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WO2022144013A1 - 一种刚玉质微纳孔绝隔热耐火材料及其制备方法 - Google Patents

一种刚玉质微纳孔绝隔热耐火材料及其制备方法 Download PDF

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WO2022144013A1
WO2022144013A1 PCT/CN2021/144043 CN2021144043W WO2022144013A1 WO 2022144013 A1 WO2022144013 A1 WO 2022144013A1 CN 2021144043 W CN2021144043 W CN 2021144043W WO 2022144013 A1 WO2022144013 A1 WO 2022144013A1
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corundum
cellulose ether
refractory material
nano
foaming
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PCT/CN2021/144043
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French (fr)
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郭会师
李文凤
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郑州轻工业大学
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/10—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by using foaming agents or by using mechanical means, e.g. adding preformed foam
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
    • C04B35/101—Refractories from grain sized mixtures
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/0051—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof characterised by the pore size, pore shape or kind of porosity
    • C04B38/0054—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof characterised by the pore size, pore shape or kind of porosity the pores being microsized or nanosized
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient

Definitions

  • 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.
  • 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.
  • 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.
  • most of the insulation materials used in kilns are refractory fiber products or lightweight insulation bricks.
  • 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.
  • 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.
  • 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.
  • VOCs fine particles will also be produced, which will seriously pollute the environment and endanger human health and surrounding crops. Production.
  • 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.
  • 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.
  • 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 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.
  • 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 ⁇ m, the average pore diameter is 0.1-30 ⁇ m, 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°C 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
  • 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%.
  • 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, ⁇ -Al 2 O 3 , ⁇ -Al 2 O 3 , ⁇ -Al 2 O 3 , ⁇ -Al 2 O 3 , ⁇ -Al 2 O 3 , ⁇ -Al 2 O 3.
  • 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.
  • 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%.
  • 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.
  • 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.
  • the weight percent content of SiO 2 in its chemical composition is above 92%.
  • the silica raw materials are ⁇ -quartz, ⁇ -quartz, ⁇ -tridymite, ⁇ -tridymite, ⁇ -cristobalite, ⁇ -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.
  • 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 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.
  • 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.
  • 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.
  • 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 ⁇ m or less, preferably 4 ⁇ m or less, more preferably 3 ⁇ m or less, and particularly preferably 1 ⁇ m 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.
  • the heat transfer mechanism of the material includes heat transfer in addition to heat conduction.
  • 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 ⁇ m or less, preferably 4 ⁇ m or less, more preferably 3 ⁇ m or less, and particularly preferably 1 ⁇ m or less.
  • 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.
  • 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 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).
  • 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.
  • 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, ⁇ -olefin One or more combinations of sodium sulfonate, dodecyl dimethyl betaine, fatty alcohol polyoxyethylene ether carboxylate, and sodium dodecyl benzene sulfonate.
  • 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
  • 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
  • the water glass contains sodium silicate, or potassium silicate, or a combination of the two.
  • 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%.
  • 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 ⁇ m.
  • 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 copoly
  • 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.
  • 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.
  • the cell regulator is selected from one or a combination of two or more selected from cellulose ether, starch ether, lignocellulose, and saponin.
  • 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
  • a method for preparing a corundum micro-nano-porous insulating and heat-insulating refractory material comprising the following steps:
  • 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;
  • the technical key to preparing the lightweight thermal insulation material lies in the introduction of its internal pores.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 ⁇ m, or no higher than 44 ⁇ m, or no higher than 30 ⁇ m.
  • 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.
  • 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.
  • the dispersion includes ball milling and ultrasonic dispersion.
  • 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.
  • 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%.
  • the three raw materials in the base material are preferably pre-mixed uniformly by the same method when used.
  • 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.
  • 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.
  • 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.
  • the average particle size of solid particles in the mixture can be made not higher than 74 ⁇ m.
  • the average particle size of the solid particles is not higher than 50 ⁇ m; further preferably, the average particle size of the solid particles is not higher than 44 ⁇ m; more particularly preferably, the average particle size of the solid particles is not higher than 30 ⁇ m.
  • 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.
  • 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.
  • 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.
  • 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.
  • the ceramic slurry becomes a uniform foamed ceramic slurry.
  • 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.
  • 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.
  • 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%.
  • 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.
  • 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%.
  • the drying heat source may be power heating or hot air
  • the drying temperature is 30-110° C.
  • the drying time is 12-48 h.
  • 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.
  • 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
  • the drying time is 0.5-3h
  • the drying temperature of the freeze-drying machine is -180°C ⁇ -30°C, and the drying time is 3 ⁇ 6h;
  • the drying temperature of the vacuum drying box is 35 ⁇ 50°C
  • the vacuum pressure is 130 ⁇ 0.1Pa
  • the drying time is 3 ⁇ 8h
  • the wavelength of the infrared rays is 2.5-100 ⁇ m, preferably 2.5-50 ⁇ m, preferably 2.5-30 ⁇ m, more preferably 2.5-15 ⁇ m, more particularly preferably 2.5-8 ⁇ m, and the drying time is 0.5-5h;
  • 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.
  • 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.
  • 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°C, keep for 1 ⁇ 10h, then cool down to 1100°C at 10 ⁇ 20°C/min, keep at 1100°C for 0.5 ⁇ 1.5h, then cool down to 500°C at 5 ⁇ 30°C/min, then at 500°C 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.
  • Fig. 1 is the macrophotograph of the corundum micro-nano-porous insulating and insulating refractory material of Example 1 of the present invention
  • Example 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
  • Example 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 );
  • Example 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
  • Example 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.
  • the mass percentage of Al 2 O 3 in the chemical composition is ⁇ 65%, and the particle size is ⁇ 0.08mm.
  • the mass percentage of Al 2 O 3 in the chemical composition is ⁇ 70%, and the particle size is ⁇ 0.08mm.
  • Industrial alumina, ⁇ -Al 2 O 3 , ⁇ -Al 2 O 3 , ⁇ -Al 2 O 3 , ⁇ -Al 2 O 3 , ⁇ -Al 2 O 3 , ⁇ -Al 2 O 3 , ⁇ -Al 2 In O 3 and ⁇ -Al 2 O 3 the mass percentage of Al 2 O 3 is ⁇ 98%, and the particle size is ⁇ 0.08 mm.
  • 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.
  • 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.
  • 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 ⁇ 5 ⁇ m.
  • FIGS 1 and 2 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.
  • 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.
  • the alumina raw material is composed of industrial Al(OH) 3 , diaspore, and ⁇ -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 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.
  • 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 5 ⁇ m.
  • the main crystal phases are flaky corundum phase and needle-like mullite phase
  • 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.
  • 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 ⁇ m) 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 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.
  • 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 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.
  • 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 ⁇ m.
  • the main crystalline phases are flaky corundum phase and needle-like mullite phase
  • 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.
  • 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.
  • 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 ⁇ m.
  • the main crystal phases are flaky corundum phase and columnar mullite phase
  • 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.
  • the alumina raw material is composed of industrial Al(OH) 3 and ⁇ -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.
  • Y 2 O 3 , MgO, V 2 O 5 , rutile, and ZrSiO 4 are all of industrial grade, and the particle size is ⁇ 5 ⁇ m.
  • 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.
  • the alumina raw material is made of industrial alumina, ⁇ -Al 2 O 3 , ⁇ -Al 2 O 3 , ⁇ -Al 2 O 3 , ⁇ -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.
  • 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 ⁇ m.
  • 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 ⁇ -Al 2 O 3 , ⁇ -Al 2 O 3 , ⁇ -Al 2 O 3 , ⁇ -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.
  • 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 ⁇ m.
  • 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.
  • the alumina raw material is composed of ⁇ -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 ⁇ -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.
  • 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 ⁇ m.
  • the main crystal phase is a granular corundum phase
  • 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.
  • the alumina raw material is composed of ⁇ -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.
  • 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 ⁇ m.
  • the main crystal phase is a granular corundum phase
  • 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.
  • the alumina raw material is composed of ⁇ -Al 2 O 3 (Al 2 O 3 mass percentage ⁇ 99%, particle size ⁇ 5 ⁇ m) 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.
  • 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 ⁇ m.
  • the main crystal phase is a granular corundum phase
  • 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.
  • the alumina raw material is composed of ⁇ -Al 2 O 3 (Al 2 O 3 mass percentage ⁇ 99%, particle size ⁇ 5 ⁇ m) 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.
  • 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 ⁇ m.
  • the main crystal phase is a granular corundum phase
  • 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 ⁇ -Al 2 O 3 (Al 2 O 3 mass percentage ⁇ 99.5%, particle size ⁇ 5 ⁇ m), fused corundum powder (Al 2 O 3 mass percentage ⁇ 99%, particle size ⁇ 5 ⁇ m) 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.
  • Y 2 O 3 , TiO 2 , and silica gel are all industrially pure, and the particle size is less than or equal to 5 ⁇ m.
  • 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 ⁇ -Al 2 O 3 (Al 2 O 3 mass percentage ⁇ 99.999%, particle size ⁇ 5 ⁇ m), fused corundum powder (Al 2 O 3 mass percentage ⁇ 99.99%, particle size ⁇ 5 ⁇ m) 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.
  • 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 (
  • 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 ⁇ m.
  • the main crystal phase is a granular corundum phase
  • 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 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;
  • infrared sunscreening agent foaming agent, organic curing agent and cell regulator are the same as those in Example 11;
  • TiO 2 and alumina gel are both industrial pure, and the particle size is less than or equal to 5 ⁇ m.
  • the main crystal phase is a granular corundum phase
  • the mass percentage of Al 2 O 3 in the chemical composition of the material is 99%
  • 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 ⁇ -Al 2 O 3 (Al 2 O 3 mass percentage ⁇ 99.5%, particle size ⁇ 5 ⁇ m), fused corundum powder (Al 2 O 3 mass percentage ⁇ 99%, particle size ⁇ 5 ⁇ m) 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.
  • the main crystal phase is a granular corundum phase
  • 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.
  • 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:
  • 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.
  • 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;
  • 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
  • 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.
  • the preparation method of the present implementation describes the preparation of the corundum insulating and heat-insulating refractory material in Example 2, as follows:
  • 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;
  • 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;
  • 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 °C, the corundum micro-nano-porous insulating refractory material is obtained.
