18.2 - 1.9 1.92 8 ^V> γ- oven +10 1420 930 330 1.00 3.15 1,04 0.08 n / a 14 21.3 68,4

one 2 3 4 5 b 7 8 nine 10 eleven 12 thirteen 14 fifteen sixteen 17 eighteen nineteen twenty 21 22 23 24 25 26 27 28 29th 4.1 m and + g + o; KK-4 - - - 36,2 - 2,5 1.92 one hundred 0 4x 150 0 1400 970 270 by 12 1,0 0.93 2.04 1.23 11.5 75.0 0 thirteen 48 4.2 m + P - 4 (see text) PC- 4.1 0.08 0.06 0.5 36.0 2,5 1.96 -12 35 +16 1370 950 250 90 2 1,5 1.00 2.04 1.23 5.8 46.0 nineteen twenty 56 PC- 4.2 0.08 0.15 0.7 36.0 - 2,5 1.96 -eighteen 40 +21 1370 945 230 85 2 1,5 1,02 1.46 0.65 1,1 25.8 28 eighteen 66 6.1 from and, g. marl KK- 6.1 - - 0 - 2,8 2.00 one hundred 0 3 x 52.7 0 1450 1010 450 50 ^1sh 21 1.8 0.94 2.78 5.52 10.3 48.5 0 16.5 45 + A.6.1 PC- 6.1 0.67 0.8 0.95 0 - 2,8 2.00 -22 0 +29.8 1490 1060 480 58 ^1U sixteen 2.0 1.00 2.64 5.95 6.5 30.1 +22 25.8 64 6.2 from and, g, silica gel kk- 6.2 - - - 0 - 1,1 1.93 one hundred 0 0 1550 1080 520 85 ¹ ^ 25 1,0 0.92 3.01 17.02 7.2 45,2 0 19.5 55 + P.6.2 cf. for a series, incl. PC- 6.2 cf. 21 = 1 21 0 - 1,1 1.95 -25 0 +27.6 1570 1100 540 δ? ⁵⁵ 10 1,0 1.00 7.5 7.6 1,5 23,4 +28 30.8 72 + A.6.2.1 PC- 6.2.1 21 21 21 0 - 1,1 1.95 -25 0 +27.6 1570 1100 540 85 ¹⁸⁾ 10 1,0 1.00 7.5 7.6 1,5 22.4 +27 31,0 71 btg + A.6.2.2 PC- 6.2.2 0.64 0.7 0.7 0 - 1,1 1.95 -27 0 +29.2 1590 1120 560 87 ¹ ^ 8 1,0 1.00 7.5 7.6 1,2 20.8 +33 34.0 76 btz + A.6.2.3 PC- 6.2.3 1.23 1.23 1.23 0 - 1,1 1.95 -24 0 OK. +25 1560 1090 530 85 ^1st > eleven 1,0 1.00 7.5 7.6 1.8 25.1 +25 36.5 69 1570 1100 540 85 ^14> 1.35 1.35 1.35 0 - 1,1 1.95 -26 0 approx. + 28 1550 1080 520 85 ¹ ^ 8 1,0 1.00 7.5 7.6 1,6 22.9 +25 26.3 65 540 1.34 1.4 1.4 0 - 1,1 1.95 -29 0 +30 1590 from 570 87 ^u 6 1,0 1.00 7.5 7.6 1.4 30.5 +28 35.8 77

Notes. 1. Wet (m), dry (s) cement production methods; 2. Limestone (s), chalk (m), clay (g), pyrite cinder (o), others, see separate notes; 3. Promoter compositions - see text; 4. Ν ⁰ - the initial estimated amount of the motor according to the formulas (5 - 17); ^ _Nach .fak _tons. - the actual initial amount of the promoter, Ν _ορ - the actual average amount of the promoter, wt.% clinker; 5. The moisture content of the sludge with a wet production method, wt.%; 6. Additionally introduced mineralizer, the composition, see the text, wt.% Clinker; 7. The fineness of grinding the raw mix, wt.% The residue on sieve No. 02 (with cells 200 μm = 0.2 mm); 8. Reducing specific fuel consumption, wt.% Fuel consumption in the control mode of firing - without a promoter; 9. Reducing the temperature of the furnace body in the sintering zone, ° C, compared with the control mode; 10. Designation of the type of process fuel: gas (g), fuel oil (m), coal dust (y); 11. Characteristics of the operation of furnaces: 0 x b - diameter x length, m; DR _furnace - an increase in productivity, wt.% In relation to the firing mode of the control clinker (control mode); the temperature in the sintering zone is measured with an infrared pyrometer or P1 / P1 - K-thermocouple set in the furnace head; flue gas temperature - chromel / alumel thermocouple in the dusty chamber of the furnace. Dust rotation - refers to the ratio of dust return to clinker mass,% .; 12. Average data, including microhardness — according to the data on the PMT device designed by M.M. Khrushchev, ΔΡ mills — an increase in the productivity of cement mills with normalized grinding load, corresponding to an increased grinding capacity of the clinker, wt.% When grinding the control clinker; compressive strength of cement in standard solutions: K ₁ 159

160 at the age of 1 day, K ₂₈ - the same at 28 days of age; 13. According to the petrographic analysis in accordance with the formula: КН “1 0.4х [belite / (alite + belite)], where through“ alite ”and“ belite ”the fractions of the area of these minerals are indicated, approximately corresponding to wt.%, - s taking into account the difference in the density of these minerals - in polished sections or in immersion preparations, which in this case gives: KN = 1 - 0.4 [15 / (74 + 15)] and 0.93; 14. Designations: Ba is hyperalite, and £ c is an analogue of calcium aluminoferrite indicated in the description of the invention; 15. For sintering in an electric furnace, this column provides relative data on the consumption of electricity for sintering, which is reduced due to the acceleration of sintering before assimilation of free lime; the determination of the content of free lime is carried out every 5 minutes; 16. The increase in furnace productivity is taken equal to the reduction in firing time; therefore, the data in columns 12 and 15 are the same, but have opposite signs; 17. The results of the strength tests in lines 3.1 - 3.12 are obtained by recounting the data obtained from tests of cubes with an edge of 1.41 cm on the scale specified in the description of the invention; all clinkers fired in a γ - furnace and electric furnace are characterized by hydraulic activity in such samples; 18. After water bleaching.

Table 5

Comparison of optimization of the content (wt.% Clinker) and the composition of the 4.2 promoter in the calcined material with the characteristics of the resulting clinker and cement based on it (control and optimal modes are shown in bold)

No. p / p The composition of the promoter ⁰ С ₃ 8 С ₂ 8 С ₃ А С ₄ АР С12А7 С А С15Р 8а С 8 КА С Basicity eaten Promoter supplement % Δ0 ² furnaces ² · *,% Conductivity at 1200 ° C, Ohm 'm \ x10 ⁸ The content of clusters in alite, wt% The cellular structure in alite wt% X-ray amorphous alit, wt% The content of the magnetic fraction, wt% MDO Alite,% of the total MgO content in clinker The content of K ₂ O / (C1 ₂ A ₇ + PCBA ₃ ) in clinker, wt% SL mg / kg wedge kera CaO _sv1 % _? according to chemical analysis CaO _sv2 % according to x-ray _phase analysis CaO _0v3 %, RA CaO _sv1 CaO _sv2 Molar ratio C / 8 Microhardness, MPa, cf clinker samples Κι MPa (designation see table 4) K ₂ 8 MPa (designation see table 4) one 2 3 4 5 6 7 8 nine 10 eleven 12 thirteen 14 fifteen sixteen 17 eighteen nineteen twenty one - - - 0 5 85 0 0 eighteen fifty 1,08 / 4,5 21 0.3 0.3 0 3 75 thirteen 48 2 50 14 4.5 12.5 3.5 2 2 7.5 3.25 1.25 2.5 106,412 0.06 0 7 80 0 0 sixteen 48 0.95 / 3.0 eighteen 1,0 1,0 0 3 60 fifteen 52 3 Same Same o> 1 + 3 23 60 twenty 5 fifteen 35 0.9 / 1.5 7 1,0 "0.9 "0.1 3 51 fifteen 55 4 - - 0.15 + 7 48 40 40 10 12 28 0.85 / 1.0 5 1,0 0.7 0.3 3 42 fifteen 59 5 - - 0.3 + And 65 thirty fifty thirteen 10 25 0.8 / 0.5 3 1,0 0.5 0.5 3 57 sixteen 60 6 - - 0.5 + 15 91 fifteen 70 twenty 2 twenty 0.75 / 0 2.0 1.3 0.7 0.6 3 thirty eighteen 61 7 - - 0.7 ³⁾ + 21 120 0 one hundred 25 0 fifteen 0.75 / 0 1.8 1,6 0.8 0.8 3 25.8 eighteen 66 ³ > 8 0.9 + 21 110 0 one hundred twenty 0 eighteen 0.78 / 0 1,5 1 _? 6 1,2 0.4 3.05 2.6 eighteen 65 nine - - 1,2 + 17 90 0 one hundred eighteen 0 25 0.8 / 0 2.0 1,6 1.4 0.2 3.10 thirty 17 60 10 55 106 15 1 1 1 52 1.5 7 4 · ¹ 104,502 0.5 + 18 115 0 one hundred 29th 0 10 0.75 / 0 twenty 1.8 1,2 0.6 3.17 35 fifteen 57 eleven 45 183 1063 3 10 4 5 10D ⁵ * 99,000 1,0 ⁵⁾ + 3 27 40 40 10 0 37 0.85 / 1.0 2.0 1,0 0.7 0.3 2.7 35 sixteen 54 12 55 10 5 16 2 1.5 1 5 1 5 0.5 2 2.5 ⁶⁾ 100,347 0.6 + 16 95 0 90 23 0 sixteen 0.8 / 0 1.8 1,5 one 0.5 2,8 28 eighteen 62

Notes: 1 - wt. mineral ratio, §а - calcium sulfoaluminate С ₄ А У, КА - alkaline aluminates and ferrites. 2 - change in furnace productivity. 3 - optimum. 4 maximum basicity for the content of CaO in the promoter, not coinciding with the maximum level of basicity according to the invention In _Rgot . 5 - does not satisfy the requirements of the present invention in terms of basicity; 6 - non-optimal composition according to the invention near the lower acceptable level of basicity of the promoter

Table 6

The results of rational chemical analysis of samples of control clinkers (CC) and promoted clinkers (PC)

Pro- ba Component (mineral) Content, wt.% Mass ratio Molar relationship The composition of the component (mineral) XRF Alita ¹ 8U ₂ A1 ₂ Oz Re ₂ Oz CaO MgO 80h SG ₂ 0Z p ₂ 0 ₅ Amount C / 8 C / A C / R C / 8 C / A C / R one 2 3 4 5 6 7 8 nine 10 eleven 12 thirteen 14 fifteen sixteen 17 eighteen nineteen KK-2 Alit 16.30 0.15 0.06 45.78 0.38 0.09 0.08 0,03 62.87 2,833 305.2 763 3.00 554.5 2179 SzAossg 8 When <1 = 1,76 · • U 'peak ^10m 2; There are no DR doublets. Whitens 7.56 0.09 0.02 14.39 0.08 0.10 0,03 0.04 22.31 1,903 159.9 719.5 2.04 290.7 2055 CrA), 0034 ^ 0.98 Tricalcium Aluminate 0,03 1.45 0,07 2.44 0.02 0.06 = 0 ao 4.07 81.3 1,683 34.86 86,99 3,059 99.56 Sz, obARo, 01 Alumoferrite Ca 0.05 1.91 3.29 4,53 0.28 0.09 0.04 0.01 10,20 90.6 2,372 1,377 96.90 4,312 3,933 C4Ao.9 ₃ P1.02 Amount 23.94 3.60 3.44 67.14 0.76 0.34 0.15 0.08 99.45 - - - - - - - PC-2 Alit 21.68 0.02 = 0 61.14 0.16 0.02 0.01 = 0 83.03 2,820 3057 “OO 3.02 5558 and oo Sz, 02§ There are 3 peaks, another 2 other doublets. Whitens Tricalcium Aluminate 0.01 1.40 0.02 2,58 0.01 0.04 = 0 = 0 4.06 258 1,843 129 275.9 3.35 268.5 Sz, 35ARo, 0027 Alumoferrite Ca 0.21 2.14 3.41 5.02 0.87 0.36 0.21 0.17 12.39 23.9 2,345 1,472 25.57 4,265 4,205 S ₄ Ao.94rO, 95 Amount 21.90 3.56 3.43 68.74 1,04 0.42 0,03 0.17 99.48 - - - - - - -

Notes. 1 - XRD data refer to a powder x-ray, CuK _a radiation,

A1 filter. Doublets in usually single reflexes are the result of the formation of solid solutions. In promoted clinkers, doublets are also found at C3A at the analytical peak at 4 = 2.69 · 10 ^-10 m, at C ₄ AR at the analytical peak at 4 = 2.69 · 10 ^-10 m at

161

162 a clear decrease in the intensity, in the presence of doublets at the alkaline derivatives of these phases, etc. On the whole, this characterizes the apparent deviations of the X-ray diffraction patterns and the structure of the crystal lattices of clinker minerals in promoted clinkers, which was indicated by the term “hybridization” above, since there were no other reasons than the introduction of promoter in the composition of the calcined material, and the crystal structure of the minerals of the promoter to the maximum extent differed from that characteristic of Portland cement clinkers.

