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WO2016056947A1 - Procédé de transformation de matière première contenant de l'oxyde d'aluminium et procédé de découpage de matière première contenant de l'oxyde d'aluminium - Google Patents

Procédé de transformation de matière première contenant de l'oxyde d'aluminium et procédé de découpage de matière première contenant de l'oxyde d'aluminium Download PDF

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Publication number
WO2016056947A1
WO2016056947A1 PCT/RU2015/000601 RU2015000601W WO2016056947A1 WO 2016056947 A1 WO2016056947 A1 WO 2016056947A1 RU 2015000601 W RU2015000601 W RU 2015000601W WO 2016056947 A1 WO2016056947 A1 WO 2016056947A1
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solution
stage
alum
iron
aluminum
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Russian (ru)
Inventor
Руслан Хажсетович ХАМИЗОВ
Лилия Петровна МОРОШКИНА
Наталья Сергеевна ВЛАСОВСКИХ
Султан Хажсетович ХАМИЗОВ
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"newchem Technology" LLC
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"newchem Technology" LLC
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Priority claimed from RU2014140246/05A external-priority patent/RU2574247C1/ru
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Priority to AU2015328791A priority Critical patent/AU2015328791B2/en
Publication of WO2016056947A1 publication Critical patent/WO2016056947A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/20—Preparation of aluminium oxide or hydroxide from aluminous ores using acids or salts
    • C01F7/26—Preparation of aluminium oxide or hydroxide from aluminous ores using acids or salts with sulfuric acids or sulfates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/30—Preparation of aluminium oxide or hydroxide by thermal decomposition or by hydrolysis or oxidation of aluminium compounds

