CN114133229A

CN114133229A - Anorthite micro-nano-pore heat insulation refractory material and preparation method thereof

Info

Publication number: CN114133229A
Application number: CN202111668442.XA
Authority: CN
Inventors: 郭会师; 李文凤
Original assignee: Zhengzhou University of Light Industry
Current assignee: Zhengzhou University of Light Industry
Priority date: 2020-12-31
Filing date: 2021-12-31
Publication date: 2022-03-04
Also published as: WO2022144012A1

Abstract

The invention belongs to the field of refractory materials, and particularly relates to a anorthite micro-nano-pore heat insulation refractory material and a preparation method thereof. The anorthite micro-nano hole heat insulation refractory material is mainly prepared from a basic raw material, an additive and water. The anorthite microporous heat insulation refractory material is white, faint yellow or yellow in appearance, the main crystal phase of the product is anorthite, the mass content of CaO in the chemical composition is 4-22 wt%, the pore diameter of pores is distributed between 0.006-250 mu m, the average pore diameter is 0.1-19 mu m, and the pore structure with the micro-nano size ensures the good heat insulation performance of the product under low volume density and high strength. The preparation method is environment-friendly and pollution-free, and the structure and the performance of the product are easy to accurately regulate and control.

Description

Anorthite micro-nano-pore heat insulation refractory material and preparation method thereof

Technical Field

The invention belongs to the field of refractory materials, and particularly relates to a anorthite micro-nano hole heat insulation refractory material and a preparation method thereof, in particular to an anorthite micro-nano hole heat insulation refractory material which has a micro-nano size pore structure, an ultralow heat conductivity coefficient, a volume density, a high porosity, a high strength and is environment-friendly and controllable.

Background

The high-temperature industry is the main energy consumption industry in the industrial production in China, the low heat energy utilization rate of various kilns is the main reason of large energy consumption, if the average heat efficiency can be improved by 20 percent according to the national requirement, the energy saving is equivalent to 2.2 hundred million tons of standard coal, and the energy saving potential of the high-temperature industry in China is huge. In order to improve the heat efficiency of the industrial kiln, the most important thing is to develop a high-efficiency heat preservation technology, and an advanced heat insulation material is adopted to enhance the heat preservation effect of the kiln body and reduce the heat dissipation loss.

At present, although the heat insulation materials in China are continuously improved and perfected, the heat insulation materials still cannot meet the increasingly harsh heat insulation environment and requirements of high-temperature industry. The heat insulating material for the kiln at present mostly adopts refractory fiber products or light heat insulating bricks.

Although the heat insulation performance of the refractory fiber product is good, the refractory fiber product is sensitive to a firing atmosphere and is easy to react with reducing and corrosive gases, so that the refractory fiber product loses good heat insulation performance; and the composite material is in service in a high-temperature environment for a long time, and the formed particles are easy to crystallize and grow up to cause stress concentration, so that the pulverization of a heat insulation layer is caused, and the service life is shortened; in addition, ceramic fibers are also a health hazard and have been classified as secondary carcinogens by the european union.

Although the traditional light heat-insulating brick can overcome the defects of the refractory fiber product, the traditional light heat-insulating brick is mostly prepared by a method of adding a large amount of pore-forming agents (such as polystyrene particles, sawdust, charcoal, smokeless coal ash, coke powder and the like), the pore-forming agents occupy certain space in a blank body, and after the blank body is fired, the pore-forming agents leave the original position in a matrix to form pores, so that the light heat-insulating refractory material is obtained. In addition, the pore-forming agents adopted in the preparation process are mostly organic burnt materials, so that the cost of raw materials is higher, a large amount of toxic and harmful gases are emitted during the burning process, such as anthracite, sawdust, coke powder and the like, a large amount of sulfur oxides can be generated at lower temperature, polystyrene particles generate styrene, toluene, nitrogen/carbon/oxides, dioxin and the like, and meanwhile, a large amount of VOCs (volatile organic compounds) fine particles can be generated, so that the environment is seriously polluted, and the human health and the production of peripheral crops are harmed. In recent years, with the continuous enhancement of the environmental protection management and control strength of China, a plurality of enterprises have reduced production or shut down. Therefore, research and development of novel heat insulation refractory materials for high-temperature industry, which have good heat insulation, durability and mechanical properties and are prepared in a green and controllable manner, are urgently needed.

Anorthite (CaO. Al)₂O₃·2SiO₂) Belongs to a triclinic system, is a framework silicate mineral, has a melting point of 1550 ℃, and has a low volume density (2.76 g/cm)³) And thermal conductivity (3.67W/m.K), small thermal expansion coefficient (4.82X 10)^-6/° c), excellent thermal shock resistance, spalling resistance, carbon reduction resistance, alkaline steam corrosion resistance and the like, is a novel high-quality refractory material with good performance, and has attracted attention in recent years. If air holes can be introduced into the anorthite material, the anorthite heat-insulating refractory material is prepared, the heat conductivity of the anorthite heat-insulating refractory material can be further reduced, and the anorthite heat-insulating refractory material has the characteristics of small density, low thermal expansion coefficient, good thermal shock resistance and the like, is particularly suitable for heat preservation and heat insulation of thermal equipment in the industrial departments of metallurgy, mechanical manufacturing, petrochemical industry, electric power and the like, and has very wide development space and application prospect.

The subject group has carried out a great deal of application research on the light heat-insulating refractory material in the early stage, and research results such as the microporous kyanite-based light heat-insulating refractory material (CN103951452A), the microporous light silica brick (CN105565850A) and the like are formed. Under the same strength grade, how to further effectively reduce the volume density and the thermal conductivity of the heat-insulating refractory material, thereby being beneficial to the construction of a light environment-friendly kiln becomes the next research focus.

Disclosure of Invention

The invention aims to provide a anorthite micro-nano-pore heat insulation refractory material which has the characteristics of micro-nano-size pore diameter, closed spherical pore structure, low volume density, ultralow heat conductivity, high porosity, high strength and the like, and can effectively reduce the volume density and the heat conductivity under the condition of ensuring that the material strength meets the requirement, thereby being beneficial to the construction of light environment-friendly kilns.

The second purpose of the invention is to provide a preparation method of the anorthite micro-nano hole heat insulation refractory material. The preparation method has the advantages of green and pollution-free process, easy and accurate control of the structure and performance of the product, and high yield, and can solve the problems that the heat-insulating refractory material prepared by the existing preparation method cannot give consideration to low heat conduction, low volume density, high strength and high yield of the material.

In order to realize the purpose, the technical scheme of the anorthite micro-nano hole heat insulation refractory material is as follows:

a anorthite micro-nano hole heat insulation refractory material is prepared from a base raw material, an additive and water, wherein the mass content of CaO in the chemical composition of the product is 4-22%;

the base raw material comprises the following raw materials in percentage by weight: 6-50% of calcareous raw material, 0-36% of alumina raw material, 0-79% of aluminum-silicon raw material and 0-42% of silicon dioxide raw material;

the additive at least comprises foaming materials, and additives are used or not used; the foaming material consists of a foaming agent, an inorganic curing agent, an organic curing agent and a cell regulator, wherein the addition mass of the foaming agent, the inorganic curing agent, the organic curing agent and the cell regulator is respectively 0.01-10%, 0.1-20%, 0.1-2% and 0.01-1% by taking the mass of a basic raw material as a reference; when the additive is used, the additive is selected from one or the combination of more than two of a dispersing agent, a suspending agent, a mineralizer and an infrared opacifier, and the addition mass of the mineralizer and the infrared opacifier is not more than 10% based on the mass of the basic raw material;

the mass of the water is 30-300% of the mass of the basic raw material.

Dispersing agent, suspending agent, infrared opacifier and mineralizer forming additive, which are added relative to the base raw material. The dispersant and the suspending agent promote the formation of stable and uniformly dispersed suspended slurry during the pulping of the refractory material, thereby avoiding the precipitation and agglomeration; the infrared opacifier further effectively reduces the radiation heat transfer of the material at high temperature, so that the heat conductivity is reduced; the mineralizer is used for reducing the sintering temperature, promoting the growth and development of beneficial crystals such as anorthite, mullite and the like, and is beneficial to the improvement of the product performance.

The foaming material is mainly used for forming a micro-nano pore structure in the heat-insulating refractory material, is an important component of raw materials used by the anorthite micro-nano pore heat-insulating refractory material, enables a product to finally present a micro-nano pore diameter, and ensures better heat-insulating performance of the product under low volume density and high strength.

The anorthite microporous heat insulation refractory material provided by the invention is white, light yellow or yellow in appearance, the main crystal phase is anorthite phase, and the balance is a small amount of mullite phase, corundum phase and/or quartz phase; the volume density of the prepared heat insulation refractory material is 0.25-1.0 g/cm³The porosity is 40-95%, the closed porosity is 20-60%, the normal temperature compressive strength is 0.8-80 MPa, the thermal conductivity at room temperature is 0.02-0.15W/(mK), the thermal conductivity at 350 ℃ is 0.03-0.19W/(mK), the thermal conductivity at 1100 ℃ is 0.04-0.2W/(mK), the use temperature is less than or equal to 1500 ℃, and the re-firing line change rate of heat preservation at 1300 ℃ for 24h is-0.4-0%, preferably-0.3-0%, more preferably-0.2-0%, more particularly-0.1-0%. In the insulating refractory material, the pore diameter of pores is distributed between 0.006 and 250 mu m, the average pore diameter is 0.1 to 19 mu m, and the spherical pore structure with micro-nano size ensures better insulating performance of the product under low volume density and high strength.

The finally prepared refractory material can meet the requirements of low heat conduction and light weight and ensure higher strength by regulating and controlling the dosage of each raw material and the process. Compared with the prior art, the anorthite microporous heat-insulating refractory material provided by the invention has the characteristics of ultralow heat conduction, low volume density, high porosity, high strength and the like, is an anorthite shaped heat-insulating refractory product with the best heat-insulating property, has excellent comprehensive performance, can be suitable for hot surface linings, back linings, filling sealing and heat-insulating materials of industrial kilns in the industries of metallurgy, petrifaction, building materials, ceramics, machinery and the like, and can also be used in the fields of vehicles, military industry, aerospace and the like. And because the heat conductivity coefficient is extremely low, the thickness of the furnace wall of the furnace can be greatly reduced under the condition of meeting the requirement of environmental temperature, thereby greatly reducing the weight of the furnace, accelerating the temperature rise rate of the furnace and being beneficial to the construction of a novel light environment-friendly furnace.

Preferably, the dosage of the aluminum oxide raw material, the aluminum-silicon raw material and the silicon dioxide raw material in the basic raw material cannot be 0% at the same time. The chemical composition of the calcareous raw material contains more than 30 percent of CaO by mass; al in chemical composition of alumina raw material₂O₃The mass percentage of the component (A) is more than 45%; in the chemical composition of the aluminum-silicon material, the mass percent of alumina is 18-90%, and the mass percent of silicon dioxide is 8-75%; chemical composition of silicon dioxide raw material SiO₂The mass content of (A) is more than 18%.

The calcareous material provides CaO component, and is selected from limestone, quicklime, hydrated lime, wollastonite, dolomite, calcite, CaO, CaCO₃、Ca(OH)₂、CaSO₄One or a combination of two or more of them. Preferably, the calcareous material is calcium silicate and/or calcium aluminate, or the calcareous material is calcium silicate and/or calcium aluminate and limestone, quicklime, slaked lime, wollastonite, dolomite, calcite, CaO, CaCO₃、Ca(OH)₂、CaSO₄One or a combination of two or more of them. The calcium silicate is CaO SiO₂The calcium aluminate is mCaO. qAl₂O₃·pFe₂O₃. Wherein n is 1 to 4, m is 1 to 12, q is 1 to 7, and p is 0 to 2. The particle size of the calcareous raw material is not higher than 0.08 mm. The calcium oxide material with the granularity has higher surface activity and is easy to contact with the surrounding Al-rich material at high temperature₂O₃-SiO₂The vitreous phase reaction generates anorthite.

Proper alumina material is introduced into the basic material to replenish Al in the product₂O₃Content, high yield of anorthite. Preferably, the alumina source material is alumina source material or Al is generated at high temperature₂O₃Contains alumina raw material, and the chemical composition of the alumina raw material contains Al₂O₃The mass percentage content of (A) is higher than 85%. Further preferred, wherein Al₂O₃The mass percentage of the component (A) is 95-99.9%. More preferably, wherein Al₂O₃The mass percentage of the component (A) is 98-99%. The particle size of the alumina raw material is not higher than 0.08 mm. The alumina material with the granularity has higher surface activity and is easy to be contacted with the surrounding CaO-SiO at high temperature₂Or rich in SiO₂Reacting the glass phase to generate anorthite or secondary mullite.

The alumina raw material is specifically industrial alumina and beta-Al₂O₃、γ-Al₂O₃、δ-Al₂O₃、χ-Al₂O₃、κ-Al₂O₃、ρ-Al₂O₃、θ-Al₂O₃、η-Al₂O₃、α-Al₂O₃One or more of fused corundum powder, sintered corundum powder and tabular corundum powder. Preferably, it is industrial alumina, gamma-Al₂O₃、α-Al₂O₃And sintered corundum powder.

The alumina source used in the base material may also be an alumina-containing source which decomposes at high temperatures to form Al₂O₃Chemical composition of alumina-containing raw material₂O₃The mass percentage content of (A) is more than 45%. Further preferably, the chemical composition of the alumina-containing raw material contains Al₂O₃The mass percentage of the component (A) is 65-87%.

The alumina-containing raw material which can be decomposed at a high temperature to produce alumina is specifically one or more of aluminum hydroxide, boehmite, diaspore, n-butoxide, aluminum isopropoxide, aluminum sec-butoxide, aluminum chloride hexahydrate and aluminum nitrate nonahydrate. Preferably, it is aluminum hydroxide.

