WO2022144013A1

WO2022144013A1 - Corundum-based micro-nano-porous heat insulating refractory material and preparation method therefor

Info

Publication number: WO2022144013A1
Application number: PCT/CN2021/144043
Authority: WO
Inventors: 郭会师; 李文凤
Original assignee: 郑州轻工业大学
Priority date: 2020-12-31
Filing date: 2021-12-31
Publication date: 2022-07-07
Also published as: CN114105676A; CN114105676B

Abstract

The present invention relates to the technical field of refractory materials, and specifically relates to a corundum-based micro-nano-porous heat-insulating refractory material and a preparation method therefor. The heat-insulating refractory material is mainly prepared from base materials, additive materials, and water; the preparation process is environmentally friendly and non-polluting, simple, and easy to control; the main crystal phase of the material is a corundum phase, and the appearance of the product is white or light yellow; the pore size distribution is 0.003-250 μm and the average pore size is 0.1-30 μm; and the closed spherical micro-nano sized pore structure ensures better heat-insulating performance of the material at lower bulk density and high strength. The present invention, by means of regulating the amount of raw materials and the process, enables the prepared refractory material to meet ultra-low thermal conductivity and light weight requirements, and also ensures better mechanical performance.

Description

A kind of corundum micro-nano-porous insulating refractory material and preparation method thereof

technical field

The invention belongs to the technical field of refractory materials, and in particular relates to a corundum micro-nano-porous insulating and heat-insulating refractory material with micro-nano size pore structure, ultra-low thermal conductivity and bulk density, high porosity, high strength and green controllable preparation and the same Preparation.

Background technique

High temperature industry is the main energy-consuming industry in my country's industrial production. The low utilization rate of thermal energy of various types of kilns is the main reason for their large energy consumption. If the average thermal efficiency can be increased by 20% according to the national requirements, it can save energy equivalent to 220 million tons of standard coal. To improve the thermal efficiency of industrial kilns, the most important thing is to develop high-efficiency thermal insulation technology, use advanced thermal insulation materials, strengthen the thermal 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 demanding thermal insulation environment and requirements of the high temperature industry. At present, most of the insulation materials used in kilns are refractory fiber products or lightweight insulation bricks. Although the thermal properties of refractory fibers are good, they are sensitive to the firing atmosphere and are prone to react with reducing and corrosive gases, causing them to lose their good thermal insulation properties; and their long-term service in high temperature environments, the composition particles are easy to separate The growth of crystal grains causes stress concentration, which leads to the pulverization of the thermal insulation layer and shortens the service life; in addition, ceramic fibers are also harmful to human health, and the European Union has listed them as secondary carcinogens.

Although light-weight insulating bricks can overcome the above-mentioned defects of refractory fiber products, they are mostly made by adding a large amount of pore-forming agents (such as polystyrene particles, sawdust, charcoal, anthracite ash, coke powder, etc.). The pore-forming agent occupies a certain space in the green body. After firing, the pore-forming agent leaves the original position in the matrix to form pores, thereby obtaining a lightweight heat-insulating refractory material. The method is simple and easy to control, and the production efficiency is high, but this The material made by the method has low porosity, large pore diameter, poor thermal insulation effect, and is prone to stress concentration and cracking, resulting in low strength. In addition, most of the pore-forming agents used in the preparation process are organic lost-on-burning substances, which makes the raw material cost relatively high, and emits a large amount of toxic and harmful gases during sintering, such as anthracite, sawdust and coke powder at lower temperatures. A large amount of sulfur oxides are produced, while polystyrene particles produce styrene, toluene, nitrogen/carbon/oxides and dioxins, etc. At the same time, a large amount of VOCs fine particles will also be produced, which will seriously pollute the environment and endanger human health and surrounding crops. Production.

In addition to the pore-making method, the corundum heat-insulating refractory can also be made of alumina hollow sphere products by the alumina hollow sphere method. These products can be used in a high temperature environment above 1600 ° C, with high strength and good creep resistance. It can be directly used as the lining of high temperature furnace. However, the bulk density of such products is usually large, and the preparation of alumina hollow spheres is a secondary process, which consumes a lot of energy and costs a lot. In addition, in order to ensure the structural stability of the product, the hollow spheres of different particle sizes need to be particle graded during the preparation process. The larger the product size, the larger the critical particle size. Therefore, from the perspective of microstructure, the final particles left inside the material The pores are large and small, and the pore size distribution is extremely uneven. Therefore, there is an urgent need to research and develop new thermal insulation, thermal insulation and refractory materials for high temperature industrial use with excellent thermal insulation, durability and mechanical properties and green preparation.

SUMMARY OF THE INVENTION

The purpose of the present invention is to provide a corundum micro-nano-porous insulating and heat-insulating refractory material, the refractory material has the characteristics of micro-nano size aperture, closed spherical pore structure, ultra-low thermal conductivity and bulk density, high porosity, high strength and the like, It can effectively reduce thermal conductivity and bulk density while ensuring that the strength meets the requirements, which is conducive to the construction of environmentally friendly light-duty kilns.

Another object of the present invention is to provide a method for preparing a corundum micro-nano-porous insulating and heat-insulating refractory material. The preparation method is green and pollution-free, the structure and performance of the material are easily and precisely controlled, the yield is high, and the The heat insulating and refractory materials obtained by the existing preparation methods cannot take into account the problems of low thermal conductivity, high strength and high yield of materials.

To achieve the above object, the concrete technical scheme of the corundum micro-nano-porous insulating refractory material of the present invention is:

A corundum-based micro-nano-porous insulating and thermal-insulating refractory material, the corundum-based micro-nano-porous insulating and thermal insulating refractory material is made of basic materials, additives and water; the mass percentage content of Al ₂ O ₃ in the chemical composition of the product 75 to 99.9%, or 85 to 99.9%, or 90 to 99.9%, or 98 to 99.9%, or 98 to 99.9%, or 99 to 99.9%;

The basic material is composed of the following components in mass fractions: 10-100% of alumina raw materials, 0-90% of aluminum-silicon raw materials, and 0-20% of siliceous raw materials. and is 100%;

The additives at least include foaming materials, with or without additives; the foaming materials are composed of a foaming agent, an inorganic curing agent, an organic curing agent and a cell regulator, and are foamed based on the quality of the base material. The added mass of the filler, 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, sintering aid, and infrared sunscreen, based on the quality of the base material, the added mass of both the sintering aid and the infrared sunscreen is not more than 10%;

The quality of the water is 20-200% or 30-200% of the quality of the base material.

The corundum micro-nano-porous insulating and heat-insulating refractory material of the present invention has a main crystal phase of corundum phase and a small amount of mullite phase or glass phase, and has lower bulk density and higher compressive strength. The use temperature can reach 1800°C, and the re-fired linear change rate at 1732°C for 24 hours is ≦1.8%, preferably ≦1.2%, preferably ≦0.8%, more preferably ≦0.6%, more particularly preferably ≦0.2%.

The final refractory material can not only meet the requirements of low thermal conductivity and light weight, but also ensure high strength by adjusting the amount of each raw material and the process. Compared with the prior art, the corundum micro-nano-porous insulating refractory material provided by the present invention has the characteristics of low bulk density, low thermal conductivity, high strength, high porosity, small pore diameter, etc., and has the best thermal insulation performance. Corundum shaped heat-insulating refractory material with excellent comprehensive properties, suitable for hot-face lining, backing, filling, sealing and heat-insulating materials of industrial kilns used in metallurgy, petrochemical, building materials, ceramics, machinery and other industries, and also used in engine engines Thermal insulation parts and fields such as military industry and aerospace. And because of its extremely low thermal conductivity, it can greatly reduce the thickness of the furnace wall under the condition of meeting the environmental temperature requirements, thereby greatly reducing the weight of the furnace, and speeding up the heating rate of the furnace, which is beneficial to the new lightweight and environmentally friendly furnace. construction.

The main crystal phase in the material is corundum phase, and the rest are a small amount of mullite phase or glass phase; the morphology of corundum phase is flake or granular.

The pore diameter of the corundum micro-nano-porous insulating and heat-insulating refractory material is distributed in the range of 0.003-250 μm, the average pore diameter is 0.1-30 μm, the total porosity is 30-92%, and the closed-mouth porosity is 15-65%; the bulk density It is 0.3～2.0g/cm ³ , the compressive strength at room temperature is 2～190MPa, the thermal conductivity at room temperature is 0.03～0.18W/(m·K), and the thermal conductivity at 350℃ is 0.04～0.26W/(m·K). K), the thermal conductivity at 1100°C is 0.05 to 0.35W/(m·K). The smaller pore diameter and higher porosity effectively reduce the bulk density and thermal conductivity of the material, and the formation of closed pores can effectively improve the thermal insulation effect and increase the load capacity of the material.

The alumina-based raw material is an alumina raw material or an alumina-containing raw material, and the alumina-containing raw material refers to a substance that can be decomposed to generate alumina at high temperature. The mass percentage content of alumina in the alumina raw material is 65-99.9%.

For the alumina raw material, the weight percentage of Al ₂ O ₃ in its chemical composition is more than 90%, preferably ≧93%, preferably ≧95%, more preferably ≧96%, particularly preferably ≧98%, more particularly preferably ≧99 %. The alumina raw materials are industrial alumina, β-Al ₂ O ₃ , γ-Al ₂ O ₃ , δ-Al ₂ O ₃ , χ-Al ₂ O ₃ , ρ-Al ₂ O ₃ , κ-Al ₂ O _3. One or more of θ-Al ₂ O ₃ , η-Al ₂ O ₃ , α-Al ₂ O ₃ , fused corundum, sintered corundum, and tabular corundum.

For the alumina-containing raw material capable of generating alumina at high temperature, the weight percent content of alumina in its chemical composition is ≧65%. The alumina-containing raw materials are industrial Al(OH) ₃ , industrial Al(OH) ₃ , boehmite, diaspore, aluminum n-butoxide, aluminum isopropoxide, aluminum sec-butoxide, aluminum chloride hexahydrate , one or more of aluminum nitrate nonahydrate. The particle size of alumina raw material is less than or equal to 1mm. Preferably, the particle size of the alumina raw material is less than or equal to 0.08 mm.

The introduction of appropriate aluminum-silicon raw materials into the base material can generate a small amount of primary and secondary mullite at high temperature, which can promote the sintering of corundum materials, increase the strength, and improve the thermal shock resistance. The alumino-silicon raw materials are sintered mullite, fused mullite, kaolin, bauxite, alumino-silicon homogeneous material, coal gangue, kyanite, andalusite, sillimanite, pyrophyllite, potassium Stone, albite, anorthite, barium feldspar, china stone, alkali stone, mica, spodumene, perlite, montmorillonite, illite, halloysite, diceyite, coke gemstone, clay, Guangxi One or more of white clay, Suzhou soil, wood knot soil, fly ash, and bleaching beads. The weight percentage content of Al ₂ O ₃ in the alumino-silicon raw material is 18-90%, and the mass percentage content of silicon dioxide is 8-75%. Further preferably, in the chemical composition of the alumino-siliceous raw material, the mass percentage of alumina is 32-72%, and the mass percentage of silica is 25-64%. More preferably, in the chemical composition of the alumino-siliceous raw material, the mass percentage of alumina is 38-50%, and the mass percentage of silica is 45-58%. Preferably, the particle size of the alumino-silicon raw material is ≦1 mm. Further preferably, the particle size of the alumino-silicon raw material is 0.6-1 mm. Ceramic powder particles with higher surface activity are obtained after ball milling in the later stage.

Appropriate siliceous raw materials are appropriately introduced into the base material, which reacts with alumina-based raw materials at high temperature to form secondary mullite, which promotes the sintering of corundum-based materials and further optimization and improvement of mechanical properties. The siliceous raw material is a silica raw material or a silica-containing raw material. The mass percentage content of silica in the siliceous raw material is 28-99%, and the particle size is less than or equal to 0.08 mm.

For the silica raw material, the weight percent content of SiO ₂ in its chemical composition is above 92%. The silica raw materials are α-quartz, β-quartz, α-tridymite, β-tridymite, α-cristobalite, β-cristobalite, vein quartz, sandstone, quartzite, flint, cemented silica, river sand , one or more of sea sand, white carbon black, diatomaceous earth, and microsilica.

The siliceous raw material can also be a silica-containing raw material that can be decomposed to form silica at high temperature, and the weight percent content of SiO ₂ in its chemical composition is more than 18%; preferably more than 28%. The silica-containing raw material is one or more of rice husk, carbonized rice husk, rice husk ash, methyl orthosilicate, ethyl orthosilicate and methyltrimethoxysilane.

Dispersing agent, suspending agent, sintering aid, infrared light shielding agent form additives, and foaming agent, inorganic curing agent, organic curing agent and cell regulator form foaming material. The function and selection of each component are described in detail below.

Based on the quality of the base material, the added mass of the dispersing agent is no more than 1%, and the added mass of the suspending agent is no more than 10%.

The addition of the dispersant effectively improves the dispersion uniformity of the ceramic powder and other additives in the slurry, and avoids their agglomeration in the slurry. Preferably, the dispersant is a polycarboxylic acid type dispersant, a polycarboxylate ether dispersant, a sulfonated melamine polycondensate, a naphthalene type dispersant, a lignosulfonate type dispersant, a sulfamic acid type dispersant, One or more of sodium ethylenediaminetetraacetate, melamine formaldehyde polycondensate, sodium polyphosphate, sodium polyacrylate, sodium citrate, sodium humate, sodium phosphate, and sodium carbonate. Described polycarboxylic acid dispersant is methacrylate type polycarboxylic acid dispersant, allyl ether type polycarboxylic acid dispersant, amide/imide type polycarboxylic acid dispersant, polyamide/polyethylene glycol At least one of the polycarboxylic acid dispersants. The lignosulfonate dispersant is at least one of calcium lignosulfonate, sodium lignosulfonate and potassium lignosulfonate.

When the base material contains more barren raw materials, the suspension performance of the slurry is poor. A suspending agent can be introduced to effectively improve the suspension stability of the ceramic slurry and prevent sedimentation and stratification. The suspending agent is bentonite, sepiolite, attapulgite, polyaluminum chloride, polyaluminum sulfate, chitosan, xanthan gum, gum arabic, welan gum, agar, polyethylene glycol, polyvinyl alcohol, polyvinyl One or more of acrylamide, polyacrylamide, polyvinylpyrrolidone, casein, cetyl alcohol, sucrose, dextrin, microcrystalline cellulose, cellulose fibers, cellulose nanofibers, and cellulose nanocrystals. Preferably, the suspending agent is bentonite, sepiolite, attapulgite, polyaluminum chloride, chitosan, welan gum, polyvinylpyrrolidone, casein, microcrystalline cellulose, cellulose fiber, cellulose nanocrystal , at least one of soluble starch.

Among them, 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, which form an electric double layer structure on the surface of the base material particles. , the base material particles are suspended in the slurry by electrostatic repulsion, but the dosage is relatively large, generally, the dosage is less than 10%; and when it is selected from polyaluminum chloride, polyaluminum sulfate, chitosan, Welland Gum, agar, polyethylene glycol, polyvinyl alcohol, polyacrylamide, polyacrylamide, polyvinylpyrrolidone, casein, cetyl alcohol, sucrose, dextrin, microcrystalline cellulose, cellulose fibers, cellulose nanocrystals , soluble starch and other organic suspending agents, it is found that adding a small amount can play a better effect, and it can produce a suspension effect in the slurry through the steric hindrance effect or electrostatic steric hindrance effect. The amount can be relatively small, generally, the amount of the amount is ≦3%, preferably ≦1%, more preferably ≦0.5%.

The melting point of alumina is as high as 2054 °C, the sintering temperature is high, and it is difficult to sinter. Therefore, the introduction of an appropriate amount of sintering aids can effectively improve the sintering of the material, promote the progress of the sintering reaction and the growth of beneficial crystals (such as corundum, mullite, etc.) development, which is beneficial to the improvement of material properties. The sintering aids are ZnO, Fe ₂ O ₃ , V ₂ O ₅ , SiF ₄ , AlF ₃ , AlF ₃ ·3H ₂ O, MnO ₂ , CuO, CuSO ₄ , CaO, MgO, SrO, BaO, WO ₃ , One or more of Er ₂ O ₃ , Cr ₂ O ₃ , La ₂ O ₃ , YbO, Y ₂ O ₃ and CeO ₂ . The particle size of the sintering aid is 5 μm or less, preferably 4 μm or less, more preferably 3 μm or less, and particularly preferably 1 μm or less.

