CN114149276A

CN114149276A - Micro-nano hole heat insulation refractory material containing zirconium oxide and preparation method thereof

Info

Publication number: CN114149276A
Application number: CN202111668416.7A
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: 2022-03-08
Anticipated expiration: 2041-12-31
Also published as: CN114149276B

Abstract

The invention belongs to the field of refractory materials, and particularly relates to a micro-nano hole heat insulation refractory material containing zirconium oxide and a preparation method thereof. The micro-nano hole heat insulation refractory material containing zirconium oxide is prepared from a base raw material, an additive and water; ZrO in refractory materials₂The mass content of (A) is 5-98%. The micro-nano pore heat insulation refractory material containing zirconium oxide is white, light yellow or light pink in appearance, the pore diameter of spherical pores in the refractory material is distributed between 0.006 and 250 mu m,the average pore diameter is 0.1-20 mu m, and the existence of the micro-nano pore structure ensures better heat insulation performance of the product under low volume density and high strength. The preparation method is environment-friendly and pollution-free, the structure and the performance of the product are easy to accurately control, and the finally prepared refractory material can meet the requirements of ultralow heat conduction and light weight and has higher strength by regulating and controlling the dosage of each raw material and the process.

Description

Micro-nano hole heat insulation refractory material containing zirconium oxide and preparation method thereof

Technical Field

The invention belongs to the technical field of refractory materials, and particularly relates to a micro-nano hole heat insulation refractory material containing zirconium oxide and a preparation method thereof. In particular to a zirconium oxide-containing micro-nano pore heat insulation refractory material which has a micro-nano pore structure, ultralow heat conduction and volume density, high porosity, high strength and green and controllable preparation.

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 insulating refractory materials which have good heat insulation, durability and mechanical properties and are prepared in a green and controllable manner for high-temperature industry are urgently needed.

The zirconia refractory material has the characteristics of high temperature resistance (the melting point of zirconia can reach 2715 ℃), corrosion resistance, extremely low thermal conductivity (only 1.675W/m.K), good mechanical and thermal shock stability and the like, is one of new materials which are developed rapidly in recent years, and is gradually applied to the fields of metallurgy, electronics, environmental protection, biology, chemical industry, aerospace and the like. If the air holes can be effectively introduced into the zirconia material, the thermal conductivity of the zirconia material can be further reduced, so that the zirconia porous ceramic material with lower thermal conductivity can be prepared, and the product is very suitable for heat insulation and preservation in a high-temperature environment, heat insulation parts of an engine and the like, particularly the application field in an ultrahigh-temperature environment above 1800 ℃.

The subject group has carried out a great deal of application research on the light heat-insulating refractory material in the earlier 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. The zirconia heat-insulating refractory material has low heat conductivity coefficient, good heat-insulating effect and melting pointHigh-temperature-resistant heat-insulating ceramic material, but the density of the zirconia is high (5.89 g/cm)³) Thus, it is difficult to prepare a low-density, high-porosity heat-insulating product. 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 micro-nano hole heat insulation refractory material containing zirconium oxide, which has the characteristics of micro-nano size aperture, closed spherical pore structure, ultralow heat conductivity, ultralow volume density, high porosity, high strength and the like. The volume density can be effectively reduced under the condition that the strength of the material is ensured to meet the requirement, thereby being beneficial to the construction of a light environment-friendly high-grade kiln.

The second purpose of the invention is to provide a preparation method of the micro-nano hole heat insulation refractory material containing zirconium oxide. 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 achieve the purpose, the technical scheme of the micro-nano hole heat insulation refractory material containing zirconia is as follows:

the micro-nano hole heat insulation refractory material containing the zirconium oxide is prepared from a base material, an additive and water. ZrO in articles₂The mass percentage of the component (A) is 5-100%;

the base raw material comprises the following raw materials in percentage by weight: 30-100% of zirconia raw material, 0-30% of alumina raw material, 0-40% of aluminum-silicon raw material, 0-20% of silica raw material and 0-20% of calcium oxide 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 base 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 base material;

the mass of the water is 20-200% of that of the base material.

The dispersing agent and the suspending agent are promoted to form stable and uniformly dispersed suspension slurry when the refractory material is pulped; 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 beneficial to the growth and development of beneficial crystals, can promote sintering and is beneficial to further improvement of the mechanical property of the material.

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

The micro-nano hole heat insulation refractory material containing zirconia provided by the invention is white, light pink or light yellow in appearance, and the product can contain mullite phase, corundum phase and/or quartz phase and the like besides zirconia. The volume density of the refractory material is 0.3-3 g/cm³The porosity is 50-95%, the closed porosity is 20-70%, the normal temperature compressive strength is 0.6-220 MPa, the thermal conductivity at room temperature is 0.02-0.25W/(mK), the thermal conductivity at 350 ℃ is 0.03-0.33W/(mK), the thermal conductivity at 1100 ℃ is 0.06-0.4W/(mK), the use temperature is less than or equal to 2300 ℃, and the change rate of a re-firing line is-0.4-0%, preferably-0.3-0%, more preferably-0.2-0%, and more particularly-0.1-0% when the temperature is kept at 1400-1732 ℃ for 24 h. In the insulating refractory material, the pore diameter of pores is distributed between 0.006 to 250 μm, and the average pore diameter isThe aperture is 0.1-20 mu m, and the spherical pore structure with the micro-nano size ensures better heat insulation performance of the product under low volume density and high strength.

Compared with the prior art, the zirconia micro-nano hole 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 a molded heat-insulating refractory product containing zirconia with the best heat-insulating property, has excellent comprehensive performance, can be mainly used 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 engine heat-insulating parts, war 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 novel light environment-friendly furnaces.

Further preferably, the base raw material consists of 100% zirconia raw material by mass percentage; or 60-95% of zirconia raw material and 5-40% of aluminum-silicon raw material or silicon dioxide raw material or calcium oxide raw material; or the composite material consists of two of an aluminum oxide raw material, an aluminum-silicon raw material, a silicon dioxide raw material or a calcium oxide raw material (the mass ratio of the two raw materials is preferably (1-2): 1-2)) and 40-60% of a zirconia raw material; or 30-40% of zirconia raw material, 10-30% of alumina raw material, 20-40% of aluminum-silicon raw material and 10-20% of silicon dioxide raw material;

the zirconia raw material mainly provides ZrO₂The components can be selected from one or more than two groups of zircon, baddeleyite, zirconia corundum, monoclinic zirconia, tetragonal zirconia, cubic zirconia and partially stabilized zirconia; the partially stabilized zirconia is Y₂O₃Stabilized zirconia, Y₂O₃The molar ratio of (A) is 3-9%.

Proper alumina material is introduced into the basic material to replenish Al in the product₂O₃And (4) content. Preferably, the alumina raw material is alumina raw material or aluminaCan be decomposed at the temperature to generate Al₂O₃Contains 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 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 temperature to form alumina, preferably, Al in the chemical composition of the alumina-containing source₂O₃The 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%.

Al is decomposed at high temperature₂O₃The alumina-containing raw material (A) is one or more of aluminum hydroxide, boehmite, diaspore, n-butanol aluminum, aluminum isopropoxide, aluminum sec-butoxide, aluminum chloride hexahydrate and aluminum nitrate nonahydrate. Preferably, it is aluminum hydroxide.

The particle size of the alumina raw material is less than 0.08 mm. The alumina material with the granularity has higher surface activity and is easy to be mixed with the surrounding ZrO at high temperature₂CaO, CaO-rich SiO₂Or rich in SiO₂Liquid phase reaction to produce corundum-zirconia, calcium hexaluminate or anorthite or mullite crystal.

Providing Al from an aluminum-silicon material₂O₃、SiO₂The components are beneficial to generating mullite or anorthite crystals at high temperature, promote sintering and are beneficial to improving the mechanical property of the material. The aluminum-silicon material can be selected from one or more of mullite, kaolin, bauxite, homogeneous material, coal gangue, kyanite, andalusite, sillimanite, pyrophyllite, potash feldspar, albite, anorthite, celsian, porcelain stone, alkali stone, mica, spodumene, perlite, montmorillonite, illite, halloysite, dickite, flint clay, Guangxi white clay, Suzhou soil, knarth, fly ash and floating bead; further preferably, the chemical composition of the aluminum-silicon material is Al₂O₃The mass percentage of the SiO is 32-72 percent₂The mass percentage of the component (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%.

Proper introduction of proper silicon dioxide material into the basic material can effectively supplement SiO in the product₂The content of the silicon carbide is high, the sintering is promoted, and the improvement of the mechanical property of the material is facilitated. Preferably, the silica raw material is a silica raw material or a raw material containing silica, and the chemical composition of the silica raw material is SiO₂The mass percentage content of (A) is higher than 80%. Preferably, wherein SiO₂The mass percentage of the component (A) is 90-99.9%.

Preferably, the particle size of the aluminum-silicon raw material is less than or equal to 1 mm. More preferably, the particle size of the aluminum-silicon raw material is ≦ 0.08 mm. And ceramic powder particles with higher surface activity are easily obtained after ball milling in the later period.

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 silica material in the base material may be decomposed at high temperature to form SiO₂Of a silica-containing raw materialSiO in silica-containing raw materials₂The mass percentage content is more than 18 percent. Preferably, the above-mentioned material is capable of decomposing to form SiO₂The raw material of the fertilizer is one or more of rice husk, carbonized rice husk, rice husk ash, methyl orthosilicate, ethyl orthosilicate and methyl trimethoxysilane.

The particle size of the silica raw material is less than or equal to 0.08 mm. The silica raw material with the granularity is easy to react with the surrounding calcium, aluminum oxide or zirconia raw materials at high temperature to generate anorthite, mullite or zirconium silicate crystals.

Proper introduction of proper calcium oxide raw materials into the basic raw materials can generate a small amount of beneficial crystals such as anorthite or calcium hexaluminate and the like in products, thereby being beneficial to the light weight of samples and further reducing the thermal conductivity of the materials. The calcareous raw materials are limestone, quicklime, hydrated lime, wollastonite, dolomite, calcite, CaO and CaCO₃、Ca(OH)₂、CaSO₄One or a combination of two or more of them. The calcium oxide raw material is calcium silicate and/or calcium aluminate, or the calcium oxide raw 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 nCaO. 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 less than 0.08 mm. The calcium oxide material with the granularity has higher surface activity and is easy to react with surrounding alumina or Al-rich at high temperature₂O₃-SiO₂The liquid phase reaction generates crystals such as calcium hexaluminate or anorthite and the like.

Wherein, Al in the chemical composition of the alumina raw material₂O₃The mass percentage of the component (A) is more than 45%; the aluminum-silicon material comprises 18-90% by mass of aluminum oxide and 8-75% by mass of silicon dioxide; chemical composition of silicon dioxide raw material SiO₂The mass content of (A) is more than 18%; calcia sourceThe mass content of CaO in the chemical composition of the material is more than 30 percent.

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

Generally, the amount of water is 20 to 200% by mass of the base material. Preferably 30 to 180%, more preferably 40 to 160%, still more preferably 70 to 140%, particularly preferably 60 to 120%, and still more preferably 70 to 100%. 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 capillary pores can be left in the sample after the blank body is dried and fired. 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-insulating refractory material is that water and air are utilized to generate a micro-nano-sized spherical pore structure in the high-temperature resistant material, and the volume density, the porosity, the thermal conductivity, the mechanical strength and other properties of the product can be correspondingly regulated and controlled according to the water consumption to a certain extent. In this step, if a dispersant, a suspending agent, a mineralizer, an infrared screening agent, or the like is used, the above components and the base are dispersed into a slurry suspension. 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.