By regulating and controlling Al in the aluminum-silicon raw material₂O₃And SiO₂The content of (b) is such that the generated anorthite main crystal phase can be optimized, and further preferably, the chemical composition of the aluminum-silicon material contains Al₂O₃The mass percentage of the SiO is 32-72 percent₂The mass percentage of (A) is 25-64%. More preferably, the chemical composition of the aluminum-silicon material is Al₂O₃38-50% of SiO₂The mass percentage of the component (A) is 45-58%.

The aluminum-silicon material can effectively provide Al₂O₃、SiO₂The component can be selected from one or more of mullite, kaolin, bauxite, alumino-silica homogeneous material, coal gangue, kyanite, andalusite, sillimanite, pyrophyllite, potash feldspar, albite, anorthite, celsian, porcelain stone, alkali stone, mica, spodumene, montmorillonite, illite, halloysite, dickite, flint stone, perlite, Suzhou soil, Guangxi soil, knacky soil, fly ash and floating bead.

Preferably, the particle size of the aluminum-silicon raw material is less than 1 mm. More preferably, the particle diameter of the aluminum-silicon material is 0.6-1 mm. And the ceramic powder particles with higher surface activity are obtained after ball milling in the later period.

Proper introduction of proper silicon dioxide material into the basic material can effectively supplement SiO in the product₂Content, regulating the generation amount of anorthite at high temperature, preferably, the silicon dioxide raw material is silicon dioxide raw material or raw material containing silicon dioxide, and SiO is in the chemical composition of the silicon dioxide raw material₂The mass percentage content of (A) is higher than 80%. Preferably, wherein SiO₂The mass percentage of the component (A) is 90-99%.

The silica raw material is one or more of alpha-quartz, beta-quartz, alpha-tridymite, beta-tridymite, alpha-cristobalite, beta-cristobalite, gangue quartz, sandstone, quartzite, flint, cemented silica, river sand, sea sand, white carbon black, diatomite and silica micropowder. Preferably, the silica gel is one of cemented silica, diatomite and fine silica powder.

The silicon dioxide material in the base material can also be SiO generated by decomposing at high temperature₂Of SiO in the chemical composition of the silica-containing raw material₂The mass percentage of the content is more than 18 percent. Preferably, the above-mentioned material is capable of decomposing to form SiO₂The raw materials comprise one or more of rice husk, carbonized rice husk, rice husk ash, methyl orthosilicate, ethyl orthosilicate and methyl trimethoxy silane.

The particle size of the silica raw material is less than or equal to 0.08 mm. The silicon dioxide raw material with the granularity is easy to generate CaO-SiO at high temperature₂Or rich in SiO₂The glass phase can react with the surrounding alumina, calcia and aluminum-silicon materials to generate anorthite or secondary mullite.

The cell regulator is one or more of cellulose ether, starch ether, lignocellulose and saponin. The cellulose ether is selected from one or a combination of two or more of water-soluble cellulose ethers, methyl cellulose ethers, carboxymethyl methyl cellulose ethers, carboxymethyl hydroxyethyl cellulose ethers, carboxymethyl hydroxypropyl cellulose ethers, carboxymethyl hydroxybutyl cellulose ethers, hydroxymethyl cellulose ethers, hydroxyethyl methyl cellulose ethers, hydroxyethyl ethyl cellulose ethers, ethyl methyl cellulose ethers, propyl cellulose ethers, hydroxypropyl methyl cellulose ethers, hydroxypropyl ethyl cellulose ethers, hydroxypropyl hydroxybutyl cellulose ethers, hydroxybutyl methyl cellulose ethers, sulfonic acid ethyl cellulose ethers. The bubble hole regulator is matched with the foaming agent for use, so that the size, the circularity, the uniformity, the closure and the like of bubbles in slurry can be effectively regulated, and the effect of effectively and accurately regulating the pore structure in a burnt product is achieved.

The inorganic curing agent is selected from silica sol, alumina sol, silica-alumina sol, silica gel, alumina gel, silica-alumina gel, Al₂O₃Micropowder, dicalcium silicate, calcium dialuminate, tricalcium silicate, tricalcium aluminate, monocalcium aluminate, SiO₂Micro powder and iron aluminateOne or more of calcium, aluminum phosphate, dodecacalcium heptaluminate, water glass and soft bonding clay. In the raw materials, the water glass contains sodium silicate or potassium silicate or the combination of the sodium silicate and the potassium silicate; SiO 2₂The micro powder not only plays the role of an inorganic curing agent, but also can be used as a silicon dioxide raw material; al (Al)₂O₃The micro powder not only plays the role of an inorganic curing agent, but also serves as an aluminum oxide raw material; dicalcium silicate, calcium dialuminate, tricalcium silicate, tricalcium aluminate, monocalcium aluminate, tetracalcium aluminoferrite and dodecacalcium heptaluminate play a role of an inorganic curing agent and can also be used as a calcareous raw material; silica-alumina sols are also known as aluminum-silica sols.

The inorganic curing agent particles have an average particle diameter of 5 μm or more, preferably 4 μm or more, more preferably 3 μm or more, still more preferably 2 μm or more, particularly preferably 1 μm or more, and still more particularly preferably 100nm or less; the inorganic curing agent is all industrial pure. The chemical composition of the silica sol is SiO₂The mass percentage of the component (A) is 25-40%; chemical composition of alumina sol containing Al₂O₃The mass percentage content of the composition is not less than 20 percent; al in chemical composition of silicon-aluminum sol₂O₃Mass percentage of not less than 30 percent and SiO₂The mass percentage content of the composition is not less than 20 percent. The inorganic curing agents can penetrate into gaps of ceramic powder particles after hydration, and the powder particles are mechanically embedded to form a good rigid framework structure, so that the mechanical strength of a blank is increased.

The organic curing agent is selected from one or more of polymer resin, low methoxyl pectin, carrageenin, hydroxypropyl guar gum, locust bean gum, gellan gum, curdlan, alginate and konjac gum; the polymer resin is selected from vinyl acetate and ethylene copolymer, vinyl acetate homopolymer, acrylic ester polymer, ethylene and vinyl acetate copolymer, ethylene and vinyl chloride copolymer, vinyl acetate and vinyl versatate copolymer, acrylic ester and styrene copolymer, vinyl acetate and higher fatty acid vinyl ester copolymer, one or more of vinyl acetate and ethylene and vinyl chloride copolymer, vinyl acetate and ethylene and acrylate copolymer, isobutylene and maleic anhydride copolymer, ethylene and vinyl chloride and vinyl laurate copolymer, vinyl acetate and ethylene and higher fatty acid copolymer, vinyl acetate and ethylene and vinyl laurate copolymer, vinyl acetate and acrylate and higher fatty acid vinyl ester copolymer, and vinyl acetate and vinyl versatate and acrylate copolymer. The organic curing agent is water-soluble. A small amount of organic curing material is dispersed to the gaps of the ceramic powder particles, a continuous high-molecular film can be formed on the surfaces of the ceramic powder particles after hydration of the organic curing material, the film forms flexible connection among the powder particles, the cohesion among the ceramic powder particles is improved through the intermolecular force of organic molecules, the green body strength is increased, the collision damage generated in the carrying process of the green body is avoided, the yield is greatly improved, and the production cost is obviously reduced.

Generally, since the inorganic curing agent generates liquid phase at a higher temperature, so as to lower the softening temperature of the product, the amount of the inorganic curing agent should be gradually reduced and the amount of the organic curing agent should be increased correspondingly to increase the strength of the green body as the firing and using temperature is gradually increased. When preparing high density samples, the required amount of curing agent is correspondingly reduced because the spacing between the ceramic powder particles in the green body is shorter.

Preferably, the foaming agent is a surfactant and/or a protein foaming agent, and the foaming ratio is 8-60; the surfactant is selected from one or more of cationic surfactant, anionic surfactant, nonionic surfactant, amphoteric surfactant, Gemini type surfactant, Bola type surfactant and Dendrimer type surfactant.

The foaming agent is one or a combination of more than two of Gemini type surfactant, Bola type surfactant, Dendrimer type surfactant, protein type foaming agent, sulfonate type anionic surfactant with 8-20 carbon atoms in a carbon chain, sulfate type anionic surfactant with 8-18 carbon atoms in a carbon chain, amide ester quaternary ammonium salt cationic surfactant, double long-chain ester quaternary ammonium salt cationic surfactant, triethanolamine stearate quaternary ammonium salt cationic surfactant, polyoxyethylene type nonionic surfactant, fatty alcohol amide type nonionic surfactant, polyhydric alcohol type nonionic surfactant, amino acid type zwitterionic surfactant and betaine type zwitterionic surfactant. The foaming ratio of the foaming agent is 8-60 times.

The Gemini surfactant is one or more of quaternary ammonium salt Gemini surfactant, carboxylate Gemini surfactant, betaine Gemini surfactant and sulfate Gemini surfactant.

The Bola surfactant is a semi-cyclic, single-chain or double-chain Bola surfactant.

The Dendrimer type surfactant is polyether, polyester, polyamide, polyaromatic hydrocarbon or polyorganosilicon type Dendrimer surfactant.

The protein foaming agent is animal protein foaming agent, plant protein foaming agent or sludge protein foaming agent.

Sulfonate anionic surfactants with carbon number of 8-20 in carbon chain, such as sodium dodecyl benzene sulfonate, alpha-olefin sodium sulfonate, and the like; sulfate anionic surfactants with carbon number of 8-18 in carbon chain, such as ammonium dodecyl sulfate, sodium cetyl ether sulfate, etc.

Polyoxyethylene type nonionic surfactant such as higher fatty alcohol polyoxyethylene ether, fatty alcohol polyoxyethylene ester, etc.

Betaine type zwitterionic surfactants such as dodecyl dimethyl betaine and the like.

Further preferably, the foaming agent is selected from one or more of quaternary ammonium type Gemini surfactants, semi-ring type Bola surfactants, carboxylate type Gemini surfactants, lauramidopropyl sulphobetaine, sodium lauryl polyoxyethylene ether carboxylate, sodium alpha-olefin sulfonate, dodecyl dimethyl betaine surfactants, sodium fatty alcohol polyoxyethylene ether carboxylate, sulfate type Gemini surfactants, polyether type Dendrimer surfactants, vegetable protein foaming agents, sludge protein foaming agents, animal protein foaming agents, sodium dodecyl benzene sulfonate, polyamide type Dendrimer surfactants and double-chain type Bola surfactants.

The selection of each raw material in the additive will be described below.

Based on the mass of the basic raw material, the addition mass of the dispersing agent is not more than 2 percent; the dispersant is one or the combination of more than two of polycarboxylic acid dispersant, polycarboxylic acid ether dispersant, sodium polyacrylate, naphthalene dispersant, FS10, FS20, lignin dispersant, sulfonated melamine polycondensate, melamine formaldehyde polycondensate, aliphatic dispersant, sulfamate dispersant, sodium citrate, sodium tripolyphosphate, sodium hexametaphosphate and sodium carbonate. The polycarboxylic acid dispersant is at least one of a methacrylate type polycarboxylic acid dispersant, an allyl ether type polycarboxylic acid dispersant, an amide/imide type polycarboxylic acid dispersant, and a polyamide/polyethylene glycol type polycarboxylic acid dispersant. The lignin dispersing agent is at least one of calcium lignosulfonate, potassium lignosulfonate and sodium lignosulfonate.

Based on the mass of the basic raw material, the addition mass of the suspending agent is not more than 10 percent; the suspending agent is one or the combination of more than two of bentonite, sepiolite, attapulgite, polyaluminium chloride, polyaluminium sulfate, chitosan, xanthan gum, Arabic gum, welan gum, agar, acrylamide, polyacrylamide, polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol, casein, hexadecanol, sucrose, dextrin, tris (hydroxymethyl) aminomethane, microcrystalline cellulose sodium, cellulose fiber, cellulose nanocrystal and soluble starch. If clay raw materials with plasticity are used as the basic raw materials, the slurry has certain suspension capacity, and the addition of a suspending agent can be properly reduced or eliminated.

Generally, when organic suspending agents such as polyaluminum chloride, polyaluminum sulfate, chitosan, welan gum, agar, polyethylene glycol, polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone, casein, cetyl alcohol, sucrose, dextrin, microcrystalline cellulose, cellulose fiber, cellulose nanocrystal and the like are selected, it is found that a good effect can be exerted by adding a small amount of the suspending agents, and the suspending agents can generate a suspending effect on the slurry through a steric hindrance effect or an electrostatic steric hindrance effect in the slurry, so that the adding amount of the suspending agents can be relatively small, generally, the using amount of the suspending agents is less than or equal to 3%, preferably less than or equal to 1%, and more preferably less than or equal to 0.5%; when the inorganic mineral raw materials such as bentonite, sepiolite, attapulgite and the like are selected, the inorganic mineral raw materials can be rapidly hydrolyzed in slurry and decomposed into ions with charges, the ions form an electric double layer structure on the surface of basic raw material particles, and the basic raw material particles generate a suspension effect in the slurry by electrostatic repulsion, but the dosage of the inorganic mineral raw materials is relatively large, and is generally less than or equal to 10%.

The mineralizer is ZnO or Fe₂O₃、Fe₃O₄、V₂O₅、SiF₄、CaF₂、AlF₃、AlF₃·3H₂O、MnO₂、CuO、CuSO₄、MgO、SrO、BaO、WO₃、Er₂O₃、Cr₂O₃、La₂O₃、YbO、Y₂O₃、CeO₂One or a combination of two or more of them. The mineralizer has an average particle size of 5 μm or less, preferably 4 μm or less, preferably 3 μm or less, more preferably 2 μm or less, particularly preferably 1 μm or less, and still more particularly 100nm or less. The mineralizer can promote the growth and development of beneficial crystals such as anorthite, mullite and the like, reduce the sintering temperature and promote the sintering reaction.