The thermal insulation mechanism of the thermal insulation refractory material is that there are a large number of pores inside, and the thermal conductivity of the air in the pores is much smaller than that of the pore wall, so the heat transfer rate of the entire thermal insulation material is slowed down and has thermal insulation performance. The heat conduction mechanism of the material is mainly composed of three parts: heat conduction, convection heat transfer and radiation heat transfer. In the present invention, because the pore diameter of the pores in the corundum micro-nano-porous insulating refractory material is small, and most of the pores are closed type structure, the gas circulation is difficult, so the convective heat transfer can be basically ignored, and because the corundum micro-nanoporous insulating refractory material will be mainly used in high temperature environments, the heat transfer mechanism of the material includes heat transfer in addition to heat conduction. . In order to further effectively reduce radiation heat transfer, the present invention introduces an infrared sunscreen agent to increase the effective reflection and absorption of infrared radiation, weaken its penetrability, and reduce thermal conductivity. The infrared sunscreen agent is rutile, TiO ₂ , TiC, K ₄ TiO ₄ , K ₂ Ti ₆ O ₁₃ , Sb ₂ O ₃ , Sb ₂ O ₅ , ZrO ₂ , CoO, Co(NO ₃ ) ₂ , CoCl ₂ , One or more of NiCl ₂ , Ni(NO ₃ ) ₂ , ZrSiO ₄ , Fe ₃ O ₄ , B ₄ C, and SiC. The average particle diameter of the infrared light-shielding agent is 5 μm or less, preferably 4 μm or less, more preferably 3 μm or less, and particularly preferably 1 μm or less.

Preferably, the foaming agent is a surfactant and or a protein-based foaming agent. The foaming multiple of the foaming agent is 8 to 60 times. The surfactant is one of anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, Gemini surfactants, Bola surfactants and Dendrimer surfactants. one or more.

Further, the anionic surfactant is a sulfonate surfactant with a carbon number of 8 to 20 in the carbon chain or a sulfate surfactant with a carbon number of 8 to 18 in the carbon chain; the cationic surfactant The surfactants are amide ester quaternary ammonium salts, double long-chain ester quaternary ammonium salts and triethanolamine stearate quaternary ammonium salts; the non-ionic surfactants are polyoxyethylene type (such as high-carbon fatty alcohol polymer). oxyethylene ether, fatty alcohol polyoxyethylene ester), fatty alcohol amide type and polyol type; the amphoteric surfactant is amino acid type or betaine type amphoteric surfactant; the Gemini type surfactant is quaternary ammonium salt Bola type or carboxylate type or sulfate type Gemini surfactant; the Bola type surfactant is a half-ring type, single-chain type or double-chain type Bola surfactant; the Dendrimer type surfactant is polyether, Polyester, polyamide, polyaromatic, polysilicon-based Dendrimer surfactants.

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

Preferably, the foaming agent is selected from quaternary ammonium type Gemini surfactants, semi-cyclic Bola surfactants, polyether type Dendrimer surfactants, carboxylate type Gemini surfactants, sulfate type Gemini surfactants, polyether surfactants Amide Dendrimer surfactant, vegetable protein foaming agent, sludge protein foaming agent, animal protein foaming agent, sodium lauryl polyoxyethylene ether carboxylate, lauric acid amidopropyl sulfobetaine, α-olefin One or more combinations of sodium sulfonate, dodecyl dimethyl betaine, fatty alcohol polyoxyethylene ether carboxylate, and sodium dodecyl benzene sulfonate.

Preferably, the mass of the inorganic curing agent is 0.1-15% of the mass of the base material, and the mass of the organic curing agent is 0.1-1% of the mass of the base material. More preferably, the mass of the organic curing agent is 0.1-0.5% of the mass of the base material. Particularly preferably, the mass of the organic curing agent is 0.1-0.2% of the mass of the base material.

The inorganic curing agent is alumina sol, silica alumina sol, silica sol, alumina gel, silica alumina gel, silica gel, Al ₂ O ₃ micropowder, SiO ₂ micropowder, dicalcium silicate, dialuminum One or more of calcium acid, tricalcium silicate, tricalcium aluminate, monocalcium aluminate, aluminum phosphate, dodecacalcium heptaaluminate, water glass, tetracalcium ferric aluminate, and soft binding clay. The water glass contains sodium silicate, or potassium silicate, or a combination of the two. In the chemical composition of the alumina sol, the mass percentage content of Al ₂ O ₃ is ≧ 20%; in the chemical composition of the silica sol, the mass percentage content of SiO ₂ is 25-40%; in the chemical composition of the silica-alumina sol The mass percentage content of Al ₂ O ₃ ≧30%, and the mass percentage content of SiO ₂ ≧20%. These inorganic curing agents can penetrate into the gaps of the ceramic powder particles after hydration, and mechanically embed the powder particles to form a good rigid skeleton structure, which increases the mechanical strength of the green body. Preferably, the inorganic curing agent is one or more of alumina gel, silica gel, SiO ₂ micropowder, alumina gel, and silica-alumina gel. The average particle size of the inorganic curing agent is less than or equal to 5 μm.

The organic curing agent is selected from water-soluble polymer resin, low methoxy pectin, carrageenan, carrageenan, hydroxypropyl guar gum, locust gum, locust bean gum, gellan gum, keratin gum, One or more combinations of alginate and konjac gum; the water-soluble polymer resin is selected from vinyl acetate and ethylene copolymer, vinyl acetate homopolymer, acrylate polymer, ethylene and vinyl acetate Copolymer, ethylene and vinyl chloride copolymer, vinyl acetate and tertiary vinyl 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 acrylate and One or more combinations of higher fatty acid vinyl ester copolymer, vinyl acetate and ethylene and vinyl laurate copolymer, vinyl acetate and tertiary vinyl carbonate and acrylate copolymer. A small amount of organic solidified material is dispersed into the gaps of the ceramic powder particles. After hydration, a continuous polymer film can be formed on the surface of the ceramic powder particles. This film forms a flexible connection between the powder particles, and then passes through the organic molecules. The intermolecular force improves the cohesion between the ceramic powder particles, increases the strength of the green body, avoids the collision and damage of the green body during the handling process, greatly improves the yield, and significantly reduces the production cost. Preferably, the organic curing agent is one or more of vinyl acetate and ethylene and higher fatty acid copolymer, konjac gum, ethylene and vinyl chloride and lauric acid copolymer, ethylene and vinyl acetate copolymer, sodium alginate kind. The above-mentioned inorganic and organic curing agents are all technically pure.

In general, since the inorganic curing agent will produce a liquid phase at a higher temperature, the softening temperature of the product will decrease. Therefore, with the gradual increase of the firing and use temperature, the amount of the inorganic curing agent should be gradually reduced, and the appropriate amount should be increased accordingly. The amount of organic curing agent to enhance the strength of the green body.

The cell regulator used in the invention can effectively adjust the size, circularity, uniformity and closure of the bubbles in the slurry, thereby effectively adjusting the cell structure in the fired product. Preferably, the cell regulator is selected from one or a combination of two or more selected from cellulose ether, starch ether, lignocellulose, and saponin. More preferably, the cellulose ether is selected from methyl cellulose ether, water-soluble cellulose ether, carboxymethyl cellulose ether, carboxymethyl methyl cellulose ether, carboxymethyl ethyl cellulose ether, carboxymethyl cellulose ether 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, hydroxyethyl ethyl cellulose ether, ethyl cellulose ether, ethyl methyl cellulose ether, propyl cellulose ether, hydroxypropyl cellulose ether, hydroxypropyl One or more combinations of methyl cellulose ether, hydroxypropyl ethyl cellulose ether, hydroxypropyl hydroxybutyl cellulose ether, hydroxybutyl methyl cellulose ether, and sulfonic acid ethyl cellulose ether.

The specific technical scheme of the preparation method of the corundum micro-nano-porous insulating and insulating refractory material of the present invention is as follows:

A method for preparing a corundum micro-nano-porous insulating and heat-insulating refractory material, comprising the following steps:

(1) When additives are used, the base materials and additives are dispersed in water into a suspension slurry; when no additives are used, the base materials and additives are dispersed in water into a suspension slurry;

(2) subjecting the foaming agent, inorganic curing agent, organic curing agent, cell regulator and suspension slurry to stirring, shearing and foaming to obtain foam slurry;

(3) The foam slurry is injected into the mold for curing, and the green body is obtained after demoulding; the green body is dried and sintered at a temperature of 1200-1800°C.

The technical key to preparing the lightweight thermal insulation material lies in the introduction of its 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 foaming agent, an inorganic curing agent, an organic The functional foaming components composed of curing agent and cell regulator are mixed and foamed by stirring, which is beneficial to maintain the integrity of the bubbles and improve the formation rate of closed pores; during the curing process, the bubbles in the foam slurry are transformed into the green body. Spherical pores, which provide space for the growth and development of beneficial crystals in the subsequent firing process, so that the crystal development is perfect and the product performance is improved. At the same time, the inventor also accidentally discovered in the long-term research process that because the holes in the green body made by the present invention are tiny micron or nanometer spherical voids, the concave surface of the holes has a very large radius of curvature, which makes corundum, molybdenum, etc. The nucleation and growth driving force of beneficial crystals such as tolite in this hole is further enhanced, so the growth size of the crystal is larger and the physical properties of the product are better.

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

The appearance of the corundum micro-nano-porous insulating refractory material of the present invention is white, light yellow or yellow.

In the preparation method of the present invention, preferably, the amount of water described in step (1) accounts for 20-200% of the weight of the base material, preferably 50-180%, and preferably, the amount of water is 50-150% of the weight of the base material %, further preferably, the amount of water used is 100-120% of the mass of the base material. When a large amount of water is added, most of the water can be converted into a liquid film of bubbles in the slurry during the stirring process, while a small amount of water that does not become a liquid film of bubbles exists in the form of liquid water. Tiny capillary pores remain in the sample. That is to say, the added water is finally transformed into micro- and nano-sized pores in the product. Therefore, the essence of this process technology to prepare thermal insulation and refractory materials is to use water and air to generate micro- and nano-sized pores in the refractory material. Therefore, to a certain extent, the bulk density, porosity, thermal conductivity and mechanical strength in the product can be adjusted according to the amount of water consumption. In this step, if components such as dispersing agent, suspending agent, mineralizer, infrared sunscreen agent are used, the above-mentioned components and base material are dispersed into a suspension slurry. If no dispersing agent, suspending agent, mineralizer, infrared sunscreen agent and other components are used, or only one or more of them are used, the corresponding components can be dispersed.

In step (1), in order to form a fine, uniform and stable suspension slurry, the average particle size of the solid particles in the slurry should be controlled to be no higher than 1 mm, preferably no higher than 74 μm, or no higher than 44 μm, or no higher than 30 μm. In order to achieve the above-mentioned mixing effect, one of the methods such as mechanical stirring, ball milling, and ultrasonic, or a combination of two or more methods can be used for mixing. If the particle size of the raw material is fine, and it is easy to disperse into a suspension slurry, it can be done by mechanical stirring. Preferably, the dispersion includes ball milling and ultrasonic dispersion. Specifically: dispersing agent, suspending agent, sintering aid and infrared light-shielding agent are mixed to obtain an additive, and then the additive is mixed with a base material and a water ball mill to obtain a mixed material, and then ultrasonicated. Among them, the aluminum-silicon raw material, the alumina-based raw material and the siliceous raw material in the base material are also preferably mixed uniformly in advance.

Dispersing agent, suspending agent, sintering aid and infrared sunscreen agent are mixed and the mixer used for mixing the foaming material adopts the existing mixer such as three-dimensional mixer, V-type mixer, double cone mixer, planetary mixer, forced mixer, non- Gravity mixer is enough, and the mixing degree is ≧95%. Likewise, the three raw materials in the base material are preferably pre-mixed uniformly by the same method when used.

Preferably, the material of the grinding balls in the ball mill is zirconia, alumina, mullite, zirconium corundum, silicon carbide, silicon nitride or tungsten carbide or a mixture of several materials. Further preferably, the size specification of the grinding ball is a large ball

middle ball

small ball

The large ball, the medium ball and the small ball are combined according to the weight ratio of (1～1.5):(1～3):(6～10), more preferably, the large ball, the medium ball and the small ball are combined according to (1～1.5):( 1-2): (6-8) weight ratio combination.

Preferably, the material/ball weight ratio of the ball-milling mixture is 1: (0.8-1.5), and the ball-milling time is 0.5-12h. Through ball milling, the average particle size of solid particles in the mixture can be made not higher than 74 μm. Preferably, the average particle size of the solid particles is not higher than 50 μm; further preferably, the average particle size of the solid particles is not higher than 44 μm; more particularly preferably, the average particle size of the solid particles is not higher than 30 μm. These ball-milled ceramic powder particles have high surface activity, and after being modified by surfactant molecules (foaming agent), they have excellent hydrophobic properties. Under the action of mechanical stirring, they will irreversibly adsorb on the bubble liquid film. At the gas-liquid interface, the high-energy gas-liquid interface is replaced by the low-energy liquid-solid and gas-solid interfaces, which reduces the total free energy of the system and improves the foam stability. At the same time, some powder particles accumulate in the Plateau channel between the bubbles. It effectively prevents the liquid film from draining and resists unstable factors such as foam rupture, liquid draining, disproportionation, and Oswald aging, thereby obtaining a very stable foamed ceramic slurry.

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

Step (2) In the preparation process of the foam slurry, depending on the variety of raw materials, if the foaming agent, the inorganic curing agent, the organic curing agent, and the cell regulator are all dry solid raw materials, the dry raw materials are first dry mixed to obtain the product. The foaming composition is then added to the suspending slurry, followed by stirring for foaming. If some of the foaming agents, inorganic curing agents, organic curing agents, and cell regulators are liquid raw materials, it is preferable to dry-mix the dry raw materials first, and then add the dry mixture and liquid raw materials to the suspension. In the slurry, stir and foam again. The foaming agent can also be pre-prepared by the foaming machine, and then added to the suspension slurry with the mixture of inorganic curing agent, organic curing agent and cell regulator, and then stirring and shearing foaming.

The stirring and foaming in the step (2) adopts the high-speed shearing mixing and foaming of the stirring blades of a vertical mixer, the linear velocity of the outer edge of the stirring blade is 20-200 m/s, and the stirring and shearing time is 1-30 min. Further preferably, the linear velocity is 50-200m/s; the further preferred linear velocity is 80-200m/s; the further preferred linear velocity is 100-200m/s; the further preferred linear velocity is 150-200m/s; The linear velocity is preferably 180 to 200 m/s. The stirring paddle quickly stirs and mixes the slurry and introduces a large amount of air, and a large amount of foam is generated under the action of the foaming agent, which makes the volume of the slurry expand rapidly. Micro bubbles with a size of 0.01 to 200 μm, the ceramic slurry becomes a uniform foamed ceramic slurry. Generally, the larger the linear velocity of the outer edge of the stirring paddle, the smaller the size of the bubbles formed, the more uniform and stable it is, and the more favorable the formation of micro- and nano-scale pores in the obtained corundum insulating refractory material. The pores can effectively inhibit the heat transfer of free gas molecules, further reduce the thermal conductivity, and at the same time ensure that the mechanical properties meet the needs of use and have good thermal insulation and fire resistance.

In the step (3), the foam slurry is poured into the mould, and the mould used is selected from one or more of the following, but is not limited to: be a metal mould, a plastic mould, a resin mould, a rubber mould, a foam mould, a plaster mould , glass mold, glass fiber reinforced plastic mold or wood or bamboo or bamboo plastic mold, and the above-mentioned several materials composite mold, the shape of the mold can be changed according to the design requirements, and is suitable for the preparation of special-shaped products.

In step (3), the curing is curing in an environment with an air temperature of 1-35° C. and a humidity of 50-99.9% for 0.2-12 hours, so that the slurry can be quickly cured and shaped; the curing is preferably carried out in an environment of constant temperature and humidity. The air temperature in the curing environment is 1-35°C, preferably 5-30°C, more preferably 10-30°C, more preferably 20-30°C, particularly preferably 25-30°C, more particularly preferably 27-30°C; the air humidity is 50-99.9%, preferably 60-99%, more preferably 70-97%, more preferably 80-95%, particularly preferably 85-93%, more particularly preferably 88-92%. In 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 will increase rapidly, and rapid demoulding will be realized.

During the research, it was found that due to the very short demoulding time of the green body, the turnover rate of the mold was greatly accelerated, and the overall preparation process was also accelerated, and the production efficiency was greatly improved, which was difficult to achieve in the past. It is understandable that after the green body is cured, it needs to be demolded first and then dried. Since the strength of the green body increases rapidly after curing, rapid dehydration and drying of the green body can be achieved in step (3). , or a combination of any two or more of them. The moisture content in the final dried green body is less than or equal to 3wt%.