The inorganic curing agent is selected from zirconia sol, alumina sol, silica-alumina sol, zirconia gel, alumina gel, silica-alumina gel, dicalcium silicate, calcium dialuminate, SiO₂Micro powder, tricalcium silicate, monocalcium aluminate and Al₂O₃One or more of micro powder, dodecacalcium heptaluminate, tetracalcium aluminoferrite, aluminum phosphate and water glass. In the above raw materials, the water glass contains sodium silicate, potassium silicate or a combination of the two. SiO 2₂The micro powder not only plays the role of an inorganic curing agent, but also serves 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 not only play the role of an inorganic curing agent, but also can be used as a calcareous raw material. The silica-alumina sol in the inorganic curing agent is also referred to as an alumina-silica sol.

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. In the silica sol, SiO₂The mass percentage content is not less than 25%. 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; ZrO in zirconia sol₂The mass percentage content of the composition is not less than 10 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 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 one or more of vinyl acetate homopolymer, acrylic ester polymer, ethylene-vinyl acetate copolymer, ethylene-vinyl chloride copolymer, vinyl acetate-vinyl versatate copolymer, acrylic ester-styrene copolymer, vinyl acetate-vinyl higher fatty acid copolymer, isobutylene-maleic anhydride copolymer, ethylene-vinyl chloride-vinyl laurate copolymer, vinyl acetate-ethylene-higher fatty acid copolymer, vinyl acetate-ethylene-vinyl laurate copolymer, vinyl acetate-acrylic ester-vinyl higher fatty acid copolymer, and vinyl acetate-vinyl versatate-vinyl 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 polymer film can be formed on the surfaces of the ceramic powder particles after hydration, the film forms flexible connection among the powder particles, the cohesion among the ceramic powder particles is increased through the intermolecular force of organic molecules, the green body strength is improved, the collision damage generated in the carrying process of the green body is avoided, and the yield is greatly improved.

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.

The foaming agent is a surfactant and/or a protein foaming agent, and the foaming times are 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; the protein foaming agent is an animal protein foaming agent, a plant protein foaming agent and/or a sludge protein foaming agent.

The foaming agent is one or more 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.

Preferably, the foaming agent is selected from one or a combination of more than two of quaternary ammonium type Gemini surfactant, carboxylate type Gemini surfactant, sulfate type Gemini surfactant, animal protein foaming agent, sodium dodecyl benzene sulfonate, sodium alpha-olefin sulfonate, high-carbon sodium fatty alcohol polyoxyethylene ether carboxylate, dodecyl dimethyl betaine, fatty alcohol polyoxyethylene ether, fatty alcohol polyoxyethylene ester, double-chain type Bola surfactant, alkylphenol polyoxyethylene ether, polyether type Dendrimer surfactant, sodium lauryl alcohol polyoxyethylene ether carboxylate, polyamide type Dendrimer surfactant and sodium fatty alcohol polyoxyethylene ether carboxylate.

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

Based on the mass of the base material, the addition mass of the dispersing agent is not more than 3 percent; the dispersant is one or more than two of polycarboxylic acid dispersant, sodium polyacrylate, naphthalene dispersant, FS10, FS20, lignin dispersant, sulfonated melamine polycondensate, melamine formaldehyde polycondensate, sodium citrate, sodium polyphosphate, 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, sodium lignosulfonate and potassium lignosulfonate. The addition amount of the dispersant is preferably 0.01 to 10%.

Based on the mass of the base material, the addition mass of the suspending agent is not more than 10 percent; the suspending agent is one or more than two of bentonite, sepiolite, attapulgite, polyaluminium chloride, polyaluminium sulfate, chitosan, xanthan gum, Arabic gum, agar, sucrose, dextrin, acrylamide, polyacrylamide, polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol, casein, cetyl alcohol, 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 bentonite, sepiolite, attapulgite and other inorganic mineral raw materials are selected, the bentonite, sepiolite, attapulgite and other 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 base material particles, and the base material particles generate a suspension effect in the slurry by electrostatic repulsion, but the dosage of the base material particles is relatively large, and is generally less than or equal to 10%.

The mineralizer is CaO or CaF₂、MgO、ZnO、Fe₂O₃、YbO、V₂O₅、AlF₃、SiF₄、MnO₂、TiO₂、CuO、CuSO₄、SrO、BaO、WO₃、Er₂O₃、Cr₂O₃、La₂O₃、Yb₂O₃、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 stability of the crystal form of the zirconium oxide and the growth and development of beneficial crystals, can 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 conduction mechanism of the material mainly comprises three parts of heat conduction, convection heat transfer and radiation heat transfer, and in the invention, the micro-nano hole heat insulation refractory material containing zirconium oxide is preparedThe pore diameter of pores in the material is small, most pores are of a closed structure, gas circulation is difficult, so that convective heat transfer can be basically ignored, and the micro-nano pore heat insulation refractory material containing zirconium oxide is mainly used at high temperature, so that the heat transfer mechanism of the material also comprises radiative heat transfer besides heat conduction. To further effectively reduce radiative heat transfer, the present invention introduces infrared opacifiers to increase reflection or absorption of infrared radiation, reduce its penetration, and reduce thermal conductivity. Especially for high-porosity, low-heat-conductivity heat-insulating refractory materials, the reduction of the heat conductivity coefficient is particularly obvious. In order to further improve the heat insulation performance of the product, the infrared opacifier is preferably selected from rutile and TiO₂、TiC、K₄TiO₄、K₂Ti₆O₁₃、Sb₂O₃、Sb₂O₅、ZnO₂、NiO、NiCl₂、Ni(NO₃)₂、CoO、Co(NO₃)₂、CoCl₂、ZrSiO₄、Fe₃O₄、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 using amount of the infrared opacifier is preferably 1-10% of the mass of the base raw material, and the application effect of the infrared opacifier in the heat-insulating refractory material with low volume density and high porosity is particularly remarkable.

The technical scheme of the preparation method of the zirconium oxide-containing micro-nano hole heat insulation refractory material comprises the following steps:

a preparation method of a micro-nano hole heat insulation refractory material containing zirconium oxide comprises the following steps:

1) when the additive is used, the basic raw materials, the additive composition and water are mixed and dispersed to prepare suspension slurry; when the additive is not used, mixing and dispersing the basic raw material and water to prepare suspended 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 base material, the additive and water are mixed to form suspension slurry, and then the suspension 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 completeness of bubbles is kept, and the generation rate of closed pores is improved; in the curing process, the bubbles in the foam slurry are converted into spherical air holes in the blank, and the air holes provide space for the growth and development of beneficial crystals such as zirconia, mullite, anorthite, calcium hexaluminate 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 pores in the green body prepared by the invention are tiny micron-sized or nano-sized spherical gaps, and the concave surfaces of the pores have extremely large curvature radius, so that the nucleation and growth driving force of beneficial crystals in the pores is further enhanced, the growth size of the crystals is larger, and the physical properties of the product are better.

The preparation method of the zirconium oxide-containing micro-nano hole heat insulation refractory material provided by the invention is environment-friendly and pollution-free, and the preparation process is simple and easy to control. The product has a micro-nano pore structure, and can effectively regulate and control volume density, mechanical strength, porosity, thermal conductivity and the like 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 are improved by more than several times, and the product is more suitable for the application requirements of modern kilns and equipment on light-weight, high-strength, ultralow-heat-conduction and heat-insulation refractory materials.

In the preparation method, taking the use of the additive as an example, in the step 1), the base raw material, the dispersing agent, the suspending agent and the mineralizing agent are premixed, and then water is added to mix the premixed raw material, the dispersing agent, the suspending agent and the mineralizing agent 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 slurry suspension, a simple mechanical stirring method is used. More preferably, the dispersing agent, the suspending agent and the mineralizer are premixed to obtain the additive, and then the additive is mixed with the basic raw material and the water; preferably, the base stock and additive combination is ball milled with water. Further preferably, the slurry after ball milling may be subjected to ultrasonic dispersion in order to obtain a more uniform suspension slurry. Wherein, the zirconia raw material, the aluminum-silicon raw material, the alumina raw material, the silicon dioxide raw material and the calcium raw material in the basic 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%. Likewise, the five materials of the base material are preferably premixed in the same manner at the time of use.

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 more than44 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 after ball milling have high surface activity, and then have excellent hydrophobic property after being modified by surfactant (foaming agent) molecules, 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 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 composition, then the foaming composition 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 raw materials, it is preferable that dry solid raw materials are dry-mixed, then the dry mixture and liquid raw materials are added to the suspension slurry, and then the mixture is stirred, sheared and foamed. The foaming agent can also be prepared into foam by a foaming machine, and then the foam, the inorganic curing agent, the organic curing agent and the foam cell regulator are mixed into the suspension slurry obtained in the step 1, and the mixture is further stirred, sheared and foamed.

Preferably, in the step 2), the stirring foaming is high-speed stirring, shearing, mixing and foaming by using a stirring blade of a vertical stirrer, 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, the small bubbles in the slurry are converted into spherical closed pores in the dried blank, and the spherical pore structure can provide development space for the growth of zirconia and other beneficial crystals in a fired product, thereby being beneficial to the growth improvement of the crystals and the mechanical property improvement of the product. 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.

In step 3), the casting mold is selected from one or more of the following, but not limited to: metal mold, plastic mold, resin mold, rubber mold, polyurethane mold, polystyrene foam mold, plaster mold, glass fiber reinforced plastic mold, wood mold or bamboo glue mold, and composite mold.

The shape of the mold can be changed according to design requirements and is suitable for preparing special-shaped products.

In the step 3), the curing is performed for 0.1-24 hours at the temperature of 1-35 ℃ and the humidity of 40-99.9%, and preferably for 0.1-2 hours. The curing is preferably performed in a constant temperature and humidity environment. In the curing process, the foam slurry is quickly 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 25-27 ℃; 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 is 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.

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%. In the above process, the combined action of the organic and inorganic curing agents greatly improves the strength of the green body obtained after curing and drying the foam slurry, 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 transportation and kiln loading can be avoided or greatly reduced, 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 0.2-2 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 preferably 1350 to 1850 ℃. In order to further optimize the sintering effect and promote the formation of equiaxial granular zirconium oxide crystals, preferably, the sintering is carried out at 400-600 ℃ for 0.5-1.5 h; then heating to 1000-1200 ℃ and preserving the heat for 0.5-1.5 h; then heating to 1350-1850 ℃ and preserving the heat for 1-10 h; then cooling to 1000-1200 ℃ and preserving heat for 0.5-1 h, then cooling to 400-600 ℃ and preserving heat for 0.5-1 h, and then cooling to 50-80 ℃.

Preferably, the rate of heating from room temperature to 400-600 ℃ is 1-5 ℃/min, the rate of heating to 1000-1200 ℃ is 5-30 ℃/min, the rate of heating to 1350-1850 ℃ is 1-10 ℃/min, the rate of cooling to 1000-1200 ℃ is 10-20 ℃/min, the rate of cooling to 400-600 ℃ is 5-10 ℃/min, and the rate of cooling to 50-80 ℃ is 1-5 ℃/min.