The heat insulation mechanism of the heat insulation refractory material is that a large number of air holes exist in the heat insulation refractory material, and the heat conductivity coefficient of air in the air holes is far smaller than that of air hole walls, so that the heat transfer rate of the whole heat insulation material is reduced, and the heat insulation refractory material has heat insulation performance. The heat conducting mechanism of the material mainly comprises three parts of heat conduction, convection heat transfer and radiation heat transfer, in the invention, because the pore diameter of the pores in the prepared anorthite micro-nano hole heat-insulating refractory material is small, most pores are of a closed structure, and the gas circulation is difficult, the convection heat transfer can be basically ignored, and because the anorthite micro-nano hole heat-insulating refractory material is mainly used at high temperature, the heat transfer mechanism of the material also comprises the radiation heat transfer besides the heat transfer. To further effectively reduce radiative heat transfer, the present invention incorporates infrared opacifiers to increase reflection or absorption of infrared radiation and attenuate itThe material has penetrability and reduced thermal conductivity, and particularly has obvious reduction on the thermal conductivity coefficient for high-porosity and low-thermal conductivity heat-insulation refractory materials. To further improve the insulation properties of the article, it is preferred in the present invention that the infrared opacifier is selected from rutile, TiO₂、TiC、K₄TiO₄、K₂Ti₆O₁₃、Sb₂O₃、Sb₂O₅、ZrO₂、NiCl₂、Ni(NO₃)₂、CoO、Co(NO₃)₂、CoCl₂、ZrSiO₄、B₄C. One or a combination of two or more of SiC. The infrared-shading agent has an average particle diameter of 5 μm or less, preferably 4 μm or less, more preferably 3 μm or less, still more preferably 2 μm or less, particularly preferably 1 μm or less, and still more preferably 100nm or less. The dosage of the infrared opacifier is preferably 1-10% of the mass of the basic raw materials.

The technical scheme of the preparation method of the anorthite micro-nano hole heat insulation refractory material is as follows:

a preparation method of a anorthite micro-nano-pore heat insulation refractory material comprises the following steps:

1) when the additive is used, the basic raw material, the additive and water are mixed to prepare suspension slurry; when the additive is not used, mixing the basic raw material with water to prepare suspension slurry;

2) adding a foaming agent, an inorganic curing agent, an organic curing agent and a foam pore regulator into the suspension slurry to carry out stirring, shearing and foaming to prepare foam slurry containing micro-nano bubbles;

3) injecting the foam slurry into a mold for curing (solidifying and shaping), and demolding to obtain a blank; and then drying and sintering the green body.

The technical key point of preparing the light heat-insulating material lies in the introduction of the internal pores, and in the preparation method, the basic raw material, the additive and water are mixed to form suspended slurry, and then the suspended slurry is mixed with the functional foaming component consisting of the foaming agent, the inorganic curing agent, the organic curing agent and the cell regulator and is stirred for foaming, so that the integrity of bubbles is maintained, and the generation rate of closed pores is improved; in the curing process, the air bubbles in the foam slurry are converted into spherical air holes in the blank body, and the air holes provide space for the growth and development of beneficial crystals such as anorthite, mullite and the like in the subsequent firing process, so that the crystal development is complete, and the product performance is improved. Meanwhile, the inventor also finds that the holes in the green body prepared by the invention are tiny micron or nano spherical gaps, and the concave surfaces of the holes have extremely large curvature radius, so that the nucleation and growth driving forces of beneficial crystals such as anorthite, mullite and the like in the holes are further enhanced, the growth size of the crystals is larger, and the physical properties of the product are better.

The preparation method of the anorthite micro-nano-pore heat insulation refractory material provided by the invention has the advantages of simple and easily-controlled preparation process, environmental friendliness and no pollution. The product has micro-nano pore diameter, and can effectively regulate and control the volume density, the pore structure, the mechanical property and the heat insulation property in a larger range. Under the volume density and porosity similar to those of the prior art, the compression strength and the heat insulation performance of the product can be improved by more than several times, and the product is more suitable for the application requirements of modern kilns and equipment on light, high-strength and ultralow heat conduction and heat insulation refractory materials.

In the preparation method, in the step 1), the addition amount of water is 30-300% of the mass of the basic raw material. Preferably 30 to 250%, more preferably 30 to 200%, still more preferably 30 to 150%, particularly preferably 30 to 100%, and still more particularly preferably 30 to 50%. When the water is added in a large amount, most of the water can be converted into a liquid film of bubbles in the slurry in the stirring process, and a small part of the water which is not converted into the liquid film of bubbles exists in the form of liquid water, so that tiny-sized pores can be left in the sample after the blank body is dried and burnt. That is to say, the added water is finally converted into micro-nano-sized pores in the product, so the essence of the process technology for preparing the heat insulation refractory material is that the micro-nano-sized pore structure is generated in the refractory material by using water and air, and the volume density, the porosity, the thermal conductivity, the mechanical strength and the like in the product can be correspondingly regulated and controlled to a certain extent according to the water consumption. In this step, if components such as a dispersant, a suspending agent, a mineralizer, an infrared screening agent, etc. are used, the above components and the base material are dispersed to form a suspension slurry. If no dispersing agent, suspending agent, mineralizer, infrared opacifier and other ingredients are used or only one or more of the ingredients are used, the corresponding components are dispersed.

In the step 1), the basic raw material, the dispersing agent, the suspending agent and the mineralizing agent are premixed, and then water is added to mix to prepare the suspended slurry. In order to form a fine, uniform and stable slurry, the average particle size of the solid particles in the slurry should be controlled to be not more than 1mm, preferably not more than 74 μm. In order to achieve the mixing effect, one or a combination of means such as mechanical stirring, ball milling, ultrasound and the like can be adopted for mixing. When the raw material has a fine particle size and is easily dispersed to obtain a suspension slurry, a simple mechanical stirring manner may be employed. More preferably, the dispersing agent, the suspending agent, the mineralizer and the infrared opacifier are premixed to obtain the additive, and then the additive is mixed with the basic raw material and water; preferably, the base material and the additive are ball milled by adding water. Further preferably, the ball abrasive slurry may be ultrasonically dispersed in order to obtain a more uniform slurry suspension. Wherein, the basic raw materials of the calcium raw material, the aluminum-silicon raw material, the aluminum oxide raw material and the silicon dioxide raw material are preferably mixed uniformly in advance.

The additive and the foaming material can be respectively premixed by a three-dimensional mixer, a V-shaped mixer, a double-cone mixer, a planetary mixer, a forced mixer and a non-gravity mixer, and the mixing uniformity of the materials is not less than 95%, preferably not less than 99%. Also, the four materials of the base material are preferably mixed in advance in the same manner when used.

During ball milling, the weight ratio of the materials to the balls is 1: (0.8-1.5) and the ball milling time is 0.5-12 h. The grinding ball is made of one or more of cobblestone, corundum, mullite, zirconia corundum, silicon carbide and tungsten carbide; the size specification of the grinding ball is a big ball

Middle ball

Small ball

The large, medium and small balls are (1-1.5): (1-3): (6-10) in combination by weight. Further preferably, the large, medium and small balls are prepared according to the following formula (1-1.5): (1-2): (6-8) in combination by weight. The average particle size of the solid particles in the mixture can be made not higher than 74 μm by ball milling. Preferably, the solid particles have an average particle size of not more than 50 μm; further preferably, the average particle diameter of the solid particles is not higher than 44 μm; more particularly preferably, the solid particles have an average particle size of not more than 30 μm. The inventor finds that the ceramic powder particles have high surface activity after ball milling, and then have excellent hydrophobic property after being modified by surfactant molecules (foaming agents), the ceramic powder particles can be irreversibly adsorbed on a gas-liquid interface on a bubble liquid film under the action of mechanical stirring, the gas-liquid interface in a high energy state is replaced by a liquid-solid and gas-solid interface in a low energy state, so that the total free energy of a system is reduced, the stability of foam is improved, and also finds that part of the powder particles are accumulated in Plateau channels among bubbles, so that liquid film drainage is effectively prevented, unstable factors such as rupture, drainage, disproportionation, Oswald curing and the like of the foam are resisted, and therefore, the stable foamed ceramic slurry is obtained.

And the ultrasonic treatment further and rapidly improves the mixing and dispersing uniformity of each component in the suspension slurry, the power of the ultrasonic treatment is 500-2000W, and the time is 4-15 min.

In the step 2), in the preparation process of the foam slurry, if the foaming agent, the inorganic curing agent, the organic curing agent and the cell regulator are dry solid raw materials according to the variety of the raw materials, dry mixing is firstly carried out on the dry raw materials to prepare a foaming material, then the foaming material is added into the suspension slurry, and then stirring and foaming are carried out. If some of the foaming agent, inorganic curing agent, organic curing agent and cell regulator are liquid materials, it is preferable to dry-blend the dry solid materials, add the dry blend and liquid materials to the suspension slurry, and stir for foaming. The foaming agent can also be prepared into foam by a foaming machine, and then the foam is added into the suspension slurry with the mixture of the inorganic curing agent, the organic curing agent and the cell regulator, and then the mixture is further stirred and foamed.

Preferably, in the step 2), a stirring blade of a vertical stirrer is adopted for high-speed stirring, shearing, mixing and foaming during stirring and foaming, and the linear speed of the outer edge of the stirring blade is 20-200 m/s. And (3) quickly mixing for 1-30 min by using a stirring paddle of the stirrer. The shearing linear velocity is the linear velocity of the outer edge of the paddle of the stirring paddle, the stirring paddle quickly stirs, mixes and entrains air in the slurry, so that the volume of the slurry is quickly expanded, large bubbles in the slurry are gradually sheared into small bubbles with the diameter of 0.01-200 mu m along with the time extension, and the suspended slurry is changed into uniform foam slurry. After the foam slurry is solidified and dried, small bubbles in the slurry are converted into spherical closed air holes in a dried blank, and the spherical air hole structure can provide development space for the growth of anorthite and other beneficial crystals in a fired product, so that the growth improvement of the crystals and the improvement of the mechanical property of the product are facilitated. The linear velocity of the outer edge of the stirring paddle is preferably 50 to 200m/s, more preferably 80 to 200m/s, more preferably 100 to 200m/s, particularly preferably 150 to 200m/s, and more particularly preferably 180 to 200 m/s.

Preferably, in the step 3), the curing is performed at a temperature of 1-35 ℃ and a humidity of 40-99.9% for 0.1-24 h, preferably for 0.1-2 h. The curing is preferably performed in a constant temperature and humidity environment. In the curing process, the foam slurry is cured and shaped, and then the foam slurry can be demoulded and dried. In the curing process, the air temperature is preferably 5-30 ℃, more preferably 10-30 ℃, more preferably 20-30 ℃, particularly preferably 25-30 ℃, and more particularly preferably 27-30 ℃; the relative humidity of the air is preferably 60 to 99%, more preferably 70 to 97%, still more preferably 80 to 95%, particularly preferably 85 to 93%, and still more preferably 88 to 92%. In the curing process, inorganic and organic curing agents and the like in the blank can accelerate the hydration reaction and the curing and condensation, so that the strength of the blank is rapidly increased, and the rapid demoulding can be realized.

Researches find that the turnover rate of the die is greatly increased due to the very short demoulding time of the blank, the integral preparation process is also accelerated, and the production efficiency is greatly improved, which is difficult to realize in the past.

The casting mold in step 3) is selected from one or more of the following, but is not limited to: metal mould, plastic mould, resin mould, rubber mould, foam mould, plaster mould, glass fibre reinforced plastic mould or wood or bamboo glue mould, and mould made up by using said several materials. The shape of the mold can be changed according to design requirements and is suitable for preparing special-shaped products.

It will be appreciated that the green body is cured and then demoulded and then dried. Because the strength of the green body after curing is rapidly increased, the green body can be rapidly dehydrated and dried in the step 3), and the drying can be one or the combination of more than two of normal pressure drying, supercritical drying, freeze drying, vacuum drying, infrared drying and microwave drying. The water content in the finally dried green body is less than or equal to 3 wt%. In the above process, the strength of the green body obtained after the foam slurry is cured and dried is greatly improved by the combined action of the organic and inorganic curing agents, the compressive strength of the dried green body is not less than 0.7MPa, the damage to the green body caused by collision in the processes of carrying and kiln loading can be avoided or greatly reduced, the yield is greatly improved, the yield is not less than 90%, preferably not less than 95%, more preferably not less than 98%, more particularly preferably not less than 99%, the production cost is remarkably reduced, and the green body can be effectively mechanically processed.

Preferably, when the drying is carried out under normal pressure, the drying heat source can be power supply heating or hot air, the drying temperature is 30-110 ℃, and the drying time is 12-48 hours. Preferably, the drying system is as follows: heating to 30 ℃ at a speed of 1-5 ℃/min, preserving heat at 30 ℃ for 0.5-5 h, heating to 50 ℃ at a speed of 1-5 ℃/min, preserving heat at 50 ℃ for 2-5 h, heating to 70 ℃ at a speed of 1-5 ℃/min, preserving heat at 70 ℃ for 2-5 h, heating to 90 ℃ at a speed of 2-5 ℃/min, preserving heat at 90 ℃ for 2-5 h, heating to 100-110 ℃ at a speed of 2-5 ℃/min, and preserving heat at 100-110 ℃ for 5-24 h.

