CN114149276B - A micro-nanoporous heat-insulating refractory material containing zirconia and its preparation method - Google Patents

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

A micro-nanoporous heat-insulating refractory material containing zirconium oxide and a preparation method thereof

Technical Field

The present invention belongs to the technical field of refractory materials, and specifically relates to a micro-nano porous thermal insulation refractory material containing zirconium oxide and a preparation method thereof. In particular, it relates to a micro-nano porous thermal insulation refractory material containing zirconium oxide having a micro-nano pore structure, ultra-low thermal conductivity and volume density, high porosity, high strength, and green and controllable preparation.

Background Art

High temperature industry is the main energy-consuming industry in my country's industrial production. The low thermal energy utilization rate of various kilns is the main reason for their high energy consumption. If the average thermal efficiency can be increased by 20% according to national requirements, energy can be saved equivalent to 220 million tons of standard coal. It can be seen that my country's high temperature industry has great energy-saving potential. To improve the thermal efficiency of industrial kilns, the most important thing is to develop efficient insulation technology, use advanced insulation materials, strengthen the insulation effect of the kiln body, and reduce heat dissipation losses.

At present, although my country's thermal insulation materials are constantly improving and perfecting, they still cannot meet the increasingly harsh thermal insulation environment and requirements of high-temperature industries. Currently, thermal insulation materials for kilns are mostly refractory fiber products or lightweight thermal insulation bricks.

Although the thermal insulation performance of refractory fiber products is good, they are sensitive to the firing atmosphere and easily react with reducing and corrosive gases, causing them to lose their good thermal insulation performance. Moreover, when they serve in a high-temperature environment for a long time, the constituent particles are prone to crystallization and growth, causing stress concentration, leading to pulverization of the thermal insulation layer and shortening the service life. In addition, ceramic fibers are also harmful to human health, and the European Union has listed them as a secondary carcinogen.

Although traditional lightweight insulation bricks can overcome the above-mentioned defects of refractory fiber products, they are mostly prepared by adding a large amount of pore-forming agents (such as polystyrene particles, sawdust, charcoal, anthracite ash, coke powder, etc.). These pore-forming agents occupy a certain space in the green body. After firing, the pore-forming agents leave their original positions in the matrix to form pores, thereby obtaining lightweight insulation refractory materials. The method is simple and easy to control, and the production efficiency is high. However, the porosity of the products made by this method is not high, the pore diameter is large, the insulation effect is poor, and stress concentration and cracking are easily generated, resulting in low strength. In addition, the pore-forming agents used in the preparation process are mostly organic burnt materials, which makes the raw material cost high, and a large amount of toxic and harmful gases are released during firing. For example, anthracite, sawdust and coke powder can produce a large amount of sulfur oxides at a relatively low temperature, and polystyrene particles produce styrene, toluene and nitrogen/carbon/oxides and dioxins, etc. At the same time, a large amount of VOCs fine particles will be produced, which seriously pollutes the environment, endangers human health and the production of surrounding crops. In recent years, with the continuous strengthening of environmental protection control in my country, many enterprises have reduced production or stopped working. Therefore, it is urgent to research and develop new high-temperature industrial insulating refractory materials with excellent thermal insulation, durability and mechanical properties and green and controllable preparation.

Zirconia refractory materials have the characteristics of high temperature resistance (zirconia melting point can reach 2715℃), corrosion resistance, extremely low thermal conductivity (only 1.675W/m·K), good mechanical and thermal shock stability, etc. It is one of the emerging materials that has developed rapidly in recent years and is gradually being used in metallurgy, electronics, environmental protection, biology, chemical industry, aerospace and other fields. If pores can be effectively introduced into zirconia materials, their thermal conductivity can be further reduced, thereby preparing zirconia porous ceramic materials with low thermal conductivity. The products are very suitable for thermal insulation and heat preservation in high temperature environments, engine heat insulation components, etc., especially in ultra-high temperature environment applications above 1800℃.

Our research group has conducted a lot of application research on lightweight thermal insulation refractory materials in the early stage, and has formed research results such as microporous kyanite-based lightweight thermal insulation refractory materials (CN103951452A) and microporous lightweight silica bricks (CN105565850A). Zirconia thermal insulation refractory materials are high-temperature resistant thermal insulation ceramic materials with low thermal conductivity, good thermal insulation effect and high melting point. However, due to the high density of zirconium oxide itself (5.89g/ ^cm3 ), it is difficult to prepare low-density, high-porosity thermal insulation products. Under the same strength grade, how to further effectively reduce the volume density and thermal conductivity of thermal insulation refractory materials, so as to facilitate the construction of lightweight and environmentally friendly kilns, has become the next research focus.

Summary of the invention

The purpose of the present invention is to provide a micro-nano porous heat-insulating refractory material containing zirconium oxide, which has the characteristics of micro-nano pore size, closed spherical pore structure, ultra-low thermal conductivity and volume density, high porosity, high strength, etc. It can effectively reduce the volume density while ensuring that the material strength meets the requirements, thereby facilitating the construction of lightweight, environmentally friendly and high-end kilns.

The second object of the present invention is to provide a method for preparing the above-mentioned micro-nanoporous insulating refractory material containing zirconium oxide. The preparation method is green and pollution-free, the structure and performance of the product are easy to accurately control, and the yield rate is high. It can also solve the problem that the insulating refractory material obtained by the existing preparation method cannot take into account the low thermal conductivity, low bulk density, high strength and high yield rate of the material.

To achieve the above object, the technical solution of the micro-nanoporous insulating refractory material containing zirconium oxide of the present invention is:

A micro-nano-porous insulating refractory material containing zirconium oxide, which is made of a base material, an additive and water. The mass percentage of _ZrO2 in the product is 5-100%;

The basic raw material is composed of the following raw materials in weight percentage: 30-100% of zirconium oxide raw material, 0-30% of aluminum oxide raw material, 0-40% of aluminum silicon raw material, 0-20% of silicon dioxide raw material, and 0-20% of calcium oxide raw material;

The additives at least include foaming materials, with or without additives; the foaming materials are composed of foaming agents, inorganic curing agents, organic curing agents and cell regulators, and the added masses of the foaming agents, inorganic curing agents, organic curing agents and cell regulators are 0.01-10%, 0.1-20%, 0.1-2% and 0.01-1% respectively based on the mass of the base material; when additives are used, the additives are selected from one or a combination of two or more of dispersants, suspending agents, mineralizers and infrared sunscreens, and the added masses of mineralizers and infrared sunscreens are 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.

Dispersants, suspending agents, infrared sunscreen agents and mineralizers form additives, which are external components relative to basic raw materials. Dispersants and suspending agents promote the formation of stable and evenly dispersed suspended slurries during slurrying of refractory materials; infrared sunscreen agents further effectively reduce the radiation heat transfer of materials at high temperatures, thereby reducing thermal conductivity; mineralizers are beneficial to the growth and development of beneficial crystals, and can promote sintering, which is beneficial to further improvement of the mechanical properties of materials.

The foaming material formed by the foaming agent, inorganic curing agent, organic curing agent and cell regulator is mainly used for the formation of micro-nano pore structure in thermal insulation refractory materials. It is an important component of the raw materials used for the micro-nano pore thermal insulation refractory materials containing zirconium oxide of the present invention, so that the final product presents micro-nano pore diameter, ensuring that the product has better thermal insulation performance at lower volume density and high strength.

The micro-nanoporous heat-insulating refractory material containing zirconium oxide provided by the present invention has a white, light pink or light yellow appearance. In addition to zirconium oxide, the product may also contain a mullite phase, a corundum phase and/or a quartz phase. The refractory material has a bulk density of 0.3-3 g/cm ³ , a porosity of 50-95%, a closed-mouth porosity of 20-70%, a normal-temperature compressive strength of 0.6-220 MPa, a thermal conductivity of 0.02-0.25 W/(m·K) at room temperature, a thermal conductivity of 0.03-0.33 W/(m·K) at 350°C, a thermal conductivity of 0.06-0.4 W/(m·K) at 1100°C, a use temperature of ≦2300°C, and a reburning line change rate of -0.4-0% after keeping at different temperatures of 1400°C-1732°C for 24 hours, preferably -0.3-0%, more preferably -0.2-0%, and particularly preferably -0.1-0%. In this heat-insulating refractory material, the pore diameter is distributed between 0.006 and 250 μm, with an average pore diameter of 0.1 to 20 μm. The micro-nano-sized spherical pore structure ensures that the product has better heat-insulating performance at low volume density and high strength.

Compared with the prior art, the zirconia micro-nanoporous heat-insulating refractory material provided by the present invention has the characteristics of ultra-low thermal conductivity, low bulk density, high porosity and high strength, and is a shaped heat-insulating refractory product containing zirconia with the best heat-insulating performance. It has excellent comprehensive performance, so that it can be mainly used for the hot surface lining, backing and filling seal and heat-insulating materials of industrial kilns in the metallurgy, petrochemical, building materials, ceramics, machinery and other industries, and can also be used for engine heat-insulating parts and military and aerospace fields. Because of its extremely low thermal conductivity, the thickness of the kiln wall can be greatly thinned under the condition of meeting the ambient temperature requirements, thereby greatly reducing the weight of the kiln, and accelerating the kiln heating rate, which is conducive to the construction of a new lightweight and environmentally friendly kiln.

Further preferably, the base raw material is composed of 100% zirconia raw material, or 60-95% zirconia raw material and 5-40% alumina siliceous raw material or silica raw material or calcia raw material, or two of alumina raw material, alumina siliceous raw material, silica raw material or calcia raw material (the mass ratio of the two raw materials is preferably (1-2): (1-2)) and 40-60% zirconia raw material, or 30-40% zirconia raw material, 10-30% alumina raw material, 20-40% alumina siliceous raw material, 10-20% silica raw material.

The zirconia raw material mainly provides _ZrO2 component, which can be selected from one or a combination of two or more of zircon, baddeleyite, zirconium corundum, monoclinic zirconia, tetragonal _{zirconia ,} cubic zirconia, and partially stabilized zirconia; the partially stabilized zirconia is _Y2O3 stabilized zirconia, and the molar proportion of _Y2O3 is 3-9%.

Introducing appropriate alumina raw materials into the basic raw materials can effectively supplement the Al ₂ O ₃ content in the product. Preferably, the alumina raw material used is an alumina raw material or an alumina-containing raw material that can be decomposed to generate Al ₂ O ₃ at high temperature, and the mass percentage of Al ₂ O ₃ in the chemical composition of the alumina raw material is higher than 85%. Further preferably, the mass percentage of Al ₂ O ₃ is 95-99.9%. More preferably, the mass percentage of Al ₂ O ₃ is 98-99%.

The above-mentioned alumina raw material is specifically one or more of industrial alumina, β-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-like corundum powder. Preferably, it is at least one of industrial alumina, γ-Al ₂ O ₃ , α-Al ₂ O ₃ , and sintered corundum powder.

The alumina raw material used in the basic raw material can also be a raw material containing alumina, which can be decomposed to generate alumina at high temperature. Preferably, the mass percentage of _Al2O3 in the chemical composition of the alumina-containing raw _material is greater than 45%. More preferably, the mass percentage of _Al2O3 in the chemical composition of the _alumina -containing raw material is 65-87%.

The alumina-containing raw material that can be decomposed to generate Al ₂ O ₃ at high temperature is specifically 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 0.08 mm. The alumina raw material with this particle size has high surface activity and is easy to react with the surrounding _ZrO2 , CaO, CaO-rich _SiO2 or _SiO2 -rich liquid at high temperature to form zirconium corundum, calcium hexaaluminate or calcium feldspar or mullite crystals.

_The aluminum siliceous raw material provides _Al2O3 and _SiO2 components, which are conducive to the formation of mullite or calcium feldspar crystals at high temperature, promote sintering, and improve the mechanical properties of the material. The aluminum siliceous raw material can be selected from one or more combinations of mullite, kaolin, bauxite, homogenous material, coal gangue, kyanite, andalusite, sillimanite, pyrophyllite, potassium feldspar, sodium feldspar, calcium feldspar, barium feldspar, porcelain stone, soda stone, mica, spodumene, perlite, montmorillonite, illite, halloysite, dickite, pyrope stone, clay, Guangxi white clay, Suzhou soil, Mujie soil, fly ash, and floating beads; further preferably, the mass percentage of _Al2O3 in the chemical composition of the aluminum siliceous raw _material is 32-72%, and the mass percentage of _SiO2 is 25-64%. More preferably, in the chemical composition of the aluminum-silicon raw material, the mass percentage of Al ₂ O ₃ is 38-50%, and the mass percentage of SiO ₂ is 45-58%.

Proper introduction of suitable silicon dioxide raw materials into the basic raw materials can effectively supplement the _SiO2 content in the product, promote sintering, and improve the mechanical properties of the material. Preferably, the silicon dioxide raw material is a silicon dioxide raw material or a silicon dioxide-containing raw material, and the mass percentage of _SiO2 in the chemical composition of the silicon dioxide raw material is higher than 80%. Preferably, the mass percentage of _SiO2 is 90-99.9%.

Preferably, the particle size of the aluminum siliceous raw material is ≤1 mm. Further preferably, the particle size of the aluminum siliceous raw material is ≤0.08 mm. Ceramic powder particles with high surface activity can be easily obtained after ball milling.

The silicon dioxide raw material is specifically one or more of α-quartz, β-quartz, α-tridymite, β-tridymite, α-cristobalite, β-cristobalite, vein quartz, sandstone, quartzite, flint, cemented silica, river sand, sea sand, white carbon black, diatomaceous earth, and silicon powder. Preferably, it is one of cemented silica, diatomaceous earth, and silicon powder.

The silicon dioxide raw material in the basic raw material can also be a silicon dioxide-containing raw material that can decompose to generate SiO ₂ at high temperature, and the mass percentage of SiO ₂ in the silicon dioxide-containing raw material is greater than 18%. Preferably, the raw material that can decompose to generate SiO ₂ is 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 ≤ 0.08 mm. The silica raw material with this particle size is easy to react with surrounding calcium, aluminum oxide or zirconium oxide raw materials at high temperature to form anorthite, mullite or zirconium silicate crystals.

Proper introduction of suitable calcium oxide raw materials into the basic raw materials can generate a small amount of beneficial crystals such as calcium feldspar or calcium hexaaluminate in the product, which is beneficial to the lightweight of the sample and further reduce the thermal conductivity of the material. The calcium raw material is one or a combination of two or more of limestone, quicklime, slaked lime, wollastonite, dolomite, calcite, CaO, CaCO ₃ , Ca(OH) ₂ , and CaSO _4. The calcium oxide raw material is calcium silicate and/or calcium aluminate, or the calcium oxide raw material is a combination of calcium silicate and/or calcium aluminate and one or more of limestone, quicklime, slaked lime, wollastonite, dolomite, calcite, CaO, CaCO ₃ , Ca(OH) ₂ , and CaSO _4. The calcium silicate is nCaO·SiO ₂ , and the calcium aluminate is mCaO·qAl ₂ O ₃ ·pFe ₂ O ₃ . Wherein n=1~4, m=1~12, q=1~7, p=0~2.

The particle size of the calcium oxide raw material is less than 0.08 mm. The calcium oxide raw material with this particle size has a high surface activity and is easy to react with the surrounding aluminum oxide or Al ₂ O ₃ -SiO ₂ -rich liquid phase at high temperature to form crystals such as calcium hexaaluminate or calcium feldspar.