The sintered micro-nano hole heat insulation refractory material containing zirconium oxide 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, has no pollution, is simple and easy to control in process, is very short in demoulding 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 showing the external appearance of a micro-nano porous heat insulating refractory prepared in example 7;

FIG. 2 is a photograph showing the pore structure of a micro-nano pore heat insulating refractory material prepared in example 7;

FIG. 3 is a photograph of a pore wall of a micro-nano pore heat insulating refractory containing zirconia prepared in example 7;

FIG. 4 is an EDS analysis of point 1 in panel 3;

FIG. 5 is an EDS analysis of point 2 in panel 3;

FIG. 6 is an X-ray diffraction (XRD) pattern of a micro-nano porous heat insulating refractory prepared in example 7 and containing zirconium oxide;

FIG. 7 is a pore size distribution graph of a micro-nano pore insulating refractory material prepared in example 7.

Detailed Description

The following examples are provided to further illustrate the practice of the invention. The starting materials referred to in the following examples are all available from commercially conventional sources.

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. Alternative manufacturers of the main raw materials are given below in an exemplary form.

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

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

Co-polymerization of acrylate and styreneThe polymers were purchased from national starch Co

Ethylene copolymers with vinyl chloride and vinyl laurate 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 Wei group company (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 purchased from Shanxi three-dimensional group company (SWF-04);isobutylene and maleic anhydride copolymers were purchased from clony, japan (ISOBAM-04); the konjac gum powder is purchased from Shanghai Beilian Biotech limited; curdlan was purchased from Hengmei technology, Inc.; sucrose, dextrin, agar and gellan gum are purchased from Jiangsu Gubei Biotech limited; hydroxypropyl guar was purchased from wilkinson chemical company; sodium alginate was purchased from ancient shellfish biotechnology, Jiangsu; xanthan gum was purchased from Shandong Fufeng fermentation company; acacia is purchased from zhengzhou dewang chemical company; acrylamide and polyacrylamide were purchased from Shandong Ruihai Miyashan chemical company; polyethylene glycol, cetyl alcohol, and polyvinyl alcohol are available from clony, japan; tris was purchased from commercial dune tengfei biotechnology; microcrystalline cellulose and cellulose nanocrystals were purchased from Jiangsu Xin and sourced Biotech.

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 ether was purchased from dow chemical company, usa; carboxymethyl ethyl cellulose ether was purchased from american methylene; propyl cellulose ether was 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; saponin is purchased from Xian Tian Guangyuan company.

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 dispersant, available from basf, germany. Methacrylate type polycarboxylic acid dispersants, available from Hencus technologies, Inc.

First, a specific embodiment of the micro-nano hole heat insulation refractory material containing zirconium oxide and the preparation method thereof

Example 1

The micro-nano hole insulating and fire-resistant material containing zirconium oxide is prepared from a base raw material, a suspending agent, a mineralizer, an infrared opacifier, a foaming agent, an inorganic curing agent, an organic curing agent, a foam hole regulator and water. The kinds and amounts of the raw materials in this example are as follows:

basic raw materials: 0.4 ton zircon, 0.1 ton industrial Al (OH)₃0.1 ton of boehmite, 0.3 ton of kaolin and 0.1 ton of silica micropowder. Chemical composition of zircon in which ZrO₂The mass percentage of the SiO is 64-67 wt percent₂The mass percentage of the catalyst is 32-35 wt%, and the particle size is less than or equal to 0.08 mm; industrial Al (OH)₃In the chemical composition of (1) Al₂O₃The mass percentage of the composite material is not less than 65 wt%, and the particle size is not less than 0.08 mm; chemical composition of boehmite Al₂O₃The mass percentage is not less than 70 percent, and the particle size is not less than 0.08 mm; chemical composition of kaolin Al₂O₃35-37 wt% of SiO₂The mass percentage of the composite is 59-62%, and the particle size is 0.6-1 mm; SiO in the chemical composition of the silicon micropowder₂The mass percentage content of the nano-particles is not less than 95 wt%, and the particle size is not less than 5 mu m.

Suspending agent: 100kg of bentonite, Al in the chemical composition of the 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.

Mineralizing agent: 40kg of Y₂O₃、20kgCeO₂、30kg AlF₃、10kgZnO；Y₂O₃、CeO₂、AlF₃ZnO is all industrial pure, and the particle size is less than or equal to 5 mu m.

Infrared opacifier: 50kg rutile, 25kg ZrSiO₄、25kg B₄C; rutile, ZrSiO₄、B₄C is all industrial pure, and the particle size is less than or equal to 5 mu m.

Foaming agent: 1kg of quaternary ammonium type Gemini type surfactant, 39kg of plant protein foaming agent and 60kg of sludge protein foaming agent.

Inorganic curing agent: 100kg of silica sol, SiO₂The content is not less than 30%.

Organic curing agent: 5kg of a copolymer of vinyl acetate and ethylene, 15kg of a copolymer of vinyl acetate and ethylene and a higher fatty acid; commercial purity, particle size ≦ 5 μm.

Cell regulator: 8kg of carboxymethyl hydroxypropyl cellulose ether; commercial purity, particle size ≦ 5 μm.

Water: 2 tons.

The specific preparation process of the micro-nano hole heat insulation refractory material containing zirconium oxide in the embodiment is as follows:

(1) weighing 0.4 ton of zirconite, 0.1 ton of industrial Al (OH)₃0.1 ton of boehmite, 0.3 ton of kaolin and 0.1 ton of silicon micropowder are poured into a forced mixer and are dry-mixed for 5min to obtain the basic raw material. Weighing 100kg of bentonite and 40kg of Y₂O₃、20kgCeO₂、30kg AlF₃10kg of ZnO, 50kg of rutile, 25kg of ZrSiO₄、25kg B₄And C, pouring the mixture into a three-dimensional mixer and dry-mixing for 5min to obtain the additive.

(2) Weighing 1kg of quaternary ammonium Gemini type surfactant, 39kg of plant protein foaming agent, 60kg of sludge protein foaming agent, 5kg of vinyl acetate-ethylene copolymer, 15kg of vinyl acetate-ethylene-higher fatty acid copolymer and 8kg of carboxymethyl hydroxypropyl cellulose ether, pouring into a V-shaped mixer, and mixing for 5min to obtain the uniform foaming composition.

(3) Pouring the basic raw materials and the additives obtained in the step (1) into a roller ball mill, adding 2 tons of water, carrying out ball milling and mixing for 12 hours to ensure that the average particle size of solid particles in the slurry is not more than 30 mu m, then carrying out ultrasonic oscillation for 4min (ultrasonic power 2000W) to obtain uniform suspension slurry, injecting the suspension slurry into a stirrer, then adding the silica sol and the foaming composition obtained in the step (2) into the suspension slurry, and rapidly mixing the mixture for 2min by a stirring paddle in the stirrer at a linear speed of 180m/s to obtain uniform foam slurry; during ball milling, the grinding balls in the ball mill are made of tungsten carbide 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.

(4) and (4) injecting the foam slurry obtained in the step (3) into a stainless steel mold, and curing for 12 hours in an environment with the air temperature and the relative humidity of 10 ℃ and 60% respectively until the foam slurry is cured.

(5) Demoulding the solidified green body by using CO₂Removing water and CO in the blank by a supercritical drying method₂The pressure is controlled to be 9MPa, the temperature is 42 ℃, and the supercritical drying time is 2 hours, so that the dry porous blank is obtained. 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 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, preserving heat at 400 ℃ for 0.5h, raising the temperature to 1000 ℃ at 5 ℃/min, preserving heat for 0.5h, raising the temperature to 1350 ℃ at 1 ℃/min, preserving heat for 10h, reducing the temperature to 1000 ℃ at 10 ℃/min, preserving heat for 0.5h at 1000 ℃, reducing the temperature to 600 ℃ at 5 ℃/min, preserving heat for 0.5h at 600 ℃, and finally reducing the temperature to 50 ℃ at 1 ℃/min to obtain the micro-nano-hole heat insulating refractory material containing zirconium oxide.

Examples 2 to 17

The formulation composition of the micro-nano pore heat insulation refractory material containing zirconia of examples 2 to 17 is shown in table 1 and table 2 below:

table 1 examples 2 to 9 formulations of micro-nano-pore heat insulating and fire resisting material containing zirconia

Table 2 examples 10 to 17 formulation of micro-nano hole heat insulation refractory material containing zirconium oxide

The preparation process of the micro-nano hole insulating refractory material containing zirconia in the embodiment 2 is as follows:

(1) weighing zircon, industrial alumina and beta-Al according to formula₂O₃、γ-Al₂O₃Pouring the coal gangue, the diatomite and the beta-tridymite into a planetary mixer and carrying out dry mixing for 5min to obtain a basic raw material; weighing bentonite, polyaluminium chloride and Y₂O₃、MgO、V₂O₅、NiO、K₂Ti₆O₁₃、Sb₂O₅And pouring the mixture into a double cone mixer and dry-mixing the mixture for 5min to obtain the additive.

(2) Weighing quaternary ammonium Gemini type surfactant, animal protein foaming agent, silica gel, vinyl acetate, ethylene and acrylate copolymer, hydroxyethyl cellulose ether, hydroxyethyl ethyl cellulose ether and hydroxypropyl cellulose ether, pouring into a V-shaped mixer, and mixing for 5min to obtain the uniform foaming composition.

(3) Pouring the basic raw materials and the additives obtained in the step (1) into a roller ball mill, adding 2 tons of water, carrying out ball milling and mixing for 10 hours to ensure that the average particle size of solid particles is not more than 30 mu m, then carrying out ultrasonic oscillation for 5min (the ultrasonic power is 1500W) to obtain uniform suspension slurry, injecting the suspension slurry into a stirrer, then adding the foaming composition and the alumina sol obtained in the step (2) into the suspension slurry, and rapidly mixing for 2min by a stirring paddle in the stirrer at a linear speed of 200m/s to obtain uniform foam slurry; during ball milling, the grinding balls in the ball mill adopt silicon carbide 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.

(4) and (4) injecting the foam slurry obtained in the step (3) into a stainless steel mold, and curing for 24 hours in an environment with the air temperature and the relative humidity of 1 ℃ and 40% respectively until the foam slurry is cured.

(5) Demoulding the solidified green body by using CO₂Removing water and CO in the blank by a supercritical drying method₂The pressure is controlled to be 9MPa, the temperature is 42 ℃, and the supercritical drying time is 1.5h, so that the dry porous blank is obtained. 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 0.9 MPa. Firing the dried blank body by adopting a high-temperature tunnel kiln, firstly heating to 500 ℃ from room temperature at a heating rate of 2 ℃/min, preserving heat for 0.5h at 500 ℃, then heating to 1000 ℃ at 5 ℃/min, preserving heat for 0.5h, then heating to 1400 ℃ at 3 ℃/min, preserving heat for 8h, then cooling to 1000 ℃ at 10 ℃/min, preserving heat for 0.5h at 1000 ℃, then cooling to 500 ℃ at 6 ℃/min, preserving heat for 0.5h at 500 ℃, and finally cooling to 50 ℃ at 2 ℃/min to obtain the zirconium oxide-containing green bodyThe micro-nano hole heat insulation refractory material.