Table 7 Selection of the mode of promoting mineral formation during clinker firing by means of an adaptive iterative approach and technological methods for dust return in combination with the supply of a promoter (P), a mineralizer (M) for various types of fuel (fuel oil - m, coal - y) and types of feed to the raw material furnace mixture (ss) and dust return (p) captured from the furnace exhaust gas

No. p / p Promoter number Additive P,% May. clinker Mineralization No. ra Additives,% May. clinker Type of fuel (M, y) Δ <2 ovens % Temperature, ° С, in zones ⁴ 'fuel consumption ΔΕ furnace% ⁵ ' AA Ch. drive% ⁶ ' ΔΑ smoke sa% Δν _η % ⁷⁾ max. Lu _d % ⁸ 'max. Vacuum,%, in The content in the exhaust gas,% 1 / Vna cold about cut%, ¹² ' HF at the inlet to the filter%, ¹³ ' ΔΡ% dust mass ¹⁴ ' δα ¹⁵⁾ Hung. first air% ΔΑ ¹⁶⁾ Hung. second, air,% Types ¹⁷ 'feed PD1i DUST Types ¹⁸ 's. and processing "28, MPa nineteen) sintering / decarbonization heating flail this topic ¹⁵ OTX. ² 'gases second, air ³ ' furnace head HALL. sawn-off ⁹ 'furnace before smoke with ₂ w) about ₂ I) one 2 3 4 5 6 7 8 nine 10 P 12 thirteen 14 fifteen sixteen 17 eighteen nineteen twenty 21 22 23 24 25 26 27 28 29th thirty 31 one - - - - m 0 1400/970 570 375 270 690 one hundred 0 0 0 0 0 one hundred one hundred one hundred 24 1.8 one hundred one hundred 0 0 0 - BUT 48 2 4.2 0.06 - - 0 1450/1000 600 390 280 695 one hundred -one +2 0 0 0 105 110 105 25 1.7 95 98 0 0 0 BUT BUT - ₃ 20) 0.06 - - +2.5 1420/980 575 380 270 700 +1.5 0 +1.5 + 1 0 0 one hundred one hundred one hundred 25 1,6 96 99 - 0.5 0 0 BUT BUT 52 4 0.1 - - +2.5 1450/1000 600 390 280 700 +1.5 - 1.5 + 2 + 1 0 0 105 by 105 25 1.7 95 98 - one 0 0 BUT BUT - 5 od - + 3 1420/980 575 380 270 705 + 2 - 2 0 + 2 0 0 one hundred one hundred one hundred 25 1.7 94 96 - 3 0 +2.5 BUT BUT 55 6 0.15 - - + 3 1480/1020 610 400 290 705 + 2 - 2 0 + 2 0 0 110 115 105 1.9 95 95 96 - 4 + 1 +2.5 BUT BUT - 7 0.15 - + 7 1450/990 580 390 280 710 + 3 - 2.5 -1.5 + 4 0 0 105 110 one hundred 25 1.7 94 95 - 10 + 2 +3.5 BUT BUT 59 8 0.3 - - + 7 1480/1015 615 405 205 710 + 3 - 2.5 -1.5 + 4 0 0 110 115 105 25 1.9 95 94 - 10 +2.5 +3.5 BUT BUT - nine 0.3 - +11 1450/980 590 400 280 725 + 4 - 3 - 2 + 5 0 0 105 by one hundred 25 1.7 93 90 - sixteen +5.5 + 4 BUT BUT 60 10 0.5 - - +11 1480/1010 620 410 300 725 + 4 - 10 - 5 + 5 0 0 110 115 105 25 1.9 90 88 - nineteen +6.5 + 4 BUT BUT - eleven 0.5 - - +15 1450/990 600 400 280 740 + 5 - eleven -5.5 + 6 0 0 105 by one hundred 26 1.7 85 86 - 21 +8.5 +5.5 BUT BUT 61 12 0.7 - - +15 1490/1025 630 420 310 745 + 5 - 12 - 6 + 7 0 0 110 115 105 25 1.9 83 85 - 24 + 9 +7.5 BUT BUT - thirteen 0.7 - - +21 1450/1000 610 400 280 750 + 7 - 12 - 6 + 7 0 0 105 110 one hundred 26 1.7 81 83 - 28 + 11 + 9 BUT BUT 66 14 - - one 0.35 + 3 1370/950 550 350 260 650 - 1.5 + 1 + 2 + 1 0 0 one hundred one hundred 110 23 2.0 105 102 + 3 + 1 0 BUT BUT 49 0.06 " ’’ + 3 1430/1000 610 400 290 700 - 2 0 0 + 2 - 5 - 5 105 by 115 22 2.0 3 95 - 2 + 1 0 BUT - - sixteen 0.06 + 4 1400/980 570 380 275 710 0 - 1.5 0 + 1 0 0 one hundred one hundred 110 25 1.7 90 92 - 5 + 1 + 2 BUT BUT 56 17 0.15 ... + 4 1480/1020 615 405 285 715 + 1 - 3 - 4 + 2 0 0 110 by 115 25 1.8 87 89 - thirteen + 2 + 3 BUT BUT - eighteen 0.15 -10 1450/990 590 390 280 720 + 3 - 5 - 5 + 4 0 0 105 105 110 25 1,6 82 84 - 21 + 5 + 5 BUT BUT 64 nineteen 0.5 = 10 1500/1030 630 410 290 740 + 3 - thirteen - 5 + 4 0 0 110 by 115 24 2.0 80 82 - 25 + 5 + 5 BUT BUT - twenty 0.5 +19 1470/1000 610 390 280 745 + 5 - thirteen - 5 + 6 0 0 105 105 110 25 1.8 80 82 - 25 + 7 + 7 BUT BUT 65 21 0.7 +19 1490/1020 625 405 290 755 + 5 - fifteen - 6 + 7 0 0 110 110 115 25 2.0 70 75 - 32 + 7 + 8 BUT BUT - 22 0.7 +25 1460/1000 605 395 285 750 + 7 - fifteen - 6 + 7 0 0 105 105 110 25 1.7 70 72 - thirty + 10 + 12 BUT BUT 70 23 0.7 - - +22 1440/995 600 390 270 750 + 7 - 12 - 6 + 7 0 0 105 110 one hundred 25 167 80 80 - thirty + 12 + 9 < BUT 70 24 0.7 - +21 1440/995 600 390 270 750 + 7 - 12 - 6 + 7 0 0 105 by one hundred 25 167 80 80 - thirty + 12 + 9 B, G1 BUT 70 25 0.7 - - +22 1440/995 600 390 270 750 + 7 - 12 - 6 + 7 0 0 105 by one hundred 25 167 80 80 - thirty + 12 + 9 G2 BUT 70 26 0.7 one 0.35 +24 1470/1000 605 395 285 750 + 7 - 14 - 6 + 7 0 0 105 105 110 25 167 70 72 - thirty + 10 + 10 DE1,2 BUT 70 27 0.7 +22 1430/980 600 380 280 750 + 7 - sixteen - 8 + 7 0 0 one hundred by one hundred 26 166 75 77 - 28 + 12 + 10 G1 BUT 65 28 0.7 +25 1450/1000 605 395 285 750 + 7 - 14 - 6 + 7 0 0 105 by one hundred 25 157 55 57 - 40 + 16 + 12 m, n BUT 68

one 2 3 4 5 6 7 8 nine 10 eleven 12 thirteen 14 fifteen sixteen 17 eighteen nineteen twenty 21 22 23 24 25 26 27 28 29th thirty 31 29th 4.2 0.7 | 21) 0.35+ 16.75 m +30 1400/970 580 365 270 750 + 9 - 5 - 7 + 9 0 0 one hundred one hundred one hundred 26 1,6 fifty fifty - fifty + 15 + 15 G2 B 70 thirty 2,5 one 0.35+ 21.75 At +20 1450/1000 605 395 290 700 ₊ 10 ²² ' - 5 + 5 +15 10 10 one hundred one hundred one hundred 26 166 82 80 - 25 + 15 + 15 G2 B 60 31 0.7 - - m +18 1430/980 600 380 280 750 + 7 - 14 - 6 + 7 0 0 105 105 110 25 1.7 80 82 - 25 + 7 + 7 s and BUT 65, 62 ²³ ' 32 0.7 - +10 1450/1000 570 365 270 690 + 5 - 8 - 2 +10 0- (-5) 0 95 105 110 25 1.8 92 94 - 12 + 5 + 4 to BUT 55 33 0.7 - - +13 1420/980 590 390 280 700 + 4 - 10 - 5 + 5 0 0 one hundred one hundred one hundred 25 1.7 90 92 - fifteen + 7 + 7 l BUT 58 34 - - +20 1500/1050 630 Zzg 430 770 + 5 - 10 - 5 +10 0 0 one hundred 120 110 28 0.8 120 123 + 20 + 20 + 15 - IN 49 35 0.7 - - +30 1500/1070 640 450 770 + 10 - fifteen - 12 + 7 0 0 110 110 but 26 1.3 95 97 - 5 + 18 + 15 BUT IN 54 36 0.7 one 0.35 +32 1490/1050 630 - 430 760 + 11 - 12 - 8 + 9 0 0 105 110 115 25 1,6 92 92 - 7 + 20 +20 BUT IN 59 37 - - - - gas 0 1450/1000 600 450 ^ 640 ^D ' one hundred 0 0 0 0 0 one hundred one hundred one hundred 25.7 0.7 one hundred one hundred 0 0 0 - BUT 45 38 6.1 0.67 ² ” - - +6.4 1476/1050 620 - 470 * 0 655 +1 -6 -3 +2 0 0 105 by 105 26.1 0.5 78 80 -25 -6 +35.9 B BUT 54 ³⁰ ' 39 0.95 ² ” - - +7.5 1410/1060 630 - 480 670 +3 -8 -6 +3 0 0 107 by by 27.0 0.35 55 60 -35 - - B BUT 84 ^

Notes. 1 - at the exit from the chain system; 2 - exhaust gases on a cold edge of the furnace; 3 - secondary air in the shaft of the refrigerator; 4 - current, m ³ / h or t / h, in% of the amount during firing of the control clinker; 5 - change in energy consumption for rotation of the furnace,%; 6 - change in the amperage of the main drive of the furnace; in the next column - the change in the amperage of the smoke exhaust,%; 7 - frequency of rotation of the furnace,% of maximum value; 8 - the same, smoke exhaust; 9 - change in vacuum at the entrance to the dust chamber compared to the control mode during firing of the control clinker; 10 - change in the content of CO ₂ in the exhaust gas; 11 the same, O ₂ ; carbon monoxide in the exhaust gases appears sporadically and is among the alarms, not regulation; 12 - change of dust content of exhaust gases on a cold edge of the furnace by absorption of γ - radiation with the calculation of dust removal according to the proportional dependence of Lambert - Baer (1.B - law); 13 the same, on the exhaust gas path before entering the electrostatic precipitator; 14 - change in the current mass of captured dust on a belt scale at the installation for returning dust to the furnace; 15 - change in the amperage of the primary air fan; 16 change of amperage of the secondary air fan; 17 - techniques for supplying a promoter (P), a mineralizer (M), when applied and returning dust (p) to the calcined material: A - P