Among them, the mass percentage _{of Al2O3} in the chemical composition of the aluminum oxide raw material is more than 45%; the mass percentage of aluminum oxide in the aluminum silica raw material is 18-90%, and the mass percentage of silicon dioxide is 8-75%; the mass content of _SiO2 in the chemical composition of the silicon dioxide raw material is more than 18%; the mass content of CaO in the chemical composition of the calcium oxide raw material is more than 30%.

The cell regulator is selected from one or more of cellulose ether, starch ether, lignocellulose and saponin. Cellulose ether is selected from one or more of methyl cellulose ether, water-soluble cellulose ether, carboxymethyl cellulose ether, carboxymethyl 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 cellulose ether, hydroxyethyl methyl cellulose ether, ethyl cellulose ether, ethyl methyl cellulose ether, hydroxyethyl ethyl cellulose ether, propyl cellulose ether, hydroxypropyl cellulose ether, hydroxypropyl methyl cellulose ether, hydroxypropyl ethyl cellulose ether, hydroxypropyl hydroxybutyl cellulose ether, hydroxybutyl methyl cellulose ether and sulfonic acid ethyl cellulose ether. The cell regulator is used in combination with the foaming agent to effectively adjust the size, circularity, uniformity and closure of the bubbles in the slurry, so as to achieve the effect of effectively and accurately adjusting the pore structure in the fired product.

Generally speaking, the amount of water used is 20-200% of the mass of the basic raw material. Preferably 30-180%, more preferably 40-160%, more preferably 70-140%, particularly preferably 60-120%, and more particularly preferably 70-100%. When the amount of water added is large, most of the water can be transformed into a liquid film of bubbles in the slurry during the stirring process, while a small part of the water that does not become a bubble liquid film exists in the form of liquid water, and after the green body is dried and fired, tiny capillary pores can be left in the sample. In other words, the added water is eventually transformed into micro-nano-sized pores in the product. Therefore, the essence of this process technology for preparing heat-insulating refractory materials is to use water and air to produce micro-nano-sized spherical pore structures in high-temperature resistant materials, so to a certain extent, the volume density, porosity, thermal conductivity and mechanical strength of the product can be adjusted accordingly according to the amount of water used. In this step, if components such as dispersants, suspending agents, mineralizers, infrared sunscreens, etc. are used, the above components and the base material are dispersed into a suspended slurry. If dispersants, suspending agents, mineralizers, infrared shading agents and other ingredients are not used, or only one or several of them are used, the corresponding components can be dispersed.

The inorganic curing agent can be selected from one or more combinations of zirconium oxide sol, aluminum oxide sol, silica sol, silica-alumina sol, zirconium oxide gel, aluminum oxide gel, silica gel, silica-alumina gel, dicalcium silicate, calcium dialuminate, _SiO2 micropowder, _tricalcium silicate, monocalcium aluminate, _Al2O3 micropowder, calcium heptaaluminate, tetracalcium aluminoferrate, aluminum phosphate, and water glass. Among the above raw materials, water glass contains sodium silicate or potassium silicate or a combination of the two. _SiO2 micropowder not only plays the role of an inorganic curing agent, but also serves as a silica raw material. _{Al2O3 micropowder} not only plays the 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 aluminoferrate, and calcium heptaaluminate not only play the role of an inorganic curing agent, but also can serve as a calcium raw material. The silica-alumina sol in the inorganic curing agent is also called aluminum silica sol.

The average particle size of the inorganic curing agent particles is ≦5μm, preferably ≦4μm, more preferably ≦3μm, more preferably ≦2μm, particularly preferably ≦1μm, and even more particularly preferably ≦100nm; the inorganic curing _agents are all industrially pure. In the silica sol, the mass percentage of _SiO2 is ≧25%. The mass percentage of _Al2O3 in the alumina sol is ≧20%; the mass percentage of _Al2O3 in the silica- _alumina sol is ≧30%, and the mass percentage of _SiO2 is ≧20%; the mass percentage of _ZrO2 in the zirconium oxide sol is ≧10%. After hydration, these inorganic curing agents can penetrate into the gaps between the ceramic powder particles, mechanically embed the powder particles, form a good rigid skeleton structure, and increase the mechanical strength of the green body.

The organic curing agent is selected from one or more combinations of water-soluble polymer resin, low methoxyl pectin, carrageenan, carrageenan, hydroxypropyl guar gum, locust gum, locust bean gum, gellan gum, curdlan gum, alginate, and konjac gum; the water-soluble polymer resin is selected from one or more combinations of vinyl acetate homopolymer, acrylate polymer, ethylene and vinyl acetate copolymer, ethylene and vinyl chloride copolymer, vinyl acetate and versatate vinyl ester copolymer, acrylate and styrene copolymer, vinyl acetate and higher fatty acid vinyl ester copolymer, isobutylene and maleic anhydride copolymer, ethylene and vinyl chloride and lauric acid vinyl ester copolymer, vinyl acetate and ethylene and higher fatty acid copolymer, vinyl acetate and ethylene and lauric acid vinyl ester copolymer, vinyl acetate and acrylate and higher fatty acid vinyl ester copolymer, vinyl acetate and versatate vinyl ester and acrylate copolymer. All organic curing agents are water-soluble substances. A small amount of organic solidifying material is dispersed into the gaps between ceramic powder particles. After hydration, it can form a continuous polymer film on the surface of the ceramic powder particles. This film forms a flexible connection between the powder particles, and then the intermolecular force of the organic molecules increases the cohesive force between the ceramic powder particles, thereby improving the strength of the green body, avoiding damage to the body during transportation, and greatly improving the yield rate.

Generally, since inorganic curing agents will produce liquid phase at higher temperatures, which will reduce the softening temperature of the product, as the firing and use temperatures gradually increase, the amount of inorganic curing agents should be gradually reduced, and the amount of organic curing agents should be increased accordingly to increase the strength of the green body. When preparing high-density samples, the amount of curing agent required is reduced accordingly because the spacing between ceramic powder particles in the green body is shorter.

The foaming agent is a surfactant and/or a protein-type foaming agent, and the foaming multiple is 8 to 60 times; the surfactant is selected from one or more of a cationic surfactant, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, a Gemini-type surfactant, a Bola-type surfactant, and a Dendrimer-type surfactant; the protein-type foaming agent is an animal protein foaming agent, a plant protein foaming agent and/or a sludge protein foaming agent.

The foaming agent is one or more of Gemini surfactant, Bola surfactant, Dendrimer surfactant, protein foaming agent, sulfonate anionic surfactant with carbon number of 8 to 20 in carbon chain, sulfate anionic surfactant with carbon number of 8 to 18 in carbon chain, amide ester quaternary ammonium salt cationic surfactant, di-long chain ester quaternary ammonium salt cationic surfactant, stearic acid triethanolamine ester quaternary ammonium salt cationic surfactant, polyoxyethylene nonionic surfactant, fatty alcohol amide nonionic surfactant, polyol nonionic surfactant, amino acid zwitterionic surfactant, betaine zwitterionic surfactant. The foaming multiple of the foaming agent is 8 to 60 times.

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

Bola type surfactants are semi-cyclic, single-chain or double-chain Bola surfactants.

Dendrimer surfactants are polyether, polyester, polyamide, polyaromatic or polysilicone dendrimer surfactants.

The protein-based foaming agent is an animal protein foaming agent, a vegetable protein foaming agent or a sludge protein foaming agent.

Sulfonate anionic surfactants with carbon numbers of 8 to 20 in the carbon chain, such as sodium dodecylbenzene sulfonate, sodium α-olefin sulfonate, etc.; sulfate anionic surfactants with carbon numbers of 8 to 18 in the carbon chain, such as ammonium dodecyl sulfate, sodium hexadecyl ether sulfate, etc.

Polyoxyethylene type nonionic surfactants such as high carbon fatty alcohol polyoxyethylene ether, fatty alcohol polyoxyethylene ester, etc.

Betaine-type zwitterionic surfactants such as dodecyl dimethyl betaine, etc.

Preferably, the foaming agent is selected from quaternary ammonium Gemini surfactants, carboxylate Gemini surfactants, sulfate Gemini surfactants, animal protein foaming agents, sodium dodecylbenzene sulfonate, sodium α-olefin sulfonate, sodium high-carbon fatty alcohol polyoxyethylene ether carboxylate, dodecyl dimethyl betaine, fatty alcohol polyoxyethylene ether, fatty alcohol polyoxyethylene ester, double-chain Bola surfactant, alkylphenol polyoxyethylene ether, polyether Dendrimer surfactant, sodium dodecanol polyoxyethylene ether carboxylate, sodium lauryl alcohol polyoxyethylene ether carboxylate, polyamide Dendrimer surfactant, sodium fatty alcohol polyoxyethylene ether carboxylate, or a combination of two or more thereof.

The selection of each raw material in the additive is explained below.

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

Based on the mass of the base material, the mass of the added suspending agent is not more than 10%; the suspending agent is one or more of bentonite, sepiolite, attapulgite, polyaluminium chloride, polyaluminium sulfate, chitosan, xanthan gum, gum arabic, agar, sucrose, dextrin, acrylamide, polyacrylamide, polyacrylamide, polyvinyl pyrrolidone, polyethylene glycol, polyvinyl alcohol, casein, hexadecanol, sucrose, dextrin, trishydroxymethylaminomethane, microcrystalline cellulose, microcrystalline cellulose sodium, cellulose fiber, cellulose nanocrystals, and soluble starch. If plastic clay raw materials are used in the base raw materials to make the slurry have a certain suspension capacity, the addition of the suspending agent can be appropriately reduced or removed. Generally, when organic suspending agents such as polyaluminum chloride, polyaluminum sulfate, chitosan, welan gum, agar, polyethylene glycol, polyvinyl alcohol, polyacrylamide, polyacrylamide, polyvinyl pyrrolidone, casein, hexadecanol, sucrose, dextrin, microcrystalline cellulose, cellulose fiber, cellulose nanocrystals, etc. are selected, it is found that adding a small amount can achieve better results. They can suspend the slurry through steric hindrance effect or electrostatic steric hindrance effect in the slurry, so their addition amount can be relatively small. Generally, their dosage is ≤3%, preferably ≤1%, and more preferably ≤0.5%. When inorganic mineral raw materials such as bentonite, sepiolite, and attapulgite are selected, it is found that they can be rapidly hydrolyzed in the slurry and decomposed into charged ions. These ions form a double electric layer structure on the surface of the base material particles. The base material particles produce a suspension effect in the slurry by electrostatic repulsion, but their dosage is relatively large. Generally, the dosage is ≤10%.

The mineralizer is _one or a combination of two or more of CaO _{, CaF2} , MgO, ZnO, _Fe2O3 , YbO, _V2O5 , _AlF3 , _SiF4 , _MnO2 , _TiO2 , CuO _{, CuSO4} , SrO, BaO, _WO3 , _Er2O3 , _Cr2O3 , _La2O3 , _Yb2O3 , _Y2O3 , and _CeO2 . The average particle size of the mineralizer is ≤5 μm, preferably ≤4 μm, preferably _{≤3 μm} , more preferably ≤2 _μm , particularly preferably ≤1 _μm , and even more particularly preferably ≤100 nm. The mineralizer can promote the stability of the zirconium oxide crystal form and the growth and development of the beneficial crystal, and can reduce the sintering temperature and promote the sintering reaction.

The thermal insulation mechanism of the insulating refractory material is due to the presence of a large number of pores inside it, and the thermal conductivity of the air in the pores is much smaller than the thermal conductivity of the pore wall, so the heat transfer rate of the entire insulating material slows down, and it has thermal insulation performance. The thermal conductivity mechanism of the material is mainly composed of three parts: heat conduction, convection heat transfer and radiation heat transfer. In the present invention, since the aperture of the pores in the prepared micro-nanoporous insulating refractory material containing zirconium oxide is small, and most of the pores are closed structures, gas circulation is difficult, so convection heat transfer can be basically ignored. Because the micro-nanoporous insulating refractory material containing zirconium oxide will be mainly used at high temperatures, the heat transfer mechanism of the material includes radiation heat transfer in addition to heat conduction. In order to further effectively reduce radiation heat transfer, the present invention introduces an infrared sunscreen to increase the reflection or absorption of infrared radiation, weaken its penetration, and reduce thermal conductivity. Especially for high-porosity, low-thermal-conductivity insulating refractory materials, the reduction of thermal conductivity is particularly obvious. In order to further improve the heat insulation performance of the product of the present invention, preferably, the infrared sunscreen agent is selected from one _or a combination of two _{or more of rutile, TiO2, TiC, K4TiO4, K2Ti6O13 , Sb2O3, Sb2O5, ZnO2, NiO, NiCl2, Ni(NO3)2 , CoO , Co ( NO3 ) 2 , CoCl2 , ZrSiO4 , Fe3O4} , _B4C , and SiC. The average particle size of the infrared sunscreen agent is ≤5μm, preferably ≤4μm, more preferably _≤3μm , more preferably ≤2μm, particularly preferably ≤1μm, and even more particularly preferably ≤100nm. The usage amount of infrared sunscreen agent is preferably 1-10% of the mass of the basic raw material, and its application effect in low bulk density and high porosity heat-insulating refractory materials is more significant.

The technical solution of the method for preparing the micro-nanoporous heat-insulating refractory material containing zirconium oxide of the present invention is:

A method for preparing a micro-nanoporous heat-insulating refractory material containing zirconium oxide comprises the following steps:

1) When using additives, the base raw material, the additive combination and water are mixed and dispersed to form a suspension slurry; when not using additives, the base raw material and water are mixed and dispersed to form a suspension slurry;

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

3) The foam slurry is injected into the mold for curing (to solidify and shape it), and the green body is obtained after demoulding; the green body is then dried and fired.

The technical key to preparing lightweight thermal insulation materials lies in the introduction of internal pores. In the preparation method of the present invention, the base material, additives and water are first mixed to form a suspension slurry, and then mixed with a functional foaming component composed of a foaming agent, an inorganic curing agent, an organic curing agent, and a pore regulator and stirred for foaming, which is beneficial for the integrity of the bubbles, thereby increasing the generation rate of closed-mouth pores; during the curing process, the bubbles in the foam slurry are transformed into spherical pores in the blank, and the pores provide space for the growth and development of beneficial crystals such as zirconium oxide, mullite, calcium feldspar and calcium hexaaluminate in the subsequent firing process, so that the crystals develop perfectly and the product performance is improved. At the same time, the inventor also accidentally discovered in the long-term research process that since the holes in the blank made by the present invention are tiny micrometer or nanometer spherical voids, the concave surface of the hole has a very large radius of curvature, which further enhances the nucleation and growth driving force of the beneficial crystals in the hole, so that the growth size of the crystal is larger and the physical properties of the product are better.

The preparation method of the micro-nanoporous insulating refractory material containing zirconium oxide provided by the present invention is green, environmentally friendly and pollution-free, and the preparation process is simple and easy to control. The product has a micro-nano pore structure, and can effectively regulate the volume density, mechanical strength, porosity, thermal conductivity, etc. within a large range. Under the volume density and porosity similar to the prior art, the compressive strength and thermal insulation performance of the product are improved by more than several times, which is more suitable for the application requirements of modern kilns and equipment for lightweight, high-strength, ultra-low thermal conductivity insulating refractory materials.