Definitions

  • the invention relates to chemistry and metallurgy, and in particular, to a method for processing alumina-containing raw materials and a method of opening such raw materials during processing to obtain metallurgical alumina and related products.
  • alkaline methods are known (Bayer method and its modification) used for processing alumina-containing raw materials (Liner A.I., Eremin N.I., Liner Yu.A., Pevzner I.Z. Production of alumina . M, Metallurgy, 1978, 394 pp. [1]; Troitsky I.A., Zheleznov V.A. Metallurgy of aluminum. - M., Metallurgy, 1977, p. 42-1 16 [2]; RF patent JV ° 2360865, published July 10, 2009 [3]; RF patent 2193525, published 27.1 1.2002
  • Alkaline methods are adjoined by methods based on the method of sintering raw materials with limestone or with limestone and soda or alkali, followed by washing the sinter with water or an aqueous solution of soda: Matveev V. A. Physico-chemical and technological bases for increasing the efficiency of complex processing of nepheline-containing raw materials by acid methods. Diss. doc tech. Sciences, Apatity, 2009, 299 pp. [5]. At present, about 40% of the alumina produced in Russia is obtained from the Kola nepheline and nepheline syenite from Siberian deposits using this method (see [5], as well as: Isakov EA, Pikalevskoe Alumina Association under new conditions.
  • Non-ferrous metals 1997 , N ° 4, p. 8 [6]).
  • the significant limitations of these methods are the high energy intensity and the need to obtain and process a large number of associated sodium-calcium-silicate products.
  • the economic efficiency of the sintering method may decrease significantly.
  • These methods include processing the raw material with hot concentrated nitric acid, filtering the resulting pulp with washing the precipitate, further processing of the filtrate with the separation of intermediate aluminum compounds and their separation from iron compounds, as well as mainly include thermal hydrolysis of these intermediate aluminum compounds with the regeneration of nitric acid and the production of hydrated or dry alumina.
  • nitric acid methods are characterized by a number of common disadvantages, including: poor filterability of pulps obtained after decomposition of easily opened aluminosilicate raw materials, for example, nepheline ores and concentrates (even when using flocculants), which makes the process more expensive and makes it more labor intensive; a small degree of opening during direct decomposition of bauxite and kaolinite-boehmite raw materials, making them necessary to pre-calcine, which also makes the process more expensive by increasing its energy intensity; insufficient degree of regeneration of nitric acid and the need for the supply and expenditure of fresh acid in large quantities; environmental hazard associated with the formation of azo oxides This and significant economic losses associated with their conversion to nitric acid.
  • Hydrochloric acid methods are known (see [7], as well as: Shvartsman B.Kh. Acidic methods for processing alumina-containing raw materials.
  • M Tsvetmetinformatsiya, 1964. 82 pp. [12]; Pustilnik G.L., Pevzner I.Z. Ki - slot methods for processing low-quality aluminum-containing raw materials.
  • M Tsvetmetinformatsiya, 1978. 52 p. [13]).
  • These methods include preliminary roasting of the raw material, leaching, separation of silica slurry by filtration, iron removal using various options, including by evaporation of the filtrate solution to obtain crystals of the "yellow salt” (A1C1 3 6H 2 O with impurities iron), which, after cooling, is washed with hydrochloric acid to obtain a “white salt” (pure crystals of aluminum chloride), which, in turn, is calcined at temperatures above 1000 ° C to obtain alumina and regeneration of hydrogen chloride in the form of a mixture with in pairs returning after absorption to the head of the process in the form of 30% hydrochloric acid.
  • the "yellow salt” A1C1 3 6H 2 O with impurities iron
  • the energy required for high-temperature drying (500 ° C) and direct firing (1300 ° C) of aluminum sulfates and their derivatives is not less than in the case of using hydrochloric acid methods, and the mixture of SO2 and SO3 gases obtained during firing requires additional capital and extinction high costs for the regeneration (synthesis) of sulfuric acid and its return to the head of the process for opening alumina raw materials.
  • This method involves the implementation of a circular (closed cyclic) process, which includes the steps of: preliminary thermal decomposition of ammonium sulfate into ammonia and ammonium bisulfate, dissolution of the latter and processing of alumina raw materials with a hot solution of ammonium hydrogen sulfate (bisulfate) with or without an admixture of ammonium sulfate in an autoclave, filtering a solution of aluminum-ammonium alum and precipitating aluminum hydroxide from it with previously cleaved ammonia, separating ammonium sulfate from the mother liquor with return his head in the process.
  • the raw material is not directly introduced into the calcination process, which allows the decomposition of pure ammonium sulfate at temperatures below 300 ° C and reduces energy costs.
  • treating alumina-containing raw materials with a hot solution of ammonium hydrogen sulfate does not lead to the loss of reagents in the form of sulfur dioxide.
  • this method makes it possible to obtain intermediate compounds that are easily filtered and easily cleaned of iron.
  • the method of M. Buchner refers to the so-called named methods in chemical technology, its second name is "Aloton"("Aloton") (Encyclopedic Die- 01
  • the disadvantage of this method is that too much energy is spent on evaporating the solution of residual ammonium sulfate during its processing in order to obtain solid ammonium sulfate, which is associated with the limited solubility of aluminum-ammonium alum in the mother liquor after decomposition using high concentrations of ammonium hydrosulfate in the initial solution reagent.
  • This leads to the need to work with a diluted reagent solution, which, in turn, leads to the need for redistribution of a large amount of water in a circular process.