163

164 is added to the finished raw material mixture directly in front of the furnace through a mixer; when using the mineralizer, it is added to the raw material mixture during grinding, and the dust is returned to the furnace from the hot end; B - P is added to the raw material mixture when grinding the latter, the rest of the materials according to item A; B - P is added to the raw material mixture by mixing with it in a vertical pool, the rest are of type A; G1 - P is mixed with the calcareous component of the raw mix, then introduced into the raw mill during joint grinding with the other components of the raw mix, the rest are of type A; G2 - the same with the glandular component; D - P and M are introduced together into the raw mix of type A; E1 - P is introduced with the calcareous component, M is mixed with the glandular component of the raw material mixture, then introduced into the raw mill during joint grinding of the components; E2 - the same, with the introduction of M into the raw mix containing P; G1 - P and dust is introduced according to type A, M, if any, is introduced from the hot end; G2 - the same, when feeding the calcareous component M from the hot end, the remaining components of M - according to the type E2. З - П and dust are added to the raw mix through the mixer separately before firing; And - the same thing, together; K - P is pre-mixed with dust and injected from the hot end; L - half of the mass P is introduced from the hot end of the furnace together with dust, the other half of P is added to the finished raw material mixture of type A; M - reception with the initial supply of dust from the hot end of the furnace to facilitate the set of coating in the sintering zone and in the preparation zones of the furnace, then the transition to the return of dust from the cold end of the furnace; H - reception with the initial supply of dust from the cold end and after a set of coating with the transition to the return of dust from the hot end of the furnace; 18 - types of supply of raw mixes to the furnace and their processing: A - according to example 4; B - the same, with the supply of about half of the lime component in the form of lime flour by blowing into the furnace from the hot end, separately from dust, also returned from the hot end; the rest of the lime and other components of the raw mix are fed into the furnace from the cold end; C - before entering the furnace, the raw material mixture is decarbonized in suspension in a model drum rotated at a speed of 0.85 - 0.98 critical, through which the furnace exhaust gases are passed, with additional heating of the drum, approximately 30% of the process fuel, with the remaining materials supplied type A; 19 - compressive strength at 28 days of age of standard samples of cement-sand mortar made in accordance with GOST 310-85 based on cement with a specific surface of 330 ± 10 m ² / kg, ground in a laboratory mill with a technical characteristic according to example 3; 20 - after a period of 4 to 5 durations of the response time of the furnace unit to a change in the furnace power, in this case (4 - 5) x 1.5 hours and (6 - 7.5) hours. Thus, each of the modes characterized in lines 3-13 and 15-22, divides the period of time on average 6-7.5 hours; the modes in lines 13 and 22 are basic - continue to completely stabilize the parameters for about 1 day; clinker firing modes, characterized in lines 23 to 36, also continue for about 1 day each; 21 - clinker firing mode, in which part of the calcareous component of the raw material mixture, counted as a component of the mineralizer, is blown from the hot end of the furnace after preliminary drying in a drum and dry grinding of limestone to obtain lime flour; to blow the latter from the hot end, use a conventional pneumatic transport pump with a minimum air flow; the remaining calculated part of the calcareous component, the clay component and the glandular component are prepared as a mixture in the usual wet way and the resulting slurry with a low KH value (not more than 0.8) is fed to the furnace from the cold end together with the promoter; 22 - the consumption of coal fuel is taken equal to 100% when converted to the thermal equivalent of fuel oil in accordance with the calorific value; during the firing period, the rotary kiln was equipped with both a grinding compartment for coal and a fuel oil facility for receiving and heating fuel oil to 110 -115 ° C before being fed to the fuel burner. The quality of cement both in the presence of a promoter during clinker burning on fuel oil and coal, and in the absence of a promoter, when switching from coal to ash-free fuel, increases by about a grade (9.8 a 10 MPa); 23 - a lower value of cement strength is noted when the promoter is jointly fed together with dust from the cold end (option I); 24 - periodic ring formation at the exit of the sintering zone; 25 - firing control clinker in the presence of an experimental decarbonizer, in which the fired material is maintained in a loose suspended state, the data relate to the degree of decarbonization in the experimental unit 85 - 90%; while in the decarbonizer spend about 40% of the process fuel; the product of the decarbonizer is fed into the rotary kiln approximately in the middle of the length through 4 hatches equipped with hinged and closing lids; thus, material does not pass through the chain system of the furnace; 26 - the promoter is fed into raw flour when it is ground before being fed to the decarbonizer; 27 - a number of stages of adaptation - iteration is omitted; 28 - at the outlet of the baking heat exchanger; 29 - at the entrance to the planetary (recuperator) refrigerator; 30 with a parallel increase in air resistance, i.e. durability after 200 cycles of moistening165

166 curing / drying of the samples after a 28-day composition by 32 and 65%, respectively.

hardening versus control Table 8 Test results of the physical and mechanical properties of cements obtained according to the proposed method and control with various types of gypsum ingredient and based on binary mixtures of promoted and conventional Portland cement clinkers

No. p / p The composition of cement, in parts by weight Physical and mechanical characteristics Clinker, content, parts by weight Gypsum component, amount, parts by weight per 100 parts by weight clinker in terms of 8O ₃ Cement paste Cement-sand, standardly made mortar 1: ³⁾ To ^υ 1x _{ng of} may. % Setting time, h, - min. W / C ²⁾ RK ⁴⁾ mm Compression strength ⁵⁾ under conditions of normal hardening, N / mm ² , aged Compressive strength, N / mm ² , after steaming ⁶⁾ through Start end 1 day 3 days 7 days 28 days 1 day 28 days one 2 3 4 5 6 7 8 nine 10 eleven 12 thirteen 14 1st series of experiments 1.1 PMK-1,100 ΙΑ- gypsum stone, 3,5 24.00 2-50 4- 45 0.4 111 20.3 32.8 45.4 60.1 32.6 63,4 1.2 ——— 1B - two-water gypsum, 2.0 24.50 2- 25 4-10 0.4 111 22.5 34.0 48.0 63.6 33.1 63.8 1.3 - ΙΒ - natural anhydrite, 1.5 25,50 1- 35 2- 45 0.4 108 20,4 33,2 46,4 66.5 30,0 65.9 1.4 ——— PA - phosphogypsum, 2.0 23.25 3- 55 5- 45 0.4 113 18.2 30.7 48.1 65.8 29.7 61.1 1.5 ——— PB - Borogypsum 2.0 23.25 4-50 5-55 0.4 113 17.9 29.4 39.9 59.7 29.6 60.8 1.6 - IV - titanogypsum 3.5 25.75 2- 35 3- 45 0.4 by 26.5 40.3 55.7 69.9 35.8 70.3 1.7 - PG - citrogypsum 2.0 23,20 3 - 40 5 - 20 0.4 113 19.6 33.5 48.0 63.7 28.6 61.9 1.8 ——— CD - Fluorohydrite 2.0 25,50 2- 55 4- 55 0.4 113 19.0 29.7 38.9 59.6 31,4 62,2 1.9 ——— ША - from coal burning, 2.0 24.00 2-40 4- 35 0.4 112 20.5 35,4 40.1 59.8 31.6 60.9 1.10 1PB - from the burning of fuel oil, 2.0 24.00 3-10 5-15 0.4 113 19.3 29.9 34.2 59.7 34.7 60.9 1.11 1UA - a mixture of ΙΑ and ΙΒ 1: 1, 2.0 24.00 3-15 4-10 0.4 112 21.6 34.7 46.8 64.6 35.0 66,2 1.12 ——— GUB1 - a mixture of ΙΑ and PA 1: 3, 2.0 24.00 3 - 40 4-40 0.4 112 19.5 32,4 49.5 66.3 34.1 67.5 1.13 ——— HUB2 - a mixture of ΙΑ and PA 1: 1, 2.0 24.00 3 - 00 4-20 0.4 112 20.9 32.9 50,4 64.0 37.0 68,4 1.14 - 1UB1 - a mixture of ΙΑ and PA 3: 1, 2.0 24.00 2- 45 4-20 0.4 112 22.4 33.7 50.7 64.0 36.5 76,2 1.15 - 1UV-mixture 1Bi2V 1: 1, 4,5 25.55 2-15 3-30 0.4 111 29.0 39.1 56.8 68.3 38,4 72,2 1.16 KK-1,100 ΙΑ - gypsum stone, 3,5 23.75 3 - 40 5- 25 0.4 111 12.0 26.0 31,0 48.7 24.7 45.6 1.17 ——— ΙΥΒ- mixture! Bi2V1: 1, 4,5 25.00 3-00 4-15 0.4 by 15.4 27.6 31,0 55.2 26.6 48.8 2nd series of experiments 2.1 PMK-1. 83 KK-1, 17 ΙΑ - gypsum stone, 3,5 24.00 3-00 4-50 0.4 111 20,0 31.7 44.0 58.9 33.5 60.0 2.2 PMK-1, 67 KK-1, 33 ——— 23.95 3-10 4- 55 0.4 111 18.9 30.5 40,2 56.0 31.8 58.4

one 2 3 4 5 6 7 8 nine 10 eleven 12 thirteen 14 2.3 PMK-1. fifty KK-1, 50 ΙΑ - gypsum stone, 3,5 23.95 3 - 15 5 - 15 0.4 111 17.3 29.9 38.6 54.5 30,0 55.5 2.4 PMK-1. 17 KK-1, 83 ——— 23.75 3 - 30 5 - 20 0.4 111 15.0 27.1 33.9 52.3 28.8 51.9

Notes: 1 - water content in cement paste of normal density; 2 - water-cement ratio corresponding to the spread of a standard cone according to GOST 310.1 108 - 113 mm on a standard shaking table with a shaking frequency of 1 min ^-1 ; 3 - according to GOST 310.2, made of cement, water and sand of the Volsky deposit, quartz, consisting of rounded grains, standard, with particles of a fraction of size 0.9 - 2 mm (90%); 4 - the cone spread on the specified shaking table, characterizing the consistency of the solution; this indicator is used to select the water content in a standard cement-sand mortar; 5 - in beam samples 4x4x16 cm in size at three-point fracture in bending and compression test of halves samples in accordance with GOST 310.4; 1 N / mm ² = 1 MPa; 6 heat-moisture treatment (TVO) mode: preliminary exposure - 2 hours, temperature rise from 20 to 80 ° С - 3 hours, isothermal heating - 6 hours, cooling to 20 ° С - 2 hours.

167

168

Table 9 The results of physical and mechanical tests of cements obtained according to the proposed method by grinding with additives: grinding intensifiers, as well as by joint or separate grinding, followed by mixing with active silica, active mineral additives, fillers, water-reducing, fibrous and water-retaining components

The composition of cement, parts by weight ^υ wedge- ker grinding intensifier ²⁾ (I) / active silica active mineral supplement filler ⁴ ) (N) / water retention additive water-lowering component ³ ) (VK) fibrous component ⁵ ) (B) 2 3 4 5 6 7

Βθ08 May. % ^b)

The increase in specific surface

Physical and mechanical characteristics cement paste cement mortar Beard test of normal density wt.% Setting time, h, - min. Decrease in water separation, May. % - av ⁸⁾ W / C ⁹⁾ Compressive strength, N / mm ² , after Start end normal hardening TVO ¹⁰⁾ , through 1 day 28 days 1 day 10 eleven 12 thirteen 14 fifteen sixteen 17

Cements obtained by the method according to the invention based on the promoted clinker

10,2

: ΙΑ 0.15

And: 1B 0.12

And: DV 0.3

I. ΙΓ 0.3

And: PA 0.15

And: PB 0.15

And: PV0.15

And: PG 0.25

And: PD 0.25

And: SHA 0.3

And: SB 0.3

And: GUA 0.3

And: lip 0.3

And: UA 0.35

And: U11A1 0.4

And: U11A2 0.5

And: U11B1 0.3

24.20

24.35

24.20

24.05

23.25

23.15

23.20

23.25

23.25

22.00

22.00

22.50

22.55

23.25

23.00

22.45

2- 35

2-20

2-30

2-45

3-10

- fifteen

2- 55

2-35

2-20

3-05

3-05

3-05

3-10

2-50

2- 45

2- 35

0.4

0.4

0.4

0.4 0.39 0.39 0.38 0.39 0.38 0.37 0.37 0.37 0.37 0.37 0.38 0.38

169

170

one 2 3 4 5 6 7 8 nine 10 eleven 12 thirteen 14 fifteen sixteen 17 fifty - - ΙΑ 104- IG 75 ¹⁴⁾ - - 11.0 28 27.75 4-15 5-20 0.4 And, 1 49.9 28.6 51 ——— - - - N: GUA 10 - 10.9 5 23.75 3 - 30 5-10 - 0.4 15.3 52,5 26.2 52 - - - N: lip 10 - Π, 7 - 23.15 3 - 40 5- 25 - 0.4 16.8 54.6 29.9 53 - - - N: GUV 10 - 11.3 - 23.10 3 - 25 5-30 - 0.4 17.4 51.0 30,0 54 PMK 1,100 - - - N: GUT 10 - 11.2 - 24.55 3-00 4- 55 - 0.41 14.6 49.3 31.8 55 - - - - 1A2.0 9.6 8 23.75 2- 25 4-15 - 84 0.4 23.5 62.7 34.6 56 - - - - - 1B 1,5 9.8 6 23.85 2-30 4-20 - 71 0.4 23.0 62.0 34.3 57 - - - - - ΙΒ 1,0 9.9 10 23.70 2-30 4- 25 - 59 0.4 22.9 61.8 33.7 58 .— - - - - ΙΓ 0.5 10.0 eleven 23.75 2-15 4-20 - 57 0.4 22.7 58.4 33,4 59 And: PB 0.18 ΙΑ 10 - - - 7.2 sixteen 24.00 2-15 4-15 - 40 0.4 21.5 66.1 39,4 60 - And: SHA 0.3 ΙΑ 10 - - - 6.8 twenty 22.50 2- 25 4-30 - 0.4 25.9 70,4 42,4 61 - And: ΠΙΑ 0.3 ΙΑ 10 PG5 N: lip5 ΙΑΙ, Ο 7.5 23 23.00 2-15 4-10 - fifty 0.39 26.9 72.5 45.1 62 ——— - - - B: UA 1.5 1B 1,5 11.3 - 24.30 3 - 10 4-20 - 0.41 23.3 57.6 35.0 63 - ”- - - - B. UB 2.5 - 12.0 - 25.00 3-15 4- 25 - 0.41 24.8 63,4 37.7 64 And: ΠΙΑ 0.3 ΙΑ 10 PG5 B: UB 2.5 ΙΑΙ, Ο 12.5 - 24.60 2- 55 4-20 no water separation 0.41 27.0 73,4 45.9 Cements based on control clinker 65 kk- 1,100 - - - - - 12.3 - 23.75 3- 25 4- 55 - 0.4 12.0 48.7 24.7 66 I1B0D2 __ - - - 11.5 6 23.55 3-10 4- 25 0.4 12.0 46.5 26.7 67 ——— And: UA0D5 - - - - 9,4 3.3 23.40 3-40 4- 55 - 0.39 14.0 51.5 28,4 68 - - ΙΑ 10 - - - 11.9 23.65 3-05 4-20 - 3,5 0.4 14.3 49.9 27.0 69 - - ΙΑ 10 - - 10.8 12 25.85 4-50 4- 45 - fifteen 0.4 P, 5 46.3 23.5 70 - - ΠΙΑ 40 - - 14.6 - 22.75 4-05 6-10 - 0.4 7.6 40.5 25,4 71 - - SHG1 - - 11.0 4,5 24.15 2- 45 4-05 - 4 0.4 13.6 50,2 26.9 72 - - - - H: IVA 10 - 12.1 - 23.65 4- 35 5- 45 - 4 0.4 9.7 43.5 24.0 73 - - - - ΙΑ 2.0 10.5 6 23.85 3-15 4- 35 - 51 0.4 14.2 49.9 25.5 74 - And: SHA 0.3 ΙΑ 10 - - - 9.1 10 23.75 3-05 4- 35 - 0.4 13.8 52.9 29.8 75 And: SHA 0.3 ΙΑ 10 PG5 B: UB 2.5 ΙΑΙ, Ο 13.8 - 24.00 3- 25 4- 25 - 60 0.4 15.1 54.5 30.1