  • the preparation method of the present implementation describes the preparation of the corundum insulating and heat insulating refractory material in Example 3, as follows:
  • 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;
  • 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;
  • 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 °C, the corundum micro-nano-porous insulating refractory material is obtained.
  • 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:
  • 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;
  • 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;
  • 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 °C, the corundum micro-nano-porous insulating refractory material is obtained.
  • 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:
  • 0.3 tons of industrial alumina 0.2 tons of ⁇ -Al 2 O 3 , 0.15 tons of ⁇ -Al 2 O 3 , 0.1 tons of ⁇ -Al 2 O 3 , 0.1 tons of ⁇ -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;
  • 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.
  • 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;
  • 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.
  • 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°C, keep for 5h, 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, keep at 500°C for 0.5h, and finally at 2°C/min Min cooling to 50 °C, that is, corundum micro-nano-porous insulating refractory material.
  • 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:
  • 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.
  • 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;
  • 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.
  • 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°C, keep for 4h, 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, keep at 500°C for 0.5h, and finally at 2°C/min Min cooling to 50 °C, that is, corundum micro-nano-porous insulating refractory material.
  • 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:
  • 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.
  • 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°C, keep 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, keep at 500°C for 0.5h, and finally heat at 2°C/min Min cooling to 50 °C, that is, corundum micro-nano-porous insulating refractory material.
  • 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:
  • 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.
  • 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;
  • 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. °C/min is cooled to 50 °C to obtain corundum micro-nano-porous insulating refractory material.
  • 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:
  • 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.
  • 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:
  • 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.
  • 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.
  • the preparation method of this implementation describes the preparation of the corundum-based micro-nano-porous insulating refractory material in Example 11, as follows:
  • 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.
  • 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;
  • 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.
  • °C/min is cooled to 50 °C to obtain corundum micro-nano-porous insulating refractory material.
  • 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:
  • 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.
  • 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;
  • 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.
  • 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.
  • 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:
  • 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;
  • 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;
  • 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:
  • 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;
  • 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;
  • 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.
  • the preparation of the base material is the same as in Example 26.