In the preparation method of the present invention, taking the use of additives as an example, in step 1), the basic raw material, dispersant, suspending agent, and mineralizer are premixed first, and then water is added to mix to form a suspension slurry. In order to form a fine, uniform and stable suspension slurry, the average particle size of the solid particles in the suspension slurry should be controlled to be no higher than 1 mm, preferably no higher than 74 μm. In order to achieve the above-mentioned mixing effect, the mixing can be carried out by one or a combination of mechanical stirring, ball milling, ultrasound and the like. When the particle size of the raw material is fine and easy to disperse to obtain a suspension slurry, a simple mechanical stirring method can be used. More preferably, the dispersant, suspending agent, and mineralizer are premixed to obtain an additive, and then the additive is mixed with the basic raw material and water; preferably, the base material and the additive combination are ball milled with water. Further preferably, in order to obtain a more uniform suspension slurry, the ball-milled slurry can be ultrasonically dispersed. Among them, the zirconium oxide raw material, aluminum silicon raw material, aluminum oxide raw material, silicon dioxide raw material and calcium raw material in the basic raw material are preferably premixed uniformly.

The additives and foaming materials can be pre-mixed separately by a three-dimensional mixer, a V-type mixer, a double cone mixer, a planetary mixer, a forced mixer, or a non-gravity mixer, and the uniformity of the materials is ≥ 95%, preferably ≥ 99%. Similarly, the five raw materials in the basic raw materials can be pre-mixed uniformly in the same way when used.

中球

小球

大、中、小球按(1～1.5)：(1～3)：(6～10)的重量比组合。进一步优选的，大、中、小球按(1～1.5)：(1～2)：(6～8)的重量比组合。通过球磨，可使混合料中固体颗粒的平均粒径不高于74μm。优选的，固体颗粒的平均粒径不高于50μm；进一步优选的，固体颗粒的平均粒径不高于44μm；更特别优选的，固体颗粒的平均粒径不高于30μm。发明人发现这些球磨后的陶瓷粉体颗粒具有较高的表面活性，后再经表面活性剂(发泡剂)分子修饰后具有优异的疏水特性，在机械搅拌作用下，会不可逆的吸附于气泡液膜上的气-液界面，高能态的气-液界面被低能态的液-固和气-固界面代替，使体系的总自由能降低，泡沫稳定性提高，同时还发现部分粉体颗粒在气泡间的Plateau通道累积，有效的阻止了液膜排液，抵制了泡沫的破裂、排液、歧化、奥斯瓦尔德熟化等不稳定因素，从而获得非常稳定的泡沫陶瓷料浆。During ball milling, the weight ratio of material to ball is 1: (0.8-1.5), and the ball milling time is 0.5-12h. The material of the grinding ball is one or more of pebble, corundum, mullite, zirconium oxide, zirconium corundum, silicon carbide, and tungsten carbide; the size of the grinding ball is large ball

Middle ball

Small Ball

The large, medium and small balls are combined in a weight ratio of (1-1.5): (1-3): (6-10). Further preferably, the large, medium and small balls are combined in a weight ratio of (1-1.5): (1-2): (6-8). By ball milling, the average particle size of the solid particles in the mixture can be no higher than 74 μm. Preferably, the average particle size of the solid particles is no higher than 50 μm; further preferably, the average particle size of the solid particles is no higher than 44 μm; more particularly preferably, the average particle size of the solid particles is no higher than 30 μm. The inventors found that these ball-milled ceramic powder particles have high surface activity, and then have excellent hydrophobic properties after being modified by surfactant (foaming agent) molecules. Under mechanical stirring, they will irreversibly adsorb on the gas-liquid interface on the bubble liquid film, and the high-energy gas-liquid interface will be replaced by the low-energy liquid-solid and gas-solid interface, so that the total free energy of the system is reduced and the foam stability is improved. At the same time, it is also found that some powder particles accumulate in the Plateau channels between bubbles, which effectively prevents the liquid film from draining and resists unstable factors such as foam rupture, drainage, disproportionation, Oswald ripening, etc., thereby obtaining a very stable foam ceramic slurry.

Ultrasound further and quickly improves the mixing and dispersion uniformity of each component in the suspended slurry. The power of ultrasound is 500-2000W and the time is 4-15min.

In step 2), during the preparation of the foam slurry, depending on the raw material varieties, if the foaming agent, inorganic curing agent, organic curing agent, and cell regulator are all dry solid raw materials, the dry raw materials are first dry-mixed to obtain a foaming composition, and then the foaming composition is added to the suspension slurry, and then stirred for foaming. If some varieties of the foaming agent, inorganic curing agent, organic curing agent, and cell regulator are liquid raw materials, it is preferred that the dry solid raw materials are first dry-mixed, and then the dry mixture and the liquid raw materials are added to the suspension slurry, and then stirred and sheared for foaming. The foaming agent can also be pre-prepared into foam using a foaming machine, and then added to the suspension slurry obtained in step 1 with the mixture composed of the inorganic curing agent, organic curing agent, and cell regulator, and then further stirred and sheared for foaming.

Preferably, in step 2), the stirring and foaming is a high-speed stirring, shearing, mixing and foaming using a stirring blade of a vertical mixer, and the linear velocity of the outer edge of the stirring blade is 20 to 200 m/s. Use the stirring blade of the mixer to quickly mix for 1 to 30 minutes. The shear linear velocity is the linear velocity of the outer edge of the stirring blade. The stirring blade quickly stirs, mixes and vents in the slurry, causing the slurry volume to expand rapidly. As time goes by, the large bubbles in the slurry are gradually sheared into small bubbles with a diameter of 0.01 to 200 μm, and the suspended slurry becomes a uniform foam slurry. After the foam slurry is solidified and dried, the small bubbles in the slurry will be transformed into spherical closed pores in the dried blank. This spherical pore structure can provide a development space for the growth of zirconium oxide and other beneficial crystals in the fired product, which is beneficial to the growth and improvement of the crystals and the mechanical properties of the product. The linear velocity of the outer edge of the stirring blade is preferably 50 to 200 m/s, more preferably 80 to 200 m/s, more preferably 100 to 200 m/s, particularly preferably 150 to 200 m/s, and even more particularly preferably 180 to 200 m/s.

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

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

In step 3), the curing is carried out at a temperature of 1 to 35°C and a humidity of 40 to 99.9% for 0.1 to 24 hours, preferably for 0.1 to 2 hours. Curing is preferably carried out in a constant temperature and humidity environment. During the curing process, the foam slurry is quickly solidified and shaped, and then it can be demoulded and dried. During the curing process, the air temperature is preferably 5 to 30°C, more preferably 10 to 30°C, more preferably 20 to 30°C, particularly preferably 25 to 30°C, and more particularly preferably 25 to 27°C; the relative humidity of the air is preferably 60 to 99%, more preferably 70 to 97%, more preferably 80 to 95%, particularly preferably 85 to 93%, and more particularly preferably 88 to 92%. During the curing process, the inorganic and organic curing agents in the green body will accelerate the hydration reaction and solidify and condense, so that the strength of the green body increases rapidly and rapid demolding is achieved.

The study found that due to the very short demoulding time of the blank, the turnover rate of the mold was greatly accelerated, and the overall preparation process was also accelerated, greatly improving production efficiency, which was difficult to achieve in the past.

It is understandable that after the green body is cured, it is necessary to demould first and then dry it. Since the strength of the green body increases rapidly after curing, the green body can be quickly dehydrated and dried in step (3), and the drying can be selected from one or more combinations of atmospheric pressure drying, supercritical drying, freeze drying, vacuum drying, infrared drying, and microwave drying. The moisture content in the finally dried green body is ≤3%. In the above process, the combined effect of organic and inorganic curing agents greatly improves the strength of the green body obtained after the foam slurry is cured and dried, and the compressive strength of the green body after drying is ≥0.7MPa, which can avoid or greatly reduce the damage caused by bumping during transportation and kiln loading, greatly improve the yield rate, the yield rate is ≥90%, preferably ≥95%, more preferably ≥98%, and more preferably ≥99%, which significantly reduces the production cost, and the green body can be effectively machined.

Wherein, preferably, when drying at normal pressure, the drying heat source can be power supply heating or hot air, the drying temperature is 30-110°C, and the drying time is 12-48h. Preferably, the drying system is: firstly heating to 30°C at 1-5°C/min, keeping at 30°C for 0.5-5h, then heating to 50°C at 1-5°C/min, keeping at 50°C for 2-5h, then heating to 70°C at 1-5°C/min, keeping at 70°C for 2-5h, then heating to 90°C at 2-5°C/min, keeping at 90°C for 2-5h, then heating to 100-110°C at 2-5°C/min, keeping at 100-110°C for 5-24h.

During supercritical drying, the drying medium is carbon dioxide, the temperature of carbon dioxide supercritical drying is 31-45°C, the pressure in the reactor is controlled at 7-10MPa, and the drying time is 0.5-3h.

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

During vacuum drying, the drying temperature is 35-50°C, the vacuum pressure is 130-0.1Pa, and the drying time is 3-8h.

During infrared drying, the wavelength of the infrared rays is 2.5 to 100 μm, preferably 2.5 to 50 μm, more preferably 2.5 to 30 μm, particularly preferably 2.5 to 15 μm, and even more particularly preferably 2.5 to 8 μm. The drying time is 0.5 to 5 h.

During microwave drying, the microwave frequency is 300 to 300000 MHz, preferably 300 to 10000 MHz, more preferably 300 to 3000 MHz, particularly preferably 300 to 1000 MHz, and even more particularly preferably 600 to 1000 MHz, and the drying time is 0.2 to 2 h.

After the green body is quickly dried and dehydrated, a porous structure with higher strength is formed. It is found that its weight is much lighter than that before drying and that of the green body made by the traditional method of adding pore-forming agents, and its strength is greatly increased. Therefore, the labor intensity of workers in transporting green bodies and loading kilns is greatly reduced, and it is very suitable for mechanized operation, which improves work efficiency and the rate of finished products.

Preferably, the firing in step 3) is optionally carried out in a shuttle kiln, a resistance kiln, a high-temperature tunnel kiln or a microwave kiln. During firing, preferably, the firing temperature is 1350-1850°C. In order to further optimize the effect of firing and promote the formation of equiaxed granular zirconium oxide crystals, preferably, during firing, first at 400-600°C and keep warm for 0.5-1.5h; then heated to 1000-1200°C and keep warm for 0.5-1.5h; then heated to 1350-1850°C and keep warm for 1-10h; then cooled to 1000-1200°C and keep warm for 0.5-1h, then cooled to 400-600°C and keep warm for 0.5-1h, and then cooled to 50-80°C.

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

The fired micro-nanoporous thermal insulating refractory material containing zirconium oxide can be cut, ground or punched into a desired shape according to actual requirements.

Compared with the prior art, the preparation method of the present invention is green, environmentally friendly, pollution-free, the process is simple and easy to control, the demoulding and drying cycles of the green body are very short, the green body has high strength, high yield rate and excellent product performance, and is very suitable for large-scale, mechanized, modern and intelligent production operations, and is conducive to promotion and application.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG1 is a photograph of the appearance of a micro-nanoporous thermal insulating refractory material containing zirconium oxide prepared in Example 7;

FIG2 is a photograph of the pore structure of the micro-nanoporous thermal insulating refractory material containing zirconium oxide prepared in Example 7;

FIG3 is a photograph of the pore wall of the micro-nanoporous thermal insulating refractory material containing zirconium oxide prepared in Example 7;

Figure 4 is the EDS analysis of point 1 in picture 3;

Figure 5 is the EDS analysis of point 2 in picture 3;

FIG6 is an X-ray diffraction (XRD) pattern of the micro-nanoporous thermal insulation refractory material containing zirconium oxide prepared in Example 7;

FIG. 7 is a pore size distribution curve of the micro-nanoporous thermal insulating refractory material containing zirconium oxide prepared in Example 7.

DETAILED DESCRIPTION

The following is a further description of the embodiments of the present invention in conjunction with specific examples. The raw materials involved in the following examples can all be obtained through conventional commercial channels.

The specific implementation process of the present invention is described in detail below in conjunction with specific embodiments. It should be particularly noted that the embodiments given in the specification of the present invention are only intended to help understand the present invention, and they do not have any limiting effect, that is, the present invention may also have other implementations in addition to the embodiments given in the specification. Therefore, any technical solution formed by equivalent replacement or equivalent transformation forms falls within the protection scope required by the present invention.

All raw materials used in the following examples are commercially available conventional products. The optional manufacturers of the main raw materials are given below in illustrative form.

乙烯与乙酸乙烯酯共聚物购自德国瓦克化学公司

丙烯酸酯与苯乙烯共聚物购自美国国民淀粉公司

乙烯与氯乙烯和月桂酸乙烯酯共聚物购自德国瓦克化学公司

丙烯酸酯聚合物购自美国国民淀粉公司

醋酸乙烯酯与乙烯和高级脂肪酸共聚物购自德国瓦克化学

乙烯与氯乙烯共聚物购自德国瓦克化学

醋酸乙烯酯与乙烯和氯乙烯共聚物购自德国瓦克化学

醋酸乙烯酯与乙烯和丙烯酸酯共聚物购自德国瓦克化学

醋酸乙烯酯与乙烯和月桂酸乙烯酯共聚物购自德国瓦克化学

醋酸乙烯酯均聚物购自德国瓦克化学

醋酸乙烯酯与叔碳酸乙烯酯共聚物购自安徽皖维集团公司(WWJF-8010)；醋酸乙烯与叔碳酸乙烯酯和丙烯酸酯共聚物购自日本合成化学工业株式会社(Mowinyl-DM2072P)；醋酸乙烯酯与高级脂肪酸乙烯酯共聚物购自山西三维集团公司(SWF-04)；异丁烯与马来酸酐共聚物购自日本可乐丽公司(ISOBAM-04)；魔芋胶粉购自上海北连生物科技有限公司；可得然胶购自恒美科技有限公司；蔗糖、糊精和琼脂、结冷胶购自江苏古贝生物科技有限公司；羟丙基瓜尔胶购自任丘天诚化工公司；海藻酸钠购自江苏古贝生物科技公司；黄原胶购自山东阜丰发酵公司；阿拉伯胶购自郑州德旺化工公司；丙烯酰胺和聚丙烯酸胺购自山东瑞海米山化工公司；聚乙二醇、十六醇和聚乙烯醇购自日本可乐丽公司；三羟甲基氨基甲烷购自商丘腾飞生物科技公司；微晶纤维素和纤维素纳米晶购自江苏鑫和源生物科技公司。Vinyl acetate and ethylene copolymer were purchased from Wacker Chemical Company, Germany

Ethylene-vinyl acetate copolymer was purchased from Wacker Chemical Company, Germany

Acrylate and styrene copolymer was purchased from National Starch Company

Ethylene-vinyl chloride-vinyl laurate copolymer was purchased from Wacker Chemical Company, Germany

Acrylate polymer was purchased from National Starch Company

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

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

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

Vinyl acetate, ethylene and acrylate copolymers were purchased from Wacker Chemicals, Germany

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

Vinyl acetate homopolymer was purchased from Wacker Chemie, Germany

Copolymer of vinyl acetate and versatate was purchased from Anhui Wanwei Group Co., Ltd. (WWJF-8010); copolymer of vinyl acetate, versatate and acrylate was purchased from Nippon Synthetic Chemical Industry Co., Ltd. (Mowinyl-DM2072P); copolymer of vinyl acetate and higher fatty acid vinyl ester was purchased from Shanxi Sanwei Group Co., Ltd. (SWF-04); copolymer of isobutylene and maleic anhydride was purchased from Japan Kuraray Co., Ltd. (ISOBAM-04); konjac gum powder was purchased from Shanghai Beilian Biotechnology Co., Ltd.; and curdlan was purchased from Hengmei Technology Co., Ltd. Co., Ltd.; sucrose, dextrin, agar and gellan gum were purchased from Jiangsu Gubei Biotechnology Co., Ltd.; hydroxypropyl guar gum was purchased from Renqiu Tiancheng Chemical Company; sodium alginate was purchased from Jiangsu Gubei Biotechnology Co., Ltd.; xanthan gum was purchased from Shandong Fufeng Fermentation Company; gum arabic was purchased from Zhengzhou Dewang Chemical Company; acrylamide and polyacrylamide were purchased from Shandong Ruihai Mishan Chemical Company; polyethylene glycol, hexadecanol and polyvinyl alcohol were purchased from Japan Kuraray Co., Ltd.; trishydroxymethylaminomethane was purchased from Shangqiu Tengfei Biotechnology Co., Ltd.; microcrystalline cellulose and cellulose nanocrystals were purchased from Jiangsu Xinheyuan Biotechnology Co., Ltd.