And during supercritical drying, the drying medium is carbon dioxide, the temperature of the carbon dioxide for supercritical drying is 31-45 ℃, the pressure in the reaction kettle is controlled at 7-10 MPa, and the drying time is 0.5-3 h.

During freeze drying, the drying temperature of the freeze dryer is-180 to-30 ℃, and the drying time is 3 to 6 hours.

And during vacuum drying, the drying temperature is 35-50 ℃, the vacuum pressure is 130-0.1 Pa, and the drying time is 3-8 h.

In the infrared drying, the wavelength of the infrared ray is 2.5 to 100 μm, preferably 2.5 to 50 μm, more preferably 2.5 to 30 μm, particularly preferably 2.5 to 15 μm, more particularly preferably 2.5 to 8 μm, and the drying time is 0.5 to 5 hours.

During microwave drying, the microwave frequency is 300-300000 MHz, preferably 300-10000 MHz, more preferably 300-3000 MHz, especially preferably 300-1000 MHz, more especially preferably 600-1000 MHz, and the drying time is 0.2-3 h.

After the green body is quickly dried and dehydrated, a porous structure with higher strength is formed, and the weight of the green body is greatly reduced and the strength is greatly increased compared with the green body prepared by the traditional pore-forming agent adding method before drying, so that the labor intensity of workers in the green body transportation and kiln loading operation is greatly reduced, the green body drying method is very suitable for mechanized operation, the working efficiency is improved, and the yield is also improved.

Preferably, the firing in step 3) is optionally fired in a shuttle kiln, a resistance kiln, a high temperature tunnel kiln or a microwave kiln. In firing, the firing temperature is more preferably 1150 to 1500 ℃. In order to further optimize the sintering effect and promote the anorthite crystal to form a plate-shaped appearance, preferably, the sintering is carried out by preserving heat at 400-600 ℃ for 0.5-1.5 h; then heating to 900-1000 ℃ and preserving the heat for 0.5-1.5 h; then heating to 1150-1500 ℃ and preserving the heat for 0.5-10 h; then cooling to 900-1000 ℃, preserving heat for 0.5-1.5 h, then cooling to 400-600 ℃, preserving heat for 0.5-1 h, and then cooling to 50-80 ℃. The rate of raising the temperature from room temperature to 400-600 ℃ is 1-10 ℃/min, the rate of raising the temperature to 900-1000 ℃ is 5-30 ℃/min, the rate of raising the temperature to 1100-1500 ℃ is 1-20 ℃/min, the rate of lowering the temperature to 900-1000 ℃ is 10-20 ℃/min, the rate of lowering the temperature to 400-600 ℃ is 5-10 ℃/min, and the rate of lowering the temperature to 50-80 ℃ is 1-5 ℃/min. The calcined anorthite micro-nano hole heat insulation refractory material can be cut, ground or punched into a required shape according to actual requirements.

Compared with the prior art, the preparation method disclosed by the invention is green and environment-friendly, pollution-free, simple and easily-controlled in process, short in demolding and drying period of the blank, high in strength of the blank, high in yield and excellent in product performance, is very suitable for large-scale, mechanized, modernized and intelligent production operation, and is beneficial to popularization and application.

Drawings

FIG. 1 is a photograph of the macroscopic appearance of the anorthite micro-nanoporous insulating refractory produced in example 8;

FIG. 2 is a photograph of the microstructure of the pores of the sample prepared in example 8;

FIG. 3 is a microstructure photograph of platy anorthite produced in example 8;

FIG. 4 is an X-ray diffraction (XRD) pattern of a sample prepared in example 8;

FIG. 5 is a graph showing the pore size distribution of the sample produced in example 8.

Detailed Description

The following describes the specific implementation process of the present invention with reference to specific examples. It should be noted that the examples given in this specification are only for the purpose of facilitating understanding of the present invention, and they are not intended to be limiting, i.e., the present invention may be embodied in other forms than those shown in the specification. Therefore, any technical solutions formed by equivalent substitution or equivalent transformation fall within the protection scope of the present invention.

The starting materials used in the following examples are commercially available conventional products.

Vinyl acetate and ethylene copolymers were obtained from Wacker Chemicals, Germany

Ethylene and vinyl acetate copolymers were obtained from Wacker Chemicals, Germany

Acrylate and styrene copolymers were purchased from national starch, Inc

Ethylene and vinyl chloride andvinyl laurate copolymers from Wacker Chemicals, Germany

Acrylate polymers were purchased from national starch, Inc

Vinyl acetate copolymers with ethylene and higher fatty acids were purchased from Wacker Chemicals, Germany

Ethylene and vinyl chloride copolymers were purchased from Wacker Chemicals, Germany

Vinyl acetate and ethylene and vinyl chloride copolymers available from Wacker Chemicals, Germany

Vinyl acetate copolymers with ethylene and acrylic acid esters available from Wacker Chemicals, Germany

Vinyl acetate copolymers with ethylene and vinyl laurate from Wacker Chemicals, Germany

Vinyl acetate homopolymer from Wacker Chemicals, Germany

The copolymer of vinyl acetate and vinyl versatate is purchased from Anhui vitamin (WWJF-8010); vinyl acetate copolymers with vinyl versatate and acrylic acid esters were purchased from Nippon synthetic chemical industries, Inc. (Mowinyl-DM 2072P); vinyl acetate and higher fatty acid vinyl ester copolymers were obtained from Shanxi three-dimensional company (SWF-04); isobutylene and maleic anhydride copolymers were purchased from clony, japan (ISOBAM-04); konjac gum powder is purchased from Shanghai North Liansheng Co; curdlan was purchased from Hengmei technology, Inc.; gellan gum is purchased from Jiangsu ancient shellfish BiotechA driver; hydroxypropyl guar was purchased from wilkinson chemical company; sodium alginate was purchased from ancient shellfish biotechnology, Jiangsu).

For cell regulator raw materials, ethyl cellulose ether was purchased from aksunobel, netherlands; hydroxyethyl cellulose ethers are available from helkris, usa; hydroxyethyl methyl cellulose ether was purchased from clariant, switzerland; hydroxyethyl ethyl cellulose ether was purchased from aksunobel, the netherlands; ethyl methyl cellulose ether was purchased from dow chemical, usa; methyl cellulose ethers were purchased from dow chemical, usa; carboxymethyl cellulose ethers are available from yastra, usa; carboxymethyl methyl cellulose ethers are available from dow chemical, usa; carboxymethyl ethyl cellulose ether was purchased from american methylene; propyl cellulose ethers were purchased from methylene; hydroxypropyl cellulose ether was purchased from yashilan, usa; hydroxypropyl methylcellulose ether is available from yastra corporation, usa; hydroxypropyl ethyl cellulose ether was purchased from american methylene; hydroxymethyl cellulose ethers were purchased from dow chemical, usa; carboxymethyl hydroxymethyl cellulose ethers are available from dow chemical; carboxymethyl hydroxyethyl cellulose ethers are available from dow chemical; carboxymethyl hydroxypropyl cellulose ether was purchased from dow chemical, usa; carboxymethyl hydroxybutyl cellulose ethers were purchased from dow chemical, usa; hydroxypropyl hydroxybutyl cellulose ether was purchased from dow chemical, usa; sulfonic acid ethyl cellulose ethers were purchased from dow chemical, usa; hydroxybutyl methyl cellulose ethers were purchased from dow chemical, usa; saponin is purchased from Henmei science and technology limited; starch ethers were purchased from AVEBE, Netherlands; water-soluble cellulose ethers are available from henmei technologies ltd; lignocellulose was purchased from JRS, germany.

Quaternary ammonium type Gemini surfactant (foaming multiple 45) purchased from Hengmei science and technology Limited; semi-ring Bola surfactant (foaming ratio 50) purchased from heng scientific and technology limited; a two-chain Bola surfactant (foaming multiple 44) available from heng-mei technologies ltd; a polyether type Dendrimer surfactant (foaming ratio of 45) purchased from Hengmei science and technology Co., Ltd; a vegetable protein foaming agent (foaming ratio of 9) purchased from Shandongxin Mao chemical company; a sludge protein foaming agent (the foaming ratio is 8) purchased from Hengmei science and technology limited; carboxylate Gemini surfactant (foaming multiple of 60) purchased from Hengmei science and technology Limited; animal protein foaming agent (expansion ratio of 11) purchased from Hengmei science and technology Limited; sodium lauryl polyoxyethylene ether carboxylate (the foaming ratio is 9); lauric acid amide propyl sulfobetaine (foaming ratio 13); alpha-olefin sodium sulfonate (expansion factor of 15); dodecyl dimethyl betaine surfactant (foaming times are 17); a sulfate type Gemini surfactant (foaming multiple of 55) purchased from Hengmei science and technology, Inc.; sodium fatty alcohol polyoxyethylene ether carboxylate (expansion ratio of 15) available from Hengmei science and technology Limited; sodium dodecyl benzene sulfonate (foaming ratio is 9); polyamide type Dendrimer surfactants (foam expansion 55) were purchased from Hengmei technology, Inc.

Allyl ether type polycarboxylic acid dispersants, available from Hengmei science and technology Limited; amide polycarboxylic acid dispersants, available from Hencam technologies, Inc.; imide type polycarboxylic acid dispersants, available from Hencam technologies, Inc.; polyamide-type polycarboxylic acid dispersants, available from basf, germany; sulfonated melamine polycondensates, available from Hencl technologies, Inc.; naphthalene-based high-efficiency dispersants, available from Hengmei science and technology, Inc.; polyethylene glycol type polycarboxylic acid type dispersants available from basf, germany; polycarboxylic acid-based dispersants, available from basf, germany; melamine formaldehyde polycondensates, available from Hengmei technologies, Inc.; polycarboxylate ether dispersants, available from basf, germany; methacrylate type polycarboxylic acid dispersants, available from Hencus technologies, Inc.

In the following examples, the following specifications were used unless otherwise specified, and the further specification of the raw materials was used as the standard.

The mass percentage of CaO in the quicklime is 95-97 wt%, and the particle size is less than or equal to 0.08 mm. Al in kaolin₂O₃32-35% of SiO₂The mass percentage of the composite material is 61-64%, and the particle size is less than or equal to 0.08 mm. Al in bentonite₂O₃22-23 wt% of SiO₂The mass percentage of the composite material is 68-75%, and the particle size is less than or equal to 0.045 mm. The mass percentage of CaO in the limestone is 50-55 wt%, and the particle size is less than or equal to 0.08 mm. The CaO content of the wollastonite is 34 to c by mass percent37 wt% and the particle size is less than or equal to 0.08 mm. Industrial Al₂O₃、δ-Al₂O₃、χ-Al₂O₃、β-Al₂O₃、η-Al₂O₃、γ-Al₂O₃、θ-Al₂O₃、ρ-Al₂O₃Middle Al₂O₃The mass percentage content of the composite is equal to or more than 98 wt%, and the particle size is equal to or less than 0.08 mm. Al in wood-saving soil₂O₃32-35% of SiO₂The mass percentage of the composite material is 64-66%, and the particle size is less than or equal to 0.08 mm. Al in attapulgite₂O₃12-15 wt% of SiO₂The mass percentage of the magnesium oxide is 55-60%, the mass percentage of the MgO is 8-10 wt%, and the particle size is less than or equal to 0.045 mm. SiO in silica sol₂The percentage content of the compound is not less than 30 percent. Al in alumina sol₂O₃The mass percentage content of the composition is not less than 20 percent. Al in silica-alumina sol₂O₃Mass percentage of not less than 30 percent and SiO₂The mass percentage content of the composition is not less than 20 percent. CaO is industrial pure, and the particle size is less than or equal to 0.08 mm.

First, the specific embodiment of the anorthite micro-nano hole heat insulation refractory material and the preparation method thereof

Example 1

The anorthite microporous heat insulation refractory material is prepared from basic raw materials, a suspending agent, a mineralizer, an infrared opacifier, a foaming agent, an inorganic curing agent, an organic curing agent, a foam pore regulator and water. The kinds and amounts of the raw materials in this example are as follows:

basic raw materials: 0.06 ton quicklime, 0.3 ton kaolin, 0.1 ton potassium feldspar, 0.1 ton albite, 0.21 ton industrial Al (OH)₃0.05 ton boehmite, 0.05 ton diaspore, 0.13 ton diatomaceous earth. Al in kaolin₂O₃The mass percentage of the silicon dioxide is 32-35 percent, and the SiO₂The mass percentage of the particles is 61-64%, and the particle size is 0.6-1 mm; k in potassium feldspar₂9-11% of O and Al₂O₃The mass percentage of the SiO is 18-20 percent₂The mass percentage of the composite material is 64-66%, and the particle size is less than or equal to 0.08 mm; na in albite₂10-12% of O and Al₂O₃19-22% of SiO₂The mass percentage of the composite material is 66-69%, and the particle size is less than or equal to 0.08 mm; industrial Al (OH)₃Middle Al₂O₃The aluminum content is not less than 65 wt%, and the particle size is not less than 0.08 mm; al in boehmite and diaspore₂O₃The aluminum content is not less than 70 wt%, and the particle size is not less than 0.08 mm; SiO in diatomite₂The mass percentage of the composite material is not less than 85 wt%, and the particle size is not less than 0.08 mm.

Suspending agent: 100kg of bentonite.

Mineralizing agent: 30kg of AlF₃、50kg Fe₂O₃、10kg ZnO、10kg V₂O₅；AlF₃、Fe₂O₃、ZnO、V₂O₅The particle diameter of (b) is ≦ 5 μm.

Infrared opacifier: 70kg rutile, 20kg ZrSiO₄、10kg B₄C; rutile, ZrSiO₄、B₄The particle size of C is ≦ 5 μm.