  • 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.
  • 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.
  • 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.
  • 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.
  • Example 1 7.1 91.1 ⁇ 92 63.3 ⁇ 65
  • Example 2 30 89.2 ⁇ 90.3 33.2 ⁇ 34.5
  • Example 3 15.4 87.3 ⁇ 88.8 35.6 ⁇ 36.1
  • Example 4 11.3 83.4 ⁇ 85.5 38.7 ⁇ 39.1
  • Example 5 7.2 79.3 ⁇ 81.2 41.3 ⁇ 42.4
  • Example 6 2.7 75.6 ⁇ 76 45.6 ⁇ 46.7
  • Example 7 0.1 78 ⁇ 79.5 49.9 ⁇ 51.3
  • Example 9 1.8 66.4 ⁇ 67.5 35.7 ⁇ 36.1
  • Example 10 2.4 55.9 ⁇ 56.7 28.5 ⁇ 31.2
  • Example 11 4.3 50.3 ⁇ 53.2 23.3 ⁇ 24.5
  • Example 12 5.8 45 ⁇ 47.4 20 ⁇ 21.3
  • Example 13 6.0 52.3 ⁇ 54.7 18.2 ⁇ 19.3
  • Example 14 8.0 48.4 ⁇ 49.3 21.2 ⁇ 22.4
  • Example 15 36 47.8 ⁇ 50.2 13.2 ⁇ 14.5
  • Example 31 14.5 49.7 ⁇ 51.5 20.4 ⁇ 21.5
  • 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.
  • 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.

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Abstract

本发明属耐火材料技术领域，具体涉及一种刚玉质微纳孔绝隔热耐火材料及其制备方法。该隔热耐火材料主要由基础料、添加料和水制成，制备过程绿色环保无污染，简单易控，材料主晶相为刚玉相，制品外观呈白色或淡黄色，气孔孔径分布在0.003～250μm间，平均孔径0.1～30μm，封闭的球状微纳米尺寸气孔结构保证了材料在较低体积密度、高强度下较佳的绝隔热性能。本发明通过调控各原料用量及工艺，使制得的耐火材料既满足了超低导热和轻量化的需求，还保证了较佳的力学性能。

Description

一种刚玉质微纳孔绝隔热耐火材料及其制备方法 技术领域
本发明属耐火材料技术领域，具体涉及一种具有微纳米尺寸气孔结构、超低导热及体积密度、高气孔率、高强度并绿色可控制备的刚玉质微纳孔绝隔热耐火材料及其制备方法。
背景技术
高温工业是我国工业生产中的主要耗能产业，各类窑炉的热能利用率低是其能耗大的主要原因，若能按国家要求将平均热效率提高20％，可节约能源相当于2.2亿吨标煤。要提高工业窑炉的热效率，最重要的就是发展高效保温技术，采用先进隔热材料，加强窑体保温效果，减少散热损失。
目前，我国隔热材料虽在不断改进和完善，但仍然无法满足高温工业愈来愈苟刻的隔热环境与要求。现在窑炉用保温材料多采用耐火纤维制品或轻质隔热砖。耐火纤维的热性能虽然较好，但其对烧成气氛较敏感，易与还原和腐蚀性气体发生反应，使其失去良好的隔热性能；且其在高温环境中长期服役，组成颗粒易析晶且晶粒长大，引起应力集中，导致隔热层的粉化，缩短使用寿命；此外，陶瓷纤维还危害人体健康，欧盟已将其列为二级致癌物。
轻质隔热砖虽可克服耐火纤维制品的上述缺陷，但其多通过添加大量造孔剂(如聚苯乙烯颗粒、锯木屑、木炭、无烟煤灰、焦炭粉等)的方法制得，这些造孔剂在坯体中占据一定空间，经过烧成后，造孔剂离开基体中原来的位置而形成气孔，从而获得轻质隔热耐火材料，方法简单易控，且生产效率较高，但此法所制材料气孔率不高、气孔孔径较大、隔热效果较差且易产生应力集中而开裂，使强度较低。另外，其制备过程中采用的造孔剂多为有机烧失物，使原料成本较高，且其烧成时放出大量有毒有害气体，如无烟煤、锯木屑及焦炭粉等在较低温度下便可产生大量硫氧化物，聚苯乙烯颗粒则产生苯乙烯、甲苯及氮/碳/氧化物及二噁英等，同时还会产生大量的VOCs微细颗粒物，严重污染环境，危害人体健康及周边农作物的生产。
除了造孔法，刚玉质隔热耐火材料还可以采用氧化铝空心球法制得氧化铝空心球制品，这类制品可以在1600℃以上的高温环境中应用，强度较高，抗蠕变性能好，可直接作为高温炉的内衬使用。但是，通常这类制品的容重较大，并且氧化铝空心球的制备属于二次加工，会消耗大量能源，生产成本较大。另外，为了保证制品结构稳定性，在制备过程中需要对不同粒度的空心球做颗粒级配，制品尺寸越大，临界粒径越大，因此从微观结构上来看，最终 在材料内部留下的气孔有大有小，孔径分布极不均匀。因此，迫切需要研究开发隔热性、耐久性及力学性能俱佳且绿色制备的高温工业用新型绝隔热耐火材料。
发明内容
本发明的目的是提供一种刚玉质微纳孔绝隔热耐火材料，该耐火材料具有微纳米尺寸孔径、封闭式球状气孔结构、超低导热及体积密度、高气孔率、高强度等特点，可在保证强度满足需求的情况下，有效降低热导率和体积密度，从而利于环保轻型窑炉建造。
本发明的另一个目的是提供一种刚玉质微纳孔绝隔热耐火材料的制备方法，该制备方法过程绿色无污染，材料的结构和性能容易精确控制，且成品率较高，并可解决现有的制备方法所得的隔热耐火材料不能兼顾材料低导热和高强度且高成品率的问题。
为实现上述目的，本发明的刚玉质微纳孔绝隔热耐火材料的具体技术方案为：
一种刚玉质微纳孔绝隔热耐火材料，所述刚玉质微纳孔绝隔热耐火材料由基础料、添加料和水制成；制品的化学组成中Al 2O 3的质量百分含量为75～99.9％，或者为85～99.9％，或者为90～99.9％，或者为98～99.9％，或者为98～99.9％，或者为99～99.9％；
所述基础料由以下质量分数的组分组成：氧化铝质原料10～100％，铝硅质原料0～90％，和二氧化硅质原料0～20％，上述三种基础原料质量百分比之和为100％；
所述添加料至少包括发泡料，使用或不使用添加剂；所述发泡料由发泡剂、无机固化剂、有机固化剂和泡孔调节剂组成，以基础料的质量为基准，发泡剂、无机固化剂、有机固化剂、泡孔调节剂的添加质量分别为0.01～10％、0.1～20％、0.1～2％、0.01～1％；使用添加剂时，所述添加剂选自分散剂、悬浮剂、烧结助剂、红外遮光剂中的一种或两种以上组合，以基础料的质量为基准，烧结助剂和红外遮光剂的添加质量均不大于10％；
所述水的质量为基础料质量的20～200％或30～200％。
本发明的刚玉质微纳孔绝隔热耐火材料，主晶相为刚玉相，其余为少量莫来石相或玻璃相，其具有较低的体积密度和较高的耐压强度。使用温度可达1800℃，在1732℃下保温24h的重烧成线变化率≦1.8％，优选≦1.2％，优选≦0.8％，更优选≦0.6％，更特别优选≦0.2％。
可以通过调控各原料用量及工艺使得最终制得的耐火材料，既满足低导热和轻量的需求，还保证了较高的强度。与现有技术相比，本发明提供的刚玉质微纳孔绝隔热耐火材料具有体积密度低、导热系数小、强度高、气孔率高、气孔孔径小等特点，是隔热性能最好的刚玉质定型隔热耐火材料，综合性能优良，可适用于冶金、石化、建材、陶瓷、机械等行业用工业窑炉的热面衬里、背衬及填充密封与隔热材料，还可用于发动机引擎隔热部件及军工和航空航天等领域。又由于其导热系数极低，可在达到环境温度要求的情况下，大大减薄窑炉 炉壁的厚度，从而大大减轻窑炉的重量，并加快窑炉升温速度，有利新型轻质环保窑炉的构筑。
材料中的主晶相为刚玉相，其余为少量莫来石相或玻璃相；刚玉相的形貌为片状或颗粒状。
所述刚玉质微纳孔绝隔热耐火材料的气孔孔径分布在0.003～250μm间，平均孔径为0.1～30μm，总气孔率为30～92％，闭口型气孔率为15～65％；体积密度为0.3～2.0g/cm 3，常温耐压强度为2～190MPa，常温热导率为0.03～0.18W/(m·K)，350℃时的热导率为0.04～0.26W/(m·K)，1100℃时的热导率为0.05～0.35W/(m·K)。较小的气孔孔径、较高的气孔率有效降低了材料的体积密度以及导热率，且闭口型气孔的形成在有效提高隔热保温效果的同时增大了材料的荷载能力。
所述氧化铝质原料为氧化铝原料或含氧化铝的原料，所述含氧化铝的原料是指在高温下能够分解生成氧化铝的物质。所述氧化铝质原料中氧化铝的质量百分含量为65～99.9％。
对于氧化铝原料，其化学组成中Al 2O 3的重量百分含量在90％以上，优选≧93％，优选≧95％，更优选≧96％，特别优选≧98％，更特别优选≧99％。所述氧化铝原料为工业氧化铝、β-Al 2O 3、γ-Al 2O 3、δ-Al 2O 3、χ-Al 2O 3、ρ-Al 2O 3、κ-Al 2O 3、θ-Al 2O 3、η-Al 2O 3、α-Al 2O 3、电熔刚玉、烧结刚玉、板状刚玉中的一种或多种。
对于高温下能够生成氧化铝的含氧化铝的原料，其化学组成中氧化铝的重量百分含量为≧65％。所述含氧化铝的原料为工业Al(OH) 3、工业Al(OH) 3、勃姆石、水铝石、正丁醇铝、异丙醇铝、仲丁醇铝、六水合氯化铝、九水合硝酸铝中的一种或多种。氧化铝质原料粒径≦1mm。优选地，氧化铝质原料粒径≦0.08mm。