As for the raw materials of cell regulators, ethyl cellulose ether was purchased from Akzo Nobel of the Netherlands; hydroxyethyl cellulose ether was purchased from Hercules of the United States; hydroxyethyl methyl cellulose ether was purchased from Klein of Switzerland; hydroxyethyl ethyl cellulose ether was purchased from Akzo Nobel of the Netherlands; ethyl methyl cellulose ether was purchased from Dow Chemical of the United States; methyl cellulose ether was purchased from Dow Chemical of the United States; carboxymethyl cellulose ether was purchased from Ashland of the United States; carboxymethyl methyl cellulose ether was purchased from Dow Chemical of the United States; carboxymethyl ethyl cellulose ether was purchased from Ashland of the United States; propyl cellulose ether was purchased from Ashland of the United States; hydroxypropyl cellulose ether was purchased from Ashland of the United States; hydroxypropyl methyl cellulose ether was purchased from Ashland of the United States; hydroxypropyl ethyl cellulose ether was purchased from Ashland of the United States Cellulose ether was purchased from Ashland, USA; hydroxymethyl cellulose ether was purchased from Dow Chemical, USA; carboxymethyl hydroxymethyl cellulose ether was purchased from Dow Chemical, USA; carboxymethyl hydroxyethyl cellulose ether was purchased from Dow Chemical, USA; carboxymethyl hydroxypropyl cellulose ether was purchased from Dow Chemical, USA; carboxymethyl hydroxybutyl cellulose ether was purchased from Dow Chemical, USA; hydroxypropyl hydroxybutyl cellulose ether was purchased from Dow Chemical, USA; sulfonate ethyl cellulose ether was purchased from Dow Chemical, USA; hydroxybutyl methyl cellulose ether was purchased from Dow Chemical, USA; saponin was purchased from Hengmei Technology Co., Ltd.; starch ether was purchased from AVEBE, Netherlands; water-soluble cellulose ether was purchased from Hengmei Technology Co., Ltd.; wood cellulose was purchased from JRS, Germany; saponin was purchased from Xi'an Tianguangyuan Company.

Quaternary ammonium Gemini surfactant (foaming multiple is 45), purchased from Hengmei Technology Co., Ltd.; semi-cyclic Bola surfactant (foaming multiple is 50), purchased from Hengmei Technology Co., Ltd.; double-chain Bola surfactant (foaming multiple is 44), purchased from Hengmei Technology Co., Ltd.; polyether Dendrimer surfactant (foaming multiple is 45), purchased from Hengmei Technology Co., Ltd.; plant protein foaming agent (foaming multiple is 9), purchased from Shandong Xinmao Chemical Co., Ltd.; sludge protein foaming agent (foaming multiple is 8), purchased from Hengmei Technology Co., Ltd.; carboxylate Gemini surfactant (foaming multiple is 60), purchased from Hengmei Technology Co., Ltd.; animal protein Foaming agent (foaming multiple is 11), purchased from Hengmei Technology Co., Ltd.; sodium dodecyl alcohol polyoxyethylene ether carboxylate (foaming multiple is 9); lauric acid amide propyl sulfobetaine (foaming multiple is 13); sodium α-olefin sulfonate (foaming multiple is 15); dodecyl dimethyl betaine surfactant (foaming multiple is 17); sulfate type Gemini surfactant (foaming multiple is 55), purchased from Hengmei Technology Co., Ltd.; sodium fatty alcohol polyoxyethylene ether carboxylate (foaming multiple is 15), purchased from Hengmei Technology Co., Ltd.; sodium dodecylbenzene sulfonate (foaming multiple is 9); polyamide type Dendrimer surfactant (foaming multiple is 55), purchased from Hengmei Technology Co., Ltd.

Allyl ether type polycarboxylic acid dispersant, purchased from Hengmei Technology Co., Ltd.; amide type polycarboxylic acid dispersant, purchased from Hengmei Technology Co., Ltd.; imide type polycarboxylic acid dispersant, purchased from Hengmei Technology Co., Ltd.; polyamide type polycarboxylic acid dispersant, purchased from BASF, Germany; sulfonated melamine polycondensate, purchased from Hengmei Technology Co., Ltd.; naphthalene type high efficiency dispersant, purchased from Hengmei Technology Co., Ltd.; polyethylene glycol type polycarboxylic acid dispersant, purchased from BASF, Germany; polycarboxylic acid dispersant, purchased from BASF, Germany; melamine formaldehyde polycondensate, purchased from Hengmei Technology Co., Ltd.; polycarboxylic acid ether dispersant, purchased from BASF, Germany. Methacrylate type polycarboxylic acid dispersant, purchased from Hengmei Technology Co., Ltd.

1. Specific embodiments of the micro-nanoporous thermal insulation refractory material containing zirconium oxide and its preparation method of the present invention

Example 1

The micro-nanoporous heat-insulating refractory material containing zirconium oxide in this embodiment is made of basic raw materials, suspending agent, mineralizer, infrared light-shielding agent, foaming agent, inorganic curing agent, organic curing agent, cell regulator and water. The types and amounts of the raw materials in this embodiment are as follows:

Basic raw materials: 0.4 tons of zircon, 0.1 tons of industrial Al(OH) ₃ , 0.1 tons of boehmite, 0.3 tons of kaolin, and 0.1 tons of silica powder. The mass percentage of _ZrO2 in the chemical composition of zircon is 64-67wt%, the mass percentage of _SiO2 is 32-35wt%, and the particle size is ≦0.08mm; the mass percentage of _Al2O3 in the chemical composition of industrial Al(OH) ₃ is ≧65wt%, _and the particle size is ≦0.08mm; the mass _percentage of _Al2O3 in the chemical composition of boehmite is ≧70%, and the particle size is ≦0.08mm; the mass percentage of _Al2O3 in the chemical composition of _kaolin is 35-37wt%, the mass percentage of _SiO2 is 59-62%, and the particle size is 0.6-1mm; the mass percentage of _SiO2 in the chemical composition of silicon micropowder is ≧95wt%, and the particle size is ≦5μm.

Suspending agent: 100 kg bentonite, the chemical composition of which includes 22-23 wt% Al ₂ O ₃ and 68-75% SiO ₂ , with a particle size of ≦0.045 mm.

Mineralizer: 40kg Y ₂ O ₃ , 20kg CeO ₂ , 30kg AlF ₃ , 10kg ZnO; Y ₂ O ₃ , CeO ₂ , AlF ₃ , and ZnO are all industrially pure, with a particle size of ≦5μm.

Infrared sunscreen: 50kg rutile, 25kg ZrSiO ₄ , 25kg B ₄ C; rutile, ZrSiO ₄ , B ₄ C are all industrially pure, with a particle size of ≦5μm.

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

Inorganic curing agent: 100kg silica sol, _SiO2 content ≧30%.

Organic curing agent: 5kg of vinyl acetate and ethylene copolymer, 15kg of vinyl acetate and ethylene and higher fatty acid copolymer; industrial pure, particle size ≤5μm.

Cell regulator: 8kg carboxymethyl hydroxypropyl cellulose ether; industrial pure, particle size ≦5μm.

Water: 2 tons.

The specific preparation process of the micro-nanoporous insulating refractory material containing zirconium oxide in this embodiment is as follows:

(1) Weigh 0.4 tons of zircon, 0.1 tons of industrial Al(OH) ₃ , 0.1 tons of boehmite, 0.3 tons of kaolin, and 0.1 tons of silicon micropowder, pour them into a forced mixer, and dry mix them for 5 minutes to obtain a basic raw material. Weigh 100 kg of bentonite, 40 kg of Y ₂ O ₃ , 20 kg of CeO ₂ , 30 kg of AlF ₃ , 10 kg of ZnO, 50 kg of rutile, 25 kg of ZrSiO ₄ , and 25 kg of B ₄ C, pour them into a three-dimensional mixer, and dry mix them for 5 minutes to obtain an additive.

(2) Weigh 1 kg of quaternary ammonium Gemini surfactant, 39 kg of vegetable protein foaming agent, 60 kg of sludge protein foaming agent, 5 kg of vinyl acetate and ethylene copolymer, 15 kg of vinyl acetate and ethylene and higher fatty acid copolymer, and 8 kg of carboxymethyl hydroxypropyl cellulose ether, pour them into a V-type mixer and mix for 5 minutes to obtain a uniform foaming composition.

中球

小球

的重量比为1：1：8，料/球重量比为1：0.8。(3) pouring the basic raw materials and additives obtained in step (1) into a drum ball mill, adding 2 tons of water, and ball milling for 12 hours to make the average particle size of the solid particles in the slurry not greater than 30 μm, and then ultrasonically vibrating for 4 minutes (ultrasonic power 2000 W) to obtain a uniform suspension slurry, injecting the suspension slurry into a stirrer, and then adding the silica sol and the foaming composition obtained in step (2) to the suspension slurry, and rapidly mixing for 2 minutes at a linear speed of 180 m/s in the stirrer to obtain a uniform foam slurry; during ball milling, the grinding balls in the ball mill are made of tungsten carbide, and the large balls are

Middle ball

Small Ball

The weight ratio is 1:1:8, and the material/ball weight ratio is 1:0.8.

(4) The foam slurry obtained in step (3) is injected into a stainless steel mold and cured for 12 hours in an environment with an air temperature and relative humidity of 10° C. and 60% respectively until it solidifies.

(5) The solidified green body is demolded and the moisture in the green body is removed by CO ₂ supercritical drying method. The CO ₂ pressure is controlled at 9 MPa, the temperature is 42°C, and the supercritical drying time is 2 h to obtain a dry porous green body. The moisture content of the dry green body is ≤3wt%, and the compressive strength is ≥0.7MPa. The dried green body is fired in a high-temperature tunnel kiln, firstly from room temperature to 400°C at a heating rate of 1°C/min, and kept at 400°C for 0.5h, then heated to 1000°C at 5°C/min, kept at 0.5h, then heated to 1350°C at 1°C/min, kept at 10h, then cooled to 1000°C at 10°C/min, kept at 1000°C for 0.5h, then cooled to 600°C at 5°C/min, kept at 600°C for 0.5h, and finally cooled to 50°C at 1°C/min to obtain a micro-nanoporous insulating refractory material containing zirconium oxide.

Embodiments 2 to 17

The formula compositions of the micro-nanoporous thermal insulating refractory materials containing zirconium oxide in Examples 2 to 17 are shown in Tables 1 and 2 below:

Table 1 Formula of micro-nanoporous insulating refractory materials containing zirconium oxide in Examples 2 to 9

Table 2 Formula of micro-nanoporous insulating refractory materials containing zirconium oxide in Examples 10 to 17

The preparation process of the micro-nanoporous thermal insulation refractory material containing zirconium oxide in Example 2 is as follows:

(1) According to the formula, zircon, industrial alumina, β-Al ₂ O ₃ , γ-Al ₂ O ₃ , coal gangue, diatomaceous earth, and β-tridymite were weighed, poured into a planetary mixer and dry-mixed for 5 minutes to obtain a basic raw material; bentonite, polyaluminium chloride, Y ₂ O ₃ , MgO, V ₂ O ₅ , NiO, K ₂ Ti ₆ O ₁₃ , and Sb ₂ O ₅ were weighed, poured into a double cone mixer and dry-mixed for 5 minutes to obtain an additive.

(2) Weigh a quaternary ammonium Gemini surfactant, an animal protein foaming agent, silica gel, a copolymer of vinyl acetate, ethylene and acrylate, hydroxyethyl cellulose ether, hydroxyethyl ethyl cellulose ether and hydroxypropyl cellulose ether, pour the mixture into a V-type mixer and mix for 5 minutes to obtain a uniform foaming composition.

中球

小球

的重量比为1：1：8，料/球重量比为1：0.9。(3) Pour the basic raw materials and additives obtained in step (1) into a drum ball mill, add 2 tons of water, and mix by ball milling for 10 hours to make the average particle size of the solid particles not greater than 30 μm, then ultrasonically vibrate for 5 minutes (ultrasonic power is 1500 W) to obtain a uniform suspension slurry, inject the suspension slurry into a stirrer, and then add the foaming composition obtained in step (2) and alumina sol to the suspension slurry, and quickly mix the stirring blades in the stirrer at a linear speed of 200 m/s for 2 minutes to obtain a uniform foam slurry; during ball milling, the grinding balls in the ball mill are silicon carbide balls, large balls

Middle ball

Small Ball

The weight ratio is 1:1:8, and the material/ball weight ratio is 1:0.9.

(4) The foam slurry obtained in step (3) is injected into a stainless steel mold and cured for 24 hours in an environment with an air temperature and a relative humidity of 1° C. and 40% respectively until it solidifies.

(5) The solidified green body is demolded and the moisture in the green body is removed by CO ₂ supercritical drying method. The CO ₂ pressure is controlled at 9 MPa, the temperature is 42°C, and the supercritical drying time is 1.5 h to obtain a dry porous green body. The moisture content of the dried green body is ≤3wt%, and the compressive strength is ≥0.9MPa. The dried green body was fired in a high-temperature tunnel kiln, firstly from room temperature to 500°C at a heating rate of 2°C/min, and kept at 500°C for 0.5h, then heated to 1000°C at 5°C/min, kept at 0.5h, then heated to 1400°C at 3°C/min, kept at 8h, then cooled to 1000°C at 10°C/min, kept at 1000°C for 0.5h, then cooled to 500°C at 6°C/min, kept at 500°C for 0.5h, and finally cooled to 50°C at 2°C/min to obtain a micro-nanoporous insulating refractory material containing zirconium oxide.

In this embodiment, the chemical composition of zircon has a ZrO ₂ content of 64-67wt%, a SiO ₂ content of 32-35%, and a particle size of 0.08mm; the chemical composition of industrial alumina, β-Al ₂ O ₃ , and γ-Al ₂ O ₃ has a Al ₂ O ₃ content of ≧98%, and a particle size of ≦0.08mm; the chemical composition of coal gangue has a Al ₂ O ₃ content of 26-28%, a SiO ₂ content of 69-73%, and a particle size of 0.6-1mm; the chemical composition of diatomite has a SiO ₂ content of ≧85%, and a particle size of ≦0.08mm; the chemical composition of β-tridymite has a SiO ₂ content of ≧98%, and a particle size of ≦0.08mm; the chemical composition of bentonite has a Al ₂ O 3 content of 26-28%, a SiO 2 content of 69-73%, and a particle size of 0.6-1mm. The mass percentage of ₃ is 22-23%, the mass percentage of SiO ₂ is 68-75%, and the particle size is ≤0.045mm; the mass percentage of Al ₂ O ₃ in the alumina sol is ≥20%; polyaluminium chloride, Y ₂ O ₃ , MgO and V ₂ O ₅ are all industrially pure, and the particle size is ≤5μm.

