WO2022199967A1 - Liant réfractaire - Google Patents

Liant réfractaire Download PDF

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Publication number
WO2022199967A1
WO2022199967A1 PCT/EP2022/054462 EP2022054462W WO2022199967A1 WO 2022199967 A1 WO2022199967 A1 WO 2022199967A1 EP 2022054462 W EP2022054462 W EP 2022054462W WO 2022199967 A1 WO2022199967 A1 WO 2022199967A1
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WO
WIPO (PCT)
Prior art keywords
refractory
binder composition
group
agents
metal
Prior art date
Application number
PCT/EP2022/054462
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English (en)
Inventor
Jerzy Bugajski
Original Assignee
Jerzy Bugajski
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jerzy Bugajski filed Critical Jerzy Bugajski
Priority to EP22712285.0A priority Critical patent/EP4313907A1/fr
Publication of WO2022199967A1 publication Critical patent/WO2022199967A1/fr

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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
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    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/10—Lime cements or magnesium oxide cements
    • C04B28/105—Magnesium oxide or magnesium carbonate cements
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    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/03—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on magnesium oxide, calcium oxide or oxide mixtures derived from dolomite
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Definitions

  • the present invention is in the field of inorganic chemistry and relates to an improved chemically and hydraulically bonding refractory binder composition which after mixing with water will set and harden at ambient temperature within an acceptable predetermined and adjustable period of time.
  • the refractory binder according to the present invention is a modern, advanced binder, the use of which having in effect that after firing of the binder or of products made using said binder no significant amounts of low melting phases or bonding compounds like phosphates, silicates, sulphates, chlorides, borates, or chromates are formed, and no harmful gaseous emissions are released. Moreover, upon mixing the binder with water the setting and hardening process occurs already at ambient temperature.
  • EP3176140 discloses a magnesia cement comprising caustic magnesia and a poorly water-soluble carboxylic acid. No additional metal salts or other bonding additives are necessary to achieve firm bonding.
  • the bonding is predominantly hydraulic through the formation of brucite, i.e. magnesium hydroxide. If a higher amount of brucite is formed, this can lead to decreased mechanical strength of products bonded by said cement, particularly in the temperature range between brucite decomposition and the formation of the ceramic bond.
  • DE1471297 discloses a refractory material that contains a cementitious mixture of non-plastic fine magnesia and 0.1 to 15 % of an aliphatic hydroxy-tricarboxylic acid, preferably citric acid or a salt thereof.
  • Such strongly complexing carboxylic acids or their salts are, however, not preferred as components of the bonding system according to the present invention, because the precipitation of the bonding phases from the solution containing strongly complexed ions is substantially retarded or - in the extreme - almost entirely prevented.
  • the salts of tricarboxylic acids are therefore not regarded as suitable components of the novel binder of the present invention in the concentration range disclosed in DE1471297.
  • W0201 5036262 relates to a refractory, hydraulic binder based on at least one calcined aluminium oxide and at least one oxide or hydroxide of alkaline earth metals.
  • the bonding requires the use of sodium tricitrate as a dispersant.
  • the manufacturing process is based on a simple mixing of components.
  • WO201 1065825 (A1 ) discloses a corrosion inhibition system for reinforced concrete based on an intercalated layered double hydroxide which is effective in an environment rich in chloride ions. Ion exchange can take place within the bulk of the layered double hydroxide, thereby releasing the corrosion protective organic ions and capturing the chloride ions.
  • the intercalated layered double hydroxide used in WO201 1065825 is, however, not a component of the bonding system of the reinforced concrete.
  • WO201 71 16312 (A1 ) discloses a cement composition comprising a Portland cement clinker, limestone, gypsum and a layered double hydroxide resulting in the improvement of early strength, as compared to compositions without double layered hydroxide.
  • the Portland cement compositions in all variations are not suitable for the refractory and high temperature applications enabled by the refractory binder of the present invention.
  • the bonding concept of the Portland cements of W020171 16312 is entirely different from the one of the presently claimed binders.
  • the binders of the present invention do not comprise calcined alumina nor is the presence of salts of tricarboxylic acids required for dispersing purposes.
  • the binders in accordance with the present invention are free or essentially free from tricarboxylic acids and from salts of tricarboxylic acids, at least for the reasons mentioned hereinabove.
  • "Essentially free” in this context shall relate to an amount of 0.01 % by weight or less, relative to the total dry mass of the binder composition.
  • One embodiment of the present invention provides the use of at least one layered double hydroxide, mixed oxide, or its precursor. Manufacturing of such a component requires intensive grinding instead of simple mixing, i.e. it requires mechanical alloying, preferably together with thermal or chemical treatment, of e.g. alumina and magnesia, or of other aluminium and magnesium compounds.
  • Metal layered double hydroxides, metal layered double oxides, and their respective precursors are especially suitable as components of the bonding system in line with the present invention.
  • layered hydroxides or “double layered hydroxides” it is to be understood that these terms read on “metal layered hydroxides” or “metal layered double hydroxides”, respectively.
  • layered oxides or “double layered oxides” are meant to read on “metal layered oxides” and “metal layered double oxides”, respectively.
