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WO2024223828A1 - Procédé de modification chimique par voie humide d'une structure de silicate, produit de réaction associé et utilisation, et système de réacteur correspondant - Google Patents

Procédé de modification chimique par voie humide d'une structure de silicate, produit de réaction associé et utilisation, et système de réacteur correspondant Download PDF

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Publication number
WO2024223828A1
WO2024223828A1 PCT/EP2024/061547 EP2024061547W WO2024223828A1 WO 2024223828 A1 WO2024223828 A1 WO 2024223828A1 EP 2024061547 W EP2024061547 W EP 2024061547W WO 2024223828 A1 WO2024223828 A1 WO 2024223828A1
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Prior art keywords
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silicate
particles
silicate structure
content
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PCT/EP2024/061547
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German (de)
English (en)
Inventor
Anton LASSELSBERGER
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Lasselsberger Group GmbH
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Lasselsberger Group GmbH
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Publication date
Priority claimed from DE102023110874.3A external-priority patent/DE102023110874A1/de
Priority claimed from DE102023001707.8A external-priority patent/DE102023001707A1/de
Application filed by Lasselsberger Group GmbH filed Critical Lasselsberger Group GmbH
Publication of WO2024223828A1 publication Critical patent/WO2024223828A1/fr
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02—Granular materials, e.g. microballoons
    • C04B14/04—Silica-rich materials; Silicates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02—Granular materials, e.g. microballoons
    • C04B14/04—Silica-rich materials; Silicates
    • C04B14/10—Clay
    • C04B14/106—Kaolin
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area

Definitions

  • the invention relates to the field of hydrometallurgical wet-chemical dissolution processes.
  • the invention relates to a method for wet-chemically changing a silicate structure, in which the proportion of a metal contained in the silicate structure, based on the silicon content, is shifted to lower values within an exposure time by the action of a flowing treatment liquid within a reaction space delimited by an external boundary, whereby the silicate structure is also set in motion and flows through a flow path within the exposure time.
  • Such processes are well known, for example through the large-scale extraction of pure aluminum from natural raw materials such as kaolin, as described, for example, in US 4,239,735.
  • This document proposes a 36% hydrochloric acid (acid lye) as the treatment liquid in order to ultimately obtain essentially pure AICI3 ⁇ 6 H2O crystals from the aluminum dissolved from the silicate structure with the treatment liquid and then subjected to further treatment steps.
  • a batch reactor is used for this purpose, in the form of a stirred tank or stirred tank cascade, in which the material is exposed to the acid treatment for a predetermined period of time, such as two hours or four hours.
  • stirred tank reactors are well known to those skilled in the art for such processes, are readily available commercially and are therefore not described in more detail here.
  • Acid leaching in a stirred tank for 2 hours is also used to convert aluminosilicates that have been fired in an unusual way, namely flash-calcined, into a microporous inorganic particulate material, since a network of channels and pores is formed at bubbles created due to flash calcination, as described in DE 698 17 732 T3.
  • the invention is based on the object of further improving a method of the type mentioned at the outset, in particular with a view to obtaining the desired end product in the most satisfactory quality possible in the simplest possible process design.
  • the invention is based on the realization that a simpler process design with less operational effort is possible if one does not aim, as in the prior art, at the metal obtained by the treatment in as pure a form as possible as the end product, but at the silicate structure which still contains metal after the treatment, but in a lower ratio to silicon.
  • the exposure time thus depends, unlike in stirred tanks or their cascades, on the speed of movement of the silicate structure (flow reactor or flow reactor).
  • the invention when expressed in terms of features of the limitation, provides a further development of the method of the type mentioned at the beginning, which is essentially characterized in that the reaction chamber (100) is an elongated reaction chamber of a flow reactor (flow reactor) with a length of the outer boundary extending from the reaction chamber inlet located at the beginning (a) of the flow path to the reaction chamber outlet located at the end (b) of the flow path and a flow cross-section limited by the outer boundary at a respective length position and a ratio of the length of the outer boundary and the cubic root of the reaction chamber volume is greater than 8, preferably greater than 12, in particular greater than 16.
  • the reaction chamber (100) is an elongated reaction chamber of a flow reactor (flow reactor) with a length of the outer boundary extending from the reaction chamber inlet located at the beginning (a) of the flow path to the reaction chamber outlet located at the end (b) of the flow path and a flow cross-section limited by the outer boundary at a respective length position and a ratio of the length of the outer boundary and the cubic
  • a method is provided in which the spatial distance between the beginning and the end of the flow path is smaller than the length of the flow path, preferably by at least a factor of 2, in particular by at least a factor of 4. This allows a more favorable implementation for applying an energy input into the system.
  • a method in which the shortest fluid-communicating (fluid-communication-permitting) connection in the reaction chamber between the start and end of the flow path or between the reaction chamber inlet and outlet is not less than 60%, in particular not less than 80% of the length of the flow path. This reduces deviations from preferably laminar flow behavior.
