CN114149276B

CN114149276B - Micro-nano Kong Jue heat-insulating refractory material containing zirconia and preparation method thereof

Info

Publication number: CN114149276B
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: 2023-06-13
Anticipated expiration: 2041-12-31
Also published as: CN114149276A

Abstract

The invention belongs to the field of refractory materials, and particularly relates to a micro-nano Kong Jue heat-insulating refractory material containing zirconium oxide and a preparation method thereof. The micro-nano Kong Jue heat-insulating refractory material containing zirconium oxide is prepared from a basic raw material, an additive and water; zrO in refractory materials ₂ The mass content of (2) is 5-98%. The micro-nano Kong Jue heat-insulating refractory material containing zirconium oxide has white, light yellow or light pink appearance, spherical air holes with the pore diameters distributed between 0.006 and 250 mu m and the average pore diameter of 0.1 to 20 mu m, and the existence of the micro-nano pore structure ensures the good heat-insulating performance of the product under the conditions of 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 control accurately, 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 consumption and the process of each raw material.

Description

Micro-nano Kong Jue heat-insulating refractory material containing zirconia and preparation method thereof

Technical Field

The invention belongs to the technical field of refractory materials, and particularly relates to a micro-nano Kong Jue heat-insulating refractory material containing zirconium oxide and a preparation method thereof. In particular to a micro-nano Kong Jue heat-insulating refractory material containing zirconia, which has a micro-nano size pore structure, ultra-low heat conduction and volume density, high porosity and high strength and is prepared in a green and controllable way.

Background

The high-temperature industry is the main energy-consuming industry in the industrial production of China, the low heat energy utilization rate of various kilns is the main reason for high energy consumption, if the average heat efficiency can be improved by 20% according to the national requirements, 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. To improve the heat efficiency of the industrial kiln, the most important is to develop a high-efficiency heat preservation technology, and the advanced heat insulation material is adopted to strengthen 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 severe heat insulation environment and requirements of the high-temperature industry. At present, the heat insulation material for the kiln is mostly made of refractory fiber products or light heat insulation bricks.

Although the heat insulation performance of the refractory fiber product is good, the refractory fiber product is sensitive to firing atmosphere and is easy to react with reducing and corrosive gases, so that the refractory fiber product loses good heat insulation performance; the composite particles are easy to devitrify and grow up after long-term service in a high-temperature environment, stress concentration is caused, pulverization of the heat insulation layer is caused, and the service life is shortened; in addition, ceramic fibers are also dangerous to human health and have been classified by the European Union as secondary carcinogens.

Although the traditional light heat-insulating brick can overcome the defects of refractory fiber products, the light heat-insulating brick is mostly prepared by a method of adding a large amount of pore formers (such as polystyrene particles, sawdust, charcoal, smokeless coal ash, coke powder and the like), the pore formers occupy a certain space in a green body, and after being burnt, the pore formers leave the original position in a matrix to form pores, so that the light heat-insulating refractory material is obtained, the method is simple and easy to control, and the production efficiency is higher, but the product prepared by the method has low porosity, larger pore diameter of the pores, poorer heat-insulating effect and easy cracking caused by stress concentration, and the strength is lower. In addition, most pore formers adopted in the preparation process are organic lost materials, so that the cost of raw materials is high, a large amount of toxic and harmful gases such as anthracite, sawdust, coke powder and the like are emitted during sintering, a large amount of sulfur oxides can be generated at a lower temperature, polystyrene particles generate styrene, toluene, nitrogen/carbon/oxides, dioxin and the like, and a large amount of VOCs fine particles can be generated at the same time, so that the environment is seriously polluted, and the human health and the production of surrounding crops are endangered. In recent years, with the continuous enhancement of environmental conservation and control in China, a plurality of enterprises have reduced production or shut down. Therefore, research and development of novel insulating refractory materials for high-temperature industry, which are excellent in heat insulation, durability and mechanical properties and are prepared in a green and controllable manner, 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 the emerging materials which are developed faster in recent years, and is gradually applied to the fields of metallurgy, electronics, environmental protection, biology, chemical industry, aerospace and the like. If the pore can be effectively introduced into the zirconia material, the thermal conductivity of the zirconia porous ceramic 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 heat preservation in high-temperature environments, heat insulation components of engine and the like, and particularly for the application field in ultra-high-temperature environments above 1800 ℃.

The present subject group has been studied in a large number of applications in the early stage for lightweight heat-insulating refractory materials, and has formed research results such as microporous kyanite-based lightweight heat-insulating refractory materials (CN 103951452 a), microporous lightweight silica bricks (CN 105565850 a), and the like. The zirconia heat-insulating refractory material is a high-temperature-resistant heat-insulating ceramic material with low heat conductivity coefficient, good heat-insulating effect and higher melting point, but because the density of the zirconia is higher (5.89 g/cm) ³ ) It is therefore difficult to produce a low density, high porosity insulation product. Under the same strength grade, how to further effectively reduce the volume density and the heat conductivity of the heat insulation refractory material, thereby being beneficial to the construction of the light environment-friendly kiln and becoming the focus of the next research.

Disclosure of Invention

The invention aims to provide a micro-nano Kong Jue heat-insulating refractory material containing zirconia, which has the characteristics of micro-nano size pore diameter, 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 meets the requirement, thereby being beneficial to the construction of the light environment-friendly high-grade kiln.

The second object of the invention is to provide a method for preparing the zirconia-containing micro-nano Kong Jue heat-insulating refractory. The preparation method has the advantages of green and pollution-free process, easy and accurate control of the structure and performance of the product, higher yield and capability of solving the problem that the heat-insulating refractory material obtained by the existing preparation method cannot be compatible with low heat conduction, low volume density and high strength and high yield.

In order to achieve the purpose, the technical scheme of the zirconia-containing micro-nano Kong Jue heat insulation refractory material is as follows:

a zirconia-containing micro-nano Kong Jue heat insulating refractory material, wherein the zirconia-containing micro-nano Kong Jue heat insulating refractory material is prepared from a base material, an additive and water. ZrO in articles ₂ The mass percentage of the (B) is 5-100%;

the basic raw materials consist of 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 comprises at least foaming material, and the additive is 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% based on the mass of the base material; when the additive is used, the additive is one or more than two of dispersing agent, suspending agent, mineralizer and infrared opacifier, and the 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 the mass of the base material.

The dispersing agent, the suspending agent, the infrared opacifier and the mineralizer form additives, and compared with the additive components of the basic raw materials, the dispersing agent and the suspending agent promote the formation of stable and uniformly dispersed suspension slurry during the pulping of the refractory materials; 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 the further improvement of the mechanical properties of materials.

The foaming agent, the inorganic curing agent, the organic curing agent and the foam pore regulator form a foaming material, and are mainly used for forming micro-nano size pore structures in the heat insulation refractory material, and are important components of raw materials used for the zirconia-containing micro-nano Kong Jue heat insulation refractory material, so that the product finally presents micro-nano size pore diameters, and the good heat insulation performance of the product under the conditions of lower volume density and high strength is ensured.

The micro-nano Kong Jue heat-insulating refractory material containing zirconia provided by the invention has the appearance of white, light pink or light yellow, and the product can contain mullite phase, corundum phase and/or quartz besides zirconia. The volume density of the refractory material is 0.3-3 g/cm ³ The porosity is 50 to 95%, the closed porosity is 20 to 70%, the normal temperature compressive strength is 0.6 to 220MPa, the thermal conductivity at room temperature is 0.02 to 0.25W/(m.K), the thermal conductivity at 350 ℃ is 0.03 to 0.33W/(m.K), the thermal conductivity at 1100 ℃ is 0.06 to 0.4W/(m.K), the burn-out line change rate of the heat preservation at 1400 to 1732 ℃ for 24 hours is-0.4 to 0%, preferably-0.3 to 0%, more preferably-0.2 to 0%, and even more preferably-0.1 to 0% when the temperature is less than or equal to 2300 ℃. In the insulating refractory material, pore diameters are distributed between 0.006 and 250 mu m, the average pore diameter is between 0.1 and 20 mu m, and the spherical pore structure with micro-nano size ensures the good insulating performance of the product under the conditions of low volume density and high strength.

Compared with the prior art, the zirconia micro-nano Kong Jue 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 shaped heat-insulating refractory product containing zirconia with the best heat-insulating performance, and has excellent comprehensive performance, so that the heat-insulating refractory material can be mainly used for a hot-face lining, a backing, filling sealing and heat-insulating material of an industrial kiln 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, military industry, aerospace and the like. And because the heat conductivity coefficient is extremely low, the thickness of the furnace wall of the kiln can be greatly reduced under the condition of meeting the requirement of the ambient temperature, thereby greatly reducing the weight of the kiln, accelerating the temperature rising rate of the kiln and being beneficial to the construction of a novel light environment-friendly kiln.

Further preferably, the base stock is composed of 100% zirconia material by mass percent; or is composed of 60-95% of zirconia raw material and 5-40% of aluminum-silicon raw material or silica raw material or calcia raw material; or two of alumina raw material, aluminum-silicon raw material, silicon dioxide raw material or calcium oxide raw material (the mass ratio of the two raw materials is (1-2) and (1-2)) and 40-60% of 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 silica raw material;

The zirconia material mainly provides ZrO ₂ The component can be one or more than two of zircon, baddeleyite, zirconia corundum, monoclinic zirconia, tetragonal zirconia, cubic zirconia and partially stabilized zirconia; the partially stabilized zirconia is Y ₂ O ₃ Stabilized zirconia, Y ₂ O ₃ The molar ratio of (2) is 3-9%.

The Al in the product can be effectively supplemented by introducing proper alumina raw materials into the basic raw materials ₂ O ₃ The content is as follows. Preferably, the alumina raw material is alumina raw material or can be decomposed to generate Al at high temperature ₂ O ₃ Al in the chemical composition of the alumina-containing raw material ₂ O ₃ The mass percentage content of (2) is higher than 85%. Further preferred, wherein Al ₂ O ₃ The mass percentage of the (B) is 95-99.9%. More preferably, wherein Al ₂ O ₃ The mass percentage of the catalyst is 98-99%.

The alumina raw material is specifically industrial alumina, beta-Al ₂ O ₃ 、γ-Al ₂ O ₃ 、δ-Al ₂ O ₃ 、χ-Al ₂ O ₃ 、κ-Al ₂ O ₃ 、ρ-Al ₂ O ₃ 、θ-Al ₂ O ₃ 、η-Al ₂ O ₃ 、α-Al ₂ O ₃ Fused corundum powder, sintered corundum powder and plate-shaped corundumOne or more of the powders. Preferably, it is industrial alumina, gamma-Al ₂ O ₃ 、α-Al ₂ O ₃ At least one of sintered corundum powder.

The alumina source used in the base stock may also be an alumina-containing source capable of decomposing to form alumina at elevated temperatures, preferably Al in the chemical composition of the alumina-containing source ₂ O ₃ The mass percentage of (2) is more than 45 percent. Further preferably, al is present in the chemical composition of the alumina-containing feedstock ₂ O ₃ The mass percentage of the (C) is 65-87%.

Can decompose to Al at the high temperature ₂ O ₃ The alumina-containing raw material is one or more of aluminum hydroxide, boehmite, diaspore, aluminum n-butoxide, 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 0.08mm. The alumina material with the granularity has higher surface activity and is easy to be matched with surrounding ZrO at high temperature ₂ CaO, caO-rich SiO ₂ Or is rich in SiO ₂ And (3) carrying out liquid phase reaction to generate zirconia corundum, calcium hexaluminate, anorthite or mullite crystals.

Provision of Al from an aluminum-silicon feedstock ₂ O ₃ 、SiO ₂ The components are beneficial to the generation of mullite or anorthite crystals at high temperature, promote the sintering and facilitate the improvement of the mechanical properties of the material. The aluminum-silicon raw material can be selected from one or more than two of mullite, kaolin, bauxite, homogeneous material, coal gangue, kyanite, andalusite, sillimanite, pyrophyllite, potash feldspar, albite, celadon, porcelain stone, alkali stone, mica, spodumene, perlite, montmorillonite, illite, halloysite, dickite, flint clay, guangxi white clay, suzhou soil, mujingsu clay, fly ash and floating beads; further preferably, al in the chemical composition of the aluminum-silicon feedstock ₂ O ₃ The mass percentage of the silicon dioxide is 32-72%, siO ₂ The mass percentage of the (B) is 25-64%. Still more preferably, al in the chemical composition of the aluminum-silicon feedstock ₂ O ₃ The mass percentage of the SiO is 38-50 percent ₂ The mass percentage of the (B) is 45-58%.

The SiO in the product can be effectively supplemented by properly introducing proper silica raw materials into the basic raw materials ₂ The content promotes sintering and is beneficial to improving the mechanical property of the material. Preferably, the silica material is a silica material or a silica-containing material, and the chemical composition of the silica material is SiO ₂ The mass percentage content of (2) is higher than 80%. Preferably, wherein SiO ₂ The mass percentage of the (B) is 90-99.9%.

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

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

The silica material in the base material can also be a material which can decompose to form SiO at high temperature ₂ Silica-containing raw material of (1), siO in the silica-containing raw material ₂ The mass percentage content is more than 18 percent. Preferably, the above can decompose to form SiO ₂ The raw materials of (1) are one or more of rice husk, carbonized rice husk, rice husk ash, methyl orthosilicate, ethyl orthosilicate and methyltrimethoxysilane.

The particle size of the silica raw material is less than or equal to 0.08mm. The silica material with the particle size is easy to react with the surrounding calcareous, alumina or zirconia material and the like at high temperature to generate anorthite, mullite or zirconium silicate and other crystals.