In this example, ZrO in the chemical composition of zircon₂64 to 67 weight percent of SiO₂The mass percentage of the composite material is 32-35%, and the particle size is less than or equal to 0.08 mm; commercial alumina, beta-Al₂O₃、γ-Al₂O₃In the chemical composition of (1) Al₂O₃The mass percentage of the composite material is not less than 98 percent, and the particle size is not less than 0.08 mm; al in chemical composition of coal gangue₂O₃The mass percentage of the SiO is 26-28 percent₂The mass percentage of the composite material is 69-73%, and the particle size is 0.6-1 mm; chemical composition of diatomite is SiO₂The mass percentage of the composite material is not less than 85%, and the particle size is not less than 0.08 mm; chemical composition of SiO in beta-tridymite₂The mass percentage of the composite material is not less than 98 percent, and the particle size is not less than 0.08 mm; chemical composition of bentonite is Al₂O₃22-23% of SiO₂The mass percentage of the composite material is 68-75%, and the particle size is less than or equal to 0.045 mm; al in alumina sol₂O₃The mass percentage content of the composition is not less than 20 percent; polyaluminum chloride, Y₂O₃、MgO、V₂O₅All are industrial pure and have the particle size less than or equal to 5 mu m.

The preparation process of the micro-nano hole insulating refractory material containing zirconia in the embodiment 3 is as follows:

(1) weighing zirconium corundum, zirconite, kaolin, alpha-quartz, beta-quartz and alpha-tridymite, pouring the weighed materials into a non-gravity mixer, and carrying out dry mixing for 10min to obtain a basic raw material; weighing methacrylate type polycarboxylic acid dispersant, bentonite, polyaluminium sulfate and Y₂O₃、CeO₂、Yb₂O₃、K₂Ti₆O₁₃、TiC、B₄And C, pouring the mixture into a double cone mixer and carrying out dry mixing for 5min to obtain the additive.

(2) Weighing carboxylate Gemini surfactant, sodium dodecyl benzene sulfonate, calcium dialuminate, tricalcium silicate, ethylene-vinyl chloride-vinyl laurate copolymer, curdlan, carboxymethyl methyl cellulose ether and carboxymethyl ethyl cellulose ether, pouring into a three-dimensional mixer, and mixing for 5min to obtain the uniform foaming composition.

(3) Pouring the basic raw materials and the additives obtained in the step (1) into a roller ball mill, adding 1.6 tons of water, carrying out ball milling and mixing for 8 hours to ensure that the average particle size of solid particles in the slurry is not more than 35 mu m, then carrying out ultrasonic oscillation for 6min (the ultrasonic power is 1300W) to obtain uniform suspension slurry, then injecting the suspension slurry into a stirrer, then adding the foaming composition and the silica-alumina sol obtained in the step (2) into the suspension slurry, and rapidly mixing for 3min by a stirring paddle in the stirrer at the linear speed of 170m/s to obtain uniform foam slurry; during ball milling, the grinding balls in the ball mill adopt zirconia balls and large balls

Middle ball

Small ball

(4) and (4) injecting the foam slurry obtained in the step (3) into a plastic mould, and curing for 2h in an environment with the air temperature and the relative humidity of 20 ℃ and 80% respectively until the foam slurry is cured.

(5) Demoulding the solidified green body by using CO₂Removing liquid water in the blank by a 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 1.0 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, preserving heat for 0.5h at 500 ℃, raising the temperature to 1000 ℃ at 8 ℃/min, preserving heat for 1h, raising the temperature to 1450 ℃ at 3 ℃/min, preserving heat for 5h, then reducing the temperature to 1100 ℃ at 10 ℃/min, preserving heat for 1h at 1100 ℃, reducing the temperature to 500 ℃ at 6 ℃/min, preserving heat for 0.5h at 500 ℃, and finally reducing the temperature to 50 ℃ at 2 ℃/min to obtain the micro-nano hole heat insulation refractory material containing zirconium oxide.

In this example, ZrO in the chemical composition of the zirconia corundum₂15-17 wt% of Al₂O₃The mass percentage of the composite material is 83-85 wt%, and the particle size is less than or equal to 0.08 mm; chemical group of zirconiteMedium ZrO of₂64 to 67 weight percent of SiO₂The mass percentage of the composite material is 32-35%, and the particle size is less than or equal to 0.08 mm; chemical composition of kaolin Al₂O₃35-37 wt% of SiO₂The mass percentage of the composite is 58-61%, and the particle size is 0.6-1 mm; SiO in chemical composition of alpha-quartz, beta-quartz and alpha-tridymite₂The mass percentage of the composite material is not less than 95 wt%, and the particle size is not less than 0.044 mm; chemical composition of bentonite is Al₂O₃22-23% of SiO₂The mass percentage of the composite material is 68-75%, and the particle size is less than or equal to 0.045 mm; 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; polyaluminium sulfate, Y₂O₃、CeO₂、Yb₂O₃、K₂Ti₆O₁₃、TiC、B₄C. The calcium dialuminate and the tricalcium silicate are both industrial pure, and the grain diameter is less than or equal to 5 mu m.

The preparation process of the micro-nano pore insulating refractory material containing zirconia in the embodiment 4 is as follows:

(1) weighing zirconia corundum and alpha-Al₂O₃Pouring the diaspore, the n-butyl aluminum alkoxide, the aluminum isopropoxide and the kyanite into a forced mixer and carrying out dry mixing for 15min to obtain a basic raw material; weighing sodium polyacrylate, sodium polyphosphate, attapulgite, sepiolite, CaO and Y₂O₃、MnO₂、TiO₂、K₄TiO₄、Sb₂O₃And pouring the mixture into a double cone mixer and dry-mixing the mixture for 5min to obtain the additive.

(2) Weighing quaternary ammonium type Gemini surfactant, alpha-olefin sodium sulfonate, high-carbon fatty alcohol polyoxyethylene ether, tetracalcium aluminoferrite, acrylate and styrene copolymer, gellan gum, carboxymethyl hydroxymethyl cellulose ether, carboxymethyl hydroxyethyl cellulose ether and hydroxypropyl ethyl cellulose ether, pouring into a V-type mixer, and mixing for 5min to obtain the uniform foaming composition.

(3) Pouring the basic raw material obtained in the step (1) and additives into a roller ball mill, adding 1.4 tons of water, and carrying out ball milling and mixing for 8 hours to ensure that the average particle size of solid particles is not more than 30 mu mThen carrying out ultrasonic oscillation for 7min (the ultrasonic power is 1200W) to obtain uniform suspension slurry, then adding the foaming composition and the zirconia sol obtained in the step (2) into the suspension slurry, and rapidly mixing the foaming composition and the zirconia sol for 4min by a stirring paddle in a stirrer at the linear speed of 160m/s to obtain uniform foam slurry; during ball milling, the grinding balls in the ball mill adopt zirconia balls and large balls

Middle ball

Small ball

(4) and (4) injecting the foam slurry obtained in the step (3) into a rubber mold, and curing for 1h in an environment with air temperature and relative humidity of 25 ℃ and 90% respectively until the foam slurry is cured.

(5) Demoulding the solidified green body, removing water in the green body by using a microwave drying technology, wherein the microwave frequency is 915MHz, and drying for 0.2h to obtain a dried porous green 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. And (2) putting the dried blank body into a shuttle kiln to be sintered, firstly heating to 500 ℃ from room temperature at a heating rate of 3 ℃/min, preserving heat for 1h at 500 ℃, then heating to 1000 ℃ at 8 ℃/min, preserving heat for 1h, heating to 1500 ℃ at 4 ℃/min, preserving heat for 3h, then cooling to 1100 ℃ at 10 ℃/min, preserving heat for 1h at 1100 ℃, then cooling to 500 ℃ at 6 ℃/min, preserving heat for 0.5h at 500 ℃, and finally cooling to 60 ℃ at 2 ℃/min to obtain the micro-nano hole heat insulation refractory material containing zirconium oxide.

In this example, ZrO in the chemical composition of the zirconia corundum₂22-25 wt% of Al₂O₃The mass percentage of the composite material is 75-78 wt%, and the particle size is less than or equal to 0.08 mm; chemical composition of kyanite Al₂O₃The mass percentage of the SiO is 40-45 wt percent₂The mass percentage of the composite material is 55-58%, and the particle size is 0.6-1 mm; alpha-Al₂O₃In the chemical composition of (1) Al₂O₃The mass percentage is not less than 99.9 wt%, and the particle size is not less than 0.08 mm; al in chemical composition of diaspore₂O₃The mass percentage of the composite material is not less than 70 wt%, and the particle size is not less than 0.08 mm; al in chemical composition of n-butyl aluminum alkoxide and aluminum isopropoxide₂O₃The mass percentage of the component (A) is 44-50 wt%; al in chemical composition of 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 chemical composition of sepiolite₂The mass percentage of the magnesium oxide 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; ZrO in zirconia sol₂The mass percentage of the components is 10-15%; CaO, Y₂O₃、MnO₂、TiO₂、K₄TiO₄、Sb₂O₃The tetracalcium aluminoferrite is industrially pure and has a particle size less than or equal to 5 mu m.

The preparation process of the micro-nano hole insulating refractory material containing zirconia in the embodiment 5 is as follows:

(1) weighing corundum-zirconia, methyl orthosilicate and ethyl orthosilicate, pouring the weighed corundum-zirconia, methyl orthosilicate and ethyl orthosilicate into a forced mixer, and dry-mixing for 15min to obtain a basic raw material; weighing sulfonated melamine polycondensate, allyl ether polycarboxylic acid dispersant, bentonite, chitosan and Er₂O₃、La₂O₃、Cr₂O₃And pouring the mixture into a three-dimensional mixer and dry-mixing the mixture for 5min to obtain the additive.

(2) Weighing quaternary ammonium type Gemini surfactant, dodecyl dimethyl betaine, silica gel, alumina gel, vinyl acetate-ethylene-vinyl chloride copolymer, vinyl acetate-higher fatty acid vinyl ester copolymer and carboxymethyl hydroxybutyl cellulose ether, pouring into a V-shaped mixer, and mixing for 5min to obtain a uniform foaming composition.

(3) Pouring the basic raw material and the additive obtained in the step (1) into a roller ball mill, adding 1.2 tons of water, ball milling and mixing for 4 hours to ensure that the average particle size of solid particles is not more than 44 mu m, then carrying out ultrasonic oscillation for 8min (the ultrasonic power is 1000W) to obtain uniform suspension slurry, and then adding the foaming composition obtained in the step (2)Adding into the suspension slurry, and rapidly mixing for 10min with a stirring paddle in a stirrer at a linear speed of 40m/s to obtain uniform foam slurry; during ball milling, 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.

(4) and (4) injecting the foam slurry obtained in the step (3) into a plastic mould, and curing for 1h in an environment with the air temperature and the relative humidity of 25 ℃ and 90% respectively until the foam slurry is cured.

(5) Demoulding the solidified green body, removing water in the green body by using a microwave drying technology, wherein the microwave frequency is 2450MHz, and drying for 0.8h to obtain a dried porous green 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. Demoulding the solidified green body, removing water in the green body by using a microwave drying technology, wherein the microwave frequency is 915MHz, and drying for 0.2h to obtain a dried porous green body; putting the dried green body into a microwave kiln to be fired, firstly heating to 500 ℃ from room temperature at a heating rate of 10 ℃/min, and preserving heat for 1.5 h; then heating to 1100 ℃ at the speed of 30 ℃/min, and preserving heat for 1.5 h; then heating to 1540 ℃ at the speed of 10 ℃/min, and preserving heat for 1 h; then cooling to 1000 ℃ at a speed of 20 ℃/min and preserving heat for 1 h; then cooling to 600 ℃ at a speed of 10 ℃/min and preserving heat for 1 h; and finally, cooling to 80 ℃ at a speed of 5 ℃/min to obtain the micro-nano hole heat insulation refractory material containing zirconium oxide.