Notes: 1 - gypsum stone was used as a gypsum component in all formulations - gypsum component TA - see table. 8; 2 - as intensifiers of grinding in relative humidity) at a temperature of 20 ± 3 ° C; the liquid is aspirated by the water pump as it appears and weighed minus the solid evaporated residue, and the results of the experiments, the results of which are given in this table, use materials used also as water-reducing components, with the exception of amino alcohols (monoethanolamine GA and triethanolamine 1B - 1G); 3 water-reducing component leads to a decrease in water content in the test of normal density and the value of W / C cement-sand mortar; 4 - the filler in this case, as usual, leads to an approximately linear decrease in the strength of cement depending on its content; 5 - the fibrous component leads to an increase in bending strength by about 7-15% (not shown in this table), and only in combination with other additives, to an increase in compressive strength, since the introduction of the fibrous component somewhat reduces the content of cement of medium fraction (5-30 microns), which does not significantly increase the compressive strength of cement; 6 - fineness of cement grinding is determined by wt.% Residue on sieve No. 008; the specific surface does not completely correlate with this value for cement with additives; 7 the increase in specific surface area is determined as indicated in the text of the description; it is an indicator of the intensification of cement grinding in the presence of this additive or reflects the high grindability of active mineral additives of sedimentary origin; 8 - water separation is fixed by the liquid layer, where is attributed to the mass of cement in the composition of the test; reduction of water separation is noted in this table with the sign -; a dash means no decrease in water separation; 9 - the value of W / C of cement-sand mortar when determining the strength of cement is selected according to the spread of the cone from the specified solution on a standard shaking table with an oscillation amplitude of 1 cm at a frequency of 1s' ¹ after 30 shakes; the cone spread should be in the range of 108-113 mm; 10 - heat and humidity treatment (TVO) - according to example 3 and table. 8; 11 - a product of co-grinding; this note is indicated only when compared with separate grinding followed by mixing; in other cases, the mention of joint grinding is omitted; 12 is a product of separate grinding with subsequent mixing; 13 - when the content of the clinker component 15 wt.h. per 100 parts by weight its amount with an active mineral additive is the content of the gypsum component (omitted in the table), in all cements, with the exception of this one, taken equal to 2.7 May. hours in terms of 8O ₃ ; in this cement, the content of the gypsum component is taken to be equal to 3.5 wt.h. in terms of 8O ₃ ; 14 - cement, including 85 wt.h. active mineral additives and 15 parts by weight clinker component, receive only on the basis of a promoted clinker. On the basis of the control clinker, in view of the low strength of the composition, it is necessary to make the cementable test to be done, for example, when determining the cement setting time; determination is carried out in an air-humid environment (100% ment with standard strength characteristics fails.

171

172

Table 10

The results of physical and mechanical tests of expanding cements obtained according to the proposed method by co-grinding or separate grinding followed by

The composition of cement, wt. hours

cement mortar sand mortar

Other

Compressive strength, N / mm ² at normal hardening

Setting time, hours - min expanding component

Expansion in humid conditions, x10 ~ ⁵

Physical and mechanical characteristics ¹ ^ by mixing a promoted clinker with an expanding component and a gypsum component with gypsum stone (the table shows in terms of 8О ₃ )

Notes. 1 - designations of clinkers, see table. 1 - 4 and in the text; 2 - alumina clinker (A) or alumina clinker (B); 3 sulfoaluminate clinker (A) or material including calcium sulfoaluminate (SAK, C ₄ A ₃ $) - (B); 4 - sulfoferrite clinker (A) or material including calcium sulfoferrite (SFC, C ₄ P ₃ $) - (B); 5 - hyperalitic clinker (A) or products of its grinding in a lying state (B); 6 - metallurgical slag containing more than 10 wt.% A1 ₂ About ₃ : in the form of C12A7 (A); in the form of CA (B); 7 - rocks with 4.5 wt.% Water-soluble A12O3 and more: shale (A), bauxite (B), pumice-type euphusic rocks, high aluminate (C), liparites (G); 8 - quicklime (A); the same, in a mixture with freshly burned magnesia in a ratio of 1: 1 (B); 9 - fineness of grinding according to the size of the residue on sieve No. 008; 10 - test methods - according to GOST 310. 1 - 4; heat and moisture treatment (TVO, steaming) - according to the mode according to example 3 and table. 8; expansion tests - in samples of prisms 4x4x16 cm from a cement-sand mortar of the composition cement / sand 1: 1 by weight; samples are stored in air-wet conditions for 90 days, measurements are carried out in a device with a clock indicator; the measurement result is referred to the measurement base, therefore it is not a named number, as is customary for expansion estimates as opposed to shrinkage data; 11 - water content in the test of normal density; 12 - designations of water-reducing components - according to table 9.

173

174

Table 11

The results of physical and mechanical tests of concrete made by the method according to the invention on the basis of cements according to the invention, with the determination of the moment of completion of mixing of the concrete mixture to the maximum electric capacity (the molding and compaction period of the samples is taken constant - for 10 minutes after mixing)

No. p / p Clinker The composition of concrete, kg / m ³ / wt.h. The electric capacity of the white mixture, Ω, μF / m ² through, min: ν ⁶⁾ The volumetric mass of the mixture, kg / m ³ N cm (A) and 8 mm (B ^ Compressive Strength * ⁰ , N / mm ² , after Coef, variations, ⁹⁾ cement sand crushed stone water W / C VK additive ²⁾ Software Add- ^{on 3)} Additive WU ⁴⁾ hardening in vivo in, days your in, days type of 9 ° type of AND type of 9 ° one 3 5 7 one 3 7 28 one 28 one 2 3 4 5 6 7 8 nine 10 and 12 thirteen 14 fifteen sixteen 17 eighteen nineteen twenty 21 22 23 24 25 26 27 28 one- I'm a series experiences one PC 4.1 245 10,2 400 16.7 1550 64.6 205 8.5 0.84 - - - - - - 3,5 6 5.8 5.3 3.8 0.005 c. 2400 1,0 A 11,4 23,2 29.1 35.7 28,2 39.6 2.9 2 same - - - - x ¹⁰⁾ - - - n / a 0.058 c. 2400 1,0 A 9.3 19.5 25,4 30.6 24.6 32,2 7.6 3 - - - - - - - - _x ! °) - - n / a - 0.007 c. 2400 1,0 A 10.5 23.1 28,4 34.6 28.3 36.9 4.6 4 - x ^{1 (} ° - n / a -0.002 c. 2400 1,0 A 10,2 22.6 27.5 33.7 27.0 35.0 5.5 5 - - x ¹⁰⁾ n / a - 0.005 c. 2400 1,0 A 9.8 20.9 26.1 32.1 26.6 34.3 5,4 6 PC 4.1 390 16.5 600 25,4 1200 50.7 175 7.4 0.45 - - - - - - 5.7 8.3 8.2 7.8 4.1 0.02 c. 2365 1.5 A 18.5 30.1 45.7 66,4 40.3 65.7 3.4 7 same - - - - - - x ⁿ⁾ - - - n / a 0,07 c. 2365 1.5 A 14.0 24.7 40,2 60,2 27.9 56.3 10,4 8 - n / a - 0.002 c. 2365 1.5 A 10,4 26.0 41.9 62.5 29.8 59.8 6.0 nine - n / a - 0.005 c. 2365 1.5 A 17.3 28,4 43.5 66.1 36.0 62.9 6.4 10 —- x ⁿ > n / a -0.02 c. 2365 1.5 A 16.8 28.3 42,4 66.0 35,4 60.3 5.8 2- I'm a series experiences eleven PC 4.1 397 611 1221 150 0.38 BUT od -______ _ _ _ 5.3 8.0 7.6 7.1 3.3 0.02 c. 2380 2.0 A 23.7 35.8 49.1 77.0 31,2 52.8 4,5 ¹²⁾ 16.7 25.7 51.3 6.3 2.9 12 ______ 402 611 1201 156 0.39 B OD _ _ _ _ 5.1 9.8 9.3 9.0 3,5 0.04 c. 2370 2.0 A 22.8 34.6 47.5 70.1 29.1 46.3 4 ^ 3) 17.0 25.8 50.8 6.6 4.2 thirteen ______ 400 616 1185 164 0.41 IN 12 _ _ _ _ 4.2 7.0 6.3 6.0 3.6 0.05 c. 2365 2.0 A 15.3 28.9 49.7 68.5 29.8 46.0 5.0 ¹⁴⁾ 16.9 26.0 50.1 6.9 4.2 14 ___I___ 400 615 1186 163 0.41 G 12 _ _ _ _ 4.9 8.5 7.9 7.2 3,7 0.05 c. 2365 1.8 A 14.9 26.7 48.5 64,4 29.3 45.7 5.4 ¹⁵⁾ 16.9 26.0 50.1 6.9 4.2

one 2 3 4 5 6 7 8 nine 10 eleven 12 thirteen 14 fifteen sixteen 17 eighteen nineteen twenty 21 22 23 24 25 26 27 28 fifteen PC 4.1 400 16.9 611 25.9 1185 50.1 168 7.1 0.42 d od 1.7 - - - - ZD 6D 6.3 6.1 3,5 0.05 c. 2365 1.8 A 10.9 23.7 35.1 49.7 26.3 38.5 5.0 ^1b) sixteen ---P-- 400 16.9 610 25.8 1186 50.1 169 7.1 0.423 E OD 1.7 - - - - ZD 7.2 7.0 6.5 ZD 0,03 same 1.8 A 10.0 28.1 36,2 48.3 25.8 39.0 5.0 ¹⁷⁾ 17 ——— same F 1D 0.6 - - - - 4.8 8D 9.0 7.8 4.2 0.05 - ⁿ - 2.0 A 12.8 26.9 38.5 57.2 34.0 54.1 4.2 ¹⁸⁾ eighteen --- N-- 400 16.9 605 25.6 1195 50,5 165 7.0 0.413 3 OD 2,5 - - - - 6.0 10 9D 9.3 3,5 0.05 - 2.0 A 18.2 32,7 48.9 69.7 39.2 70.3 ZD ¹⁹⁾ nineteen ——— same AND OD 2.9 - - - - 6.1 9.9 9D 9,4 3,5 0.05 ——— 2.0 A 19,4 33.9 50.3 71.6 40,2 72.9 ZD ²⁰⁾ twenty ——— to OD 3.3 - - - - 4D 8.2 7D 7.3 3,5 0.05 ——— 1.8 A 14.3 27.5 49.5 62.3 30.1 49.2 4.9 ² " 21 ——— ——— l od 3.8 - - - - 4D 7.3 7.1 6D 3.8 0.04 ——— 1.8 A 12.8 n / a 43.7 53.1 29.6 48.3 5.7 ²²⁾ 22 ——— ——— m od 3.8 - - - - 3.8 5D 5.2 5.3 healthy 0.04 - and - 1.6 A 16.1 n / a n / a 52.0 33.8 53.0 5.5 ²³⁾ 23 ——— 400 16.9 607 25.7 1198 50.7 160 6.8 0.4 n OD 2.9 - - - - 6.0 9.9 9.5 9.2 3,5 0.05 ——— 2.0 A 20.9 n / a n / a 72,2 46.2 70.0 5.2 ²⁴⁾ 24 ——— same ABOUT od 3.8 - - - - 5.5 8.0 7D 7D 3,5 0.05 ——— 2.0 A 17.6 n / a and / def 70.5 35.1 58.3 5.0 ²⁵⁾ 25 - - ¹¹ - P od 3.8 - - - - 5.2 9,4 9.2 9.0 3,5 0.05 - ”- 2.0 A 19.0 n / a n / a 64.1 37.8 65,2 5.2 ²⁶⁾ 3rd series of experiments 26 - n-- 470 63.5 - - 270 ² 36.5 0.68 - - BUT 6.85 od - - 9.7 eighteen nineteen 18.3 6.2 0.05 740 ²⁸⁾ 123 B OD 1.7 4.3 6.0 3.8 5.9 6D ²⁹⁾ 27 ——— same - - B 6.85 0.93 - - 9.3 sixteen 17 16.5 6.5 0.05 740 ²⁸⁾ 130 B OD 1.4 4.0 5.3 3.4 5.5 6.3 ^DA) 28 ——— 470 65.3 —- - 250 ³¹ 34.7 0.53 B OD 0.08 BUT 6.85 0.95 - - 8.8 thirteen 12 11.8 4.2 0.05 720 ³²⁾ 130 B 1,2 2.0 5,6 7.8 4,5 7D 5.2 ³³⁾

one 1 2 1 ΠΊ 1 ⁴ 1 5 | 1 ⁶ 1 7 1 ^{8 nine 10} Pn ¹² 1 ¹³ 1 ¹⁴ 1 1 15 1 1 16 1 eleven? one ^eighteen PP 1 20 PP ΠΊ ^{23 24} 1 ^{25 26} 1 ²⁷ 1 28 4- - I'm a series experiences 29th - 470 65.3 - - 250 34.7 0.53 B OD 0.08 BUT 6.85 0.95 BUT od 0,07 11.5 23.7 25.8 24.8 6D 0.1 720 ³²⁾ 145 B 1.4 2,3 5.8 8.2 5.8 8.3 5.5 ³⁴⁾ thirty ——— same 0.53 B OD 0.08 BUT 6.85 0.95 BUT OD 0,07 12.6 24.3 25.9 25.1 6.7 0.18 720 ³²⁾ 148 B 1,5 2,4 6.2 9.0 5.9 9.2 5.4 ³⁵ >