Preferably, when drying at atmospheric pressure, the drying heat source may be power heating or hot air, the drying temperature is 30-110° C., and the drying time is 12-48 h. Preferably, the drying system is as follows: firstly, the temperature is raised to 30°C at 1-5°C/min, kept at 30°C for 5-10 hours, then heated to 50°C at 1-5°C/min, and kept at 50°C for 2-5 hours. Then raise the temperature to 70°C at 1～5°C/min, keep at 70°C for 2～5h, then raise the temperature at 1～5°C/min to 90°C, keep at 90°C for 2～5h, then heat at 1～5°C/min The temperature was raised to 110°C, and the temperature was kept at 110°C for 12 to 24 hours;

Wherein, when supercritical drying technology is adopted, the medium of supercritical drying is carbon dioxide, the drying temperature is 31-45°C, the pressure of the reactor is controlled at 7-10MP, and the drying time is 0.5-3h;

Wherein, when the freeze-drying method is adopted, the drying temperature of the freeze-drying machine is -180℃～-30℃, and the drying time is 3～6h;

Wherein, when the vacuum drying method is adopted, the drying temperature of the vacuum drying box is 35～50℃, the vacuum pressure is 130～0.1Pa, and the drying time is 3～8h;

Wherein, when using the infrared drying method, the wavelength of the infrared rays is 2.5-100 μm, preferably 2.5-50 μm, preferably 2.5-30 μm, more preferably 2.5-15 μm, more particularly preferably 2.5-8 μm, and the drying time is 0.5-5h;

Wherein, when the microwave drying method is adopted, the microwave frequency is selected from 300 to 300000 MHz, preferably 300 to 10000 MHz, preferably 300 to 3000 MHz, more preferably 300 to 1000 MHz, more particularly preferably 600 to 1000 MHz, and the drying time is 0.3 to 3 hours.

After the green body is quickly dried and dehydrated, a porous structure with high strength is formed. It is found that its weight is greatly reduced and the strength is greatly increased compared with that of the green body before drying and the traditional method of adding pore-forming agent. It greatly reduces the labor intensity of workers in transporting green bodies and kiln loading operations, and is very suitable for mechanized operations, improving work efficiency and improving yield.

In the above process, the organic and inorganic curing agents work together to greatly improve the strength of the green body obtained after curing and drying the foam slurry, and its compressive strength is ≥ 0.7MPa, which can greatly reduce or avoid the green body during transportation and kiln loading. The damage caused by the bump greatly improves the yield, the yield is ≧90%, preferably ≧95%, more preferably ≧98%, more particularly preferably ≧99%, the production cost is significantly reduced, and the green body can be effectively processed. Mechanical processing such as cutting and drilling.

The firing option is fired in a high temperature tunnel kiln, shuttle kiln, resistance kiln or microwave kiln.

Further preferably, the sintering system is as follows: from room temperature to 500°C at 1-5°C/min, then to 1000°C at 5-30°C/min, holding for 0.5-1.5h, and then heating at 1-30°C/min to 1200～1800℃, keep for 1～10h, then cool down to 1100℃ at 10～20℃/min, keep at 1100℃ for 0.5～1.5h, then cool down to 500℃ at 5～30℃/min, then at 500℃ Heat preservation for 0.5h, and finally cool down to 50-80°C at 1-10°C/min to obtain corundum micro-nano-porous insulating refractory material, which can be punched, cut or ground according to actual requirements. shape.

Description of drawings

Fig. 1 is the macrophotograph of the corundum micro-nano-porous insulating and insulating refractory material of Example 1 of the present invention;

2 is a photo of the microstructure of the corundum micro-nano-porous insulating and insulating refractory material of Example 1 of the present invention;

3 is a photo of the microstructure inside the pores of the corundum micro-nano-porous insulating refractory material of Example 1 of the present invention;

FIG. 4 is an EDS diagram of the corundum micro-nano-porous insulating refractory material of Example 1 of the present invention (corresponding to point 1 in FIG. 3 );

FIG. 5 is an EDS diagram of the corundum micro-nano-porous insulating refractory material of Example 1 of the present invention (corresponding to point 2 in FIG. 3 );

6 is a photo of the microstructure of the pore structure of the corundum micro-nano-porous insulating and insulating refractory material of Example 12 of the present invention;

7 is a photo of the microstructure of the pore wall of the corundum micro-nano-porous insulating and heat-insulating refractory material of Example 12 of the present invention;

FIG. 8 is a pore size distribution diagram of the corundum micro-nano-porous insulating and thermal insulating refractory material according to Example 6 of the present invention.

Detailed ways

The specific implementation process of the present invention will be specifically described below with reference to specific embodiments. All raw materials used in the following examples are commercially available conventional products. If there are no special instructions, the specifications of the relevant raw materials are as follows. If there are special instructions, the specifications of the raw materials shall be subject to the special instructions.

Industrial Al(OH) ₃ , the mass percentage of Al ₂ O ₃ in the chemical composition is ≧65%, and the particle size is ≦0.08mm. For diaspore, the mass percentage of Al ₂ O ₃ in the chemical composition is ≧70%, and the particle size is ≦0.08mm. Industrial alumina, β-Al ₂ O ₃ , γ-Al ₂ O ₃ , δ-Al ₂ O ₃ , χ-Al ₂ O ₃ , α-Al ₂ O ₃ , κ-Al ₂ O ₃ , θ-Al ₂ In O ₃ and η-Al ₂ O ₃ , the mass percentage of Al ₂ O ₃ is ≧ 98%, and the particle size is ≦0.08 mm. In sintered corundum and fused corundum, the mass percentage of Al ₂ O ₃ is ≧98%, and the particle size is ≦0.08mm. Boehmite, the mass percentage of Al ₂ O ₃ in the chemical composition is ≧70%, and the particle size is ≦0.08mm. Potassium feldspar, the mass percentage content of K ₂ O in the chemical composition is 9-11%, the mass percentage content of Al ₂ O ₃ is 18-20%, the mass percentage content of SiO ₂ is 64-66%, and the particle Diameter≦0.08mm. Coal gangue, the mass percentage content of Al ₂ O ₃ in the chemical composition is 20-25%, the mass percentage content of SiO ₂ is 66-75%, and the particle size is 0.6-1 mm. Albite, the mass percentage content of Na ₂ O in the chemical composition is 10-12%, the mass percentage content of Al ₂ O ₃ is 19-22%, and the mass percentage content of SiO ₂ is 66-69%. Diameter≦0.08mm. Kaolin, in the chemical composition, the mass percentage of Al ₂ O ₃ is 32-35%, the mass percentage of SiO ₂ is 61-64%, and the particle size is less than or equal to 0.08mm. For kyanite, the mass percentage content of Al ₂ O ₃ in the chemical composition is 52-55%, the mass percentage content of SiO ₂ is 44-46%, and the particle size is 0.6-1 mm. Silicon micropowder, the mass percentage of SiO ₂ in the chemical composition is ≧92%, and the particle size is ≦5μm.

1. The specific embodiment of the corundum micro-nano-porous insulating and insulating refractory material of the present invention

Example 1

The macroscopic and microstructure photos of the corundum micro-nanoporous insulating refractory material of this embodiment are shown in Figures 1 and 2. It can be seen from the figures that the appearance of the material is white, and there are a large number of tiny pores inside. Figure 3 shows the microstructure of the inside of the pores of the material. It can be seen from the figure that there are a large number of flaky and needle-shaped crystals in the material. and needle-like crystals are corundum phase and mullite phase, respectively, as shown in Figure 4 and Figure 5.

In the chemical composition of the corundum-based micro-nano-porous insulating and thermal insulating refractory material of the present embodiment, the mass percentage content of Al ₂ O ₃ is 75-77%, which is made from the base material and the following raw materials that account for the total weight percentage of the base material: suspension 10% of sintering agent, 10% of sintering aid, 10% of infrared light-shielding agent, 0.4% of foaming agent, 10% of inorganic curing agent, 1.5% of organic curing agent, and 0.3% of cell regulator.

The used base material is composed of the following components by mass percentage: 80% of alumina raw material and 20% of siliceous raw material. Among them, the alumina raw material is composed of industrial Al(OH) ₃ , diaspore, and γ-Al ₂ O ₃ in a mass ratio of 2:1:5; the siliceous raw material is composed of diatomite (its chemical composition). The mass percentage of SiO ₂ is ≧ 85%, and the particle size is ≦ 0.08mm), and the silicon powder is mixed in a mass ratio of 1:1.

The suspending agent is composed of bentonite (the mass percentage of Al ₂ O ₃ is 22 to 23%, the mass percentage of SiO ₂ is 68 to 75%, and the particle size is less than or equal to 0.045mm) and welan gum in a mass ratio of 9:1. The sintering aid is a mixture composed of AlF ₃ ·3H ₂ O, ZnO, V ₂ O ₅ , La ₂ O ₃ and BaO in a mass ratio of 1:1:1:1:1; infrared sunscreen agent It is a mixture composed of TiC, K ₄ TiO ₄ , B ₄ C and Sb ₂ O ₃ in a mass ratio of 1:1:2:1.

The foaming agent is composed of quaternary ammonium type Gemini surfactant (Hengmei Technology Co., Ltd., foaming ratio of 45) and semi-cyclic Bola surfactant (Hengmei Technology Co., Ltd., foaming ratio of 50) according to the mass ratio of 1:1 The composition of the mixture; the inorganic curing agent is a mixture composed of alumina gel and Al ₂ O ₃ micropowder in a mass ratio of 2:3; the organic curing agent is a copolymer of vinyl acetate, ethylene and higher fatty acids (Wacker Chemicals, Germany) company,

), vinyl acetate and ethylene copolymer (WACKER CHEMICALS AG, Germany,

) in a mass ratio of 2:1; the cell regulator is composed of hydroxyethyl ethyl cellulose ether (Netherlands AkzoNobel) and saponin (Hengmei Technology Co., Ltd.) in a mass ratio of 2:1 mixture.

Among them, AlF ₃ ·3H ₂ O, ZnO, V ₂ O ₅ , La ₂ O ₃ , BaO, TiC, K ₄ TiO ₄ , B ₄ C, Sb ₂ O ₃ , alumina gel, and Al ₂ O ₃ fine powder are all It is industrial pure, and the particle size is less than 5μm.

Example 2

In the corundum micro-nano-porous insulating and thermal insulating refractory material of this embodiment, the main crystal phases are flaky corundum phase and needle-like mullite phase, and the mass percentage content of Al ₂ O ₃ in the chemical composition of the material is 78~ 79%, made from the base material and the following raw materials in the total weight percentage of the base material: dispersant 0.05%, suspending agent 5.3%, sintering aid 9%, infrared shading agent 6%, foaming agent 10%, inorganic curing agent 20% %, organic curing agent 0.1%, cell regulator 0.01%.

The used base material is composed of the following components by mass percentage: 80% of alumina raw materials, 5% of aluminum-silicon raw materials, and 15% of siliceous raw materials. Among them, the alumina raw material is made by mixing industrial Al(OH) ₃ and sintered corundum (the mass percentage of Al ₂ O ₃ in its chemical composition is 97%, and the particle size is less than or equal to 5 μm) according to the mass ratio of 3:5; The aluminosilicate raw material is potassium feldspar; the siliceous raw material is silicon micropowder.

The dispersant is an amide-type polycarboxylic acid dispersant (Hengmei Technology Co., Ltd.) and a polycarboxylate ether dispersant in a mass ratio of 3:2; the suspending agent is composed of bentonite (Al ₂ O ₃ with a mass percentage of 22 to 23 %, the mass percentage of SiO ₂ is 68-75%, the particle size is less than or equal to 0.045mm) and the cellulose fiber (Dow Chemical Company, USA) in a mass ratio of 50:3; the sintering aid is composed of MnO ₂ , ZnO The mixture with V ₂ O ₅ according to the mass ratio of 1:1:1; the infrared sunscreen agent is the mixture of TiC, K ₄ TiO ₄ , Sb ₂ O ₃ according to the mass ratio of 1:1:1.

The foaming agent is composed of polyether type Dendrimer surfactant (Hengmei Technology Co., Ltd., foaming ratio of 45), vegetable protein foaming agent (Shandong Xinmao Chemical Co., Ltd., foaming ratio of 9) and sludge protein foaming agent. (Hengmei Technology Co., Ltd., the foaming ratio is 8) a mixture composed of a mass ratio of 0.1:2.9:7; the inorganic curing agent is alumina sol (Al ₂ O ₃ content ≧ 20%), silica sol (SiO ₂ content ≧ 30%) in a mass ratio of 3:2; the organic curing agent is composed of Kederan gum (Hengmei Technology Co., Ltd.) and gellan gum (Jiangsu Gubei Biotechnology Co., Ltd.) in a mass ratio of 1:1 The mixture of cellulose; the cell regulator is composed of carboxymethyl ethyl cellulose ether (US Asialand Company), carboxymethyl hydroxymethyl cellulose ether, carboxymethyl hydroxyethyl cellulose ether (US Dow Chemical Company) ) in a mass ratio of 5:3:2.

Among them, MnO ₂ , ZnO, V ₂ O ₅ , TiC, K ₄ TiO ₄ , Sb ₂ O ₃ , and silica gel are all industrially pure, and the particle size is less than or equal to 5 μm.

Example 3

In the corundum-based micro-nanoporous insulating and thermal insulating refractory material of this embodiment, the main crystalline phases are flaky corundum phase and needle-like mullite phase, and the mass percentage of Al ₂ O ₃ in the chemical composition of the material is 81~ 83%, made from the base material and the following raw materials that account for the total weight of the base material: 0.1% of dispersant, 4% of suspension agent, 8% of sintering aid, 6% of infrared sunscreen agent, 5.1% of foaming agent, 15% of inorganic curing agent %, organic curing agent 0.5%, cell regulator 0.06%.

The base material used is composed of the following components by mass percentage: 85% of alumina raw materials and 15% of siliceous raw materials. Among them, the alumina raw material is composed of industrial Al(OH) ₃ , boehmite, aluminum n-butoxide, aluminum isopropoxide, and aluminum sec-butoxide in a mass ratio of 30:10:1:1:0.5; silica The raw materials are silicon micropowder, methyl orthosilicate, ethyl orthosilicate, and methyltrimethoxysilane in a mass ratio of 2:1:1:1.

The dispersing agent is a mixture of imide-type polycarboxylic acid dispersing agent (Hengmei Technology Co., Ltd.) and naphthalene-based dispersing agent in a mass ratio of 1:1; chemical) in a mass ratio of 3:1; sintering aid is a mixture of MnO ₂ , ZnO, V ₂ O ₅ in a mass ratio of 3:3:2; infrared sunscreen agent is K ₂ Ti ₆ O ₁₃ , K ₄ TiO ₄ , Ni(NO ₃ ) ₂ in a mass ratio of 1:1:1.

The foaming agent is a mixture of carboxylate-type Gemini surfactant (Hengmei Technology, foaming ratio of 60) and animal protein foaming agent (Hengmei Technology, foaming ratio of 11) in a mass ratio of 1:50; inorganic The curing agent is silica-alumina sol (Al ₂ O ₃ content ≧ 30%, SiO ₂ content ≧ 20%); the organic curing agent is Ukeran gum (Hengmei Technology Co., Ltd.), gellan gum (Jiangsu Gubei Biotechnology Co., Ltd.) ) in a mass ratio of 3:2; the cell regulator is a mixture of ethyl cellulose sulfonate and methyl cellulose ether (The Dow Chemical Company, USA) in a mass ratio of 2:1.

Among them, MnO ₂ , ZnO, V ₂ O ₅ , K ₂ Ti ₆ O ₁₃ , K ₄ TiO ₄ , and Ni(NO ₃ ) ₂ are all technically pure, and the particle size is ≦5 μm.

Example 4

In the corundum micro-nanoporous insulating and thermal insulating refractory material of the present embodiment, the main crystal phases are flaky corundum phase and columnar mullite phase, and the mass percentage content of Al ₂ O ₃ in the chemical composition of the material is 84-85%. %, made from the base material and the following raw materials in the total weight percentage of the base material: dispersant 0.15%, suspending agent 3%, sintering aid 6%, infrared shading agent 4%, foaming agent 0.2%, inorganic curing agent 12% , 1% organic curing agent, 0.2% cell regulator.

The base material used is composed of the following components by mass percentage: 85% of alumina-based raw materials and 15% of aluminum-silicon raw materials. Among them, the alumina raw material is composed of industrial Al(OH) ₃ and α-Al ₂ O ₃ (the mass percentage content of Al ₂ O ₃ in its chemical composition is all ≧99%, and the particle size is ≦0.08mm) according to the ratio of 8:9. The composition of the mass ratio; the aluminum-silica raw material is composed of coal gangue, albite, and kaolin in a mass ratio of 1:1:1;

The dispersant is sulfonated melamine polycondensate; the suspending agent is a mixture of attapulgite and polyaluminum chloride in a mass ratio of 2:1; the sintering aid is Y ₂ O ₃ , MgO, V ₂ O ₅ by mass The mixture is composed of a ratio of 1:1:1; the infrared sunscreen agent is a mixture of rutile and ZrSiO ₄ in a mass ratio of 1:1.