In this example, ZrO in the chemical composition of the zirconia corundum₂39-41 wt% of Al₂O₃The mass percentage of the catalyst is 59-61 wt%, and the particle size is less than or equal to 5 mu m; SiO in chemical composition of methyl orthosilicate and ethyl orthosilicate₂The mass percentage of the component (A) is 28-35 wt%; chemical composition of bentonite is Al₂O₃22-23% of SiO₂The mass percentage of (B) is 68-75Percent, particle size ≦ 0.045 mm; er₂O₃、La₂O₃、Cr₂O₃The silica gel and the alumina gel are all industrial pure and have the grain diameter less than or equal to 5 mu m.

The preparation process of the micro-nano pore insulating refractory material containing zirconia in the embodiment 6 is as follows:

(1) weighing 8 mol% of Y₂O₃Stabilized zirconia,. eta. -Al₂O₃、ρ-Al₂O₃Pouring the alpha-tridymite, the rice hull, the carbonized rice hull and the rice hull ash into a forced mixer and carrying out dry mixing for 5min to obtain a basic raw material; weighing polyamide type polycarboxylic acid dispersant, naphthalene dispersant, welan gum, polyvinylpyrrolidone and WO₃、TiO₂、NiCl₂、Ni(NO₃)₂And pouring the mixture into a three-dimensional mixer and dry-mixing the mixture for 5min to obtain the additive.

(2) Weighing sulfate type Gemini surfactant, fatty alcohol-polyoxyethylene ether, aluminum-silicon gel, vinyl acetate-ethylene-vinyl laurate copolymer, isobutylene-maleic anhydride copolymer, hydroxypropyl guar gum, propyl cellulose ether, water-soluble cellulose ether and ethyl methyl cellulose ether, pouring into a three-dimensional mixer, and mixing for 5min to obtain the uniform foaming composition.

(3) Pouring the basic raw materials and the additives obtained in the step (1) into a roller ball mill, adding 1.2 tons of water, carrying out ball milling and mixing for 4 hours to ensure that the average particle size of solid particles is not more than 44 mu m, then carrying out ultrasonic oscillation for 10min (the ultrasonic power is 800W) to obtain uniform suspension slurry, then adding the foaming composition obtained in the step (2) into the suspension slurry, and rapidly mixing for 5min by a stirring paddle in a stirrer at the linear speed of 150m/s to obtain uniform foam slurry; during ball milling, the material of the grinding balls in the ball mill is alumina, and the large balls

Middle ball

Small ball

(4) and (5) injecting the foam slurry obtained in the step (4) into an aluminum alloy mold, and curing for 1 hour in an environment with the air temperature and the relative humidity of 25 ℃ and 90% respectively until the foam slurry is cured.

(5) Demoulding the solidified green body, and removing water in the green body by adopting a microwave drying method, wherein the microwave frequency is 915MHz, and the microwave drying time is 1h, so as to obtain a dried porous green 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. 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; then heating to 1200 ℃ at the speed of 10 ℃/min, and preserving heat for 0.5 h; heating to 1550-1580 ℃ at the speed of 8 ℃/min, and preserving heat for 0.5 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; and finally, cooling to 50 ℃ at a speed of 5 ℃/min to obtain the micro-nano hole heat insulation refractory material containing zirconium oxide.

In this example, 8 mol% Y₂O₃ZrO in stabilized zirconia₂The content of (a) is 86-88 wt%, and the particle size is less than or equal to 0.08 mm; eta-Al₂O₃、ρ-Al₂O₃In the chemical composition of (1) Al₂O₃The mass percentage of the composite material is not less than 99 wt%, and the particle size is not less than 0.08 mm; SiO in chemical composition of alpha-tridymite₂The mass percentage of the composite material is not less than 99 wt%, and the particle size is not less than 0.08 mm; SiO in chemical composition of rice husk, carbonized rice husk and rice husk ash₂The mass percentage of the composite material is not less than 18 wt%, and the particle size is not less than 0.08 mu m; WO₃、TiO₂、NiCl₂、Ni(NO₃)₂The aluminum-silicon gel is all industrial pure, and the grain diameter is less than or equal to 1 mu m.

The preparation process of the micro-nano pore insulating refractory material containing zirconia in the embodiment 7 is as follows:

(1) adding 5 mol% of Y₂O₃Stabilized zirconia, gamma-Al₂O₃、κ-Al₂O₃、θ-Al₂O₃Pouring andalusite, alpha-cristobalite and cemented silica into a non-gravity mixer, and carrying out dry mixing for 15min to obtain a base raw material; weighing methacrylate type polyCarboxylic acid dispersant, naphthalene dispersant, casein, cellulose fiber, and Y₂O₃、Fe₂O₃、WO₃、TiO₂、Sb₂O₅And pouring the mixture into a V-shaped mixer and dry-mixing the mixture for 5min to obtain the additive.

(2) Weighing a sulfate type Gemini surfactant, fatty alcohol polyoxyethylene ester, silicon-aluminum gel, ethylene and vinyl chloride copolymer, an acrylate polymer, a vinyl acetate homopolymer, hydroxybutyl methyl cellulose ether and hydroxyethyl methyl cellulose ether, pouring into a V-shaped mixer, and mixing for 5min to obtain a uniform foaming composition.

(3) Pouring the basic raw materials and the additives obtained in the step (1) into a roller ball mill, adding 0.9 ton of water, carrying out ball milling and mixing for 1.5h to ensure that the average particle size of solid particles is not more than 44 mu m, then carrying out ultrasonic oscillation for 12min (the ultrasonic power is 800W) to obtain uniform suspension slurry, then adding the foaming composition obtained in the step (2) into the suspension slurry, and rapidly mixing for 5min by a stirring paddle in a stirrer at the linear speed of 140m/s to obtain uniform foam slurry; during ball milling, the grinding balls in the ball mill are made of zirconium corundum 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: 1.1.

(4) and (4) injecting the foam slurry obtained in the step (3) into a resin mold, and curing for 0.8h in an environment with the air temperature and the relative humidity of 25 ℃ and 93% respectively until the foam slurry is cured.

(5) And demolding the solidified blank, removing the water in the blank by using a freeze drying method, drying at the temperature of-130 to-100 ℃ for 6 hours 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 1.0 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 1200 ℃ at the speed of 8 ℃/min, and keeping the temperature for 1 h; heating to 1570-1600 ℃ at the speed of 3 ℃/min, and preserving heat for 3-5 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, and preserving heat for 0.5 h; and finally, cooling to 50 ℃ at the speed of 2 ℃/min to obtain the zirconium oxide-containing micro-nano hole super heat insulation refractory material.

In this example, 5 mol% Y₂O₃Chemical composition of stabilized zirconia₂The content of (a) is 90-93 wt%, and the particle size is less than or equal to 0.08 mm; gamma-Al₂O₃、κ-Al₂O₃、θ-Al₂O₃In the chemical composition of (1) Al₂O₃The mass percentage of the composite material is not less than 99 wt%, and the particle size is not less than 0.08 mm; chemical composition of andalusite containing Al₂O₃The mass percentage of the composite material is 45-50 wt%, and the particle size is less than or equal to 0.08 mm; SiO in chemical composition of alpha-cristobalite and cemented silica₂The mass percentage of the catalyst is 98 wt%, and the particle size is less than or equal to 0.08 mm; y is₂O₃、Fe₂O₃、WO₃、TiO₂、Sb₂O₅The alumina-silica gel is all industrial pure, and the grain diameter is less than or equal to 5 mu m.

The preparation process of the micro-nano pore insulating refractory material containing zirconia in the embodiment 8 is as follows:

(1) adding 5 mol% of Y₂O₃Pouring the stabilized zirconia, the sintered corundum, the fused white corundum powder, the andalusite, the quartzite and the vein quartz into a non-gravity mixer and dry-mixing for 15min to obtain a basic raw material; weighing imide type polycarboxylic acid dispersant, melamine dispersant, polyacrylamide, soluble starch, SrO and Cr₂O₃、BaO、Sb₂O₅、Co(NO₃)₂And pouring the mixture into a V-shaped mixer and dry-mixing the mixture for 5min to obtain the additive.

(2) Weighing a double-chain type Bola surfactant, alkylphenol ethoxylates, alumina gel, a copolymer of vinyl acetate, vinyl versatate and acrylic ester, a copolymer of vinyl acetate and vinyl versatate, sulfonic ethyl cellulose ether and lignocellulose, pouring into a three-dimensional mixer, and mixing for 5min to obtain a uniform foaming composition.

(3) Pouring the basic raw materials and the additives obtained in the step (1) into a roller ball mill, adding 0.8 ton of water, carrying out ball milling and mixing for 1h to ensure that the average particle size of solid particles is not more than 44 mu m, then carrying out ultrasonic oscillation for 13min (the ultrasonic power is 600W) to obtain uniform suspension slurry, then adding the foaming composition obtained in the step (2) into the suspension slurry, and rapidly mixing the foaming composition and the suspension slurry by a stirring paddle in a stirrer at the linear speed of 130m/s for 6min to obtain uniform foam slurry; during ball milling, 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.

(4) and (4) injecting the foam slurry obtained in the step (3) into a rubber mold, and curing for 0.7h in an environment with air temperature and relative humidity of 25 ℃ and 95% respectively until the foam slurry is cured.

(5) Demolding the cured blank, and removing liquid water in the blank by adopting an infrared drying method, wherein 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 1.0 MPa. And (3) putting the dried blank body into a shuttle kiln to be sintered, heating the dried blank body from room temperature to 500 ℃ at a heating rate of 3 ℃/min, heating the dried blank body to 1200 ℃ at 8 ℃/min, preserving heat for 1h, heating the dried blank body to 1580-1610 ℃ at 3 ℃/min, preserving heat for 3h, cooling the dried blank body to 1000 ℃ at 10 ℃/min, preserving heat for 1h at 1000 ℃, cooling the dried blank body to 500 ℃ at 6 ℃/min, preserving heat for 0.5h at 500 ℃, and finally cooling the dried blank body to 50 ℃ at 2 ℃/min to obtain the micro-nano hole heat insulation refractory material containing zirconium oxide.

In this example 8, 5 mol% Y₂O₃Chemical composition of stabilized zirconia₂The content of (a) is 90-93 wt%, and the particle size is less than or equal to 0.08 mm; al in chemical composition of sintered corundum and electric fused white corundum powder₂O₃Mass percentage of not less than 99wt%, the particle size is less than or equal to 0.08 mm; chemical composition of andalusite containing Al₂O₃54-58 wt% of SiO₂The mass percentage of the composite material is 36-40%, and the particle size is less than or equal to 0.08 mm; SiO in chemical composition of quartzite and vein quartz₂The mass percentage content is not less than 98 wt%, and the particle size is not less than 0.045 mm; SrO, Cr₂O₃、BaO、Sb₂O₅、Co(NO₃)₂The alumina gel is all industrial pure, and the grain size is less than or equal to 5 mu m.