Foaming agent: 5kg of quaternary ammonium type Gemini type surfactant and 3kg of semi-ring type Bola surfactant.

Inorganic curing agent: 150kg of silica sol, liquid, SiO₂The content is not less than 30%.

Organic curing agent: 10kg of a copolymer of vinyl acetate and ethylene, 10kg of a copolymer of ethylene and vinyl acetate.

Cell regulator: 0.4kg of hydroxyethyl ethyl cellulose ether.

Water: 3 tons.

The specific preparation process of the anorthite micro-nano hole insulating refractory material of the embodiment is as follows:

(1) weighing 0.06 ton quicklime, 0.3 ton kaolin, 0.1 ton potassium feldspar, 0.1 ton albite, 0.21 ton industrial Al (OH)₃Pouring 0.05 ton of boehmite, 0.05 ton of diaspore and 0.13 ton of diatomite into a forced mixer and dry-mixing for 15min to obtain a basic raw material; 100kg of bentonite and 30kg of AlF are weighed₃、50kg Fe₂O₃、10kg ZnO、10kg V₂O₅70kg of rutile, 20kg of ZrSiO₄、10kg B₄C, pouring the mixture into a three-dimensional mixer and carrying out dry mixing for 5min to obtain an additive;

(2) weighing 5kg of quaternary ammonium type Gemini surfactant, 3kg of semi-ring type Bola surfactant, 10kg of vinyl acetate-ethylene copolymer, 10kg of ethylene-vinyl acetate copolymer and 0.4kg of hydroxyethyl ethyl cellulose ether, pouring the materials into a V-shaped mixer, and mixing for 5min to obtain a uniform foamed material;

(3) pouring the basic raw materials and the additives obtained in the step (1) into a roller ball mill, adding 3 tons of water, ball-milling and mixing for 12 hours, and performing ultrasonic oscillation (ultrasonic power 2000W) for 4 minutes to obtain uniform suspension slurry (wherein the particle size of solid particles is less than or equal to 30 mu m); the grinding balls in the ball mill adopt alumina balls and large balls

Middle ball

Small ball

The weight ratio of (1): 1: 8, the weight ratio of the materials to the balls is 1: 0.8;

and (3) injecting the suspension slurry into a stirrer, pre-stirring for 1min (the linear velocity of a stirring paddle in the pre-stirring process is 5m/s), then adding 150kg of silica sol and the foamed material obtained in the step (2) into the stirrer, and quickly mixing the mixture for 3min by the stirring paddle at the linear velocity of 80m/s to obtain uniform foamed slurry.

(4) Injecting the foam slurry into a stainless steel mold, and curing for 2h in an environment with air temperature and relative humidity of 25 ℃ and 95% respectively until the foam slurry is cured and shaped;

(5) and (3) demolding the solidified and shaped blank, and removing water in the blank by using a carbon dioxide supercritical drying method, wherein the carbon dioxide is controlled at the pressure of 9MPa and the temperature of 42 ℃ for 2h, so as to obtain the dried porous blank. The water content of the dried green body is less than or equal to 3 wt%, and the compressive strength is greater than or equal to 0.8 MPa. And firing the dried blank body by adopting a high-temperature tunnel kiln, raising the temperature from room temperature to 400 ℃ at a heating rate of 1 ℃/min, raising the temperature to 1000 ℃ at 5 ℃/min, preserving the heat for 1.5h, raising the temperature to 1150 ℃ at 1 ℃/min, preserving the heat for 10h, then lowering the temperature to 1000 ℃ at 10 ℃/min, preserving the heat for 1.5h at 1000 ℃, lowering the temperature to 500 ℃ at 5 ℃/min, preserving the heat for 1h at 500 ℃, and finally lowering the temperature to 50 ℃ at 1 ℃/min to obtain the anorthite micro-nano-hole insulating and heat-insulating refractory material.

Examples 2 to 15

The formulation compositions of the anorthite micro-nano-pore insulating refractory of examples 2 to 15 are shown in tables 1 and 2 below:

TABLE 1 examples 2-8 formulation of anorthite microporous insulating refractory

TABLE 2 formulation of the sillimanite micro-nano-pore insulating refractory of examples 9-16

The following is a brief description of the process for producing the anorthite microporous heat-insulating and fire-resistant material of examples 2 to 14, and the mixing process of the base material, the additive and the foam can be referred to from step (1) to step (2) in example 1, and only the differences between the remaining steps will be described below.

In example 2, the base material and the additive obtained in step (1) were poured into a roller ball mill, 2.8 tons of water were added, ball milling and mixing were carried out for 10 hours, and then ultrasonic oscillation (ultrasonic power 1500W) was carried out for 6min to obtain uniform suspension slurry (particle size of solid particles is less than or equal to 30 μm); the grinding balls in the ball mill adopt alumina balls and large balls

Middle ball

Small ball

The weight ratio of (1): 1: 8, the weight ratio of the materials to the balls is 1: 0.9;

and (3) injecting the suspension slurry into a stirrer, pre-stirring for 1min (the linear velocity of a stirring paddle in the pre-stirring process is 5m/s), adding the foamed material obtained in the step (2), 120kg of silica sol and 80kg of alumina sol into the stirrer, and quickly mixing the foamed material, the silica sol and the alumina sol for 3min by the stirring paddle at the linear velocity of 80m/s to obtain uniform foam slurry.

Injecting the foam slurry into an aluminum alloy mold, and curing for 3.5h in an environment with the air temperature and the relative humidity of 1 ℃ and 40% respectively until the foam slurry is cured;

and (3) demolding the solidified blank, and removing water in the blank by using a carbon dioxide supercritical drying method, wherein the carbon dioxide is controlled at the pressure of 9MPa and the temperature of 42 ℃ for 2h, so as to obtain the dried porous blank. The water content of the dried green body is less than or equal to 3 wt%, and the compressive strength is greater than or equal to 0.75 MPa. And firing the dried blank body by adopting a high-temperature tunnel kiln, raising the temperature from room temperature to 500 ℃ at a heating rate of 2 ℃/min, raising the temperature to 1000 ℃ at 8 ℃/min, preserving the heat for 1h, raising the temperature to 1150 ℃ at 3 ℃/min, preserving the heat for 8h, then reducing the temperature to 1100 ℃ at 10 ℃/min, preserving the heat for 1h at 1100 ℃, reducing the temperature to 500 ℃ at 6 ℃/min, preserving the heat for 0.5h at 500 ℃, and finally reducing the temperature to 50 ℃ at 2 ℃/min to obtain the anorthite micro-nano-pore insulating refractory material.

In example 2, Al in Suzhou soil₂O₃42-45% of SiO₂The mass percentage of the composite material is 52-55%, and the particle size is less than or equal to 0.075 mm; the mass percentage of BaO in the barium feldspar is 16-18%, and Al₂O₃The mass percentage of the SiO is 25-28 percent₂The mass percentage of the composite material is 54-56%, and the particle size is less than or equal to 0.08 mm; al in fly ash₂O₃29-33% of SiO₂The mass percentage of the composite material is 48-55%, and the particle size is less than or equal to 0.08 mm; floating bead Al₂O₃33-36% of SiO₂The mass percentage of the composite material is 48-52%, and the particle size is less than or equal to 0.08 mm; SiO in white carbon black₂The mass percentage of the composite material is not less than 95 wt%, and the particle size is not less than 0.045 mm; AlF₃、CaF₂、ZnO、V₂O₅、TiO₂、ZrSiO₄、B₄C. SiC is all industrial pure, and the grain size is less than or equal to 5 mu m.

In example 3, the base material and the additive obtained in step (1) were poured into a roller ball mill, 2.5 tons of water were added, ball milling and mixing were carried out for 8 hours, and then ultrasonic oscillation (ultrasonic power 1500W) was carried out for 6min to obtain uniform suspension slurry (particle size of solid particles is less than or equal to 30 μm); the grinding balls in the ball mill adopt alumina balls and large balls

Middle ball

Small ball

The weight of (A) is 1: 1: 8, the weight ratio of the materials to the balls is 1: 0.9;

and (3) injecting the suspension slurry into a stirrer, pre-stirring for 1min (the linear velocity of a stirring paddle in the pre-stirring process is 5m/s), then adding 50kg of silica sol, 50kg of alumina sol and the foamed material obtained in the step (2) into the stirrer, and rapidly mixing for 3min by the stirring paddle at the linear velocity of 80m/s to obtain uniform foamed slurry.

Injecting the foam slurry into a plastic mold, and curing for 2 hours in an environment with air temperature and relative humidity of 25 ℃ and 92% respectively until the foam slurry is cured;

and (3) demolding the solidified green body, and removing water in the green body by using a carbon dioxide supercritical drying method, wherein the drying process is the same as that in the example 1. And firing the dried blank body by adopting a high-temperature tunnel kiln, raising the temperature from room temperature to 500 ℃ at a heating rate of 5 ℃/min, raising the temperature to 1000 ℃ at 8 ℃/min, preserving the heat for 1h, raising the temperature to 1230 ℃ at 3 ℃/min, preserving the heat for 5h, reducing the temperature to 1100 ℃ at 10 ℃/min, preserving the heat for 1h at 1100 ℃, reducing the temperature to 500 ℃ at 6 ℃/min, preserving the heat for 0.5h at 500 ℃, and finally reducing the temperature to 50 ℃ at 2 ℃/min to obtain the anorthite micro-nano-hole insulating and heat-insulating refractory material.

In this embodiment 3, the mass percentage of CaO in the hydrated lime is 70 to 75 wt%, and the particle size is less than or equal to 0.08 mm; al in gangue₂O₃40-53 wt% of SiO₂45-48% by mass and 0.6-1 mm in particle size; SiO in rice husk, carbonized rice husk and rice husk ash₂The mass percentage of the particles is equal to or more than 18 wt%, and the particle size is equal to or less than 0.08 mm; SiO in sepiolite₂The mass percentage of the MgO is 65-71%, the mass percentage of the MgO is 25-27%, and the particle size is less than or equal to 0.08 mm; MnO₂、ZnO、V₂O₅All are industrial pure and have the particle size less than or equal to 5 mu m.

In example 4, the base material and the additive obtained in step (1) were poured into a roller ball mill, 2 tons of water were added, ball milling and mixing were carried out for 8 hours, and then ultrasonic oscillation (ultrasonic power 1500W) was carried out for 6 minutes to obtain uniform suspension slurry (where the particle size of the solid particles is ≦ 30 μm); the grinding balls in the ball mill are made of mullite or large balls

Middle ball

Small ball

and (3) injecting the suspension slurry into a stirrer, pre-stirring for 1min (the linear velocity of a stirring paddle in the pre-stirring process is 5m/s), adding the foamed material obtained in the step (2) and the aluminum-silicon sol into the stirrer, and quickly mixing the foamed material and the aluminum-silicon sol for 5min by the stirring paddle at the linear velocity of 80m/s to obtain uniform foam slurry.

Injecting the foam slurry into a rubber mold, and curing for 2 hours in an environment with air temperature and relative humidity of 25 ℃ and 92% respectively until the foam slurry is cured;

and (3) demolding the solidified green body, and removing water in the green body by using a carbon dioxide supercritical drying method, wherein the drying process is the same as that in the example 1. The water content of the dried green body is less than or equal to 3 wt%, and the compressive strength is greater than or equal to 0.75 MPa. And firing the dried blank body by adopting a high-temperature tunnel kiln, raising the temperature from room temperature to 500 ℃ at a heating rate of 3 ℃/min, raising the temperature to 1000 ℃ at 8 ℃/min, preserving the heat for 1h, raising the temperature to 1300 ℃ at 3 ℃/min, preserving the heat for 3h, reducing the temperature to 1100 ℃ at 10 ℃/min, preserving the heat for 1h at 1100 ℃, reducing the temperature to 500 ℃ at 6 ℃/min, preserving the heat for 0.5h at 500 ℃, and finally reducing the temperature to 50 ℃ at 2 ℃/min to obtain the anorthite micro-nano-hole heat-insulating refractory material.

In example 4, Al is contained in aluminum n-butoxide, aluminum isopropoxide, aluminum sec-butoxide, aluminum chloride hexahydrate, and aluminum nitrate nonahydrate₂O₃The mass percentage of the component (A) is 45-51 wt%; al in pyrophyllite₂O₃27-31% by mass of SiO₂The mass percentage of the composite material is 66-68%, and the particle size is less than or equal to 0.08 mm; na in porcelain stone₂4-5% of O and Al₂O₃The mass percentage of the SiO is 18-20 percent₂The mass percentage of the composite material is 74-77%, and the particle size is less than or equal to 0.08mm; SiO in methyl orthosilicate, ethyl orthosilicate and methyltrimethoxysilane₂The mass percentage of the component (A) is 28-35 wt%; dicalcium silicate, tricalcium silicate, tetracalcium aluminoferrite, MnO₂、ZnO、La₂O₃、NiCl₂、K₂Ti₆O₁₃、Sb₂O₃All are industrial pure and have the particle size less than or equal to 5 mu m.

In example 5, the base material and the additive in step (1) are poured into a roller ball mill, 1.5 tons of water are added, ball milling and mixing are carried out for 4 hours, and then ultrasonic oscillation (ultrasonic power 1500W) is carried out for 6 minutes to obtain uniform suspension slurry (wherein the particle size of solid particles is less than or equal to 44 μm); the grinding balls in the ball mill are zirconia balls and large balls

Middle ball

Small ball

The weight ratio of (1.5): 2: 6.5, the weight ratio of the materials to the balls is 1: 1;

2) preparation of foam slurry

And (3) injecting the suspension slurry into a stirrer, pre-stirring for 1min (the linear velocity of a stirring paddle in the pre-stirring process is 5m/s), adding the foaming material obtained in the step (2) into the stirrer, and quickly mixing the foaming material for 4min by the stirring paddle at the linear velocity of 100m/s to obtain uniform foam slurry.