  • CAC calcium aluminate cement
  • hydratable alumina cement the hydratable alumina cement
  • the CAC introduces lime to the refractory material bonded by this cement, which can lower the refractoriness and chemical resistance of the resulting products. Bonding using the hydratable alumina is not very strong at lower amounts of this kind of cement and the use of higher amounts thereof results in a marked increase of water demand and consequently in some undesirable side-effects like increased porosity and difficult heat-up.
  • Inorganic metal salts selected from the group of aluminium sulfate, aluminium chloride, magnesium chloride, magnesium sulfate, and zirconium oxychloride are sometimes applied as additives to other cementing mixtures for achieving an improvement in strength, but usually they are regarded as less suitable for dispersing mixtures, and they are not environmentally friendly due to the generation of harmful fumes during heat-up.
  • the metal salts of carboxylic acids are frequently used as additives or compounds of the bonding system, for example zirconium acetate, a water-glass bonding cement adhesive offered e.g. by Zircar Zirconia, Inc., USA.
  • zirconium acetate a water-glass bonding cement adhesive offered e.g. by Zircar Zirconia, Inc., USA.
  • a major drawback of this organic metal salt is the fact that bonding of waterglass cement in the presence of this organic metal salt does not occur at ambient temperature. Bonding with the waterglass will take place only at increased temperatures, whereupon the zirconium silicate ceramic bond will be formed.
  • sol/gel- technique of ceramic processing A wide field of applications in numerous industries is covered by the sol/gel- technique of ceramic processing.
  • the present invention is focused on improving the bonding characteristics of a ceramic system at ambient temperature without the need of adding typical components of the sol/gel-technique such as metal alcoho- lates and/or non-aqueous organic liquids.
  • the present invention relates to a chemically and hydraulically bonding refractory binder which after mixing with water will set and harden at ambient temperature.
  • the formation of poorly water-soluble bonding phases or amorphous species occurs as the result of chemical interaction of the ingredients including acid-base reactions, hydration, hydrolysis, ion exchange and precipitation, as well as crystal seeding and crystal growth.
  • Typical ingredients comprise metal salts and/or esters of carboxylic acids having neutral, acidic or amphoteric character, and/or carboxylates or carboxylate esters, as a first main component C1 , in combination with basic metal oxides, metal hydroxides, metal layered double hydroxides, precursors of metal layered double hydroxides, mixed metal oxides, precursors of mixed metal oxides, and carbonates, as a second main component C2.
  • the main objective of the present invention namely gaining control over the rate of the aforementioned chemical processes and, consequently, over the rate of setting and hardening, has been achieved by adjusting the surface and bulk reactivity of the main components, optionally in combination with the use of supplementary additives.
  • the reactivity of the main components of the present binder can be adjusted by varying their chemical and physical composition, and/or their particle size, and/or their specific surface area, and, in addition, by mechanical alloying, mechanochemical synthesis, and by thermal and/or surface treatment of said components.
  • the species of the main component C1 of the refractory binder are preferably selected from the group consisting of aluminium acetate, aluminium glycolate, aluminium formate, aluminium malonate, aluminium ascorbate, zirconium acetate, zirconium glycolate, zirconium malonate, and polyacrylate esters
  • the species of main component C2 are typically selected from the group consisting of magnesium oxide, magnesium carbonate, magnesium hydroxide, magnesium-aluminium layered double hydroxide, precursor of magnesium- aluminium layered double hydroxide, magnesium-aluminium mixed oxide, precursor of magnesium-aluminium mixed oxide, yttrium carbonate, yttrium oxide, lanthanum oxide, and cerium acetate.
  • Supplementary additives may be applied for adjusting a desired period of time for setting and hardening of the binder composition, such additives typically selected from the group consisting of pH buffering agents, acid-base reaction retarding agents, hydration retarding agents, ion complexing agents, ion exchanging agents, wetting agents, dispersing agents, agents for modifying precipitation and setting, crystal seeding and growth agents, and agents for absorption of water.
  • the additives are usually present in a total amount of from 0.05 to 25 wt %, relative to the total dry mass of the binder composition.
  • the agents for pH buffering and for modifying the precipitation and setting may be selected from the group consisting of phosphate buffers and carboxylic acid based buffers; while the ion exchanging agents may be selected from the group consisting of layered double hydroxides and ion exchange polymers; and the agents for ion complexing and for retarding hydration may be selected from the group consisting of fatty acids and their salts, monosaccharides, polysaccharides, sugar alcohols, lactones, boric acids, and salts of boric acids.
  • the present refractory binder After heat-up the present refractory binder is characterized by high purity and high refractoriness phases, and is especially suitable for high performance refractories, ceramics and fireproof products. However, even without any heat-up, the present binder is well suitable for low temperature applications where special chemical resistance or exceptional physical properties are required, for instance for bonding of waste materials, including nuclear wastes.
  • binder compositions that are based on the layered double hydroxides or oxides. It is well known in the art that the layered double hydroxides and oxides can be excellent ion exchangers, and may function as absorbents of harmful ionic species. Combining this absorbent activity with the ability of bonding solid matter allows broadening the scope of traditional applications of the refractory binder into various new fields of application.