The preparation process of the micro-nano pore insulating refractory material containing zirconium oxide in the embodiment 9 is as follows:

(1) adding 5 mol% of Y₂O₃Pouring the stable zirconia and the andalusite into a forced mixer and carrying out dry mixing for 5min to obtain a basic raw material; weighing polyamide polycarboxylic acid dispersant, naphthalene high-efficiency dispersant, microcrystalline cellulose, casein, CaO and MnO₂、Cr₂O₃、CoO、K₂Ti₆O₁₃And pouring the mixture into a V-shaped mixer and dry-mixing the mixture for 5min to obtain the additive.

(2) Weighing polyether type Dendrimer surfactant, lauryl alcohol polyoxyethylene ether, zirconia gel, ethylene-vinyl acetate copolymer, locust bean gum, methyl cellulose ether and carboxymethyl cellulose ether, pouring into a three-dimensional mixer, and mixing for 5min to obtain a uniform foaming composition.

(3) Pouring the basic raw materials and the additives obtained in the step (1) into a roller ball mill, adding 0.7 ton of water, carrying out ball milling and mixing for 1h to ensure that the average particle size of solid particles is not more than 44 mu m, then carrying out ultrasonic oscillation for 15min (the ultrasonic power is 500W) to obtain uniform suspension slurry, then adding the foaming composition obtained in the step (2) into the suspension slurry, and rapidly mixing for 6min by a stirring paddle in a stirrer at the linear speed of 125m/s to obtain uniform foam slurry; during ball milling, the grinding balls in the ball mill are made of mullite 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.

(4) and (4) injecting the foam slurry obtained in the step (3) into a foam mold, and curing for 0.6h in an environment with the air temperature and the relative humidity of 27 ℃ and 95% respectively until the foam slurry is cured.

(5) Demolding the cured blank, and removing liquid water in the blank by adopting an infrared drying method, wherein the infrared wavelength is 12-15 mu m, and the drying time is 1h 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 1.0 MPa. And (3) putting the dried blank body into a shuttle kiln to be sintered, heating the dried blank body from room temperature to 500 ℃ at a heating rate of 3 ℃/min, heating the dried blank body to 1200 ℃ at 8 ℃/min, preserving heat for 1h, heating the dried blank body to 1600-1650 ℃ at 3 ℃/min, preserving heat for 3h, cooling the dried blank body to 1000 ℃ at 10 ℃/min, preserving heat for 1h at 1000 ℃, cooling the dried blank body to 500 ℃ at 6 ℃/min, preserving heat for 0.5h at 500 ℃, and finally cooling the dried blank body to 50 ℃ at 2 ℃/min to obtain the micro-nano hole heat insulation refractory material containing zirconium oxide.

In this example, 5 mol% Y₂O₃Chemical composition of stabilized zirconia₂The mass percentage of the composite material is 90-93 wt%, and the particle size is less than or equal to 0.08 mm; chemical composition of andalusite containing Al₂O₃54-58 wt% of SiO₂The mass percentage of the composite material is 36-40%, and the particle size is 0.6-1 mm; CaO, MnO₂、Cr₂O₃、CoO、K₂Ti₆O₁₃The zirconia gel is all industrial pure, and the particle size is less than or equal to 5 mu m.

The preparation process of the micro-nano pore insulating and heat-insulating refractory material containing zirconia in the embodiment 10 is as follows:

(1) 3 mol% of Y₂O₃Pouring the stable zirconia and the sillimanite into a planetary mixer and dry-mixing for 15min to obtain a basic raw material; weighing polyethylene glycol type polycarboxylic acid dispersant, potassium lignosulfonate, cellulose fiber, MgO, YbO and TiO₂、K₂Ti₆O₁₃And pouring into a planetary mixer and dry-mixing for 5min to obtain the additive.

(2) Weighing quaternary ammonium type Gemini surfactant, sodium laureth carboxylate, zirconia gel, ethylene-vinyl acetate copolymer, propyl cellulose ether and hydroxypropyl hydroxybutyl cellulose ether, pouring into a V-shaped mixer, and mixing for 5min to obtain the uniform foaming composition.

(3) Pouring the basic raw materials and the additives obtained in the step (1) into a roller ball mill, adding 0.6 ton of water, carrying out ball milling and mixing for 1h to ensure that the average particle size of solid particles is not more than 50 mu m, then carrying out ultrasonic oscillation for 10min (the ultrasonic power is 1000W) to obtain uniform suspension slurry, then adding the foaming composition obtained in the step (2) into the suspension slurry, and rapidly mixing for 7min by a stirring paddle in a stirrer at the linear speed of 80m/s to obtain uniform foam slurry; during ball milling, the grinding balls in the ball mill are made of zirconium corundum and large balls

Middle ball

Small ball

(4) and (4) injecting the foam slurry obtained in the step (3) into a wood mold, and curing for 0.5h in an environment with the air temperature and the relative humidity of 27 ℃ and 97% respectively until the foam slurry is cured.

(5) Demolding the cured blank, and removing liquid water in the blank by adopting an infrared drying method, wherein the infrared wavelength is 5-7 mu m, and the drying time is 0.5h 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 1.0 MPa. And (3) putting the dried blank body into a shuttle kiln to be sintered, heating the dried blank body from room temperature to 500 ℃ at a heating rate of 3 ℃/min, heating the dried blank body to 1200 ℃ at 8 ℃/min, preserving heat for 1h, heating the dried blank body to 1650-1700 ℃ at 3 ℃/min, preserving heat for 3h, cooling the dried blank body to 1000 ℃ at 10 ℃/min, preserving heat for 1h at 1100 ℃, cooling the dried blank body to 500 ℃ at 6 ℃/min, preserving heat for 0.5h at 500 ℃, and finally cooling the dried blank body to 50 ℃ at 2 ℃/min to obtain the micro-nano hole heat insulation refractory material containing zirconium oxide.

In this example, 3 mol% Y₂O₃Chemical composition of stabilized zirconia₂The mass percentage of the silicon carbide is 94-96 wt%, and Al in the chemical composition of the sillimanite₂O₃55-60 wt% of SiO₂The mass percentage of the two raw materials is 39-44%, and the particle size of the two raw materials is less than or equal to 0.08 mm; MgO, YbO, TiO₂、K₂Ti₆O₁₃The zirconia gel is all industrial pure, and the particle size is less than or equal to 5 mu m.

The preparation process of the micro-nano pore insulating refractory material containing zirconium oxide in the embodiment 11 is as follows:

(1) 9 mol% of Y₂O₃And pouring the stable zirconia and the fused mullite into a forced mixer and carrying out dry mixing for 15min to obtain the basic raw material. Weighing allyl ether type polycarboxylic acid dispersant, sodium lignosulfonate, polyvinylpyrrolidone and Er₂O₃、K₂Ti₆O₁₃And pouring the mixture into a double cone mixer and dry-mixing the mixture for 5min to obtain the additive.

(2) Weighing polyamide type Dendrimer surfactant, zirconia gel, konjac gum powder, starch ether and hydroxypropyl methyl cellulose ether, pouring into a double-cone mixer, and mixing for 5min to obtain a uniform foaming composition.

(3) Pouring the basic raw materials and the additives obtained in the step (1) into a roller ball mill, adding 0.4 ton of water, carrying out ball milling and mixing for 1h to ensure that the average particle size of solid particles is not more than 60 mu m, then carrying out ultrasonic oscillation for 8min (the ultrasonic power is 1500W) to obtain uniform suspension slurry, then adding the foaming composition obtained in the step (2) into the suspension slurry, and mixing for 8min by a stirring paddle in a stirrer at the linear speed of 40m/s to obtain uniform foam slurry; during ball milling, the grinding balls in the ball mill are made of zirconium corundum and large balls

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.

(4) and (4) injecting the foam slurry obtained in the step (3) into a glass mold, and curing for 0.3h in an environment with the air temperature and the relative humidity of 30 ℃ and 99% respectively until the foam slurry is cured.

(5) Demoulding the solidified green body, and removing liquid water in the green body by adopting a normal pressure drying method, wherein the drying system is as follows: heating to 30 ℃ at a speed of 2 ℃/min, preserving heat at 30 ℃ for 3h, heating to 50 ℃ at a speed of 2 ℃/min, preserving heat at 50 ℃ for 2h, heating to 70 ℃ at a speed of 3 ℃/min, preserving heat at 70 ℃ for 2h, heating to 90 ℃ at a speed of 3 ℃/min, preserving heat at 90 ℃ for 3h, heating to 110 ℃ at a speed of 3 ℃/min, preserving heat at 110 ℃ for 12h, and obtaining 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 1.0 MPa. And (3) placing the dried blank body into a high-temperature resistance kiln to be fired, raising the temperature from room temperature to 500 ℃ at a heating rate of 3 ℃/min, raising the temperature to 1200 ℃ at 8 ℃/min, preserving the heat for 1h, raising the temperature to 1700-1750 ℃ at 3 ℃/min, preserving the heat for 3h, then reducing the temperature to 1000 ℃ at 10 ℃/min, preserving the heat for 1h, reducing the temperature to 500 ℃ at 6 ℃/min, preserving the heat for 0.5h, and finally reducing the temperature to 50 ℃ at 2 ℃/min to obtain the micro-nano hole heat insulation refractory material containing zirconium oxide.

In this example, 3 mol% Y₂O₃Chemical composition of stabilized zirconia₂The mass percentage of the mullite is 94-96 wt%, and Al in the chemical composition of the electrofused mullite₂O₃69-72 wt% of SiO₂The mass percentage of the two raw materials is 26-30%, and the particle size of the two raw materials is less than or equal to 0.08 mm; er₂O₃、K₂Ti₆O₁₃The zirconia gel is all industrial pure, and the particle size is less than or equal to 5 mu m.

The preparation process of the micro-nano pore insulating and heat-insulating refractory material containing zirconia in the embodiment 12 is as follows:

(1) monoclinic zirconia is used as a basic raw material; then weighing allyl ether type polycarboxylic acid dispersant, melamine formaldehyde polycondensate and Y₂O₃、CeO₂、BaO、TiO₂And pouring into a planetary mixer and dry-mixing for 5min to obtain the additive.

(2) Weighing polyamide type Dendrimer surfactant, zirconia gel, potassium alginate, ethyl cellulose ether and hydroxymethyl cellulose ether, pouring into a double-cone mixer, and mixing for 5min to obtain a uniform foaming composition.

(3) Pouring the basic raw materials and the additives obtained in the step (1) into a roller ball mill, adding 0.2 ton of water, carrying out ball milling and mixing for 0.5h to ensure that the average particle size of solid particles is not more than 74 mu m, then carrying out ultrasonic oscillation for 5min (the ultrasonic power is 2000W) to obtain uniform suspension slurry, then adding the foaming composition obtained in the step (2) into the suspension slurry, and mixing for 8min by a stirring paddle in a stirrer at the linear speed of 20m/s to obtain uniform foam slurry; during ball milling, the grinding balls in the ball mill adopt tungsten carbide balls or large balls

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.

(4) and (4) injecting the foam slurry obtained in the step (3) into a glass mold, and curing for 0.1 hour in an environment with the air temperature and the relative humidity of 35 ℃ and 99.9% respectively until the foam slurry is cured.