Proper introduction of the proper calcia raw material into the basic raw material can generate a small amount of anorthite or calcium hexaluminate and other beneficial crystals in the product, which is beneficial to the weight reduction of the sample and the further reduction of the thermal conductivity coefficient of the material. The calcareous raw material is stoneLimestone, quicklime, slaked lime, wollastonite, dolomite, calcite, caO, caCO ₃ 、Ca(OH) ₂ 、CaSO ₄ One 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, limestone, quicklime, slaked lime, wollastonite, dolomite, calcite, caO and CaCO ₃ 、Ca(OH) ₂ 、CaSO ₄ One or a combination of two or more of them. The calcium silicate is nCaO.SiO ₂ The calcium aluminate is mCaO qAl ₂ O ₃ ·pFe ₂ O ₃ . Where n=1 to 4, m=1 to 12, q=1 to 7,p =0 to 2.

The particle size of the calcium oxide raw material is less than 0.08mm. The calcia material with the granularity has higher surface activity, and is easy to be mixed with surrounding alumina or Al-rich at high temperature ₂ O ₃ -SiO ₂ And (3) liquid phase reaction to generate crystals such as calcium hexaluminate or anorthite.

Wherein, al in the chemical composition of the alumina raw material ₂ O ₃ The mass percentage of (2) is more than 45%; the mass percentage of alumina in the aluminum-silicon raw material is 18-90%, and the mass percentage of silicon dioxide is 8-75%; siO in chemical composition of silica raw material ₂ The mass content of (2) is more than 18%; the mass content of CaO in the chemical composition of the calcia raw material is more than 30%.

The cell regulator is one or more selected from cellulose ether, starch ether, lignocellulose and saponin. The cellulose ether is selected from one or more of methyl cellulose ether, water-soluble cellulose ether, carboxymethyl ethyl cellulose ether, carboxymethyl hydroxymethyl 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 ethyl cellulose ether sulfonate. The bubble regulator is matched with the foaming agent to effectively regulate the size, the circularity, the uniformity, the closure and the like of bubbles in slurry, so as to achieve the effect of effectively and accurately regulating the pore structure in the burnt product.

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 adding amount is large, most of water can be converted into a liquid film of bubbles in slurry in the stirring process, and a small part of water does not become the liquid film of bubbles, and the liquid water exists in a liquid state, so that tiny capillary pores can be left in a sample after a green body is dried and burned. That is, the added water is finally converted into micro-nano size air holes in the product, so that the essence of the process technology for preparing the insulating refractory material is that the micro-nano size spherical air hole structure is generated in the high temperature resistant material by utilizing water and air, and the volume density, the porosity, the thermal conductivity, the mechanical strength and other performances of the product can be correspondingly regulated and controlled according to the water consumption to a certain extent. In this step, if components such as a dispersing agent, a suspending agent, a mineralizing agent, an infrared light shielding agent and the like are used, the above components and a base material are dispersed into a suspension slurry. If no dispersing agent, suspending agent, mineralizer, infrared opacifier and other components are used, or only one or more of the components 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, siO ₂ Micro powder, tricalcium silicate, monocalcium aluminate and Al ₂ O ₃ One or more of micropowder, dodecacalcium heptaluminate, tetracalcium aluminoferrite, aluminum phosphate and water glass. Among the above raw materials, the water glass contains sodium silicate, or potassium silicate, or a combination of both. SiO (SiO) ₂ The micro powder not only plays a role of an inorganic curing agent, but also serves as a silica raw material. Al (Al) ₂ O ₃ The micro powder not only plays a role of an inorganic curing agent, but also serves as an alumina raw material. Dicalcium silicate, calcium dialuminate, tricalcium silicate, tricalcium aluminate, monocalcium aluminate, tetracalcium aluminoferrite and dodecacalcium heptaluminate serve as inorganic curing agents and calcium raw materials. Silica alumina sol in the inorganic curing agent is also called as alumina silica sol.

The average particle size of the inorganic hardener particles is less than or equal to 5. Mu.m, preferably less than or equal to 4. Mu.m, more preferably less than or equal to 3. Mu.m, more preferably less than or equal to 2. Mu.m, particularly preferably less than or equal to 1. Mu.m, and even more preferably less than or equal to 100nm; the inorganic curing agents are all industrially pure. In the silica sol, siO ₂ The mass percentage of (C) is larger than or equal to 25 percent. Al in alumina sol ₂ O ₃ The mass percentage content of (2) is not less than 20%; al in silica-alumina sol ₂ O ₃ The mass percentage of (2) is not less than 30 percent, siO ₂ The mass percentage content of (2) is not less than 20%; zrO in zirconia sol ₂ The mass percentage of (C) is not less than 10 percent. The inorganic curing agents can permeate into gaps among ceramic powder particles after hydration, and mechanically embed and fix the powder particles to form a good rigid framework structure, so that the mechanical strength of a green body is increased.

The organic curing agent is selected from one or more than two of water-soluble polymer resin, low methoxy pectin, carrageenan, hydroxypropyl guar gum, locust bean gum, gellan gum, curdlan, alginate and konjak gum; the water-soluble polymer resin is selected from one or more than two of vinyl acetate homopolymer, acrylic ester polymer, copolymer of ethylene and vinyl acetate, copolymer of ethylene and vinyl chloride, copolymer of vinyl acetate and vinyl versatate, copolymer of acrylic ester and styrene, copolymer of vinyl acetate and vinyl higher fatty acid, copolymer of isobutene and maleic anhydride, copolymer of ethylene and vinyl chloride and vinyl laurate, copolymer of vinyl acetate and ethylene and higher fatty acid, copolymer of vinyl acetate and ethylene and vinyl laurate, copolymer of vinyl acetate and acrylic ester and vinyl higher fatty acid, copolymer of vinyl acetate and vinyl versatate and acrylic ester. The organic curing agents are all water-soluble substances. A small amount of organic curing material is dispersed into gaps among ceramic powder particles, and after hydration, a continuous polymer film can be formed on the surfaces of the ceramic powder particles, wherein the film forms flexible connection among the powder particles, and the cohesive force among the ceramic powder particles is increased by intermolecular force of organic molecules, so that the green strength is improved, the damage and damage of a blank body in the carrying process are avoided, and the yield is greatly improved.

Generally, since the inorganic curing agent generates a liquid phase at a higher temperature to lower the softening temperature of the product, the amount of the inorganic curing agent should be gradually reduced along with the gradual increase of the firing and use temperatures, and the amount of the organic curing agent should be correspondingly increased in a proper amount to increase the strength of the green body. When preparing high-density samples, the amount of curing agent required is correspondingly reduced due to the shorter spacing of the ceramic powder particles in the green body.

The foaming agent is a surfactant and/or a protein foaming agent, and the foaming multiple is 8-60 times; the surfactant is one or more selected from cationic surfactant, anionic surfactant, nonionic surfactant, amphoteric surfactant, gemini surfactant, bola surfactant and Dendrimer 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 than two of Gemini type surfactant, bola type surfactant, dendrimer type surfactant, protein type foaming agent, sulfonate anionic surfactant with 8-20 carbon atoms in the carbon chain, sulfate anionic surfactant with 8-18 carbon atoms in the carbon chain, amido 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, polyol type nonionic surfactant, amino acid type amphoteric ionic surfactant and betaine type amphoteric ionic surfactant. The foaming times of the foaming agent are 8-60 times.

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

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

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

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

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

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

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

Preferably, the foaming agent is selected from one or 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, alpha-olefin sulfonate, high-carbon fatty alcohol polyoxyethylene ether sodium carboxylate, dodecyl dimethyl betaine, fatty alcohol polyoxyethylene ether, fatty alcohol polyoxyethylene ester, double-chain Bola surfactant, alkylphenol polyoxyethylene ether, polyether type Dendrimer surfactant, sodium dodecyl polyoxyethylene ether carboxylate, sodium laureth carboxylate, polyamide type Dendrimer surfactant and fatty alcohol polyoxyethylene ether sodium carboxylate.

The selection of the respective raw materials in the additive is described below.

The addition mass of the dispersing agent is not more than 3% based on the mass of the base material; the dispersing agent is one or more than two of polycarboxylic acid dispersing agent, sodium polyacrylate, naphthalene dispersing agent, FS10, FS20, lignin dispersing agent, sulfonated melamine polycondensate, melamine formaldehyde polycondensate, sodium citrate, sodium polyphosphate, sodium hexametaphosphate and sodium carbonate. The polycarboxylic acid dispersing agent is at least one of a methacrylate type polycarboxylic acid dispersing agent, an allyl ether type polycarboxylic acid dispersing agent, an amide/imide type polycarboxylic acid dispersing agent and a polyamide/polyethylene glycol type polycarboxylic acid dispersing agent. The lignin dispersing agent is at least one of calcium lignosulfonate, sodium lignosulfonate and calcium potassium lignosulfonate. The amount of the dispersant added is preferably 0.01 to 10%.

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, polyaluminum chloride, polyaluminum sulfate, chitosan, xanthan gum, acacia gum, agar, sucrose, dextrin, acrylamide, polyacrylamide, polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol, casein, cetyl alcohol, sucrose, dextrin, tris (hydroxymethyl) aminomethane, microcrystalline cellulose sodium, cellulose fibers, cellulose nanocrystals and soluble starch. If a clay-type material with plasticity is used as the base material, the slurry has a certain suspending capacity, and the addition of suspending agent can be properly reduced or eliminated. Generally, when organic suspending agents such as polyaluminium chloride, polyaluminium sulfate, chitosan, welan gum, agar, polyethylene glycol, polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone, casein, cetyl alcohol, sucrose, dextrin, microcrystalline cellulose, cellulose fibers, cellulose nanocrystals and the like are selected, the addition of a small amount is found to exert a good effect, and the slurry can generate a suspension effect through a steric hindrance effect or an electrostatic steric hindrance effect in the slurry, so that the addition amount can be relatively small, and generally, the addition amount 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 inorganic mineral raw materials such as bentonite, sepiolite and attapulgite are selected, the inorganic mineral raw materials can be rapidly hydrolyzed in slurry and decomposed into charged ions, the ions form an electric double layer structure on the surfaces of base material particles, the base material particles generate a suspension effect in the slurry by electrostatic repulsive force, but the dosage of the inorganic mineral raw materials is relatively large, and the dosage of the inorganic mineral raw materials is less than or equal to 10 percent.

The mineralizer is CaO and CaF ₂ 、MgO、ZnO、Fe ₂ O ₃ 、YbO、V ₂ O ₅ 、AlF ₃ 、SiF ₄ 、MnO ₂ 、TiO ₂ 、CuO、CuSO ₄ 、SrO、BaO、WO ₃ 、Er ₂ O ₃ 、Cr ₂ O ₃ 、La ₂ O ₃ 、Yb ₂ O ₃ 、Y ₂ O ₃ 、CeO ₂ One 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 even more preferably 100nm or less. The mineralizer can promote the stability of zirconia crystal form and the growth and development of beneficial crystals, reduce the sintering temperature and promote the sintering reaction.

The heat insulating mechanism of the heat insulating refractory material is that a large number of air holes exist in the heat insulating refractory material, and the heat conductivity coefficient of air in the air holes is far smaller than that of the air hole wall, so that the heat transfer rate of the whole heat insulating material to heat is slow, and the heat insulating refractory material has heat insulating performance. The heat conduction mechanism of the material mainly comprises three parts of heat conduction, convection heat conduction and radiation heat conduction, in the invention, because the pore diameter of pores in the prepared zirconia-containing micro-nano Kong Jue heat insulation refractory material is smaller, and most of pores are of a closed structure, the gas circulation is difficult, so that the convection heat conduction can be basically ignored, and because the zirconia-containing micro-nano Kong Jue heat insulation refractory material is mainly used at high temperature, the heat conduction mechanism of the material also comprises radiation heat conduction besides the heat conduction. In order to further effectively reduce radiation heat transfer, the invention introduces an infrared opacifier to increase reflection or absorption of infrared radiation, weaken penetrability and reduce thermal conductivity. Particularly, the heat conduction coefficient of the high-porosity low-heat conduction heat insulation refractory material is obviously reduced. The invention is to further improve the insulating property of the product, preferably, the infrared opacifier is selected from rutile and TiO ₂ 、TiC、K ₄ TiO ₄ 、K ₂ Ti ₆ O ₁₃ 、Sb ₂ O ₃ 、Sb ₂ O ₅ 、ZnO ₂ 、NiO、NiCl ₂ 、Ni(NO ₃ ) ₂ 、CoO、Co(NO ₃ ) ₂ 、CoCl ₂ 、ZrSiO ₄ 、Fe ₃ O ₄ 、B ₄ C. One or a combination of two or more of SiC. The average particle size of the infrared opacifier is less than or equal to 5. Mu.m, preferably less than or equal to 4. Mu.m, more preferably less than or equal to 3. Mu.m, more preferably less than or equal to 2. Mu.m, particularly preferably less than or equal to 1. Mu.m, and even more preferably less than or equal to 100nm. The use amount of the infrared opacifier is preferably 1-10% of the mass of the basic raw material, and the application effect of the infrared opacifier in the heat-insulating refractory material with low volume density and high porosity is more remarkable.

The technical scheme of the preparation method of the zirconia-containing micro-nano Kong Jue heat-insulating refractory material is as follows:

a preparation method of a micro-nano Kong Jue heat-insulating refractory material containing zirconia comprises the following steps:

1) When the additive is used, the basic raw materials, the additive combination and water are mixed and dispersed to prepare suspension slurry; when no additive is used, the basic raw material and water are mixed and dispersed to prepare suspension slurry;

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

3) Injecting the foam slurry into a mould for curing (curing and shaping) and demoulding to obtain a blank; and drying and sintering the green body.