Notes: 1 - quantity, kg / m ³ / wt.h .; 2

- water-reducing component; substance A calcium salt of the condensation product of β-naphthalene sulfonic acid with formaldehyde; B the same, sodium salt; B — calcium salt of the condensation product of melamine sulfonic acid with formaldehyde; G is the same, sodium salt; D technical calcium lignosulfonate; E - on a sodium base; F last, processed phenol formaldehyde 175

176 resin (in a ratio of 4: 1 by weight); H complex calcium salt with low molecular weight monosaccharides C ₃ -C ₅ and H ₂ 8O ₄ ; And - the same, with NYO ₃ ; K - the same with UNSD; L is the same with CH ₃ COOH; M is a complex salt of magnesium with monosaccharides C ₃ -C ₅ and H ₂ 8O ₄ ; H - a mixture of substances B and C in a mass ratio of 4: 1; Oh - the same, B and W in May. 4: 1 ratio; P - the same, F and W in wt. 4: 1 ratio; 3 - foaming agent: A mixture of kleukanifolny emulsion with urea and polyamide resins in the presence of Ca (OH) ₂ and No. YUN; ratio - see in the text of the description; B - the same in May. a ratio of 5: 2: 1: 0.5: 1, parts by weight; 4 - water retention component: A, B, C, D - designations - according to the table. nine; 5 time to reach the maximum electric capacity of the concrete mixture, min .; 6 - rate of change of electric capacitance ν = 6Ω / 61. in μF / m ² s, at the moment of fixing the maximum electric capacitance, i.e. at Ω max; the minus sign in the column means that at the end of mixing the electric capacity of the mixture does not increase, but decreases; therefore, these compositions do not correspond to the method according to the invention; 7 -characteristic of the consistency of heavy concrete mix - sediment cone according to Abrams (A), cm; aerated concrete mixture, in this case, a foam concrete mixture, the cylinder spread according to Suttard (C), mm; 8 - compressive strength of sample cubes 1 × 10 × 10 cm, hardened in air-wet conditions: in natural conditions, that is, without heat-moisture treatment (TBO) - at a temperature of 20 ± 3 ° C and a relative humidity of 100%; for heavy concrete the data are given in terms of samples of 15x15x15 cm by multiplying by a factor of 0.85; for cellular concrete, data are given without recounting. TVO mode for heavy concrete

- according to example 3, for aerated concrete: holding for 2 hours, raising the temperature to 80-85 ° C for 3 hours, isothermal heating for 6 hours, cooling for 2 hours to a temperature of 20 ± 3 ° C; 9 - coefficient of variation of strength, average over 4 test periods of samples hardened in natural conditions; 10

- the time to reach the maximum electric capacity is not determined; mixing is carried out until a fixed time indicated by x; at the same time, concrete is obtained, the indicators of which are below the optimum (given in row 1) in terms of strength - by 1.7-6.8%, in heterogeneity (coefficient of variation) higher by 22-38%; 11 - the same for the second composition of concrete with increased consumption of cement; similarly receive data below the optimum; the following lines contain data only for the optimal mixing mode; non-optimal data are not provided; only the notes indicate the limits of the decrease in indicators when the optimum timing of mixing mixtures is not observed; 12 - the same, in compositions with non-optimal mixing times, the strength indicators (K) are 2.6-8.9% lower and the coefficient. variations (K) 25-46 rel.% higher; 13 - the same, in compositions with non-optimal mixing times, K is lower by 2.8–9.3% and K is higher by 28–54 rel.%; 14 - the same, in compositions with non-optimal mixing times, K is lower by 3.2-10.6% and K is higher by 22-51 rel.%; 15 - the same, in compositions with non-optimal mixing times, K is lower by 4.0-11.0% and K is higher by 25-53 rel.%; 16 - the same, in compositions with non-optimal mixing times, K is lower by 3.3-10.5% and K is higher by 21-52 rel.%; 17 the same, in compositions with non-optimal mixing times, K is lower by 3.5-10.7% and K is higher by 18-45 rel.%; 18 - the same, in compositions with non-optimal mixing times, K is lower by 2.5-8.7% and K is higher by 21-38 rel.%; 19 - the same, in compositions with non-optimal mixing times, K is lower by 4.0-12.0% and K is higher by 26-49 rel.%; 20 - the same, in compositions with non-optimal mixing times, K is lower by 4.3-15.0% and K is higher by 27 - 49 rel.%; 21 - the same, in compositions with non-optimal mixing times, K is lower by 5.2-14.0% and K is higher by 21-38 rel.%; 22 the same, in compositions with non-optimal mixing times, K is lower by 5.5 - 12.0% and K is higher by 20-35 rel.%; 23 - the same, in compositions with non-optimal mixing times, K is lower by 3.0-8.5% and K is higher by 15-42 rel.%; 24 - the same, in compositions with non-optimal mixing times, K is lower by 5.3-11.0% and K is higher by 17-52 rel.%; 25 - the same, in compositions with non-optimal mixing times, K is 5.9-12.0% lower and K higher by 20-29 rel.%; 26 - the same, in compositions with non-optimal mixing times, K is lower by 4.0-10.2% and K is higher by 22-31 rel.%; 27 including foam 160, mixing water 110 parts by weight; 28 - in the wet state; in dry condition - about 20% less, i.e. about 600 kg / m ³ ; 29 - the same, in compositions with non-optimal mixing times, K is lower by 7.018.5% and K is higher by 23-40 rel.%; 30 - in compositions with non-optimal mixing times, K is lower by 9.0-21.3% and K is higher by 25-43 rel.%; 31 including foam 160, mixing water 90 parts by weight;

- in a wet state; when dry, approximately 18% less, i.e. about 590 kg / m ³ ;

- in compositions with non-optimal mixing times, K is lower by 12-23% and K higher by 30-49 rel.%; 34 - in compositions with non-optimal mixing times, K is lower by 14-27% and K higher by 35-52 rel.%; 35 - in compositions with non-optimal mixing times, K is 15–31% lower and K is 32–54 relative% higher; in the presence of the rest of the cellulose polyesters discussed above, approximately the same data are obtained.

177

178

Table 12 The results of physical and mechanical tests of concrete samples, molded and compacted according to the method according to the invention (together with precast concrete products and structures after mixing the concrete mixture according to the regime specified in Table 11) 15-20 minutes before the appearance of 8-H-gel

No. p / p Option No. in the table. eleven Mixing time of the mixture after mixing to the maximum electric capacity, min Mixing time control, min Appearance time8-Ngel, min Forming / densification interval, min, from the beginning of mixing The dependence of the strength and resistance of concrete on the position of the interval molding / compaction on the timeline permissible real Compressive strength, N / mm ² , after Frost resistance of freeze / thaw cycles natural hardening MSW from before from before 1 day 3 days 28 days 1 day 28 days one 2 3 4 5 6 7 8 nine 10 eleven 12 thirteen 14 fifteen one 6 3.8 - 48 3.8 28 3.8 7 18.5 30.1 66,4 40.3 65.7 about 430 2 7 - 3 55 3 35 3 6 14.0 24.7 60,2 27.9 56.3 about 400 3 - 3.8 - 48 3.8 28 25 28 21,2 34.6 72.3 43.5 70.1 about 450 4 - - 55 3 35 32 35 16.1 25.3 61,4 29.3 58.6 about 425 5 eleven 3.3 - 59 3.3 39 s, s 7 23.7 35.8 77.0 31,2 52.8 about 445 6 - - 3 68 3 48 3 6 22.4 34.7 75.9 30,0 51.5 about 430 7 - 3.3 - 59 3.3 39 35 39 27.8 39.6 83.5 45.7 78.0 about 480 8 - - 3 68 3 48 45 49 25.1 38,2 79.1 36,4 59.1 about 460 nine 26 6.2 - 120 6.2 one hundred 6.2 10 0.9 1.7 6.0 3.8 6.9 about 35 10 - - 4 145 4 125 7 nine 0.4 1,0 3,5 2.0 3.9 about 25 eleven - 6.2 - 120 6.2 one hundred eighteen 22 0 _? nine 1.9 7.5 4.4 8.0 about 40 12 - - 4 145 4 125 21 25 0.4 1.3 4.2 2,8 5.1 about 30

Formula of the Invention

Claims (59)