  • the Reynolds number when flowing along the flow path does not exceed 4000, preferably does not exceed 3000, more preferably does not exceed 2500, in particular does not exceed 2000.
  • a method is provided in which a volume flow of the treatment liquid measured in m 3 /s together with entrained silicate structure particles is not greater than 8%, preferably not greater than 2%, in particular not greater than 0.8% of the movement speed of the silicate structure measured in m/s. This allows a favorable configuration for efficient energy input.
  • a method is preferably provided in which a cross section through which the treatment liquid and the flowing silicate structure particles flow (the flow cross section) is averaged over the flow path no larger than 4 dm 2 , preferably no larger than 1 dm 2 , even more preferably no larger than 40 cm 2 , even more preferably no larger than 20 cm 2 , even more preferably no larger than 6 cm 2 , in particular no larger than 4 cm 2 or even 2 cm 2 .
  • This cross section could be that of a tubular, in particular hose-shaped boundary.
  • a hose is provided as the boundary, in particular made of a plastic material, such as a PFA hose. The hose could be inserted in a groove of a wall heating system and/or arranged wound up like a coil.
  • the quotient of the area of the outer boundary and the volume of the reaction space measured in cm' 1 is greater than TT 1/2 /10, preferably greater than TT 1/2 /5, more preferably than (n75) 1/2 , even than (4n76) 1/2 .
  • a method is provided in which the reaction space is subjected to an energy input provided by an energy source, in particular a heating device.
  • a method is preferably provided in which the silicate structure particles are added in a comminuted state, with a maximum transverse dimension of at least 95% of the silicate structure particles being less than 12%, preferably 10%, in particular 8% of the flow cross-sectional dimension (diameter or effective diameter) of the reaction chamber, and/or a transverse dimension of at least 50% of the silicate structure particles being greater than 0.04%, preferably greater than 0.1%, in particular greater than 0.3% of the flow cross-sectional dimension.
  • the maximum size of the particles in their largest spatial extent is preferably not more than 40%, in particular 30% of the (in particular smallest) flow cross-sectional dimension of the reaction chamber.
  • a method is preferably provided in which the movement speed is controlled to an exposure time of less than or equal to 30 minutes, preferably less than or equal to 20 minutes, more preferably less than or equal to 15 minutes, in particular less than or equal to 10 minutes and/or to an exposure time of at least 20 seconds, preferably at least 2 minutes. This promotes the shift towards significantly lower, but still present desired metal proportions.
  • the length of the flow path is preferably at least 1m, in particular at least 5m and/or not more than 500 m, in particular not more than 300 m.
  • metal on its own or in terms such as “metal content” is not limited to the exclusively metallic form with oxidation state 0, but generally also includes mixed forms in the form of mixed oxides, carbonates or sulfates, such as those typically found in layered silicates.
  • the weight ratio of silicate structure particles to treatment liquid is greater than 5%, preferably greater than 10%, more preferably than 15%, in particular than 20% and/or 60%, preferably 50%, in particular does not exceed 40%.
  • a method in which the flowing treatment liquid carrying the silicate structure particles is under a pressure of more than 1 bar, preferably more than 2 bar, in particular more than 4 bar, wherein the pressure preferably does not exceed 20 bar, more preferably does not exceed 18 bar, in particular does not exceed 15 bar.
  • a process is provided which is below a temperature of at least 70°C, preferably at least 100°C, more preferably at least 120°C, in particular at least 140°C, and/or does not exceed 220°C, more preferably does not exceed 210°C, in particular does not exceed 200°C.
  • the treatment liquid contains an acid in a concentration of at least 5%, preferably at least 12%, more preferably at least 18%, in particular at least 24%, wherein the concentration is preferably less than 50%, more preferably not exceeding 40%, in particular not exceeding 30%.
  • the composition of the reactants is changed by adding a reactant, in particular acid, downstream of the reaction chamber inlet at a distance from the latter, with the reaction chamber between the inlet and the addition point preferably being continuous.
  • a reactant in particular acid
  • Such an addition could also take place more than once, for example at further addition points located further downstream.
  • the acid or acid mixture used could be used as a reactant, in particular hydrochloric acid, can be added multiple times in this way.
  • Such an addition is not restricted to addition in liquid form, it could also be carried out by introducing, for example, gaseous HCl.
  • reaction kinetics can be influenced as desired by increasing the reactant concentration. This can also influence the energy efficiency of the process.
  • a high dissolution rate of aluminum can be achieved even with Al:Cl ratios of less than 1:3.
  • An AlCh solution could also be considered as an alternative to HCl.
  • meta-kaolin calcined kaolin
  • reactant 1 the raw material
  • other comparable materials e.g. enriched kaolin, not calcined.
  • calcined clays metalakaolin
  • non-flash calcined clays are preferred, in which the layer structure is not subjected to any effects caused by flash calcination.
  • a reaction mixture fed to the flow reactor (referred to as the first suspension) can first be placed in a mixing container made of water, e.g. hydrochloric acid and raw material.