In the preparation method of the invention, the basic material, the additive and the water are mixed to form suspension slurry, and then the suspension slurry is mixed with the functional foaming components consisting of the foaming agent, the inorganic curing agent, the organic curing agent and the foam pore regulator to be stirred and foamed, so that the integrity of bubbles is maintained, and the generation rate of closed-type air holes is improved; in the solidification process, 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 perfect, and the product performance is improved. Meanwhile, the inventor also discovers accidentally in the long-term research process that as the holes in the blank body manufactured by the invention are tiny micro-scale or nano-scale spherical gaps, the concave surfaces of the holes have extremely large curvature radius, so that the nucleation and growth driving force of beneficial crystals in the holes 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 zirconia-containing micro-nano Kong Jue heat-insulating refractory material is environment-friendly and pollution-free, and the preparation process is simple and easy to control. The product has a micro-nano-sized air hole structure, and can effectively regulate and control volume density, mechanical strength, porosity, thermal conductivity and the like in a larger range. The compressive strength and the insulating property of the product are improved by more than several times under the condition of volume density and porosity similar to those of the prior art, and the product is more suitable for the application requirements of modern kilns and equipment on light, high-strength and ultra-low heat conduction insulating refractory materials.

In the preparation method of the invention, taking the additive as an example, in the step 1), the basic raw materials, the dispersing agent, the suspending agent and the mineralizing agent are premixed first, and then water is added for mixing to prepare suspension slurry. In order to form a fine, uniform and stable suspension slurry, the average particle diameter of the solid particles in the suspension slurry should be controlled to be not more than 1mm, preferably not more than 74. Mu.m. To achieve the above mixing effect, one or a combination of mechanical stirring, ball milling, ultrasonic and other means can be adopted for mixing. When the raw materials have finer granularity and are easy to disperse to obtain suspension slurry, the suspension slurry can be obtained by a simple mechanical stirring mode. More preferably, the dispersant, the suspending agent and the mineralizer are premixed to obtain the additive, and then the additive is mixed with the basic raw materials and the water; preferably, the base material and additive combination are ball milled with water. Further preferably, in order to obtain a more uniform suspension slurry, the slurry after ball milling may be subjected to ultrasonic dispersion. Wherein the zirconia raw material, the aluminum-silicon raw material, the alumina raw material, the silica 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 equal to or greater than 95%, preferably equal to or greater than 99%. Similarly, the five materials of the base materials are preferably pre-mixed in the same manner as the use.

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

Middle ball->

Ball->

Large, medium and small ball (1-1.5): (1-3): (6-10) by weight ratio. Further preferably, the ratio of the large, medium and small spheres is (1 to 1.5): (1-2): (6-8) in a weight ratio. 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 diameter of not more than 50. Mu.m; further preferably, the average particle diameter of the solid particles is not more than 44 μm; more particularly, the average particle diameter of the solid particles is not more than 30. Mu.m. The inventor finds that the ball-milled ceramic powder particles have higher surface activity, and then have excellent hydrophobic property after being modified by surfactant (foaming agent) molecules, and can be irreversibly adsorbed on a gas-liquid interface on a bubble liquid film under the action of mechanical stirring, the gas-liquid interface with high energy state is replaced by a liquid-solid interface with low energy state and a gas-solid interface, so that the total free energy of the system is reduced, the foam stability is improved, and meanwhile, the inventor also finds that part of powder particles accumulate in Plateau channels among bubbles, liquid film liquid drainage is effectively prevented, and unstable factors such as foam rupture, liquid drainage, disproportionation, oswald ripening and the like are resisted, so that the very stable foam ceramic slurry is obtained.

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

In the step 2), according to the variety of raw materials, if the foaming agent, the inorganic curing agent, the organic curing agent and the foam pore regulator are all dry solid raw materials, dry mixing the dry raw materials to prepare a foaming composition, adding the foaming composition into the suspension slurry, and stirring for foaming. If some of the foaming agent, inorganic curing agent, organic curing agent, and cell regulator are liquid materials, it is preferable that dry solid materials be dry-blended first, then the dry blend and liquid materials be added to the suspension slurry, and then stirring, shearing and foaming be performed. The foaming agent can also be prepared into foam by a foaming machine, and then the foam is added into the suspension slurry obtained in the step 1 together with a mixture composed of an inorganic curing agent, an organic curing agent and a foam cell regulator, and then the suspension slurry is further stirred, sheared and foamed.

Preferably, in the step 2), the stirring foaming is stirring, shearing and mixing foaming at a high speed by adopting 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 (5) rapidly mixing for 1-30 min by using a stirring paddle of a stirrer. The shearing line speed is the line speed of the outer edge of the stirring paddle blade, the stirring paddle rapidly stirs, mixes and entrains air in the slurry, so that the volume of the slurry is rapidly expanded, and the time is prolonged, the large bubbles in the slurry are gradually sheared into small bubbles with the diameter of 0.01-200 mu m, and the suspended slurry becomes uniform foam slurry. After the foam slurry is solidified and dried, the small bubbles in the slurry are converted into spherical closed air holes in the dried blank, and the spherical air hole structure can provide development space for the growth of zirconia and other beneficial crystals in the sintered product, thereby being beneficial to the growth perfection of the crystals and the improvement of the mechanical properties 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, still more preferably 100 to 200m/s, particularly preferably 150 to 200m/s, and still more particularly preferably 180 to 200m/s.

In step 3), the casting mold is selected from one or more of the following, but is not limited to: metal mold, plastic mold, resin mold, rubber mold, polyurethane mold, polystyrene foam mold, gypsum mold, glass fiber reinforced plastic mold, wood mold, bamboo mold, or bamboo colloid mold, and mold compounded with the above materials.

The shape of the mould 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 to 24 hours, preferably 0.1 to 2 hours at a temperature of 1 to 35 ℃ and a humidity of 40 to 99.9%. The curing is preferably performed in a constant temperature and humidity environment. In the curing process, the foam slurry is quickly solidified and shaped, and then can be demoulded and dried. During curing, the air temperature is preferably 5 to 30 ℃, more preferably 10 to 30 ℃, more preferably 20 to 30 ℃, particularly preferably 25 to 30 ℃, and more particularly preferably 25 to 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 green body can accelerate hydration reaction and curing coagulation, so that the strength of the green body is rapidly increased, and quick demoulding is realized.

Researches show that the demolding time of the blank is very short, so that the turnover rate of the mold is greatly increased, the whole preparation process is accelerated to run, and the production efficiency is greatly improved, which is difficult to realize in the past.

It will be appreciated that the green body needs to be demolded and then dried after curing. 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 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 percent. In the process, the combined action of the organic curing agent and the inorganic curing agent greatly improves the strength of the blank body obtained after the foam slurry is cured and dried, the compressive strength of the dried blank body is not less than 0.7MPa, the damage to the blank body caused by collision in the carrying and kiln loading processes can be avoided or greatly reduced, the yield is greatly improved, the yield is not less than 90%, preferably not less than 95%, more preferably not less than 98%, more preferably not less than 99%, the production cost is obviously reduced, and the blank body can be subjected to effective mechanical processing.

Preferably, in normal pressure drying, 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 h. Preferably, the drying system is as follows: firstly, heating to 30 ℃ at 1-5 ℃/min, preserving heat for 0.5-5 h at 30 ℃, then heating to 50 ℃ at 1-5 ℃/min, preserving heat for 2-5 h at 50 ℃, then heating to 70 ℃ at 1-5 ℃/min, preserving heat for 2-5 h at 70 ℃, then heating to 90 ℃ at 2-5 ℃/min, preserving heat for 2-5 h at 90 ℃, then heating to 100-110 ℃ at 2-5 ℃/min, and preserving heat for 5-24 h at 100-110 ℃.

In the supercritical drying process, the drying medium is carbon dioxide, the temperature of the supercritical carbon dioxide 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.

When in freeze drying, the drying temperature of the freeze dryer is minus 180 ℃ to minus 30 ℃ and the drying time is 3 to 6 hours.

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

In the case of infrared drying, the wavelength of infrared rays is 2.5 to 100. Mu.m, preferably 2.5 to 50. Mu.m, more preferably 2.5 to 30. Mu.m, particularly preferably 2.5 to 15. Mu.m, still more preferably 2.5 to 8. Mu.m, and the drying time is 0.5 to 5 hours.

In the case of microwave drying, the microwave frequency is 300 to 300000MHz, preferably 300 to 10000MHz, more preferably 300 to 3000MHz, particularly preferably 300 to 1000MHz, even more preferably 600 to 1000MHz, and the drying time is 0.2 to 2 hours.

After the green body is quickly dried and dehydrated, a porous structure with higher strength is formed, the weight of the porous structure is found to be greatly reduced compared with that of the green body prepared by the prior drying and traditional pore-forming agent adding method, and the strength is greatly increased, so that the labor intensity of workers in the process of transporting the green body and kiln loading operation is greatly reduced, the porous structure 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 firing in a shuttle kiln, a resistance kiln, a high temperature tunnel kiln or a microwave kiln. In the firing, the temperature of the firing is preferably 1350 to 1850 ℃. In order to further optimize the sintering effect and promote the formation of equiaxed granular zirconia crystals, preferably, the temperature is kept between 400 and 600 ℃ for 0.5 to 1.5 hours during the sintering; heating to 1000-1200 deg.c and maintaining for 0.5-1.5 hr; heating to 1350-1850 deg.c and maintaining for 1-10 hr; then cooling to 1000-1200 ℃ and preserving heat for 0.5-1 h, cooling to 400-600 ℃ and preserving heat for 0.5-1 h, and cooling to 50-80 ℃.

Further preferably, the temperature is raised from room temperature to 400-600deg.C at a rate of 1-5deg.C/min, raised to 1000-1200deg.C at a rate of 5-30deg.C/min, raised to 1350-1850deg.C at a rate of 1-10deg.C/min, lowered to 1000-1200deg.C at a rate of 10-20deg.C/min, lowered to 400-600deg.C at a rate of 5-10deg.C/min, and lowered to 50-80deg.C at a rate of 1-5deg.C/min.

The sintered micro-nano Kong Jue heat-insulating refractory material containing zirconia can be cut, ground or punched into a required shape according to actual requirements.

Compared with the prior art, the preparation method provided by the invention is environment-friendly, pollution-free, simple and easy to control in technological process, short in demolding and drying periods of the green body, high in green body strength, high in yield and excellent in product performance, is very suitable for large-scale, mechanized, modern and intelligent production operation, and is beneficial to popularization and application.

Drawings

FIG. 1 is a photograph showing the appearance of a micro-nano Kong Jue heat insulating refractory containing zirconia produced in example 7;

FIG. 2 is a photograph showing the pore structure of the zirconia-containing micro-nano Kong Jue heat insulation refractory prepared in example 7;

FIG. 3 is a photograph of the pore walls of the zirconia-containing micro-nano Kong Jue insulation refractory 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 the zirconia-containing micro-nano Kong Jue insulation refractory prepared in example 7;

FIG. 7 is a graph showing the pore size distribution of the zirconia-containing micro-nano Kong Jue heat insulating refractory produced in example 7.

Detailed Description

Embodiments of the present invention will be further described with reference to the following specific examples. The starting materials for the following examples are all available from conventional sources on the market.

The following describes the practice of the present invention in detail with reference to specific examples. It should be noted that the examples described in this specification are only for the purpose of aiding in understanding the invention, and they should not be construed as limiting the invention in any way, i.e. the invention may be practiced otherwise than as specifically described. Therefore, any technical scheme formed by adopting equivalent substitution or equivalent transformation forms falls within the protection scope of the invention.

The starting materials used in the examples below are all commercially available conventional products. The following gives an alternative manufacturer of the main raw materials in an exemplary form.

Vinyl acetate and ethylene copolymers are available from the German Wake chemical company

Ethylene and vinyl acetate copolymers were purchased from Walch chemical Co., germany>

Acrylic ester and styrene copolymer from America national starch company +.>

Copolymers of ethylene with vinyl chloride and vinyl laurate are available from German Wacker chemical company +.>

Acrylic ester polymers are available from America starch Inc

Copolymers of vinyl acetate with ethylene and higher fatty acids were purchased from German Wacker chemical

Ethylene and vinyl chloride copolymers were purchased from Walch chemical +.>

Copolymers of vinyl acetate with ethylene and vinyl chloride are available from German Wacker Chemie +.>

Vinyl acetate copolymers with ethylene and acrylic acid esters were purchased from German Wacker Chemie +.>

Copolymers of vinyl acetate with ethylene and vinyl laurate were purchased from the German Wacker Chemie +.>

Vinyl acetate homopolymer was purchased from German Wacker Chemie->

Vinyl acetate and vinyl versatate copolymer was purchased from Anhui vitamin group Co., ltd (WWJF-8010); vinyl acetate and vinyl versatate and acrylate copolymers were purchased from japan synthetic chemical industry co-ltd (Mowinyl-DM 2072P); vinyl acetate and higher fatty acid vinyl ester copolymers were purchased from Shanxi three-dimensional group Co., ltd (SWF-04); copolymers of isobutylene and maleic anhydride are available from Japanese colali company (ISOBAM-04); konjak gum powder is available from Shanghai North Lian Biotechnology Co., ltd; curdlan is purchased from heng mei science and technology limited; sucrose, dextrin and agar, gellan gum were purchased from Jiangsu palettes biotechnology limited; hydroxypropyl guar was purchased from samphire chemical company; sodium alginate was purchased from Jiangsu palettes biotechnology company; xanthan gum was purchased from Shandong Fufeng fermentation company; acacia gum is available from zhengzhou de wang chemical company; acrylamide and polyacrylamide were purchased from shandong rui haimi mountain chemical company; polyethylene glycol, cetyl alcohol and polyvinyl alcohol were purchased from the company colali japan; tris (hydroxymethyl) aminomethane was purchased from commercial dune free-wheeler biotechnology company; microcrystalline cellulose and cellulose nanocrystals were purchased from Jiangsu Xin and source biotechnology company.