在基础料中引入适当的铝硅质原料可在高温下生成少量的一次及二次莫来石，促进刚玉质材料的烧结，提高强度，改善抗热震性。所述铝硅质原料为烧结莫来石、电熔莫来石、高岭土、铝矾土、铝硅系均质料、煤矸石、蓝晶石、红柱石、硅线石、叶蜡石、钾长石、钠长石、钙长石、钡长石、瓷石、碱石、云母、锂辉石、珍珠岩、蒙脱石、伊利石、埃洛石、迪开石、焦宝石、黏土、广西白土、苏州土、木节土、粉煤灰、漂珠中的一种或多种。所述铝硅质原料中Al 2O 3的重量百分含量为18～90％，二氧化硅的质量百分含量为8～75％。进一步优选的，所述铝硅质原料的化学组成中氧化铝的质量百分含量为32～72％，二氧化硅的质量百分比为25～64％。更进一步优选的，所述铝硅质原料的化学组成中氧化铝的质量百分含量为38～50％，二氧化硅的质量百分比为45～58％。优选的，所述铝硅质原料的颗粒粒径≦1mm。进一步优选的，所述铝硅质原料的颗粒粒径为0.6～1mm。后期经球磨后获得具有较高表面活 性的陶瓷粉体颗粒。
在基础料中适当引入适当二氧化硅质原料，其在高温下与氧化铝质原料反应生成二次莫来石，促进刚玉质材料的烧结及力学性能的进一步优化改善。所述二氧化硅质原料是二氧化硅原料或含二氧化硅的原料。所述二氧化硅质原料中二氧化硅的质量百分含量为28～99％，颗粒粒径≦0.08mm。
对于二氧化硅原料，其化学组成中SiO 2的重量百分含量在92％以上。所述二氧化硅原料为α-石英、β-石英、α-鳞石英、β-鳞石英、α-方石英、β-方石英、脉石英、砂岩、石英岩、燧石、胶结硅石、河砂、海砂、白炭黑、硅藻土、硅微粉中的一种或多种。
所述二氧化硅质原料还可为高温下能够分解生成二氧化硅的含二氧化硅的原料，其化学组成中SiO 2的重量百分含量在18％以上；优选为28％以上。所述含二氧化硅的原料为稻壳、碳化稻壳、稻壳灰、正硅酸甲酯、正硅酸乙酯、甲基三甲氧基硅烷中的一种或多种。
分散剂、悬浮剂、烧结助剂、红外遮光剂形成添加剂，发泡剂、无机固化剂、有机固化剂、泡孔调节剂形成发泡料。以下对各组分的作用和选择进行详细介绍。
以基础料的质量为基准，分散剂的添加质量不大于1％，悬浮剂的添加质量均不大于10％。
分散剂的加入有效提高了陶瓷粉体及其它各添加剂在料浆中的分散均匀性，避免了其在浆体中的团聚。优选的，所述分散剂为聚羧酸类分散剂、聚羧酸醚分散剂、磺化蜜胺缩聚物、萘系分散剂、木质素磺酸盐类分散剂、氨基磺酸系分散剂、乙二胺四乙酸钠、三聚氰胺甲醛缩聚物、多聚磷酸钠、聚丙烯酸钠、柠檬酸钠、腐殖酸钠、磷酸钠、碳酸钠中的一种或多种。所述聚羧酸分散剂为甲基丙烯酸酯型聚羧酸分散剂、烯丙基醚型聚羧酸分散剂、酰胺/酰亚胺型聚羧酸分散剂、聚酰胺/聚乙烯乙二醇型聚羧酸分散剂中的至少一种。所述木质素磺酸盐分散剂为木质素磺酸钙、木质素磺酸钠、木质素磺酸钾中的至少一种。
在基础料含有较多瘠性原料时，料浆的悬浮性能较差，可引入悬浮剂来有效提高陶瓷料浆的悬浮稳定性，防止沉淀分层。所述悬浮剂为膨润土、海泡石、凹凸棒、聚合氯化铝、聚合硫酸铝、壳聚糖、黄原胶、阿拉伯胶、韦兰胶、琼脂、聚乙二醇、聚乙烯醇、聚丙烯酰胺、聚丙烯酸胺、聚乙烯吡咯烷酮、干酪素、十六醇、蔗糖、糊精、微晶纤维素、纤维素纤维、纤维素纳米纤维、纤维素纳米晶中的一种或多种。优选的，所述悬浮剂为膨润土、海泡石、凹凸棒、聚合氯化铝、壳聚糖、韦兰胶、聚乙烯吡咯烷酮、干酪素、微晶纤维素、纤维素纤维、纤维素纳米晶、可溶性淀粉中的至少一种。
其中，当选用膨润土、海泡石、凹凸棒等无机矿物原料时，发现其在料浆中可快速水 解，并分解成带电荷的离子，此离子在基础料颗粒的表面形成了双电层结构，基础料颗粒靠静电斥力在料浆中产生了悬浮效果，但其用量相对较多，一般的，用量≦10％；而当其选用聚合氯化铝、聚合硫酸铝、壳聚糖、韦兰胶、琼脂、聚乙二醇、聚乙烯醇、聚丙烯酰胺、聚丙烯酸胺、聚乙烯吡咯烷酮、干酪素、十六醇、蔗糖、糊精、微晶纤维素、纤维素纤维、纤维素纳米晶、可溶性淀粉等有机悬浮剂时，发现加入很少的量便可以发挥较好的效果，其在料浆中可通过空间位阻效应或静电位阻效应使料浆产生了悬浮效果，因此其加入量可以相对较少，一般的，其用量≦3％，优选≦1％，更优选≦0.5％。
氧化铝的熔点高达2054℃，烧成温度较高，难以烧结，因此引入适量的烧结助剂可有效改善材料的烧结，促进烧结反应的进行及有益晶体(如刚玉、莫来石等)的生长发育，有利材料性能的改善。所述烧结助剂为ZnO、Fe 2O 3、V 2O 5、SiF 4、AlF 3、AlF 3·3H 2O、MnO 2、CuO、CuSO 4、CaO、MgO、SrO、BaO、WO 3、Er 2O 3、Cr 2O 3、La 2O 3、YbO、Y 2O 3、CeO 2中的一种或多种。所述烧结助剂的粒径为5μm以下，优选4μm以下，更优选3μm以下，特别优选1μm以下。
隔热耐火材料的隔热机理是由于其内部存在大量气孔，而气孔中空气的导热系数远小于气孔壁的导热系数，因此整个隔热材料对热量的传递速率变慢，具备了隔热性能。材料的导热机制主要由热传导、对流传热和辐射传热三部分组成，在本发明中，由于所制刚玉质微纳孔绝隔热耐火材料中气孔的孔径较小，且大部分气孔为封闭型结构，气体流通困难，因此对流传热可基本忽略，又因刚玉质微纳孔绝隔热耐火材料将主要用于高温环境，因此材料的传热机制除存在热传导外，还包括辐射传热。为进一步有效减少辐射传热，本发明引入了红外遮光剂，以增大对红外辐射的有效反射和吸收，弱化其穿透性，降低热导率。所述红外遮光剂为金红石、TiO 2、TiC、K 4TiO 4、K 2Ti 6O 13、Sb 2O 3、Sb 2O 5、ZrO 2、CoO、Co(NO 3) 2、CoCl 2、NiCl 2、Ni(NO 3) 2、ZrSiO 4、Fe 3O 4、B 4C、SiC中的一种或多种。所述红外遮光剂的平均粒径为5μm以下，优选4μm以下，更优选3μm以下、特别优选1μm以下。
优选的，所述发泡剂为表面活性剂和或蛋白质型发泡剂。所述发泡剂的发泡倍数为8～60倍。所述表面活性剂为阴离子型表面活性剂、阳离子型表面活性剂、非离子型表面活性剂、两性表面活性剂、Gemini型表面活性剂、Bola型表面活性剂、Dendrimer型表面活性剂中的一种或多种。
进一步的，所述阴离子型表面活性剂为碳链中碳数为8～20的磺酸盐类表面活性剂或碳链中碳数为8～18的硫酸盐类表面活性剂；所述阳离子型表面活性剂为酰胺酯基季铵盐、双长链酯基季铵盐和硬脂酸三乙醇胺酯季铵盐；所述非离子型表面活性剂为聚氧乙烯型(如高 碳脂肪醇聚氧乙烯醚、脂肪醇聚氧乙烯酯)、脂肪醇酰胺型和多元醇型；所述两性表面活性剂为氨基酸型或甜菜碱型两性表面活性剂；所述Gemini型表面活性剂为季铵盐型或羧酸盐型或硫酸盐型Gemini表面活性剂；所述Bola型面活性剂为半环型、单链型或双链型Bola表面活性剂；所述Dendrimer型表面活性剂为聚醚、聚酯、聚酰胺、聚芳烃、聚有机硅型Dendrimer表面活性剂。
所述蛋白质型发泡剂为动物蛋白发泡剂或植物蛋白发泡剂或污泥蛋白发泡剂。
优选地，发泡剂选自季铵型Gemini表面活性剂、半环型Bola表面活性剂、聚醚型Dendrimer表面活性剂、羧酸盐型Gemini表面活性剂、硫酸盐型Gemini表面活性剂、聚酰胺型Dendrimer表面活性剂、植物蛋白发泡剂、污泥蛋白发泡剂、动物蛋白发泡剂、十二醇聚氧乙烯醚羧酸钠、月桂酸酰胺丙基磺基甜菜碱、ɑ-烯烃磺酸钠、十二烷基二甲基甜菜碱、脂肪醇聚氧乙烯醚羧酸钠、十二烷基苯磺酸钠中的一种或两种以上组合。
优选的，所述无机固化剂的质量为基础料质量的0.1～15％，所述有机固化剂的质量为基础料质量的0.1～1％。更进一步优选的，所述有机固化剂的质量为基础料质量的0.1～0.5％。特别优选的，有机固化剂的质量为基础料质量的0.1～0.2％。
所述无机固化剂为氧化铝溶胶、硅铝溶胶、氧化硅溶胶、氧化铝凝胶、硅铝凝胶、氧化硅凝胶、Al 2O 3微粉、SiO 2微粉、硅酸二钙、二铝酸钙、硅酸三钙、铝酸三钙、铝酸一钙、磷酸铝、七铝酸十二钙、水玻璃、铁铝酸四钙、软质结合黏土中的一种或多种。水玻璃中包含硅酸钠、或硅酸钾或二者的组合。所述氧化铝溶胶的化学组成中Al 2O 3的质量百分含量≧20％；氧化硅溶胶的化学组成中，SiO 2的质量百分含量为25～40％；硅铝溶胶的化学组成中Al 2O 3的质量百分含量≧30％、SiO 2的质量百分含量≧20％。这些无机固化剂水化后可渗透至各陶瓷粉体颗粒的间隙，对粉体颗粒进行机械嵌固，形成良好的刚性骨架结构，使坯体机械强度增加。优选的，所述无机固化剂为氧化铝凝胶、氧化硅凝胶、SiO 2微粉、氧化铝凝胶、硅铝凝胶中的一种或多种。所述无机固化剂的平均粒径≦5μm。
所述有机固化剂选自水溶性聚合物树脂、低甲氧基果胶、鹿角菜胶、卡拉胶、羟丙基瓜尔胶、刺槐树胶、刺槐豆胶、结冷胶、可得然胶、海藻酸盐、魔芋胶中的一种或两种以上组合；所述水溶性聚合物树脂选自醋酸乙烯酯与乙烯共聚物、醋酸乙烯酯均聚物、丙烯酸酯聚合物、乙烯与乙酸乙烯酯共聚物、乙烯与氯乙烯共聚物、醋酸乙烯酯与叔碳酸乙烯酯共聚物、丙烯酸酯与苯乙烯共聚物、醋酸乙烯酯与高级脂肪酸乙烯酯共聚物、醋酸乙烯酯与乙烯和氯乙烯共聚物、醋酸乙烯酯与乙烯和丙烯酸酯共聚物、异丁烯与马来酸酐共聚物、乙烯与氯乙烯和月桂酸乙烯酯共聚物、醋酸乙烯酯与乙烯和高级脂肪酸共聚物、醋酸乙烯酯与丙烯 酸酯及高级脂肪酸乙烯酯共聚物、醋酸乙烯酯与乙烯和月桂酸乙烯酯共聚物、醋酸乙烯与叔碳酸乙烯酯和丙烯酸酯共聚物中的一种或两种以上组合。少量的有机固化材料分散至陶瓷粉体颗粒的间隙，其水化后可在陶瓷粉体颗粒表面形成一连续的高分子薄膜，此薄膜在粉体颗粒间构成柔韧性连接，再通过有机分子的分子间作用力使陶瓷粉体颗粒间的内聚力提高，使生坯强度增加，避免了坯体在搬运过程中产生的碰损破坏，使成品率大为提高，生产成本显著降低。优选的，所述有机固化剂为醋酸乙烯酯与乙烯和高级脂肪酸共聚物、魔芋胶、乙烯与氯乙烯和月桂酸共聚物、乙烯与乙酸乙烯酯共聚物、海藻酸钠中的一种或多种。上述无机和有机固化剂均为工业纯。