  • the source of the acid can preferably be set up spatially separate from a protective container containing the reactor.
  • This first suspension can be continuously stirred at room temperature and pumped into the flow reactor using a pumping device (it is understood that the pump and flow settings depend on the overall setting and are particularly important in the can be set within the values given above, the same applies to the temperature and pressure settings).
  • the reaction mixture (hereinafter referred to as the second suspension) can be collected in a slurry container.
  • the proportion of the metal contained based on the silicon content, which is shifted to lower values by the treatment in the reaction space, it is preferred that this shift occurs by dissolving the metal from the silicate structure, with preferably more than 60%, more preferably more than 70%, in particular more than 75%, even more than 77% of the metal, preferably aluminum in many examples, being dissolved out.
  • more than 3%, preferably more than 5%, more preferably more than 7%, even more than 9% of the originally contained metal, in particular aluminum remain in the silicate structure.
  • control technology it is particularly intended to meter the reactant, such as HCl, in the form of a control, in particular via inline pH measurements and/or viscosity measurements of the reaction solution.
  • precise metering can thus reduce or avoid the risk of overdosing, which otherwise potentially exists depending on the fluctuating starting material.
  • the temperature of the process is also preferably monitored. In particular, the temperature is recorded at one or more of the following positions in the process by temperature sensors, in particular those attached externally: in the mixing tank, near the pump for pumping into the reaction chamber, the slurry tank for collecting the reaction mixture.
  • Further temperature recordings can be provided between heating reactors, which generate the heat that causes the energy input for the reaction, if necessary also between a heating reactor outlet and a cooling water bath inlet, as well as in the cooling water bath or at the cooling water bath outlet.
  • the room temperature can also be measured and fed to the control system.
  • a method is provided in which the media-contacting inner surfaces of the outer boundary are designed to be corrosion-resistant and in particular comprise one or more of the group SiC, glass, ceramic or a plastic such as PTFE or PFA as the material.
  • a method is preferably provided in which the silicate structure still containing metal after this displacement/action is separated from the treatment liquid after it has flowed through the flow path.
  • the separation could be carried out by a continuous separation, but also in a batch manner, although the latter is also preferred.
  • a chamber filter press can be used for the separation.
  • the liquid phase resulting from the separation which contains polyaluminium chloride, can be collected in a container of a given size, the capacity of which is preferably a multiple of the reactor volume. It can be further analyzed if necessary and, if required, transported to interested customers or further processed.
  • the (starting) silicate structure is formed from a natural aluminum silicate, in particular a layered silicate, preferably kaolin or metakaolin produced by its dehydration (but also preferably by conventional calcination, i.e. not by flash calcination).
  • the invention further relates to a reactor system with a reaction chamber delimited by an external boundary, designed and controlled to carry out a method according to one of the preceding aspects.
  • the reaction chamber defining the flow path can have one or more addition openings separated from its entrance and from one another to form the addition points explained above.
  • the reactor chamber can be coupled to a heating device in order to enable energy to be introduced.
  • direct heating is considered on the one hand, for example in the form of one or more electrical heating devices, for example via resistance heating, or also microwave radiation.
  • indirect heating via a heat transfer medium is also considered, preferably in the form of thermal oil or hot steam. Combinations of direct and indirect heating can also be provided.
  • reaction hose delimiting the reaction chamber
  • the reaction hose is sufficiently resistant to high temperatures and sufficiently resistant to the chemicals used.
  • the reaction tube can, for example, consist of a smooth tube made of plastic and also be provided with an external reinforcement, such as a braid made of stainless steel.
  • the tube itself can be formed as a smooth tube made of a material such as PTFE as a core.
  • the reaction tube can be wound up in such a way that the reaction space has a volume of at least 0.2 l, more preferably at least 0.4 l, in particular at least 0.6 l.
  • the volume of the reaction space is not greater than 8 l, more preferably not greater than 6 l, even more preferably not greater than 4 l, in particular not greater than 2 l.
  • the reaction volume could be approximately 0.75 l.
  • An external oil bath can be used for the heating system coupled to the interior of the hollow cylinders, and a thermal HS oil, e.g. based on silicone, can be used as the tempering fluid.
  • a thermal HS oil e.g. based on silicone
  • the volume flow through the reaction chamber is controlled to at least one liter per hour, preferably at least two liters per hour, more preferably at least three liters per hour, even higher, such as four liters per hour or more. It is also preferred if this volume flow (flow) is not more than 20 liters per hour, also preferably not more than 16 liters per hour, more preferably not more than 12 liters per hour, even not more than 8 liters per hour. It is understood that the invention also takes into account larger systems that achieve a significantly higher total flow overall. For such designs, however, it is preferred to feed several reaction chambers in parallel, so that the above-mentioned values are preferably achieved in at least one, preferably several, in particular the majority of the parallel reaction chambers used.