In terms of cell regulator raw materials, ethyl cellulose ether was purchased from akthunobel company, netherlands; hydroxyethyl cellulose ethers are available from hercules, usa; hydroxyethyl methyl cellulose ether was purchased from clariant, switzerland; hydroxyethyl ethyl cellulose ether is available from akthunobel company, netherlands; ethyl methyl cellulose ether is available from the united states dow chemical; methyl cellulose ether is available from the united states dow chemical; carboxymethyl cellulose ether is available from the company us, oshan; carboxymethyl cellulose ether is available from the american dow chemical company; carboxymethyl ethyl cellulose ether is available from the company us, oshan; propyl cellulose ether was purchased from the company us asian; hydroxypropyl cellulose ether was purchased from the company us, oshan; hydroxypropyl methylcellulose ether was purchased from the company us, oshan; hydroxypropyl ethyl cellulose ether was purchased from the company us, oshan; hydroxymethyl cellulose ethers are available from the united states dow chemical; carboxymethyl hydroxymethyl cellulose ether is available from the american dow chemical; carboxymethyl hydroxyethyl cellulose ether is available from the american dow chemical; carboxymethyl hydroxypropyl cellulose ether is available from the united states dow chemical; carboxymethyl hydroxybutyl cellulose ether is available from the U.S. dow chemical; hydroxypropyl hydroxybutyl cellulose ether is available from the U.S. dow chemical; ethyl cellulose sulfonate ether is available from the american dow chemical; hydroxybutyl methyl cellulose ether is available from the U.S. dow chemical; saponin is available from Hengmei technology Co., ltd; starch ethers were purchased from AVEBE corporation, netherlands; the water-soluble cellulose ether is purchased from Hengmei technology Co., ltd; lignocellulose is available from JRS company, germany; saponin was purchased from the Guangdong company of Siam.

Quaternary ammonium type Gemini surfactant (foaming multiple 45), available from heng mei technology limited; semi-ring Bola surfactant (expansion ratio 50), available from heng mei technology limited; double-stranded Bola surfactant (expansion 44), available from heng mei technology limited; polyether Dendrimer surfactant (foaming factor 45), available from Hengmei technology Co., ltd; vegetable protein foaming agent (foaming multiple 9) from Shandong Xin chemical company; sludge protein foaming agent (foaming multiple is 8), purchased from Henmei technology Co., ltd; carboxylate type Gemini surfactant (foaming multiple 60) purchased from Henmei technology Co., ltd; animal protein foaming agent (foaming multiple 11), available from Henmei technology Co., ltd; sodium dodecyl polyoxyethylene ether carboxylate (foaming multiple 9); lauric acid amide propyl sulfobetaine (foaming multiple 13); alpha-sodium olefin sulfonate (foaming multiple is 15); dodecyl dimethyl betaine surfactant (foaming multiple 17); sulfate type Gemini surfactant (foaming multiple 55), purchased from Henmei technology Co., ltd; sodium fatty alcohol polyoxyethylene ether carboxylate (expansion ratio 15), available from Henmei technology Co., ltd; sodium dodecyl benzene sulfonate (foaming multiple 9); polyamide type Dendrimer surfactant (foaming factor 55), available from Heng Mei technology Co.

Allyl ether type polycarboxylic acid dispersant, available from Henmei technology Co., ltd; amide type polycarboxylic acid dispersant, available from Henmei technology Co., ltd; imide type polycarboxylic acid dispersants available from Henmei technology Co., ltd; polyamide type polycarboxylic acid dispersants, available from basf, germany; sulfonated melamine polycondensates, available from Henmei technology Co; naphthalene-based high-efficiency dispersants available from Henmei technology Co., ltd; polyethylene glycol type polycarboxylic acid type dispersant, available from basf, germany; polycarboxylic acid dispersants available from basf, germany; melamine formaldehyde polycondensates, available from heng mei science and technology limited; polycarboxylic ether dispersants, commercially available from basf, germany. Methacrylate type polycarboxylic acid dispersants were purchased from Henmei technology Co.

1. The invention relates to a micro-nano Kong Jue heat insulation refractory material containing zirconia and a specific embodiment of a preparation method thereof

Example 1

The micro-nano Kong Jue heat-insulating refractory material containing zirconia of the embodiment is prepared from a base raw material, a suspending agent, a mineralizing agent, an infrared opacifying agent, a foaming agent, an inorganic curing agent, an organic curing agent, a cell regulator and water. The types and amounts of the respective raw materials in this example are described as follows:

The basic raw materials are as follows: 0.4 ton zircon and 0.1 ton industrial Al (OH) ₃ 0.1 ton of boehmite, 0.3 ton of kaolin and 0.1 ton of silica micropowder. ZrO in chemical composition of zircon ₂ The mass percentage of the catalyst is 64 to 67 percent, and SiO ₂ 32 to 3 mass percent5wt% of the material, and the grain size is less than or equal to 0.08mm; industrial Al (OH) ₃ Al in the chemical composition of (2) ₂ O ₃ The mass percentage of the catalyst is not less than 65wt%, and the particle size is not more than 0.08mm; chemical composition of boehmite Al ₂ O ₃ The mass percentage content is not less than 70%, and the particle size is not less than 0.08mm; chemical composition of kaolin Al ₂ O ₃ The mass percentage of the catalyst is 35 to 37 percent, siO ₂ 59-62% by mass and 0.6-1 mm particle diameter; siO in chemical composition of silicon micropowder ₂ The mass percent of the catalyst is not less than 95 weight percent, and the particle size is not more than 5 mu m.

Suspending agent: 100kg of bentonite, al in the chemical composition of bentonite ₂ O ₃ The mass percentage of the catalyst is 22-23 wt percent, siO ₂ The mass percentage of the catalyst is 68-75%, and the grain diameter is less than or equal to 0.045mm.

Mineralizing agent: 40kg Y ₂ O ₃ 、20kgCeO ₂ 、30kg AlF ₃ 、10kgZnO；Y ₂ O ₃ 、CeO ₂ 、AlF ₃ ZnO is industrially pure and has a particle size of 5 μm or less.

Infrared opacifying agent: 50kg of rutile, 25kg of ZrSiO ₄ 、25kg B ₄ C, performing operation; rutile, zrSiO ₄ 、B ₄ C is industrially pure and has a particle size of 5 μm or less.

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

Inorganic curing agent: 100kg of silica sol, siO ₂ The content is not less than 30%.

Organic curing agent: 5kg of a copolymer of vinyl acetate with ethylene, 15kg of a copolymer of vinyl acetate with ethylene and a higher fatty acid; the particle size is less than or equal to 5 μm.

Cell regulator: 8kg of carboxymethyl hydroxypropyl cellulose ether; the particle size is less than or equal to 5 μm.

Water: 2 tons.

The specific preparation process of the micro-nano Kong Jue heat insulation refractory material containing zirconia in the embodiment is as follows:

(1) Weighing 0.4 ton zircon and 0.1 ton industrial Al (OH) ₃ Pouring 0.1 ton of boehmite, 0.3 ton of kaolin and 0.1 ton of silicon micropowderAnd (5) carrying out forced stirring and dry mixing for 5min to obtain the basic raw material. Weighing 100kg of bentonite and 40kg of Y ₂ O ₃ 、20kgCeO ₂ 、30kg AlF ₃ 10kg ZnO, 50kg rutile, 25kg ZrSiO ₄ 、25kg B ₄ C, pouring the mixture into a three-dimensional mixer and dry-mixing the mixture for 5 minutes to obtain the additive.

(2) 1kg of quaternary ammonium Gemini type surfactant, 39kg of vegetable 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 are weighed, poured into a V-shaped mixer and mixed for 5min, and a uniform foaming composition is obtained.

(3) Pouring the basic raw materials and additives obtained in the step (1) into a roller ball mill, adding 2 tons of water, ball milling and mixing for 12 hours, enabling the average particle size of solid particles in the slurry to be not more than 30 mu m, then carrying out ultrasonic vibration for 4 minutes (ultrasonic power 2000W) to obtain uniform suspension slurry, injecting the suspension slurry into a stirrer, then adding silica sol and the foaming composition obtained in the step (2) into the suspension slurry, and rapidly mixing the mixture for 2 minutes at a linear speed of 180m/s by a stirring paddle in the stirrer 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->

Ball->

The weight ratio of (2) is 1:1:8, the weight ratio of the material to the ball is 1:0.8.

(4) Injecting the foam slurry obtained in the step (3) into a stainless steel die, 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) Demolding the solidified blank, and utilizing CO ₂ Supercritical drying method for removing water and CO from green body ₂ The control pressure of (2) is 9MPa, the temperature is 42 ℃, and the supercritical drying time is 2h, obtaining a dry porous green body. The moisture content of the dried green body is less than or equal to 3 weight percent, and the compressive strength is less than or equal to 0.7MPa. The method comprises the steps of firing a dried blank by a high-temperature tunnel kiln, firstly raising the temperature to 400 ℃ from room temperature at a heating rate of 1 ℃/min, preserving heat for 0.5h at 400 ℃, 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 reducing the temperature to 50 ℃ at 1 ℃/min to obtain the micro-nano Kong Jue heat-insulating refractory material containing zirconia.

Examples 2 to 17

The formulation compositions of the zirconia-containing micro-nano Kong Jue heat insulating refractory of examples 2 to 17 are shown in tables 1 and 2 below:

table 1 examples 2 to 9 formulation of zirconia-containing micro-nano Kong Jue insulation refractory

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Table 2 formulas of micro-nano Kong Jue heat insulation refractory containing zirconia according to examples 10 to 17

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The preparation process of the zirconia-containing micro-nano Kong Jue heat insulation refractory of example 2 is as follows:

(1) Weighing zircon, industrial alumina and beta-Al according to a formula ₂ O ₃ 、γ-Al ₂ O ₃ Pouring gangue, diatomite and beta-tridymite into a planetary mixer and dry-mixing for 5min to obtain a basic raw material; weighing bentonite, polyaluminum chloride and Y ₂ O ₃ 、MgO、V ₂ O ₅ 、NiO、K ₂ Ti ₆ O ₁₃ 、Sb ₂ O ₅ Pouring into a double cone mixer and dry-mixing for 5min to obtain the additive.

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

(3) Pouring the basic raw material obtained in the step (1) and the additive into a roller ball mill, adding 2 tons of water, ball milling and mixing for 10 hours, enabling the average particle diameter of solid particles to be not more than 30 mu m, then carrying out ultrasonic vibration for 5 minutes (the ultrasonic power is 1500W) to obtain uniform suspension slurry, injecting the suspension slurry into a stirrer, then adding the foaming composition obtained in the step (2) and the alumina sol into the suspension slurry, and rapidly mixing the suspension slurry for 2 minutes at the linear speed of 200m/s by a stirring paddle in the stirrer to obtain uniform foam slurry; during ball milling, silicon carbide balls and large balls are adopted as grinding balls in the ball mill

Middle ball->

Ball->

The weight ratio of (2) is 1:1:8, the weight ratio of the material to the ball is 1:0.9.

(4) Injecting the foam slurry obtained in the step (3) into a stainless steel die, 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) Demolding the solidified blank, and utilizing CO ₂ Supercritical drying method for removing water and CO from green body ₂ The control pressure of (2) is 9MPa, the temperature is 42 ℃, and the supercritical drying time is 1.5h, so as to obtain the dried porous blank. The moisture content of the dried green body is less than or equal to 3 weight percent, and the compressive strength is less than or equal to 0.9MPa. The method comprises the steps of firing a dried blank by a high-temperature tunnel kiln, firstly raising the temperature to 500 ℃ from room temperature at a heating rate of 2 ℃/min, preserving heat for 0.5h at 500 ℃, raising the temperature to 1000 ℃ at 5 ℃/min, preserving heat for 0.5h, raising the temperature to 1400 ℃ at 3 ℃/min, preserving heat for 8h, reducing the temperature to 1000 ℃ at 10 ℃/min, preserving heat for 0.5h at 1000 ℃, reducing the temperature to 500 ℃ at 6 ℃/min, preserving heat for 0.5h at 500 ℃, and reducing the temperature to 50 ℃ at 2 ℃/min to obtain the micro-nano Kong Jue heat-insulating refractory material containing zirconia.

In this example, zrO in the chemical composition of zircon ₂ 64-67 wt% of SiO ₂ The mass percentage of the particles is 32-35%, and the particle size is less than or equal to 0.08mm; industrial alumina, beta-Al ₂ O ₃ 、γ-Al ₂ O ₃ Al in the chemical composition of (2) ₂ O ₃ The mass percentage of the particles is not less than 98%, and the particle size is not less than 0.08mm; al in the chemical composition of gangue ₂ O ₃ 26-28% of SiO ₂ The mass percentage of the catalyst is 69-73%, and the grain diameter is 0.6-1 mm; siO in the chemical composition of diatomite ₂ The mass percentage of the catalyst is not less than 85%, and the particle size is not less than 0.08mm; siO in the chemical composition of beta-tridymite ₂ The mass percentage of the particles is not less than 98%, and the particle size is not less than 0.08mm; chemical composition of bentonite Al ₂ O ₃ The mass percentage of the silicon dioxide is 22-23%, siO ₂ The mass percentage of the particles is 68-75%, and the particle size is less than or equal to 0.045mm; al in alumina sol ₂ O ₃ The mass percentage content of (2) is not less than 20%; polyaluminum chloride, Y ₂ O ₃ 、MgO、V ₂ O ₅ All are industrially pure, and the grain diameter is less than or equal to 5 mu m.

The preparation process of the zirconia-containing micro-nano Kong Jue heat insulation refractory of example 3 is as follows:

(1) Weighing zirconia corundum, zircon, kaolin, alpha-quartz, beta-quartz and alpha-tridymite, pouring the zirconia corundum, the zircon, the kaolin, the alpha-quartz, the beta-quartz and the alpha-tridymite into a non-gravity mixer, and dry-mixing for 10min to obtain a basic raw material; weighing methacrylate type polycarboxylic acid dispersing agent, bentonite, polyaluminium sulfate and Y ₂ O ₃ 、CeO ₂ 、Yb ₂ O ₃ 、K ₂ Ti ₆ O ₁₃ 、TiC、B ₄ C, pouring the mixture into a double-cone mixer and dry-mixing the mixture for 5 minutes to obtain the additive.