  • a novel binder composition comprising a first main component C1 selected from the group consisting of neutral, acidic or amphoteric metal salts or esters of carboxylic acids, carboxylates, carboxylate esters, poly electrolytes, and complexing and dispersing agents, a second main component C2 selected from the group consisting of metal oxides, metal hydroxides, metal carbonates, layered double hydroxides, layered double oxides, mixed oxides, pre cursors of layered double hydroxides, precursors of mixed-oxides, and doped oxides, and, optionally as a third component, supplementary additives, which binder composition after mixing with water will set and harden at ambient temperature within a well acceptable, predetermined, adjustable period of time.
  • a first main component C1 selected from the group consisting of neutral, acidic or amphoteric metal salts or esters of carboxylic acids, carboxylates, carboxylate esters, poly electrolytes, and complexing and dispersing agents
  • a second main component C2
  • the setting and hardening behaviour of the binder composition upon mixing with water or with an aqueous solution or with an aqueous suspension is primarily caused by the bulk and surface reactivity of the main components, and, optionally by the influence of at least one supplementary additive.
  • the reactivity of the main components C1 and C2 toward acid-base reaction, complexing, hydration, ion exchange, hydrolysis, precipitation, crystal seeding and growth, and, consequently, the setting and hardening behaviour of the binder is typically adjusted by way of varying at least one of the following parameters: amount, composition, particle size, specific surface area, mechanical alloying, mechanochemical synthesis, and thermal and surface treatment, of the main components.
  • Adjusting the reactivity of the component C1 and C2 is preferably accomplished by a method chosen from the group of
  • the coating agents are typically selected from the group consisting of aqueous and non-aqueous solutions forming poorly water-soluble or poorly wettable layers on the components C1 and/or C2, preferably solutions forming poorly soluble magnesium compounds such as magnesium hydroxide, magnesium layered double hydroxides, magnesium salts of fatty acids, magnesium carbonates, and magnesium silicates; or, alternatively, solutions forming aluminium salts of fatty acids or solutions forming aluminium and zirconium salts of carboxylic acids.
  • Surface treatment may, however, also be applied by coating using polymers soluble in aqueous or non- aqueous solvents.
  • a desirable setting and hardening time is adjustable and may be pre-determined by varying the composition and amounts of the above ingredients.
  • a proper dispersion of the binder is important to achieve advantageous rheological behaviour and mechanical properties.
  • This process requires special attention and specific solutions if the binder comprises soluble metal salts, as is the case with the present binder. It is known in the art that a proper dispersion of such mixtures especially when containing species of high charge and concentration is difficult to accomplish due to the possible collapse of the electrostatic or electrosteric dispersion action.
  • amphoteric character of some metal salts of carboxylic acids is an additional issue when providing a refractory binder, because after the acid-base reactions, i.e. neutralization reactions, the precipitation of poorly soluble species may often occur only within a certain pH-range. At too low or too high pH-values, the soluble species may remain stable, i.e. dissolved, and no bonding occurs.
  • metal salts and/or esters of carboxylic acids such as, for instance, aluminium formate or zirconium acetate
  • carboxylic acids such as, for instance, aluminium formate or zirconium acetate
  • metal oxides, hydroxides, carbonates, mixed-oxides, layered double hydroxides and/or precursors of any of these compounds are used as the main components of the binder.
  • the reactivity of the reactive components of the present binder can be adjusted by mechanical, thermal and surface treatment, and by admixture of supplementary additives.
  • layered double hydroxides LDH and mixed oxides (MO) shall be understood to also comprise intermediate products and semi-products.
  • Numerous methods of manufacturing layered double hydroxides and mixed oxides are known in the art e.g. precipitation methods, hydrothermal, mechano-chemical method, mechanical alloying and subsequent wet treatment.
  • the LDHs are known for their ion exchange property. Combining this behaviour with the bonding ability of the other components of the present refractory binder opens up numerous possibilities of application.
  • a useful method of adjusting the rate of formation of bonding species and hence the setting and hardening behaviour of the present binder is the admixture of supplementary additives which can effectively act even if high reactivity compo nents are used.
  • the selection of proper, compatible supplementary additives for a refractory binder comprising soluble metal salts can sometimes be challenging. In practice, only non-ionic additives or very low amounts of ionic additives can be applied beneficially, if well dispersed mixtures are envisaged as the ultimate goal.
  • the acid-base reactions during the setting process of the binder are generally exothermic. Accordingly, one group of supplementary additives is preferably chosen among compounds that provide a strong cooling effect, i.e. compounds characterized by a high heat of solution.
  • Various low molecular weight polyols including sugar alcohols are known for their high heat of solution properties, i.e. for withdrawing the required dissolution energy from the aqueous solvent, thereby cooling the solvent.
  • Suitable examples are erythritol having a heat of solution demand of 180 J/g, and mannitol (1 1 1 J/g). The cooling effect causes retardation of setting.
  • Another group of supplementary additives comprises complexing agents, wherein only weak metal complexes are desired, because otherwise too strong retardation or even hindrance of precipitation might occur.