  • the flow reactor can be designed as a plug-flow reactor. However, variants with areas of turbulent flow are also considered. Even then, it is preferred if the average residence time (volume of the reaction space/throughput) does not deviate by more than 30%, preferably not more than 20%, in particular not more than 10% from a reference time defined by purely laminar flow under otherwise identical conditions.
  • the invention is not fundamentally restricted with regard to the pump technology used for the flow through the flow reactor.
  • peristaltic pumps and/or gear pumps are used.
  • at least one pump is arranged upstream in the reaction chamber.
  • a further pump can also be provided downstream of the reaction chamber, for example between a filter device and a tank arranged downstream of the reaction chamber.
  • the control of the system can preferably use inline measured values such as pH and/or viscosity.
  • corresponding measuring probes could be provided inline, for example at or near the exit of the reaction chamber.
  • the silicate structural particles could be separated using a membrane filter press, for example, and the separated material could be dried using conventional drying technology.
  • Output containers can be provided to provide/as a source of treatment liquid and (initial) silicate structure. Acidic wash water, which is drawn off downstream of the separation step, could be returned to these.
  • the silicate structure particles obtained in this way have properties that make them suitable for use as additives for building materials such as concrete.
  • the invention thus also relates in general to a material which can be used as an additive for a building material such as concrete which is flowable after the addition of water and can solidify with the formation of strength-forming CSH phases.
  • Such additives for e.g. cement, mortar, concrete or other hydraulic binders are widely known in technology and serve to improve individual or multiple properties of the building materials in use right up to the parts manufactured from them.
  • tensile strength-increasing reinforcing agents that have been used for a long time, for example in the form of reinforcing steel or in the form of fiber reinforcements through additives in the form of added fibers made of various materials.
  • microsilicas that are also commercially available and are often and usually used as additives, with their very high SiO2 contents, e.g. of 97% (e.g.
  • EP 0 517 869 B1 describes how a carbonate donor can be added to a Portland cement-based system with the aim of rapidly to achieve higher strengths. Additives such as sodium carbonate, sodium sulfate and calcium hydroxide are described in DE 4223494 C2, also for achieving high early strengths.
  • the invention is generally also based on the object of advantageously developing an additive of the aforementioned type, in particular with a view to a suitable combination of both technical properties, such as a satisfactory achieved compressive strength and in particular satisfactory flexural strength, and the appearance of the end product.
  • the invention provides a further development of a material which can be used as such an additive of the aforementioned type, which is essentially characterized in that the material comprising silicate-containing particles comprises aluminum, wherein the sum of the aluminum content of the material, calculated as Al2O3, the content of any and preferably intended proportion of titanium in the material, calculated as TiO?, and any and preferably intended proportion of zirconium in the material, calculated as ZrC>2, is at least 0.6%, but the Al content is less than 32%, preferably less than 24%, in particular less than 16%, wherein the percentage values (here and below) are to be understood as weight percent (wt.%).
  • the material comprising silicate-containing particles comprises aluminum, wherein the sum of the aluminum content of the material, calculated as Al2O3, the content of any and preferably intended proportion of titanium in the material, calculated as TiO?, and any and preferably intended proportion of zirconium in the material, calculated as ZrC>2, is at least 0.6%, but the Al content is less than 32%,
  • the Al content based on AI2O3 is at least 0.36%, preferably at least 0.42%, in particular at least 0.48%, but proportions of at least 0.6%, even at least 0.75% are also considered.
  • Al weight percentages (based on AI2O3) of more than 3%, preferably more than 3.6%, in particular more than 4.2% are also considered in this context.
  • the main material proportion is formed by silicon (based on SiC>2), in particular with proportions calculated as SiC>2 of more than 64%, preferably more than 80%, more preferably more than 84%, in particular more than 88%, Si proportions of less than 94.5%, even less than 94%, even 93.5% are also considered, especially with higher Al proportions.
  • Si contents are also considered, such as 95% or more, 96% or more, or even 97% or more.
  • the silicate matrix of the particles is preferably layered.
  • the material has reactive SiC>2 and has a pozzolanic effect.
  • the titanium content calculated as TiC>2, is at least 0.2%, preferably at least 0.3%, more preferably at least 0.4%, although variants of at least 0.5% are also conceivable.
  • Zr calculated as ZrO2 is present in at least 0.02%, preferably at least 0.03%, more preferably at least 0.04%.
  • TiC>2 values of less than 0.96%, preferably less than 0.88%, more preferably less than 0.8% or even less than 0.75% are also conceivable.
  • the ZrO2 content is preferably less than 1.0%, preferably less than 0.8%, also less than 0.5%, even less than 0.3%.
  • the above-mentioned proportions of Al, Ti and Zr in their previously quantified proportions are part of the silicate matrix of the particles, i.e. are incorporated into the silicate matrix or silicate structure of the particles, and are not merely added in the form of further particles or only adhere to the particles with the silicate matrix.