(2) The carboxylate type Gemini surfactant, sodium dodecyl benzene sulfonate, calcium dialuminate, tricalcium silicate, copolymer of ethylene, chloroethylene and vinyl laurate, curdlan, carboxymethyl methyl cellulose ether and carboxymethyl ethyl cellulose ether are weighed, poured into a three-dimensional mixer and mixed for 5min, and a uniform foaming composition is obtained.

(3) Pouring the basic raw material obtained in the step (1) and the additive into a roller ball mill, adding 1.6 tons of water, ball milling and mixing for 8 hours, enabling the average particle size of solid particles in the slurry to be not more than 35 mu m, then performing ultrasonic vibration for 6 minutes (the ultrasonic power is 1300W) to obtain uniform suspension slurry, then injecting the suspension slurry into a stirrer, then adding the foaming composition obtained in the step (2) and the silica-alumina sol into the suspension slurry, and rapidly mixing the mixture for 3 minutes at the linear speed of 170m/s by a stirring paddle in the stirrer to obtain uniform foam slurry; during ball milling, zirconia balls and large balls are adopted as grinding balls in the ball mill

Middle ball->

Ball with ball shape

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

(5) Demolding the solidified blank, and utilizing CO ₂ The supercritical drying method is used for removing liquid water from the green body, and the drying process is the same as that of the example 1; the moisture content of the dried green body is less than or equal to 3 weight percent, and the compressive strength is less than or equal to 1.0MPa. The method comprises the steps of firing a dried blank by a high-temperature tunnel kiln, firstly heating to 500 ℃ from room temperature at a heating rate of 3 ℃/min, preserving heat for 0.5h at 500 ℃, heating to 1000 ℃ at 8 ℃/min, preserving heat for 1h, heating to 1450 ℃ at 3 ℃/min, preserving heat for 5h, cooling to 1100 ℃ at 10 ℃/min, preserving heat for 1h at 1100 ℃, cooling to 500 ℃ at 6 ℃/min, preserving heat for 0.5h at 500 ℃, and cooling to 50 ℃ at 2 ℃/min to obtain the micro nano Kong Jue heat-insulating refractory material containing zirconium oxide.

In this example, zrO in the chemical composition of zirconia corundum ₂ 15-17 wt% of Al ₂ O ₃ 83-85 wt% of the mixture, and the particle size is less than or equal to 0.08mm; zrO in chemical composition of zircon ₂ 64-67 wt% of SiO ₂ The mass percentage of the particles is 32-35%, and the particle size is less than or equal to 0.08mm; chemical composition of kaolin Al ₂ O ₃ 35-37 wt% of SiO ₂ 58-61% by mass and 0.6-1 mm particle diameter; siO in chemical composition of alpha-quartz, beta-quartz and alpha-tridymite ₂ The mass percentage of the catalyst is not less than 95 weight percent, and the particle size is not less than 0.044mm; chemical composition of bentonite Al ₂ O ₃ The mass percentage of the silicon dioxide is 22-23%, siO ₂ The mass percentage of the particles is 68-75%, and the particle size is less than or equal to 0.045mm; al in silica-alumina sol ₂ O ₃ The mass percentage of (2) is not less than 30 percent, siO ₂ The mass percentage content of (2) is not less than 20%; polymeric sulfurAluminum acid, Y ₂ O ₃ 、CeO ₂ 、Yb ₂ O ₃ 、K ₂ Ti ₆ O ₁₃ 、TiC、B ₄ C. The calcium dialuminate and the tricalcium silicate are all industrially pure, and the grain size is less than or equal to 5 mu m.

The preparation process of the zirconia-containing micro-nano Kong Jue heat insulation refractory of example 4 is as follows:

(1) Weighing zirconia corundum, alpha-Al ₂ O ₃ Pouring boehmite, aluminum n-butoxide, aluminum isopropoxide and kyanite into a forced stirrer and dry-mixing for 15min to obtain a basic raw material; weighing sodium polyacrylate, sodium polyphosphate, attapulgite, sepiolite, caO and Y ₂ O ₃ 、MnO ₂ 、TiO ₂ 、K ₄ TiO ₄ 、Sb ₂ O ₃ Pouring into a double cone mixer and dry-mixing for 5min to obtain the additive.

(2) Weighing quaternary ammonium type Gemini surfactant, alpha-olefin sodium sulfonate, high-carbon fatty alcohol polyoxyethylene ether, tetra-calcium aluminoferrite, acrylic ester 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 a uniform foaming composition.

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

Middle ball->

Ball->

(4) Injecting the foam slurry obtained in the step (3) into a rubber mold, 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) Demolding the solidified green body, removing water in the green body by utilizing a microwave drying technology, and drying for 0.2h at the microwave frequency of 915MHz to obtain a dried porous green body; the moisture content of the dried green body is less than or equal to 3 weight percent, and the compressive strength is less than or equal to 1.0MPa. The dried blank is put into a shuttle kiln to be burned, firstly, the temperature is raised to 500 ℃ from room temperature at the heating rate of 3 ℃/min, the temperature is kept for 1h at 500 ℃, then the temperature is raised to 1000 ℃ at 8 ℃/min, the temperature is kept for 1h, then the temperature is raised to 1500 ℃ at 4 ℃/min, the temperature is kept for 3h, then the temperature is lowered to 1100 ℃ at 10 ℃/min, the temperature is kept for 1h at 1100 ℃, then the temperature is lowered to 500 ℃ at 6 ℃/min, the temperature is kept for 0.5h at 500 ℃, and finally the temperature is lowered to 60 ℃ at 2 ℃/min, so that the micro nano Kong Jue heat insulation refractory material containing zirconia is obtained.

In this example, zrO in the chemical composition of zirconia corundum ₂ The mass percentage of the aluminum alloy is 22 to 25 percent, and the aluminum alloy is Al ₂ O ₃ The mass percentage of the catalyst is 75-78 wt%, and the particle size is less than or equal to 0.08mm; chemical composition of kyanite Al ₂ O ₃ The mass percentage of the SiO is 40-45 wt% ₂ 55-58% by mass and 0.6-1 mm particle diameter; alpha-Al ₂ O ₃ Al in the chemical composition of (2) ₂ O ₃ The mass percentage content is larger than or equal to 99.9wt percent, and the particle size is smaller than or equal to 0.08mm; chemical composition of diaspore Al ₂ O ₃ The mass percentage of the catalyst is not less than 70 weight percent, and the particle size is not less than 0.08mm; al in the chemical composition of aluminum n-butoxide and aluminum isopropoxide ₂ O ₃ The mass percentage of (2) is 44-50wt%; chemical composition of attapulgite ₂ O ₃ The mass percentage of the SiO is 12-15 wt% ₂ 55-60% by mass, 8-10% by mass of MgO, and the grain size is less than or equal to 0.045mm; siO in chemical composition of sepiolite ₂ The mass percentage of MgO is 65-71%, the mass percentage of MgO is 25-27%, and the grain diameter is less than or equal to 0.08mm; zrO in zirconia sol ₂ Is 1 mass percent0～15％；CaO、Y ₂ O ₃ 、MnO ₂ 、TiO ₂ 、K ₄ TiO ₄ 、Sb ₂ O ₃ The tetracalcium aluminoferrite is industrially pure, and the grain diameter is less than or equal to 5 mu m.

The preparation process of the zirconia-containing micro-nano Kong Jue heat insulation refractory of example 5 is as follows:

(1) Weighing zirconia corundum, methyl orthosilicate and ethyl orthosilicate, pouring into a forced stirrer, and dry-mixing for 15min to obtain a basic raw material; weighing sulfonated melamine polycondensate, allyl ether type polycarboxylic acid dispersing agent, bentonite, chitosan and Er ₂ O ₃ 、La ₂ O ₃ 、Cr ₂ O ₃ Pouring into a three-dimensional mixer and dry-mixing for 5min to obtain the additive.

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

(3) Pouring the basic raw material obtained in the step (1) and the additive into a roller ball mill, adding 1.2 tons of water, ball milling and mixing for 4 hours to ensure that the average granularity of solid particles is not more than 44 mu m, then carrying out ultrasonic vibration for 8 minutes (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 the suspension slurry with a stirring paddle in a stirrer at the linear speed of 40m/s for 10 minutes to obtain uniform foam slurry; during ball milling, the grinding balls in the ball mill are zirconia balls and big balls

Middle ball->

Ball->

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

(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) Demolding the solidified green body, removing water in the green body by utilizing a microwave drying technology, and drying for 0.8h at the microwave frequency of 2450MHz to obtain a dried porous green body; the moisture content of the dried green body is less than or equal to 3 weight percent, and the compressive strength is less than or equal to 1.0MPa. Demolding the solidified green body, removing water in the green body by utilizing a microwave drying technology, and drying for 0.2h at the microwave frequency of 915MHz to obtain a dried porous green body; the dried blank is put into a microwave kiln to be burned, firstly, the temperature is raised to 500 ℃ from the room temperature at the heating rate of 10 ℃/min, and the heat is preserved for 1.5h; heating to 1100 ℃ at 30 ℃/min, and preserving heat for 1.5h; heating to 1540 ℃ at 10 ℃/min, and preserving heat for 1h; then cooling to 1000 ℃ at 20 ℃/min and preserving heat for 1h; then cooling to 600 ℃ at 10 ℃/min and preserving heat for 1h; finally, the temperature is reduced to 80 ℃ at 5 ℃/min, and the micro-nano Kong Jue heat-insulating refractory material containing zirconia is obtained.

In this example, zrO in the chemical composition of zirconia corundum ₂ The mass percentage of the aluminum alloy is 39 to 41 weight percent, and the aluminum alloy is Al ₂ O ₃ The 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 orthosilicate ₂ 28 to 35 weight percent; chemical composition of bentonite Al ₂ O ₃ The mass percentage of the silicon dioxide is 22-23%, siO ₂ The mass percentage of the particles is 68-75%, and the particle size is less than or equal to 0.045mm; er (Er) ₂ O ₃ 、La ₂ O ₃ 、Cr ₂ O ₃ The silica gel and the alumina gel are all industrially pure, and the particle size is less than or equal to 5 mu m.

The preparation process of the zirconia-containing micro-nano Kong Jue heat insulation refractory of example 6 is as follows:

(1) Weigh 8mol% Y ₂ O ₃ Stabilized zirconia, eta-Al ₂ O ₃ 、ρ-Al ₂ O ₃ Pouring alpha-tridymite, rice husk, carbonized rice husk and rice husk ash into a forced stirrer and dry-mixing for 5min to obtain a basic raw material; weighing polyamide type polycarboxylic acid dispersing agent, naphthalene type dispersing agent, welan gum, polyvinylpyrrolidone and WO ₃ 、TiO ₂ 、NiCl ₂ 、Ni(NO ₃ ) ₂ Pouring into a three-dimensional mixer and dry-mixing for 5min to obtain the additive.

(2) The sulfate type Gemini surfactant, fatty alcohol polyoxyethylene ether, aluminum silicate gel, copolymer of vinyl acetate and ethylene and vinyl laurate, copolymer of isobutene and maleic anhydride, hydroxypropyl guar gum, propyl cellulose ether, water-soluble cellulose ether and ethyl methyl cellulose ether are weighed, poured into a three-dimensional mixer and mixed for 5min, and a uniform foaming composition is obtained.

(3) Pouring the basic raw material obtained in the step (1) and the additive into a roller ball mill, adding 1.2 tons of water, ball milling and mixing for 4 hours to ensure that the average granularity of solid particles is not more than 44 mu m, then carrying out ultrasonic vibration for 10 minutes (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 the suspension slurry with a stirring paddle in a stirrer at the linear speed of 150m/s for 5 minutes to obtain uniform foam slurry; during ball milling, the grinding balls in the ball mill are made of alumina and large balls

Middle ball->

Ball->

(4) Injecting the foam slurry obtained in the step (4) into an aluminum alloy mold, 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) Demolding the solidified green body, 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 moisture content of the dried green body is less than or equal to 3 weight percent, and the compressive strength is less than or equal to 1.0MPa. The dried blank is put into a microwave kiln for sintering, the temperature is raised to 500 ℃ from the room temperature at the heating rate of 5 ℃/min, and the temperature is kept for 0.5h; heating to 1200 ℃ at 10 ℃/min, and preserving heat for 0.5h; heating to 1550-1580 ℃ at 8 ℃/min, and preserving heat for 0.5h; then cooling to 1000 ℃ at 20 ℃/min and preserving heat for 0.5h; then cooling to 500 ℃ at 10 ℃/min and preserving heat for 0.5h; finally, the temperature is reduced to 50 ℃ at 5 ℃/min, and the micro-nano Kong Jue heat-insulating refractory material containing zirconia is obtained.

In this example, 8mol% Y ₂ O ₃ ZrO in stabilized zirconia ₂ The content of (2) is 86-88 wt%, and the grain diameter is less than or equal to 0.08mm; eta-Al ₂ O ₃ 、ρ-Al ₂ O ₃ Al in the chemical composition of (2) ₂ O ₃ The mass percentage of the catalyst is larger than or equal to 99wt percent, and the particle size is smaller than or equal to 0.08mm; siO in chemical composition of alpha-tridymite ₂ The mass percentage of the catalyst is larger than or equal to 99wt percent, and the particle size is smaller than or equal to 0.08mm; siO in chemical composition of rice husk, carbonized rice husk and rice husk ash ₂ The mass percentage of the catalyst is not less than 18wt%, and the particle size is not more than 0.08 mu m; WO (WO) ₃ 、TiO ₂ 、NiCl ₂ 、Ni(NO ₃ ) ₂ The aluminum-silicon gel is industrially pure, and the grain diameter is less than or equal to 1 mu m.