  • Useful members of this group are derivatives of lactic and gluconic acid, sugar alcohols, PEG and PVP.
  • Yet another group of supplementary additives comprises pH buffers, which may be required in specific embodiments of the invention for adjusting the pH to a desired value for effecting the precipitation of bonding phases or amorphous species after neutralization of the metal salt(s) of carboxylic acid(s).
  • Another group of useful supplementary additives acts as water absorbent or siccative agents, typically selected from the group of metal hydroxides and layered double hydroxides.
  • the present binder comprises layered double hydroxides as supplementary additives
  • such additives differ from the LDH species used as main components C2 in that they are either chemically different layered double hydroxides or chemically identical but thermally treated differently, e.g. at different temperatures.
  • a layered double hydroxide, for instance, showing good water absorption quality is suitable as a supplementary additive.
  • a layered double hydroxide used as a main component C2 shall, however, be reactive with the first main component C1 . This is usually ensured by selecting a component C2 having sufficiently high basicity.
  • a refractory binder comprises as a main component C1 at least one metal salt or ester of a carboxylic acid, at least one carboxylate or carboxylate ester, together with a complexing and dispers ing agent, and as a second component C2 at least one of a metal oxide, metal hydroxide, and metal carbonate, and/or at least one of a layered double hydroxide, layered double oxide, mixed oxide, doped oxide, precursor of a layered double hydroxide, precursor of a layered double oxide, and precursor of a mixed oxide.
  • the binder After mixing with water, the binder will set and harden at ambient temperature and the rate of setting and hardening is controlled and adjusted via application of prop erly reactive species of components C1 and/or C2, as well as via the use of supple mentary additives, as set forth in more detail in the examples hereinafter.
  • the desired reactivity of the components C1 and C2 is typically achieved by either proper selection of applicable species, and/or by specific preparation methods using mechanical, surface and/or thermal pre-treatment.
  • the main components C1 and C2 of the binder and the supplementary additives may be provided as a mixture of dry powders or, in the alternative, as a two-part bonding system comprising an aqueous solution or suspension on one hand, and a solid part on the other hand, as shown in the Examples hereinafter.
  • the reactivity of the main components C1 and C2 with respect to processes typi cally occurring during the bonding process such as the acid-base reactions, hydra tion, ion exchange, hydrolysis, precipitation, crystal seeding and crystal growth can be tuned via a proper selection of mineralogical and chemical composition, particle size, and specific surface area, as well as via mechanical, surface and/or thermal pre-treatment of the species of the C1 and/or C2 components.
  • the best practical proof of proper selection and adjustment of the reactivity of the main components C1 and C2 is the resulting setting and hardening time upon mixing the binder, or all of its constituents, as the case may be, including mixtures and materials comprising the binder or its constituents, with water or aqueous solutions or suspensions.
  • Preliminary information on the reactivity of component C1 may be retrieved from literature data or product sheets on the solubility, dissolution rate, acidity constant. pH of the solution, and neutralization rate. Basicity and hydration rate are, on the other hand, also important for the selection or preparation of the species of compo nent C2.
  • the basicity of the C2 components may be determined using known tech niques, such as, for example, the citric acid activity test, or the adsorption and heat of adsorption test for determining surface basicity.
  • the weight ratio of the main components C1 versus C2 may range from 0.001 to 500, wherein the very low values typically relate to binder compositions comprising precursors of the layered double hydroxides, while the values at the upper end of the range mainly point to binder compositions comprising high amounts of salts or esters of one or more carboxylic acids.
  • the refractory binder comprises the main components C1 and C2 in a total amount of at least 2 wt %, preferably in an amount of from 5 to 98 wt %, relative to the total dry mass of the refractory binder.
  • the average particle size of the main components C1 and C2 is less than 1000 miti, and preferably is within a range of from 0.01 to 45 miti.
  • Components C1 and C2 can also be used in the form of a solution or suspension.
  • the component C1 comprises at least one of a metal salt of a carboxylic acid, an ester of a carboxylic acid, a carboxylate, a carboxylate ester, and a poly electrolyte
  • the metal in said metal salt is preferably selected from the group consisting of alkaline metals, alkaline earth metals, transition metals, post transition metals, and lanthanides
  • the carboxylic acid in the metal salt, ester, or carboxylate is preferably selected from the group consisting of methanoic acid, ethanoic acid, propanoic acid, propenoic acid, fatty acids, amino acids, keto acids, dicarboxylic acids, tetracarboxylic acids, polycarboxylic acids, alpha-, beta-, gamma- hydroxyacids, and polyhydroxy-carboxylic acids.
  • the carboxylates referred to herein also comprise polycarboxylates, hydroxy-carboxylates and esters of polycarbox
  • the main component C1 may be selected from the group consisting of aluminium acetate, basic aluminium acetate, aluminium citrate, aluminium acetatotartrate, aluminium glycolate, aluminium formate, aluminium malonate, aluminium ascorbate, zirconium glycolate, zirconium acetate, zirconium acetate hydroxide, zirconium malonate, zirconium ascorbate, ammonium zirconium carbonate, cerium acetate, and ester of poly(propenoic acid).