(5) Demoulding the solidified green body, and removing liquid water in the green body by adopting a normal pressure drying method, wherein the drying system is as follows: heating to 30 ℃ at a speed of 2 ℃/min, preserving heat at 30 ℃ for 3h, heating to 50 ℃ at a speed of 2 ℃/min, preserving heat at 50 ℃ for 2h, heating to 70 ℃ at a speed of 3 ℃/min, preserving heat at 70 ℃ for 2h, heating to 90 ℃ at a speed of 3 ℃/min, preserving heat at 90 ℃ for 3h, heating to 110 ℃ at a speed of 3 ℃/min, preserving heat at 110 ℃ for 12h, and obtaining 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 1.0 MPa. And (3) placing the dried blank body into a high-temperature resistance kiln to be fired, raising the temperature from room temperature to 500 ℃ at the heating rate of 3 ℃/min, preserving heat for 0.5h, raising the temperature to 1200 ℃ at 8 ℃/min, preserving heat for 1h, raising the temperature to 1800-1850 ℃ at 3 ℃/min, preserving heat for 2-3 h, then reducing the temperature to 1000 ℃ at 10 ℃/min, preserving heat for 1h, reducing the temperature to 500 ℃ at 6 ℃/min, preserving heat for 0.5h, and finally reducing the temperature to 50 ℃ at 2 ℃/min to obtain the micro-nano-hole heat insulation refractory material containing zirconium oxide.

In example 12, the chemical composition of the monoclinic zirconia was ZrO₂The mass percentage of the composite material is not less than 99 wt%, and the particle size is not less than 0.08 mm; y is₂O₃、CeO₂、BaO、TiO₂The zirconia gel is all industrial pure, and the particle size of the raw materials is less than or equal to 5 mu m.

The preparation process of the micro-nano pore insulating and heat-insulating refractory material containing zirconia in the embodiment 13 is as follows:

example 13 was prepared essentially as in example 12 except that the ingredients were formulated without the addition of mineralizers and infrared opacifiers.

The preparation process of the micro-nano pore insulating and heat-insulating refractory material containing zirconia in the embodiment 14 is as follows:

(1) weighing corundum-zirconia, limestone, quicklime, hydrated lime and CaCO₃Pouring into a forced mixer and dry-mixing for 15min to obtain a basic raw material; FS10, FS20, aliphatic dispersant, sucrose, dextrin, tris (hydroxymethyl) aminomethane, polyvinyl alcohol and polyacrylamide are weighed, poured into a double cone mixer and dry-mixed for 5min to obtain the additive.

(2) Weighing double-chain Bola surfactant, alpha-olefin sodium sulfonate, fatty alcohol-polyoxyethylene ether sodium carboxylate, monocalcium aluminate, dodecacalcium heptaluminate, vinyl acetate-ethylene copolymer, sodium alginate, carboxymethyl hydroxymethyl cellulose ether and carboxymethyl hydroxypropyl cellulose ether, pouring into a V-type mixer, and mixing for 5min to obtain the uniform foaming composition.

(3) Pouring the basic raw materials and the additives obtained in the step (1) into a stirrer, adding 1.6 tons of water, and stirring and mixing for 0.5h to obtain suspended slurry; and (3) adding the foaming composition obtained in the step (2) and alumina sol into the suspension slurry, and quickly mixing the mixture for 3min by a stirring paddle at the linear speed of 170m/s to obtain uniform foam slurry.

(4) And (4) injecting the foam slurry obtained in the step (3) into a rubber mold, and curing for 1.5 hours in an environment with the air temperature and the relative humidity of 25 ℃ and 90% respectively until the foam slurry is cured.

(5) 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 1.0 MPa. Firing the dried green body by adopting a high-temperature tunnel kiln, heating to 500 ℃ from room temperature at a heating rate of 3 ℃/min, and preserving heat for 1h at 500 ℃; then heating to 1000 ℃ at the speed of 8 ℃/min, and preserving heat for 1 h; heating to 1470-1480 ℃ at the speed of 5 ℃/min, and keeping the temperature for 3 h; then cooling to 1100 ℃ at a speed of 15 ℃/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 ℃; and finally, cooling to 60 ℃ at a speed of 3 ℃/min to obtain the micro-nano hole heat insulation refractory material containing zirconium oxide.

In the micro-nano-pore heat insulation refractory material containing zirconia obtained in the embodiment, the main crystal phase is zirconia and calcium hexaluminate, and in the used raw materials, ZrO in the chemical composition of zirconia corundum₂23-25 wt% of Al₂O₃The mass percentage of the composite material is 75-77 wt%, and the particle size is less than or equal to 0.05 mm; the mass percentage of CaO in the limestone is 53-55 wt%, and the particle size is less than or equal to 0.05 mm; the mass percentage of CaO in the quicklime is 95-97 wt%, and the particle size is less than or equal to 0.05 mm; the mass percentage of CaO in the hydrated lime is 70-75 wt%, and the particle size is less than or equal to 0.05 mm; CaSO₄The mass percentage of the CaO in the composite is 40-42 wt%, and the particle size is less than or equal to 0.05 mm; al in alumina sol₂O₃The mass percentage content of the composition is not less than 20 percent; the monocalcium aluminate and the dodecacalcium heptaluminate are both industrially pure and have the particle size less than or equal to 5 mu m.

The preparation process of the micro-nano pore insulating and heat-insulating refractory material containing zirconia in the embodiment 15 is as follows:

(1) weighing zircon, industrial alumina and beta-Al₂O₃Wollastonite, dolomite, calcite, CaO, Ca (OH)₂And pouring the mixture into a forced mixer and performing dry mixing for 15min to obtain the basic raw material.

(2) Weighing carboxylate Gemini surfactant, dodecyl dimethyl betaine surfactant, sodium fatty alcohol polyoxyethylene ether carboxylate, dicalcium silicate, sodium silicate, vinyl acetate-vinyl versatate copolymer, gellan gum, carboxymethyl hydroxymethyl cellulose ether, carboxymethyl hydroxyethyl cellulose ether and saponin, pouring into a V-type mixer, and mixing for 5min to obtain the uniform foaming composition.

(3) Pouring the basic raw materials obtained in the step (1) into a stirrer, adding 1.6 tons of water, and stirring and mixing for 0.5h to obtain suspended slurry; and (3) adding the foaming composition obtained in the step (2) and silica sol into the suspension slurry, and quickly mixing the mixture for 3min by a stirring paddle at the linear speed of 180m/s to obtain uniform foam slurry.

(5) 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 1.0 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 1400 ℃ at the speed of 3 ℃/min, and preserving heat 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 ℃; and finally, cooling to 50 ℃ at the speed of 2 ℃/min to obtain the micro-nano hole heat insulation refractory material containing zirconium oxide.

In the micro-nano-pore insulating refractory material containing zirconia obtained in this example 15, the main crystal phases are zirconia and anorthite, and in the used raw materials, ZrO is included in the chemical composition of zircon₂The mass percentage of the SiO is 64-67 percent₂The mass percentage of the composite material is 32-35%, and the particle size is less than or equal to 0.05 mm; industrial Al₂O₃And beta-Al₂O₃Middle Al₂O₃The mass percentage of the composite material is not less than 98 percent, and the particle size is not less than 0.05 mm; the mass percentage of CaO in the wollastonite is 34-37%, and the particle size is less than or equal to 0.05 mm; the mass percentage of CaO in the dolomite is 29-31%, the mass percentage of MgO is 20-21%, and the particle size is less than or equal to 0.05 mm; the mass percentage of CaO in the calcite is 50-52%, and the particle size is less than or equal to 0.05 mm; silica solSiO 2₂The mass percentage content of the composition is not less than 30 percent; CaO and Ca (OH)₂The dicalcium silicate and sodium silicate are all industrial pure materials, and the particle size is less than or equal to 5 mu m.

The preparation process of the micro-nano pore insulating and heat-insulating refractory material containing zirconia in the embodiment 16 is as follows:

the preparation process is basically the same as that in example 15, except that the green body is cured for 5 hours in an environment with air temperature and relative humidity of 25 ℃ and 90% respectively, and then the cured green body is cured and demoulded, and when the green body is dried by normal-pressure hot air, 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 0.5 MPa.

The preparation process of the micro-nano pore insulating refractory material containing zirconia of example 17 is as follows:

(1) the base material and additives were prepared essentially as in example 14, except that dicalcium silicate and calcium dialuminate were incorporated into the base material.

(2) And weighing monocalcium aluminate, dodecacalcium heptaluminate, vinyl acetate-ethylene copolymer, sodium alginate, carboxymethyl hydroxymethyl cellulose ether and carboxymethyl hydroxypropyl cellulose ether, pouring into a V-shaped mixer, and mixing for 5min to obtain the uniform foaming composition. Simultaneously, pre-preparing quaternary ammonium double-chain Bola surfactant, alpha-olefin sodium sulfonate and fatty alcohol-polyoxyethylene ether sodium carboxylate into foam by using a foaming machine;

(3) pouring the basic raw materials and the additives obtained in the step (1) into a stirrer, adding 1.6 tons of water, and stirring and mixing for 0.2h to obtain suspended slurry; and (3) adding the foaming composition obtained in the step (2), the prefabricated foam and the alumina sol into the suspension slurry, and quickly mixing for 3min by a stirring paddle at the linear speed of 170m/s to obtain uniform foam slurry.

Then, the pouring, the body curing, the drying and the firing of the foam slurry are basically the same as those in example 11, and the micro-nano hole heat insulation refractory material containing calcium hexaluminate is obtained. Except that the green body after drying had a compressive strength of 0.7 MPa.

In this example 17, the physical and chemical specifications of the base material and the foaming composition used were the same as those of example 14, and dicalcium silicate and calcium dialuminate were commercially pure and had particle sizes less than or equal to 5 μm.

Second, Experimental example

Experimental example 1

In this experimental example, the appearance of the micro-nano porous insulating refractory material containing zirconium oxide prepared in example 7 was observed, and the appearance picture thereof is shown in fig. 1, and the microstructure picture thereof is shown in fig. 2 and 3.

As can be seen from FIG. 1, the refractory produced in the examples was white and showed no mottling.

As can be seen from FIGS. 2 and 3, the insulating refractory material contains a large number of spherical micro pores with a pore size of less than or equal to 250 μm, and further analysis with reference to FIG. 3 shows that the pore wall structure of the pores is dense (see FIG. 3), and the pore wall is formed by tightly bonding two kinds of particles. EDS analysis revealed corundum (FIG. 4) and zirconia (FIG. 5).

Experimental example 2

In this experimental example, the micro-nano porous heat insulating and refractory material containing zirconium oxide prepared in example 7 was subjected to X-ray diffraction (XRD) analysis, and the XRD spectrum thereof is shown in fig. 6.

As can be seen from the figure, the main crystal phases of the micro-nano hole heat insulation refractory material are zirconia and corundum phases.

Experimental example 3

In this experimental example, the pore diameter of the micro-nano pore heat insulating and fire resisting material containing zirconium oxide prepared in example 7 was analyzed, and the result is shown in fig. 7.

As can be seen from the figure, the refractory brick has small pore diameter and the coexistence characteristic of micro-nano pores, and the pore diameter of the pores is distributed between 0.006 and 200 mu m.