The preparation process of the micro-nanoporous thermal insulation refractory material containing zirconium oxide in Example 3 is as follows:

(1) Weigh zirconium corundum, zircon, kaolin, α-quartz, β-quartz, and α-tridymite, pour them into a non-gravity mixer and dry mix them for 10 minutes to obtain a basic raw material; weigh methacrylate type polycarboxylic acid dispersant, bentonite, _polyaluminum sulfate, _Y2O3 , _CeO2 , _{Yb2O3 , K2Ti6O13} , TiC, and _B4C , pour _them into _a double cone mixer and dry mix them for 5 minutes to obtain an additive.

(2) Weigh carboxylate-type Gemini surfactant, sodium dodecylbenzene sulfonate, calcium dialuminate, tricalcium silicate, ethylene-vinyl chloride-vinyl laurate copolymer, curdlan, carboxymethyl methyl cellulose ether, and carboxymethyl ethyl cellulose ether, pour into a three-dimensional mixer and mix for 5 minutes to obtain a uniform foaming composition.

中球

小球

的重量比为1：1：8，料/球重量比为1：0.9。(3) Pour the basic raw materials and additives obtained in step (1) into a drum ball mill, add 1.6 tons of water, and mix by ball milling for 8 hours to make the average particle size of the solid particles in the slurry not greater than 35 μm, then ultrasonically vibrate for 6 minutes (ultrasonic power is 1300 W) to obtain a uniform suspension slurry, and then inject the suspension slurry into a stirrer, and then add the foaming composition obtained in step (2) and the silica-alumina sol to the suspension slurry, and quickly mix the stirring blades in the stirrer at a linear speed of 170 m/s for 3 minutes to obtain a uniform foam slurry; during ball milling, the grinding balls in the ball mill are zirconium oxide balls, large balls

Middle ball

Small Ball

The weight ratio is 1:1:8, and the material/ball weight ratio is 1:0.9.

(4) The foam slurry obtained in step (3) is injected into a plastic mold and cured for 2 hours in an environment with an air temperature and a relative humidity of 20° C. and 80% respectively to allow it to solidify.

(5) Demolding the solidified green body, and removing the liquid water in the green body by _CO2 supercritical drying method, the drying process is the same as that in Example 1; the moisture content of the dried green body is ≤3wt%, and the compressive strength is ≥1.0MPa. The dried green body is fired in a high-temperature tunnel kiln, firstly heating from room temperature to 500°C at a heating rate of 3°C/min, and keeping at 500°C for 0.5h, then heating to 1000°C at 8°C/min, keeping at 1h, then heating to 1450°C at 3°C/min, keeping at 5h, then cooling to 1100°C at 10°C/min, and keeping at 1100°C for 1h, then cooling to 500°C at 6°C/min, keeping at 500°C for 0.5h, and finally cooling to 50°C at 2°C/min, to obtain a micro-nanoporous insulating refractory material containing zirconium oxide.

In this embodiment, the mass percentage of _ZrO2 in the chemical composition of zircon corundum is 15-17wt%, the mass percentage of _Al2O3 is 83-85wt%, and the particle size is ≦0.08mm; the mass percentage of _ZrO2 in the chemical composition of zircon is 64-67wt _% , the mass percentage of _SiO2 is 32-35%, and the particle size is ≦0.08mm; the mass percentage of _Al2O3 in the chemical composition of _kaolin is 35-37wt%, the mass percentage of _SiO2 is 58-61%, and the particle size is 0.6-1mm; the mass percentage of _SiO2 in the chemical composition of ɑ-quartz, β-quartz, and ɑ-tridymite is ≧95wt%, and the particle size is ≦0.044mm; the mass percentage of _Al2O3 in the chemical composition of bentonite is 22-23%, and the mass percentage of _SiO2 is 35-37wt%. The mass percentage of ₂ is 68-75%, and the particle size is ≦0.045mm; the mass percentage of Al ₂ O ₃ in the silica-alumina sol is ≧30%, and the mass percentage of SiO ₂ is ≧20%; polyaluminium sulfate, Y ₂ O ₃ , CeO ₂ , Yb ₂ O ₃ , K ₂ Ti ₆ O ₁₃ , TiC, B ₄ C, calcium dialuminate, and tricalcium silicate are all industrially pure, and the particle size is ≦5μm.

The preparation process of the micro-nanoporous thermal insulation refractory material containing zirconium oxide in Example 4 is as follows:

(1) Weigh zirconium corundum, α-Al ₂ O ₃ , diaspore, aluminum n-butoxide, aluminum isopropoxide, and kyanite, pour them into a forced mixer, and dry mix them for 15 minutes to obtain a basic raw material; weigh sodium polyacrylate, sodium polyphosphate, attapulgite, sepiolite, CaO, Y ₂ O ₃ , MnO ₂ , TiO ₂ , K ₄ TiO ₄ , and Sb ₂ O ₃ , pour them into a double cone mixer, and dry mix them for 5 minutes to obtain an additive.

(2) Weigh a quaternary ammonium Gemini surfactant, sodium α-olefin sulfonate, high-carbon fatty alcohol polyoxyethylene ether, tetracalcium ferrite, acrylate and styrene copolymer, gellan gum, carboxymethyl hydroxymethyl cellulose ether, carboxymethyl hydroxyethyl cellulose ether, and hydroxypropyl ethyl cellulose ether, pour the mixture into a V-type mixer and mix for 5 minutes to obtain a uniform foaming composition.

中球

小球

的重量比为1：1：8，料/球重量比为1：0.8。(3) Pour the basic raw materials and additives obtained in step (1) into a drum ball mill, add 1.4 tons of water, and mix by ball milling for 8 hours to make the average particle size of the solid particles not greater than 30 μm, then ultrasonically vibrate for 7 minutes (ultrasonic power is 1200 W) to obtain a uniform suspension slurry, and then add the foaming composition and zirconium oxide sol obtained in step (2) to the suspension slurry, and quickly mix the stirring blades in the stirrer at a linear speed of 160 m/s for 4 minutes to obtain a uniform foam slurry; during ball milling, the grinding balls in the ball mill are zirconium oxide balls, large balls

Middle ball

Small Ball

The weight ratio is 1:1:8, and the material/ball weight ratio is 1:0.8.

(4) Inject the foam slurry obtained in step (3) into a rubber mold and cure it for 1 hour in an environment with an air temperature and relative humidity of 25° C. and 90% respectively until it solidifies.

(5) Demolding the solidified green body, removing the moisture in the green body by microwave drying technology, the microwave frequency is 915MHz, drying for 0.2h to obtain a dry porous green body; the moisture content of the dry green body is ≤3wt%, and the compressive strength is ≥1.0MPa. The dry green body is placed in a shuttle kiln for firing, firstly heating from room temperature to 500℃ at a heating rate of 3℃/min, and keeping at 500℃ for 1h, then heating to 1000℃ at 8℃/min, keeping at 1h, then heating to 1500℃ at 4℃/min, keeping at 3h, then cooling to 1100℃ at 10℃/min, keeping at 1100℃ for 1h, then cooling to 500℃ at 6℃/min, keeping at 500℃ for 0.5h, and finally cooling to 60℃ at 2℃/min, thus obtaining a micro-nanoporous insulating refractory material containing zirconium oxide.

In this embodiment, the mass percentage of ZrO ₂ in the chemical composition of zirconium corundum is 22-25wt%, the mass percentage of Al ₂ O ₃ is 75-78wt%, and the particle size is ≦0.08mm; the mass percentage of Al ₂ O ₃ in the chemical composition of kyanite is 40-45wt%, the mass percentage of SiO ₂ is 55-58%, and the particle size is 0.6-1mm; the mass percentage of Al _{2 O 3 in the chemical composition of α-Al 2 O 3 is ≧99.9wt%, and the particle size is ≦0.08mm; the mass percentage of Al 2 O 3 in the chemical composition of diaspore is ≧70wt%, and the particle size is ≦0.08mm; the mass percentage of Al 2 O 3 in the chemical composition of} aluminum n-butoxide and aluminum isopropoxide is 44-50wt%; the mass percentage of Al ₂ O ₃ in the chemical composition of attapulgite is 12-15wt%, SiO 2 is 55-58%, and the particle size is 0.6-1mm. The mass percentage of _SiO2 is 55-60%, the mass percentage of MgO is 8-10wt%, and the particle size is ≤0.045mm; the mass percentage of _SiO2 in the chemical composition of sepiolite is 65-71%, the mass percentage of MgO is 25-27%, and the particle size is ≤0.08mm; the mass percentage of _ZrO2 in the zirconium oxide sol is 10-15%; CaO, _{Y2O3 ,} MnO2, _TiO2 , _{K4TiO4 , Sb2O3 ,} and tetracalcium aluminoferrite are all industrially pure, _with a particle size ≤5μm.

The preparation process of the micro-nanoporous thermal insulation refractory material containing zirconium oxide in Example 5 is as follows:

(1) Weigh zirconium corundum, methyl orthosilicate, and ethyl orthosilicate, pour them into a forced mixer and dry mix them for 15 minutes to obtain a basic raw material; weigh sulfonated melamine polycondensate, allyl ether type polycarboxylic acid dispersant, bentonite, chitosan, _Er2O3 , _La2O3 , _{and Cr2O3} , pour them _{into a} three-dimensional mixer and dry mix them for 5 minutes to obtain an additive.

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

中球

小球

的重量比为1.5：2：6.5，料/球重量比为1：1。(3) Pour the basic raw materials and additives obtained in step (1) into a drum ball mill, add 1.2 tons of water, and mix by ball milling for 4 hours to make the average particle size of the solid particles not greater than 44 μm, then ultrasonically vibrate for 8 minutes (ultrasonic power of 1000 W) to obtain a uniform suspension slurry, and then add the foaming composition obtained in step (2) to the suspension slurry, and rapidly mix for 10 minutes at a linear speed of 40 m/s in the stirrer to obtain a uniform foam slurry; during ball milling, the grinding balls in the ball mill are zirconium oxide balls, large balls

Middle ball

Small Ball

The weight ratio is 1.5:2:6.5, and the material/ball weight ratio is 1:1.

(4) The foam slurry obtained in step (3) is injected into a plastic mold and cured for 1 hour in an environment with an air temperature and a relative humidity of 25° C. and 90% respectively to allow it to solidify.

(5) Demolding the solidified green body, and removing moisture from the green body by microwave drying technology, with a microwave frequency of 2450 MHz, and drying for 0.8 h to obtain a dry porous green body; the moisture content of the dried green body is ≤3wt%, and the compressive strength is ≥1.0MPa. The solidified green body is demoulded, and the moisture in the green body is removed by microwave drying technology, the microwave frequency is 915 MHz, and the green body is dried for 0.2 h to obtain a dry porous green body; the dry green body is placed in a microwave kiln for firing, firstly from room temperature to 500°C at a heating rate of 10°C/min, and kept warm for 1.5 h; then heated to 1100°C at 30°C/min, and kept warm for 1.5 h; then heated to 1540°C at 10°C/min, and kept warm for 1 h; then cooled to 1000°C at 20°C/min and kept warm for 1 h; then cooled to 600°C at 10°C/min and kept warm for 1 h; finally cooled to 80°C at 5°C/min to obtain a micro-nanoporous insulating refractory material containing zirconium oxide.

In this embodiment, the mass percentage of _ZrO2 in the chemical composition of zirconium corundum is 39-41wt%, the mass percentage _{of Al2O3} is 59-61wt%, and the particle size is ≦5μm; the mass percentage of _SiO2 in the chemical composition of methyl orthosilicate and ethyl orthosilicate is 28-35wt%; the mass percentage of _Al2O3 in the chemical composition of bentonite is _22-23 %, the mass percentage of _SiO2 is 68-75%, and the particle size is ≦ _{0.045mm ; Er2O3} , _La2O3 , _Cr2O3 , silica gel _and alumina gel are all industrially pure, with a particle size of ≦5μm.

The preparation process of the micro-nanoporous thermal insulating refractory material containing zirconium oxide in Example 6 is as follows:

(1 ₎ Weigh 8 mol% _Y2O3 stabilized zirconia, η- _Al2O3 , ρ- _Al2O3 , α- _tridymite , rice husk, carbonized rice husk, and rice _husk ash, pour them into a forced mixer and dry mix them for 5 minutes to obtain a basic raw material; weigh a polyamide type polycarboxylic acid dispersant, a naphthalene-based dispersant, welan gum, polyvinyl pyrrolidone, _WO3 , _TiO2 , _NiCl2 , and Ni( _NO3 ) ₂ , pour them into a three-dimensional mixer and dry mix them for 5 minutes to obtain an additive.

(2) Weigh sulfate-type Gemini surfactant, fatty alcohol polyoxyethylene ether, aluminum silica gel, copolymer of vinyl acetate, ethylene and vinyl laurate, copolymer of isobutylene and maleic anhydride, hydroxypropyl guar gum, propyl cellulose ether, water-soluble cellulose ether, and ethyl methyl cellulose ether, pour into a three-dimensional mixer and mix for 5 minutes to obtain a uniform foaming composition.

中球

小球

的重量比为1.5：2：6.5，料/球重量比为1：1。(3) Pour the basic raw materials and additives obtained in step (1) into a drum ball mill, add 1.2 tons of water, and mix by ball milling for 4 hours to make the average particle size of the solid particles not greater than 44 μm, then ultrasonically vibrate for 10 minutes (ultrasonic power is 800 W) to obtain a uniform suspension slurry, and then add the foaming composition obtained in step (2) to the suspension slurry, and quickly mix the stirring blades in the stirrer at a linear speed of 150 m/s for 5 minutes to obtain a uniform foam slurry; during ball milling, the grinding balls in the ball mill are made of alumina, and the large balls are

Middle ball

Small Ball

The weight ratio is 1.5:2:6.5, and the material/ball weight ratio is 1:1.

(4) The foam slurry obtained in step (4) is injected into an aluminum alloy mold and cured for 1 hour in an environment with an air temperature and a relative humidity of 25° C. and 90% respectively to allow it to solidify.

(5) Demolding the solidified green body, removing the moisture in the green body by microwave drying, the microwave frequency is 915MHz, the microwave drying time is 1h, and obtaining a dried porous green body; the moisture content of the dried green body is ≤3wt%, and the compressive strength is ≥1.0MPa. The dried green body is placed in a microwave kiln for firing, heating from room temperature to 500℃ at a heating rate of 5℃/min, and keeping the temperature for 0.5h; then heating to 1200℃ at 10℃/min, and keeping the temperature for 0.5h; then heating to 1550-1580℃ at 8℃/min, and keeping the temperature for 0.5h; then cooling to 1000℃ at 20℃/min and keeping the temperature for 0.5h; then cooling to 500℃ at 10℃/min and keeping the temperature for 0.5h; finally cooling to 50℃ at 5℃/min, and obtaining a micro-nanoporous insulating refractory material containing zirconium oxide.

In this embodiment, the content of _ZrO2 in 8mol% _Y2O3 stabilized _zirconia is 86-88wt%, and the particle size is ≦0.08mm; the mass percentage of _Al2O3 in the chemical composition of η- _{Al2O3 and} ρ- _Al2O3 is ≧99wt%, and the particle size is ≦ _0.08mm ; the mass percentage of _SiO2 in the chemical composition of ɑ- _tridymite is ≧99wt%, and the particle size is ≦0.08mm; the mass percentage of _SiO2 in the chemical composition of rice husk, carbonized rice husk and rice husk ash is ≧18wt%, and the particle size is ≦0.08μm; _WO3 , _TiO2 , _NiCl2 , Ni( _NO3 ) ₂ and alumina silica gel are all industrially pure, and the particle size is ≦1μm.