  • the main component C2 may be selected from the group consisting of magnesium oxide, magnesium hydroxide, metal layered double hydroxide, precursor of a metal layered double hydroxide, metal layered double oxide, doped metal oxide, mixed metal oxide, precursor of a mixed metal oxide, magnesium carbonate, and basic magnesium carbonate; as well as from the group consisting of products and minerals comprising magnesia including caustic magnesia, dead-burned magnesia, fused magnesia, magnesia-rich and stoichiometric alumina spinel, magnesium silicates, magnesia-chromia; and also from the group of minerals such as hydro- talcite and the hydrotalcite group minerals, meixnerite, talc, calcium oxide, calcium hydroxide, calcium carbonate, yttrium oxide, lanthanum oxide, cerium oxide, zirconium oxide, zirconium hydroxide, zirconium basic carbonate, aluminium oxide and aluminium hydroxide.
  • precursor in this context shall refer to a preliminary product or an inter mediate product.
  • the one or more supplementary additives may be selected from the group consisting of agents for pH-buffering, agents for retarding the acid - base reaction, agents for retarding the hydration, agents for ion complexing, for ion exchanging, wetting, and dispersing. Further additives are selected from the group consisting of agents for modifying precipitation and setting, agents for crystal seeding and crystal growth, and agents for the absorption of water.
  • the supplementary additives are typically present in a total amount of from 0.05 to 25 wt %, relative to the total dry mass of the binder.
  • Suitable supplementary additives for pH buffering and modifying the precipitation may be selected from the group consisting of phosphate buffers and carboxylic acid based buffers.
  • the supplementary additives for ion exchange may be selected from the group consisting of ion exchange polymers and layered double hydroxides, while the supplementary additives for complexing metal ions and retarding hydration may be selected from the group consisting of fatty acids and their salts, monosaccharides, polysaccharides, low molecular weight polyols including sugar alcohols, lactones, boric acids, and salts of boric acids.
  • Adjusting the reactivity of the main components C1 and/or C2 may be effected by a method selected from the group consisting of: mechanical alloying, mechanochemical synthesis, thermal and surface treatment, such as, for instance, calcining or coating using solid, liquid, vaporous or gaseous coating agents, wherein said coating agents are selected from the group consisting of aqueous and non-aqueous solutions forming poorly water soluble or poorly wettable layers on the components C1 and C2, preferably solutions generating poorly water-soluble magnesium compounds such as magnesium hydroxide, magnesium layered double hydroxides, magnesium salts of fatty acids, magnesium carbonates, magnesium silicates, or else generating compounds such as aluminium salts of fatty acids, aluminium and zirconium salts of carboxylic acids.
  • coating agents may, however, also be selected from water- soluble or organic solvent-soluble polymers.
  • the invention also refers to materials and products bonded by the present refractory binder or by the entirety of its constituents, if the latter are being applied separately in two or more parts or portions, wherein any such bonded material comprises at least 1 wt % of the refractory binder or of the entirety of its constituents, in combination with 1 to 99 wt % of one or more other refractory and/or ceramic and/or construction raw materials, and optionally 0.05 to 25 wt % of one or more functional additives.
  • Said one or more other refractory and/or ceramic and/or construction raw materials preferably comprise:
  • metal oxides and/or minerals selected from the group of alkaline earth metal oxides, transition metal oxides, post transition metal oxides and rear earth metal oxides; and/or
  • construction raw materials selected from the group consisting of common components of construction concrete, renewable raw materials and metallic or non-metallic strengtheners, or functional materials.
  • Said one or more other refractory and/or ceramic and/or construction raw materials are typically of a particulate nature and are selected such as to have an average particle size of from 0.01 miti to 10 mm, or which are present in the form of wires, nets, fibers, sheets, ribbons, or parts thereof.
  • the functional additives are preferably selected from the group consisting of dispersing agents, wetting agents, setting and hardening accelerators or retardants, fibers for safe heat-up, and additives conferring to the material desired physical and chemical characteristics.
  • the invention relates to the use of the refractory binder or its constituents, as the case may be, or of a material bonded by the refractory binder, in the manufacture of at least one product selected from the group consisting of refractory slurries, concretes, free-flowing or thixotropic castables, mortars, mixes for slip casting, mixes for tape casting, shotcrete mixes, gunning mixes, ramming mixes, repairing mixes, bonding or joining agents, and coating agents.
  • the invention relates to the use of the refractory binder or of its constituents referred to herein, or of a material bonded by the refractory binder, in the manufacture of dense refractory products, insulating refractory products, ceramic products, functional products, fireproof products, monolithic lining, precast shapes, construction elements, for use as parts of furnaces or other devices used in the refractory, metallurgical, cement, glass, ceramic, electronic, construction industry, and other industries.
  • the preparation of the binder composition according to the present invention is rather uncomplicated if the main components C1 , C2, and suitable supplementary additives are available.
  • a two-part liquid-solid version of the refractory binder may comprise one part that is an aqueous solution or suspension of one or more main components and, optionally, supplementary additives, while the second part comprising other main components and, optionally, supplementary additives, is in the form of a dry powder.