一般的，由于无机固化剂在较高温度下会产生液相，使制品软化温度降低，因此随着烧成和使用温度的逐渐升高，应逐渐减少无机固化剂的用量，并相应的适量增多有机固化剂的用量，以增强坯体的强度。
本发明所用泡孔调节剂能够有效调节料浆中气泡的尺寸大小、圆形度、均匀度和闭合性等，从而有效调节烧后制品中的气孔结构。优选的，所述泡孔调节剂选自纤维素醚、淀粉醚、木质纤维素、皂素中的一种或两种以上组合。更优选的，所述纤维素醚选自甲基纤维素醚、水溶性纤维素醚、羧甲基纤维素醚、羧甲基甲基纤维素醚、羧甲基乙基纤维素醚、羧甲基羟甲基纤维素醚、羧甲基羟乙基纤维素醚、羧甲基羟丙基纤维素醚、羧甲基羟丁基纤维素醚、羟甲基纤维素醚、羟乙基纤维素醚、羟乙基甲基纤维素醚、羟乙基乙基纤维素醚、乙基纤维素醚、乙基甲基纤维素醚、丙基纤维素醚、羟丙基纤维素醚、羟丙基甲基纤维素醚、羟丙基乙基纤维素醚、羟丙基羟丁基纤维素醚、羟丁基甲基纤维素醚、磺酸乙基纤维素醚中的一种或两种以上组合。
本发明的刚玉质微纳孔绝隔热耐火材料的制备方法的具体技术方案为：
一种刚玉质微纳孔绝隔热耐火材料的制备方法，包括以下步骤：
(1)使用添加剂时，将基础料、添加剂在水中分散成悬浮料浆；不使用添加剂时，将基础料、在水中分散成悬浮料浆；
(2)将发泡剂、无机固化剂、有机固化剂、泡孔调节剂与悬浮料浆进行搅拌剪切发泡，制得泡沫浆料；
(3)将泡沫料浆注入模具中养护，脱模后得到坯体；坯体干燥后在1200～1800℃的温度下烧结。
制备轻质隔热材料的技术关键在于其内部孔隙的引入，在本发明的制备方法中，先将基础料、添加剂及水混合形成悬浮料浆，然后再与发泡剂、无机固化剂、有机固化剂、泡孔 调节剂组成的功能发泡成分混合并搅拌发泡，有利气泡保持完整性从而提高闭口型气孔的生成率；在固化过程中，泡沫浆料中的气泡转变为坯体中的球状气孔，此气孔又为后续烧制过程中有益晶体的生长发育提供了空间，使晶体发育完善，制品性能提高。同时，发明人在长期的研究过程中还偶然发现，由于本发明所制坯体中的孔洞为微小的微米或纳米级球状的空隙，此孔洞的凹面具有极大的曲率半径，使得刚玉、莫来石等有益晶体在此孔洞中的成核和生长驱动力进一步增强，因此晶体的生长尺寸更大，制品的物理性能更优。
与现有技术相比，本发明的制备方法绿色环保，无污染，工艺过程简单易控，且坯体的脱模和干燥周期较短，坯体的强度高，成品率高，非常适合大规模、机械化、现代化和智能化的生产作业，利于推广应用。
本发明的刚玉质微纳孔绝隔热耐火材料外观呈白色、淡黄色或黄色。
本发明的制备方法中，优选的，步骤(1)中所述水的用量占基础料重量的20～200％，优选50～180％，优选的，水的用量为基础料质量的50～150％，进一步优选的，水的用量为基础料质量的100～120％。当加水量较多时，搅拌过程中绝大部分水可转变成为料浆中气泡的液膜，而少量没有成为气泡液膜的则以液态水的形式存在，待坯体干燥并烧成后可在试样中留下微小的毛细孔隙。也就是说，添加的水最终转变成了制品中的微纳米尺寸的气孔，因此，此工艺技术制备绝隔热耐火材料的本质就是利用水和空气在耐火材料中产生微纳米尺寸的气孔结构，所以在一定程度上来说，可以相应的可根据用水量的多少来调控制品中体积密度及气孔率、热导率和力学强度等的大小。该步骤中，如使用了分散剂、悬浮剂、矿化剂、红外遮光剂等成分，则将上述组分与基础料分散成悬浮料浆。如没有使用分散剂、悬浮剂、矿化剂、红外遮光剂等成分，或仅使用了其中一种或几种，则将相应组分进行分散即可。
步骤(1)中，为了形成细腻均匀稳定的悬浮料浆，应控制料浆中固体颗粒的平均粒径不高于1mm，优选不高于74μm，或不高于44μm，或不高于30μm。为达到上述混合效果，混合可采用机械搅拌、球磨和、超声等手段之一或者两种以上手段的组合。如果原料的粒度较细，且容易分散成悬浮料浆，则通过机械搅拌方式即可。优选的，所述分散包括进行球磨和超声分散。具体为：分散剂、悬浮剂、烧结助剂以及红外遮光剂混合得添加剂，然后将添加剂与基础料、水球磨混合得混合料，然后超声。其中基础料中铝硅质原料、氧化铝质原料以及二氧化硅质原料同样优选预先混合均匀。
分散剂、悬浮剂、烧结助剂以及红外遮光剂混合以及发泡物混合所用搅拌机采用现有的搅拌机如三维混合机、V型混合机、双锥混合机、行星式搅拌机、强制式搅拌机、非重力搅拌机即可，混合均匀程度≧95％。同样，基础料中的三种原料在使用时优选可用同样的方 法预先混合均匀。
优选的，所述球磨机中研磨球的材质为氧化锆质、氧化铝质、莫来石质、锆刚玉质、碳化硅、氮化硅或碳化钨质或几种材质的混合。进一步优选的，所述研磨球的尺寸规格为大球
Figure PCTCN2021144043-appb-000001
中球
Figure PCTCN2021144043-appb-000002
小球
Figure PCTCN2021144043-appb-000003
大球、中球、小球按(1～1.5)：(1～3)：(6～10)重量比组合，进一步优选的，大球、中球、小球按(1～1.5)：(1～2)：(6～8)重量比组合。
优选的，所述球磨混合的料/球重量比为1：(0.8～1.5)，球磨时间为0.5～12h。通过球磨，可使混合料中固体颗粒平均粒径不高于74μm。优选的，固体颗粒平均粒径不高于50μm；进一步优选的，固体颗粒平均粒径不高于44μm；更特别优选的，固体颗粒平均粒径不高于30μm。这些经球磨后的陶瓷粉体颗粒具有较高表面活性，后经表面活性剂分子(发泡剂)修饰后具有优异的疏水特性，在机械搅拌作用下，会不可逆的吸附于气泡液膜上的气-液界面，高能态的气-液界面被低能态的液-固和气-固界面代替，使体系总自由能降低，泡沫稳定性提高，同时部分粉体颗粒在气泡间的Plateau通道累积，有效阻止了液膜排液，抵制了泡沫的破裂、排液、歧化、奥斯瓦尔德熟化等不稳定因素，从而获得了非常稳定的泡沫陶瓷料浆料。
超声进一步并且快速提高了悬浮料浆中各组分的混合分散均匀性，超声的功率为500～2000W，时间为4～15min。
步骤(2)泡沫料浆的制备过程中，视原料品种，如果发泡剂、无机固化剂、有机固化剂、泡孔调节剂均为干的固态原料，则先将干原料进行干混制得发泡组合物，然后再将发泡组合物加入悬浮料浆中，再搅拌发泡。如果发泡剂、无机固化剂、有机固化剂、泡孔调节剂中的部分品种为液体原料，则优选可先将干的原料进行干混，然后再将干混物和液体状原料加入悬浮料浆中，再进行搅拌发泡。发泡剂也可先由发泡机预制备出泡沫，然后再与无机固化剂、有机固化剂和泡孔调节剂所组成的混合物加入悬浮料浆，再进行搅拌剪切发泡。
步骤(2)中所述搅拌发泡采用立式搅拌机的搅拌桨叶高速剪切混合发泡，搅拌桨外缘的线速度为20～200m/s，搅拌剪切的时间为1～30min。进一步优选的，线速度为50～200m/s；进一步优选线速度为80～200m/s；进一步优选线速度为100～200m/s；更进一步优选线速度为150～200m/s；更特别进一步优选线速度为180～200m/s。搅拌桨对浆体快速搅拌、混合并引入大量空气，在发泡剂作用下产生大量泡沫，使浆体体积快速膨胀，且随搅拌时间的延长，浆体中的大气泡逐渐被剪切分散成尺寸为0.01～200μm间的微小气泡，陶瓷料浆变成均匀的泡沫陶瓷料浆。一般的，搅拌桨外缘的线速度愈大，则形成的气泡尺寸愈小、且愈均匀并稳定、越有利在所得刚玉质绝隔热耐火材料中形成微纳米级的孔隙，较小尺寸的气孔可有效抑制自由气体分子的传热，使导热系数进一步降低，同时可确保力学性能满足使用需求且隔热耐火 性能好。
步骤(3)中将泡沫料浆浇注到模具中，所用的模具选用下列这些中的一种或多种，但不限于：为金属模具、塑料模具、树脂模具、橡胶模具、泡沫模具、石膏模具、玻璃模具、玻璃钢模具或木质或竹质或竹胶质模具，和上述几种材质复合的模具，模具形状可根据设计要求改变，并适于制备异形制品。
步骤(3)中，养护为在空气温度为1～35℃、湿度为50～99.9％的环境中养护0.2～12h，使浆体快速固化定型；养护优选在恒温恒湿的环境中进行。养护环境中的空气温度为1～35℃，优选5～30℃，更优选10～30℃，更优选20～30℃，特别优选25～30℃，更特别优选27～30℃；空气湿度为50～99.9％，优选60～99％，更优选70～97％，更优选80～95％，特别优选85～93％，更特别优选88～92％。在养护过程中，坯体中的无机和有机固化剂等会加快发生水化反应并固化凝结，使得坯体的强度迅速增加，实现快速脱模。
研究过程中发现由于坯体的脱模时间非常短，大大加快了模具的周转速率，并且还使整体的制备工艺加快运行，生产效率大为上升，这在以往是很难实现的。可以理解的是，坯体养护后需要先脱模，然后再进行干燥。由于坯体养护后的强度迅速增加，因此步骤(3)中可实现对坯体的快速脱水干燥，所述干燥任选常压干燥、超临界干燥、冷冻干燥、真空干燥、红外干燥、微波干燥，或它们中任何两种或多种的组合。最终干燥好的坯体中含水率≦3wt％。
优选的，采用常压干燥时，干燥热源可为电源加热或热风，干燥温度为30～110℃，干燥时间为12～48h。优选的，其干燥制度为：先以1～5℃/min升温至30℃，在30℃保温5～10h，再以1～5℃/min升温至50℃，在50℃保温2～5h，再以1～5℃/min升温至70℃，在70℃保温2～5h，再以1～5℃/min升温至90℃，在90℃保温2～5h，再以1～5℃/min升温至110℃，在110℃保温12～24h；
其中，采用超临界干燥技术时，超临界干燥的介质为二氧化碳，干燥温度为31～45℃，反应釜压力控制在7～10MP，干燥时间为0.5～3h；
其中，采用冷冻干燥法时，冷冻干燥机的干燥温度为-180℃～-30℃，干燥时间为3～6h；