  • Another disadvantage is caused by the irreversible consumption of the hydrosulfate reagent associated with the relatively high content of alkaline and alkaline earth elements in aluminosilicate raw materials. A gradual decrease in the effectiveness of the reagent solution from cycle to cycle associated with the use of reverse ammonium hydrogen sulfate in a circular process is associated with this.
  • the opening of alumina-containing raw materials involves heat treatment at a temperature of 400 550 ° C in the presence of a reagent — aqueous solutions of magnesium chloride and leaching of cake with the subsequent extraction of aluminum compounds from the resulting solution.
  • This method is adjacent to the known sintering methods [5, 6] (in particular, related to the opening of raw materials), and therefore retains their drawback, which consists in high energy intensity, although it is somewhat reduced in this method.
  • the present invention related to the method of opening clay-alumina raw materials during its processing is closest to the opening method implemented in the M. Buchner method [29].
  • Buchner's method includes the preparation and heating of a reagent solution containing ammonium hydrosulfate, processing of the raw materials with this solution and separation of the resulting pulp into an undecomposed solid residue and a mother liquor of aluminum and other alum for the subsequent extraction of aluminum compounds from it.
  • alumina-containing raw materials are calcined together with ammonium sulfate
  • the autopsy carried out in the M. Buchner method is applicable only to easily decomposable aluminosilicate minerals (see [33]), but not to bauxite raw materials, including high-silicon bauxite raw materials.
  • the first of the proposed inventions related to a method of processing alumina-containing raw materials is aimed at overcoming the above-mentioned disadvantages of the closest known method and achieving a technical result, which consists in the possibility of processing any alumina-containing raw materials with a simultaneous reduction in energy consumption as in initial processing of the entire mass of the feedstock by providing the possibility of this treatment at a lower temperature, and in subsequent stages due to the creation of niyu conditions to reduce the volume of redistribution of water in a circular process; PT / RU2015 / 000601
  • the invention is aimed at reducing losses of reagents and the volume of their replenishment during the implementation of the circular process. Further, when disclosing the essence of the invention and when considering examples illustrating it, other types of technical result achieved can be mentioned.
  • the proposed method for processing alumina-containing raw materials is a circular process, including:
  • stage of obtaining solid ammonium sulfate - stage thermal decomposition of solid ammonium sulfate, which receive ammonium hydrosulfate and ammonia, used, respectively, at the stage of opening in the preparation of the reagent solution and at the stage of deposition.
  • the pre-purified mother liquor is processed in the form of a sequence of operations, including the restoration of the iron contained in this solution to a bivalent state,
  • sulfuric acid is extracted from the pre-purified mother liquor obtained at the stage of purification after separation of aluminum-alum crystals from it during said processing,
  • the processed pre-purified mother liquor, from which the crystals of aluminum-ammonium alum are separated, passed through the indicated column, is combined with the residual ammonium sulfate solution obtained in the separation stage, and then this combined solution is used as the initial product for the production of solid ammonium sulfate .
  • the processing of the clay-containing raw material by the present invention is not a solution of ammonium hydrogen sulfate and not a mixed solution of a mixture of ammonium hydrosulfate and ammonium sulfate, but a solution of ammonium hydrosulfate with the addition of sulfuric acid leads to a fundamentally new quality of the process: it becomes universal, allowing along with with with aluminosilicates (nepheline, kaolin, sillimanite, argillite, ash, etc.) to process difficultly decomposable alumina-containing raw materials, for example, bauxite and even red mud - waste le bauxite processing.
  • aluminosilicates nepheline, kaolin, sillimanite, argillite, ash, etc.
  • the reagent solution according to the proposed method allows the decomposition of easily decomposable raw materials, for example, aluminosilicates such as nefelin, at temperatures lower than those of M. Buchner (up to 75 ° C) .
  • the proposed method completely closes the cycle and ammonia (see equations (3) and (7)).
  • the method of M. Buchner as can be seen from a comparison of equations (3) and (5), in a circular process it is necessary to produce more ammonia than is required. If the ammonia cycle is closed and only 4.8 moles of ammonia are produced per mole of the initial clay-containing raw material, then from cycle to cycle the reagent becomes less and less “acidic” (i.e., less effective) due to the enrichment of the hydrosulphate ammonium admixture of ammonium sulfate.
  • the proposed method due to the presence in it of the operation of separating sulfuric acid by passing through a column with a strongly basic anion exchange resin in the sulfate form of an acidic mother liquor obtained during processing at the purification stage after separation of aluminum-ammonium alum crystals from it, allows returning circular 0601
  • Alum is precipitated in solid form and falls into the composition of the non-decomposed residue, which leads to loss of aluminum or requires the use of a large amount of washing water; at the same time, a significant part of leached aluminum is contaminated with iron, which is present in wash water in concentrations commensurate with aluminum. All this reduces the profitability of the process.
  • acid retention does not provide a significant increase in the degree of extraction of aluminum, but is associated with additional costs for introducing more acid into the circular process and processing a larger mass of the reagent solution.
  • the temperature is maintained in the range of 75-180 ° C.