Experimental example 4

In the experimental example, the micro-nano hole heat insulation and fire resistance material containing zirconia prepared in the example is subjected to performance tests such as heat conductivity. 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 performance test of micro-nano-pore heat insulation refractory material containing zirconium oxide in example

According to the test results in table 3, the performance indexes of the micro-nano hole insulating refractory material containing zirconia in the examples are summarized as follows: the bulk density is 0.3 to 3g/cm³The porosity is 50-95%, the closed porosity is 20-70%, the normal temperature compressive strength is 0.6-220 MPa, the room temperature thermal conductivity is 0.02-0.25W/(mK), the thermal conductivity at 350 ℃ is 0.03-0.33W/(mK), part of the formula reaches 0.1-0.13W/(mK), the thermal conductivity at 1100 ℃ is 0.06-0.4W/(mK), the use temperature is less than or equal to 2300 ℃, the re-firing line change rate is-0.4-0% (keeping the temperature at 1400-1732 ℃ for 24h), and part of the formula is-0.1-0%.

Compared with the examples 1-2, the water consumption for introducing the dispersing agent is obviously reduced under the condition that the density of the prepared samples is not different; compared with examples 12-13, the introduction of the infrared opacifier obviously reduces the high-temperature thermal conductivity of the sample; as can be seen from comparison of examples 5-7, the pore diameter of the pores of the sample is effectively reduced with the increase of the regulating dosage of the pores; compared with the examples 3-12, under the condition that the drying strength of the sample blank 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 1-2, the average pore diameter and the volume density of the sample are 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 from comparison of examples 2-12, the density of the sample after burning gradually increases with the decrease of the water consumption; comparing examples 12 and 13, it can be seen that the introduction of the mineralizer gradually reduced the sintering temperature and increased the density of the sample; comparing examples 4 and 5, it can be seen that the appropriate extension of the grinding time results in a finer particle size of the solid particles in the slurry and a lower sintering temperature. Comparing examples 3 and 14-15, it can be seen that after the base material passes through the grinding ball and the suspension slurry is subjected to ultrasound, the sintering performance of the sample is better, the density of the sample is increased, and the strength is remarkably improved. Comparing examples 15 and 16, it can be seen that when no organic curing agent is added, the curing time required for the green body is greatly prolonged, the demolding can be realized, the strength of the dried green body is greatly reduced, the pore diameter of pores in a fired sample is obviously increased, the density and the thermal conductivity are increased, and the total porosity, the closed porosity and the strength are both obviously reduced. As is clear from examples 14 and 17, when the foaming agent is prefoamed, the stirring time of the foam slurry is shortened, but the strength of the green body after drying is weakened, the porosity, pore size distribution and average pore size of the fired product are increased, the bulk density, closed porosity and strength are lowered, and the thermal conductivity is increased.

The insulating refractory material of the embodiment can realize controllability and adjustability in the aspects of pore structure, heat insulation and mechanical properties, and can show more excellent mechanical and insulating 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 the micro-nano pore structure in the zirconium oxide-containing micro-nano pore insulating refractory material, thereby having better practical significance in practical engineering and technical application. The composite material is very suitable for hot surface lining, back lining, filling sealing and heat insulating material of industrial kilns in the industries of metallurgy, petrifaction, building materials, ceramics, machinery and the like, and can also be suitable for heat insulating parts of engine engines, the fields of war industry, aerospace and the like.

Claims

1. The micro-nano hole heat insulation refractory material containing zirconia is characterized by being prepared from a base material, an additive and water; ZrO in articles₂The mass percentage of the component (A) is 5-100%;

the mass of the water is 20-200% of that of the base material.

2. The micro-nano pore heat insulation refractory material containing zirconium oxide according to claim 1, wherein the volume density of the micro-nano pore heat insulation refractory material is 0.3-3 g/cm³The porosity is 50 to 95%, the closed porosity is 20 to 70%, the room-temperature compressive strength is 0.6 to 220MPa, the thermal conductivity at room temperature is 0.02 to 0.25W/(mK), the thermal conductivity at 350 ℃ is 0.03 to 0.33W/(mK), and the thermal conductivity at 1100 ℃ is 0.06 to 0.4W/(mK).

3. The micro-nano pore insulating and fire-resistant material containing zirconium oxide according to claim 1, wherein the base raw material consists of 100% of zirconium oxide raw material in percentage by mass; or 60-95% of zirconia raw material and 5-40% of aluminum-silicon raw material or silicon dioxide raw material or calcium oxide raw material; or the material consists of two of an aluminum oxide material, an aluminum-silicon material, a silicon dioxide material and a calcium oxide material and 40-60% of a zirconia material; or 30-40% of zirconia raw material, 10-30% of alumina raw material, 20-40% of aluminum-silicon raw material and 10-20% of silicon dioxide raw material.

4. The micro-nano hole insulating refractory material containing zirconia according to any one of claims 1 to 3, wherein the zirconia raw material is one or a combination of two or more of zircon, baddeleyite, zirconia corundum, monoclinic zirconia, tetragonal zirconia, cubic zirconia and partially stabilized zirconia; the partially stabilized zirconia is Y₂O₃Stabilized zirconia, Y₂O₃The molar ratio of (A) is 3-9%;

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

the aluminum-silicon material is one or the combination of more than two of mullite, kaolin, bauxite, 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, Guangxi white clay, Suzhou 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.

The calcium oxide material is limestoneQuick lime, hydrated lime, wollastonite, dolomite, calcite, CaO, CaCO₃、Ca(OH)₂、CaSO₄One or a combination of two or more of them;

wherein, Al in the chemical composition of the alumina raw material₂O₃The mass percentage of the component (A) is more than 45%; the aluminum-silicon material comprises 18-90% by mass of aluminum oxide and 8-75% by mass of silicon dioxide; chemical composition of silicon dioxide raw material SiO₂The mass content of (A) is more than 18%; the CaO content in the chemical composition of the calcium oxide raw material is more than 30 percent by mass.

5. The micro-nano hole heat insulation refractory material containing zirconium oxide as claimed in claim 1, wherein the calcium oxide raw material is calcium silicate and/or calcium aluminate, or the calcium oxide raw 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.

6. The micro-nano pore insulating and fire resisting material containing zirconium oxide of claim 1, wherein the cell regulator is one or a combination of more than two of cellulose ether, starch ether, lignocellulose and saponin; the cellulose ether is selected from one or a combination of two or more of methyl cellulose ether, water-soluble cellulose ether, carboxymethyl methyl cellulose ether, carboxymethyl ethyl cellulose ether, carboxymethyl hydroxymethyl cellulose ether, carboxymethyl hydroxypropyl cellulose ether, carboxymethyl hydroxybutyl cellulose ether, hydroxymethyl cellulose ether, hydroxyethyl methyl cellulose ether, ethyl methyl cellulose ether, hydroxyethyl ethyl cellulose ether, propyl cellulose ether, hydroxypropyl methyl cellulose ether, hydroxypropyl ethyl cellulose ether, hydroxypropyl hydroxybutyl cellulose ether, hydroxybutyl methyl cellulose ether, and sulfonic ethyl cellulose ether.

7. The micro-nano hole insulating and refractory material containing zirconium oxide according to claim 1, wherein the inorganic curing agent is selected from zirconium oxide sol, aluminum oxide sol, silicon aluminum sol, zirconium oxide gel, aluminum oxide gel, silicon aluminum gel, dicalcium silicate, calcium dialuminate, SiO₂Micro powder, monocalcium aluminate, tricalcium silicate and Al₂O₃One or more of micro powder, dodecacalcium heptaluminate, tetracalcium aluminoferrite, aluminum phosphate and water glass;

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.

8. The micro-nano hole insulating and fire-resistant material containing zirconium oxide according to claim 1, wherein the foaming agent is a surfactant and/or a protein type 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 protein foaming agent is an animal protein foaming agent, a plant protein foaming agent and/or a sludge protein foaming agent.

9. The micro-nano-pore insulating and fire-resistant material containing zirconia according to claim 1 or 8, wherein the foaming agent is one or more of sulfonate anionic surfactants having 8 to 20 carbon atoms, sulfate anionic surfactants having 8 to 18 carbon atoms, amide ester quaternary ammonium salt cationic surfactants, double-long-chain ester quaternary ammonium salt cationic surfactants, triethanolamine stearate quaternary ammonium salt cationic surfactants, polyoxyethylene nonionic surfactants, fatty alcohol amide nonionic surfactants, polyhydric alcohol nonionic surfactants, amino acid zwitterionic surfactants and betaine zwitterionic surfactants.

10. The micro-nano hole heat insulation refractory material containing zirconium oxide according to claim 1, wherein the addition mass of the dispersing agent is not more than 3% based on the mass of the base material; the dispersant is one or more than two of polycarboxylic acid dispersant, sodium polyacrylate, naphthalene dispersant, FS10, FS20, lignin dispersant, sulfonated melamine polycondensate, melamine formaldehyde polycondensate, aliphatic dispersant, sulfamate dispersant, sodium citrate, sodium polyphosphate, sodium hexametaphosphate and sodium carbonate.

11. The micro-nano hole heat insulation refractory material containing zirconium oxide according to 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 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, cetyl alcohol, sucrose, dextrin, tris (hydroxymethyl) aminomethane, microcrystalline cellulose sodium, cellulose fiber, cellulose nanocrystal and soluble starch.

12. The micro-nano pore insulating and refractory material containing zirconium oxide according to claim 1, wherein the mineralizer is selected from CaO and CaF₂、MgO、ZnO、Fe₂O₃、YbO、V₂O₅、AlF₃、SiF₄、MnO₂、TiO₂、CuO、CuSO₄、SrO、BaO、WO₃、Er₂O₃、Cr₂O₃、La₂O₃、Yb₂O₃、Y₂O₃、CeO₂One or a combination of two or more of them.

13. The micro-nano pore insulating and fireproof material containing zirconium oxide according to claim 1 or 12, wherein the infrared opacifier is selected from rutile and TiO₂、TiC、K₄TiO₄、K₂Ti₆O₁₃、Sb₂O₃、Sb₂O₅、ZnO₂、NiO、NiCl₂、Ni(NO₃)₂、CoO、CoCl₂、Co(NO₃)₂、ZrSiO₄、Fe₃O₄、B₄C. One or a combination of two or more of SiC.

14. The preparation method of the zirconium oxide-containing micro-nano hole insulating refractory material according to any one of claims 1 to 13, comprising the following steps:

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

15. The method for preparing the zirconium oxide-containing micro-nano hole insulating refractory material according to claim 14, wherein in the step 1), the average particle size of solid particles in the suspension slurry 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.

16. The preparation method of the micro-nano hole insulating and fire-resistant material containing zirconium oxide according to claim 14, wherein in the step 2), the linear velocity of the outer edge of the stirring paddle is 20-200 m/s, or 50-200 m/s, or 80-200 m/s, or 100-200 m/s, or 150-200 m/s, or 180-200 m/s during stirring, shearing and foaming.

17. The preparation method of the zirconium oxide-containing micro-nano hole insulating and fire-resisting material as claimed in claim 14, wherein 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.

18. The preparation method of the zirconium oxide-containing micro-nano hole insulating and refractory material according to claim 14, wherein in the step 3), the green body is dried by one or a combination of two or more groups selected from atmospheric drying, supercritical drying, freeze drying, vacuum drying, infrared drying and microwave drying; drying the green body until the water content is less than or equal to 3 wt%, and the compressive strength of the dried green body is greater than or equal to 0.7 MPa.

19. The preparation method of the zirconium oxide-containing micro-nano hole insulating refractory material as claimed in any one of claims 14 to 18, wherein the firing is performed in a high temperature tunnel kiln, a shuttle kiln, a resistance kiln or a microwave kiln; the sintering temperature is 1350-1850 ℃.