其中，采用真空干燥法时，真空干燥箱的干燥温度为35～50℃，真空压力为130～0.1Pa，干燥时间为3～8h；
其中，采用红外干燥法时，红外线的波长取2.5～100μm，优选2.5～50μm，优选2.5～30μm，更优选2.5～15μm，更特别优选2.5～8μm，干燥时间为0.5～5h；
其中，采用微波干燥法时，微波频率选取300～300000MHz，优选300～10000MHz，优选300～3000MHz，更优选300～1000MHz，更特别优选600～1000MHz，干燥时间为0.3～3h。
坯体快速干燥脱水后，形成了具有较高强度的多孔结构，发现它的重量较干燥前和传统的添加造孔剂法所制的坯体的重量大为减轻，强度大为增加，因此大幅度减轻了工人在运输坯体和装窑作业时的劳动强度，并且并非常适合机械化的操作，提高了工作效率，也提高了成品率。
以上过程中，有机、无机固化剂共同作用使得泡沫浆料在固化并干燥后所得坯体的强度大大提高，其耐压强度≧0.7MPa，可大大减少或避免了坯体在运输和装窑过程中因磕碰造成的破坏，使成品率大为提高，成品率≧90％，优选≧95％，更优选≧98％，更特别优选≧99％，生产成本显著降低，并可对坯体进行有效的切磨、打孔等机械加工处理。
所述烧制选择在高温隧道窑、梭式窑、电阻窑炉或微波窑炉中烧成。
进一步优选的，烧结制度为：从室温以1～5℃/min升温至500℃，再以5～30℃/min升温至1000℃，保温0.5～1.5h，再以1～30℃/min升温至1200～1800℃，保温1～10h，后以10～20℃/min降温至1100℃，并在1100℃保温0.5～1.5h，再以5～30℃/min降温至500℃，于500℃保温0.5h，最后以1～10℃/min降温至50～80℃，即得刚玉质微纳孔绝隔热耐火材料，此材料可根据实际要求进行打孔、切割或磨削加工成所需形状。
附图说明
图1为本发明实施例1的刚玉质微纳孔绝隔热耐火材料的宏观照片；
图2为本发明实施例1的刚玉质微纳孔绝隔热耐火材料的显微结构照片；
图3为本发明实施例1的刚玉质微纳孔绝隔热耐火材料的气孔内部的显微结构照片；
图4为本发明实施例1的刚玉质微纳孔绝隔热耐火材料的EDS图(对应图3中点1)；
图5为本发明实施例1的刚玉质微纳孔绝隔热耐火材料的EDS图(对应图3中点2)；
图6为本发明实施例12的刚玉质微纳孔绝隔热耐火材料气孔结构的显微结构照片；
图7为本发明实施例12的刚玉质微纳孔绝隔热耐火材料气孔壁的显微结构照片；
图8为本发明实施例6的刚玉质微纳孔绝隔热耐火材料的孔径分布图。
具体实施方式
下面结合具体实施例具体说明本发明的具体实施过程。以下实施例中所用各原料均为市售常规产品。如无特殊说明，相关原料规格说明如下，如有特别说明，原料规格以特别说明为准。
工业Al(OH) 3，化学组成中Al 2O 3的质量百分含量≧65％，粒径≦0.08mm。水铝石，化学组成中Al 2O 3的质量百分含量≧70％，粒径≦0.08mm。工业氧化铝、β-Al 2O 3、γ-Al 2O 3、δ-Al 2O 3、χ-Al 2O 3、α-Al 2O 3、κ-Al 2O 3、θ-Al 2O 3、η-Al 2O 3中，Al 2O 3的质量百分含量≧98％， 粒径≦0.08mm。烧结刚玉、电熔刚玉中，Al 2O 3质量百分含量≧98％，粒径≦0.08mm。勃姆石，化学组成中Al 2O 3质量百分含量≧70％，粒径≦0.08mm。钾长石，化学组成中K 2O的质量百分含量为9～11％，Al 2O 3的质量百分含量为18～20％，SiO 2的质量百分含量为64～66％，粒径≦0.08mm。煤矸石，化学组成中Al 2O 3的质量百分含量为20～25％，SiO 2的质量百分含量为66～75％，粒径为0.6～1mm。钠长石，化学组成中Na 2O的质量百分含量为10～12％，Al 2O 3的质量百分含量为19～22％，SiO 2的质量百分含量为66～69％，粒径≦0.08mm。高岭土，化学组成中Al 2O 3的质量百分含量32～35％，SiO 2的质量百分含量为61～64％，粒径≦0.08mm。蓝晶石，化学组成中Al 2O 3的质量百分含量为52～55％，SiO 2的质量百分含量为44～46％，粒径为0.6～1mm。硅微粉，化学组成中SiO 2的质量百分含量≧92％，粒径≦5μm。
一、本发明的刚玉质微纳孔绝隔热耐火材料的具体实施例
实施例1
本实施例的刚玉质微纳孔绝隔热耐火材料的宏观和显微结构照片如图1、图2所示，从图中可以看出，材料外观呈白色，内部存在大量微小气孔。图3为材料气孔内部的显微结构图，从图中可以看出，材料中存在大量片状和针状晶体，通过对其进行EDS分析(分别针对点1和点2)可知，该片状和针状晶体分别为刚玉相和莫来石相，如图4、图5所示。
本实施例的刚玉质微纳孔绝隔热耐火材料的化学组成中Al 2O 3的质量百分含量为75～77％，其由基础料及以下占基础料总重量百分比的原料制成：悬浮剂10％，烧结助剂10％，红外遮光剂10％，发泡剂0.4％，无机固化剂10％，有机固化剂1.5％，泡孔调节剂0.3％。
所用基础料由以下质量百分比的组分组成：80％的氧化铝质原料，20％的二氧化硅质原料。其中，氧化铝质原料由工业Al(OH) 3、水铝石、γ-Al 2O 3按照2：1：5的质量比混合而成；二氧化硅质原料由硅藻土(其化学组成中SiO 2的质量百分含量≧85％，粒径≦0.08mm)、硅微粉按照1：1的质量比混合而成。
悬浮剂为由膨润土(Al 2O 3的质量百分含量为22～23％，SiO 2的质量百分含量为68～75％，粒径≦0.045mm)与韦兰胶按9：1的质量比组成的混合物；烧结助剂为由AlF 3·3H 2O、ZnO、V 2O 5、La 2O 3、BaO按1：1：1：1：1的质量比组成的混合物；红外遮光剂为由TiC、K 4TiO 4、B 4C、Sb 2O 3按1：1：2：1的质量比组成的混合物。
发泡剂为由季铵型Gemini表面活性剂(恒美科技有限公司，发泡倍数为45)与半环型Bola表面活性剂(恒美科技有限公司，发泡倍数为50)按照1：1的质量比组成的混合物；无机固化剂为由氧化铝凝胶、Al 2O 3微粉按2：3的质量比组成的混合物；有机固化剂为由醋酸乙烯酯与乙烯和高级脂肪酸共聚物(德国瓦克化学公司，
Figure PCTCN2021144043-appb-000004
)、醋酸乙烯 酯与乙烯共聚物(德国瓦克化学公司，
Figure PCTCN2021144043-appb-000005
)按2：1的质量比组成的混合物；泡孔调节剂为由羟乙基乙基纤维素醚(荷兰阿克苏诺贝尔公司)、皂素(恒美科技有限公司)按2：1的质量比组成的混合物。
其中，AlF 3·3H 2O、ZnO、V 2O 5、La 2O 3、BaO、TiC、K 4TiO 4、B 4C、Sb 2O 3、氧化铝凝胶、Al 2O 3微粉均为工业纯，粒径≦5μm。
实施例2
本实施例的刚玉质微纳孔绝隔热耐火材料，主晶相为片状的刚玉相和针状的莫来石相，材料的化学组成中Al 2O 3的质量百分含量为78～79％，由基础料及以下占基础料总重量百分比的原料制成：分散剂0.05％，悬浮剂5.3％，烧结助剂9％，红外遮光剂6％，发泡剂10％，无机固化剂20％，有机固化剂0.1％，泡孔调节剂0.01％。
所用基础料由以下质量百分比的组分组成：80％的氧化铝质原料，5％的铝硅质原料，15％的二氧化硅质原料。其中，氧化铝质原料由工业Al(OH) 3、烧结刚玉(其化学组成中Al 2O 3的质量百分含量为97％，粒径≦5μm)按照3：5的质量比混合而成；铝硅质原料为钾长石；二氧化硅质原料为硅微粉。
分散剂为酰胺型聚羧酸分散剂(恒美科技有限公司)与聚羧酸醚分散剂按3：2的质量比组成；悬浮剂由膨润土(Al 2O 3的质量百分含量为22～23％，SiO 2的质量百分含量为68～75％，粒径≦0.045mm)与纤维素纤维(美国陶氏化学公司)按照50：3的质量比组成；烧结助剂为由MnO 2、ZnO与V 2O 5按照1：1：1的质量比组成的混合物；红外遮光剂为由TiC、K 4TiO 4、Sb 2O 3按照1：1：1的质量比组成的混合物。
发泡剂为由聚醚型Dendrimer表面活性剂(恒美科技有限公司，发泡倍数为45)、植物蛋白发泡剂(山东鑫茂化工公司，发泡倍数为9)与污泥蛋白发泡剂(恒美科技公司，发泡倍数为8)按照0.1：2.9：7的质量比组成的混合物；无机固化剂为氧化铝溶胶(Al 2O 3含量≧20％)、氧化硅溶胶(SiO 2含量≧30％)按3：2的质量比组成的混合物；有机固化剂为由可得然胶(恒美科技有限公司)、结冷胶(江苏古贝生物科技有限公司)按1：1的质量比组成的混合物；泡孔调节剂为由羧甲基乙基纤维素醚(美国亚士兰公司)、羧甲基羟甲基纤维素醚、羧甲基羟乙基纤维素醚(美国陶氏化学公司)按照5：3：2的质量比混合而成的混合物。
其中，MnO 2、ZnO、V 2O 5、TiC、K 4TiO 4、Sb 2O 3、氧化硅凝胶均为工业纯，粒径≦5μm。
实施例3
本实施例的刚玉质微纳孔绝隔热耐火材料，主晶相为片状的刚玉相和针状的莫来石相， 材料的化学组成中Al 2O 3的质量百分含量为81～83％，由基础料及以下占基础料总重量百分比的原料制成：分散剂0.1％，悬浮剂4％、烧结助剂8％，红外遮光剂6％，发泡剂5.1％，无机固化剂15％，有机固化剂0.5％，泡孔调节剂0.06％。
所用基础料由以下质量百分比的组分组成：85％的氧化铝质原料，15％的二氧化硅质原料。其中，氧化铝质原料由工业Al(OH) 3、勃姆石、正丁醇铝、异丙醇铝、仲丁醇铝按照30：10：1：1：0.5的质量比组成；二氧化硅质原料为硅微粉、正硅酸甲酯、正硅酸乙酯、甲基三甲氧基硅烷按照2：1：1：1的质量比混合而成。