  • aluminum-ammonium alum precipitates, which does not allow correct lead the process.
  • the decomposition rate increases, however, an increase in temperature to more than 180 ° C leads to additional costs that are not offset by a decrease in the decomposition time.
  • the choice of temperature determines the hardware design of the method, for example, at temperatures above 100 ° C, autoclave or microwave equipment is used.
  • the decomposition process can last 2 - ⁇ - 5 hours.
  • demineralized water formed at the stage of production of solid ammonium sulfate can be used as the latter. It makes sense to use the ratio of the mass of the reagent solution and the processed raw materials not less than 3: 1. This is due to the fact that for the implementation of an effective decomposition process it is necessary that the mass amount of components of the reagent solution is greater than the total mass amount of raw material components, s which undergo reaction reactions during decomposition. Even if we assume that such raw materials contain alumina with virtually no iron oxide impurities, this ratio should be applied to raw materials containing no more than 15% alumina. Substandard types of raw materials with a lower alumina content would correspond to lower ratios.
  • Purification of wash water (or wash water and alum mother liquor) from iron by the precipitation method carried out at the stage of purification after said separation of the pulp at the opening stage, with washing of solid residues with water and separate collection of the mother liquor of alum and wash water, can be carried out by their ammonization, i.e. adding ammonia to them, and separating the resulting iron hydroxide.
  • the aforementioned purification of wash water (or alum mother liquor and wash water) from iron is carried out until the ratio of the mass concentrations of aluminum and iron in the preliminary purified mother liquor is at least 10: 1.
  • the solution must be introduced into it too much reducing agent in relation to the mass of the resulting final product, which makes the process uneconomical.
  • the operation of reducing the iron contained in this solution to a divalent state is carried out using ammonium sulfite or sulfur dioxide or a metal aluminum powder as a reducing agent.
  • ammonium sulfite or sulfur dioxide or a metal aluminum powder as a reducing agent.
  • the use of such reducing agents is preferable since it does not lead to undesirable formation of components not present in said solution.
  • Recovery is carried out to prevent the formation of iron-ammonium alum co-crystallizing with aluminum-ammonium alum.
  • the ratio in the solution of alum purified from iron impurities obtained by processing the pre-purified mother liquor, the mass concentrations of aluminum and iron is less than 1500: 1
  • an additional purification of this solution from iron is carried out, which is carried out until the specified ratio is reached or exceeded using the molecular method sorption, or ion exchange, or liquid-phase or solid-phase extraction using sorbents, filaments or extractants with functional groups selective for iron.
  • the preparation of solid ammonium sulfate can be carried out, for example, by evaporating a solution obtained by combining the processed pre-purified alum mother liquor passed through a NewCem column with the residual ammonium sulfate solution obtained after separation of the precipitated aluminum hydroxide.
  • desalted condensed water is obtained, which can later be used as pure water for washing off the acid retained on the anion exchange resin in the NewKem column, as well as for dissolving the crystals of aluminum-ammonium alum. ny and separated from the pre-purified mother liquor cooled after the recovery operation.
  • the proposed method can be supplemented with a stage for producing alumina by dehydration and calcination of an intermediate in the form of aluminum hydroxide obtained in the stage of separation of precipitated aluminum hydroxide.
  • a limitation of the acid retention method is that for efficient separation acids and salts it is necessary that in the sorption column there was practically no free space between the sorbent granules.
  • layers strongly squeezed under high pressure are used with “flattened” sorbent granules (US patent _V ° 4,673,507, published June 16, 1987 [37]; Sheedy M, Recoflo ion exchange technology. Proceedings of the TMS Annual Meeting held in 1998 in San Antonio Texas (1998) [38]).
  • this approach is not suitable for mixed colloidal systems and suspensions, which are formed during the processing of iron-containing solutions (when neutralizing the passing solution with acid retention).
  • columns are used in which the sorption layer is completely filled with an organic liquid (for example, decanol, pelargonic acid), which is retained in the column during the processing of mixed solutions containing acids and their salts.
  • an organic liquid for example, decanol, pelargonic acid
  • Operations with decomposition solutions of alumina-containing raw materials are facilitated, because: a) supersaturated solutions and colloidal systems containing iron compounds are stabilized in New em columns, and precipitation occurs outside of them; b) the transmission of the processed solutions (unlike the standard method of acid retention) is carried out in the direction from top to bottom, and colloidal particles are more easily removed from the column.
  • the acid returned to the circular process allows the regeneration of ammonium hydrosulfate (under mild conditions, without the use of thermal decomposition) from a substantial part residual ammonium sulfate.
  • the amount of ammonium hydrosulfate is equivalent to the number of iron compounds involved in the process of soft hydrolysis.
  • the method according to the first proposed invention takes advantage of the conjugation with NewKem acid retention technology, namely, the reduction of ferric iron to a divalent state in the combined solution before precipitation and separation of aluminum-ammonium alum.
  • the second proposed invention related to the method of opening alumina-containing raw materials during processing, is aimed at achieving a technical result, which consists in the possibility of opening any aluminum-containing raw materials without high-temperature (200 ° C and above) processing with an increase in the degree of decomposition and extraction aluminum compounds.