The foaming agent is a mixture of carboxylate-type Gemini surfactant (Hengmei Technology, foaming ratio of 60) and semi-cyclic Bola surfactant (Hengmei Technology, foaming ratio of 50) in a mass ratio of 1:1 ; Inorganic curing agent is alumina sol (Al ₂ O ₃ content ≧ 30%); Organic curing agent is a mixture formed by locust bean gum and locust gum (Hengmei Technology Co., Ltd.) in a mass ratio of 1:1; Cell regulator It is a mixture of carboxymethyl ethyl cellulose ether (Asian Company, USA) and hydroxyethyl ethyl cellulose ether (Akzo Nobel Company, Netherlands) in a mass ratio of 1:1.

Among them, Y ₂ O ₃ , MgO, V ₂ O ₅ , rutile, and ZrSiO ₄ are all of industrial grade, and the particle size is ≦5 μm.

Example 5

In the corundum-based micro-nanoporous insulating and thermal insulating refractory material of this embodiment, the main crystal phases are granular corundum phase and short columnar mullite phase, and the mass percentage content of Al ₂ O ₃ in the chemical composition of the material is 86~ 88%, made from the base material and the following raw materials in the total weight percentage of the base material: dispersant 0.2%, suspending agent 2%, sintering aid 5%, foaming agent 0.44%, inorganic curing agent 5%, organic curing agent 1 %, cell regulator 0.4%.

The base material used is composed of the following components by mass percentage: 85% of alumina-based raw materials and 15% of aluminum-silicon raw materials. Among them, the alumina raw material is made of industrial alumina, β-Al ₂ O ₃ , γ-Al ₂ O ₃ , δ-Al ₂ O ₃ , χ-Al ₂ O ₃ according to 6:4:3:2:2 Aluminosilicate raw material is composed of kyanite, kaolin, barium feldspar (in its chemical composition, the mass percentage of BaO is 16-18%, and the mass percentage of Al ₂ O ₃ is 25-28%, The mass percentage of SiO ₂ is 54-56%, and the particle size is less than or equal to 0.08mm) according to the mass ratio of 1:1:1;

The dispersing agent is a mixture of polyamide type polycarboxylic acid dispersing agent (Hengmei Technology Co., Ltd.) and sodium polyacrylate in a mass ratio of 2:3; The mixture is composed of a mass ratio of 1:1; the sintering aid is a mixture composed of MnO ₂ , SiF ₄ and Cr ₂ O ₃ in a mass ratio of 2:2:1.

The foaming agent is composed of carboxylate type Gemini surfactant (Hengmei Technology, foaming ratio of 60) and sodium dodecyl polyoxyethylene ether carboxylate (foaming ratio of 9) according to the mass ratio of 1:3 mixture. The inorganic curing agent is a mixture of silica gel, dodecacalcium heptaaluminate, tetracalcium ferric aluminate, and alumina gel in a mass ratio of 1:1:1:2; the organic curing agent is ethylene and vinyl acetate Ester copolymer (WACKER CHEMICALS AG, Germany,

), Kederan gum (Hengmei Technology Co., Ltd.), and gellan gum (Jiangsu Gubei Biotechnology Co., Ltd.) in a mass ratio of 2:2:1; the cell regulator is a mixture of carboxymethyl hydroxybutyl A mixture of cellulose ether and hydroxypropyl hydroxybutyl cellulose ether (The Dow Chemical Company, USA) in a mass ratio of 1:1.

Among them, MnO ₂ , SiF ₄ , Cr ₂ O ₃ , dodecacalcium heptaaluminate, and tetracalcium ferric aluminate are all industrial pure, and the particle size is less than or equal to 5 μm.

Example 6

In the corundum micro-nanoporous insulating and thermal insulating refractory material of the present embodiment, the main crystal phases are granular corundum phase and short columnar mullite phase, and the mass percentage content of Al ₂ O ₃ in the chemical composition of the material is 87~ 89%, made from the base material and the following raw materials in the total weight percentage of the base material: dispersant 0.3%, suspending agent 1%, sintering aid 4%, infrared opacifier 3%, foaming agent 0.39%, Inorganic curing agent 5 %, organic curing agent 1%, cell regulator 0.6%.

The base material used is composed of the following components by mass percentage: 85% of alumina-based raw materials and 15% of aluminum-silicon raw materials. The alumina raw material is composed of α-Al ₂ O ₃ , κ-Al ₂ O ₃ , θ-Al ₂ O ₃ , η-Al ₂ O ₃ in a mass ratio of 10:3:2:2; aluminum-silicon The quality raw materials are composed of kyanite and porcelain stone (the mass percentage of Na ₂ O is 4-5%, the mass percentage of Al ₂ O ₃ is 18-20%, and the mass percentage of SiO ₂ is 74-77%. %, particle size≤0.08mm), coke gemstone (38-40% by mass of Al ₂ O ₃ , 44-47% by mass of SiO ₂ , particle size≤0.08mm) according to 2:1: 2 mass ratio composition;

The dispersant is a mixture of sulfamic acid dispersant and sodium humate in a mass ratio of 2:1; the suspending agent is a mixture of cellulose nanofibers, polyethylene glycol and polyvinyl alcohol in a ratio of 2:2:1 The mixture is composed of mass ratio; the sintering aid is the mixture composed of AlF ₃ ·3H ₂ O, BaO and V ₂ O ₅ according to the mass ratio of 1:2:1; the infrared sunscreen agent is composed of Ni(NO ₃ ) ₂ , Fe A mixture of ₃ O ₄ in a mass ratio of 2:1.

The foaming agent is a mixture of carboxylate type Gemini surfactant (Hengmei Technology, foaming ratio of 60) and lauric acid amidopropyl sulfobetaine (foaming ratio of 13) in a mass ratio of 1:12 . The inorganic curing agent is silica-alumina gel (in its chemical composition, the content of Al ₂ O ₃ is 40%, and the content of SiO ₂ is 60%); the organic curing agent is carrageenan, konjac gum (Shanghai Beilian Biotechnology Co., Ltd.), acrylate Polymers (National Starch Company,

), vinyl acetate with ethylene and acrylate copolymers (WACKER CHEMICALS AG, Germany,

), ethylene and vinyl chloride copolymer (Wacker Chemicals, Germany,

) according to the mass ratio of 1:1:1:1:1; the cell regulator is composed of hydroxypropyl hydroxybutyl cellulose ether (Dow Chemical Company, USA), lignocellulose (Hengmei Technology Co., Ltd.) The mixture is composed in a mass ratio of 1:2.

Among them, AlF ₃ ·3H ₂ O, BaO, V ₂ O ₅ , Ni(NO ₃ ) ₂ , Fe ₃ O ₄ and silica-alumina gel are all technically pure, and the particle size is less than or equal to 5 μm.

Example 7

In the corundum-based micro-nanoporous insulating refractory material of this embodiment, the main crystal phases are granular corundum phase and short columnar mullite phase, and the mass percentage content of Al ₂ O ₃ in the chemical composition of the material is 88～ 89%, made from the base material and the following raw materials in the total weight percentage of the base material: dispersant 0.4%, suspending agent 0.6%, sintering aid 3%, infrared shading agent 3%, foaming agent 0.32%, inorganic curing agent 5% %, organic curing agent 1.2%, cell regulator 1%.

The used base material is composed of the following components by mass percentage: 10% alumina raw material and 90% aluminum siliceous raw material. Among them, the alumina raw material is composed of α-Al ₂ O ₃ and sintered corundum in a mass ratio of 3:7; the aluminum siliceous raw material is composed of high alumina bauxite (Al ₂ O ₃ with a mass percentage of 89-90% , the mass percentage of SiO ₂ is 8 to 9%, and the particle size is 0.6 to 1 mm), sintered mullite (Al ₂ O ₃ mass percentage of 59 to 61%, and SiO ₂ mass percentage of 37%) ~39%, the particle size is 0.6 ~ 1mm) according to the mass ratio of 17:1.

The dispersant is composed of polycarboxylate ether dispersant (BASF, Germany) and melamine formaldehyde polycondensate in a mass ratio of 1:1; the suspending agent is composed of cetyl alcohol, sucrose and dextrin in a mass ratio of 1:1:1; sintered The auxiliary agent is composed of SrO, WO ₃ and Er ₂ O ₃ according to the mass ratio of 1:1:1; the infrared sunscreen agent is composed of CoCl ₂ , Ni(NO ₃ ) ₂ , Fe ₃ O ₄ according to the mass ratio of 3:2:1 composition.

The foaming agent is a mixture of quaternary ammonium type Gemini surfactant (Hengmei Technology Co., Ltd., with a foaming ratio of 45) and sodium α-olefin sulfonate (with a foaming ratio of 15) in a mass ratio of 1:15. The inorganic curing agent is a mixture of dicalcium silicate and calcium dialuminate in a mass ratio of 2:3; the organic curing agent is a copolymer of vinyl acetate, ethylene and higher fatty acids (Wacker Chemicals, Germany,

) and vinyl acetate with ethylene and vinyl laurate copolymers (WACKER CHEMICALS AG, Germany,

) in a mass ratio of 2:1; the cell regulator is a mixture of hydroxypropyl ethyl cellulose ether and propyl cellulose ether (US Asialand) in a mass ratio of 1:1.

Among them, SrO, WO ₃ , Er ₂ O ₃ , CoCl ₂ , Ni(NO ₃ ) ₂ , Fe ₃ O ₄ , dicalcium silicate, and calcium dialuminate are all industrial pure, and the particle size is less than or equal to 5 μm.

Example 8

In the corundum-based micro-nanoporous insulating and heat-insulating refractory material of the present embodiment, the main crystal phase is a granular corundum phase, and the mass percentage content of Al ₂ O ₃ in the chemical composition of the material is 92-93%, which is composed of the base material and the following. The total weight percentage of the base material is made of raw materials: dispersant 0.5%, suspending agent 0.4%, sintering aid 2%, infrared sunscreen agent 2%, foaming agent 0.26%, inorganic curing agent 4%, organic curing agent 1.3%, Cell regulator 0.7%.

The used base material is composed of the following components by mass percentage: 90% of alumina-based raw materials and 10% of aluminum-silicon-based raw materials. Among them, the alumina raw material is composed of α-Al ₂ O ₃ and fused corundum according to the mass ratio of 2:7; the aluminum siliceous raw material is wood knot soil (the mass percentage of Al ₂ O ₃ in its chemical composition is 32%) ~35%, the mass percentage of SiO ₂ is 64-66%, and the particle size is less than or equal to 0.08mm).

The dispersant is a mixture of sulfonated melamine polycondensate (Hengmei Technology Co., Ltd.) and sodium citrate in a mass ratio of 3:2; the suspending agent is composed of cellulose nanocrystals and dextrin in a mass ratio of 3:1 The sintering aid is a mixture of Er ₂ O ₃ and CeO ₂ in a mass ratio of 1:1; the infrared sunscreen agent is a mixture of K ₄ TiO ₄ and SiC in a mass ratio of 1:1.

The foaming agent is composed of quaternary ammonium type Gemini surfactant (Hengmei Technology Co., Ltd., foaming ratio of 45) and dodecyl dimethyl betaine surfactant (foaming ratio of 17) according to the mass ratio of 1:12 The composition of the mixture; the inorganic curing agent is aluminum phosphate; the organic curing agent is acrylate and styrene copolymer (National Starch Company, USA,

), acrylate polymers (National Starch Company, USA,

) according to the mass ratio of 7:6; the cell regulator is composed of ethyl cellulose ether (Netherlands AkzoNobel) and hydroxymethyl cellulose ether (Dow Chemical Company, USA) in a mass ratio of 2:5 than the composition of the mixture.

Among them, Er ₂ O ₃ , CeO ₂ , K ₄ TiO ₄ , SiC, and aluminum phosphate are all industrial pure, and the particle size is less than or equal to 5 μm.

Example 9

In the corundum-based micro-nanoporous insulating and heat-insulating refractory material of this embodiment, the main crystal phase is a granular corundum phase, and the mass percentage content of Al ₂ O ₃ in the chemical composition of the material is 95-97%, which is made up of the basic material and below. The total weight percentage of the base material is made of raw materials: dispersant 0.6%, suspending agent 0.3%, sintering aid 1%, infrared sunscreen agent 2%, foaming agent 0.18%, inorganic curing agent 3%, organic curing agent 1.4%, Cell regulator 0.5%.

The base material used is composed of the following components by mass percentage: 95% of alumina-based raw materials and 5% of aluminum-silicon raw materials. Among them, the alumina raw material is composed of α-Al ₂ O ₃ (Al ₂ O ₃ mass percentage ≧ 99%, particle size ≦ 5 μm) and fused corundum powder in a mass ratio of 1.5:8; the aluminum siliceous raw material is Andalusite (the mass percentage of Al ₂ O ₃ is 54-56%, the mass percentage of SiO ₂ is 42-44%, and the particle size is less than or equal to 0.08 mm).

The dispersing agent is a mixture of polycarboxylate ether dispersing agent (BASF, Germany) and naphthalene-based high-efficiency dispersing agent (Hengmei Technology Co., Ltd.) in a mass ratio of 1:1; : 2 mass ratio; sintering aid is composed of MgO, SrO according to 1:1 mass ratio; infrared sunscreen agent is composed of K ₂ Ti ₆ O ₁₃ , Sb ₂ O ₃ , Sb ₂ O ₅ according to 2: 1: 1 mass ratio composition;

The foaming agent is composed of sulfate type Gemini surfactant (Hengmei Technology Co., Ltd., foaming ratio is 55) and fatty alcohol polyoxyethylene ether carboxylate (Hengmei Technology Co., Ltd., foaming ratio is 15) according to 1:8 the mass ratio of the composition of the mixture. The inorganic curing agent is alumina gel; the organic curing agent is a copolymer of ethylene, vinyl chloride and vinyl laurate (German Wacker Chemical Company,

), vinyl acetate and higher fatty acid vinyl ester copolymer (Shanxi Sunway Group Corporation, SWF-04), vinyl acetate homopolymer (German Wacker Chemicals,

) according to the mass ratio of 2:2:3; the cell regulator is composed of hydroxybutyl methyl cellulose ether (Dow Chemical Company, USA), water-soluble cellulose ether (Hengmei Technology Co., Ltd.) and starch ether (Netherlands AVEBE Company) ) according to the mass ratio of 2:1:2.

Among them, MgO, SrO, K ₂ Ti ₆ O ₁₃ , Sb ₂ O ₃ , Sb ₂ O ₅ , and alumina gel are all industrial pure, and the particle size is less than or equal to 5 μm.

Example 10

In the corundum-based micro-nanoporous insulating and heat-insulating refractory material of this embodiment, the main crystal phase is a granular corundum phase, and the mass percentage content of Al ₂ O ₃ in the chemical composition of the material is 95-97%, which is made up of the basic material and below. The total weight percentage of the base material is made of raw materials: dispersant 0.7%, suspending agent 0.2%, sintering aid 0.5%, infrared shading agent 1%, foaming agent 0.12%, inorganic curing agent 2%, organic curing agent 1.6%, Cell regulator 0.4%.

The base material used is composed of the following components by mass percentage: 95% of alumina-based raw materials and 5% of aluminum-silicon raw materials. Among them, the alumina raw material is composed of α-Al ₂ O ₃ (Al ₂ O ₃ mass percentage ≧ 99%, particle size ≦ 5 μm) and fused corundum powder in a mass ratio of 1:8.5; It is sillimanite (the mass percentage of Al ₂ O ₃ is 58-60%, the mass percentage of SiO ₂ is 38-41%, and the particle size is less than or equal to 0.08 mm).

The dispersant is a mixture of polycarboxylate ether dispersant (BASF, Germany) and sodium polyphosphate in a mass ratio of 2:5; the suspending agent is composed of Welan gum and cellulose nanocrystals in a mass ratio of 1:1 The sintering aid is WO ₃ ; the infrared sunscreen agent is a mixture composed of TiO ₂ and Sb ₂ O ₅ in a mass ratio of 1:1.

The foaming agent is a mixture of sulfate-type Gemini surfactant (Hengmei Technology Co., Ltd., with a foaming ratio of 55) and sodium dodecylbenzenesulfonate (with a foaming ratio of 9) in a mass ratio of 1:5. . The inorganic curing agent is alumina gel; the organic curing agent is a copolymer of ethylene, vinyl chloride and vinyl laurate (German Wacker Chemical Company,

), isobutylene and maleic anhydride copolymer (Japan's Leli Company, ISOBAM-04) and vinyl acetate and ethylene and vinyl chloride copolymer (German Wacker Chemicals,

) in a mass ratio of 2:1:1; the cell regulator is composed of carboxymethyl hydroxypropyl cellulose ether, hydroxypropyl hydroxybutyl cellulose ether (Dow Chemical Company, USA) and starch ether ( Hengmei Technology Co., Ltd.) is a mixture composed of a mass ratio of 1:1:2.

Among them, WO ₃ , TiO ₂ , Sb ₂ O ₅ , and alumina gel are all industrially pure, and the particle size is less than or equal to 5 μm.