Injecting the foam slurry into a polyurethane mold, and curing for 1 hour in an environment with air temperature and relative humidity of 25 ℃ and 93 percent respectively until the foam slurry is cured;

and demolding the solidified blank, removing the water in the blank by using a freeze drying method, wherein the drying temperature is-130 to-100 ℃, and drying for 6 hours to obtain a dried porous blank. The water content of the dried green body is less than or equal to 3 wt%, and the compressive strength is greater than or equal to 0.75 MPa. The dried green body is put into a shuttle kiln to be sintered, the temperature is raised to 500 ℃ from room temperature at the heating rate of 3 ℃/min, and the temperature is kept for 0.5 h; heating to 1100 deg.C at 8 deg.C/min, and maintaining for 1 h; then heating to 1350 ℃ at the speed of 3 ℃/min, and preserving heat for 3 h; then cooling to 1100 ℃ at a speed of 10 ℃/min, and preserving heat for 1h at 1100 ℃; then cooling to 500 ℃ at the speed of 6 ℃/min, and preserving heat for 0.5h at 500 ℃; finally, the temperature is reduced to 50 ℃ at the speed of 2 ℃/min, and the anorthite micro-nano hole heat insulation refractory material is obtained.

In example 5, α -Al₂O₃Middle Al₂O₃The mass percentage of the composite material is not less than 99 wt%, and the particle size is not less than 0.08 mm; al in pearlite₂O₃12-15% of SiO₂The mass percentage of the composite material is 75-80%, and the particle size is 0.6-1 mm. MnO₂、BaO、Er₂O₃、TiC、Sb₂O₅The silica gel, the monocalcium aluminate and the calcium dialuminate are all industrial pure materials, and the particle size is less than or equal to 5 mu m.

In example 6, the base material and the additive obtained in step (1) were poured into a roller ball mill, 1.2 tons of water were added, ball milling and mixing were carried out for 4 hours, and then ultrasonic oscillation (ultrasonic power 1500W) was carried out for 6min to obtain uniform suspension slurry (where the particle size of the solid particles is less than or equal to 44 μm); the grinding balls in the ball mill are made of zirconia and are large balls

Middle ball

Small ball

and (3) injecting the suspension slurry into a stirrer, pre-stirring for 1min (the linear velocity of a stirring paddle in the pre-stirring process is 5m/s), adding the foaming material obtained in the step (2) into the stirrer, and quickly mixing the foaming material for 4min by the stirring paddle at the linear velocity of 120m/s to obtain uniform foam slurry.

Injecting the foam slurry into an aluminum alloy mold, and curing for 1 hour in an environment with air temperature and relative humidity of 25 ℃ and 93 percent respectively until the foam slurry is cured;

and demolding the cured blank, removing the water in the blank by adopting a microwave drying method, wherein the microwave frequency is 915MHz, and drying for 1h by using microwaves to obtain a dried porous blank. The water content of the dried green body is less than or equal to 3 wt%, and the compressive strength is greater than or equal to 0.75 MPa. Putting the dried blank body into a microwave kiln to be fired, heating to 500 ℃ from room temperature at the heating rate of 5 ℃/min, and preserving heat for 0.5 h; heating to 1100 deg.C at a rate of 10 deg.C/min, and maintaining for 0.5 h; then heating to 1400 ℃ at the speed of 8 ℃/min, and preserving heat for 2 h; then cooling to 1000 ℃ at a speed of 20 ℃/min and preserving heat for 0.5 h; then cooling to 500 ℃ at a speed of 10 ℃/min and preserving heat for 0.5 h; finally, the temperature is reduced to 50 ℃ at the speed of 5 ℃/min, and the anorthite micro-nano hole heat insulation refractory material is obtained.

In this example 6, Industrial Al (OH)₃Middle Al₂O₃The mass percentage of the composite material is not less than 87 wt%, and the particle size is not less than 0.08 mm; al in kyanite₂O₃52-55% of SiO in percentage by mass₂The mass percentage of the composite is 44-46%, and the particle size is 0.6-1 mm; al in flint clay₂O₃32-35% of SiO₂The mass percentage of the particles is 61-64%, and the particle size is 0.6-1 mm; alumina gel, tricalcium aluminate, AlF₃、WO₃、Y₂O₃、CeO₂、TiO₂And ZrO₂All are industrial pure and have the particle size less than or equal to 1 mu m.

In example 7, the base material and the additive obtained in step (1) were poured into a roller ball mill, 1 ton of water was added, ball milling and mixing were performed for 1.5h, and then ultrasonic oscillation (ultrasonic power 1000W) was performed for 8min to obtain a uniform suspension slurry (where the particle size of the solid particles is ≦ 44 μm); the grinding ball in the ball mill is made of zirconium corundum and big ball

Middle ball

Small ball

The weight ratio of (1.5): 2: 6.5, the weight ratio of the materials to the balls is 1: 1.1;

and (3) injecting the suspension slurry into a stirrer, pre-stirring for 1min (the linear velocity of a stirring paddle in the pre-stirring process is 4m/s), adding the foaming material obtained in the step (2) into the stirrer, and quickly mixing the foaming material for 1min by the stirring paddle at the linear velocity of 200m/s to obtain uniform foam slurry.

Injecting the foam slurry into a resin mold, and curing for 0.8 hour in an environment with air temperature and relative humidity of 25 ℃ and 95 percent respectively until the foam slurry is cured;

and (3) demolding the cured blank body, and removing water in the blank body by adopting a microwave drying method, wherein the microwave frequency is 2450MHz, and the drying time is 0.5h, so as to obtain a dried porous blank body. The water content of the dried green body is less than or equal to 3 wt%, and the compressive strength is greater than or equal to 1.0 MPa. The sintering process is the same as that in example 6, and the anorthite microporous heat insulation refractory material is obtained.

In example 7, Al in the Al-Si gel₂O₃73-76% of SiO₂The mass percentage of the magnesium oxide is 12-15%, the mass percentage of the MgO is 10-13%, and the particle size is less than or equal to 5 μm; polyaluminium sulfate, Fe₂O₃、WO₃、SrO、TiO₂、Sb₂O₅All are industrial pure and have the particle size less than or equal to 5 mu m.

In example 8, the base material and the additive obtained in step (1) were poured into a roller ball mill, 0.9 ton of water was added, ball milling and mixing were performed for 1 hour, and then ultrasonic oscillation (ultrasonic power 1000W) was performed for 8min to obtain a uniform suspension slurry (where the particle size of the solid particles is ≦ 44 μm); the grinding balls in the ball mill are made of zirconia and are large balls

Middle ball

Small ball

The weight ratio of (1.5): 2: 6.5, the ratio of material to ball is 1: 1.2;

and (3) injecting the suspension slurry into a stirrer, pre-stirring for 1min (the linear velocity of a stirring paddle in the pre-stirring process is 4m/s), adding the foaming material obtained in the step (2) into the stirrer, and quickly mixing the foaming material for 1.3min by the stirring paddle at the linear velocity of 150m/s to obtain uniform foam slurry.

Injecting the foam slurry into a rubber mold, and curing for 0.7 hour in the environment with the air temperature and the relative humidity of 27 ℃ and 95 percent respectively until the foam slurry is cured;

and (3) demolding the cured blank, and removing water in the blank by adopting a microwave drying method, wherein the microwave frequency is 2850MHz, and the microwave drying time is 0.4h, so as to obtain a dried porous blank. The water content of the dried green body is less than or equal to 3 wt%, and the compressive strength is greater than or equal to 0.75 MPa. The sintering process is the same as that in example 6, and the anorthite microporous heat insulation refractory material is obtained.

In this example 8,. alpha. -Al₂O₃Middle Al₂O₃The mass percentage of the composite material is not less than 99.9 wt%, and the particle size is not less than 0.08 mm; SiO in vein quartz, sandstone, quartzite and flint₂The mass percentage of the composite material is not less than 95 percent, and the particle size is not less than 0.044 mm; SrO, BaO, WO₃、Sb₂O₅、CoO、Co(NO₃)₂The alumina gel is all industrial pure, and the grain size is less than or equal to 5 mu m.

In example 9, the base material and the additive obtained in step (1) were poured into a roller ball mill, 0.8 ton of water was added, ball milling and mixing were performed for 1 hour, and then ultrasonic oscillation (ultrasonic power 1000W) was performed for 8min to obtain a uniform suspension slurry (where the particle size of the solid particles is ≦ 44 μm); the grinding balls in the ball mill are made of zirconia and are large balls

Middle ball

Small ball

The weight ratio of (1.5): 2: 6.5, the weight ratio of the materials to the balls is 1: 1.2;

and (3) injecting the suspension slurry into a stirrer, pre-stirring for 1min (the linear velocity of a stirring paddle in the pre-stirring process is 4m/s), adding the foaming material obtained in the step (2) into the stirrer, and quickly mixing the foaming material for 7min by the stirring paddle at the linear velocity of 130m/s to obtain uniform foam slurry.

Injecting the foam slurry into a foam mold, and curing for 0.6 hour in the environment with the air temperature and the relative humidity of 27 ℃ and 95 percent respectively until the foam slurry is cured and shaped;

demolding the shaped blank, and removing water in the blank by adopting an infrared drying method, wherein the length of the infrared wavelength is 11-13 mu m, and the drying time is 1.2h, so as to obtain a dried porous blank; the water content of the dried green body is less than or equal to 3 wt%, and the compressive strength is greater than or equal to 0.75 MPa. The dried green body is put into a shuttle kiln to be sintered, the temperature is raised to 500 ℃ from room temperature at the heating rate of 3 ℃/min, and the temperature is kept for 0.5 h; heating to 1100 deg.C at 8 deg.C/min, and maintaining for 1 h; then the temperature is raised to 1430 ℃ at the speed of 3 ℃/min, and the temperature is kept for 1.5 h; then cooling to 1100 ℃ at a speed of 10 ℃/min, and preserving heat for 1h at 1100 ℃; then cooling to 500 ℃ at the speed of 6 ℃/min, and preserving heat for 0.5h at 500 ℃; finally, the temperature is reduced to 50 ℃ at the speed of 2 ℃/min, and the anorthite micro-nano hole heat insulation refractory material is obtained.

In this example 9,. alpha. -Al₂O₃Middle Al₂O₃The mass percentage of the composite material is not less than 99.9 wt%, and the particle size is not less than 0.08 mm; ca (OH)₂The mass percentage of the CaO in the composite is 70-75 wt%, and the particle size is less than or equal to 0.08 mm; al in andalusite₂O₃54-57% of SiO₂The mass percentage of the composite material is 44-47%, and the particle size is less than or equal to 0.08 mm; al in sillimanite₂O₃The mass percentage of the SiO is 58-61 percent₂The mass percentage of the composite material is 38-41%, and the particle size is less than or equal to 0.08 mm; SiO in alpha-scale quartz and beta-scale quartz₂The mass percentage of the composite material is not less than 95 percent, and the particle size is not less than 0.044 mm; AlF₃、YbO、Cr₂O₃、TiO₂、K₂Ti6O₁₃The alumina gel and the dodecacalcium heptaluminate are all industrial pure, and the particle size is less than or equal to 5 mu m.

In example 10, the base material and the additive obtained in step (1) were poured into a roller ball mill, 0.7 ton of water was added, ball milling and mixing were performed for 1 hour, and then ultrasonic oscillation (ultrasonic power 1000W) was performed for 8min to obtain uniform suspension slurry (where the particle size of the solid particles is less than or equal to 50 μm); the grinding ball in the ball mill is made of zirconium corundum and big ball

Middle ball

Small ball

and (3) injecting the suspension slurry into a stirrer, pre-stirring for 1min (the linear velocity of a stirring paddle in the pre-stirring process is 4m/s), adding the foaming material obtained in the step (2) into the stirrer, and quickly mixing the foaming material with the stirring paddle at the linear velocity of 20m/s for 10min to obtain uniform foam slurry.

Injecting the foam slurry into a wood mold, and curing for 0.5 hour in the environment with the air temperature and the relative humidity of 28 ℃ and 95 percent respectively until the foam slurry is cured;

and demolding the cured blank, and removing water in the blank by adopting an infrared drying method, wherein the length of the infrared wavelength is 5-7 mu m, and the drying time is 3h, so as to obtain a dried porous blank. The water content of the dried green body is less than or equal to 3 wt%, and the compressive strength is greater than or equal to 0.75 MPa. The dried green body is put into a shuttle kiln to be sintered, the temperature is raised to 500 ℃ from room temperature at the heating rate of 3 ℃/min, and the temperature is kept for 0.5 h; heating to 1100 deg.C at 8 deg.C/min, and maintaining for 1 h; then heating to 1450 ℃ at the speed of 3 ℃/min, and preserving heat for 1 h; then cooling to 1100 ℃ at a speed of 10 ℃/min, and preserving heat for 1h at 1100 ℃; then cooling to 500 ℃ at the speed of 6 ℃/min, and preserving heat for 0.5h at 500 ℃; finally, the temperature is reduced to 50 ℃ at the speed of 2 ℃/min, and the anorthite micro-nano hole heat insulation refractory material is obtained.

In this example 10, CaCO₃The mass percentage of the CaO in the composite is 53-54 wt%, and the particle size is less than or equal to 0.08 mm; al in sintered corundum₂O₃The mass percentage of the composite material is not less than 99.9 wt%, and the particle size is not less than 0.08 mm; al in Guangxi soil₂O₃The mass percentage of SiO is 34-36 wt%₂The mass percentage of the composite material is 58-62%, and the particle size is less than or equal to 0.08 mm; SiO in alpha-quartz and beta-quartz₂The mass percentage of the composite material is not less than 98 percent, and the particle size is not less than 0.044 mm; AlF₃、YbO、TiO₂、K₂Ti₆O₁₃The alumina gel is all industrial pure, and the grain size is less than or equal to 5 mu m.