  • these proportions are also found in the interior of the particles due to their integration into the silicate matrix, which themselves are preferably mesoporous - in contrast to a microporosity, as would arise during flash calcination due to the bubble formation effect of the flash calcination.
  • the invention does not exclude the inclusion of further of these components or further material proportions in the material in a manner not integrated into the silicate matrix.
  • the invention therefore does not exclude materials which are a composite material of the previously explained silicate-containing particles with the portions incorporated in their silicate matrix as a first component and a second component (or further components), whereby the values given so far and below, including the upper limit for the Al content given above, would then refer to this first component.
  • iron calculated as Fe2O3, of 0.01%, even 0.02%, but preferably not more than 1.5%, more preferably not more than 0.5%, in particular not more than 0.3% is incorporated into the silicate matrix of the particles.
  • the particles deviate considerably from a spherical shape in that they have a small dimension in one spatial direction compared to the dimension of the particles in the plane orthogonal thereto.
  • this ratio is preferably greater than 0.03, more preferably than 0.04, in particular than 0.05, the values for this ratio referring to the value averaged over the particles of the material (arithmetic mean).
  • at least 60%, more preferably at least 70%, in particular at least 80% of the individual particles have ratios in these ranges.
  • the areal extent is preferably along the layers in a preferably layered silicate matrix.
  • This asymmetrical design of the particles compared to a spherical shape also allows the growth direction of the CSH phases to be specified anisotropically, namely with a predominantly directional component orthogonal to the small expansion direction (platelet thickness) of the respective particles.
  • the structure of the particles forms a support for CSH phases leading to an anisotropic CSH phase growth direction.
  • the invention thus discloses as independently protectable a material which can be used as an additive for a building material which, after the addition of water, is capable of flowing and solidifying to form strength-forming CSH phases, and which has silicate-containing particles, with an aluminum content of the particles based on Al2O3 of preferably less than 32%, more preferably less than 24%, in particular less than 16%, in which the structure of the particles forms a carrier for CSH phases which directs an anisotropic CSH phase growth direction. This promotes a compressive strength and flexural strength of a building material for which the additive is used.
  • the material has an activity index of greater than 104%, preferably greater than 106%, in particular greater than 108% according to EN 196-1:2016, and/or an activity index related to flexural strength of greater than 105%, preferably greater than 107%, in particular greater than 109%, wherein a flexural strength test according to EN 196-1:2016 is used instead of the compressive strength test of the aforementioned standard for determining the activity index.
  • the BET surface area of the material is at least 70 m 2 /g, preferably at least 100 m 2 /g, in particular at least 130 m 2 /g, and/or less than 400 m 2 /g, preferably less than 370 m 2 /g, in particular than 340 m 2 /g, and/or the oil number of the material is greater than 30, preferably than 35, in particular than 40, and/or less than 110, preferably less than 100, in particular less than 90.
  • the BET surface area is less than 180 m 2 /g, more preferably less than 165 m 2 /g, in particular less than 150 m 2 /g.
  • the BET surface area of the material is within these parameters before any (possible) thermal post-treatment affecting the BET surface area.
  • the material has a whiteness L* (in the LAB color space) of greater than 92, preferably greater than 95, again preferably greater than 96, in particular greater than 97.
  • L* in the LAB color space
  • the invention also provides a Puzzoian white pigment for building materials.
  • the invention also discloses, as independently protectable, a pozzoian white pigment containing silicate particles, which can be used in particular as an additive for a building material which is flowable after the addition of water and can solidify to form strength-forming CSH phases, with a whiteness L* of greater than 92, preferably greater than 95, again preferably greater than 96, in particular greater than 97.
  • a whiteness L* of greater than 92, preferably greater than 95, again preferably greater than 96, in particular greater than 97.
  • an aluminum content (calculated as Al2O3) is preferably not greater than 32%, more preferably less than 24%, in particular less than 16%.
  • a Zr content of less than 0.6% by weight, in particular less than 0.5% by weight, more preferably than 0.35% by weight, in particular than 0.2% by weight is also preferred, again calculated as ZrO2.
  • dgs of the particles is less than 70 pm, preferably less than 60 pm, more preferably less than 50 pm. It is also preferred that in wet sieving with a mesh size of 125 pm the residue is less than 2%, and/or in wet sieving with a mesh size of 63 pm the residue is less than 3%.
  • the passage during wet sieving with a mesh size of 25 pm is less than 40%, preferably 30%, in particular 20%.
  • the passage during wet sieving with a mesh size of 20 pm is less than 40%, preferably 30%, in particular 20%.
  • the passage during wet sieving with a mesh size of 15 pm is less than 40%, preferably 30%, in particular 20%. This provides a good combination of satisfactory activity and not too high a water requirement when the material is used in a building material mixture.
  • the particles originate from a starting material, in particular a natural one, which also has a platelet-like shape, with the values given above also being preferred with regard to the dimensions.
  • a shape factor of the starting material of greater than 24, preferably greater than 27, in particular greater than 30 and/or less than 56, preferably less than 53, in particular less than 50 is also preferred.