Example 11

In the corundum-based micro-nanoporous insulating and thermal insulating refractory material of this embodiment, the main crystal phase is a granular corundum phase, and the mass percentage content of Al ₂ O ₃ in the chemical composition of the material is 98-99%, which is composed of the basic material and below. The total weight percentage of the base material is made of raw materials: dispersant 0.8%, suspending agent 0.1%, sintering aid 0.1%, infrared sunscreen agent 0.6%, foaming agent 0.06%, inorganic curing agent 1%, organic curing agent 1.8%, Cell regulator 0.2%.

The base material used consists of 100% alumina raw material. Alumina raw materials are composed of α-Al ₂ O ₃ (Al ₂ O ₃ mass percentage≧99.5%, particle size≦5μm), fused corundum powder (Al ₂ O ₃ mass percentage≧99%, particle size≦5 μm) 0.08mm) according to the mass ratio of 2:8;

Dispersing agent is a mixture of sulfonated melamine polycondensate and melamine formaldehyde polycondensate (Hengmei Technology Co., Ltd.) in a mass ratio of 1:1; suspending agent is a mixture of casein and polyvinylpyrrolidone in a mass ratio of 1:1 The composition of the mixture; the sintering aid is Y ₂ O ₃ ; the infrared sunscreen agent is TiO ₂ .

The foaming agent is a mixture of sulfate-type Gemini surfactant (Hengmei Technology Co., Ltd., with a foaming ratio of 55) and sodium dodecylbenzenesulfonate (with a foaming ratio of 9) in a mass ratio of 1:2. . The inorganic curing agent is silica gel; the organic curing agent is a copolymer of ethylene, vinyl chloride and vinyl laurate (German Wacker Chemical Company,

), vinyl acetate and tertiary ethylene carbonate and acrylate copolymer (Japan Synthetic Chemical Industry Co., Ltd., Mowinyl-DM2072P), vinyl acetate and tertiary ethylene carbonate copolymer (Anhui Wanwei Group Corporation, WWJF-8010) according to 2:3 : 4 in a mass ratio; the cell regulator is a mixture of hydroxybutyl methyl cellulose ether and sulfonic acid ethyl cellulose ether (Dow Chemical Company, USA) in a ratio of 1:3.

Among them, Y ₂ O ₃ , TiO ₂ , and silica gel are all industrially pure, and the particle size is less than or equal to 5 μm.

Example 12

Figures 6 and 7 show the microstructure photos of the corundum micro-nanoporous insulating refractory material in this embodiment. It can be seen from the figures that the distribution of pores in the material is relatively regular, and the pore walls are dense. It consists of corundum crystals. In the chemical composition of the material, the mass percentage content of Al ₂ O ₃ is 99.9%. Inorganic curing agent 0.1%, organic curing agent 2%, cell regulator 0.1%.

The base material used consists of 100% alumina raw material. Alumina raw materials are composed of α-Al ₂ O ₃ (Al ₂ O ₃ mass percentage≧99.999%, particle size≦5μm), fused corundum powder (Al ₂ O ₃ mass percentage≧99.99%, particle size≦5μm) 0.08mm) is mixed according to the mass ratio of 2:8;

The dispersant is a compound composed of melamine formaldehyde polycondensate (Hengmei Technology Co., Ltd.) and sodium lignosulfonate in a mass ratio of 1:1; the sintering aid is a 1:1 composition of Y ₂ O ₃ and La ₂ O ₃ mass ratio of the composition of the mixture.

The foaming agent is a polyamide-type Dendrimer surfactant (Hengmei Technology Co., Ltd., with a foaming ratio of 55); the inorganic curing agent is alumina gel; the organic curing agent is konjac gum powder (produced by Shanghai Beilian Biotechnology Co., Ltd. ) and sodium alginate (Jiangsu Gubei Biotechnology Co., Ltd.) in a mass ratio of 1:1; the cell regulator is starch ether (Hengmei Technology Co., Ltd.) and propyl cellulose ether (Azilan Corporation, USA). ) in a mass ratio of 1:1.

Among them, Y ₂ O ₃ , La ₂ O ₃ , and alumina gel are all analytically pure, and the particle size is less than or equal to 5 μm.

Example 13

In the corundum-based micro-nanoporous insulating and thermal insulating refractory material of this embodiment, the main crystal phase is a granular corundum phase, and the mass percentage content of Al ₂ O ₃ in the chemical composition of the material is 98-99%, which is composed of the basic material and below. The raw materials in the total weight percentage of the base material are: 0.8% of dispersant, 0.6% of infrared shading agent, 0.06% of foaming agent, 1% of inorganic curing agent, 1.8% of organic curing agent, and 0.6% of cell regulator.

The type and proportion of the base material used are the same as in Example 11;

The dispersant is a mixture of polyamide-type polycarboxylic acid dispersant and melamine formaldehyde polycondensate (Hengmei Technology Co., Ltd.) in a mass ratio of 1:1; the inorganic curing agent is alumina gel;

The types and proportions of infrared sunscreening agent, foaming agent, organic curing agent and cell regulator are the same as those in Example 11;

Among them, TiO ₂ and alumina gel are both industrial pure, and the particle size is less than or equal to 5 μm.

Example 14

In the corundum-based micro-nano-porous insulating and insulating refractory material of this embodiment, the main crystal phase is a granular corundum phase, and the mass percentage of Al ₂ O ₃ in the chemical composition of the material is 99%, and the base material and the following account for the base material. The raw materials in the total weight percentage are: 1% of a foaming agent, 0.5% of an inorganic curing agent, 1.8% of an organic curing agent, and 0.2% of a cell regulator.

The base material used consists of 100% alumina raw material. Alumina raw materials are composed of α-Al ₂ O ₃ (Al ₂ O ₃ mass percentage≧99.5%, particle size≦5μm), fused corundum powder (Al ₂ O ₃ mass percentage≧99%, particle size≦5 μm) 1mm) according to the mass ratio of 2:8;

The foaming agent is a vegetable protein foaming agent (Shandong Xinmao Chemical Co., Ltd., the foaming multiple is 9);

The inorganic curing agent is alumina sol;

The organic curing agent is composed of vinyl acetate, vinyl tertiary carbonate and acrylate copolymer (Japan Synthetic Chemical Industry Co., Ltd., Mowinyl-DM2072P) (produced by Shanghai Beilian Biotechnology Co., Ltd.) and disperse latex (Wacker Chemicals, Germany,

) in a mass ratio of 1:1;

The cell regulator is a mixture of hydroxyethyl ethyl cellulose ether (Netherlands AkzoNobel Company) and hydroxyethyl cellulose ether (American Hercules Company) in a mass ratio of 1:1.

Example 15

In the corundum-based micro-nanoporous insulating and thermal insulating refractory material of this embodiment, the main crystal phase is a granular corundum phase, and the mass percentage content of Al ₂ O ₃ in the chemical composition of the material is 98-99%, which is composed of the basic material and below. The raw materials of the total weight percentage of the base material are made: the types and proportions of the raw materials used in the preparation of the product are basically the same as those in Example 14, the only difference being that no organic curing agent is used in the technical solution of this example.

Second, the specific embodiment of the preparation method of the corundum micro-nano-porous insulating and insulating refractory material of the present invention

Example 16

The preparation method of the present implementation describes the preparation of the corundum insulating and heat-insulating refractory material in Example 1, and the details are as follows:

(1) Preparation of base material, additive and foaming composition

1) Preparation of base material

Pour 0.2 ton of Al(OH) ₃ , 0.1 ton of diaspore, 0.5 ton of γ-Al ₂ O ₃ , 0.1 ton of diatomite, and 0.1 ton of microsilica into a forced mixer and dry-mix for 15 minutes to obtain the base material;

2) Preparation of additives

Weigh 90kg bentonite, 10kg Welan gum, 20kgAlF ₃ ·3H ₂ O, 20kgZnO, 20kgV ₂ O ₅ , 20kgLa ₂ O ₃ , 20kgBaO, 20kgTiC, 20kgK ₄ TiO ₄ , 40kgB ₄ C, 20kgSb ₂ O ₃ and pour into planetary type Mixer and dry mixing for 5min to obtain additives;

3) Preparation of foaming composition

Weigh 2kg of quaternary ammonium type Gemini surfactant, _2kg of semi-cyclic Bola surfactant, 40kg of alumina gel, 60kg of _Al2O3 micropowder, 10kg of vinyl acetate and ethylene and higher fatty acid copolymer, 5kg of vinyl acetate and ethylene Copolymer, 2kg hydroxyethyl ethyl cellulose ether, and 1kg saponin were poured into a planetary mixer and dry mixed for 5min to obtain a uniform foaming composition;

(2) Preparation of suspension slurry and foam slurry

1) Preparation of suspension slurry

Pour the base material and additives into a roller ball mill, add 2 tons of water, mix by ball milling for 2 hours, and then ultrasonically vibrate (ultrasonic power 2000W) for 4 minutes to obtain a uniform suspension slurry (wherein the particle size of solid particles is ≦30 μm); grinding balls in the ball mill Using alumina balls, large balls

middle ball

small ball

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

2) Preparation of foam slurry

The suspension slurry was injected into the mixer, pre-stirred for 1 min (the linear speed of the stirring paddle during the pre-stirring process was 5 m/s), and then the foaming composition was added to the mixer, and the stirring paddle was rapidly mixed at a linear speed of 200 m/s for 1 min to obtain a uniform mixture. Foam slurry.

(3) Pouring and maintenance

The foam slurry was injected into the rubber mold, and cured for 12 hours in an environment with an air temperature and humidity of 1°C and 50%, respectively;

(4) Drying and firing

The solidified green body is demolded, and the water in the green body is removed by carbon dioxide supercritical drying method. The carbon dioxide control pressure is 9MPa, the temperature is 42°C, and the supercritical drying time is 4h to obtain a dry green body; the moisture content of the dry green body ≦ 2wt%, compressive strength≧0.7MPa.

Put the dried green body into a resistance kiln for firing, from room temperature to 500°C at a heating rate of 1°C/min, then to 1000°C at 5°C/min, holding for 1.5h, and then heating at 1°C/min to 1200～1230℃, hold for 10h, then cool down to 1100℃ at 10℃/min, keep at 1100℃ for 1.5h, then cool down to 500℃ at 5℃/min, hold at 500℃ for 0.5h, and finally heat at 1℃ /min to cool down to 50℃ to obtain corundum micro-nano-porous insulating refractory material;

Example 17

The preparation method of the present implementation describes the preparation of the corundum insulating and heat-insulating refractory material in Example 2, as follows:

(1) Preparation of base materials, additives and foams

1) Preparation of base material

Pour 0.3 tons of industrial Al(OH) ₃ , 0.5 tons of sintered corundum, 0.05 tons of potassium feldspar, and 0.15 tons of silicon micropowder into a non-gravity mixer and dry-mix for 15 minutes to obtain the base material;

2) Preparation of additives

Weigh 0.3kg amide type polycarboxylic _acid dispersant, 0.2kg polycarboxylate ether dispersant, 50kg bentonite, 3kg cellulose fiber, _30kgMnO2 , _30kgZnO , _30kgV2O5 , _20kgTiC , _20kgK4TiO4 , _20kgSb2O3 Pour into the double cone mixer and dry mix for 5min to get the additive;

3) Preparation of foaming composition

Weigh 1kg of polyether type Dendrimer surfactant, 29kg of vegetable protein foaming agent, 70kg of sludge protein foaming agent, 120kg of alumina sol, 80kg of silica sol, 0.5kg of Kederan gum, 0.5kg of gellan gum, 0.05 kg carboxymethyl ethyl cellulose ether, 0.03 kg carboxymethyl hydroxymethyl cellulose ether, 0.02 kg carboxymethyl hydroxyethyl cellulose ether, poured into a double cone mixer and dry mixed for 5 minutes to obtain uniform foaming combination;

(2) Preparation of suspension slurry and foam slurry

1) Preparation of suspension slurry

Pour the base material and additives into a roller ball mill, add 1.8 tons of water, mix by ball milling for 10 hours, and then ultrasonically vibrate (ultrasonic power 1500W) for 6 minutes to obtain a uniform suspension slurry (wherein the particle size of solid particles is less than or equal to 30 μm). Alumina ball, large ball

middle ball

small ball

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

2) Preparation of foam slurry

The suspension slurry was injected into the mixer, and the foaming composition was added to the mixer after pre-stirring for 1 min (the linear speed of the stirring paddle was 5 m/s during the pre-stirring process), and the stirring paddle was rapidly mixed for 5 min at a linear speed of 50 m/s to obtain Homogeneous foam slurry;

(3) Pouring and maintenance

The foam slurry was injected into the plastic mold, and cured for 6 hours in an environment with an air temperature and humidity of 10°C and 60%, respectively, until it was cured;

(4) Drying and firing

Demoulding the solidified green body, using carbon dioxide supercritical drying method to remove the moisture in the green body, the control pressure of carbon dioxide is 9MPa, the temperature is 42 ℃, the supercritical drying time is 4h, and the dry green body is obtained; the water content of the dry green body is rate≦2wt%, compressive strength≧0.74MPa.

The dried green body is fired in a high-temperature tunnel kiln, first from room temperature to 500 °C at a heating rate of 2 °C/min, then to 1000 °C at 8 °C/min, holding for 1 hour, and then heated to 1280 °C at 3 °C/min ～1310°C, hold for 8h, then cool down to 1100°C at 10°C/min, hold at 1100°C for 1h, then cool down to 500°C at 6°C/min, hold at 500°C for 0.5h, and finally cool down at 2°C/min To 50 ℃, the corundum micro-nano-porous insulating refractory material is obtained.

Example 18

The preparation method of the present implementation describes the preparation of the corundum insulating and heat insulating refractory material in Example 3, as follows:

(1) Preparation of base materials, additives and foams

1) Preparation of base material

0.6 tons of Al(OH) ₃ , 0.2 tons of boehmite, 20kg of aluminum n-butoxide, 20kg of aluminum isopropoxide, 10kg of aluminum sec-butoxide, 60kg of silicon micropowder, 30kg of methyl orthosilicate, 30kg of ethyl orthosilicate , 30kg methyltrimethoxysilane was poured into the forced mixer and dry mixed for 5min to obtain the base material;

2) Preparation of additives

Weigh 0.5kg of imide-type polycarboxylic acid dispersant, 0.5kg of naphthalene-based dispersant, 30kg of sepiolite, 10kg of chitosan, 30kg of MnO ₂ , 30kg of ZnO, 20kg of V ₂ O ₅ , 20kg of K ₂ Ti ₆ O ₁₃ , 20kg K ₄ TiO ₄ , 20kg Ni(NO ₃ ) ₂ were poured into the V-type mixer and dry mixed for 5min to obtain the additive;

3) Preparation of foaming composition

Weigh 1kg of carboxylate-type Gemini surfactant, 50kg of animal protein foaming agent, 3kg of gellan gum, 2kg of gellan gum, 0.4kg of ethyl cellulose sulfonate, 0.2kg of methylcellulose ether, and poured into V-type mixer and dry mixing for 5min to obtain a uniform foaming composition;

(2) Preparation of suspension slurry and foam slurry

1) Preparation of suspension slurry

Pour the base material and additives into a roller ball mill, add 1.6 tons of water, ball mill and mix for 8 hours, and then ultrasonically vibrate (ultrasonic power 1500W) for 6 minutes to obtain a uniform suspension slurry (wherein the particle size of the solid particles is ≦30 μm); grinding balls in the ball mill Using alumina balls, large balls

middle ball

small ball

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

2) Preparation of foam slurry

The suspension slurry was injected into the mixer, pre-stirred for 1 min (the linear speed of the stirring paddle during the pre-stirring process was 5 m/s), and then the foaming composition and 150 kg of silica-alumina sol were added to the mixer, and the stirring paddle was fast at a linear speed of 100 m/s. Mix for 4 minutes to obtain a uniform foam slurry;

(3) Pouring and maintenance

The foam slurry was injected into the stainless steel mold, and cured for 2 hours in an environment with an air temperature and humidity of 20°C and 70%, respectively, until it was cured;

(4) Drying and firing

The solidified body is demolded, and the moisture in the body is removed by carbon dioxide supercritical drying method. The control pressure of carbon dioxide is 9MPa, the drying temperature is 42°C, and the supercritical drying time is 4h to obtain a dry body; The moisture content of the body is less than or equal to 2wt%, and the compressive strength is greater than or equal to 0.76MPa.

The dried green body is fired in a high-temperature tunnel kiln, first from room temperature to 500 °C at a heating rate of 5 °C/min, then to 1000 °C at 8 °C/min, holding for 1 hour, and then heated to 1370 °C at 3 °C/min ～1400°C, hold for 7h, then cool down to 1100°C at 10°C/min, hold at 1100°C for 1h, then cool down to 500°C at 6°C/min, hold at 500°C for 0.5h, and finally cool down at 2°C/min To 50 ℃, the corundum micro-nano-porous insulating refractory material is obtained.