The preparation process of the micro-nanoporous thermal insulation refractory material containing zirconium oxide in Example 7 is as follows:

(1 ₎ 5 mol% _Y2O3 -stabilized zirconia, γ- _{Al2O3 ,} κ- _Al2O3 , θ- _{Al2O3 ,} andalusite, α-cristobalite, and cemented silica are poured into a non-gravity mixer and dry-mixed for 15 min to obtain a basic raw material; methacrylate type polycarboxylic acid dispersant, naphthalene- _based dispersant, casein _, cellulose fiber, _Y2O3 , _Fe2O3 , _WO3 , _TiO2 , and _Sb2O5 are weighed, poured into a V-type mixer and dry-mixed for ₅ min to obtain _an additive.

(2) Weigh sulfate Gemini surfactant, fatty alcohol polyoxyethylene ester, silica-alumina gel, ethylene-vinyl chloride copolymer, acrylate polymer, vinyl acetate homopolymer, hydroxybutyl methyl cellulose ether, and hydroxyethyl methyl cellulose ether, pour into a V-type mixer and mix for 5 minutes to obtain a uniform foaming composition.

中球

小球

的重量比为1.5：2：6.5，料/球重量比为1：1.1。(3) Pour the basic raw materials and additives obtained in step (1) into a drum ball mill, add 0.9 tons of water, and mix by ball milling for 1.5 hours to make the average particle size of the solid particles not greater than 44 μm, then ultrasonically vibrate for 12 minutes (ultrasonic power is 800 W) to obtain a uniform suspension slurry, and then add the foaming composition obtained in step (2) to the suspension slurry, and rapidly mix for 5 minutes at a linear speed of 140 m/s in the stirrer to obtain a uniform foam slurry; during ball milling, the grinding balls in the ball mill are made of zirconium corundum, and the large balls are

Middle ball

Small Ball

The weight ratio is 1.5:2:6.5, and the material/ball weight ratio is 1:1.1.

(4) The foam slurry obtained in step (3) is injected into a resin mold and cured for 0.8 h in an environment with an air temperature and a relative humidity of 25° C. and 93% respectively to allow it to solidify.

(5) Demolding the solidified green body, removing the moisture in the green body by freeze drying, the drying temperature is -130℃～-100℃, and drying for 6h to obtain a dry porous green body. The moisture content of the dry green body is ≤3wt%, and the compressive strength is ≥1.0MPa. The dry green body is loaded into a shuttle kiln for firing, heating from room temperature to 500℃ at a heating rate of 3℃/min, and keeping it warm for 0.5h; then heating to 1200℃ at 8℃/min, and keeping it warm for 1h; then heating to 1570～1600℃ at 3℃/min, and keeping it warm for 3～5h; then cooling to 1000℃ at 10℃/min, and keeping it warm for 1h; then cooling to 500℃ at 6℃/min, and keeping it warm for 0.5h; finally cooling to 50℃ at 2℃/min to obtain a micro-nanoporous super insulating refractory material containing zirconium oxide.

In this embodiment, the content of ZrO ₂ in the chemical composition of 5 mol% Y ₂ O ₃ stabilized zirconia is 90-93wt%, and the particle size is ≦0.08mm; the mass percentage of Al ₂ O 3 in the chemical composition of γ- _{Al 2} O ₃ , κ-Al 2 O ₃ , and θ-Al ₂ O ₃ is ≧ _99wt %, and the particle size is ≦0.08mm; the mass percentage of Al ₂ O ₃ in the chemical composition of andalusite is 45-50wt%, and the particle size is ≦0.08mm; the mass percentage of SiO ₂ in the chemical composition of α-cristobalite and cemented silica is 98wt%, and the particle size is ≦0.08mm; Y ₂ O ₃ , Fe ₂ O ₃ , WO ₃ , TiO ₂ , Sb ₂ O ₅ , and alumina silica gel are all industrially pure, and the particle size is ≦5μm.

The preparation process of the micro-nanoporous thermal insulating refractory material containing zirconium oxide in Example 8 is as follows:

(1) 5 mol% _{Y2O3 -} stabilized zirconia, sintered corundum, fused white corundum powder, andalusite, quartzite, and vein quartz are poured into a non-gravity mixer and dry-mixed for 15 minutes to obtain a basic raw material; an imide-type polycarboxylic acid dispersant, a melamine dispersant, polyacrylamide, soluble starch, SrO, _Cr2O3 , BaO, _Sb2O5 , and Co( _NO3 ) _{2 are} weighed, poured into _a V-type mixer and dry-mixed for 5 minutes to obtain an additive.

(2) Weigh a double-chain Bola surfactant, alkylphenol polyoxyethylene ether, alumina gel, a copolymer of vinyl acetate, versatate vinyl ester and acrylate, a copolymer of vinyl acetate and versatate vinyl ester, sulfonic acid ethyl cellulose ether and wood cellulose, pour them into a three-dimensional mixer and mix for 5 minutes to obtain a uniform foaming composition.

中球

小球

的重量比为1.5：2：6.5，料/球比为1：1.2。(3) Pour the basic raw materials and additives obtained in step (1) into a drum ball mill, add 0.8 tons of water, and mix by ball milling for 1 hour to make the average particle size of the solid particles not greater than 44 μm, then ultrasonically vibrate for 13 minutes (ultrasonic power is 600 W) to obtain a uniform suspension slurry, and then add the foaming composition obtained in step (2) to the suspension slurry, and rapidly mix for 6 minutes at a linear speed of 130 m/s in the stirrer to obtain a uniform foam slurry; during ball milling, the grinding balls in the ball mill are made of zirconium oxide, and the large balls are

Middle ball

Small Ball

The weight ratio is 1.5:2:6.5, and the material/ball ratio is 1:1.2.

(4) The foam slurry obtained in step (3) is injected into a rubber mold and cured for 0.7 h in an environment with an air temperature and a relative humidity of 25° C. and 95% respectively to allow it to solidify.

(5) Demolding the solidified green body, removing the liquid water in the green body by infrared drying, the infrared wavelength is 11-13 μm, the drying time is 1.2 h, and a dried porous green body is obtained; the moisture content of the dried green body is ≤3wt%, and the compressive strength is ≥1.0 MPa. The dried green body is placed in a shuttle kiln for firing, heating from room temperature to 500°C at a heating rate of 3°C/min, then heating to 1200°C at 8°C/min, keeping the temperature for 1 h, then heating to 1580-1610°C at 3°C/min, keeping the temperature for 3 h, then cooling to 1000°C at 10°C/min, keeping the temperature at 1000°C for 1 h, then cooling to 500°C at 6°C/min, keeping the temperature at 500°C for 0.5 h, and finally cooling to 50°C at 2°C/min, thus obtaining a micro-nanoporous insulating refractory material containing zirconium oxide.

In this Example 8, the chemical composition of 5mol% _Y2O3 stabilized _zirconia has a _ZrO2 content of 90-93wt%, and a particle size of ≦0.08mm; the chemical composition of sintered corundum and fused white corundum powder has a mass percentage of _Al2O3 of ≧ _99wt %, and a particle size of ≦0.08mm; the chemical composition of _andalusite has a mass percentage of _Al2O3 of 54-58wt%, a mass percentage of _SiO2 of 36-40%, and a particle size of ≦0.08mm; the chemical composition of quartzite and vein quartz has a mass percentage of _SiO2 of ≧98wt%, and a particle size of ≦0.045mm; SrO, _Cr2O3 , BaO _{, Sb2O5} , Co( _NO3 ) ₂ , and alumina gel are all industrially pure, _with a particle size of ≦5μm.

The preparation process of the micro-nanoporous thermal insulation refractory material containing zirconium oxide in Example 9 is as follows:

(1) 5 mol% _Y2O3 -stabilized zirconia and _andalusite were poured into a forced mixer and dry-mixed for 5 minutes to obtain a basic raw material; polyamide-type polycarboxylic acid dispersant, naphthalene-based high-efficiency dispersant, microcrystalline cellulose, casein, CaO, _MnO2 , _Cr2O3 , CoO, and _{K2Ti6O13 were weighed} , poured into a V-type mixer and dry _- mixed for 5 minutes to obtain an additive.

(2) Weigh a polyether type Dendrimer surfactant, polyoxyethylene lauryl alcohol ether, zirconium oxide gel, ethylene-vinyl acetate copolymer, locust bean gum, methyl cellulose ether, and carboxymethyl cellulose ether, pour them into a three-dimensional mixer and mix for 5 minutes to obtain a uniform foaming composition.

中球

小球

的重量比为1.5：2：6.5，料/球重量比为1：1.2。(3) Pour the basic raw materials and additives obtained in step (1) into a drum ball mill, add 0.7 tons of water, and mix by ball milling for 1 hour to make the average particle size of the solid particles not greater than 44 μm, then ultrasonically vibrate for 15 minutes (ultrasonic power is 500 W) to obtain a uniform suspension slurry, and then add the foaming composition obtained in step (2) to the suspension slurry, and rapidly mix for 6 minutes at a linear speed of 125 m/s in the stirrer to obtain a uniform foam slurry; during ball milling, the grinding balls in the ball mill are made of mullite, and the large balls are

Middle ball

Small Ball

The weight ratio is 1.5:2:6.5, and the material/ball weight ratio is 1:1.2.

(4) The foam slurry obtained in step (3) is injected into a foam mold and cured for 0.6 h in an environment with an air temperature and a relative humidity of 27° C. and 95% respectively to allow it to solidify.

(5) Demolding the solidified green body, removing the liquid water in the green body by infrared drying, the infrared wavelength is 12-15 μm, the drying time is 1 hour, and a dried porous green body is obtained; the moisture content of the dried green body is ≤3wt%, and the compressive strength is ≥1.0MPa. The dried green body is placed in a shuttle kiln for firing, heating from room temperature to 500°C at a heating rate of 3°C/min, then heating to 1200°C at 8°C/min, keeping the temperature for 1 hour, then heating to 1600-1650°C at 3°C/min, keeping the temperature for 3 hours, then cooling to 1000°C at 10°C/min, and keeping the temperature at 1000°C for 1 hour, then cooling to 500°C at 6°C/min, keeping the temperature at 500°C for 0.5 hour, and finally cooling to 50°C at 2°C/min, thus obtaining a micro-nanoporous insulating refractory material containing zirconium oxide.

In this embodiment, the mass percentage of ZrO ₂ in the chemical composition of 5 mol% Y ₂ O ₃ stabilized zirconia is 90-93wt%, and the particle size is ≦0.08mm; the mass percentage of Al ₂ O ₃ in the chemical composition of andalusite is 54-58wt%, the mass percentage of SiO ₂ is 36-40%, and the particle size is 0.6-1mm; CaO, MnO ₂ , Cr ₂ O ₃ , CoO, K ₂ Ti ₆ O ₁₃ , and zirconia gel are all industrially pure, and the particle size is ≦5μm.

The preparation process of the micro-nanoporous thermal insulating refractory material containing zirconium oxide in Example 10 is as follows:

(1) 3 mol% _{Y2O3 -} stabilized zirconia and sillimanite were poured into a planetary mixer and dry-mixed for 15 minutes to obtain a basic raw material; polyethylene glycol type polycarboxylic acid dispersant, potassium lignin sulfonate, cellulose fiber, MgO, YbO, _TiO2 , _{K2Ti6O13 were} weighed, poured into _a planetary mixer and dry-mixed for 5 minutes to obtain an additive.

(2) Weigh a quaternary ammonium Gemini surfactant, sodium lauryl polyoxyethylene ether carboxylate, zirconium oxide gel, ethylene-vinyl acetate copolymer, propyl cellulose ether, and hydroxypropyl hydroxybutyl cellulose ether, pour them into a V-type mixer and mix for 5 minutes to obtain a uniform foaming composition.

中球

小球

的重量比为1.5：2：6.5，料/球重量比为1：1.2。(3) Pour the basic raw materials and additives obtained in step (1) into a drum ball mill, add 0.6 tons of water, and mix by ball milling for 1 hour to make the average particle size of the solid particles not greater than 50 μm, then ultrasonically vibrate for 10 minutes (ultrasonic power of 1000 W) to obtain a uniform suspension slurry, and then add the foaming composition obtained in step (2) to the suspension slurry, and rapidly mix for 7 minutes at a linear speed of 80 m/s in the stirrer to obtain a uniform foam slurry; during ball milling, the grinding balls in the ball mill are made of zirconium corundum, and the large balls are

Middle ball

Small Ball

The weight ratio is 1.5:2:6.5, and the material/ball weight ratio is 1:1.2.

(4) The foam slurry obtained in step (3) is injected into a wooden mold and cured for 0.5 h in an environment with an air temperature and a relative humidity of 27° C. and 97% respectively until it solidifies.

(5) Demolding the solidified green body, removing the liquid water in the green body by infrared drying, the infrared wavelength is 5-7 μm, the drying time is 0.5 h, and a dried porous green body is obtained; the moisture content of the dried green body is ≤3wt%, and the compressive strength is ≥1.0 MPa. The dried green body is placed in a shuttle kiln for firing, heating from room temperature to 500°C at a heating rate of 3°C/min, then heating to 1200°C at 8°C/min, keeping the temperature for 1 h, then heating to 1650-1700°C at 3°C/min, keeping the temperature for 3 h, then cooling to 1000°C at 10°C/min, keeping the temperature at 1100°C for 1 h, then cooling to 500°C at 6°C/min, keeping the temperature at 500°C for 0.5 h, and finally cooling to 50°C at 2°C/min, thus obtaining a micro-nanoporous insulating refractory material containing zirconium oxide.

In this embodiment, the mass percentage of ZrO ₂ in the chemical composition of 3 mol% Y ₂ O ₃ stabilized zirconia is 94-96wt%, the mass percentage of Al ₂ O ₃ in the chemical composition of sillimanite is 55-60wt%, and the mass percentage of SiO ₂ is 39-44%. The particle sizes of the above two raw materials are all ≦0.08mm; MgO, YbO, TiO ₂ , K ₂ Ti ₆ O ₁₃ , and zirconia gel are all industrially pure, with a particle size of ≦5μm.

The preparation process of the micro-nanoporous thermal insulating refractory material containing zirconium oxide in Example 11 is as follows:

(1) 9 mol% _{Y2O3 -} stabilized zirconia and fused mullite were poured into a forced mixer and dry mixed for 15 minutes to obtain a basic raw material. Allyl ether type polycarboxylic acid dispersant, sodium lignin sulfonate _{, polyvinyl pyrrolidone, Er2O3, K2Ti6O13 were weighed ,} poured into _a double cone mixer and dry mixed for 5 minutes to obtain an additive.

(2) Weigh polyamide Dendrimer surfactant, zirconium oxide gel, konjac gum powder, starch ether, and hydroxypropyl methylcellulose ether, pour them into a double cone mixer and mix for 5 minutes to obtain a uniform foaming composition.

中球

小球

的重量比为1.5：2：6，料/球重量比为1：1.4。(3) Pour the basic raw materials and additives obtained in step (1) into a drum ball mill, add 0.4 tons of water, and mix by ball milling for 1 hour to make the average particle size of the solid particles not greater than 60 μm, then ultrasonically vibrate for 8 minutes (ultrasonic power is 1500 W) to obtain a uniform suspension slurry, and then add the foaming composition obtained in step (2) to the suspension slurry, and mix for 8 minutes at a linear speed of 40 m/s in the stirrer to obtain a uniform foam slurry; during ball milling, the grinding balls in the ball mill are made of zirconium corundum, and the large balls are

Middle ball

Small Ball

The weight ratio is 1.5:2:6, and the material/ball weight ratio is 1:1.4.