  • the particles arise from a process in which an aluminum-containing layered silicate, in particular kaolin, possibly converted into metakaolin after dehydration, has experienced a shift in its Al content relative to the Si content to lower values due to the action of an acid.
  • the exposure time of the acid for example HCl, is less than 30 minutes, preferably less than 20 minutes, more preferably less than 12 minutes, more preferably less than 15 minutes, in particular less than or equal to 10 minutes, with exposure times of at least 2 minutes being preferred, preferably in a flow reactor, in particular a plug-flow reactor.
  • the exposure times could also be chosen to be longer, for example by using a multi-stage process.
  • the aluminum-containing layered silicate is particularly preferably selected from the group of non-calcined layered silicates and calcined but not flash-calcined layered silicates. Of the latter, layered silicates calcined for a period of at least 2 minutes are preferred, in particular layered silicates calcined in a rotary kiln. In this way, microporosity of the layered structure (due to the blistering effect) can be avoided.
  • the invention relates to a material mixture and assortment comprising the material according to the invention as a component, comprising at least two different materials or such material mixtures according to one of the preceding aspects, wherein a difference lies in the Al content, Ti content, the BET surface area, grain size and/or the reactivity, individually or in combination.
  • the invention relates to the use of a material according to one of the preceding aspects as an additive for a building material that is flowable after addition of water and can solidify with the formation of strength-forming CSH phases.
  • a silicate structure provided by the invention which is produced from a method according to one of the preceding aspects and is obtained from the silicate structure separated (and dried) after the separation step, represents a preferred embodiment of such a material according to the above material-technical point of view.
  • the solid phase obtained after the separation step could also be cleaned, for example by washing processes with water, even repeated washing processes with water, for example until the washing water is pH-neutral.
  • the silicate structure particles (hereinafter also referred to as the material) with reduced metal content obtained in this way can preferably be particles that are formed via the process with process parameters such as the exposure time, concentration of the media, pressure and/or temperature and have one or more of the properties already listed above from a material technology point of view and in particular the following properties:
  • the particles can have aluminum as metal, wherein the sum of the aluminum content, calculated as Al2O3, the content of any and preferably intended content of titanium, calculated as TO2, and any and preferably intended content of zirconium, calculated as ZrC>2, is at least 0.6%, but the Al content is less than 32%, preferably less than 24%, in particular less than 16%, wherein the percentage values (here and below) are to be understood as weight percent (wt.%).
  • the Al content based on Al2O3 can be at least 0.36%, preferably at least 0.42%, in particular at least 0.48%, but proportions of at least 0.6%, even at least 0.75% are also considered.
  • Al weight percentages (based on Al 2 O 3 ) of more than 3%, preferably more than 3.6%, in particular more than 4.2% are also considered in this context.
  • the main material proportion is formed by silicon (based on SiO2), in particular with proportions calculated as SiO2 of more than 64%, preferably more than 80%, more preferably more than 84%, in particular more than 88%, Si proportions of less than 94.5%, even less than 94%, even 93.5% are also considered, especially with higher Al proportions.
  • the silicate matrix of the particles is preferably layered.
  • the titanium content calculated as TiO 2
  • Zr calculated as ZrO 2
  • ZrO 2 can be present in at least 0.02%, preferably at least 0.03%, more preferably at least 0.04%.
  • values of less than 0.84%, preferably less than 0.8%, even less than 0.75% are also conceivable.
  • the ZrO 2 content is preferably less than 1.0%, preferably less than 0.8%, even less than 0.5%, even less than 0.3%.
  • a composite material could also be formed from the particles produced in this way, namely from the silicate-containing particles produced in this way with the proportions incorporated into their silicate matrix as a first component and a second component (or further components), whereby the values given so far and below, including the upper limit for the Al content given above, would then refer to this first component.
  • iron calculated as Fe 2 Os, of 0.01%, also 0.02%, but preferably not more than 5%, more preferably not more than 1.5%, in particular not more than 0.5%, is also incorporated into the silicate matrix of the particles, likewise small components of calcium, calculated as CaO, of preferably not more than 0.2%, and/or magnesium, calculated as MgO, of preferably not more than 0.3%, possibly also potassium, calculated as K 2 O, of preferably not more than 2%, in particular 1%, could be incorporated.
  • the process is controlled via the starting material in such a way that the particles deviate significantly from a spherical shape by having a shape in one spatial direction relative to the expansion of the particles have a small extent in the plane orthogonal thereto.
  • this ratio is preferably greater than 0.03, more preferably than 0.04, in particular than 0.05, the values for this ratio referring to the value averaged over the particles of the material (arithmetic mean).
  • at least 60%, also at least 70%, even at least 60%, more preferably at least 70%, in particular at least 80% of the individual particle ratios have in these ranges.
  • the areal extension is preferably along the layers in a preferably layered silicate matrix.