  • the proposed method for opening alumina-containing raw materials involves the preparation and heating of a reagent solution containing ammonium hydrosulfate, the decomposition of alumina-containing raw materials with this solution to obtain pulp in the form of a solution of aluminum-ammonium and other alum together with solid decomposition residues and separation of the pulp into solid and liquid phases to obtain undecomposed solid residues and alum mother liquor.
  • the decomposition of the alumina-containing raw material by the invention proposed by the solution of ammonium hydrosulfate with the addition of sulfuric acid leads to the fact that the process becomes universal, allowing, along with aluminosilicates, the opening of difficultly decomposed alumina-containing raw materials, for example, bauxites and even red mud - waste after bauxite processing.
  • the reagent solution according to the proposed method allows to decompose easily decomposable raw materials at lower temperatures, for example, aluminosilicates such as nepheline, i.e. the method becomes universal, and the use of the described techniques when separating the resulting pulp increases, ultimately, the degree of extraction of aluminum compounds.
  • the alum mother liquor obtained after separation of the pulp is enriched in aluminum more than an order of magnitude with respect to iron. It also turns out that commensurate concentrations of aluminum and iron are obtained in the wash water, which, if separated separately, can be processed separately in the future.
  • the decomposition rate increases, however, an increase in temperature by more than 180 ° ⁇ leads to additional costs, which are not compensated by a decrease in the decomposition time.
  • the choice of temperature mode determines the instrument design of the method, for example, at temperatures above 100 ° C, autoclave or microwave equipment is used. Under the above conditions, the decomposition takes 2–5 hours. It is preferable to use the ratio of the masses of the reagent solution and the raw material to be opened not less than 3: 1. This is due to the fact that for the implementation of an effective decomposition process it is necessary that the mass amount of the components of the reagent solution is greater than the total mass quantity of the components of the raw material, s which undergo reaction reactions during decomposition.
  • Separation of pulp into liquid and solid phases can be carried out by known methods, such as filtration, centrifugation, decantation, which are equivalent in terms of influence on the possibility of achieving a technical result, which is the aim of the proposed opening method alumina-containing raw materials.
  • the invention is illustrated by the diagrams of FIG. 1 to 6 and the following examples.
  • the circuit shown in several parts in FIG. 1 to 4 shows the sequence and relationship of the operations of the method according to the first of the proposed inventions related to the method of processing gly- nosem-containing raw materials, without the use of signs characterizing this method in particular cases of its implementation.
  • FIG. 5 and FIG. 6 illustrates, in a simplified form, an industrial process for processing alumina-containing raw materials by the same method.
  • the examples also illustrate a method for processing alumina-containing raw materials in general using a number of features that are preferred in various particular cases of the method, and reflect several possible combinations of such features.
  • the corresponding parts of the above schemes and examples illustrate the method of the second of the proposed inventions, since it is part of the method of the first invention.
  • the second invention corresponds to FIG. 1, blocks 1 to 3, FIG. 5, p.p. "A”, "B” and subparagraph 1 of paragraph "C" of example 1, as well as examples 4, 5, 36 in the part corresponding to the indicated paragraphs of example 1, and the table to examples 6 - 35.
  • FIG. 5 Parts of the circuit of FIG. 5, FIG. 6 are labeled K, L, M, N, P, showing how these parts are connected to each other.
  • This diagram shows a closed circular process of processing alumina-containing raw materials, in which part of desalted water obtained at the final stages of the process, namely, at the stage of production of solid ammonium sulfate, is used to prepare the reagent solution (block 8).
  • wash water is used that is obtained after the separation of aluminum hydroxide from an alum solution purified from iron impurities during its ammonization (block 7; in the diagram they are shown as “wash water 2”).
  • Solid ammonium hydrosulfate obtained in a circular process after the operation of isolation and thermal decomposition of solid ammonium sulfate is also used to obtain a reagent solution (block 9).
  • a reagent solution partially used is the acid returned from the NewKem treatment step (block 1 1), and partly a fresh portion of technical sulfuric acid.
  • the resulting reagent solution is heated (block 1) and hot mixed with ground alumina-containing raw materials.
  • decomposition block 2 for 2 5 hours the mixture is kept hot in an unpressurized (open) reactor or autoclave (depending U2015 / 000601
  • the suspension after decomposition is separated (block 3), for example, using filter presses or vacuum filters to obtain a primary hot filtrate (alum mother liquor separated from solid decomposition residues). Then the filters with the indicated residues are washed with hot water (for example, technical softened water) to obtain wash water.
  • hot water for example, technical softened water
  • the washings are evaporated and partially ammoniated (block 4) to convert the acidic solution into a slightly acidic solution to precipitate and separate iron hydroxide, for example, by filtration.
  • the filtration residue (hot) after filtration is combined with the hot primary filtrate to obtain a combined filtrate (pre-purified mother liquor) into which a reducing agent, for example, ammonium sulfite, is introduced (block 5).
  • a reducing agent for example, ammonium sulfite