Formula of the Invention 1. A method of manufacturing cement, forming a quick-dissolving and interacting cementitious material with high early strength after mixing with a liquid by sintering in a clinker kiln using solid and / or liquid and / or gaseous fuel or another energy source of a cement raw material mixture, including mineral forms, the main oxides from the group: calcium oxide, silicon oxide, alumina, iron oxide, the main minor components from the group: magnesium oxide, sulfur trioxide, potassium oxide, oxide on triium, the remaining small components are impurities, as well as chemical compounds returned to the specified furnace with dust trapped from the exhaust gases, with the formation of Portland cement clinker containing three or more clinker minerals from the group: tricalcium silicate (3СОСОЮ ₂ ), dicalcium silicate (2СаОЮЮ ₂ ) tricalcium aluminate (3СаО ^ Л1 ₂ О ₃ ), calcium aluminoferrite [2СаО ^ (Л1 ₂ О ₃ ) х (Its ₂ О ₃ ) 1 _- х], 1>х> 0, followed by cooling and grinding of clinker, characterized in that in the cement raw material mixture fed to the calcination or in the calcined mater al additionally introduced mineralization promoter, which is a mineral oxide additive comprising two or more of clinker minerals of the groups I trohkaltsievy silicate (3SaOYa1O _2), dicalcium silicate (2SaOYaYu ₂₎ trohkaltsievy aluminate (3SaO ^ A1 ₂ O _3), alumina ferrite calcium [ 2СаО ^ (Л1 ₂ О ₃ ) x (Her ₂ О ₃ ) 1 _- х], 2/3>х> 1/3, and / or II mayenite (12СаО ^ 7Л1 ₂ О ₃ ), calcium monoaluminate (CaО ^ Л1 ₂ O ₃ ), dicalcium and monocalcium ferrites (2СаО + е ₂ О ₃ , CaО + е ₂ О ₃ ), and / or III - alkaline, sulfate and halide derivatives of minerals of the indicated groups, and / or IV sul calcium phoaluminate (4СаО ^ 3Л1 ₂ О ₃ ^ 8О ₃ ), calcium sulfate (Ca8О ₄ ) and / or their mixtures and derivatives, and / or V - aluminates, and / or silicates, and / or alkali metal ferrites; VI a mixture of minerals from these groups between themselves and / or with free calcium oxide, mechanical and / or obtained together in the form of clinker, or sinter, or slag, or precipitate, or suspension, the composition of the promoter and the promoted clinker obtained in its presence is chosen , correct and support according to the criterion of basicity, exceeding the basicity of the eutectic clinker melt in the composition of Portland cement clinker in the phase diagram of CaO - L1 ₂ O ₃ - _{8 2} - Her ₂ O ₃ , without taking into account the small components of the crystallizing and 1338 ° С, and as the basis for the measure of the basicity of the promoter and the promoter clinker obtained in the presence of the promoter, the calculated values of the electronegativity of the chemical compounds in the compositions of the indicated promoter and the promoter clinker are used, in comparison with a similarly calculated measure of the basicity of the eutectic clinker melt. 2. The method according to claim 1, characterized in that the values of the basicity measure of the indicated promoter and the promoted clinker are selected, adjusted and maintained within approximately 1.005-1.07 and 1,00031.04 times higher than the values of the basicity measure of the specified eutectic clinker melt. 3. The method according to claims 1 and 2, characterized in that the firing of the promoted clinker is carried out in the presence of a mineralizer containing additionally introduced components 179 180 from the group: mineral salts, minerals, oxides, and including the mentioned minor constituents, as well as chemical compounds returned to the specified furnace with dust collected from the exhaust gases, and the content of the mineralizer in the calcined material and the composition of the mineralizer are selected according to the criterion of basicity of the calcined material in it the presence of a mineralized clinker exceeding the basicity of the control clinker, calcined without a promoter and without additionally introduced mineralizer components, taking into account the indicated small components in values of the calculated basicity of both of the above clinkers, and as a basis for the measure of basicity of the latter, the calculated values of the electronegativity of their compounds are used. 4. The method according to p. 3, characterized in that, when using solid fuel, a complex mineralizer is used, which additionally includes a highly basic, namely calcareous part, in the form of powdered materials from the group: lime, calcium carbonate, limestone, dolomite, their mixtures, and the low basic, namely aluminosilicate part, in the form of powdery, or granular, or sludge-like materials from the group: ash and slag from thermal coal, granular, or crushed, or ground metallurgical sludge and, as well as chemical compounds from dust trapped from the air used to cool the clinker and / or the ash of said solid fuel, which sits on the calcined material in the sintering zone of the clinker kiln, in a total amount of up to about 22% of the mass of the specified cement raw material in terms of to the clinker. 5. The method according to PP. 1-4, characterized in that the basicity values of the indicated promoter, promoted clinker, eutectic clinker melt, as well as the mineralizer, mineralized clinker and control clinker are selected, corrected, maintained and calculated with the representation of basic values of chemical compounds, namely minerals, oxides, mineral salts, halides that are part of these materials, in the form of a decreasing base series of sums of quantities inverse to algebraic sums of the electronegativity of the incoming these atoms. 6. The method according to claims 1, 2 and 5, characterized in that the values of the calculated relative basicity of the promoter B _rgot and the promoted clinker B _pc , are selected, corrected and maintained at fixed values equal to the products of the basicity of the eutectic clinker melt in _Witz and calculated basicity coefficient K _p values of said promoter and promoter clinker mineralogical composition and selection of the promoter and promoter of clinker is carried out by calculation of the sum of products of values of Σ osnovnos The compounds and _{Hg; n} , which are part of the promoter, and the values of the mass fractions of the mentioned compounds Νρ ^ in the promoter, in the form Σ _ριχ№ (In _{rt |||} \ ' _{rt |||} ) and similarly to the products of the basicity of the compounds In _rssh1n included in the promoted clinker , and the values of the mass fractions of the mentioned compounds \ ' _{rst |||} in a promoted clinker, in the form Σ ^ (In _{rst | n} \ ' _{rst | n} ). equivalent to the indicated fixed values, in accordance with the following formulas: е ите Н Н ((ΒοχΒεΝοχϊάε), е п п (((ΒοχίάβΝοχίάβ) ₅ g> rs pc у ст где Ч где где где где where B is the calculated relative basicity expressed in arbitrary units (abbreviated below) and equal to the algebraic sum of the inverse values of the chemical negativity chemical compounds, namely in minerals and / or oxides - components of these materials, including for the promoter and eutectic clinker melt - without taking into account small components, divided by a constant value equal to 2.24, while: In _{| |} - the indicated value for oxides included in the chemical composition of the eutectic clinker melt; N - mass and stoichiometric coefficients for the components of the indicated promoter and clinker - in mass percent, for the specified melt - in mole fractions, while: Νο ^ - the indicated stoichiometric coefficients for oxides included in the chemical composition of the eutectic clinker melt; at the same time, B _eite c is a constant value equal to 2.24 in the inverse Pauling units and taken as 1 or 100 conv. units in mathematical expressions, including the amounts of chemical elements and their compounds, respectively, in molar fractions or in wt.%, and in these formulas taken equal to 100 srvc. units, and the values of K _p are selected in the range from the minimum (K ¹ p), equal to about 1,0003, to the maximum (K ^max p), equal to about 1.07. 7. The method according to PP.3 and 4, characterized in that the value of the calculated relative basicity of the specified mineralized clinker Wts are selected, adjusted and maintained at a fixed value equal to the product of the basicity value of the control clinker B _ss obtained from the calcined material181 182 la in the absence of a promoter and an additionally introduced mineralizer, and the calculated value of the basicity coefficient K _{t of the} indicated mineralized clinker, and the selection of the mineralogical composition of the indicated mineralized clinker is carried out according to the calculated value of the sum E _{ts of the} products of the basicity of compounds B _mt , included in the _{composition of the} mineralized clinker with taking into account the minor constituents and weight fraction of the compounds mentioned values \ _shsshsh in mineralized clinker, in the form of X _are (C ^ _{TCT TCT} s), equated to the AUC Anna fixed value, in accordance with the following the formulas: where In _ss - the current value of the relative basicity value of the specified control clinker, calculated as the sum of E _{ss of the} products of the basicity values In _s ; _n compounds that are part of the control clinker and include clinker minerals and small components, and the mass fractions of the mentioned compounds Ν ^ _ω ^ in the control clinker, in the form Σ ^ (Vststhstst), while the basicity coefficient of the specified mineralized clinker is selected in the range minimum (K ¹ t), equal to about 1.01, to maximum (K t ^max t), equal to about 1.10. 8. The method according to claims 1, 2, 5 and 6, characterized in that the basicity values of said promoter, promoter and control clinker are selected, corrected and maintained taking into account the constituent minerals and / or oxides, the content of which in said materials exceeds about 0.5 wt.%. 9. A method according to claims 1-8, characterized in that the magnitude of the initial content of promoter ukazannoht0 y0 N _{WGPA / cc} in absence or N _WGPA / _are additionally introduced in the presence of a mineralizer, in mass% clinker, is selected and calculated for a given value of B _pc basicity promoter clinker value Vss basicity controlling clinker, calculated excluding small components, and the largest current or specified basicity said promoter B * _WGPA, and in the presence of a mineralizer further administered analogously, taking into account adannoy value Ws basicity mineralized clinker according to the formulas wherein B ^mw _pc - minimum setpoint value basicity promoter clinker, cond. units; In ^tach _pc - the maximum specified value of the basicity value of the promoted clinker, conv. units; In ^TT _TT - the minimum specified value of the basicity of mineralized clinker, conv. units; In ^max _tc - the maximum specified value of the basicity of mineralized clinker, conv. units, while the values of the magnitude of the current basicity of the promoter of B * _rgot are selected in the range of about (1.005-1.07) V _ei , the values of the basicity of the promoted clinker or mineralized clinker are in the above ranges between their minimum and maximum values. 10. The method according to claims 1 to 9, characterized in that as a cement raw material mixture in the preparation of decorative Portland cement clinker, a mixture of calcareous and aluminosilicate raw material components is used, containing compounds comprising coloring oxides of iron, manganese, chromium only in mineral forms included in the composition of these raw materials. 11. The method according to PP.1, 3-5, 9, characterized in that as a cement raw material mixture, the specified promoter and the specified complex mineralizer upon receipt of a white Portland cement clinker using white compositions containing not more than about 1 wt.% The total amount of iron compounds , manganese and chromium in terms of oxides of these metals in a promoted white clinker. 12. The method according to claims 1-11, characterized in that the color raw materials are used as the cement raw material mixture and the specified promoter upon receipt of the colored Portland cement clinker, in which the calculated basicity of the indicated promoter is controlled within the specified limits by the color intensity of the coloring minerals. 13. The method according to PP.1, 3-5, 7, 9-12, characterized in that as the salt part of the specified mineralizer using substances from the group: alkali and / or alkaline earth metal fluoride; sulfate of alkali and / or alkaline earth metals; alkali chloride 183 184 metal and / or alkaline earth metals; alkaline and / or alkaline earth metal silicofluoride; mixtures of these substances; materials containing by-products or wastes, including these substances or mixtures thereof. 14. The method according to p. 1, characterized in that as components of the cement raw material mixture, by-products and / or secondary products from the group are used: slags and / or sludges of ferrous and non-ferrous metallurgy, chemical industry, ash and slag of thermal coal, and also tailings of concentration plants , burned rocks, spent molding materials, analogues of these materials. 15. The method according to PP.1, 5, 8-14, characterized in that as the specified promoter use a material in the form of a powder or aqueous suspension, including dicalcium silicate (2CaO-81O ₂ ), an alkaline derivative of the latter (I ₂ O-23CaO -1181O ₂ ), alkali metal silicate (mT ₂ O-p81O ₂ ) at p / t 2.8-4.8, lime in anhydrous or hydrated forms, with the following ratio of components, wt.%: Dicalcium silicate (2СаО-81О ₂ ) 30-65 Alkaline derivative of dicalcium silicate (Я ₂ О-23СаО-118Ю ₂ ) 10-30 Alkali metal silicate (tYa ₂ O-p8Yu ₂ ) 0.5-25 Lime (CaO) in anhydrous or hydrated forms 0.05-40 Mix the rest 16. The method according to PP.1, 5, 8, 9, 12-14, characterized in that as the specified promoter use a material in the form of a powder, comprising as a tricalcium silicate of variable composition a component of the composition [(3,3-3 , 5) CaO-8U ₂ ], idiomorphic alite, dicalcium silicate (2CaO-81O ₂ ), as calcium aluminoferrite - a component of the composition [(4.8-7) CaO- (0.7-0.9) A1 ₂ O ₃ -P ₂ O ₃ - (0.5-1.5) occupies 8 _2] and the free calcium oxide (CaO) in the following ratio, wt%: component composition [(3.3-3.5) CaO-81O. ₂ ] as a phase idiomorphic to alite 50-85 Dicalcium silicate (2СаО-81О ₂ ) 0.05-28 The component of the composition [(4.8-7) CaO- (0.7-0.9) L1 ₂ O ₃ -Pe ₂ O ₃ - (0.5-1.5) 81O ₂ ] 8-30 Free calcium oxide (CaO) 0.1-18 Mix the rest 17. The method according to PP.1, 5, 8, 9, 12-14, characterized in that as the specified promoter use material in the form of a powder, including tricalcium silicate (3CaO-81O ₂ ), dicalcium silicate (2 CaO · 81O ₂ ), tricalcium aluminate (3CaOA1 ₂ O ₃ ), calcium aluminoferrite (4CaO · L1 ₂ O ₃ Te ₂ O ₃ ), mayenite (12CaO ^ 7L1 ₂ O ₃ ), calcium monoaluminate (CaO ^ L1 ₂ O ₃ ), calcium ferrites ( 2СаОНе ₂ О ₃ , СаОНе ₂ О ₃ ), calcium sulfoaluminate (4СаОЛЛ1 ₂ О ₃ ЯО ₃ ), calcium sulfate (Ca8О ₄ ) and calcium oxide (CaО), aluminates and ferrites of alkali metals [I (A1, Fe) O ₂ ] in the following relation to mponentov% wt./wt. Trohkaltsievy silicate (3SaOYa1O ₂₎ 55-80 Dicalcium silicate (2СаОЯ1О ₂ ) 10-13 Tricalcium aluminate (3СаОА1 ₂ О ₃ ) 4-15 Four-calcium aluminoferrite (4СаОА1 ₂ О ₃ Е ₂ О ₃ ) 10-18 Mayenite (12СаО ^ 7Л1 ₂ О ₃ ) 1-3 Calcium monoaluminate (CaO ^ L1 ₂ O ₃ ) 1-1.5 Calcium Ferrites (2СаОЕе ₂ О ₃ , CaOTe2O ₃ ) 1-1.5 Calcium sulfoaluminate (4СаОЭЛ12О ₃ ЯО ₃ ) 5-11 Calcium Sulphate (Ca8O4) 1.5-3.5 Alkali metal luminates and ferrites [I (A1, Pe) O ₂ ] 0.1-1.5 Calcium Oxide (CaO) 0.1-5 Mix the rest 18. The method according to claims 1, 5, 8, 9, 12-14, characterized in that the materials of the используют groups including dicalcium silicate (2СаОЯ1О ₂ ) and / or the alkaline derivative of the latter (K ₂ О ^ 23СаОТ181О ₂ ), and / or alkali metal silicate (tK ₂ Osh81O ₂ ) at p / t 2.84.8, and / or lime, and / or ΙΙ - including components of composition as a three-calcium silicate of variable composition [(3 , 3-3.5) SaOYa1O _2] idiomorphic alitame, dicalcium silicate (2SaOYaYu ₂₎ as calcium alyumoferrita composition component [(4,8-7) CaO _£ 0,7-0,9) A1 ₂ O ₃ · Re ₂ About ₃ (0.5-1.5) 81O ₂ ] and freedoms ny calcium oxide (CaO) and / or ΙΙΙ - including tricalcium silicate (3SaOYa1O _2), dicalcium silicate (2SaOYa1O _2), tricalcium aluminate (3SaO ^ A1 ₂ O ₃₎ and tetracalcium alumina ferrite (4SaOA1 ₂ O ₃ is not ₂ O ₃₎ , mayenite (12СаО ^ 7Л1 ₂ О ₃ ), calcium monoaluminate (CaОА1 ₂ О ₃ ), calcium ferrites (2СаОН ₂ О ₃ , СаОНе ₂ О ₃ ), calcium sulfoaluminate (4СаОЭЛ1 ₂ О ₃ ЯО ₃ ), calcium sulfate (Ca8О4) , aluminates and ferrites of alkali metals [I (A1, Fe) O ₂ ], calcium oxide (CaO), Ιν including materials from these groups or their components in a mixture with additionally introduced by mixing or co-grinding with a calcium sulfate ingredient, mainly gypsum, in an amount in terms of 8O _{3 of} 0.5-9 wt.