  • the BET surface area of the material after the process and before any thermal post-treatment is then preferably at least 70 m 2 /g, preferably at least 100 m 2 /g, in particular at least 130 m 2 /g, and/or less than 400 m 2 /g, preferably less than 370 m 2 /g, in particular 340 m 2 /g, and/or the oil number of the material is greater than 30, preferably 35, in particular 40, and/or less than 110, preferably less than 100, in particular less than 90.
  • the BET surface area is less than 180 m 2 /g, more preferably less than 165 m 2 /g, in particular less than 150 m 2 /g.
  • dgs of the particles is less than 70 pm, preferably less than 60 pm, more preferably less than 50 pm. It is also preferred that in wet sieving with a mesh size of 125 pm the residue is less than 2%, and/or in wet sieving with a mesh size of 63 pm the residue is less than 3%.
  • the passage during wet sieving with a mesh size of 25 pm is less than 40%, preferably 30%, in particular 20%.
  • the passage during wet sieving with a mesh size of 20 pm is less than 40%, preferably 30%, in particular 20%.
  • the Passage during wet sieving with a mesh size of 15 pm is less than 40%, preferably 30%, in particular 20%.
  • the material can then have a whiteness L* (in the LAB color space) of greater than 86, preferably greater than 92, more preferably greater than 95, again preferably greater than 96, in particular greater than 97.
  • a product of the process according to the invention can also be used as a pozzolanic white pigment for building materials.
  • the particles originate from a natural starting material, its comminuted particles can also have a platelet-like shape, with the values given above also being preferred with regard to the dimensions.
  • a shape factor of the starting material of greater than 24, preferably greater than 27, in particular greater than 30 and/or less than 56, preferably less than 53, in particular less than 50 is also preferred.
  • such a product of the process according to the invention could thus be used as an additive for a building material which, after addition of water, is flowable and can solidify to form strength-forming CSH phases, for example in order to increase its flexural strength.
  • Fig. 1 shows a schematic representation of a system for carrying out the method according to the invention.
  • the core of the reactor arrangement 1000 shown purely schematically in Fig. 1 is the reaction chamber 100, which is delimited by an outer boundary 110.
  • a volume flow of a treatment liquid f with entrained particles p of a silicate structure is generated, in this embodiment kaolin, along a flow path s from a to b with a length of approximately 25 m in this embodiment and is subject to an effect during this movement which dissolves metal from the silicate structure particles p.
  • the solution in the form of an acid here For example, hydrochloric acid, here about 33%, is present in the treatment liquid, part of the aluminum contained in the kaolin is dissolved out.
  • a source of the treatment liquid f is designated 60, whereby concentrated hydrochloric acid can be added via dosing device 80 in the area of the reaction path or is only added in order to keep the acid concentration at a desired level. Treatment liquid can also be recirculated again via recirculation 70 and the supply of concentrated acid adjusted accordingly.
  • Reference number 90 designates an energy source that applies heat to the reactor.
  • the invention is not limited to the components and dimensions shown in this embodiment. Variations, particularly in the dimensions, are also conceivable. For an overall upscaling, however, not only larger dimensions of the individual components or in particular of the reaction chamber are considered, but also the multiple parallel use of reaction chambers and possibly other components within an overall system.
  • the starting particles p are crushed kaolin fragments, but could also be metakaolin fragments or other crushed ores, but preferably aluminum-containing layered silicates provided from a source 50 (preferably the metakaolin fragments or layered silicates are not flash-calcined); details of crushing processes to dimensions of preferably in the range 10-500 microns are known to the person skilled in the art and are not explained in more detail here.
  • an acidolysis of meta-kaolin (20% slurry) was carried out with HCl in a flow reactor as described above.
  • the acid was added as 22% hydrochloric acid, the flow rate was varied in several test series by an acid flow rate of 5.6 liters per hour in the range of +-15%, and a target residence time of 8 minutes in a range of +- approx. 15%.
  • the temperature between the heating reactor outlet and the cooling water bath inlet was 145°C.
  • the composition of the meta-kaolin used varied slightly within the range of usual composition values, with between 80 and 87% of the aluminum being dissolved out.
  • acidolysis of meta-kaolin (10% slurry) was carried out not with hydrochloric acid, but with AICH as the acid.
  • the flow rate for various test examples was somewhat lower than in the previous examples, ranging between 2.3 and 4.4 liters per hour, and the residence times were correspondingly longer (approx. 10 to 20 minutes).
  • the temperature control was essentially the same as in the previous examples.
  • the amount of aluminum dissolved out varied between 78 and 81% of the aluminum originally present in the raw material.
  • the metakaolin can be obtained from calcination in a rotary kiln over several minutes.
  • the silicate structure particles q with reduced metal content are separated from the treatment liquid fm (now enriched with dissolved metal) in a separating device 200.
  • the separating device 200 can have one or more separation stages, for example with the filter technology of a membrane filter press or a filter technology based on a vacuum belt filter, vacuum drum filter, centrifugation, sedimentation and the like, in the case of continuous or discontinuous discharge.