  • the resulting solution is cooled to crystallize aluminum-ammonium alum
  • the crystals are separated from the acidic pre-purified mother liquor by filtration (if necessary, washed with a cold concentrated solution of ammonium sulfate, as shown in Example 1 below, but not shown in the diagram here) , then the crystals are dissolved in demineralized water to obtain an alum solution purified from iron impurities, which is briefly called a secondary solution in the scheme (block 6).
  • the secondary solution is subjected to ammonization (block 7) using ammonia obtained in the last stages of the process by thermal decomposition of the solid ammonium sulfate obtained previously (block 9).
  • ammonia obtained in the last stages of the process by thermal decomposition of the solid ammonium sulfate obtained previously (block 9).
  • pure aluminum hydroxide is released, which is filtered washed from the residual solution of ammonium sulfate and washed on the filter with demineralized water (block 7).
  • the washed aluminum hydroxide is sent for drying and calcination (calcination) (block 1 1) to obtain metallurgical alumina. (If necessary, the secondary solution is subjected to deeper purification from iron by sorption or extraction methods; not shown in the diagram).
  • the acidic mother liquor, from which the alum crystals are separated (block 5), is subjected to NewKem processing (block 10).
  • the sulfuric acid solution obtained in each cycle of this treatment is returned to the head of the process at the stage of preparation of the reagent solution (block 1), and NewChem-filtrate — the solution without acid, is maintained to precipitate iron hydroxide (if necessary, oxidized with atmospheric oxygen, which is not shown in the diagram) ), the indicated hydroxide is separated, and the resulting solution is combined (block 8) with the residual solution of ammonium sulfate.
  • the combined solution is subjected to evaporation and crystallization of ammonium sulfate (block 8).
  • the condensate of the residue namely demineralized water, is used at the opening stage during the preparation of the reagent solution (block 1), for dissolving pure aluminum-ammonium alum separated from the mother liquor (block 6), washing the aluminum hydroxide and desorbing (washing off) the acid solution to NewChem processing stages (block 10) (in this case, the brine residue after crystallization is processed with the addition of lime and crystallization of sodium and potassium sulfates, as described in example 1, but not shown in the diagram).
  • the obtained ammonium sulfate is dehydrated, for example, by centrifugation and drying and is subjected to thermal decomposition (block 9) with the release of ammonia used for ammonization (block 7) of the alum solution (secondary solution) purified from iron impurities, as well as ammonium hydrosulfate, sent to the head of the process at the opening stage for the preparation of the reagent solution (block 1).
  • Blocks 1 to 3 in FIG. 5 correspond to the second of the proposed inventions related to the method of opening alumina-containing raw materials, ending with separate collection of the alum mother liquor (“primary filtrate” in the diagram) and washing water when the pulp is separated into liquid and solid phases. Corresponding operations are also presented in FIG. one.
  • Timan bauxite which has the following composition (wt.%), Are also added:
  • the obtained crystals are washed at a temperature of 20 ° C using 200 g of a 42.1% solution of ammonium sulfate, the washing solution (or filtrate N ° 4, 201, 2 g) is left for use at the appropriate processing stage (see section "E").
  • the resulting alum is mixed with heating (75 ° C) with 58 g of condensate (demineralized) water and an alum solution purified from iron impurities is obtained. 42 g of a 24% ammonia solution are added to this solution (see paragraph "G").
  • 220 g of a suspension are obtained containing aluminum hydroxide in a solution of ammonium sulfate.
  • the suspension is filtered on a Buchner funnel with a water-jet pump to obtain a filtrate of ⁇ ° 3 in an amount of 200 g and a precipitate in an amount of 19.13 g containing aluminum hydroxide and moisture (20%).
  • the filtrate N ° 3 is used as a solution for washing crystals of aluminum alum in a subsequent process cycle.
  • the precipitate is processed in the following stages (see paragraph "K").
  • One part namely, 57.3 g, is used in the next technological cycle at the stage of deposition of aluminum alum in accordance with paragraph “D”.
  • the second part (66 g) is also used in the subsequent cycle for the preparation of various technological solutions in accordance with pl. “B”, “G”, “G” and “3”, finally, the third part (35 g) is used in the following cycles to prepare the reagent solution.
  • washing water obtained in the previous cycle at the stage of washing the intermediate product - aluminum hydroxide in accordance with paragraph "K", namely, 50 g is directed to: washing the precipitate after decomposition of bauxite and filtration (19.7 g , see paragraph “B”); on the preparation of a reagent solution (28.9 g in accordance with paragraph “A”); for the preparation of milk of lime (1.4 g, in accordance with paragraph. And).
  • Example 2 The process is carried out in accordance with Example 1, except that in the step described in paragraph "D", 0.15 g of aluminum chips is added to the Nsl filtrate. At the final stage, 7.15 g of pure alumina is obtained, which corresponds to the quality of metallurgical alumina (GO) in the content of the main components. The degree of through extraction of alumina is 75%.
  • - processing of raw materials in the decomposition process is carried out for 5 hours in an open reactor at a temperature of 98 ° C.
  • nepheline concentrate of the Kola deposit having the following composition (wt.%) is used as raw material:
  • a reagent solution is prepared with a content of 45% ammonium hydrosulfate and 1% sulfuric acid;
  • the composition of the washings makes it possible to obtain a mixture of easily decomposing aluminum and iron hydroxides during ammonization, but with a ratio typical for high-quality bauxite, and iron oxide pigments or ore for ferrous metallurgy can be obtained from washings.