The preparation process of the zirconia-containing micro-nano Kong Jue heat insulation refractory of example 7 is as follows:

(1) 5mol% Y ₂ O ₃ Stabilized zirconia, gamma-Al ₂ O ₃ 、κ-Al ₂ O ₃ 、θ-Al ₂ O ₃ Pouring andalusite, alpha-cristobalite and cemented silica into a non-gravity mixer and dry-mixing for 15min to obtain a basic raw material; weighing methacrylate type polycarboxylic acid dispersing agent, naphthalene type dispersing agent, casein, cellulose fiber and Y ₂ O ₃ 、Fe ₂ O ₃ 、WO ₃ 、TiO ₂ 、Sb ₂ O ₅ Pouring into a V-shaped mixer and dry-mixing for 5min to obtain the additive.

(2) The sulfate type Gemini surfactant, fatty alcohol polyoxyethylene ester, silica-alumina gel, ethylene and vinyl chloride copolymer, acrylic ester polymer, vinyl acetate homopolymer, hydroxybutyl methyl cellulose ether and hydroxyethyl methyl cellulose ether are weighed, poured into a V-shaped mixer and mixed for 5min, and then the uniform foaming composition is obtained.

(3) Pouring the basic raw materials and additives obtained in the step (1) into a rollerAdding 0.9 ton of water into a ball mill, ball milling and mixing for 1.5 hours to ensure that the average granularity of solid particles is not more than 44 mu m, then carrying out ultrasonic vibration for 12 minutes (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 5 minutes at the linear speed of 140m/s by a stirring paddle in a stirrer to obtain uniform foam slurry; during ball milling, the grinding balls in the ball mill are made of zirconia corundum and large balls

Middle ball->

Ball->

The weight ratio of (2) is 1.5:2:6.5, the weight ratio of the material to the ball is 1:1.1.

(4) And (3) 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) Demoulding the solidified green body, removing water in the green body by a freeze drying method, and drying at the drying temperature of minus 130 ℃ to minus 100 ℃ for 6 hours to obtain a dried porous green body. The moisture content of the dried green body is less than or equal to 3 weight percent, and the compressive strength is less than or equal to 1.0MPa. Firing the dried blank in a shuttle kiln, heating to 500 ℃ from room temperature at a heating rate of 3 ℃/min, and preserving heat for 0.5h; heating to 1200 ℃ at 8 ℃/min, and preserving heat for 1h; heating to 1570-1600 ℃ at 3 ℃/min, and preserving heat for 3-5 h; then cooling to 1000 ℃ at 10 ℃/min, and preserving heat for 1h; cooling to 500 ℃ at a speed of 6 ℃/min, and preserving heat for 0.5h; finally, the temperature is reduced to 50 ℃ at 2 ℃/min, and the micro-nano Kong Chaoji insulating refractory material containing zirconia is obtained.

In this example, 5mol% Y ₂ O ₃ Stabilization of ZrO in the chemical composition of zirconia ₂ The content of (2) is 90-93 wt%, and the grain diameter is less than or equal to 0.08mm; gamma-Al ₂ O ₃ 、κ-Al ₂ O ₃ 、θ-Al ₂ O ₃ Al in the chemical composition of (2) ₂ O ₃ The mass percentage of (C) is greater than or equal to 99wt, the grain diameter is less than or equal to 0.08mm; al in the chemical composition of andalusite ₂ O ₃ The mass percentage of the catalyst is 45-50wt% and the grain diameter is less than or equal to 0.08mm; siO in chemical composition of alpha-cristobalite and cemented silica ₂ The mass percentage of the catalyst is 98wt%, and the particle size is less than or equal to 0.08mm; y is Y ₂ O ₃ 、Fe ₂ O ₃ 、WO ₃ 、TiO ₂ 、Sb ₂ O ₅ The aluminum-silicon gel is industrially pure and has the particle size of less than or equal to 5 mu m.

The preparation process of the zirconia-containing micro-nano Kong Jue heat insulation refractory of example 8 is as follows:

(1) 5mol% Y ₂ O ₃ Stabilized zirconia, sintered corundum, fused white corundum powder, andalusite, quartzite and gangue, pouring the materials into a non-gravity mixer and dry-mixing the materials for 15 minutes to obtain a basic raw material; weighing imide type polycarboxylic acid dispersing agent, melamine dispersing agent, polyacrylamide, soluble starch, srO and Cr ₂ O ₃ 、BaO、Sb ₂ O ₅ 、Co(NO ₃ ) ₂ Pouring into a V-shaped mixer and dry-mixing for 5min to obtain the additive.

(2) Weighing double-chain Bola surfactant, alkylphenol ethoxylates, alumina gel, copolymer of vinyl acetate and versatic acid vinyl ester and acrylic ester, copolymer of vinyl acetate and versatic acid vinyl ester, sulfonic acid 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 material and the additive obtained in the step (1) into a roller ball mill, adding 0.8 ton of water, ball milling and mixing for 1h to ensure that the average granularity of solid particles is not more than 44 mu m, then carrying out ultrasonic vibration 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 a stirring paddle in a stirrer for 6min at the linear speed of 130m/s to obtain uniform foam slurry; during ball milling, the grinding balls in the ball mill are made of zirconia and large balls

Middle ball->

Ball->

The weight ratio of (2) is 1.5:2:6.5, a material/ball ratio of 1:1.2.

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

(5) Demolding the solidified green body, removing liquid water in the green body by adopting an infrared drying method, and taking the infrared wavelength of 11-13 mu m, wherein the drying time is 1.2h, thus obtaining a dried porous green body; the moisture content of the dried green body is less than or equal to 3 weight percent, and the compressive strength is less than or equal to 1.0MPa. Firing the dried blank in a shuttle kiln, heating to 500 ℃ from room temperature at a heating rate of 3 ℃/min, heating to 1200 ℃ at a temperature of 8 ℃/min, preserving heat for 1h, heating to 1580-1610 ℃ at a temperature of 3 ℃/min, preserving heat for 3h, cooling to 1000 ℃ at a temperature of 10 ℃/min, preserving heat for 1h at 1000 ℃, cooling to 500 ℃ at a temperature of 6 ℃/min, preserving heat for 0.5h at a temperature of 500 ℃, and cooling to 50 ℃ at a temperature of 2 ℃/min to obtain the micro-nano Kong Jue heat-insulating refractory material containing zirconium oxide.

In this example 8, 5mol% Y ₂ O ₃ Stabilization of ZrO in the chemical composition of zirconia ₂ The content of (2) is 90-93 wt%, and the grain diameter is less than or equal to 0.08mm; al in chemical composition of sintered corundum and electro-fused white corundum powder ₂ O ₃ The mass percentage of the catalyst is larger than or equal to 99wt percent, and the particle size is smaller than or equal to 0.08mm; al in the chemical composition of andalusite ₂ O ₃ The mass percentage of the catalyst is 54 to 58 percent, siO ₂ The mass percentage of the catalyst is 36-40%, and the grain diameter is less than or equal to 0.08mm; siO in the chemical composition of quartz rock and vein quartz ₂ The mass percentage of the catalyst is not less than 98wt%, and the particle size is not more than 0.045mm; srO, cr ₂ O ₃ 、BaO、Sb ₂ O ₅ 、Co(NO ₃ ) ₂ The alumina gel is industrially pure, and the grain diameter is less than or equal to 5 mu m.

The preparation process of the zirconia-containing micro-nano Kong Jue heat insulation refractory of example 9 is as follows:

(1) 5mol% Y ₂ O ₃ StabilizationPouring the zirconia and andalusite into a forced mixer and dry-mixing for 5min to obtain a basic raw material; weighing polyamide type polycarboxylic acid dispersing agent, naphthalene type efficient dispersing agent, microcrystalline cellulose, casein, caO and MnO ₂ 、Cr ₂ O ₃ 、CoO、K ₂ Ti ₆ O ₁₃ Pouring into a V-shaped mixer and dry-mixing for 5min to obtain the additive.

(2) Polyether type Dendrimer surfactant, dodecanol polyoxyethylene ether, zirconia gel, ethylene-vinyl acetate copolymer, locust bean gum, methyl cellulose ether and carboxymethyl cellulose ether are weighed, poured into a three-dimensional mixer and mixed for 5min, and a uniform foaming composition is obtained.

(3) Pouring the basic raw material and the additive obtained in the step (1) into a roller ball mill, adding 0.7 ton of water, ball milling and mixing for 1h to ensure that the average granularity of solid particles is not more than 44 mu m, then carrying out ultrasonic vibration 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 the suspension slurry with a stirring paddle in a stirrer for 6min 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 big balls

Middle ball->

Ball->

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

(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 solidified.

(5) Demolding the solidified green body, removing liquid water in the green body by adopting an infrared drying method, and taking the infrared wavelength of 12-15 mu m, wherein the drying time is 1h, thus obtaining a dried porous green body; the moisture content of the dried green body is less than or equal to 3 weight percent, and the compressive strength is less than or equal to 1.0MPa. Firing the dried blank in a shuttle kiln, heating to 500 ℃ from room temperature at a heating rate of 3 ℃/min, heating to 1200 ℃ at a temperature of 8 ℃/min, preserving heat for 1h, heating to 1600-1650 ℃ at a temperature of 3 ℃/min, preserving heat for 3h, cooling to 1000 ℃ at a temperature of 10 ℃/min, preserving heat for 1h at 1000 ℃, cooling to 500 ℃ at a temperature of 6 ℃/min, preserving heat for 0.5h at a temperature of 500 ℃, and cooling to 50 ℃ at a temperature of 2 ℃/min to obtain the micro-nano Kong Jue heat-insulating refractory material containing zirconium oxide.

In this example, 5mol% Y ₂ O ₃ Stabilization of ZrO in the chemical composition of zirconia ₂ The mass percentage of the catalyst is 90-93 wt%, and the grain diameter is less than or equal to 0.08mm; al in the chemical composition of andalusite ₂ O ₃ 54 to 58 weight percent of SiO ₂ 36-40% of the total mass and 0.6-1 mm of the particle size; caO, mnO ₂ 、Cr ₂ O ₃ 、CoO、K ₂ Ti ₆ O ₁₃ The zirconia gel is industrially pure and has a particle size of less than or equal to 5 mu m.

The preparation process of the zirconia-containing micro-nano Kong Jue heat insulation refractory of example 10 is as follows:

(1) 3mol% Y ₂ O ₃ Pouring the stabilized zirconia and sillimanite into a planetary mixer and dry-mixing for 15min to obtain a basic raw material; weighing polyethylene glycol type polycarboxylic acid dispersing agent, potassium lignosulfonate, cellulose fiber and MgO, ybO, tiO ₂ 、K ₂ Ti ₆ O ₁₃ 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-type mixer, and mixing for 5min to obtain uniform foaming composition.

(3) Pouring the basic raw materials and additives obtained in the step (1) into a roller ball mill, adding 0.6 ton of water, ball milling and mixing for 1h to ensure that the average granularity of solid particles is not more than 50 mu m, then carrying out ultrasonic vibration 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 taking the linear speed of a stirring blade in a stirrer as the linear speed 80m/s is quickly mixed for 7min to obtain uniform foam slurry; during ball milling, the grinding balls in the ball mill are made of zirconia corundum and large balls

Middle ball->

Ball->

(4) Injecting the foam slurry obtained in the step (3) into a wood die, 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 solidified green body, removing liquid water in the green body by adopting an infrared drying method, and taking the infrared wavelength of 5-7 mu m, wherein the drying time is 0.5h, thus obtaining a dried porous green body; the moisture content of the dried green body is less than or equal to 3 weight percent, and the compressive strength is less than or equal to 1.0MPa. Firing the dried blank in a shuttle kiln, heating to 500 ℃ from room temperature at a heating rate of 3 ℃/min, heating to 1200 ℃ at a temperature of 8 ℃/min, preserving heat for 1h, heating to 1650-1700 ℃ at a temperature of 3 ℃/min, preserving heat for 3h, cooling to 1000 ℃ at a temperature of 10 ℃/min, preserving heat for 1h at 1100 ℃, cooling to 500 ℃ at a temperature of 6 ℃/min, preserving heat for 0.5h at 500 ℃, and cooling to 50 ℃ at a temperature of 2 ℃/min to obtain the micro-nano Kong Jue heat-insulating refractory material containing zirconium oxide.

In this example, 3mol% Y ₂ O ₃ Stabilization of ZrO in the chemical composition of zirconia ₂ 94-96 wt% of Al in chemical composition of sillimanite ₂ O ₃ The mass percentage of the SiO is 55 to 60 percent of that of the SiO ₂ The mass percentage of the raw materials is 39-44%, and the grain size of the two raw materials is less than or equal to 0.08mm; mgO, ybO, tiO ₂ 、K ₂ Ti ₆ O ₁₃ The zirconia gel is industrially pure and has a particle size of less than or equal to 5 mu m.

The preparation process of the zirconia-containing micro-nano Kong Jue heat insulation refractory of example 11 is as follows:

(1) 9mol% Y ₂ O ₃ Pouring the stabilized zirconia and the fused mullite into a forced stirrer and dry-mixing for 15min to obtain a basic raw material. Weighing allyl ether type polycarboxylic acid dispersing agent, sodium lignin sulfonate, polyvinylpyrrolidone and Er ₂ O ₃ 、K ₂ Ti ₆ O ₁₃ Pouring into a double cone mixer and dry-mixing for 5min to obtain the additive.

(2) The polyamide type Dendrimer surfactant, zirconia gel, konjak flour, starch ether and hydroxypropyl methyl cellulose ether are weighed, poured into a double cone mixer and mixed for 5min, and a uniform foaming composition is obtained.

(3) Pouring the basic raw material and the additive obtained in the step (1) into a roller ball mill, adding 0.4 ton of water, ball milling and mixing for 1h to ensure that the average granularity of solid particles is not more than 60 mu m, then performing ultrasonic vibration 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 a stirring paddle in a stirrer for 8min 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 zirconia corundum and large balls

Middle ball->

Ball->

The weight ratio of (2) is 1.5:2:6, the weight ratio of the material to the ball is 1:1.4.