Example 19

The preparation method of the present implementation describes the preparation of the corundum insulating and heat-insulating refractory material in Example 4, and the details are as follows:

(1) Preparation of base materials, additives and foams

1) Preparation of base material

Pour 0.4 ton of industrial Al(OH) ₃ , 0.45 ton of α-Al ₂ O ₃ , 0.05 ton of coal gangue, 0.05 ton of albite, and 0.05 ton of kaolin into a planetary mixer and dry mixed for 15 minutes to obtain the base material;

2) Preparation of additives

Weigh 1.5kg of sulfonated melamine polycondensate, 20kg of attapulgite, 10kg of polyaluminum chloride, 20kg of Y ₂ O ₃ , 20kg of MgO, 20kg of V ₂ O ₅ , 20kg of rutile, 20kg of ZrSiO ₄ , poured into a three-dimensional mixer and dry mixed 5min to get additives;

3) Preparation of foaming composition

Weigh 1kg carboxylate type Gemini surfactant, 1kg semi-cyclic Bola surfactant, 5kg locust bean gum, 5kg locust gum, 1kg carboxymethyl ethyl cellulose ether, 1kg hydroxyethyl ethyl cellulose ether, Pour into a three-dimensional mixer and dry mix for 5min to obtain a homogeneous foaming composition;

(2) Preparation of suspension slurry and foam slurry

1) Preparation of suspension slurry

Pour the base material and additives into a roller ball mill, add 1.4 tons of water, mix by ball milling for 8 hours, and then ultrasonically vibrate (ultrasonic power 1500W) for 6 minutes to obtain a uniform suspension slurry (wherein the particle size of the solid particles is ≦30 μm); grinding balls in the ball mill The material is mullite, large ball

middle ball

small ball

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

2) Preparation of foam slurry

The suspension slurry was injected into the mixer, and the foaming composition and 120kg of alumina sol were added to the mixer after pre-stirring for 1min (the linear velocity of the stirring paddle was 5m/s during the pre-stirring process), and the stirring paddle was 130 m/s at the linear speed. s Quickly mix for 3 minutes to obtain a uniform foam slurry;

(3) Pouring and maintenance

The foam slurry was injected into the glass mold, and cured for 1.5 hours in an environment with an air temperature and humidity of 25°C and 80%, respectively, until it was cured;

(4) Drying and firing

The cured green body is demolded, and the moisture in the green body is removed by carbon dioxide supercritical drying method. The control pressure of carbon dioxide is 9MPa, the temperature is 42°C, and the supercritical drying time is 4h to obtain a dry green body; The moisture content is less than or equal to 2wt%, and the compressive strength is greater than or equal to 0.8MPa.

The dried green body is fired in a high-temperature tunnel kiln, first from room temperature to 500 °C at a heating rate of 3 °C/min, then to 1000 °C at 8 °C/min, holding for 1 hour, and then heated to 1430 °C at 3 °C/min ～1470°C, hold for 6h, then cool down to 1100°C at 10°C/min, hold at 1100°C for 1h, then cool down to 500°C at 6°C/min, hold at 500°C for 0.5h, and finally cool down at 2°C/min To 50 ℃, the corundum micro-nano-porous insulating refractory material is obtained.

Example 20

The preparation method of the present implementation describes the preparation of the corundum micro-nano-porous insulating and thermal insulating refractory material in Example 5, and the details are as follows:

(1) Preparation of base materials, additives and foams

1) Preparation of base material

0.3 tons of industrial alumina, 0.2 tons of β-Al ₂ O ₃ , 0.15 tons of γ-Al ₂ O ₃ , 0.1 tons of δ-Al ₂ O ₃ , 0.1 tons of χ-Al ₂ O ₃ , 0.05 tons of kyanite, 0.05 tons of Tons of kaolin and 0.05 ton of barium feldspar are poured into a forced mixer and dry mixed for 15min to obtain the base material;

2) Preparation of additives

Weigh 0.8kg of polyamide type polycarboxylic acid dispersant, 1.2kg of sodium polyacrylate, 10kg of polyvinylpyrrolidone, 10kg of casein, 20kg of MnO ₂ , 20kg of SiF ₄ , 10kg of Cr ₂ O ₃ into a planetary mixer and dry mixed for 5min , to obtain a uniform additive;

3) Preparation of foaming composition

Weigh 1.1kg of carboxylate type Gemini surfactant, 3.3kg of sodium lauryl polyoxyethylene ether carboxylate, 10kg of silica gel, 10kg of dodecacalcium heptaaluminate, 10kg of tetracalcium ferric aluminate, 20kg of alumina Gel, 4kg ethylene and vinyl acetate copolymer, 4kg keratin, 2kg gellan gum, 2kg carboxymethyl hydroxybutyl cellulose ether, 2kg hydroxypropyl hydroxybutyl cellulose ether, pour into planetary mixer And dry mix for 5min to get a uniform foam;

(2) Preparation of suspension slurry and foam slurry

1) Preparation of suspension slurry

Pour the base material and additives into a roller ball mill, add 1.2 tons of water, mix by ball milling for 4 hours, and then ultrasonically vibrate (ultrasonic power 1500W) for 6 minutes to obtain a uniform suspension slurry (wherein the particle size of the solid particles is ≦44 μm); Material is zirconia, large ball

middle ball

small ball

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

2) Preparation of foam slurry

The suspension slurry was injected into the mixer, and the foaming composition was added to the mixer after pre-stirring for 1 min (the linear speed of the stirring paddle during the pre-stirring process was 5 m/s), and the stirring paddle was rapidly mixed for 2 minutes at a linear speed of 150 m/s. A homogeneous foam slurry is obtained.

(3) Pouring and maintenance

The foam slurry was injected into the stainless steel mold, and cured for 1.3 hours in an environment with an air temperature and humidity of 25°C and 85%, respectively, until it was cured;

(4) Drying and firing

The solidified body is demoulded, and the moisture in the body is removed by freeze-drying. The drying temperature is -85°C, and drying is performed for 12 hours to obtain a dry body; the moisture content of the dry body is ≤ 2wt%, and the compressive strength is ≧ 0.9MPa.

Put the dried green body into a resistance kiln for firing, first from room temperature to 500°C at a heating rate of 3°C/min, then to 1000°C at 10°C/min, holding for 1 hour, and then heating at 3°C/min to 1500～1540℃, keep for 5h, then cool down to 1100℃ at 10℃/min, keep at 1100℃ for 1h, then cool down to 500℃ at 6℃/min, keep at 500℃ for 0.5h, and finally at 2℃/min Min cooling to 50 ℃, that is, corundum micro-nano-porous insulating refractory material.

Example 21

The preparation method of the present implementation describes the preparation of the corundum micro-nano-porous insulating and heat-insulating refractory material in Example 6, and the details are as follows:

(1) Preparation of base materials, additives and foams

1) Preparation of base material

0.5 ton α-Al ₂ O ₃ , 0.15 ton κ-Al ₂ O ₃ , 0.1 ton θ-Al ₂ O ₃ , 0.1 ton η-Al ₂ O ₃ , 0.06 ton kyanite, 0.03 ton porcelain stone, 0.06 ton The coke gemstone is poured into the forced mixer and dry mixed for 15 minutes to obtain the base material;

2) Preparation of additives

Weigh 2kg of sulfamic acid-based dispersant, 1kg of sodium humate, 4kg of cellulose nanofibers, 4kg of polyethylene glycol, 2kg of polyvinyl alcohol, 10kg of AlF ₃ ·3H ₂ O, 20kg BaO, 10kg of V ₂ O ₅ , 20kg of Ni (NO ₃ ) _2. 10kg Fe ₃ O ₄ was poured into the double cone mixer and dry mixed for 5min to obtain a uniform additive;

3) Preparation of foaming composition

Weigh 0.3kg carboxylate type Gemini surfactant, 3.6kg lauric acid amidopropyl sulfobetaine, 50kg silica alumina gel, 2kg carrageenan, 2kg konjac gum, 2kg acrylate polymer, 2kg vinyl acetate Pour into a double cone mixer with ethylene and acrylate copolymer, 2kg of ethylene and vinyl chloride copolymer, 2kg of hydroxypropyl hydroxybutyl cellulose ether, and 4kg of lignocellulose and dry mix for 5min to obtain a uniform foaming composition;

(2) Preparation of suspension slurry and foam slurry

1) Preparation of suspension slurry

Pour the base material and additives into a roller ball mill, add 1 ton of water, ball mill and mix for 4 hours, and then ultrasonically vibrate (ultrasonic power 1500W) for 6 minutes to obtain a uniform suspension slurry (wherein the solid particle size is ≦44μm); grinding balls in the ball mill The material is zirconia, large ball

middle ball

small ball

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

2) Preparation of foam slurry

The suspension slurry was injected into the mixer, and the foaming composition was added to the mixer after pre-stirring for 1min (the linear speed of the stirring paddle during the pre-stirring process was 5 m/s), and the stirring paddle was rapidly mixed for 2 minutes at a linear speed of 170 m/s. A homogeneous foam slurry was obtained.

(3) Pouring and maintenance

The foam slurry was injected into a stainless steel mold, and cured for 1 hour in an environment with an air temperature and humidity of 25°C and 88%, respectively, until it was cured;

(4) Drying and firing

Put the dried green body into a resistance kiln for firing, first from room temperature to 500°C at a heating rate of 3°C/min, then to 1000°C at 10°C/min, holding for 1 hour, and then heating at 3°C/min to 1570～1600℃, keep for 4h, then cool down to 1100℃ at 10℃/min, keep at 1100℃ for 1h, then cool down to 500℃ at 6℃/min, keep at 500℃ for 0.5h, and finally at 2℃/min Min cooling to 50 ℃, that is, corundum micro-nano-porous insulating refractory material.

Example 22

The preparation method of the present implementation describes the preparation of the corundum micro-nano-porous insulating and heat-insulating refractory material in Example 7, and the details are as follows:

(1) Preparation of base materials, additives and foams

1) Preparation of base material

Pour 0.03 tons of α-Al ₂ O ₃ , 0.07 tons of sintered corundum, 0.85 tons of high alumina bauxite, and 0.05 tons of sintered mullite into a planetary mixer and dry-mix for 15 minutes to obtain the base material;

2) Preparation of additives

Weigh 2kg polycarboxylate ether dispersant, 2kg melamine formaldehyde polycondensate, 2kg cetyl alcohol, 2kg sucrose, 2kg dextrin, 10kg SrO, 10kg WO ₃ , 10kg Er ₂ O ₃ , 15kg CoCl ₂ , 10kg Ni(NO _{3 )} ) ₂ , 5kg Fe ₃ O ₄ is poured into the three-dimensional mixer and dry mixed for 5min to obtain a uniform additive;

3) Preparation of foaming composition

Weigh 0.2kg quaternary ammonium type Gemini surfactant, 3kgɑ-alkene sulfonate sodium, 20kg dicalcium silicate, 30kg calcium dialuminate, 8kg vinyl acetate and ethylene and higher fatty acid copolymer, 4kg vinyl acetate and ethylene and Vinyl laurate copolymer, 5kg of hydroxypropyl ethyl cellulose ether, 5kg of propyl cellulose ether, poured into a V-type mixer and dry mixed for 5min to obtain a uniform foaming composition;

(2) Preparation of suspension slurry and foam slurry

1) Preparation of suspension slurry

Pour the base material and additives into a roller ball mill, add 1 ton of water, mix by ball milling for 1.5 hours, and then ultrasonically vibrate (ultrasonic power 1000W) for 8 minutes to obtain a uniform suspension slurry (wherein the particle size of solid particles is ≦44 μm); The material of the grinding ball is zirconium corundum, the large ball

middle ball

small ball

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

2) Preparation of foam slurry

The suspension slurry was injected into the mixer, pre-stirred for 1 min (the linear speed of the stirring paddle during the pre-stirring process was 4 m/s), and then the foaming composition was added to the mixer, and the stirring paddle was rapidly mixed for 1 min at a linear speed of 200 m/s, A homogeneous foam slurry was obtained.

(3) Pouring and maintenance

Inject the foam slurry into the aluminum alloy mold, and cure it for 0.8h in an environment with an air temperature and humidity of 25°C and 92%, respectively;

(4) Drying and firing

The cured green body is demolded, and the moisture in the green body is removed by microwave drying method, the microwave frequency is 915MHz, and the microwave drying time is 2h to obtain a dry green body; the moisture content of the dried green body is ≤ 2wt%, and the compressive strength ≧1.1MPa.

The dried green body is loaded into a high-temperature tunnel kiln for firing, first from room temperature to 500°C at a heating rate of 2°C/min, then to 1000°C at 8°C/min, holding for 1 hour, and then heating at 3°C/min to 1630～1650℃, keep for 3h, then cool down to 1100℃ at 10℃/min, keep at 1100℃ for 1h, then cool down to 500℃ at 6℃/min, keep at 500℃ for 0.5h, and finally heat at 2℃/min Min cooling to 50 ℃, that is, corundum micro-nano-porous insulating refractory material.

Example 23

The preparation method of the present implementation describes the preparation of the corundum micro-nano-porous insulating and heat-insulating refractory material in Example 8, and the details are as follows:

(1) Preparation of base materials, additives and foams

1) Preparation of base material

Pour 0.2 tons of α-Al ₂ O ₃ , 0.7 tons of fused corundum, and 0.1 tons of wood knot soil into a forced mixer and dry-mix for 15 minutes to obtain the base material;

2) Preparation of additives

Weigh 3kg of sulfonated melamine polycondensate, 2kg of sodium citrate, 3kg of cellulose nanocrystals, 1kg of dextrin, 10kg of Er ₂ O ₃ , 10kg of CeO ₂ , 10kg of K ₄ TiO ₄ , 10kg of SiC and poured into a planetary mixer and dry mixed for 5min to obtain Homogeneous additives;

3) Preparation of foaming composition

Weigh 0.2kg quaternary ammonium type Gemini surfactant, 2.4kg dodecyl dimethyl betaine surfactant, 40kg aluminum phosphate, 7kg acrylate and styrene copolymer, 6kg acrylate polymer, 2kg ethyl fiber Plain ether and 5kg of hydroxymethyl cellulose ether were poured into a planetary mixer and dry mixed for 5min to obtain a uniform foaming composition;

(2) Preparation of suspension slurry and foam slurry

1) Preparation of suspension slurry

Pour the base material and additives into a roller ball mill, add 1 ton of water, mix by ball milling for 1 hour, and then ultrasonically vibrate (ultrasonic power 1000W) for 8 minutes to obtain a uniform suspension slurry (wherein the solid particle size is ≦44μm); grinding in the ball mill The material of the ball is zirconia, the large ball

middle ball

small ball

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

2) Preparation of foam slurry

The suspension slurry was injected into the mixer, and the foaming composition was added to the mixer after pre-stirring for 1 min (the linear speed of the stirring paddle during the pre-stirring process was 4 m/s), and the stirring paddle was rapidly mixed for 3 minutes at a linear speed of 150 m/s. A homogeneous foam slurry was obtained.

(3) Pouring and maintenance

Inject the foam slurry into the aluminum alloy mold, and cure it for 0.7h in an environment with an air temperature and humidity of 25°C and 93%, respectively;

(4) Drying and firing

The cured green body is demolded, and the moisture in the green body is removed by microwave drying method, the microwave frequency is 2450MHz, and the microwave drying time is 1h to obtain a dry green body; the moisture content of the dried green body is ≤ 2wt%, and the compressive strength is ≧1.0MPa;

Put the dried green body into a microwave kiln for firing, first from room temperature to 500°C at a heating rate of 5°C/min, then to 1000°C at 30°C/min, holding for 0.5h, and then at 30°C/min The temperature was raised to 1680-1700°C, kept for 1 h, then cooled to 1100°C at 20°C/min, kept at 1100°C for 0.5h, then cooled to 500°C at 30°C/min, kept at 500°C for 0.5h, and finally kept at 10°C for 0.5h. ℃/min is cooled to 50 ℃ to obtain corundum micro-nano-porous insulating refractory material.