(4) The foam slurry obtained in step (3) is injected into a glass mold and cured for 0.3 h in an environment with an air temperature and a relative humidity of 30° C. and 99% respectively to allow it to solidify.

(5) Demolding the solidified green body, and removing the liquid water in the green body by normal pressure drying method, the drying system is as follows: first heating to 30°C at 2°C/min, keeping at 30°C for 3h, then heating to 50°C at 2°C/min, keeping at 50°C for 2h, then heating to 70°C at 3°C/min, keeping at 70°C for 2h, then heating to 90°C at 3°C/min, keeping at 90°C for 3h, then heating to 110°C at 3°C/min, keeping at 110°C for 12h, to obtain a dried porous green body; the moisture content of the dried green body is ≤3wt%, and the compressive strength is ≥1.0MPa. The dried green body is loaded into a high-temperature resistance kiln for firing, with the temperature rising from room temperature to 500°C at a heating rate of 3°C/min, then rising to 1200°C at 8°C/min, keeping warm for 1h, then rising to 1700-1750°C at 3°C/min, keeping warm for 3h, then cooling down to 1000°C at 10°C/min and keeping warm for 1h, then cooling down to 500°C at 6°C/min and keeping warm for 0.5h, and finally cooling down to 50°C at 2°C/min to obtain a micro-nanoporous insulating refractory material containing zirconium oxide.

In this embodiment, the mass percentage of ZrO ₂ in the chemical composition of 3 mol% Y ₂ O ₃ stabilized zirconia is 94-96wt%, the mass percentage of Al ₂ O ₃ in the chemical composition of fused mullite is 69-72wt%, and the mass percentage of SiO ₂ is 26-30%. The particle sizes of the above two raw materials are all ≦0.08mm; Er ₂ O ₃ , K ₂ Ti ₆ O ₁₃ and zirconia gel are all industrially pure, and the particle sizes are all ≦5μm.

The preparation process of the micro-nanoporous thermal insulating refractory material containing zirconium oxide in Example 12 is as follows:

(1) Monoclinic zirconium oxide is used as a basic raw material; allyl ether type polycarboxylic acid dispersant, melamine formaldehyde polycondensate, Y ₂ O ₃ , CeO ₂ , BaO, and TiO ₂ are weighed, poured into a planetary mixer, and dry-mixed for 5 minutes to obtain an additive.

(2) Weigh polyamide Dendrimer surfactant, zirconium oxide gel, potassium alginate, ethyl cellulose ether, and hydroxymethyl cellulose ether, pour them into a double cone mixer and mix for 5 minutes to obtain a uniform foaming composition.

中球

小球

的重量比为1.5：2：6，料/球重量比为1：1.5。(3) Pour the basic raw materials and additives obtained in step (1) into a drum ball mill, add 0.2 tons of water, and mix by ball milling for 0.5 hours to make the average particle size of the solid particles not greater than 74 μm, then ultrasonically vibrate for 5 minutes (ultrasonic power is 2000 W) to obtain a uniform suspension slurry, and then add the foaming composition obtained in step (2) to the suspension slurry, and mix for 8 minutes at a linear speed of 20 m/s in the stirrer to obtain a uniform foam slurry; during ball milling, the grinding balls in the ball mill are tungsten carbide balls, and the large balls are

Middle ball

Small Ball

The weight ratio is 1.5:2:6, and the material/ball weight ratio is 1:1.5.

(4) The foam slurry obtained in step (3) is injected into a glass mold and cured for 0.1 h in an environment with an air temperature and a relative humidity of 35° C. and 99.9% respectively to allow it to solidify.

(5) Demolding the solidified green body, and removing the liquid water in the green body by normal pressure drying method, the drying system is as follows: first heating to 30°C at 2°C/min, keeping at 30°C for 3h, then heating to 50°C at 2°C/min, keeping at 50°C for 2h, then heating to 70°C at 3°C/min, keeping at 70°C for 2h, then heating to 90°C at 3°C/min, keeping at 90°C for 3h, then heating to 110°C at 3°C/min, keeping at 110°C for 12h, to obtain a dried porous green body; the moisture content of the dried green body is ≤3wt%, and the compressive strength is ≥1.0MPa. The dried green body is loaded into a high-temperature resistance kiln for firing, from room temperature to 500°C at a heating rate of 3°C/min, kept warm for 0.5h, then heated to 1200°C at 8°C/min, kept warm for 1h, then heated to 1800-1850°C at 3°C/min, kept warm for 2-3h, then cooled to 1000°C at 10°C/min and kept warm for 1h, then cooled to 500°C at 6°C/min and kept warm for 0.5h, and finally cooled to 50°C at 2°C/min to obtain a micro-nanoporous insulating refractory material containing zirconium oxide.

In this Example 12, the chemical composition of the monoclinic zirconia has a ZrO ₂ content of ≧99wt% and a particle size of ≦0.08mm; Y ₂ O ₃ , CeO ₂ , BaO, TiO ₂ and zirconia gel are all industrially pure, and the particle sizes of the above raw materials are all ≦5μm.

The preparation process of the micro-nanoporous thermal insulating refractory material containing zirconium oxide in Example 13 is as follows:

The preparation process of Example 13 is basically the same as that of Example 12, except that no mineralizer and infrared sunscreen agent are added during the batching.

The preparation process of the micro-nanoporous thermal insulating refractory material containing zirconium oxide in Example 14 is as follows:

(1) Weigh zirconium corundum, limestone, quicklime, slaked lime, and CaCO ₃ , pour them into a forced mixer and dry mix them for 15 minutes to obtain a basic raw material; weigh FS10, FS20, aliphatic dispersant, sucrose, dextrin, tris(hydroxymethyl)aminomethane, polyvinyl alcohol, and polyacrylamide, pour them into a double cone mixer and dry mix them for 5 minutes to obtain an additive.

(2) Weigh a double-chain Bola surfactant, sodium α-olefin sulfonate, sodium fatty alcohol polyoxyethylene ether carboxylate, monocalcium aluminate, dodecaluminate heptaaluminate, vinyl acetate-ethylene copolymer, sodium alginate, carboxymethyl hydroxymethyl cellulose ether, and carboxymethyl hydroxypropyl cellulose ether, pour them into a V-type mixer and mix for 5 minutes to obtain a uniform foaming composition.

(3) Pour the basic raw materials and additives obtained in step (1) into a blender, add 1.6 tons of water, and stir for 0.5 h to obtain a suspension slurry; then add the foaming composition obtained in step (2) and the alumina sol into the suspension slurry, and stir with a stirring paddle at a linear speed of 170 m/s for 3 min to obtain a uniform foam slurry.

(4) The foam slurry obtained in step (3) is injected into a rubber mold and cured for 1.5 hours in an environment with an air temperature and a relative humidity of 25° C. and 90% respectively until it solidifies.

(5) Demold the solidified green body, and remove the moisture in the green body by hot air drying at normal pressure. The drying temperature is controlled at 35℃～45℃, and the drying time is 48h to obtain a dried porous green body. The moisture content of the dried green body is ≤3wt%, and the compressive strength is ≥1.0MPa. The dried green body is fired in a high-temperature tunnel kiln, and the temperature is increased from room temperature to 500℃ at a heating rate of 3℃/min, and kept at 500℃ for 1h; then the temperature is increased to 1000℃ at 8℃/min, and kept at 1h; then the temperature is increased to 1470～1480℃ at 5℃/min, and kept at 3h; then the temperature is reduced to 1100℃ at 15℃/min, and kept at 1100℃ for 1h; then the temperature is reduced to 500℃ at 6℃/min, and kept at 500℃ for 0.5h; finally, the temperature is reduced to 60℃ at 3℃/min to obtain a micro-nanoporous insulating refractory material containing zirconium oxide.

In the micro-nanoporous insulating refractory material containing zirconium oxide obtained in this embodiment, the main crystal phases are zirconium oxide and calcium hexaaluminate. In the raw materials used, the mass percentage of _ZrO2 in the chemical composition of zirconium corundum is 23-25wt%, the mass percentage of _Al2O3 is 75-77wt%, and the particle size is ≦0.05mm; the mass percentage of CaO in limestone is 53-55wt%, and the particle size is ≦0.05mm; the mass percentage of CaO in quicklime is 95-97wt%, _and the particle size is ≦0.05mm; the mass percentage of CaO in slaked lime is 70-75wt%, and the particle size is ≦0.05mm; the mass percentage of CaO in _CaSO4 is 40-42wt%, and the particle size is ≦0.05mm; the mass percentage of _Al2O3 in alumina sol is 100-150wt%, and the particle size is ≦0.05mm. The mass percentage of ₃ is ≧20%; both monocalcium aluminate and dodecacalcium heptaaluminate are industrial pure, with a particle size of ≦5μm.

The preparation process of the micro-nanoporous thermal insulation refractory material containing zirconium oxide in Example 15 is as follows:

(1) Weigh zircon, industrial alumina, β-Al ₂ O ₃ , wollastonite, dolomite, calcite, CaO, and Ca(OH) ₂ , put them into a forced mixer, and dry-mix them for 15 minutes to obtain a basic raw material.

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

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

(4) The foam slurry obtained in step (3) is injected into a rubber mold and cured for 1.5 hours in an environment with an air temperature and a relative humidity of 25° C. and 90% respectively until it solidifies.

(5) Demold the solidified green body, remove the moisture in the green body by hot air drying at normal pressure, control the drying temperature at 35℃～45℃, and dry for 48h to obtain a dry porous green body. The moisture content of the dry green body is ≤3wt%, and the compressive strength is ≥1.0MPa. The dry green body is placed in a shuttle kiln for firing, heating from room temperature to 500℃ at a heating rate of 3℃/min, and keeping it warm for 0.5h; then heating to 1100℃ at 8℃/min, and keeping it warm for 1h; then heating to 1400℃ at 3℃/min, and keeping it warm for 1.5h; then cooling to 1100℃ at 10℃/min, and keeping it warm at 1100℃ for 1h; then cooling to 500℃ at 6℃/min, and keeping it warm at 500℃ for 0.5h; finally cooling to 50℃ at 2℃/min to obtain a micro-nanoporous insulating refractory material containing zirconium oxide.

In the micro-nanoporous insulating refractory containing zirconium oxide obtained in Example 15, the main crystal phases are zirconium oxide and calcium feldspar. Among the raw materials used, the mass percentage of _ZrO2 in the chemical composition of zircon is 64-67%, the mass percentage of _SiO2 is 32-35%, and the particle size is ≦0.05mm; the mass _percentage of _{Al2O3 in} industrial _Al2O3 and β- _Al2O3 is ≧98%, and the particle size is ≦0.05mm; the mass percentage of CaO in wollastonite is 34-37%, and the particle size is ≦0.05mm; the mass _percentage of CaO in dolomite is 29-31%, the mass percentage of MgO is 20-21%, and the particle size is ≦0.05mm; the mass percentage of CaO in calcite is 50-52%, and the particle size is ≦0.05mm; the mass percentage of SiO2 in silica sol is 100-200%. The mass percentage of ₂ is ≧30%; CaO and Ca(OH) ₂ , dicalcium silicate and sodium silicate are all industrially pure, with a particle size of ≦5 μm.

The preparation process of the micro-nanoporous thermal insulating refractory material containing zirconium oxide in Example 16 is as follows:

Its preparation process is basically the same as that of Example 15, except that it is cured for 5 hours in an environment with an air temperature and a relative humidity of 25°C and 90% respectively, and then it can be cured and demolded, and when the green body is dried by hot air at normal pressure, the temperature is 35°C to 45°C, and the drying time is 72 hours. The drying time is greatly extended, and the compressive strength of the green body after drying is only 0.5MPa.

The preparation process of the micro-nanoporous thermal insulating refractory material containing zirconium oxide in Example 17 is as follows:

(1) The preparation of the base material and additives is basically the same as that of Example 14, the only difference being that dicalcium silicate and calcium dialuminate are introduced into the base material.

(2) Weighing monocalcium aluminate, calcium dodecaaluminate, vinyl acetate and ethylene copolymer, sodium alginate, carboxymethyl hydroxymethyl cellulose ether, and carboxymethyl hydroxypropyl cellulose ether, pouring into a V-type mixer and mixing for 5 minutes to obtain a uniform foaming composition. At the same time, quaternary ammonium double-chain Bola surfactant, α-olefin sulfonate sodium, and fatty alcohol polyoxyethylene ether carboxylate sodium are pre-prepared into foam using a foaming machine;

(3) Pour the basic raw materials and additives obtained in step (1) into a blender, add 1.6 tons of water, and stir for 0.2 hours to obtain a suspension slurry; then add the foaming composition obtained in step (2), the prefabricated foam, and the alumina sol into the suspension slurry, and stir with a stirring paddle at a linear speed of 170 m/s for 3 minutes to obtain a uniform foam slurry.

The subsequent pouring of the foam slurry, green body curing, drying and firing are basically the same as in Example 11, and a micro-nanoporous insulating refractory material containing calcium hexaaluminate is obtained. The only difference is that the compressive strength of the green body after drying is 0.7 MPa.

In this Example 17, the physical and chemical indicators of the basic raw materials and the foaming composition used are the same as those of Example 14, and the dicalcium silicate and calcium dialuminate are industrially pure with a particle size of ≦5 μm.

2. Experimental Examples

Experimental Example 1

In this experimental example, the morphology of the micro-nanoporous thermal insulating refractory material containing zirconium oxide prepared in Example 7 was observed. Its appearance picture is shown in FIG1 , and its microstructure pictures are shown in FIGS. 2 and 3 .

As can be seen from FIG1 , the refractory material prepared in the embodiment is white without any other colors.

As can be seen from Figures 2 and 3, the insulating refractory material contains a large number of spherical tiny pores with a pore size of ≤250μm. Further analysis combined with Figure 3 shows that the pore wall structure of the pores is relatively dense (see Figure 3), and the pore wall is composed of two types of particles, large and small, tightly combined. EDS analysis shows that the two are corundum (see Figure 4) and zirconium oxide (Figure 5).

Experimental Example 2

In this experimental example, X-ray diffraction (XRD) analysis was performed on the micro-nanoporous thermal insulating refractory material containing zirconium oxide prepared in Example 7, and its XRD spectrum is shown in FIG6 .

It can be seen from the figure that the main crystal phases of the micro-nano porous thermal insulation refractory material are zirconia and corundum phases.

Experimental Example 3

In this experimental example, pore diameter analysis was performed on the micro-nanoporous thermal insulating refractory material containing zirconium oxide prepared in Example 7. The results are shown in FIG. 7 .

As can be seen from the figure, the pore diameter of refractory bricks is small, with the coexistence of micro-nano pores, and the pore diameter distribution is between 0.006 and 200 μm.

Experimental Example 4

This experimental example tests the thermal conductivity and other properties of the micro-nanoporous insulating refractory material containing zirconium oxide prepared in the embodiment. The bulk density and total porosity of the sample are tested according to the Chinese national standard GB/T2998-2001, and the closed porosity of the GB/T2997-2000 test sample is used; the compressive strength is tested according to GB/T 3997.2-1998; the reburning line change rate is tested according to GB/T 3997.1-1998; the thermal conductivity is tested according to YB/T4130-2005; the average pore size and pore size distribution of the sample are measured by mercury intrusion method, and the test results are shown in Table 3.