(4) Injecting the foam slurry obtained in the step (3) into a glass die, 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) Demolding the solidified green body, and removing liquid water in the green body by adopting a normal pressure drying method, wherein a drying system is as follows: heating to 30 ℃ at 2 ℃/min, preserving heat for 3 hours at 30 ℃, heating to 50 ℃ at 2 ℃/min, preserving heat for 2 hours at 50 ℃, heating to 70 ℃ at 3 ℃/min, preserving heat for 2 hours at 70 ℃, heating to 90 ℃ at 3 ℃/min, preserving heat for 3 hours at 90 ℃, heating to 110 ℃ at 3 ℃/min, and preserving heat for 12 hours at 110 ℃ to obtain a dry porous blank; the moisture content of the dried green body is less than or equal to 3 weight percent, and the compressive strength is less than or equal to 1.0MPa. Firing the dried blank in a high-temperature resistance kiln, heating to 500 ℃ from room temperature at a heating rate of 3 ℃/min, heating to 1200 ℃ at a heating rate of 8 ℃/min, preserving heat for 1h, heating to 1700-1750 ℃ at a heating rate of 3 ℃/min, preserving heat for 3h, cooling to 1000 ℃ at a cooling rate of 10 ℃/min, preserving heat for 1h, cooling to 500 ℃ at a cooling rate of 6 ℃/min, preserving heat for 0.5h, and cooling to 50 ℃ at a cooling rate of 2 ℃/min to obtain the micro-nano Kong Jue heat-insulating refractory material containing zirconium oxide.

In this example, 3mol% Y ₂ O ₃ Stabilization of ZrO in the chemical composition of zirconia ₂ 94-96 wt% of Al in the chemical composition of the electrofused mullite ₂ O ₃ The mass percentage of the catalyst is 69-72 wt percent, siO ₂ The mass percentage of the raw materials is 26-30%, and the grain size of the two raw materials is less than or equal to 0.08mm; er (Er) ₂ O ₃ 、K ₂ Ti ₆ O ₁₃ The zirconia gel is industrially pure and has the particle size of less than or equal to 5 mu m.

The preparation process of the zirconia-containing micro-nano Kong Jue heat insulation refractory of example 12 is as follows:

(1) Monoclinic zirconia is used as a base raw material; weighing allyl ether type polycarboxylic acid dispersing agent, melamine formaldehyde polycondensate and Y ₂ O ₃ 、CeO ₂ 、BaO、TiO ₂ Pouring into a planetary mixer and dry-mixing for 5min to obtain the additive.

(2) The polyamide type Dendrimer surfactant, zirconia gel, potassium alginate, ethyl cellulose ether and hydroxymethyl cellulose ether were weighed, poured into a double cone mixer and mixed for 5 minutes 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 0.2 ton of water, ball milling and mixing for 0.5h to ensure that the average granularity of solid particles is not more than 74 mu m, then carrying out ultrasonic vibration 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 the suspension slurry with a stirring paddle in a stirrer for 8min at the linear speed of 20m/s to obtain the foam A uniform foam slurry; during ball milling, tungsten carbide balls and large balls are adopted as grinding balls in the ball mill

Middle ball->

Ball->

The weight ratio of (2) is 1.5:2:6, the weight ratio of the material to the ball is 1:1.5.

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

(5) Demolding the solidified green body, and removing liquid water in the green body by adopting a normal pressure drying method, wherein a drying system is as follows: heating to 30 ℃ at 2 ℃/min, preserving heat for 3 hours at 30 ℃, heating to 50 ℃ at 2 ℃/min, preserving heat for 2 hours at 50 ℃, heating to 70 ℃ at 3 ℃/min, preserving heat for 2 hours at 70 ℃, heating to 90 ℃ at 3 ℃/min, preserving heat for 3 hours at 90 ℃, heating to 110 ℃ at 3 ℃/min, and preserving heat for 12 hours at 110 ℃ to obtain a dry porous blank; the moisture content of the dried green body is less than or equal to 3 weight percent, and the compressive strength is less than or equal to 1.0MPa. Firing the dried blank in a high-temperature resistance kiln, heating to 500 ℃ at a heating rate of 3 ℃/min from room temperature, preserving heat for 0.5h, heating to 1200 ℃ at 8 ℃/min, preserving heat for 1h, heating to 1800-1850 ℃ at 3 ℃/min, preserving heat for 2-3 h, cooling to 1000 ℃ at 10 ℃/min, preserving heat for 1h, cooling to 500 ℃ at 6 ℃/min, preserving heat for 0.5h, and cooling to 50 ℃ at 2 ℃/min to obtain the micro-nano Kong Jue heat-insulating refractory material containing zirconium oxide.

In this example 12, zrO in the chemical composition of the monoclinic zirconia ₂ The mass percentage of the catalyst is larger than or equal to 99wt percent, and the particle size is smaller than or equal to 0.08mm; y is Y ₂ O ₃ 、CeO ₂ 、BaO、TiO ₂ The zirconia gel is industrially pure, and the grain size of the raw materials is less than or equal to 5 mu m.

The preparation process of the zirconia-containing micro-nano Kong Jue heat insulation refractory of example 13 is as follows:

the preparation process of example 13 is substantially the same as that of example 12, except that no mineralizer or infrared opacifier is added during dosing.

The preparation process of the zirconia-containing micro-nano Kong Jue heat insulation refractory of example 14 is as follows:

(1) Weighing zirconia corundum, limestone, quicklime, slaked lime and CaCO ₃ Pouring into a forced mixer and dry-mixing for 15min to obtain a basic raw material; weighing FS10, FS20, aliphatic dispersant, sucrose, dextrin, tris (hydroxymethyl) aminomethane, polyvinyl alcohol and polyacrylamide, pouring into a double-cone mixer, and dry-mixing 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 a uniform foaming composition.

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

(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) Demoulding the solidified green body, removing water in the green body by adopting a normal pressure hot air drying method, controlling the drying temperature to be 35-45 ℃ and the drying time to be 48 hours, thus obtaining the dried porous green body. The moisture content of the dried green body is less than or equal to 3 weight percent, and the compressive strength is less than or equal to 1.0MPa. Firing the dried green body by adopting a high-temperature tunnel kiln, raising the temperature to 500 ℃ from room temperature at a heating rate of 3 ℃/min, and preserving the temperature for 1h at 500 ℃; heating to 1000 ℃ at 8 ℃/min, and preserving heat for 1h; heating to 1470-1480 ℃ at 5 ℃/min, and preserving heat for 3h; then cooling to 1100 ℃ at 15 ℃/min, and preserving heat for 1h at 1100 ℃; cooling to 500 ℃ at a speed of 6 ℃/min, and preserving heat for 0.5h at 500 ℃; finally, the temperature is reduced to 60 ℃ at 3 ℃/min, and the micro-nano Kong Jue heat-insulating refractory material containing zirconia is obtained.

In the micro-nano Kong Jue heat-insulating refractory material containing zirconia obtained in the embodiment, the main crystal phase is zirconia and calcium hexaaluminate, and ZrO in the chemical composition of zirconia corundum is used as the raw materials ₂ The mass percentage of the aluminum alloy is 23 to 25 percent by weight, and the aluminum alloy is Al ₂ O ₃ The mass percentage of the catalyst is 75-77 wt%, and the particle size is less than or equal to 0.05mm; the mass percentage of CaO in the limestone is 53-55wt%, and the grain diameter is less than or equal to 0.05mm; the mass percentage of CaO in the quicklime is 95-97wt%, and the grain diameter is less than or equal to 0.05mm; the mass percentage of CaO in the slaked lime is 70-75wt%, and the grain diameter is less than or equal to 0.05mm; caSO (Caso-like conductor) ₄ The mass percentage of CaO in the steel is 40-42 wt%, and the grain diameter is less than or equal to 0.05mm; al in alumina sol ₂ O ₃ The mass percentage content of (2) is not less than 20%; the monocalcium aluminate and the dodecacalcium heptaluminate are all industrially pure, and the grain diameter is less than or equal to 5 mu m.

The preparation process of the zirconia-containing micro-nano Kong Jue heat insulation refractory of example 15 is as follows:

(1) Weighing zircon, industrial alumina and beta-Al ₂ O ₃ Wollastonite, dolomite, calcite, caO, ca (OH) ₂ Pouring into a forced mixer and dry-mixing for 15min to obtain the basic raw material.

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

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

(5) Demoulding the solidified green body, removing water in the green body by adopting a normal pressure hot air drying method, controlling the drying temperature to be 35-45 ℃ and the drying time to be 48 hours, thus obtaining the dried porous green body. The moisture content of the dried green body is less than or equal to 3 weight percent, and the compressive strength is less than or equal to 1.0MPa. Firing the dried blank in a shuttle kiln, heating to 500 ℃ from room temperature at a heating rate of 3 ℃/min, and preserving heat for 0.5h; heating to 1100 ℃ at 8 ℃/min, and preserving heat for 1h; heating to 1400 ℃ at 3 ℃/min, and preserving heat for 1.5h; then cooling to 1100 ℃ at 10 ℃/min, and preserving heat for 1h at 1100 ℃; cooling to 500 ℃ at a speed of 6 ℃/min, and preserving heat for 0.5h at 500 ℃; finally, cooling to 50 ℃ at 2 ℃/min to obtain the micro-nano Kong Jue heat-insulating refractory material containing zirconium oxide.

In the micro-nano Kong Jue heat insulating refractory containing zirconia obtained in example 15, the main crystal phases are zirconia and anorthite, and ZrO in the chemical composition of zircon in the raw materials ₂ The mass percentage of the silicon dioxide is 64-67%, siO ₂ 32-35% of the mass percentage of the material, and the grain diameter is less than or equal to 0.05mm; industrial Al ₂ O ₃ And beta-Al ₂ O ₃ Al of (C) ₂ O ₃ The mass percentage of the particles is not less than 98%, and the particle size is not less than 0.05mm; the mass percentage of CaO in the wollastonite is 34-37%, and the grain diameter is less than or equal to 0.05mm; the mass percentage of CaO in the dolomite is 29-31%, the mass percentage of MgO is 20-21%, and the grain diameter is less than or equal to 0.05mm; the mass percentage of CaO in calcite is 50-52%, and the grain diameter is less than or equal to 0.05mm; siO in silica sol ₂ The mass percentage content of (2) is not less than 30%; caO and Ca (OH) ₂ The dicalcium silicate and sodium silicate are all industrially pure, and the grain size is less than or equal to 5 mu m.

The preparation process of the zirconia-containing micro-nano Kong Jue heat insulation refractory of example 16 is as follows:

the preparation process is basically the same as that of example 15, except that curing is carried out for 5 hours in an environment with the air temperature and the relative humidity of 25 ℃ and 90% respectively, curing and demolding can be carried out after curing, and when the green body is dried by adopting normal-pressure hot air, the drying time is 72 hours at the temperature of 35-45 ℃, the drying time is greatly prolonged, and the compressive strength of the dried green body is only 0.5MPa.

The preparation process of the zirconia-containing micro-nano Kong Jue heat insulation refractory of example 17 is as follows:

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

(2) Weighing monocalcium aluminate, dodecacalcium heptaluminate, vinyl acetate and 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 uniform foaming composition. Simultaneously, preparing a 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 material and the additive obtained in the step (1) into a stirrer, adding 1.6 tons of water, stirring and mixing for 0.2h to obtain suspension slurry; and (2) adding the foaming composition, the preformed foam and the alumina sol obtained in the step (2) into the suspension slurry, and rapidly mixing the suspension slurry for 3min at a linear speed of 170m/s by using a stirring paddle to obtain uniform foam slurry.

And pouring, blank maintenance, drying and sintering the foam slurry are basically the same as in example 11, so as to obtain the micro-nano Kong Jue heat-insulating refractory material containing calcium hexaaluminate. The difference is only that the compressive strength of the dried green body is 0.7MPa.

In this example 17, the physical and chemical indexes of the base material and foaming composition used were the same as in example 14, and dicalcium silicate and calcium dialuminate were industrially pure and had a particle size of 5 μm or less.

2. Experimental example

Experimental example 1

The morphology observation is carried out on the zirconia-containing micro-nano Kong Jue heat insulation refractory prepared in the embodiment 7, the appearance picture is shown in figure 1, and the microstructure picture is shown in figures 2 and 3.

As can be seen from FIG. 1, the refractory material produced in the examples was white, and no mottle was found.

As can be seen from the figures 2 and 3, the insulating refractory material contains a large number of spherical tiny air holes with the diameters less than or equal to 250 mu m, and the air hole wall structure of the air holes is compact (see figure 3) by combining with the figure 3 for further analysis, and the air hole wall is formed by tightly combining two particles with the sizes. As can be seen by EDS analysis, the two are corundum (see FIG. 4) and zirconia (FIG. 5), respectively.

Experimental example 2

This experimental example was subjected to X-ray diffraction (XRD) analysis on the zirconia-containing micro-nano Kong Jue heat insulation refractory prepared in example 7, and its XRD pattern is shown in fig. 6.

As can be seen from the figure, the main crystal phase of the micro-nano Kong Jue heat insulation refractory material is zirconia and corundum phases.

Experimental example 3

In this experimental example, pore diameter analysis was performed on the zirconia-containing micro-nano Kong Jue heat insulation refractory prepared in example 7, and the results are shown in fig. 7.

As can be seen from the figure, the pore diameter of the refractory brick is smaller, and the refractory brick has the characteristic of micro-nano Kong Bingcun, and the pore diameter distribution is between 0.006 and 200 mu m.

Experimental example 4

The thermal conductivity and other properties of the zirconia-containing micro-nano Kong Jue heat insulation refractory prepared in the embodiment are tested in the experimental example. The volume density and the total porosity of the sample are tested according to the Chinese national standard GB/T2998-2001, and meanwhile, the closed porosity of a GB/T2997-2000 test pattern is adopted; compressive strength was measured according to GB/T3997.2-1998; the rate of change of the burn line was tested according to GB/T3997.1-1998; thermal conductivity was tested according to YB/T4130-2005; the average pore diameter and pore diameter distribution of the sample were measured by mercury intrusion, and the measurement results are shown in table 3.