  • the first part i.e. the aqueous solution or suspension can be prepared by usual methods, wherein a proper selection of the components to be dissolved is important though. For example, it is recommendable preparing a solution comprising an ester of polyacrylic acid and a sugar alcohol, or a solution comprising a sugar alcohol and zirconium acetate, but not a solution comprising an ester of polyacrylic acid and zirconium acetate.
  • the examples disclosed hereinafter will further illustrate this issue.
  • the process of manufacturing the binder is somewhat more complex. Typically, intensive, prolonged, substantially dry grinding is necessary to attain a desirable mixture of ingredients. More details on these issues are provided hereinafter in the Examples section. Reliable control of the co-grinding progress can be achieved using XRD measurements and determination of the resulting crystalline and amorphous phases.
  • the present invention is not confined to embodiments relating to the provision and use of the refractory binder but also to embodiments relating to the use of its components and additives if separately added in a process of manufacture of refractory elements. It is a special advantage of the present invention that numerous different refractory or ceramic raw materials but also common components of construction concrete, renewable raw materials, and metallic or non- metallic strengtheners or functional materials may be bonded by the binder in accordance with the invention. If, for example, the binder is based on a layered double hydroxide and/or its precursors, and the ceramic raw material is also a layered double hydroxide, a material can be created that has considerable capacity to absorb and bond harmful or hazardous wastes.
  • the wide range of grain size intended for the solid raw materials defines the ambit of possible practical applications of the binder.
  • a very fine grained material bonded by the refractory binder can be applied for coating purposes, or for cementing of big shaped materials, or for filling thin fissures.
  • Coarsely grained material bonded by the refractory binder is better suited for other products like refractory or construction concrete.
  • raw materials which may be selected for making the refractory binder bonded material are magnesia, calcium oxide, chromia, alumina, titania, zirconia, ceria, numerous silicates, carbonates and minerals and compounds of all above mentioned metal oxides like spinels, perovskite group, doped oxides.
  • Other examples of raw materials comprise non-oxide refractory and ceramic raw materials such as, e.g., graphite, carbides, borides, nitrides, silicides.
  • Some embodiments of the present invention not only provide an improved binder as compared to those known in the art, but also an entirely novel concept of a binder, e.g., a binder based on layered double hydroxides, mixed oxides, or precursors thereof, or a binder comprising a zirconium salt.
  • a zirconium salt binder may, for instance, significantly improve the wear resistance of the refractories manufactured using this kind of binder. This is due to the fact that zirconia present in the fine grained matrix of refractories renders such products less wettable and more resistant against slags and metal melts. Accordingly, the present refractory binder goes with an improved functionality and allows for new applications of said binder and of materials comprising said binder or its constituents.
  • a refractory binder comprising the main components: zirconium acetate powder supplied by S. Goldmann GmbH & Co., Germany, caustic calcined magnesia (CCM1 ) obtained by calcination of the magnesium hydroxide grade 98 % Mg(OH) 2 , and mannitol for pharmaceutical applications as the supplementary additive.
  • CCM1 caustic calcined magnesia
  • the reactivity of the caustic magnesia determined by the known citric acid activity test, e.g. as disclosed in EP 3176140 (B1 ), equals 12 seconds.
  • the binder having the composition given in Table 1 should preferably be used along with a dispersant. The nature and amount of the dispersant depends on the characteristics of the refractory or ceramic material bonded by said binder.
  • a refractory binder comprising the components already mentioned in Example 1 and, additionally, an ester of polyacrylic acid (PAE1 ) available on the marked, as well as xylitol of food grade.
  • PAE1 polyacrylic acid
  • the mentioned ester PAE1 serves both as the main component of the bonding system and the dispersing agent.
  • the binder disclosed in Example 2 comprises two distinctly different parts: one is an aqueous solution or suspension of a main component and a supplementary additive, and the second part comprising another main component and additives is in the form of a dry powder.
  • the two part liquid-solid version of the refractory binder may be advantageous in cases where a better dispersion is desired or in cases where a main component or an additive is more readily available in the form of an aqueous solution.
  • either or both of the aqueous dry parts of the starting ingredients can comprise more than just one reaction component or supplementary additive.
  • the binder composition is disclosed below in Table 2.
  • a refractory binder comprising an ester of the polyacrylic acid (PAE1 ) mentioned in Example 2, and the layered double hydroxide (LDH1 ) Sorbacid 91 1 , supplied by CLARIANT, Germany.
  • calcination of Sorbacid 91 1 was necessary to remove the hydrophobic coating and to adjust the proper reactivity.
  • the binder is composed as follows (Table 3): Table 3
  • a refractory binder comprising components mentioned in previous Examples, and, additionally, aluminium triformate, technical grade, and lithium carbonate, technical grade.
  • the binder composition is shown in Table 4.
  • a refractory binder comprising an ester of the polyacrylic acid (PAE1 ) mentioned in Examples 2 and 3 and, additionally, a precursor of the layered double hydroxide prepared for the purpose of the present invention (LDH2).