Example 24

The preparation method of the present implementation describes the preparation of the corundum micro-nano-porous insulating and thermal insulating refractory material in Example 9, and the details are as follows:

(1) Preparation of base materials, additives and foams

1) Preparation of base material

Pour 0.15 tons of α-Al ₂ O ₃ , 0.8 tons of fused corundum, and 0.05 tons of andalusite into a non-gravity mixer and dry mix for 15 minutes to obtain the base material;

2) Preparation of additives

Weigh 3kg polycarboxylate ether dispersant, 3kg naphthalene-based dispersant, 1kg polyvinylpyrrolidone, 2kg polyacrylate amine, 5kg MgO, 5kg SrO, 10kg K ₂ Ti ₆ O ₁₃ , 5kg Sb ₂ O ₃ , 5kg Sb ₂ O _5. Pour into a three-dimensional mixer and dry mix for 5 minutes to obtain a uniform additive;

3) Preparation of foaming composition

Weigh 0.2kg sulfate type Gemini surfactant, 1.6kg fatty alcohol polyoxyethylene ether carboxylate sodium, 30kg alumina gel, 4kg ethylene, vinyl chloride and vinyl laurate copolymer, 4kg vinyl acetate and higher fatty acid Vinyl ester copolymer, 6kg vinyl acetate homopolymer, 2kg hydroxybutyl methyl cellulose ether, 1kg water-soluble cellulose ether, 2kg starch ether, poured into a double cone mixer and dry mixed for 5min to obtain a uniform foaming composition ;

(2) Preparation of suspension slurry and foam slurry

1) Preparation of suspension slurry

Pour the base material and additives into a roller ball mill, add 0.9 tons of water, mix by ball milling for 1 hour, and then ultrasonically vibrate (ultrasonic power 1000W) for 8 minutes to obtain a uniform suspension slurry (wherein the solid particle size is ≦44μm); grinding in the ball mill The material of the ball is zirconia, the large ball

middle ball

small ball

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

2) Preparation of foam slurry

The suspension slurry was injected into the mixer, and the foaming composition was added to the mixer after pre-stirring for 1 min (the linear speed of the stirring paddle during the pre-stirring process was 4 m/s), and the stirring paddle was rapidly mixed for 4 minutes at a linear speed of 120 m/s. A homogeneous foam slurry was obtained.

(3) Pouring and maintenance

Inject the foam slurry into the resin mold, and cure it for 0.6h in an environment with an air temperature and humidity of 27°C and 95%, respectively;

(4) Drying and firing

Demould the solidified green body, and use the power heating and atmospheric drying method to remove the free water. First, it was heated to 30°C at 3°C/min and kept for 3h, and then heated to 50°C at 2°C/min and kept for 2h. , then heat up to 70°C at 3°C/min and hold for 4h, then heat up to 90°C at 5°C/min and hold for 4h, then heat up to 110°C at 5°C/min and hold for 12h to obtain a dry green body; The moisture content is less than or equal to 2wt%, and the compressive strength is greater than or equal to 1.1MPa.

Put the dried green body into a shuttle kiln for firing, first from room temperature to 500 °C at a heating rate of 4 °C/min, then to 1000 °C at 8 °C/min, holding for 1 hour, and then heating at 3 °C/min to 1700～1710℃, hold for 3h, then cool down to 1100℃ at 10℃/min, keep at 1100℃ for 0.5h, then cool down to 500℃ at 6℃/min, hold at 500℃ for 0.5h, and finally at 2℃ /min is cooled to 50°C to obtain corundum micro-nano-porous insulating refractory material.

Example 25

The preparation method of the present implementation describes the preparation of the corundum micro-nano-porous insulating refractory material in Example 10, and the details are as follows:

(1) Preparation of base materials, additives and foams

1) Preparation of base material

Pour 0.1 ton of α-Al ₂ O ₃ , 0.85 ton of fused corundum, and 0.05 ton of sillimanite into a non-gravity mixer and dry-mix for 15 minutes to obtain the base material;

2) Preparation of additives

Weigh 2kg polycarboxylate dispersant, 5kg sodium polyphosphate, 1kg welan gum, 1kg cellulose nanocrystal, 5kg WO ₃ , 5kg TiO ₂ , 5kg Sb ₂ O ₅ , pour into double cone mixer and dry mix 5min to obtain a uniform additive;

3) Preparation of foaming composition

Weigh 0.2kg sulfate type Gemini surfactant, 1kg sodium dodecylbenzenesulfonate, 20kg alumina gel, 8kg ethylene and vinyl chloride and vinyl laurate copolymer, 4kg isobutylene and maleic anhydride copolymer, 4kg of vinyl acetate and ethylene and vinyl chloride copolymer, 1kg of carboxymethyl hydroxypropyl cellulose ether, 1kg of hydroxypropyl hydroxybutyl cellulose ether, 2kg of starch ether, poured into a double cone mixer and dry mixed for 5min to obtain Homogeneous foaming composition;

(2) Preparation of suspension slurry and foam slurry

1) Preparation of suspension slurry

Pour the base material and additives into a roller ball mill, add 0.7 tons of water, mix by ball milling for 1 hour, and then ultrasonically vibrate (ultrasonic power 1000W) for 8 minutes to obtain a uniform suspension slurry (wherein the particle size of solid particles is ≦50μm); grinding in the ball mill The material of the ball is zirconium corundum, the large ball

middle ball

small ball

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

2) Preparation of foam slurry

The suspension slurry was injected into the mixer, and the foaming composition was added to the mixer after pre-stirring for 1 min (the linear speed of the stirring paddle during the pre-stirring process was 4 m/s), and the stirring paddle was rapidly mixed for 5 minutes at a linear speed of 80 m/s. A homogeneous foam slurry was obtained.

(3) Pouring and maintenance

Inject the foam slurry into the rubber mold, and cure it for 0.4h in an environment with an air temperature and humidity of 30°C and 97%, respectively;

(4) Drying and firing

The cured green body is demolded, and the free water in it is removed by the power heating and atmospheric drying method, that is, the temperature is first heated to 30 °C at 3 °C/min and kept for 3 hours, and then heated to 50 °C at 2 °C/min and kept warm. 2h, then heat up to 70°C at 3°C/min and hold for 4h, then heat up to 90°C at 5°C/min and hold for 4h, then heat up to 110°C at 5°C/min and hold for 12h to obtain a dry green body; The moisture content of the body is less than or equal to 2wt%, and the compressive strength is greater than or equal to 1.2MPa.

Put the dried green body into the shuttle kiln for firing, first from room temperature to 500°C at a heating rate of 3°C/min, then to 1000°C at 8°C/min, holding for 1 hour, and then heating at 3°C/min to 1700-1710°C, hold for 3h, then cool down to 1100°C at 10°C/min, keep at 1100°C for 1h, then cool down to 500°C at 6°C/min, hold at 500°C for 0.5h, and finally heat at 2°C/min. Min cooling to 50 ℃, that is, corundum micro-nano-porous insulating refractory material.

Example 26

The preparation method of this implementation describes the preparation of the corundum-based micro-nano-porous insulating refractory material in Example 11, as follows:

(1) Preparation of base materials, additives and foams

1) Preparation of base material

Pour 0.2 tons of α-Al ₂ O ₃ and 0.8 tons of fused corundum into a non-gravity mixer and dry mix for 1 min to obtain the base material;

2) Preparation of additives

Weigh 4kg of sulfonated melamine polycondensate, 4kg of melamine-formaldehyde polycondensate, 0.5kg of casein, 0.5kg of polyvinylpyrrolidone, 1kg of Y ₂ O ₃ , 6kg of TiO ₂ , poured into a V-type mixer and dry mixed for 5min to obtain a uniform additive ;

3) Preparation of foaming composition

Weigh 0.2kg sulfate type Gemini surfactant, 0.4kg sodium dodecylbenzene sulfonate, 10kg silica gel, 4kg ethylene, vinyl chloride and vinyl laurate copolymer, 6kg vinyl acetate and tertiary vinyl carbonate And acrylate copolymer, 8kg vinyl acetate and tertiary ethylene carbonate copolymer, 0.5kg hydroxybutyl methyl cellulose ether, 1.5kg ethyl cellulose sulfonate ether, poured into a double cone mixer and dry mixed for 5min to obtain uniform hair. foam composition;

(2) Preparation of suspension slurry and foam slurry

1) Preparation of suspension slurry

Pour the base material and additives into the roller ball mill, add 0.4 tons of water, mix the ball mill for 0.6h, and then ultrasonically vibrate (ultrasonic power 1800W) for 5min to obtain a uniform suspension slurry (wherein the particle size of the solid particles is ≦60μm); The material of the grinding ball is zirconium corundum, the large ball

middle ball

small ball

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

2) Preparation of foam slurry

The suspension slurry was injected into the mixer, and the foaming composition was added to the mixer after pre-stirring for 1 min (the linear speed of the stirring paddle during the pre-stirring process was 4 m/s), and the stirring paddle was rapidly mixed for 7 minutes at a linear speed of 50 m/s. A homogeneous foam slurry was obtained.

(3) Pouring and maintenance

The foam slurry was injected into the bamboo mold, and cured for 0.3h in an environment with an air temperature and humidity of 30°C and 99%, respectively, until it was cured;

(4) Drying and firing

The cured green body is demoulded, and the free water in it is removed by the atmospheric pressure hot air drying method, that is, the temperature is first heated to 30 °C at 3 °C/min and kept for 3 hours, and then heated to 50 °C at 2 °C/min and kept for 2 hours. , then heat up to 70°C at 3°C/min and hold for 4h, then heat up to 90°C at 5°C/min and hold for 4h, then heat up to 110°C at 5°C/min and hold for 12h to obtain a dry green body; The moisture content is less than or equal to 2wt%, and the compressive strength is greater than or equal to 1.3MPa.

The dried green body is put into the shuttle kiln and fired, first from room temperature to 500°C at a heating rate of 1°C/min, then to 1000°C at 10°C/min, holding for 0.5h, and then at 8°C/min The temperature was raised to 1750-1760°C, kept for 2h, then cooled to 1100°C at 10°C/min, kept at 1100°C for 0.5h, then cooled to 500°C at 7°C/min, kept at 500°C for 0.5h, and finally kept at 4°C for 0.5h. ℃/min is cooled to 50 ℃ to obtain corundum micro-nano-porous insulating refractory material.

Example 27

The preparation method of the present implementation describes the preparation of the corundum micro-nano-porous insulating refractory material in Example 12, and the details are as follows:

(1) Preparation of base materials, additives and foams

1) Preparation of base material

Pour 0.2 tons of α-Al ₂ O ₃ and 0.8 tons of fused corundum into a non-gravity mixer, and dry-mix for 15 minutes to obtain the base material;

2) Preparation of additives

Weigh 5kg of melamine formaldehyde polycondensate, 5kg of sodium lignosulfonate, 0.05kg of Y ₂ O ₃ and 0.05kg of La ₂ O ₃ , pour them into a three-dimensional mixer and dry-mix for 5 minutes to obtain uniform additives;

3) Preparation of foaming composition

Weigh 0.1kg of polyamide type Dendrimer surfactant, 1kg of alumina gel, 10kg of konjac gum powder, 10kg of sodium alginate, 0.5kg of starch ether, 0.5kg of propyl cellulose ether, poured into V-type mixer, and dry mixed 5min to obtain a uniform foaming composition;

(2) Preparation of suspension slurry and foam slurry

1) Preparation of suspension slurry

Pour the base material and additives into the roller ball mill, add 0.3 tons of water, mix the ball mill for 0.5h, and then ultrasonically vibrate (ultrasonic power 2000W) for 4min to obtain a uniform suspension slurry (wherein the particle size of the solid particles is ≦74μm); Grinding ball adopts tungsten carbide ball, large ball

middle ball

small ball

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

2) Preparation of foam slurry

The suspension slurry was injected into the mixer, and the foaming composition was added to the mixer after pre-stirring for 1 min (the linear speed of the stirring paddle during the pre-stirring process was 3 m/s), and the stirring paddle was rapidly mixed for 10 minutes at a linear speed of 20 m/s. A homogeneous foam slurry was obtained.

(3) Pouring and maintenance

The foam slurry was injected into the stainless steel mold, and cured for 0.2h in an environment with an air temperature and humidity of 35°C and 99.9%, respectively, until it was cured;

(4) Drying and firing

The cured green body is demolded, and the free water of the green body is removed by the far-infrared drying method. The moisture content of the dry green body is less than or equal to 2wt%, and the compressive strength is greater than or equal to 1.5MPa. Put the dried green body into the shuttle kiln for firing, first from room temperature to 500°C at a heating rate of 1°C/min, then to 1000°C at 10°C/min, holding for 0.5h, and then at 10°C/min. The temperature was raised to 1780-1800 °C for 1 min, kept for 1 h, then cooled to 1100 °C at 10 °C/min, kept at 1100 °C for 0.5 h, then cooled to 500 °C at 10 °C/min, kept at 500 °C for 0.5 h, and finally The temperature is lowered to 80°C at 5°C/min to obtain the corundum micro-nanoporous insulating refractory material.

Example 28

The preparation method of the present implementation describes the preparation of the corundum micro-nano-porous insulating refractory material in Example 13, and the details are as follows:

(1) Preparation of base materials, additives and foams

1) Preparation of base material

Pour 0.2 ton of α-Al ₂ O ₃ micropowder and 0.8 ton of fused corundum powder into a non-gravity mixer and dry-mix for 15 minutes to obtain the base material;

2) Preparation of additives

Weigh 4kg of polyamide-type polycarboxylic acid dispersant, 4kg of melamine-formaldehyde polycondensate, and 6kg of TiO ₂ , pour them into a three-dimensional mixer and dry-mix for 5 minutes to obtain uniform additives;

3) Preparation of foaming composition: the same as in Example 26.

(2) Preparation of suspension slurry and foam slurry

1) Preparation of suspension slurry

Pour the base material and additives into the mixer, add 0.4 tons of water, and stir for 15 minutes to obtain a suspension slurry;

2) Preparation of foam slurry

The foaming composition will be added to the mixer, and then the stirring paddle will be rapidly mixed for 30min at a linear speed of 20m/s to obtain a uniform foam slurry;

(3) Pouring and maintenance

The foam slurry was injected into the stainless steel mold, cured for 0.5h in an environment with an air temperature and humidity of 30°C and 95%, respectively, to cure it, and then demolded to obtain a green body;

(4) Drying and firing

Demould the cured green body, remove the moisture by atmospheric pressure hot air drying method, and dry it at 40 ℃ ~ 55 ℃ for 24 hours to obtain a dry green body; the moisture content of the dried green body is ≤ 2wt%, and the compressive strength is ≧ 1.0 MPa. The dry green body is loaded into a shuttle kiln and fired, and the firing process is the same as that of Example 26, to obtain a corundum micro-nano-porous insulating and insulating refractory material.

Example 29

The preparation method of the present implementation describes the preparation of the corundum micro-nano-porous insulating refractory material in Example 14, and the details are as follows:

(1) Preparation of base materials, additives and foams

1) Preparation of base material

2) Preparation of foaming composition

Weigh 10kg vegetable protein foaming agent, 9kg vinyl acetate and tertiary ethylene carbonate and acrylate copolymer, 9kg disperse latex, 1kg hydroxyethyl ethyl cellulose ether, 1kg hydroxyethyl cellulose ether, pour into double cone and mix machine and dry mixing for 5min to obtain a uniform foaming composition;

(2) Preparation of suspension slurry and foam slurry

1) Preparation of suspension slurry

Pour the base material and additives into the mixer, add 0.4 tons of water, and stir for 20 minutes to obtain a suspension slurry;

2) Preparation of foam slurry

The foaming composition and 5kg of alumina sol will be added to the mixer, and then the stirring paddle is rapidly mixed for 7min at a linear speed of 50m/s to obtain a uniform foam slurry;

(3) Pouring and maintenance

(4) Drying and firing

Demould the cured green body, remove the moisture by atmospheric pressure hot air drying method, and dry it at 40 ℃ ~ 55 ℃ for 24 hours to obtain a dry green body; the moisture content of the dried green body is ≤ 2wt%, and the compressive strength is ≧ 1.2 MPa. The dry green body is loaded into a resistance kiln and fired, and the firing process is the same as that of Example 26, to obtain corundum micro-nano-porous insulating and thermal insulating refractory materials.

Example 30

This example is the preparation method of the corundum micro-nanoporous insulating and thermal insulation refractory material in Example 15. The preparation process is basically the same as that of Example 29, except that it is cured in an environment where the air temperature and humidity are 30°C and 95% respectively. It takes 5 hours to cure and demould, and when the green body is dried with normal pressure and hot air, it is dried for 36 hours in an environment of 40 ° C ~ 55 ° C, the drying time is greatly prolonged, and the compressive strength of the green body after drying is only 0.5MPa.

Example 31

(1) Preparation of base material, additive combination and foam

1) Preparation of base material

The preparation of the base material is the same as in Example 26.

2) Preparation of foaming composition and prefabricated foam

Take 15kg of ethylene with vinyl chloride and vinyl laurate copolymer (Wacker, Germany,

), 3kg acrylate polymer (American national starch,

), 0.5kg of ethyl cellulose ether (Akezo, the Netherlands), 1.5kg of hydroxybutyl methyl cellulose ether and ethyl cellulose sulfonate (Dow Chemical, USA), poured into a double cone mixer and dry mixed for 5 minutes to obtain a uniform Foaming composition: Weigh 10kg of animal protein foaming agent to prepare foam with a foaming machine.

(2) Preparation of suspension slurry and foam slurry

1) Preparation of suspension slurry

Pour the base material and additive combination into the mixer, add 0.38 tons of water, and stir for 20 minutes to obtain a suspension slurry.