Table 3 Performance test results of the micro-nanoporous insulating refractory materials containing zirconium oxide in the embodiment

According to the test results in Table 3, the performance indicators of the micro-nanoporous thermal insulating refractory materials containing zirconium oxide in the embodiments are summarized as follows: bulk density is 0.3-3 g/cm ³ , porosity is 50-95%, closed porosity is 20-70%, normal temperature compressive strength is 0.6-220 MPa, room temperature thermal conductivity is 0.02-0.25 W/(m·K), thermal conductivity at 350°C is 0.03-0.33 W/(m·K), some formulations reach 0.1-0.13 W/(m·K), thermal conductivity at 1100°C is 0.06-0.4 W/(m·K), use temperature ≦2300°C, reburning line change rate is -0.4-0% (keeping at 1400-1732°C for 24h), and some formulations are -0.1-0%.

It can be seen from the comparison of Examples 1 to 2 that, when the density of the prepared samples is not much different, the amount of water used for the introduction of the dispersant can be significantly reduced; it can be seen from the comparison of Examples 12 to 13 that the introduction of the infrared sunscreen significantly reduces the high-temperature thermal conductivity of the sample; it can be seen from the comparison of Examples 5 to 7 that with the increase of the amount of pore regulator, the pore diameter of the sample is effectively reduced; it can be seen from the comparison of Examples 3 to 12 that, when the dry strength of the sample green body remains basically stable, the amount of inorganic and organic curing agents can be reduced accordingly with the increase of the sample density; it can be seen from the comparison of Examples 1 to 2 that with the increase of the stirring speed, the average pore diameter and volume density of the sample are significantly reduced, and the strength of the green body and the fired sample is significantly increased; it can be seen from the comparison of Examples 2 to 12 that with the decrease of the amount of water, the density of the fired sample gradually increases; it can be seen from the comparison of Examples 12 and 13 that the introduction of the mineralizer gradually reduces the sintering temperature of the sample and increases the density; it can be seen from the comparison of Examples 4 and 5 that the particle size of the solid particles in the slurry can be finer and the sintering temperature can be reduced by properly extending the grinding time. Comparing Examples 3 and 14-15, it can be seen that after the base material is ball-milled and the suspended slurry is ultrasonically treated, the sintering performance of the sample is better, its density is increased, and the strength is significantly improved. Comparing Examples 15 and 16, it can be found that when no organic curing agent is added, the curing time required for the green body is greatly extended before demoulding can be achieved, and the strength of the green body after drying is greatly reduced, the pore diameter in the sample after firing is significantly increased, the density and thermal conductivity are increased, and the total porosity, closed porosity and strength are significantly reduced. Comparing Examples 14 and 17, it can be seen that when the foaming agent is pre-foamed, the stirring time of the foam slurry is shortened, but the strength of the green body after drying is weakened, the porosity, pore diameter distribution and average pore diameter of the fired product are increased, the volume density, closed porosity and strength are reduced, and the thermal conductivity is increased.

The insulating refractory material of the embodiment can be controlled and adjusted in terms of pore structure, thermal insulation and mechanical properties, and by constructing a micro-nanoporous structure in the micro-nanoporous insulating refractory material containing zirconium oxide, it can show more excellent mechanical and thermal insulation properties while ensuring that the porosity and volume density of the material are similar to those of the prior art, and has better practical significance in actual engineering and technical applications. It is very suitable for hot surface lining, backing, filling sealing and thermal insulation materials of industrial kilns used in metallurgy, petrochemical, building materials, ceramics, machinery and other industries, and can also be used in thermal insulation components of engines and military and aerospace fields.

Claims (18)

1. A micro-nanoporous heat-insulating refractory material containing zirconia, characterized in that the micro-nanoporous heat-insulation refractory material containing zirconia is made of basic raw materials, additives and water; _ZrO2 in the product The mass percentage content is 5~100%; The basic raw materials are composed of the following raw materials in weight percentages: 30-100% of zirconia raw materials, 0-30% of alumina-based raw materials, 0-40% of aluminum-silicon raw materials, 0-20% of silica-based raw materials, oxidized Calcium raw material 0~20%; The additive includes at least a foaming material, with or without additives; the foaming material is composed of a foaming agent, an inorganic curing agent, an organic curing agent and a cell regulator, based on the quality of the basic raw material, the foaming The added mass of agent, inorganic curing agent, organic curing agent and cell regulator are respectively 0.01~10%, 0.1~20%, 0.1~2%, 0.01~1%; when using additives, the additives are selected from dispersants, One or more combinations of suspending agent, mineralizer, and infrared sunscreen, based on the quality of basic raw materials, the added mass of mineralizer and infrared sunscreen should not exceed 10%; The quality of described water is 20～200% of basic raw material quality; The micro-nanoporous heat-insulating refractory material containing zirconia has a pore size distribution of 0.006-250 μm, an average pore size of 0.1-20 μm, and a normal temperature compressive strength of 13.2-220 MPa; The cell regulator is selected from one or more combinations of cellulose ether, starch ether, lignocellulose, and saponin; the cellulose ether is selected from methyl cellulose ether, carboxymethyl cellulose ether , carboxymethyl methyl cellulose ether, carboxymethyl ethyl cellulose ether, carboxymethyl hydroxymethyl cellulose ether, carboxymethyl hydroxyethyl cellulose ether, carboxymethyl hydroxypropyl cellulose ether, carboxymethyl hydroxypropyl cellulose ether, Methyl hydroxybutyl cellulose ether, hydroxymethyl cellulose ether, hydroxyethyl cellulose ether, hydroxyethyl methyl cellulose ether, ethyl cellulose ether, ethyl methyl cellulose ether, hydroxyethyl ethyl cellulose ether Hydroxypropyl cellulose ether, propyl cellulose ether, hydroxypropyl cellulose ether, hydroxypropyl methyl cellulose ether, hydroxypropyl ethyl cellulose ether, hydroxypropyl hydroxybutyl cellulose ether, hydroxybutyl methyl cellulose One or a combination of two or more of plain ether and ethyl cellulose sulfonate. 2. The micro-nanoporous heat-insulating refractory material containing zirconia according to claim 1, characterized in that the volume density of the micro-nanoporous heat-insulation refractory material is 0.3~3g/cm ³ , and the porosity is 50~95%, the closed porosity is 20~70%, the thermal conductivity at room temperature is 0.02~0.25W/(m·K), and the thermal conductivity at 350℃ is 0.03~0.33W/(m·K) , the thermal conductivity at 1100°C is 0.06~0.4W/(m·K). 3. The micro-nanoporous heat-insulating refractory material containing zirconia as claimed in claim 1, characterized in that, in terms of mass percentage, the basic raw material is composed of 100% zirconia raw material; or 60-95% zirconia raw material and 5~40% of aluminum silicon raw material or silicon dioxide raw material or calcia raw material; or by alumina raw material, aluminum silicon raw material, silica raw material, calcia raw Two of them and 40~60% zirconia raw materials; or 30~40% zirconia raw materials, 10~30% alumina raw materials, 20~40% aluminum siliceous raw materials, 10~20% Composition of silicon dioxide raw materials. 4. The zirconia-containing micro-nanoporous heat-insulating refractory material according to any one of claims 1-3, wherein the zirconia raw material is zircon, baddeleyite, zirconium corundum, One or more combinations of monoclinic zirconia, tetragonal zirconia, cubic zirconia, and partially stabilized zirconia; the partially stabilized zirconia is Y ₂ O ₃ stabilized zirconia, and the mole of Y ₂ O ₃ accounts for The ratio is 3~9%; The alumina raw materials are industrial alumina, industrial Al(OH) ₃ , boehmite, diaspore, β-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 two groups of aluminum n-butoxide, aluminum isopropoxide, aluminum sec-butoxide, aluminum chloride hexahydrate, aluminum nitrate nonahydrate, fused corundum powder, sintered corundum powder, and tabular corundum powder a combination of the above; The aluminosilicate raw materials are mullite, kaolin, bauxite, coal gangue, kyanite, andalusite, sillimanite, pyrophyllite, potassium feldspar, albite, anorthite, barium feldspar , porcelain stone, soda stone, mica, spodumene, perlite, montmorillonite, illite, halloysite, Dikai stone, coke gem, Guangxi white clay, Suzhou soil, wood section soil, fly ash, floating beads One or a combination of two or more of them; The silicon dioxide raw material is ɑ-quartz, β-quartz, ɑ-dydymite, β-dydymite, ɑ-cristobalite, β-cristobalite, vein quartz, sandstone, quartzite, flint, cemented silica, river One or more combinations of sand, sea sand, white carbon black, methyl orthosilicate, ethyl orthosilicate, methyltrimethoxysilane, rice husk, rice husk ash, diatomaceous earth, and silica powder ; The calcareous raw material is one or more combinations of limestone, quicklime, slaked lime, wollastonite, dolomite, calcite, CaO, CaCO ₃ , Ca(OH) ₂ , CaSO ₄ ; Among them, the mass percentage of Al ₂ O ₃ in the chemical composition of alumina raw materials is more than 45%; The mass content of SiO ₂ in the chemical composition of silicon dioxide raw materials is more than 18%; the mass content of CaO in the chemical composition of calcareous raw materials is more than 30%. 5. The zirconia-containing micro-nanoporous heat-insulating refractory material according to claim 1, wherein the calcareous raw material is calcium silicate and/or calcium aluminate, or the calcareous raw material It is a combination of calcium silicate and/or calcium aluminate and one or more of limestone, quicklime, slaked lime, wollastonite, dolomite, calcite, CaO, CaCO ₃ , Ca(OH) ₂ , CaSO ₄ . 6. The micro-nanoporous heat-insulating refractory material containing zirconia as claimed in claim 1, wherein the inorganic curing agent is selected from zirconia sol, alumina sol, silica sol, silica-alumina sol, oxide Zirconium gel, alumina gel, silica gel, silica-alumina gel, dicalcium silicate, calcium dialuminate, _{SiO2 micropowder} , monocalcium aluminate, tricalcium silicate, _Al2O3 micropowder, seven Calcium dodeca aluminate, tetracalcium aluminoferrate, aluminum phosphate, water glass or a combination of two or more; The organic curing agent is selected from water-soluble polymer resin, low methoxyl pectin, carrageenan, carrageenan, hydroxypropyl guar gum, locust gum, locust bean gum, gellan gum, curdlan gum, One or more combinations of alginate and konjac gum; the water-soluble polymer resin is selected from vinyl acetate and ethylene copolymers, vinyl acetate homopolymers, acrylate polymers, ethylene and vinyl acetate Copolymer, ethylene and vinyl chloride copolymer, vinyl acetate and vinyl tertiary carbonate copolymer, acrylate 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 acrylate copolymer, isobutylene and maleic anhydride copolymer, ethylene and vinyl chloride and vinyl laurate copolymer, vinyl acetate and ethylene and higher fatty acid copolymer, vinyl acetate and ethylene and lauryl One or more combinations of vinyl acetate copolymer, vinyl acetate, acrylate and higher fatty acid vinyl ester copolymer, vinyl acetate, vinyl tertiary carbonic acid ester and acrylate copolymer. 7. The micro-nanoporous heat-insulating refractory material containing zirconia as claimed in claim 1, wherein the foaming agent is a surfactant and/or a protein foaming agent, and the foaming ratio is 8~ 60 times; described surfactant is selected from cationic surfactant, anionic surfactant, nonionic surfactant, amphoteric surfactant, Gemini type surfactant, Bola type surfactant, Dendrimer type surfactant One or more of the agents; the protein foaming agent is an animal protein foaming agent, a vegetable protein foaming agent and/or a sludge protein foaming agent. 8. The zirconia-containing micro-nanoporous heat-insulating refractory material according to claim 1 or 7, wherein the foaming agent is a sulfonate anionic surfactant with a carbon number of 8-20 , Sulfate anionic surfactant with carbon number of 8~18, amide ester quaternary ammonium salt cationic surfactant, double long chain ester quaternary ammonium salt cationic surfactant, triethanolamine stearate quaternary ammonium salt Cationic surfactant, polyoxyethylene type nonionic surfactant, fatty alcohol amide type nonionic surfactant, polyol type nonionic surfactant, amino acid type zwitterionic surfactant, betaine type zwitterionic surfactant one or more of them. 9. The micro-nanoporous heat-insulating refractory material containing zirconia as claimed in claim 1, characterized in that, based on the quality of the basic raw material, the added mass of the dispersant is no more than 3%; the dispersant is poly Carboxylic acid dispersant, sodium polyacrylate, naphthalene dispersant, FS10, FS20, lignin dispersant, sulfonated melamine polycondensate, melamine, melamine formaldehyde polycondensate, aliphatic dispersant, sulfamate dispersant, One or more of sodium citrate, sodium polyphosphate, sodium hexametaphosphate, sodium carbonate. 10. The micro-nanoporous heat-insulating refractory material containing zirconia as claimed in claim 1, characterized in that, based on the quality of the basic raw materials, the added mass of the suspending agent is not more than 10%; the suspending agent is bentonite , sepiolite, attapulgite, polyaluminum chloride, polyaluminum sulfate, chitosan, xanthan gum, acacia gum, Welan gum, agar, acrylamide, polyacrylamide, polyacrylamide, polyvinylpyrrolidone, poly Ethylene glycol, polyvinyl alcohol, casein, cetyl alcohol, sucrose, dextrin, trishydroxymethylaminomethane, microcrystalline cellulose, microcrystalline cellulose sodium, cellulose fiber, cellulose nanocrystal, soluble starch one or more of two. 11. The zirconia-containing micro-nanoporous heat-insulating refractory material 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 One or more combinations of O ₃ and CeO ₂ . 12. The zirconia-containing micro-nanoporous heat-insulating refractory material according to claim 1 or 11, wherein the infrared opacifying agent 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 One or more combination of ₄ C and SiC. 13. The preparation method of the zirconia-containing micro-nanoporous insulating refractory material according to any one of claims 1-12, characterized in that it comprises the following steps: 1) When using additives, mix and disperse the basic raw materials, additive combination and water to make a suspension slurry; when not using additives, mix and disperse the basic raw materials and water to make a suspension slurry; 2) Add foaming agent, inorganic curing agent, organic curing agent, and cell regulator to the suspension slurry for stirring and shearing foaming to make a foam slurry containing micro-nano-sized bubbles; 3) The foam slurry is injected into the mold for curing, and the green body is obtained after demoulding; then the green body is dried and fired. 14. The preparation method of zirconia-containing micro-nanoporous heat-insulating refractory material according to claim 13, characterized in that, in step 1), the average particle diameter of the solid particles in the suspended slurry is not higher than 1mm , or not higher than 74 μm, or not higher than 50 μm, or not higher than 44 μm, or not higher than 30 μm. 15. The preparation method of zirconia-containing micro-nanoporous heat-insulating refractory material according to claim 13, characterized in that, in step 2), when stirring and shearing foaming, the linear speed of the outer edge of the stirring paddle is 20 ~200m/s, or 50~200m/s, or 80~200m/s, or 100~200m/s, or 150~200m/s, or 180~200m/s. 16. The preparation method of zirconia-containing micro-nanoporous heat-insulating refractories according to claim 13, characterized in that, in step 3), the curing is at a temperature of 1-35°C and a humidity of 40-99.9 % under maintenance 0.1~24h. 17. The preparation method of micro-nanoporous heat-insulating refractories containing zirconia as claimed in claim 13, characterized in that, in step 3), the body drying is selected from normal pressure drying, supercritical drying, freeze drying, Vacuum drying, infrared drying, microwave drying, or a combination of two or more; the green body is dried to a moisture content of ≦3wt%, and the compressive strength of the green body after drying is ≧0.7MPa. 18. The preparation method of the micro-nanoporous insulating refractory material containing zirconia as claimed in any one of claims 13-17, characterized in that the firing is carried out in a high-temperature tunnel kiln, shuttle kiln, resistance kiln or It is carried out in a microwave kiln; the firing temperature is 1350~1850°C.

Images