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  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

L'invention se rapporte au domaine de la chimie et de la métallurgie pour la transformation de matière première contenant de l'oxyde d'aluminium. Le procédé de transformation est réalisé sous forme d'un processus en boucle comprenant: un stade d'exploitation comprenant une décomposition de la matière première à l'aide de la solution de réactif contenant de l'hydrosulphate d'ammonium et de l'acide sulfurique, la séparation de la pulpe obtenue, avec dégagement des résidus de décomposition solides, qui sont rincés à l'eau, et d'une solution mère d'alun, la collecte séparée de la solution mère d'alun et des eaux de lavage; un stade de purification durant lequel les eaux de lavage sont nettoyées de fer contenu, réunies avec la solution mère, refroidies et soumises à la séparation des cristaux d'alun d'alumine d'ammonium; on dégage de la solution mère de l'acide sulfurique utilisé au stade d'exploitation pour la solution de réactif; un stade de sédimentation de l'hydroxyde d'aluminium qui se dépose à partir de la solution d'alun exempte d'impuretés; un stade de séparation de l'hydroxyde d'aluminium; un stade de production de sulfate d'ammonium solide; et un stade de sa décomposition thermique au cours duquel on obtient du sulfure d'ammonium et de l'ammoniac qui sont utilisés respectivement lors du stade d'exploitation afin de préparer la solution de réactif et lors du stade de sédimentation. L'invention permet de transformer tout type de matière première contenant de l'oxyde d'aluminium à des températures peu élevées, de réduire les pertes de réactifs et le volume nécessaire de leur reconstitution en cours du processus.
PCT/RU2015/000601 2014-10-06 2015-09-24 Procédé de transformation de matière première contenant de l'oxyde d'aluminium et procédé de découpage de matière première contenant de l'oxyde d'aluminium Ceased WO2016056947A1 (fr)