分散剂为由酰亚胺型聚羧酸分散剂(恒美科技有限公司)与萘系分散剂按1：1的质量比组成的混合物；悬浮剂为由海泡石、壳聚糖(美国陶氏化学)按3：1的质量比组成的混合物；烧结助剂为由MnO 2、ZnO、V 2O 5按3：3：2的质量比组成的混合物；红外遮光剂为K 2Ti 6O 13、K 4TiO 4、Ni(NO 3) 2按1：1：1的质量比组成的混合物。
发泡剂为羧酸盐型Gemini表面活性剂(恒美科技，发泡倍数为60)、动物蛋白发泡剂(恒美科技，发泡倍数为11)按1：50的质量比组成的混合物；无机固化剂为硅铝溶胶(Al 2O 3含量≧30％、SiO 2含量≧20％)；有机固化剂为由可得然胶(恒美科技有限公司)、结冷胶(江苏古贝生物科技公司)按3：2的质量比组成的混合物；泡孔调节剂为由磺酸乙基纤维素醚、甲基纤维素醚(美国陶氏化学公司)按2：1的质量比组成的混合物。
其中，MnO 2、ZnO、V 2O 5、K 2Ti 6O 13、K 4TiO 4、Ni(NO 3) 2均为工业纯，粒径为≦5μm。
实施例4
本实施例的刚玉质微纳孔绝隔热耐火材料，主晶相为片状的刚玉相和柱状的莫来石相，材料的化学组成中Al 2O 3的质量百分含量为84～85％，由基础料及以下占基础料总重量百分比的原料制成：分散剂0.15％，悬浮剂3％、烧结助剂6％，红外遮光剂4％，发泡剂0.2％，无机固化剂12％，有机固化剂1％，泡孔调节剂0.2％。
所用基础料由以下质量百分比的组分组成：85％的氧化铝质原料，15％的铝硅质原料。其中，氧化铝质原料由工业Al(OH) 3、α-Al 2O 3(其化学组成中Al 2O 3的质量百分含量均≧99％，粒径≦0.08mm)按照8：9的质量比组成；铝硅质原料由煤矸石、钠长石、高岭土按照1：1：1的质量比混合而成；
分散剂为磺化蜜胺缩聚物；悬浮剂为由凹凸棒、聚合氯化铝按2：1的质量比组成的混合物；烧结助剂为由Y 2O 3、MgO、V 2O 5按质量比1：1：1组成的混合物；红外遮光剂为由金红石、ZrSiO 4按质量比1：1组成的混合物。
发泡剂为由羧酸盐型Gemini表面活性剂(恒美科技，发泡倍数为60)、半环型Bola 表面活性剂(恒美科技，发泡倍数为50)按质量比1：1形成的混合物；无机固化剂为氧化铝溶胶(Al 2O 3含量≧30％)；有机固化剂为由刺槐豆胶、刺槐树胶(恒美科技有限公司)按质量比1：1形成的混合物；泡孔调节剂为羧甲基乙基纤维素醚(美国亚士兰公司)、羟乙基乙基纤维素醚(荷兰阿克苏诺贝尔公司)按质量比1：1组成的混合物。
其中，Y 2O 3、MgO、V 2O 5、金红石、ZrSiO 4均为工业纯，粒径为≦5μm。
实施例5
本实施例的刚玉质微纳孔绝隔热耐火材料，主晶相为颗粒状的刚玉相和短柱状的莫来石相，材料的化学组成中Al 2O 3的质量百分含量为86～88％，由基础料及以下占基础料总重量百分比的原料制成：分散剂0.2％，悬浮剂2％，烧结助剂5％，发泡剂0.44％，无机固化剂5％，有机固化剂1％，泡孔调节剂0.4％。
所用基础料由以下质量百分比的组分组成：85％的氧化铝质原料，15％的铝硅质原料。其中，氧化铝质原料为由工业氧化铝、β-Al 2O 3、γ-Al 2O 3、δ-Al 2O 3、χ-Al 2O 3按照6：4：3：2：2的质量比组成；铝硅质原料由蓝晶石、高岭土、钡长石(其化学组成中BaO的质量百分含量为16～18％，Al 2O 3的质量百分含量为25～28％，SiO 2的质量百分含量为54～56％，粒径≦0.08mm)按照1：1：1的质量比组成；
分散剂为由聚酰胺型聚羧酸分散剂(恒美科技有限公司)与聚丙烯酸钠按2：3的质量比组成的混合物；悬浮剂为由聚乙烯吡咯烷酮与干酪素(美国陶氏化学)按照1：1的质量比组成的混合物；烧结助剂为由MnO 2、SiF 4与Cr 2O 3按照2：2：1的质量比组成的混合物。
发泡剂为由羧酸盐型Gemini表面活性剂(恒美科技，发泡倍数为60)与十二醇聚氧乙烯醚羧酸钠(发泡倍数为9)按照1：3的质量比组成的混合物。无机固化剂为由氧化硅凝胶、七铝酸十二钙、铁铝酸四钙、氧化铝凝胶按照1：1：1：2的质量比组成的混合物；有机固化剂为乙烯与乙酸乙烯酯共聚物(德国瓦克化学公司，
Figure PCTCN2021144043-appb-000006
)、可得然胶(恒美科技有限公司)、结冷胶(江苏古贝生物科技有限公司)按照2：2：1的质量比组成的混合物；泡孔调节剂为由羧甲基羟丁基纤维素醚、羟丙基羟丁基纤维素醚(美国陶氏化学公司)按照1：1的质量比组成的混合物。
其中，MnO 2、SiF 4、Cr 2O 3、七铝酸十二钙、铁铝酸四钙均为工业纯，粒径≦5μm。
实施例6
本实施例的刚玉质微纳孔绝隔热耐火材料，主晶相为颗粒状的刚玉相和短柱状的莫来石相，材料的化学组成中Al 2O 3的质量百分含量为87～89％，由基础料及以下占基础料总重量百分比的原料制成：分散剂0.3％，悬浮剂1％，烧结助剂4％，红外遮光剂3％，发泡剂0.39％， 无机固化剂5％，有机固化剂1％，泡孔调节剂0.6％。
所用基础料由以下质量百分比的组分组成：85％的氧化铝质原料，15％的铝硅质原料。其中，氧化铝质原料为由α-Al 2O 3、κ-Al 2O 3、θ-Al 2O 3、η-Al 2O 3按照10：3：2：2的质量比组成；铝硅质原料由蓝晶石、瓷石(Na 2O的质量百分含量为4～5％，Al 2O 3的质量百分含量为18～20％，SiO 2的质量百分含量为74～77％，粒径≦0.08mm)、焦宝石(Al 2O 3的质量百分含量38～40％，SiO 2的质量百分含量为44～47％，粒径≦0.08mm)按照2：1：2的质量比组成；
分散剂为由氨基磺酸系分散剂与腐殖酸钠按2：1的质量比组成的混合物；悬浮剂为由纤维素纳米纤维、聚乙二醇与聚乙烯醇按照2：2：1的质量比组成的混合物；烧结助剂为由AlF 3·3H 2O、BaO与V 2O 5按照1：2：1的质量比组成的混合物；红外遮光剂为由Ni(NO 3) 2、Fe 3O 4按质量比2：1组成的混合物。
发泡剂为由羧酸盐型Gemini表面活性剂(恒美科技，发泡倍数为60)与月桂酸酰胺丙基磺基甜菜碱(发泡倍数为13)按照1：12的质量比组成的混合物。无机固化剂为硅铝凝胶(其化学组成中Al 2O 3含量40％、SiO 2含量60％)；有机固化剂为鹿角菜胶、魔芋胶(上海北连生物科技有限公司)、丙烯酸酯聚合物(美国国民淀粉公司，
Figure PCTCN2021144043-appb-000007
)、醋酸乙烯酯与乙烯和丙烯酸酯共聚物(德国瓦克化学公司，
Figure PCTCN2021144043-appb-000008
)、乙烯与氯乙烯共聚物(德国瓦克化学公司，
Figure PCTCN2021144043-appb-000009
)按照1：1：1：1：1的质量比组成的混合物；泡孔调节剂为由羟丙基羟丁基纤维素醚(美国陶氏化学公司)、木质纤维素(恒美科技有限公司)按照1：2的质量比组成的混合物。
其中，AlF 3·3H 2O、BaO、V 2O 5、Ni(NO 3) 2、Fe 3O 4与硅铝凝胶均为工业纯，粒径≦5μm。
实施例7
本实施例的刚玉质微纳孔绝隔热耐火材料，主晶相为颗粒状的刚玉相和短柱状的莫来石相，材料的化学组成中Al 2O 3的质量百分含量为88～89％，由基础料及以下占基础料总重量百分比的原料制成：分散剂0.4％，悬浮剂0.6％，烧结助剂3％，红外遮光剂3％，发泡剂0.32％，无机固化剂5％，有机固化剂1.2％，泡孔调节剂1％。
所用基础料由以下质量百分比的组分组成：10％的氧化铝质原料，90％的铝硅质原料。其中，氧化铝质原料为由α-Al 2O 3、烧结刚玉按照3：7的质量比组成；铝硅质原料为由高铝矾土(Al 2O 3质量百分含量为89～90％，SiO 2的质量百分含量为8～9％，粒径为0.6～1mm)、烧结莫来石(Al 2O 3质量百分含量为59～61％，SiO 2的质量百分含量为37～39％，粒径为0.6～1mm)按照17：1的质量比组成。
分散剂由聚羧酸醚分散剂(德国巴斯夫)与三聚氰胺甲醛缩聚物按照1：1的质量比 组成；悬浮剂由十六醇、蔗糖与糊精按1：1：1的质量比组成；烧结助剂由SrO、WO 3与Er 2O 3按照1：1：1的质量比组成；红外遮光剂由CoCl 2、Ni(NO 3) 2、Fe 3O 4按照3：2：1的质量比组成。
发泡剂为由季铵型Gemini型表面活性剂(恒美科技有限公司，发泡倍数为45)与ɑ-烯烃磺酸钠(发泡倍数为15)按照1：15的质量比组成的混合物。无机固化剂为由硅酸二钙与二铝酸钙按照2：3的质量比组成的混合物；有机固化剂为由醋酸乙烯酯与乙烯和高级脂肪酸共聚物(德国瓦克化学公司，
Figure PCTCN2021144043-appb-000010
)与醋酸乙烯酯与乙烯和月桂酸乙烯酯共聚物(德国瓦克化学公司，
Figure PCTCN2021144043-appb-000011
)按2：1的质量比组成的混合物；泡孔调节剂为由羟丙基乙基纤维素醚与丙基纤维素醚(美国亚士兰公司)按1：1的质量比组成的混合物。
其中，SrO、WO 3、Er 2O 3、CoCl 2、Ni(NO 3) 2、Fe 3O 4、硅酸二钙、二铝酸钙均为工业纯，粒径≦5μm。
实施例8
本实施例的刚玉质微纳孔绝隔热耐火材料，主晶相为颗粒状的刚玉相，材料的化学组成中Al 2O 3的质量百分含量为92～93％，由基础料及以下占基础料总重量百分比的原料制成：分散剂0.5％，悬浮剂0.4％，烧结助剂2％，红外遮光剂2％，发泡剂0.26％，无机固化剂4％，有机固化剂1.3％，泡孔调节剂0.7％。
所用基础料由以下质量百分比的组分组成：90％的氧化铝质原料，10％的铝硅质原料。其中，氧化铝质原料为由α-Al 2O 3、电熔刚玉按照2：7的质量比组成；铝硅质原料为木节土(其化学组成中Al 2O 3的质量百分含量32～35％，SiO 2的质量百分含量为64～66％，粒径≦0.08mm)。