  • the silicate structure particles q with reduced metal content can also be processed, for example dried, in a processing stage 300 (drying, chopper).
  • the treatment liquid fm enriched with the dissolved metal can then be fed to further processing steps or uses that are not explained here.
  • the silicate structure particles q can then be processed as a dry substance, such as powder or granulate, or as a suspension, e.g. used as an additive for concrete, for example, or as a pigment.
  • a dry substance such as powder or granulate
  • a suspension e.g. used as an additive for concrete, for example, or as a pigment.
  • the structure or underlying layer structures are still preserved to such an extent that they have not been subjected to flash calcination.
  • a control system for the process controls the process parameters such as concentration of the media, pressure, temperature, energy input in the reactor chamber, etc. via pump devices or heating devices, which are not fully shown in detail.
  • the material is in dry powder form, i.e. in the form of particles, and a composition in weight percent according to chemical analysis (according to EN 196-2:2013) with proportions of
  • a test for water soluble substances in the material according to EN ISO 87-3 was 0.29%.
  • the material contains soluble chloride, determined according to EN ISO 87-13, of less than 0.01% and a total chlorine content determined according to ISO 1158 of less than 0.01%.
  • the loss on ignition of the material determined according to EN 450-1 is 7.97%.
  • This material of the first embodiment shows the following results in the tests described below, in which the addition of the material based on a cement quantity of a reference cement, namely CEM I 42.5 R 5%:
  • the compressive strength was determined according to EN 196-1:2016, the values given are the mean values of six separately treated samples.
  • the start of setting for the reference cement with the added material from Example 1 was determined to be only 5 minutes later after 180 minutes than in the reference cement itself.
  • the end of setting was determined to be 240 minutes (determined in accordance with EN 196-3:2017).
  • the main components of the material are (parts with only small traces of content are omitted):
  • a particle size of no larger than 100 pm was determined, with an XD 50 of about 12 pm.
  • an activity index of 108% and a whiteness L* of 98.2 shows a favorable property as an additive for concrete, for example, due to the relative lightness and the high whiteness.
  • the material has the following composition: Other elements which are only present in trace amounts are not listed in detail.
  • the material has the composition:
  • the material has the composition:
  • natural starting materials namely a purified kaolinite
  • hydrochloric acid 22 percent
  • the particles of the material were obtained after filtration.
  • the layer structure of the starting material was essentially retained (apart from certain delamination effects) and thus essentially platelet-shaped particles are present.
  • the mesoporous silicate matrix of the particles also contains the aluminum in a desired amount as well as other components as explained above.
  • the blistering effect can be avoided and a mesoporous structure (and not a microporous structure) can be obtained.
  • materials are created as in the previous examples and separated by particle size using a sieve (e.g. mesh size 20 pm), and the coarser-grained portion is provided as material, or mixed with a fraction of the previously filtered-out portion and provided as material. Preferably, at least 60% by weight of the particles remain from the coarser-grained portion.
  • a sieve e.g. mesh size 20 pm
  • silicate structures can also be used as starting material, such as other layered silicates, framework silicates, type of processing of the starting material such as degree of comminution, etc., or others can be varied.
  • flash calcination is preferably dispensed with.
  • the invention is not restricted by details of such a production process, for example in relation to the acid or acid combination used, exposure times, special reactor types and the like.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Civil Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

L'invention concerne un procédé de modification chimique par voie humide d'une structure de silicate, la fraction, sur la base de la fraction de silicium, d'un métal contenu dans la structure de silicate étant décalée vers des valeurs inférieures par exposition à un liquide de traitement s'écoulant à l'intérieur d'un espace de réaction délimité par une limite externe, dans un temps d'exposition, la structure de silicate étant également déplacée et dans le temps d'exposition s'écoulant à travers une voie d'écoulement, et un rapport de la longueur de la voie d'écoulement ou de l'étendue longitudinale de la limite externe à la racine de cube du volume d'espace de réaction étant supérieur à 8, de préférence supérieur à 12, plus particulièrement supérieur à 16, et le produit de réaction dudit procédé, et un système de réacteur.
PCT/EP2024/061547 2023-04-27 2024-04-26 Procédé de modification chimique par voie humide d'une structure de silicate, produit de réaction associé et utilisation, et système de réacteur correspondant Pending WO2024223828A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE102023001707.8 2023-04-27
DE102023110874.3A DE102023110874A1 (de) 2023-04-27 2023-04-27 Verfahren zur nasschemischen änderung eines metallgehalts und entsprechendes reaktorsystem
DE102023110874.3 2023-04-27
DE102023001707.8A DE102023001707A1 (de) 2023-04-27 2023-04-27 Als zusatzstoff für baustoffe einsetzbares material

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EP0517869B1 (fr) 1990-12-28 1998-05-20 Holderbank Financiere Glarus Ag Liant hydraulique et procédé de son préparation
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