% of the remaining ingredients of the promoter. 19. The method according to claims 1-18, characterized in that the sintering ability of the specified raw material mixture is maintained by regulating the content of fluxes in it according to the sum of the minerals of tricalcium aluminate (3СаО ^ Л1 ₂ О ₃ ) and calcium aluminoferrite PSaОФЛРОЗХше ^ ЗрН, 1>х> 0 , or about 2.65 L1 ₂ O ₃ + 1.34 Re ₂ O ₃ in the form of oxides, at a level of at least about 12 and 8 wt.%, calculated on ordinary and white Portland cement clinkers, respectively. 185 186 20. The method according to claims 1-19, characterized in that said promoter is introduced into the calcined material first in an amount of about 0.1-0.8 parts by weight. per 1 part by weight the calculated initial content, when the operating mode of the clinker kiln is changed, fixed by changing the value of any characteristic indicator, for example, by the temperature increase in the sintering zone of the indicated kiln, the power of the latter is increased, adapting the calcination mode of the indicated promoted clinker taking into account the response time to the action of the addition of the indicated promoter by waiting for the return of the characteristic characteristic to approximately the initial value, then in parallel increase the supply of the specified motor and furnace power, and the maximum amount of the introduced promoter adapted to these firing conditions of the specified clinker is selected up to an order of magnitude in excess of the initial quantity according to the criteria of maximum cement strength obtained on the basis of the specified promoted clinker, and specifically within 0.7-3 , 5 wt.% Of the specified promoted clinker according to the criterion of maximum strength of the specified cement under standard conditions at 1-3 days of age or in the range of 0.3-1.5 wt.% Of the specified promoted clinker according to the criterion of maximum strength of the specified cement under standard conditions at 28 days of age. 21. The method according to claims 1 to 20, characterized in that the promotion of mineral formation during firing of the specified promoted clinker is carried out repeatedly using the above minerals and / or their mixtures with calcium oxide as components of the promoter, of which at least one or more components are preliminarily obtained by sintering or melting, also carried out using the above mineral formation promoter. 22. The method according to claims 1-5, 10-21, characterized in that the promotion of mineral formation during firing of the specified promoted clinker is combined with hybridization of the structure of the crystal lattices and hybridization of stoichiometric ratios in solid solutions of clinker minerals of the indicated promoted clinker, in which at least , one polymorphic modification and / or one stoichiometric ratio of the components of the solid solution of at least one mineral in the composition of the specified promoter is chosen different from the corresponding characteristics of at least one of the minerals of the same name in the specified control clinker, and criteria for hybrid polymorphic modification and / or hybrid stoichiometric ratio of the components of the solid solution, at least one of the minerals of the indicated promoted clinker, consider any statistically significant mismatch with similar characteristics recorded in minerals of the same name in the specified control clinker. 23. The method according to p. 1, characterized in that the said promoter is first introduced in an amount of about 0.01-0.7 wt.% Of the specified promoted clinker to increase the temperature of the calcined material in the sintering zone of the specified furnace compared to the control level without the promoter by about 25-50 ° С, then the furnace power is increased, adapting the firing regime of the indicated promoted clinker taking into account the response time to the action of the additive of the indicated promoter, until the mentioned temperature level returns to the control level, then increasing t supply of the indicated promoter, the furnace power is again increased by iteratively repeating these operations, and the maximum amount of input of the specified promoter adapted to the given conditions of mineral formation promotion during firing of the specified clinker is selected up to an order of magnitude in excess of the initial amount according to the equilibrium criterion of the composition of the indicated promoted clinker, moreover, as an equilibrium criterion, they are used when firing an ordinary promoted clinker - the content in the last magnetic frac cations, not exceeding about 15 wt.%, and when firing white promoted clinker - the content in the latter mayenite (12СаО-7А1 ₂ О ₃ ) and / or alkaline forms of tricalcium aluminate or alkaline calcium aluminates (В ₂ О-8СаО-Л1 ₂ О ₃ ), where B = Na, K, in an amount not exceeding a total of about 3 wt.%. 24. The method according to claims 1, 15-23, characterized in that the appearance of a cellular microstructure of the phase of tricalcium silicate (3CaO-81O ₂ ) - alite in the indicated promoted clinker is used as a criterion for the optimal content of the specified promoter in the material to be fired. 25. The method according to claims 1, 15-24, characterized in that as a criterion for the optimal content of the specified promoter in the material to be fired, the content of the crystal clusters of the phase of tricalcium silicate (3CaO-81O ₂ ) - alite in the microstructure of the indicated promoted clinker in an amount of not more than 25 wt.% Of the above phase. 26. The method according to claims 1, 6-9, 15-23, characterized in that in the indicated promoted clinker the stoichiometric composition of the phase of tricalcium silicate (3CaO-81O ₂ ) - alite is regulated within the molar ratio CaO / 81O ₂ 2,8- 3.2 by means of sybate regulation within the specified limits of the content of the specified promoter and base ratio 187 188 the indicated promoter and mineralizer, as well as the basicity of the mineral of the same name in the specified promoter. 27. The method according to PP. 1-26, characterized in that in the specified promoted clinker, the calculated content of tricalcium silicate is increased to about 70-80 wt.% Against about 55-65% in the specified control clinker by increasing the content of the specified promoter in the calcined material to the maximum amount by the criterion of reduction in that the total content of the promoted marginal clinker phases - mayenita (12SaO-7A1 ₂ O _3), its analogs and derivatives of alkali, as well as monocalcium and dicalcium ferrite (2CaO-Fe ₂ O _3, CaO-Fe ₂ O ₃₎ - up to ca. angles to 1 wt.% or less. 28. The method according to PP. 1, 23-27, characterized in that the firing of the indicated promoted clinker is carried out until a submicrocrystalline X-ray amorphous tricalcium silicate is obtained in the alite in the amount of 10-50% of the total mass of alite, maintaining the content of the indicated promoter at the maximum level according to the strength criterion of samples of 28 days old, standardly made of cement obtained from the specified promoted clinker. 29. The method according to PP. 1, 10-28, characterized in that the tricalcium silicate in the specified promoted clinker is refined by increasing the content of the specified promoter in the calcined material to a maximum amount of about 0.6-3.5 wt.% In terms of clinker according to the criterion of content in tricalcium silicate impurities - magnesium compounds in terms of oxide (MdO), about 2-10 times lower than the initial content of MdO in the specified raw material mixture, equal to about 1-7 wt.% in terms of clinker. 30. The method according to claims 1, 10-29, characterized in that the average content of alkali metal compounds in the indicated promoted clinker in terms of Na ₂ O equivalent, the amount of oxides Ni 0 + 0 658 K ₂ O - is reduced by increasing in the indicated the limits in the calcined material of the content and basicity of the indicated promoter according to the criteria of the average and temporary maximums of the content of the specified amount of oxides in the indicated promoted clinker at levels of about 50-92 and about 40-85 wt.% of the corresponding amounts in the specified control clinker. 31. The method according to PP. 1, 10-30, characterized in that the average chromate content in the indicated promoted clinker in terms of hexavalent chromium is reduced by increasing the content and basicity of the indicated promoter within the specified limits in the calcined material according to the criteria of average and temporary maxima of the chromate content in the indicated promoted clinker at levels about 20-25 and about 12-20 wt.% chromates in the specified control clinker, in terms of hexavalent chromium. 32. The method according to PP.1, 10-31, characterized in that the optimal degree of firing of the specified promoted clinker is determined by the content in the last crystalline free lime, not exceeding about 1-1.5 wt.% With a total content of free lime to about 3 wt.%. 33. The method according to p. 1, characterized in that the filing of the specified promoter in the cement raw material mixture is carried out by mixing it with the last or one of its components during its preparation or grinding, or by adding the specified promoter to the ground raw mixture before it arrives in a clinker kiln and / or by introducing the specified promoter into the cement raw material mixture during the firing of the latter. 34. The method according to claims 1, 3, 4, characterized in that the introduction of these promoter and mineralizer is carried out jointly or separately, or one of the components of the specified promoter and / or mineralizer is administered separately from their remaining components. 35. The method according to p. 1, characterized in that the mixing of the cement raw material mixture or one of its components with the specified promoter is carried out by grinding, or pneumatic, or paddle, or vortex mixers, moreover, as the first use a raw mill or additional grinding device, and as the latter, a cylindrical-conical vessel with an oblique tangential inlet of a cement raw material mixture is used, forming a vortex which spirals tapering downward, along the vertical axis of which a azanny promoter. 36. The method according to p. 1, characterized in that the promoter is used in powder form or in the form of a suspension with a specific surface area of the powder or solid phase of the suspension of at least 150 m ² / kg, mainly in the range of 250-1800 m ² / kg 37. The method according to p. 1, characterized in that the specified promoter or part thereof is pre-mixed with dust trapped from the exhaust gases of a clinker kiln. 38. The method according to p. 1, characterized in that the average content in the promoted clinker of refractory clinker dust, namely a fine fraction with granule sizes of less than 0.1 mm, comprising mainly tricalcium silicate (3CaO-81O ₂ ) -alite surrounded by a dark-colored shell from calcium aluminoferrite [2CaO- (A1 ₂ O ₃ ) _x - (Fe ₂ O ₃ ) 1- _x ], 189 190 1>x> 0, and calcium ferrites (2CaO-Ee ₂ O ₃ , CaO-Ee ₂ O ₃ ) are reduced to a level of about 5 wt.% Or less by increasing the content of the promoter to a maximum level within the specified limits and / or by choosing the alumina modulus of the promoted clinker is in the range of about 1.15-1.7, preferably 1.35-1.55. 39. The method according to claim 1, characterized in that the average content in the specified promoted clinker fine fraction with a grain size of about 0.3-2 mm is increased to a level of about 50-100 wt.% When the content of clinker dust fraction is less than 0.1 mm no more than about 0.1-5 wt.% by increasing the content of the specified promoter to a maximum level within the specified limits when choosing the value of the alumina module of the specified clinker, that is, the ratio by weight of A1 ₂ O ₃ / Her ₂ O ₃ in the range of about 0.01 -1.15. 40. The method according to claim 1, characterized in that the resistance of the indicated promoted clinker to grinding is reduced by the criterion of the average microhardness to about 10-25 MPa by increasing the content of the specified promoter to a maximum level within the specified limits and / or by choosing the value of the alumina module of the specified clinker , that is, the ratio by weight of A1 ₂ About ₃ / Its ₂ About ₃ in the range of about 0.9-2, mainly 1.35-1.8. 41. The method according to PP. 1 and 40, characterized in that in the specified cement based on the specified promoted clinker by means of joint and / or separate grinding followed by mixing, a gypsum component is additionally introduced, which use materials from groups I - natural gypsum one of the group - gypsum stone, natural gypsum gypsum, natural anhydrite; II - a gypsum-containing by-product of the chemical industry, one of the group - phosphogypsum, borogypsum, titanogypsum, citrogypsum, fluorohydrite; III - a product of desulfurization with calcium carbonate or lime of sulfur-containing exhaust gases of furnaces during the combustion of energy fuels - coal or fuel oil; IV - a mixture of natural gypsum and gypsum-containing industrial by-product in a mass ratio of from about 1: 3 to about 3: 1, with a gypsum component in the specified cement of about 1-4.5 wt.% In terms of sulfur trioxide (8O ₃ ). 