Table 3 results of Performance test of the zirconia-containing micro-nano Kong Jue insulation refractory of the examples

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According to the test results of table 3, the performance indexes of the micro-nano Kong Jue insulation refractory containing zirconia of the examples are summarized as follows: the volume density is 0.3-3 g/cm ³ The 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/(m.K), the thermal conductivity at 350 ℃ is 0.03-0.33W/(m.K), the partial formula reaches 0.1-0.13W/(m.K), the thermal conductivity at 1100 ℃ is 0.06-0.4W/(m.K), the use temperature is less than or equal to 2300 ℃, the burn-back line change rate is-0.4-0% (heat preservation is carried out for 24h at 1400-1732 ℃), and the partial formula is-0.1-0%.

As can be seen from comparative examples 1-2, the amount of water that can be used for introducing the dispersant is significantly reduced in the case of small differences in the densities of the prepared samples; as can be seen from comparative examples 12 to 13, the introduction of the infrared opacifier significantly reduced the high temperature conductivity of the samples; as can be seen from comparative examples 5 to 7, the pore size of the test sample effectively decreases with increasing cell regulating dose; as can be seen from comparative examples 3 to 12, under the condition that the dry strength of the sample blank is kept basically stable, the use amount of the inorganic and organic curing agents can be correspondingly reduced along with the increase of the sample density; as can be seen from comparative examples 1 to 2, as the stirring speed increases, the average pore size and the bulk density of the sample are significantly reduced, and the strength of the green body and the burned sample are significantly increased; as can be seen from comparative examples 2 to 12, the density of the burned sample gradually increases with the decrease of the water consumption; as can be seen from comparative examples 12 and 13, the introduction of mineralizer gradually decreases the sintering temperature and increases the density of the sample; as can be seen from comparative examples 4 and 5, the appropriate extension of the grinding time can make the particle size of the solid particles in the slurry finer and the sintering temperature lower. As can be seen from comparative examples 3 and 14 to 15, the sintering property of the test sample is better, the density is increased, and the strength is remarkably improved after the base material passes through the grinding balls and the suspension slurry is subjected to ultrasonic treatment. In comparative examples 15 and 16, it was found that when no organic curing agent was added, the curing time required for the green body was greatly prolonged to achieve demolding, the strength of the green body after drying was greatly reduced, the pore size of the air holes in the fired sample was significantly increased, the density and thermal conductivity were increased, and the total porosity and closed porosity and strength were significantly reduced. As can be seen from examples 14 and 17, when the foaming agent was pre-foamed, the stirring time of the foam slurry was shortened, but the strength of the green body after drying was reduced, the porosity, pore size distribution and average pore size of the fired product were increased, the bulk density, closed porosity and strength were decreased, and the thermal conductivity was increased.

The insulating refractory material of the embodiment can realize controllable and adjustable air hole structure, heat insulation and mechanical property, and can show more excellent mechanical and insulating properties under the condition that the porosity and volume density of the material are close to those of the prior art by constructing a micro-nano hole structure in the zirconia-containing micro-nano Kong Jue insulating refractory material, thereby having better practical significance in practical engineering and technical application. The heat-insulating material is very suitable for the hot-face lining, backing, 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 suitable for the heat-insulating parts of engine engines and the fields of military industry, aerospace and the like.

Claims

1. The micro-nano Kong Jue heat-insulating refractory containing zirconium oxide is characterized in that the micro-nano Kong Jue heat-insulating refractory containing zirconium oxide is prepared from a basic raw material, an additive and water; zrO in articles ₂ The mass percentage content of the catalyst is 5-100%;

the additive comprises at least foaming material, and the additive is 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 0.01-10%, 0.1-20%, 0.1-2% and 0.01-1% respectively based on the mass of the basic raw materials; when the additive is used, the additive is one or more than two of dispersing agent, suspending agent, mineralizer and infrared opacifier, and the mass of the mineralizer and the infrared opacifier is not more than 10% based on the mass of the basic raw materials;

The mass of the water is 20-200% of the mass of the basic raw material;

the pore diameter of the zirconia-containing micro-nano Kong Jue heat insulation refractory material is distributed between 0.006 and 250 mu m, the average pore diameter is 0.1 to 20 mu m, and the normal temperature compressive strength is 13.2 to 220MPa;

the cell regulator is one or more than two selected from cellulose ether, starch ether, lignocellulose and saponin; the cellulose ether is selected from one or more than two of methyl cellulose ether, carboxymethyl ethyl cellulose ether, carboxymethyl hydroxymethyl 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 hydroxybutyl cellulose ether, hydroxybutyl methyl cellulose ether and sulfoethyl cellulose ether.

2. The zirconia-containing micro-nano Kong Jue heat insulating refractory according to claim 1, wherein the micro-nano Kong Jue heat insulating refractory has a bulk density of 0.3-3 g/cm ³ The porosity is 50-95%, the closed porosity is 20-70%, the thermal conductivity at room temperature is 0.02-0.25W/(m.K), the thermal conductivity at 350 ℃ is 0.03-0.33W/(m.K), and the thermal conductivity at 1100 ℃ is 0.06-0.4W/(m.K).

3. The zirconia-containing micro-nano Kong Jue heat insulating refractory according to claim 1, wherein the base raw material consists of 100% zirconia raw material in mass percent; or is composed of 60-95% of zirconia raw material and 5-40% of aluminum-silicon raw material or silica raw material or calcium oxide raw material; or comprises two of an alumina raw material, an aluminum-silicon raw material, a silicon dioxide raw material and a calcium oxide raw material 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 silica raw material.

4. The zirconia-containing micro-nano Kong Jue heat insulating refractory according to any one of claims 1 to 3, wherein the zirconia-based 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 Y ₂ O ₃ Stabilized zirconia, Y ₂ O ₃ The mol ratio of (3) to (9);

the alumina raw material is industrial alumina and industrial Al (OH) ₃ Boehmite, diaspore, beta-Al ₂ O ₃ 、γ-Al ₂ O ₃ 、δ-Al ₂ O ₃ 、χ-Al ₂ O ₃ 、κ-Al ₂ O ₃ 、θ-Al ₂ O ₃ 、η-Al ₂ O ₃ 、ρ-Al ₂ O ₃ 、α-Al ₂ O ₃ 、Al(NO ₃ ) ₃ 、Al ₂ (SO ₄ ) ₃ One or more of n-butyl aluminum, isopropyl aluminum, sec-butyl aluminum, aluminum chloride hexahydrate, aluminum nitrate nonahydrate or fused corundum powder or sintered corundum powder, and platy corundum powder;

the aluminum-silicon raw material is one or more than two of mullite, kaolin, bauxite, coal gangue, kyanite, andalusite, sillimanite, pyrophyllite, potassium feldspar, albite, anorthite, celadon, alkali stone, mica, spodumene, perlite, montmorillonite, illite, halloysite, dickite, flint clay, guangxi white clay, suzhou soil, wood-saving soil, fly ash and floating beads;

the silica raw material is one or more than two of alpha-quartz, beta-quartz, alpha-tridymite, beta-tridymite, alpha-cristobalite, beta-cristobalite, pulse quartz, sandstone, quartzite, flint, cemented silica, river sand, sea sand, white carbon black, methyl orthosilicate, tetraethoxysilane, methyltrimethoxysilane, rice hull ash, diatomite and silicon micropowder;

The calcia raw materials are limestone, quicklime, slaked lime, wollastonite, dolomite, calcite, caO and CaCO ₃ 、Ca(OH) ₂ 、CaSO ₄ One or a combination of two or more of them;

wherein, al in the chemical composition of the alumina raw material ₂ O ₃ The mass percentage of (2) is more than 45%; the mass percentage of aluminum oxide in the aluminum-silicon raw material is 18-90%, and the mass percentage of silicon dioxide is 8-75%; siO in chemical composition of silica raw material ₂ The mass content of (2) is more than 18%; the mass content of CaO in the chemical composition of the calcia raw material is more than 30%.

5. The zirconia-containing micro-nano Kong Jue heat-insulating refractory according to claim 1, wherein the calcia raw material is calcium silicate and/or calcium aluminate, or the calcia raw material is calcium silicate and/or calcium aluminate and limestone, quicklime, slaked lime, wollastonite, dolomite, calcite, caO, caCO ₃ 、Ca(OH) ₂ 、CaSO ₄ One or a combination of two or more of them.

6. The zirconia-containing micro-nano Kong Jue heat insulating refractory according to claim 1, wherein the inorganic curing agent is selected from the group consisting of zirconia sol, alumina sol, silica alumina sol, zirconia gel, alumina gel, silica alumina gel, dicalcium silicate, calcium dialuminate, siO ₂ Micro powder, monocalcium aluminate, tricalcium silicate and Al ₂ O ₃ One or more of micropowder, dodecacalcium heptaluminate, tetracalcium aluminophosphate and water glass;

the organic curing agent is selected from one or more than two of water-soluble polymer resin, low methoxy pectin, carrageenan, hydroxypropyl guar gum, locust bean gum, gellan gum, curdlan, alginate and konjak gum; the water-soluble polymer resin is selected from one or more than two of vinyl acetate and ethylene copolymer, vinyl acetate homopolymer, acrylic ester polymer, ethylene and vinyl acetate copolymer, ethylene and vinyl chloride copolymer, vinyl acetate and vinyl versatate copolymer, acrylic ester and styrene copolymer, vinyl acetate and higher fatty acid vinyl ester copolymer, vinyl acetate and ethylene and vinyl chloride copolymer, vinyl acetate and ethylene and acrylic ester 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 acrylic ester and higher fatty acid vinyl ester copolymer, vinyl acetate and vinyl versatate and acrylic ester copolymer.

7. The zirconia-containing micro-nano Kong Jue heat-insulating refractory material according to claim 1, wherein the foaming agent is a surfactant and/or a protein foaming agent, and the foaming multiple is 8-60 times; the surfactant is one or more selected from cationic surfactant, anionic surfactant, nonionic surfactant, amphoteric surfactant, gemini surfactant, bola surfactant and Dendrimer surfactant; the protein foaming agent is an animal protein foaming agent, a plant protein foaming agent and/or a sludge protein foaming agent.

8. The zirconia-containing micro-nano Kong Jue heat-insulating refractory according to claim 1 or 7, wherein the foaming agent is one or more of a sulfonate anionic surfactant having 8 to 20 carbon atoms, a sulfate anionic surfactant having 8 to 18 carbon atoms, an amido quaternary ammonium salt cationic surfactant, a double long chain ester quaternary ammonium salt cationic surfactant, a triethanolamine stearate quaternary ammonium salt cationic surfactant, a polyoxyethylene nonionic surfactant, a fatty alcohol amide nonionic surfactant, a polyol nonionic surfactant, an amino acid zwitterionic surfactant, and a betaine zwitterionic surfactant.

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

10. The zirconia-containing micro-nano Kong Jue heat insulating refractory 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, polyaluminum chloride, polyaluminum sulfate, chitosan, xanthan gum, acacia gum, welan gum, agar, acrylamide, polyacrylamide, polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol, casein, cetyl alcohol, sucrose, dextrin, tris (hydroxymethyl) aminomethane, microcrystalline cellulose sodium, cellulose fibers, cellulose nanocrystals and soluble starch.

11. The zirconia containing micro-nano Kong Jue heat insulating refractory according to claim 1, wherein the mineralizer is selected from CaO, caF ₂ 、MgO、ZnO、Fe ₂ O ₃ 、YbO、V ₂ O ₅ 、AlF ₃ 、SiF ₄ 、MnO ₂ 、TiO ₂ 、CuO、CuSO ₄ 、SrO、BaO、WO ₃ 、Er ₂ O ₃ 、Cr ₂ O ₃ 、La ₂ O ₃ 、Yb ₂ O ₃ 、Y ₂ O ₃ 、CeO ₂ One or a combination of two or more of them.

12. The zirconia containing micro-nano Kong Jue heat insulating refractory according to claim 1 or 11, wherein said infrared opacifier is selected from rutile, tiO ₂ 、TiC、K ₄ TiO ₄ 、K ₂ Ti ₆ O ₁₃ 、Sb ₂ O ₃ 、Sb ₂ O ₅ 、ZnO ₂ 、NiO、NiCl ₂ 、Ni(NO ₃ ) ₂ 、CoO、CoCl ₂ 、Co(NO ₃ ) ₂ 、ZrSiO ₄ 、Fe ₃ O ₄ 、B ₄ C. One or a combination of two or more of SiC.

13. A method for preparing the zirconia-containing micro-nano Kong Jue heat insulation refractory according to any one of claims 1 to 12, comprising the steps of:

3) Injecting the foam slurry into a mould for curing, and demoulding to obtain a blank; and drying and sintering the green body.

14. The method of preparing a zirconia-containing micro-nano Kong Jue heat insulating refractory according to claim 13, wherein in step 1), the average particle diameter of the solid particles in the suspension slurry is not more than 1mm, or not more than 74 μm, or not more than 50 μm, or not more than 44 μm, or not more than 30 μm.

15. The method for preparing a zirconia-containing micro-nano Kong Jue heat-insulating refractory according to claim 13, 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.

16. The method for preparing a zirconia-containing micro-nano Kong Jue heat-insulating refractory according to claim 13, 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 hours.

17. The method for preparing a zirconia-containing micro-nano Kong Jue heat-insulating refractory according to claim 13, wherein in the step 3), the green body is dried by one or more selected from the group consisting of normal pressure 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 weight percent, wherein the compressive strength of the dried green body is less than or equal to 0.7MPa.

18. The method for preparing a zirconia-containing micro-nano Kong Jue heat-insulating refractory according to any one of claims 13 to 17, wherein the firing is performed in a high-temperature tunnel kiln, shuttle kiln, resistance kiln or microwave kiln; the firing temperature is 1350-1850 ℃.