Example 11, the procedure(1) Pouring the obtained basic raw materials and additives into a roller ball mill, adding 0.5 ton of water, carrying out ball milling and mixing for 0.6h, and then carrying out ultrasonic oscillation (ultrasonic power is 1800W) for 5min to obtain uniform suspension slurry (wherein the particle size of solid particles is less than or equal to 60 mu m); the grinding ball in the ball mill is made of zirconium corundum and big ball

Middle ball

Small ball

The weight ratio of (1.5): 2: 6, the weight ratio of the materials to the balls is 1: 1.4;

and (3) injecting the suspension slurry into a stirrer, pre-stirring for 1min (the linear velocity of a stirring paddle in the pre-stirring process is 4m/s), adding the foaming material obtained in the step (2) into the stirrer, and quickly mixing the foaming material for 8min by the stirring paddle at the linear velocity of 30m/s to obtain uniform foam slurry.

Injecting the foam slurry into a bamboo colloid mold, and curing for 0.3 hour in the environment with the air temperature and the relative humidity of 30 ℃ and 95 percent respectively until the foam slurry is cured;

demoulding the solidified green body, and removing water in the green body by adopting a normal-pressure power supply heating drying method, wherein the drying system is as follows: firstly, heating to 30 ℃ at the speed of 2 ℃/min, and preserving heat for 3h at the temperature of 30 ℃; heating to 50 deg.C at a rate of 2 deg.C/min, and maintaining at 50 deg.C for 2 h; heating to 70 deg.C at 3 deg.C/min, and maintaining at 70 deg.C for 2 h; then heating to 90 ℃ at the speed of 3 ℃/min, and preserving the heat for 3h at the temperature of 90 ℃; then heating to 110 ℃ at the speed of 3 ℃/min, and preserving the heat for 12h at the temperature of 110 ℃ to obtain a dry porous blank. The water content of the dried green body is less than or equal to 3 wt%, and the compressive strength is greater than or equal to 0.75 MPa. The dried green body is put into a high-temperature resistance kiln to be sintered, the temperature is raised to 500 ℃ from room temperature at the heating rate of 3 ℃/min, and the temperature is kept for 0.5 h; heating to 1100 deg.C at 8 deg.C/min, and maintaining for 1 h; then raising the temperature to 1480 ℃ at the speed of 5 ℃/min, and preserving the temperature for 0.8 h; then cooling to 1100 ℃ at a speed of 10 ℃/min, and preserving heat for 1 h; then cooling to 500 ℃ at the speed of 6 ℃/min and preserving heat for 0.5 h; finally, the temperature is reduced to 50 ℃ at the speed of 2 ℃/min, and the anorthite micro-nano hole heat insulation refractory material is obtained.

In example 11, aluminum phosphate and Y₂O₃、BaO、ZrSiO₄All are industrial pure and have the particle size less than or equal to 5 mu m.

In example 12, the base material and the additive obtained in step (1) were poured into a roller ball mill, 0.3 ton of water was added, ball milling and mixing were performed for 0.5h, and then ultrasonic oscillation (ultrasonic power 2000W) was performed for 4min to obtain a uniform suspension slurry (where the particle size of the solid particles was ≦ 74 μm); the grinding ball in the ball mill adopts tungsten carbide ball and large ball

Middle ball

Small ball

The weight ratio of (1.5): 2: 6, the weight ratio of the materials to the balls is 1: 1.5;

and (3) injecting the suspension slurry into a stirrer, pre-stirring for 1min (the linear velocity of a stirring paddle in the pre-stirring process is 3m/s), adding the foaming material obtained in the step (2) and the silica-alumina sol into the stirrer, and quickly mixing the foaming material and the silica-alumina sol for 7min by the stirring paddle at the linear velocity of 50m/s to obtain uniform foam slurry.

Injecting the foam slurry into a vitreous mould, and curing for 0.1 hour in an environment with air temperature and relative humidity of 35 ℃ and 99.9 percent respectively until the foam slurry is cured;

demoulding the solidified green body, and removing water in the green body by adopting a normal-pressure power supply heating drying method, wherein the drying system is as follows: heating to 30 deg.C at 2 deg.C/min, maintaining the temperature at 30 deg.C for 3h, heating to 50 deg.C at 2 deg.C/min, and maintaining the temperature at 50 deg.C for 2 h; heating to 70 deg.C at 3 deg.C/min, and maintaining at 70 deg.C for 2 h; then heating to 90 ℃ at the speed of 3 ℃/min, and preserving the heat for 3h at the temperature of 90 ℃; then heating to 110 ℃ at the speed of 3 ℃/min, and preserving the heat for 12h at the temperature of 110 ℃ to obtain a dry porous blank. The water content of the dried green body is less than or equal to 3 wt%, and the compressive strength is greater than or equal to 0.7 MPa. The dried green body is put into a high-temperature resistance kiln to be sintered, the temperature is raised to 500 ℃ from room temperature at the heating rate of 3 ℃/min, and the temperature is kept for 0.5 h; heating to 1100 deg.C at 8 deg.C/min, and maintaining for 1 h; then raising the temperature to 1500 ℃ at a speed of 5 ℃/min, and preserving the temperature for 0.5 h; then cooling to 1000 ℃ at a speed of 10 ℃/min, and preserving heat for 1 h; then cooling to 500 ℃ at the speed of 6 ℃/min, preserving the heat for 0.5h, and finally cooling to 50 ℃ at the speed of 2 ℃/min to obtain the anorthite micro-nano hole heat insulation refractory material.

In example 12, Al is contained in fused alumina₂O₃The mass percentage of the composite material is not less than 99.9 wt%, and the particle size is not less than 0.08 mm; SiO in cemented silica, river sand and sea sand₂The mass percentage of the composite material is not less than 95 percent, and the particle size is not less than 0.044 mm; y is₂O₃、TiO₂、ZrSiO₄Sodium alginate is industrially pure, and the particle size is less than or equal to 5 mu m.

In example 13, the base material and the additive obtained in step (1) were poured into a mixer, and 1 ton of water was added, followed by mixing and stirring for 0.5h to obtain a suspension slurry (without further ball milling or ultrasonic treatment);

and (3) adding the foaming material obtained in the step (2) and silica sol into the suspension slurry, and quickly mixing the mixture for 30min by a stirring paddle at the linear speed of 20m/s to obtain uniform foam slurry.

Injecting the foam slurry into a vitreous mould, and curing for 0.1 hour in an environment with air temperature and relative humidity of 35 ℃ and 99.9 percent respectively until the foam slurry is cured; and (3) demolding the cured blank, and removing water in the blank by adopting a normal-pressure hot air drying method, wherein the drying temperature is controlled to be 35-45 ℃, and the drying time is 48 hours, so as to obtain the dried porous blank. The water content of the dried green body is less than or equal to 3 wt%, and the compressive strength is greater than or equal to 0.7 MPa. The dried green body was fired in a microwave kiln by the same firing process as in example 7 to obtain a sillimanite microporous insulating refractory.

In example 13, Al is present in kyanite₂O₃52-55% of SiO in percentage by mass₂The mass percentage of the composite material is 44-46%, and the particle size is less than or equal to 0.05 mm; al in andalusite₂O₃54-57% of SiO₂The mass percentage of the composite material is 44-47%, and the particle size is less than or equal to 0.05 mm; industrial Al₂O₃Middle Al₂O₃The mass percentage content is not less than 98 wt%, and the particle size is not less than 0.05 mm; SiO in silica micropowder₂The mass percentage of the composite material is not less than 95 percent, and the particle size is not less than 5 mu m; polyaluminium sulfate, polyaluminium chloride, polyacrylamide, TiO₂All are industrial pure and have the particle size less than or equal to 5 mu m.

In example 14, the base material obtained in step (1) was poured into a mixer, 1.5 tons of water were added, and the mixture was stirred and mixed for 1 hour to obtain a suspension slurry (without additives);

and (3) adding the foaming material obtained in the step (2) into the suspension slurry, and quickly mixing for 30min by a stirring paddle at the linear speed of 100m/s to obtain uniform foam slurry.

Injecting the foam slurry into a vitreous mould, and curing for 0.1 hour in an environment with air temperature and relative humidity of 35 ℃ and 99.9 percent respectively until the foam slurry is cured; and (3) demolding the cured blank, and removing water in the blank by adopting a normal-pressure hot air drying method, wherein the drying temperature is controlled to be 35-45 ℃, and the drying time is 48 hours, so as to obtain the dried porous blank. The water content of the dried green body is less than or equal to 3 wt%, and the compressive strength is greater than or equal to 0.7 MPa. And (3) putting the dried green body into a microwave kiln for sintering, wherein the sintering process is the same as that in example 5, and the anorthite micro-nano-pore heat-insulating refractory material is obtained.

In this example 14, α -Al₂O₃Middle Al₂O₃The mass percentage of the composite material is not less than 99 wt%, and the particle size is not less than 0.08 mm; the silica gel, the monocalcium aluminate and the calcium dialuminate are all industrial pure, and the particle size is less than or equal to 5 mu m.

In example 15, the manufacturing process is substantially the same as that in example 14, except that the mold is cured for 3 hours in an environment with air temperature and relative humidity of 35 ℃ and 99.9% respectively, and then the mold is cured and demolded, and when the green body is dried by hot air at normal pressure, the drying time is 72 hours at 35 ℃ to 45 ℃, the drying time is greatly prolonged, and the compressive strength of the dried green body is only 0.3 MPa.

In example 16, the combination of the base material and the additive obtained in step (1) was poured into a mixer, 1 ton of water was added, and the mixture was stirred and mixed for 0.3 hour to obtain a suspension slurry;

(2) weighing the vinyl acetate, the ethylene and vinyl laurate copolymer, the isobutylene and maleic anhydride copolymer and the hydroxybutyl methyl cellulose ether according to the formula ratio, pouring the mixture into a V-type mixer, and mixing for 5min to obtain a uniform foam mixture; meanwhile, preparing the sulfate type Gemini surfactant and the double-chain type Bola surfactant into foam by a foaming machine;

(3) and (3) adding the foaming mixture obtained in the step (2), the pre-prepared foam and the alumina sol into the suspension slurry, and rapidly shearing and mixing the mixture for 2min by a stirring paddle at the linear speed of 150m/s to obtain uniform foam slurry.

Thereafter, the foam slurry was poured, the green body was cured, dried and fired in substantially the same manner as in example 13 to obtain a sillimanite microporous heat insulating refractory.

The physical and chemical indexes of the raw materials used in the embodiment are basically the same as that of the raw materials used in the embodiment 13, wherein tetracalcium aluminoferrite and tricalcium silicate are both industrially pure, and the particle size is less than or equal to 5 μm.

Second, Experimental example

Experimental example 1

This example characterizes the macroscopic appearance and the microscopic morphology of the anorthite micro-nano-pore insulating refractory material of example 8. The macroscopic appearance of the film is shown in FIG. 1, and the microstructure of the film is shown in FIGS. 2-3.

As can be seen from FIG. 1, the anorthite microporous insulating refractory prepared in example 8 is milky in appearance and free from mottle. As can be seen from the microstructures of FIGS. 2 and 3, the anorthite micro-nano porous insulating refractory material has different levels of pore structures, and the pores of the different levels are substantially evenly distributed on the observation plane, and no small pores or large pores are locally enriched.

Experimental example 2

In this experimental example, XRD test was performed on the anorthite micro-porous heat insulating refractory of example 8, and the result is shown in fig. 4. The results of fig. 4 show that the main crystal phases of the Anorthite micro-nano porous insulating refractory of example 8 are Anorthite (Anorthite) and a small amount of Corundum (Corundum).

Experimental example 3

This experimental example measured the pore size distribution of the anorthite micro-nano pore insulating refractory of example 8, and the results are shown in fig. 5.

As can be seen from fig. 5, the anorthite microporous heat insulating refractory material of embodiment 8 has a micro-nano pore structure, and the main pore size is distributed between 0.1 μm and 6 μm.

Experimental example 4

The experimental examples were conducted to test the refractory of each example for pressure resistance to strength, thermal conductivity, and other indicators. Wherein, the volume density and the total porosity of the sample are tested according to the Chinese national standard GB/T2998-2001, and the closed porosity of the GB/T2997-2000 test style is adopted; the compressive strength was tested according to GB/T3997.2-1998; the rate of change of the re-ignition line was tested according to GB/T3997.1-1998; the thermal conductivity is tested according to YB/T4130-2005; the average pore size and pore size distribution of the samples were measured by mercury intrusion method and the results are shown in table 3.

TABLE 3 results of the Performance test of the anorthite insulating refractory of the example

From the test results in table 3, it can be seen that the performance indexes of the anorthite insulating refractory of the examples are summarized as follows: the bulk density is 0.25 to 1.0g/cm³The porosity is 40-95%, the closed porosity is 20-60%, the normal temperature compressive strength is 0.8-80 MPa, the thermal conductivity at room temperature is 0.02-0.15W/(mK), the thermal conductivity at 350 ℃ is 0.03-0.19W/(mK), the thermal conductivity at 1100 ℃ is 0.04-0.2W/(mK), the use temperature is less than or equal to 1500 ℃, the re-firing line change rate is-0.4-0% (keeping the temperature at 1300 ℃ for 24h), and some examples are-0.1-0%.