  • LDH2 was prepared by mechanical alloying, i.e. dry, 1 hour, intensive grinding of the following components: reactive caustic calcined magnesia (CCM2), obtained by calcination of the magnesium hydroxide grade 98.6 % Mg(OH) 2 shortcut an aluminium tri-hydroxide (ATH) and basic magnesium carbonate tetra-hydrate. Finally, LDH2 was calcined at 200 °C.
  • the binder composition is shown in Table 5.
  • a refractory binder comprising components mentioned in previous Examples and additionally the precursor of the mixed oxide (M01 ) prepared for the purpose of this invention.
  • transient alumina is frequently used in the art for thermodynamically unstable crystallographic forms of alumina, particularly for the reactive species gamma- and rho-AI 2 0 3 .
  • commercially available transient alumina has been used. It shall be noted, however, that besides gamma- and rho-alumina other kinds of transient alumina may likewise be applied in accordance with the invention.
  • Table 6 exhibits the composition of the binder.
  • This example relates to fine-grained material bonded by the refractory binder, said material comprising as the main constituents alumina raw materials, supplied by Almatis GmbH, the aforesaid ester of polyacrylic acid PAE1 , and the refractory binder disclosed in Example 1 .
  • Table 7 and the subsequent tables hereinafter disclose the compositions of the dry material and the amounts of water added as recommended for achieving a proper consistency of the castable.
  • Example 8 relates to a fine-grained material bonded by the refractory binder and comprising as the main constituents magnesia raw materials, zirconium hydroxide grade XZ01274/01 supplied by S. Goldmann GmbH & Co and the refractory binder disclosed in Example 2 (liquid and solid part).
  • the magnesia raw materials, available on the marked, are fused magnesia, dead burned magnesia and caustic calcined magnesia of the grades given in Table 8.
  • the recommended amount of water is provided by the aqueous part of the refractory binder referred to in Table 8, the composition of which being disclosed in Example 2.
  • Example 9 relates to a fine-grained material bonded by the refractory binder, the material comprising as the main constituents alumina raw materials, supplied by Almatis GmbH, and the refractory binder disclosed in Example 4.
  • the dispersing agent used was the already mentioned PAE1 .
  • Example 10 relates to a fine-grained material bonded by the refractory binder and comprising as the main constituents the alumina raw materials, supplied by Almatis GmbH, and the refractory binder disclosed in Example 5.
  • Example 1 1 relates to a fine-grained material bonded by the refractory binder and comprising as the main constituents the alumina raw materials, supplied by Almatis GmbH, and the refractory binder disclosed in Example 6.
  • Example 12 relates to a fine-grained material bonded by the refractory binder and comprising as the main constituents the alumina raw materials, supplied by Almatis GmbH, and caustic calcined magnesia CCM1 , zirconium acetate, xylitol, and an ester of the polyacrylic acid PAE1 .
  • the xylitol was first dissolved in the pre-estimated amount of water and then zirconium acetate was added. Subsequently, the remaining constituents of the binder were added and mixed together. Table 12
  • Example 13 relates to a fine-grained material bonded by the refractory binder and comprising as the main constituents the zirconia raw materials, supplied by S.
  • Example 14 relates to a coarse/fine-grained material bonded by the refractory binder and comprising as the main constituents the alumina raw materials, supplied by Almatis GmbH, and the refractory binder disclosed in Example 4.
  • the bonding matrix of the resulting material obtained in this Example corresponds to the fine grained material disclosed in Example 9.
  • Example 15 relates to a coarse/fine-grained material bonded by the refractory binder and comprising as the main constituents the alumina raw materials, supplied, for example, by Almatis GmbH, and the refractory binder disclosed in Example 6.
  • the bonding matrix of the material obtained pursuant to this Example corresponds to the fine-grained material disclosed in Example 1 1 .
  • Example 16 relates to a coarse/fine-grained material bonded by the refractory binder and comprising as the main constituents the alumina raw materials, supplied by Almatis GmbH and the aforesaid caustic calcined magnesia CCM1, zirconium acetate, xylitol and an ester of the polyacrylic acid PAE1 .
  • the bonding matrix of the material obtained following the protocol of this Example corresponds to the fine-grained material disclosed in Example 12.
  • Example 17 relates to a coarse/fine-grained material bonded by the refractory binder and comprising as the main constituents the alumina raw materials, supplied by Almatis GmbH, in combination with the aforesaid precursor of the layered double hydroxide LDH2 and an ester of the polyacrylic acid PAE1 .
  • the bonding matrix of the material obtained following the protocol of this Example resembles the fine- grained material disclosed in Example 10.
  • Example 18 relates to a coarse/fine-grained material bonded by the refractory binder and comprising as the main constituents ordinary quartz sand, together with silica flour M8 and M300 offered by Euroquarz, Germany.
  • Further ingredients comprise caustic calcined magnesia CCM1 , zirconium acetate, xylitol and an ester of the polyacrylic acid PAE2, which ingredients have already been used in previous Examples, too.
  • the sugar alcohol xylitol and PAE2 were first dissolved in the pre estimated amount of water and then the quartz sand, silica flour and CCM1 were added, or vice versa, and mixed together. Finally, the zirconium acetate was added and mixed with the other ingredients.