Priority Applications (1)

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AU2015328791A AU2015328791B2 (en) 2014-10-06 2015-09-24 Method for processing alumina-containing raw material and method for breaking down alumina-containing raw material during processing

Applications Claiming Priority (2)

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RU2014140246 2014-10-06
RU2014140246/05A RU2574247C1 (ru) 2014-10-06 Способ переработки глиноземсодержащего сырья и способ вскрытия глиноземсодержащего сырья при его переработке

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WO2016056947A1 true WO2016056947A1 (fr) 2016-04-14

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PCT/RU2015/000601 Ceased WO2016056947A1 (fr) 2014-10-06 2015-09-24 Procédé de transformation de matière première contenant de l'oxyde d'aluminium et procédé de découpage de matière première contenant de l'oxyde d'aluminium

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AU (1) AU2015328791B2 (fr)
WO (1) WO2016056947A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB195998A (en) * 1921-10-12 1923-04-12 Max Buchner Improvements in the production of pure alumina
US1493320A (en) * 1921-08-30 1924-05-06 Buchner Max Process for manufacturing aluminum hydroxide
SU12159A1 (ru) * 1926-09-09 1929-12-31 Карл Штилль Способ и устройство дл выделени смолы и аммиака из газов сухой перегонки
CN1083023A (zh) * 1992-08-25 1994-03-02 王海舟 酸析法氧化铝改进工艺

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1493320A (en) * 1921-08-30 1924-05-06 Buchner Max Process for manufacturing aluminum hydroxide
GB195998A (en) * 1921-10-12 1923-04-12 Max Buchner Improvements in the production of pure alumina
SU12159A1 (ru) * 1926-09-09 1929-12-31 Карл Штилль Способ и устройство дл выделени смолы и аммиака из газов сухой перегонки
CN1083023A (zh) * 1992-08-25 1994-03-02 王海舟 酸析法氧化铝改进工艺

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AU2015328791A1 (en) 2017-05-25

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