2) Preparation of foam slurry

The foaming composition, 5kg of alumina sol (Al ₂ O ₃ content ≧ 20%) and prefabricated foam will be added to the mixer, and then the stirring paddle will be rapidly sheared and mixed at a linear speed of 50 m/s for 7 minutes to obtain a uniform foam slurry.

(3) Pouring and maintenance

The foam slurry was injected into a stainless steel mold, cured for 0.6 h in an environment with an air temperature and humidity of 30° C. and 95%, respectively, and then demolded to obtain a green body.

(4) Drying and firing

The cured green body is demoulded, and the moisture in it is removed by the atmospheric pressure hot air drying method, and dried at 40 ° C ~ 55 ° C for 24 hours to obtain a dry green body; MPa. The dry green body is loaded into a resistance kiln and fired, and the firing process is the same as that of Example 26, to obtain corundum micro-nano-porous insulating and thermal insulating refractory materials.

3. Experimental example

Experimental example 1

The pore structure test of the corundum-based micro-nano-porous insulating and insulating refractory materials in Examples 1 to 15 and 31 was carried out respectively, and the average pore size and pore size distribution of the material were measured by mercury intrusion method. The pore size distribution diagram of the material prepared in Example 6 As shown in Figure 8; the total porosity of the GB/T2998-2001 test style is used, and the closed porosity of the GB/T2997-2000 test style is used. The test results are shown in Table 1.

Table 1 Test results of pore structure

样品sample	平均孔径(μm)Average pore size (μm)	气孔率(％)Porosity (%)	闭口气孔率(％)Closed porosity (%)
实施例1Example 1	7.17.1	91.1～9291.1～92	63.3～6563.3～65
实施例2Example 2	3030	89.2～90.389.2～90.3	33.2～34.533.2～34.5
实施例3Example 3	15.415.4	87.3～88.887.3～88.8	35.6～36.135.6～36.1
实施例4Example 4	11.311.3	83.4～85.583.4～85.5	38.7～39.138.7～39.1
实施例5Example 5	7.27.2	79.3～81.279.3～81.2	41.3～42.441.3～42.4
实施例6Example 6	2.72.7	75.6～7675.6～76	45.6～46.745.6～46.7
实施例7Example 7	0.10.1	78～79.578～79.5	49.9～51.349.9～51.3
实施例8Example 8	1.21.2	72.1～73.772.1～73.7	41.2～43.541.2～43.5

实施例9Example 9	1.81.8	66.4～67.566.4～67.5	35.7～36.135.7～36.1
实施例10Example 10	2.42.4	55.9～56.755.9～56.7	28.5～31.228.5～31.2
实施例11Example 11	4.34.3	50.3～53.250.3～53.2	23.3～24.523.3～24.5
实施例12Example 12	5.85.8	45～47.445～47.4	20～21.320～21.3
实施例13Example 13	6.06.0	52.3～54.752.3～54.7	18.2～19.318.2～19.3
实施例14Example 14	8.08.0	48.4～49.348.4～49.3	21.2～22.421.2～22.4
实施例15Example 15	3636	47.8～50.247.8～50.2	13.2～14.513.2～14.5
实施例31Example 31	14.514.5	49.7～51.549.7～51.5	20.4～21.520.4～21.5

Experimental example 2

The properties of the corundum-based micro-nano-porous insulating and insulating refractory materials in Examples 1-15 and 31 were tested. GB/T 3997.2-1998 is tested; reburning line change rate is tested according to GB/T 3997.1-1998; thermal conductivity is tested according to YB/T4130-2005, and the test results are shown in Table 2.

Table 2 Performance test results

It can be seen from Table 1 and Table 2 that the corundum-based micro-nano-porous insulating refractory material of the present invention has the advantages of better micro-nano size pore size, ultra-low thermal conductivity, and high strength, and can meet different needs.

Comparing Examples 1-2 and 15-16, it can be seen that when the density of the prepared samples is not much different, the amount of water that can be used in the introduction of the dispersant is significantly reduced; The introduction of α 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 cell regulator, the pore size of the sample is effectively reduced, and the reduction of the average pore size makes the test The strength of the sample is significantly enhanced and the thermal conductivity is reduced; it can be seen from the comparative examples 7-13 that with the increase of the amount of organic curing agent introduced, the strength of the dried sample body gradually increases; the comparative examples 6-7 and From 21 to 22, it can be seen that with the increase of stirring speed, the average pore size of the sample gradually decreases. Comparing Examples 11 and 13, and 26 and 28, it can be seen that the introduction of sintering aids increases the density and strength of the fired samples; After the raw material is ball-milled, the sintered sample has better bonding, higher density and higher strength. Comparing Examples 14 and 15, and 29 and 30, it can be seen that when the organic curing agent is not added, the required curing time of the green body is greatly extended, and the mold can be demolded, and the strength of the green body after drying is greatly reduced, and the sample after burning The pore size of the pore size increased significantly, the bulk density and thermal conductivity increased significantly, and the total porosity, closed porosity and strength decreased significantly. Comparing Examples 14 and 31, it can be seen that when the foaming agent is pre-foamed, the stirring time of the foam slurry is shortened, but the curing time of the green body is prolonged, the strength of the green body is weakened after drying, and the average porosity of the fired product is reduced. The pore size increases, the porosity and high temperature thermal conductivity increase, and the bulk density and strength decrease.

The invention can realize controllable and adjustable aspects in terms of bulk density, porosity, closed porosity, pore diameter, compressive strength and thermal conductivity, and through the construction of micro-nano size pore structure in corundum insulating refractory material, It can show more excellent mechanical and thermal insulation properties while ensuring that the porosity and bulk density of the material are similar to the existing technology, and have better practical significance in practical engineering and technical applications, making it very suitable for metallurgical applications. , petrochemical, building materials, ceramics, machinery and other industries with hot surface lining, backing and filling sealing and thermal insulation materials for industrial kilns.

Claims

A corundum-based micro-nano-porous insulating and thermal-insulating refractory material, characterized in that the corundum-based micro-nano-porous insulating and thermal insulating refractory material is made of basic materials, additives and water; the chemical composition of the product is Al 2 O 3 . The content is 75-99.9%, or 85-99.9%, or 90-99.9%, or 98-99.9%, or 98-99.9%, or 99-99.9%;

The basic material is composed of the following components in mass fractions: 10-100% of alumina raw materials, 0-90% of aluminum-silicon raw materials, and 0-20% of siliceous raw materials. and is 100%;

The additive at least includes a foaming composition, 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, and is based on the quality of the base material. The added mass of foaming 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, sintering aid, and infrared sunscreen. Based on the quality of the base material, the added mass of sintering aid and infrared sunscreen is not more than 10%;

The quality of the water is 20-200% or 30-200% of the quality of the base material.
The corundum-based micro-nanoporous insulating and thermal insulating refractory material according to claim 1, wherein the average pore diameter of the corundum-based micro-nanoporous insulating and thermal insulating refractory material is 0.1-30 μm, and the total porosity is 30-92% , the porosity of the closed type is 15-65%, the bulk density is 0.3-2.0g/cm 3 , the compressive strength at room temperature is 2-190MPa, and the thermal conductivity at room temperature is 0.03-0.18W/(m·K), at 350 ℃ The thermal conductivity is 0.04~0.26W/(m·K), and the thermal conductivity at 1100℃ is 0.05~0.35W/(m·K).
The corundum-based micro-nanoporous insulating and thermal insulating refractory material according to claim 1, wherein the alumina-based raw materials are industrial alumina, industrial Al(OH) 3 , 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, sintered corundum, tabular corundum, aluminum hydroxide, boehmite, diaspore, aluminum n-butoxide, aluminum isopropoxide, aluminum sec-butoxide, aluminum chloride hexahydrate, nitric acid nonahydrate One or more of aluminum; the mass percentage content of Al 2 O 3 in the alumina raw material is 65-99.9%;

The alumino-silicon raw materials are sintered mullite, fused mullite, kaolin, bauxite, alumino-silicon homogeneous material, coal gangue, kyanite, andalusite, sillimanite, pyrophyllite, potassium Stone, albite, anorthite, barium feldspar, china stone, alkali stone, mica, spodumene, perlite, montmorillonite, illite, halloysite, dicite, pyrogem, clay, bentonite , Guangxi clay, Suzhou soil, Mujie soil, fly ash, bleaching beads one or more; the mass percentage content of Al 2 O 3 in the alumino-silicon raw material is 18-90%, and the content of SiO 2 The mass percentage is 8-75%;

The siliceous raw material is α-quartz, β-quartz, α-tridymite, β-tridymite, α-cristobalite, β-cristobalite, vein quartz, sandstone, quartzite, flint, cemented silica, river quartz One of sand, sea sand, white carbon black, diatomaceous earth, microsilica, rice husk, carbonized rice husk, rice husk ash, methyl orthosilicate, ethyl orthosilicate, methyltrimethoxysilane or A variety of; the mass percentage content of SiO2 in the siliceous raw material is 28-99%.
The corundum micro-nano-porous insulating and heat-insulating refractory material according to claim 1, characterized in that, based on the quality of the base material, the added mass of the dispersant is not more than 1%, and the added mass of the suspending agent is not more than 10%. ; Described dispersant is polycarboxylic acid dispersant, polycarboxylate ether dispersant, sulfonated melamine polycondensate, naphthalene dispersant, lignosulfonate dispersant, sulfamic acid dispersant, ethylene glycol One or more of sodium amine tetraacetate, melamine formaldehyde polycondensate, sodium polyphosphate, sodium polyacrylate, sodium citrate, sodium humate, sodium phosphate, and sodium carbonate;

The suspending agent is bentonite, sepiolite, attapulgite, polyaluminum chloride, polyaluminum sulfate, chitosan, welan gum, agar, polyethylene glycol, polyvinyl alcohol, polyacrylamide, polyacrylamide, One or more of polyvinylpyrrolidone, casein, cetyl alcohol, sucrose, dextrin, microcrystalline cellulose, cellulose fibers, cellulose nanofibers, cellulose nanocrystals, and soluble starch.
The corundum micro-nano-porous insulating and thermal insulating refractory material according to claim 1, wherein the sintering aid is ZnO, Fe 2 O 3 , V 2 O 5 , SiF 4 , AlF 3 , AlF 3 ·3H One of 2 O, MnO 2 , CuO, CuSO 4 , CaO, MgO, SrO, BaO, WO 3 , Er 2 O 3 , Cr 2 O 3 , La 2 O 3 , YbO, Y 2 O 3 , CeO 2 or more.
The corundum-based micro-nano-porous insulating and thermal insulating refractory material according to claim 1, wherein the infrared light shielding agent is rutile, TiO 2 , TiC, K 4 TiO 4 , K 2 Ti 6 O 13 , Sb 2 O 3 , one of Sb 2 O 5 , ZrO 2 , CoO, CoCl 2 , Co(NO 3 ) 2 , NiCl 2 , Ni(NO 3 ) 2 , ZrSiO 4 , Fe 3 O 4 , B 4 C, and SiC variety.
The corundum micro-nano-porous insulating and heat-insulating refractory material according to claim 1, wherein the foaming agent is a surfactant and/or a protein-based foaming agent, and the foaming ratio is 8-60 times; The surfactant is selected from one of cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, Gemini type surfactants, Bola type surfactants and Dendrimer type surfactants. one or more; the protein-based foaming agent is animal protein foaming agent, vegetable protein foaming agent and/or sludge protein foaming agent.
The corundum micro-nano-porous insulating and thermal insulating refractory material according to claim 1, wherein the inorganic curing agent is alumina sol, silica-alumina sol, silica sol, alumina gel, silica-alumina gel, Silica gel, Al 2 O 3 micropowder, SiO 2 micropowder, dicalcium silicate, calcium dialuminate, tricalcium silicate, tricalcium aluminate, monocalcium aluminate, aluminum phosphate, dodecacalcium heptaaluminate, One or more of water glass, tetracalcium ferrite aluminate, and soft bound clay;

The organic curing agent is selected from water-soluble polymer resin, low methoxy pectin, carrageenan, carrageenan, hydroxypropyl guar gum, locust gum, locust bean gum, gellan gum, keratin gum, One or more combinations of alginate, konjac gum and disperse latex; the water-soluble polymer resin is selected from vinyl acetate and ethylene copolymer, vinyl acetate homopolymer, acrylate polymer, ethylene and Vinyl acetate copolymer, ethylene and vinyl chloride copolymer, vinyl acetate and tertiary vinyl carbonate copolymer, vinyl acetate and tertiary vinyl carbonate copolymer, acrylate and styrene copolymer, vinyl acetate and higher fatty acid vinyl ester copolymer vinyl acetate and ethylene and vinyl chloride copolymers, vinyl acetate and ethylene and acrylate copolymers, isobutylene and maleic anhydride copolymers, ethylene and vinyl chloride and vinyl laurate copolymers, vinyl acetate and ethylene and One or both of copolymers of higher fatty acid, vinyl acetate and acrylate and higher fatty acid vinyl ester, copolymer of vinyl acetate and ethylene and vinyl laurate, and copolymer of vinyl acetate and tertiary vinyl carbonate and acrylate more than one combination.
The corundum micro-nano-porous insulating and heat-insulating refractory material according to claim 1, wherein the cell regulator is selected from one or both of cellulose ether, starch ether, lignocellulose and saponin combination of the above.
The corundum micro-nanoporous insulating and thermal insulating refractory material according to claim 9, wherein the cellulose ether is selected from the group consisting of water-soluble cellulose ether, methyl cellulose ether, carboxymethyl cellulose ether, carboxymethyl cellulose methyl cellulose ether, carboxymethyl ethyl cellulose ether, carboxymethyl hydroxymethyl cellulose ether, carboxymethyl hydroxyethyl cellulose ether, carboxymethyl hydroxypropyl cellulose ether, carboxymethyl hydroxymethyl cellulose ether Butyl cellulose ether, hydroxymethyl cellulose ether, hydroxyethyl cellulose ether, hydroxyethyl methyl cellulose ether, hydroxyethyl ethyl cellulose ether, ethyl cellulose ether, ethyl methyl cellulose ether, propyl cellulose ether, hydroxypropyl cellulose ether, hydroxypropyl methyl cellulose ether, hydroxypropyl ethyl cellulose ether, hydroxypropyl hydroxybutyl cellulose ether, hydroxybutyl methyl cellulose ether, One or more combinations of ethyl cellulose sulfonate ethers.
The preparation method of the corundum micro-nano-porous insulating and insulating refractory material according to any one of claims 1 to 10, characterized in that, comprising the following steps:

(1) When additives are used, the base materials and additives are dispersed in water into a suspension slurry; when no additives are used, the base materials and additives are dispersed in water into a suspension slurry;

(2) stirring and foaming the foaming agent, the inorganic curing agent, the organic curing agent, the cell regulator and the suspending slurry to obtain the foamed slurry;

(3) The foam slurry is injected into the mold for curing, and the green body is obtained after demoulding; the green body is dried and sintered at a temperature of 1200-1800 °C.
The method for preparing a corundum-based micro-nano-porous insulating and insulating refractory material according to claim 11, wherein in step (1), the average particle size of the solid particles in the suspension slurry is not higher than 1 mm, or not higher than 1 mm. higher than 74 μm, or not higher than 50 μm, or not higher than 44 μm, or not higher than 30 μm.
The preparation method of corundum micro-nano-porous insulating and heat-insulating refractory material according to claim 11, characterized in that, in step (2), stirring and foaming adopts stirring paddle high-speed stirring and shearing foaming, and the line on the outer edge of the stirring paddle is used for foaming. The speed is 20～200m/s, or 50～200m/s, or 80～200m/s, or 100～200m/s, or 150～200m/s, or 180～200m/s.
The preparation method of corundum micro-nano-porous insulating and heat-insulating refractory material according to claim 11, characterized in that, in step (3), the air temperature of the curing environment is 1-35°C, and the humidity is 50-99.9%; The time is 0.2 to 12 hours.
The method for preparing a corundum micro-nano-porous insulating and insulating refractory material according to claim 11, wherein in step (3), the drying of the green body is selected from the group consisting of atmospheric drying, supercritical drying, freeze drying, vacuum drying, One or more combinations of infrared drying and microwave drying; the green body is dried until the water content of the green body is less than or equal to 3wt%; the compressive strength of the green body after drying is greater than or equal to 0.7MPa.
The method for preparing a corundum-based micro-nano-porous insulating and insulating refractory material according to any one of claims 11-16, characterized in that, in step (3), the sintering system is: from room temperature to 1-5°C/min Heat up to 500°C, then heat up to 1000°C at 5～30°C/min, hold for 0.5～1.5h, then heat up to 1200～1800°C at 1～30°C/min, hold for 1～10h, then heat at 10～20°C Cool down to 1100°C/min, keep at 1100°C for 0.5-1.5h, then cool at 5-30°C/min to 500°C, keep at 500°C for 0.5h, and finally cool down at 1-10°C/min to 50-80°C °C.