  • EXAMPLE 19 COMPARATIVE EXAMPLE
  • This comparative example as opposed to Example 10, is disclosed to demonstrate the inferior properties of the material resulting from bonding fine-grained alumina raw material by way of separately adding each one of the main components of the binder disclosed in Example 5. Contrary to Example 10, the precursor components of the layered double hydroxide LDH2 are used in the present example without mechanical alloying i.e. without co-grinding. The results are being discussed hereinafter.
  • Comparative example 20 as opposed to Example 1 1 , is disclosed to demonstrate the inferior properties of the material resulting from a preparation method wherein the fine-grained alumina raw material is bonded by the separately added main components of the binder disclosed in Example 6. Unlike in Example 1 1 , the components of the mixed oxide precursor M01 are used in the present example without mechanical alloying, i.e. without co-grinding.
  • the refractory binder and its components disclosed in Examples 1 through 6 were used for preparing the refractory bonded material referred to in Examples 7 through 18 and in comparative Examples 19 and 20.
  • the dry components of the refractory binder and the particulate fine and/or coarse grained refractory raw material were dry mixed first and then combined and mixed together, at ambient temperature, along with the amount of water or the solution indicated in Examples 7 to 18 and in comparative Examples 19 and 20.
  • the material was cast into cylindrical forms and allowed to set and harden at ambient temperature (20 - 25°C).
  • the working time i.e. the period of time lapsed until the cast material stopped moving under vibration, was determined, and so was the setting time using a needle penetration method.
  • the cast samples were demoulded and dried in a first run for 12 hours at ambient temperature and thereafter for another 3 hours at a temperature of 1 10C.
  • CCS cold crashing strength
  • Examples 1 to 6 exhibit suitable compositions of the refractory binder according to the present invention.
  • the binders disclosed therein by way of examples comprise alumina, magnesia and zirconia bonding phases, or mixtures thereof. They do not, of course, represent an exhaustive compilation of all useful ingredients or bonding possibilities. Those skilled in the art will understand that using other metal compounds e.g. from the group of rare earths or transition metals, may result in further useful binder compositions without deviating from the spirit of the present invention.
  • the raw materials known in the art or especially prepared for the purpose of this invention i.e. the precursors of the double layered hydroxides or mixed oxides, are also disclosed in Examples 1 to 6. Bonding of fine-grained alumina or magnesia raw materials using the present refractory binder or its components in line with the invention, was performed as disclosed in Examples 7 through 13.
  • Bonding the fine-grained alumina raw materials by separately adding each one of the components of the refractory binder to the alumina raw materials in a way that is not in line with the present invention is disclosed in comparative Examples 19 and 20.
  • the results of performance tests carried out with the materials resulting from the bonding experiments using the refractory binder or its constituents are revealed in Table 21 .
  • Examples 7 to 13 teach that both a strong bonding, expressed by CCS, and desirable working and setting times can be achieved with the refractory binder in accordance with the present invention.
  • the advantages of such a binder which provides a selection of chemically different bonding phases, for instance spinel forming or magnesia and zirconia-forming phases, are particularly seen in its suitability for bonding numerous different refractory and ceramic raw materials, including materials such as alumina, magnesia, quartz or zirconia. Further useful applications of the present binder are apparent to those of skill in the art.

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  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Ceramic Products (AREA)

Abstract

L'invention se rapporte à une composition de liant réfractaire à liaison chimique et hydraulique comprenant deux constituants principaux C1 et C2, C1 comprenant au moins un composé choisi dans le groupe constitué par les sels ou les esters métalliques neutres, acides ou amphotères d'acide carboxylique, les carboxylates, les esters carboxylates et les polyélectrolytes, et C2 comprenant au moins un composé choisi dans le groupe constitué par les oxydes métalliques, les hydroxydes métalliques, les carbonates métalliques, les hydroxydes doubles en couches, les précurseurs d'hydroxydes doubles en couches, les oxydes doubles en couches, les précurseurs d'oxydes doubles en couches, les oxydes mixtes, les précurseurs d'oxydes mixtes, et les oxydes dopés, ladite composition de liant après mélange avec de l'eau étant fixée et durcie à température ambiante en une période de temps bien acceptable, prédéterminée et modulable. L'invention se rapporte en outre à des matériaux et à des produits liés avec le liant réfractaire et à leurs applications dans l'industrie des produits réfractaires, de la métallurgie, du ciment, du verre, de la céramique, de l'électronique, de la construction et d'autres industries.
PCT/EP2022/054462 2021-03-24 2022-02-22 Liant réfractaire WO2022199967A1 (fr)

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Cited By (1)

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CN116693271A (zh) * 2023-04-27 2023-09-05 中国民航大学 氧化锆陶瓷专用硅硼碳锆改性磷酸铝锆高温胶的制备方法

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116693271A (zh) * 2023-04-27 2023-09-05 中国民航大学 氧化锆陶瓷专用硅硼碳锆改性磷酸铝锆高温胶的制备方法
CN116693271B (zh) * 2023-04-27 2024-03-19 中国民航大学 氧化锆陶瓷专用硅硼碳锆改性磷酸铝锆高温胶的制备方法

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