42. The method according to claims 1, 40 and 41, characterized in that the product of the interaction of titanogypsum with kaolin or kaolin clay in the presence of free sulfuric acid, which is an impurity in titanogypsum, is additionally introduced into said cement by co-and / or separate grinding with subsequent mixing under conditions of mixing titanogypsum with kaolin at a temperature of 60-550 ° C, and in May. the ratio of titanogypsum / kaolin is regulated in the range from 1: 0.2 to 1: 2, introducing the resulting product into the cement in an amount of 1-7 wt.% of the clinker part of the latter. 43. The method according to claims 1, 40-42, characterized in that in said cement, when grinding and / or by mixing, an ordinary Portland cement clinker and / or Portland cement are additionally introduced on the basis of the latter in mass ratios of said promoted and ordinary clinker and / or cements based on them from about 5: 1 to about 1: 5. 44. The method according to claims 1, 40-43, characterized in that when grinding said cement, a grinding intensifier is additionally introduced in an amount of about 0.05-0.5 wt.% Of said cement. 45. The method according to item 44, characterized in that as an intensifier for grinding said cement, surface-active substances from the group of amino alcohols and their compositions with hardening accelerators are used; technical lignosulfonates and their compositions with electrolytes or surface-inactive substances from the group: salts of alkaline-earth and / or alkali metals of the condensation product of naphthalene sulfonic acid with formaldehyde; salts of alkaline earth and / or alkali metals of the condensation product of melamine-containing resins with formaldehyde; complex salts of alkaline earth metals and sulfuric and / or nitric and / or formic and / or acetic acids with low molecular weight monosaccharides C3-C5; paired mixtures of these materials in a mass ratio of from about 4: 1 to about 1: 4 in an amount of 0.05-0.5 wt.% the specified cement. 46. The method according to claims 1, 40-45, characterized in that, when grinding and / or by mixing, additionally added active silica in the form of materials from groups I is crushed, or granular, or ground silicate block in an amount of about 0 , 2-20 wt.% Of the specified cement or II - silica fume in powder or granular forms: a secondary product of silicon production and / or dust trapped from the exhaust gases of furnaces of ferroalloy production, in an amount of 0.2-10 wt.% Of the specified cement, granular form of microsilica The yezoma is taken with the addition of a plasticizing component, previously introduced during granulation in an amount of 0.01-0.2%, calculated on the weight of the specified cement. 47. The method according to claims 1, 40-46, characterized in that an active mineral additive and / or filler, respectively, in the form of fragments, are additionally introduced into said cement by co-and / or separate grinding with subsequent mixing 191 192 fresh or crushed forms or in pre-ground form in an amount of about 1-85 wt.% The specified cement. 48. The method according to claims 1, 40-47, characterized in that an expanding component is additionally introduced into said cement by means of joint and / or separate grinding with subsequent mixing, including artificially made and / or natural materials and / or their grinding products from groups I alumina clinker or alumina slag; II - sulfoaluminate clinker or other material, including calcium sulfoaluminates; III - sulfoferrite clinker or other material, including calcium sulfoferrites; IV - hyperalitic clinker or products of its grinding; U - metallurgical slag, including more than 10 wt.% A1 ₂ About ₃ in the form of calcium aluminates; VI - rocks, including more than 4.5 wt.% Water-soluble A1 ₂ O ₃ ; VII - a mixture of any of these materials, including at least 20% of each of them, while the content of the expanding component in the specified cement is maintained in the range from 2.5 to 50 wt.%. 49. The method according to p. 48, characterized in that as an expanding component of artificial origin, namely aluminous clinker or slag, sulfoaluminate or sulfoferrite or hyperalite clinkers or other products, including calcium minerals of the same name, take promoted materials, and in particular, obtained from the introduction of promoters of the same named minerals in a mixture of the starting or sintering or melting materials, with the estimated basicity of the promoter approximately 1.01-1.07 times higher than otnuyu basicity mentioned mixtures. 50. The method according to claims 1, 40-43, 46-49, characterized in that, when grinding, the fibrous component of inorganic and / or organic origin is additionally introduced into said cement in an amount of about 0.2-2 wt.% Of said cement. 51. The method according to claims 1, 40-43, 46-49, characterized in that in the specified cement, when grinding and / or by mixing, an additional water-reducing component is added in an amount of about 0.1-2.5 wt.% Of the clinker part of the specified cement. 52. The method according to p. 51, characterized in that as a water-lowering component of the specified cement using materials from the group: salt of alkaline-earth and / or alkali metals of the condensation product of naphthalene sulfonic acid with formaldehyde; a salt of alkaline earth and / or alkali metals of the condensation product of melamine-containing resins with formaldehyde; technical lignosulfonate of alkaline earth and / or alkali metals, conventional or modified phenolphor maldehyde resin; complex salts of alkaline earth metals and sulfuric and / or nitric and / or formic and / or acetic acids with low molecular weight monosaccharides C3-C5; paired mixtures of these materials in a mass ratio of from about 4: 1 to about 1: 4. 53. The method according to PP.1, 40-43, 46-49, characterized in that in the specified cement during grinding and / or by mixing, an additional water-retaining additive is introduced, consisting of cellulose polyesters, in an amount equal to about 0.01-1 , 5 wt.% Of the total mass of clinker minerals - tricalcium silicate (3CaO-81O ₂ ) and tricalcium aluminate (3CaO-A1 ₂ O ₃ ) - in the composition of the specified cement. 54. The method according to p. 53, characterized in that as a water-retaining additive to the specified cement using materials from the group: methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxyacetyl cellulose, sulfocellulose or their paired mixtures, in a ratio of from about 4: 1 to 1: 4 in mass. 55. A method of manufacturing concrete based on the specified cement, forming a quick-dissolving and interacting cementitious material with high early strength after mixing with a liquid obtained by sintering in a clinker kiln a cement raw material mixture comprising in the mineral forms the main oxides from the group: calcium oxide, silicon oxide, oxide aluminum, iron oxide, the main small components from the group: magnesium oxide, sulfur trioxide, potassium oxide, sodium oxide, the remaining small components are impurities, as well as chemical compounds returned to the specified furnace with dust trapped from the furnace exhaust gases, with the formation of Portland cement clinker containing three or more clinker minerals from the group: three-calcium silicate (3CaO-81O ₂ ), two-calcium silicate (2CaO · 81O ₂ ), three-calcium aluminate ( 3СаО ^ А1 ₂ О ₃ ), calcium aluminoferrite [2СаО <А1 ₂ О ₃ ) _х (Fe ₂ О ₃ ) 1 _- х], 1>х> 0, followed by cooling and grinding of clinker, including mixing cement with aggregates and liquid , which is used as water or a solution of electrolytes, and the use of flax concrete mixture for the manufacture of concrete by laying in the mold or formwork, molding and compacting the specified mixture, characterized in that when additional input into the feed cement mixture or into the calcined material of the promoter of mineral formation, which is a mineral oxide additive comprising two or more clinker minerals from groups I: three-calcium silicate (3СаО ^ 81О ₂ ), two-calcium silicate (2СаО ^ 81О ₂ ), three-calcium aluminate (3СаО ^ Л1 ₂ О ₃ ), calcium aluminoferrite 193 194 [2СаО- (А1 ₂ О ₃ ) _х - (Her ₂ О ₃ ) _1-х ], 2/3>х> 1/3, and / or II: mayenite (12СаО-7А1 ₂ О ₃ ), calcium monoaluminate (CaO-A1 ₂ O ₃ ), dicalcium and monocalcium ferrites ( ₂ CaO-Ee ₂ O ₃ , CaO-Fe ₂ O ₃ ), and / or III: alkaline, sulfate and halide derivatives of minerals of the indicated groups, and / or IV: sulfoaluminate calcium (4CaO-3A1 ₂ O ₃ -8O ₃ ), calcium sulfate (Ca8O ₄ ) and / or their mixtures and derivatives, and / or V: aluminates, and / or silicates, and / or alkali metal ferrites; VI: mixtures of minerals from these groups with each other and / or with free calcium oxide, mechanical and / or obtained together in the form of clinker, or sinter, or slag, or sediment, or suspension, as well as when selecting, adjusting, maintaining the composition of the specified promoter and the promoted clinker obtained in his presence according to a basicity criterion that exceeds the basicity of the eutectic clinker melt in the region of Portland cement clinker compositions in the CaO A1 ₂ O ₃ - 8U ₂ - Pe ₂ O ₃ phase diagram, without taking into account the small components of the crystal generated at 1338 ° C, using the calculated electronegativity of the compounds included in them as a base for the basicity measure of the indicated promoter and the promoted clinker in comparison with the similar basicity measure of the eutectic clinker melt, the specified concrete mixture is mixed during concrete preparation until the water is distributed optimally the surface of the specified cement, estimated by approaching the maximum value and achieving the minimum growth rate of the electrical capacitance Shiva mixture of about 0,0050,1 uF / m ² s, whereafter stirring of said mixture is stopped. 56. The method of manufacturing concrete according to claim 55, characterized in that an addition of a water-reducing component is additionally added to said concrete mixture in an amount of about 0.2-1 wt.% Of the clinker part of said cement, and a material from the group is used as a water-reducing component: salt alkaline earth and / or alkali metals of the condensation product of naphthalenesulfonic acid with formaldehyde; a salt of alkaline earth and / or alkali metals of the condensation product of melamine-containing resins with formaldehyde; technical lignosulfonate of alkaline earth and / or alkali metals, conventional or modified with phenol-formaldehyde resin; complex salts of alkaline earth metals and sulfuric and / or nitric and / or formic and / or acetic acids with low molecular weight C ₃ -C ₅ monosaccharides; paired mixtures of these materials in a weight ratio of from about 4: 1 to 1: 4. 57. A method of manufacturing concrete according to paragraphs 55 and 56, characterized in that the pre-foamed additive of the foaming agent in the form of an aqueous solution in the amount of about 0.05-1.5 wt.% In terms of dry active substance is additionally introduced into the specified concrete mixture of the total mass of clinker minerals - tricalcium silicate (3СаО-8Ю ₂ ) and tricalcium aluminate (3СаО-А1 ₂ О ₃ ) - in the composition of the specified cement. 58. The method according to claims 55-57, characterized in that an addition of cellulose polyesters in an amount equal to about 0.01-1 wt.% Of the total mass of clinker minerals - tricalcium silicate is additionally added to the composition of the concrete mixture based on the specified cement ( 3СаО-8Ю ₂ ) and tricalcium aluminate (3СаО-А1 ₂ О ₃ ) - as part of the specified cement. 59. A method of manufacturing concrete and reinforced concrete products or monolithic structures from the specified concrete on the basis of the specified cement, forming a quick-dissolving and interacting cementitious material with high early strength after mixing with the liquid obtained by sintering in a clinker kiln cement raw material mixture, including in the mineral forms the main oxides from groups: calcium oxide, silicon oxide, alumina, iron oxide, the main minor components from the group: magnesium oxide, sulfur trioxide, oxide Leah, sodium oxide, other small components - the impurities and the chemical compounds are returned to said furnace with dust captured from the furnace off-gases to form Portland cement clinker, comprising three or more of clinker minerals from the group of: trohkaltsievy silicate (3SaO-81O ₂ ), dicalcium silicate (2СаО-8Ю ₂ ), tricalcium aluminate (3СаО-А1 ₂ О ₃ ), calcium aluminoferrite [2СаО- (А1 ₂ О ₃ ) _х - (Its ₂ О ₃ ) _1-х ], 1>х> 0, followed by cooling and grinding of clinker, in the manufacture of the specified concrete by mixing the specified cement nt with aggregates and a liquid, which is used water or a solution of electrolytes, using the prepared concrete mixture for concrete production by laying in form or formwork, molding and compacting the specified mixture, withstanding molded and compacted concrete and reinforced concrete products or monolithic structures made of concrete until the last initial strength and with the subsequent implementation of the heat and moisture treatment of these products and structures, characterized in that when additional input to the cement raw material mixture supplied to the calcination or to the calcined material of the mineral formation promoter, which is a mineral-oxide additive comprising two or more clinker minerals from groups I - three-calcium s195 196 likate (3СаО ^ 81О ₂ ), dicalcium silicate (2СаО ^ 81О ₂ ), tricalcium aluminate (3СаО ^ Л1 ₂ О ₃ ), calcium aluminoferrite [2СаО ^ (А1 ₂ О3) х ^ (Пе ₂ О3) 1-х] , 2/3>x> 1/3, and / or II mayenite (12СаО ^ 7А1 ₂ О ₃ ), calcium monoaluminate (CaО ^ A1 ₂ О ₃ ), dicalcium and monocalcium ferrites (2СаО ^ Бе ₂ О ₃ , СаО ^ Be ₂ O ₃ ), and / or III - alkaline, sulfate and halide derivatives of minerals of the indicated groups, and / or IV calcium sulfoaluminate (4СаО ^ 3А1 ₂ О ₃ ^ 8О ₃ ), calcium sulfate (Ca8О4) and / or mixtures thereof and derivatives and / or V - aluminates and / or silicates and / or alkali metal ferrites; VI a mixture of minerals from these groups between themselves and / or with free calcium oxide, mechanical and / or obtained together in the form of clinker, or sinter, or slag, or sediment, or suspension, as well as when selecting, adjusting, maintaining the composition of the specified promoter and obtained in its presence promoted clinker Browse basicity exceeding basicity eutectic melt clinker in the composition portlandtse-clinker-element phase diagram of CaO - A1 ₂ O ₃ - 81O ₂ - Fe ₂ O _3, excluding minor constituents crista lysing at 1338 ° С, using the calculated electronegativity of the compounds included in their composition as a basis for the measure of basicity of the indicated promoter and the promoted clinker in comparison with a similar measure of the specified concrete until the optimum distribution of water over the surface of the specified cement, estimated as close to the maximum value and achieving minimum capacitance growth speed stirring mixture of about 0.005-0.1 uF / m ^2, after the termination of the last Shuffle The preparation of the specified mixture, the molding and compaction of these products and structures are completed no later than about 15-90 minutes after reaching the specified minimum, namely, before the appearance of the specified products and structures of silica hydrogel in the molded concrete, the decomposition product of the primary gel-like calcium hydrosilicate on the surface of clinker particles of the specified cement.