Compared with the examples 1-3, the water consumption for introducing the dispersing agent is obviously reduced under the condition that the density of the prepared samples is not different; as can be seen by comparing examples 2-3 and 5 and 14, the introduction of the infrared opacifier obviously reduces the high-temperature thermal conductivity of the sample; as can be seen from comparison of examples 1-3, the pore diameter of the sample is obviously reduced along with the increase of the regulating dosage of the pores; comparing examples 2-6 and 8-12, it can be seen that, under the condition that the strength of the dried green body is kept basically stable, the use amounts of the inorganic curing agent and the organic curing agent can be correspondingly reduced along with the increase of the density of the sample; compared with the examples 7-8, the average pore diameter of the sample is obviously reduced along with the increase of the stirring speed, and the strength of the blank and the sintered sample is obviously increased; as can be seen by comparing examples 2 and 6, the introduction of the mineralizer gradually lowered the sintering temperature of the sample; it can be seen from the comparison of examples 3 to 4 that the difference between the grinding efficiency of the material of the grinding balls to the base material is large, and the higher the hardness and density of the grinding balls are, the shorter the grinding time is and the higher the grinding efficiency is. Comparing examples 7 and 13 and 5 and 14, it can be seen that after the basic raw materials are subjected to ball milling and suspension slurry is subjected to ultrasonic treatment, the sample has better bonding property after sintering, the sintering compactness is higher, and the compressive strength is obviously improved. In comparative examples 14 and 15, when no organic curing agent is added, the required curing time of the green body is greatly prolonged, the green body can be demoulded, the strength of the dried green body is greatly reduced, the pore diameter of the pores of the sintered sample is obviously increased, the volume density and the thermal conductivity are increased, and the total porosity, the closed porosity and the strength are both obviously reduced. As can be seen from examples 13 and 15, when the foaming agent is pre-foamed, the stirring time of the foamed slurry is shortened, but the strength of the green body after drying is weakened, the change in the porosity, pore size distribution, average pore size and dead line of the fired product is increased, the density, closed porosity and strength are lowered, and the thermal conductivity is increased.

The invention can realize controllability and adjustability in the aspects of volume density, porosity, closed porosity, pore diameter, compressive strength and thermal conductivity, and can show more excellent mechanical and thermal insulation properties under the condition of ensuring that the porosity and the volume density of the material are close to those of the prior art through the construction of a micro-nano pore structure in the anorthite thermal insulation refractory material, thereby having better practical significance in practical engineering and technical application.

Claims

1. A anorthite micro-nano hole heat insulation refractory material is characterized in that the anorthite micro-nano hole heat insulation refractory material is prepared from a basic raw material, an additive and water; the mass content of CaO in the chemical composition of the product is 4-22%;

the mass of the water is 30-300% of the mass of the basic raw material.

2. The anorthite microporous insulating refractory of claim 1, wherein the insulating refractory has a bulk density of 0.25 to 1.0g/cm³The porosity is 40-95%, the closed porosity is 20-60%, the room-temperature compressive strength is 0.8-80 MPa, the thermal conductivity at room temperature is 0.02-0.15W/(mK), the thermal conductivity at 350 ℃ is 0.03-0.19W/(mK), the thermal conductivity at 1100 ℃ is 0.04-0.2W/(mK), and the rate of change of the dead firing line at 1300 ℃ for 24 hours is-0.4-0%.

3. The anorthite micro-nano pore insulating refractory material as claimed in claim 1, wherein the calcareous material is limestone, quicklime, slaked lime, wollastonite, dolomite, calcite, CaO, CaCO₃、Ca(OH)₂、CaSO₄One or a combination of two or more of them;

the alumina raw material is industrial alumina, industrial Al (OH)₃Boehmite, diaspore, beta-Al₂O₃、ρ-Al₂O₃、γ-Al₂O₃、δ-Al₂O₃、χ-Al₂O₃、κ-Al₂O₃、θ-Al₂O₃、η-Al₂O₃、α-Al₂O₃、Al(NO₃)₃、Al₂(SO₄)₃One or more of aluminum n-butoxide, aluminum isopropoxide, aluminum sec-butoxide, aluminum chloride hexahydrate, aluminum nitrate nonahydrate, fused corundum powder, sintered corundum powder and tabular corundum powder;

the aluminum-silicon material is one or a combination of more than two of mullite, kaolin, bauxite, aluminum-silicon homogeneous materials, coal gangue, kyanite, andalusite, sillimanite, pyrophyllite, potash feldspar, albite, anorthite, celsian, porcelain stone, alkali stone, mica, spodumene, perlite, montmorillonite, illite, halloysite, dickite, flint clay, Suzhou soil, Guangxi soil, knarth, fly ash and floating beads;

the silicon dioxide raw material is one or a combination of more than two of alpha-quartz, beta-quartz, alpha-tridymite, beta-tridymite, gangue quartz, sandstone, quartzite, flint, cemented silica, river sand, sea sand, white carbon black, methyl orthosilicate, ethyl orthosilicate, methyltrimethoxysilane, rice hull, carbonized rice hull, rice hull ash, diatomite and silica micropowder.

4. The anorthite micro-nano hole insulating refractory according to claim 1, wherein the chemical composition of the calcareous material contains 30% by mass or more of CaO; al in chemical composition of alumina raw material₂O₃The mass percentage of the component (A) is more than 45%; in the chemical composition of the aluminum-silicon material, the mass percent of alumina is 18-90%, and the mass percent of silicon dioxide is 8-75%; chemical composition of silicon dioxide raw material SiO₂The mass content of (A) is more than 18%.

5. The anorthite micro-nanoporous insulating refractory according to claim 1, wherein the calcareous material is calcium silicate and/or aluminateCalcium, or calcium material selected from calcium silicate and/or calcium aluminate, limestone, quicklime, slaked lime, wollastonite, dolomite, calcite, CaO, CaCO₃、Ca(OH)₂、CaSO₄One or a combination of two or more of them.

6. The anorthite micro-nanoporous insulating refractory of claim 1, wherein the cell regulator is selected from one or a combination of more than two of cellulose ether, starch ether, lignocellulose, and saponin.

7. The anorthite microporous insulating refractory of claim 6, wherein said cellulose ether is selected from the group consisting of one or a combination of two or more of water-soluble cellulose ethers, methyl cellulose ethers, carboxymethyl methyl cellulose ethers, carboxymethyl ethyl cellulose ethers, carboxymethyl hydroxymethyl cellulose ethers, carboxymethyl hydroxyethyl cellulose ethers, carboxymethyl hydroxypropyl cellulose ethers, carboxymethyl hydroxybutyl cellulose ethers, hydroxymethyl cellulose ethers, hydroxyethyl methyl cellulose ethers, hydroxyethyl ethyl cellulose ethers, ethyl methyl cellulose ethers, propyl cellulose ethers, hydroxypropyl methyl cellulose ethers, hydroxypropyl ethyl cellulose ethers, hydroxypropyl hydroxybutyl cellulose ethers, hydroxybutyl methyl cellulose ethers, and sulfonic ethyl cellulose ethers.

8. The anorthite micro-nanoporous insulating refractory material of claim 1, wherein the inorganic curing agent is selected from the group consisting of silica sol, alumina sol, silica-alumina sol, silica gel, alumina gel, silica-alumina gel, Al₂O₃Micropowder, dicalcium silicate, calcium dialuminate, tricalcium silicate, tricalcium aluminate, monocalcium aluminate, SiO₂One or more of micro powder, tetracalcium aluminoferrite, aluminum phosphate, dodecacalcium heptaluminate, water glass and soft bonding clay;

the organic curing agent is selected from one or more of water-soluble polymer resin, low methoxyl pectin, carrageenin, hydroxypropyl guar gum, locust bean gum, gellan gum, curdlan, alginate and konjac gum; the water-soluble polymer resin is selected from vinyl acetate and ethylene copolymer, vinyl acetate homopolymer, acrylate polymer, ethylene and vinyl acetate copolymer, ethylene and vinyl chloride copolymer, vinyl acetate and vinyl versatate copolymer, acrylate and styrene copolymer, vinyl acetate and higher fatty acid vinyl ester copolymer, one or more of vinyl acetate and ethylene and vinyl chloride copolymer, vinyl acetate and ethylene and acrylate copolymer, isobutylene and maleic anhydride copolymer, ethylene and vinyl chloride and vinyl laurate copolymer, vinyl acetate and ethylene and higher fatty acid copolymer, vinyl acetate and ethylene and vinyl laurate copolymer, vinyl acetate and acrylate and higher fatty acid vinyl ester copolymer, and vinyl acetate and vinyl versatate and acrylate copolymer.

9. The anorthite micro-nano-pore insulating and fire-resistant material as claimed in claim 1, wherein the foaming agent is a surfactant and/or a protein type foaming agent, and the foaming ratio is 8-60 times; the surfactant is selected from one or more of cationic surfactant, anionic surfactant, nonionic surfactant, amphoteric surfactant, Gemini type surfactant, Bola type surfactant and Dendrimer type surfactant.

10. The anorthite microporous insulating refractory material according to claim 1 or 9, wherein the foaming agent is one or more selected from the group consisting of quaternary ammonium type Gemini surfactants, semi-ring type Bola surfactants, carboxylate type Gemini surfactants, lauramidopropyl sulphobetaine, sodium lauryl polyoxyethylene ether carboxylate, sodium alpha-olefin sulfonate, dodecyl dimethyl betaine surfactants, fatty alcohol polyoxyethylene ethers, sodium fatty alcohol polyoxyethylene ether carboxylates, sulfate type Gemini surfactants, polyether type Dendrimer surfactants, vegetable protein foaming agents, sludge protein foaming agents, animal protein foaming agents, sodium dodecylbenzene sulfonate, polyamide type Dendrimer surfactants, and double-chain type Bola surfactants.

11. The anorthite micro-nano pore insulating refractory material as claimed in claim 1, wherein the addition mass of the dispersing agent is not more than 2% based on the mass of the base material; the dispersant is one or the combination of more than two of polycarboxylic acid dispersant, polycarboxylic acid ether dispersant, sodium polyacrylate, naphthalene dispersant, FS10, FS20, lignin dispersant, sulfonated melamine polycondensate, melamine formaldehyde polycondensate, aliphatic dispersant, sulfamate dispersant, sodium citrate, sodium tripolyphosphate, sodium hexametaphosphate and sodium carbonate.

12. The anorthite micro-nano pore insulating refractory material as claimed in claim 1, wherein the addition mass of the suspending agent is not more than 10% based on the mass of the base material; the suspending agent is one or the combination of more than two of bentonite, sepiolite, attapulgite, polyaluminium chloride, polyaluminium sulfate, chitosan, xanthan gum, Arabic gum, welan gum, agar, acrylamide, polyacrylamide, polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol, casein, hexadecanol, sucrose, dextrin, tris (hydroxymethyl) aminomethane, microcrystalline cellulose sodium, cellulose fiber, cellulose nanocrystal and soluble starch.

13. The anorthite micro-nanoporous insulating refractory according to claim 1, wherein the mineralizer is ZnO, Fe₂O₃、Fe₃O₄、V₂O₅、SiF₄、CaF₂、AlF₃、AlF₃·3H₂O、MnO₂、CuO、CuSO₄、MgO、SrO、BaO、WO₃、Er₂O₃、Cr₂O₃、La₂O₃、YbO、Y₂O₃、CeO₂One or a combination of two or more of them.

14. The anorthite nanoporous insulating refractory of claim 1, wherein the infrared opacifier is selected from rutile, TiO₂、TiC、K₄TiO₄、K₂Ti₆O₁₃、Sb₂O₃、Sb₂O₅、ZrO₂、NiCl₂、Ni(NO₃)₂、CoO、Co(NO₃)₂、CoCl₂、ZrSiO₄、Fe₃O₄、B₄C. One or a combination of two or more of SiC.

15. A method of making the anorthite micro-nanoporous insulating refractory of any one of claims 1 to 14, comprising the steps of:

2) adding a foaming agent, an inorganic curing agent, an organic curing agent and a foam pore regulator into the suspension slurry, stirring, shearing and foaming to prepare foam slurry containing micro-nano bubbles;

3) injecting the foam slurry into a mold for curing, and demolding to obtain a blank; and then drying and sintering the green body.

16. The method of making a anorthite nanoporous insulating refractory according to claim 15, wherein in step 1), the average particle size of the solid particles in the slurry in suspension is not higher than 1mm, or not higher than 74 μm, or not higher than 50 μm, or not higher than 44 μm, or not higher than 30 μm.

17. The method for preparing the anorthite micro-nano hole insulating and heat-insulating refractory material as claimed in claim 15, wherein in the step 2), the stirring shear foaming is performed by high-speed stirring shear foaming by a stirring paddle, and the linear velocity of the outer edge of the stirring paddle is 20-200 m/s, or 80-200 m/s, or 100-200 m/s, or 150-200 m/s, or 180-200 m/s.

18. The method for preparing the anorthite micro-nano hole insulating and heat-insulating refractory material as claimed in claim 15, wherein in the step 3), the air temperature of the curing environment is 1-35 ℃ and the humidity is 40-99.9%; the curing time is 0.1-24 hours or 0.1-2 hours.

19. The method for preparing the anorthite micro-nano hole insulating and heat-insulating refractory material as claimed in claim 15, wherein in the step 3), the green body is dried by one or more than two groups selected from the group consisting of atmospheric drying, supercritical drying, freeze drying, vacuum drying, infrared drying and microwave drying; drying the blank until the moisture content of the blank is less than or equal to 3 wt%; the compression strength of the dried green body is not less than 0.7 MPa.

20. The method for producing the anorthite micro-nanoporous heat insulating refractory according to claim 15, wherein in the step 3), the firing is performed in a high temperature tunnel kiln, a shuttle kiln, a resistance kiln or a microwave kiln; the sintering temperature is 1100-1500 ℃.