分散剂为由磺化蜜胺类缩聚物(恒美科技有限公司)与柠檬酸钠按3：2的质量比组成的混合物；悬浮剂为由纤维素纳米晶与糊精按照3：1的质量比组成的混合物；烧结助剂为由Er 2O 3、CeO 2按照1：1的质量比组成的混合物；红外遮光剂为由K 4TiO 4、SiC按照1：1的质量比组成的混合物。
发泡剂为由季铵型Gemini表面活性剂(恒美科技有限公司，发泡倍数为45)与十二烷基二甲基甜菜碱表面活性剂(发泡倍数为17)按照1：12的质量比组成的混合物；无机固化剂为磷酸铝；有机固化剂为丙烯酸酯与苯乙烯共聚物(美国国民淀粉公司，
Figure PCTCN2021144043-appb-000012
)、丙烯酸酯聚合物(美国国民淀粉公司，
Figure PCTCN2021144043-appb-000013
)按照7：6的质量比组成的混合物；泡孔调节剂为由乙基纤维素醚(荷兰阿克苏诺贝尔公司)与羟甲基纤维素醚(美国陶氏化学 公司)按2：5的质量比组成的混合物。
其中，Er 2O 3、CeO 2、K 4TiO 4、SiC、磷酸铝均为工业纯，粒径≦5μm。
实施例9
本实施例的刚玉质微纳孔绝隔热耐火材料，主晶相为颗粒状的刚玉相，材料的化学组成中Al 2O 3的质量百分含量为95～97％，由基础料及以下占基础料总重量百分比的原料制成：分散剂0.6％，悬浮剂0.3％，烧结助剂1％，红外遮光剂2％，发泡剂0.18％，无机固化剂3％，有机固化剂1.4％，泡孔调节剂0.5％。
所用基础料由以下质量百分比的组分组成：95％的氧化铝质原料，5％的铝硅质原料。其中，氧化铝质原料由α-Al 2O 3(Al 2O 3质量百分含量≧99％，粒径≦5μm)、电熔刚玉粉按照1.5：8的质量比组成；铝硅质原料为红柱石(Al 2O 3质量百分含量为54～56％，SiO 2的质量百分含量为42～44％，粒径≦0.08mm)。
分散剂为由聚羧酸醚分散剂(德国巴斯夫)与萘系高效分散剂(恒美科技有限公司)按1：1的质量比组成的混合物；悬浮剂为由聚乙烯吡咯烷酮与聚丙烯酸胺按1：2的质量比组成；烧结助剂为由MgO、SrO按照1：1的质量比组成；红外遮光剂为由K 2Ti 6O 13、Sb 2O 3、Sb 2O 5按照2：1：1的质量比组成；
发泡剂为由硫酸盐型Gemini表面活性剂(恒美科技有限公司，发泡倍数为55)与脂肪醇聚氧乙烯醚羧酸钠(恒美科技有限公司，发泡倍数为15)按照1：8的质量比组成的混合物。无机固化剂为氧化铝凝胶；有机固化剂为由乙烯与氯乙烯和月桂酸乙烯酯共聚物(德国瓦克化学公司，
Figure PCTCN2021144043-appb-000014
)、醋酸乙烯酯与高级脂肪酸乙烯酯共聚物(山西三维集团公司，SWF-04)、醋酸乙烯酯均聚物(德国瓦克化学，
Figure PCTCN2021144043-appb-000015
)按2：2：3的质量比组成；泡孔调节剂为由羟丁基甲基纤维素醚(美国陶氏化学公司)、水溶性纤维素醚(恒美科技有限公司)与淀粉醚(荷兰AVEBE公司)按2：1：2的质量比组成。
其中，MgO、SrO、K 2Ti 6O 13、Sb 2O 3、Sb 2O 5、氧化铝凝胶均为工业纯，粒径≦5μm。
实施例10
本实施例的刚玉质微纳孔绝隔热耐火材料，主晶相为颗粒状的刚玉相，材料的化学组成中Al 2O 3的质量百分含量为95～97％，由基础料及以下占基础料总重量百分比的原料制成：分散剂0.7％，悬浮剂0.2％，烧结助剂0.5％，红外遮光剂1％、发泡剂0.12％，无机固化剂2％，有机固化剂1.6％，泡孔调节剂0.4％。
所用基础料由以下质量百分比的组分组成：95％的氧化铝质原料，5％的铝硅质原料。其中，氧化铝质原料为由α-Al 2O 3(Al 2O 3质量百分含量≧99％，粒径≦5μm)、电熔刚玉粉 按照1：8.5的质量比组成；铝硅质原料为硅线石(Al 2O 3质量百分含量为58～60％，SiO 2的质量百分含量为38～41％，粒径≦0.08mm)。
分散剂为由聚羧酸醚分散剂(德国巴斯夫)与多聚磷酸钠按2：5的质量比组成的混合物；悬浮剂为由韦兰胶、纤维素纳米晶按照1：1的质量比组成的混合物；烧结助剂为WO 3；红外遮光剂为由TiO 2、Sb 2O 5按照1：1的质量比组成的混合物。
发泡剂为由硫酸盐型Gemini表面活性剂(恒美科技有限公司，发泡倍数为55)与十二烷基苯磺酸钠(发泡倍数为9)按照1：5的质量比组成的混合物。无机固化剂为氧化铝凝胶；有机固化剂为由乙烯与氯乙烯和月桂酸乙烯酯共聚物(德国瓦克化学公司，
Figure PCTCN2021144043-appb-000016
)、异丁烯与马来酸酐共聚物(日本乐利公司，ISOBAM-04)与醋酸乙烯酯与乙烯和氯乙烯共聚物(德国瓦克化学，
Figure PCTCN2021144043-appb-000017
)按2：1：1的质量比组成的混合物；泡孔调节剂为由羧甲基羟丙基纤维素醚、羟丙基羟丁基纤维素醚(美国陶氏化学公司)与淀粉醚(恒美科技有限公司)按1：1：2的质量比组成的混合物。
其中，WO 3、TiO 2、Sb 2O 5、氧化铝凝胶均为工业纯，粒径≦5μm。
实施例11
本实施例的刚玉质微纳孔绝隔热耐火材料，主晶相为颗粒状的刚玉相，材料的化学组成中Al 2O 3的质量百分含量为98～99％，由基础料及以下占基础料总重量百分比的原料制成：分散剂0.8％，悬浮剂0.1％，烧结助剂0.1％，红外遮光剂0.6％，发泡剂0.06％，无机固化剂1％，有机固化剂1.8％，泡孔调节剂0.2％。
所用基础料由100％的氧化铝质原料组成。氧化铝质原料由α-Al 2O 3(Al 2O 3质量百分含量≧99.5％，粒径≦5μm)、电熔刚玉粉(Al 2O 3质量百分含量≧99％，粒径≦0.08mm)按照2：8的质量比组成；
分散剂为由磺化蜜胺缩聚物与三聚氰胺甲醛缩聚物(恒美科技有限公司)按1：1的质量比组成的混合物；悬浮剂为由干酪素、聚乙烯吡咯烷酮以按照1：1的质量比组成的混合物；烧结助剂为Y 2O 3；红外遮光剂为TiO 2。
发泡剂为由硫酸盐型Gemini表面活性剂(恒美科技有限公司，发泡倍数为55)与十二烷基苯磺酸钠(发泡倍数为9)按照1：2的质量比组成的混合物。无机固化剂为氧化硅凝胶；有机固化剂为由乙烯与氯乙烯和月桂酸乙烯酯共聚物(德国瓦克化学公司，
Figure PCTCN2021144043-appb-000018
)、醋酸乙烯与叔碳酸乙烯酯和丙烯酸酯共聚物(日本合成化学工业株式会社，Mowinyl-DM2072P)、醋酸乙烯与叔碳酸乙烯共聚物(安徽皖维集团公司，WWJF-8010)按2：3：4的质量比组成的混合物；泡孔调节剂为由羟丁基甲基纤维素醚与磺酸乙基纤维素 醚(美国陶氏化学公司)按照1：3的比例组成的混合物。
其中，Y 2O 3、TiO 2、氧化硅凝胶均为工业纯，粒径≦5μm。
实施例12
本实施例的刚玉质微纳孔绝隔热耐火材料，其显微结构照片如图6、图7所示，从图中可以看出，材料中气孔分布较规则，且气孔壁致密，由颗粒状的刚玉晶体组成。材料的化学组成中Al 2O 3的质量百分含量为99.9％，由基础料及以下占基础料总重量百分比的原料制成：分散剂1％，烧结助剂0.01％，发泡剂0.01％，无机固化剂0.1％，有机固化剂2％，泡孔调节剂0.1％。
所用基础料由100％的氧化铝质原料组成。氧化铝质原料由α-Al 2O 3(Al 2O 3质量百分含量≧99.999％，粒径≦5μm)、电熔刚玉粉(Al 2O 3质量百分含量≧99.99％，粒径≦0.08mm)按照2：8的质量比混合而成；
分散剂为由三聚氰胺甲醛缩聚物(恒美科技有限公司)与木质素磺酸钠按1：1的质量比组成的化合物；烧结助剂为由Y 2O 3与La 2O 3按照1：1的质量比组成的混合物。
发泡剂为聚酰胺型Dendrimer表面活性剂(恒美科技有限公司，发泡倍数为55)；无机固化剂为氧化铝凝胶；有机固化剂为由魔芋胶粉(上海北连生物科技有限公司生产)与海藻酸钠(江苏古贝生物科技有限公司)按1：1的质量比组成的混合物；泡孔调节剂为淀粉醚(恒美科技有限公司)与丙基纤维素醚(美国亚士兰公司)按1：1的质量比组成的混合物。
其中，Y 2O 3、La 2O 3、氧化铝凝胶均为分析纯，粒径≦5μm。
实施例13
本实施例的刚玉质微纳孔绝隔热耐火材料，主晶相为颗粒状的刚玉相，材料的化学组成中Al 2O 3的质量百分含量为98～99％，由基础料及以下占基础料总重量百分比的原料制成：分散剂0.8％，红外遮光剂0.6％，发泡剂0.06％，无机固化剂1％，有机固化剂1.8％，泡孔调节剂0.6％。
所用基础料的种类及比例同实施例11；
分散剂为由聚酰胺型聚羧酸分散剂与三聚氰胺甲醛缩聚物(恒美科技有限公司)按1：1的质量比组成的混合物；无机固化剂为氧化铝凝胶；
红外遮光剂、发泡剂、有机固化剂和泡孔调节剂的种类及比例同实施例11；
其中，TiO 2、氧化铝凝胶均为工业纯，粒径≦5μm。
实施例14
本实施例的刚玉质微纳孔绝隔热耐火材料，主晶相为颗粒状的刚玉相，材料的化学组 成中Al 2O 3的质量百分含量为99％，由基础料及以下占基础料总重量百分比的原料制成：发泡剂1％，无机固化剂0.5％，有机固化剂1.8％，泡孔调节剂0.2％。
所用基础料由100％的氧化铝质原料组成。氧化铝质原料由α-Al 2O 3(Al 2O 3质量百分含量≧99.5％，粒径≦5μm)、电熔刚玉粉(Al 2O 3质量百分含量≧99％，粒径≦1mm)按照2：8的质量比组成；
发泡剂为植物蛋白发泡剂(山东鑫茂化工公司，发泡倍数为9)；
无机固化剂为氧化铝溶胶；
有机固化剂为由醋酸乙烯与叔碳酸乙烯酯和丙烯酸酯共聚物(日本合成化学工业株式会社，Mowinyl-DM2072P)(上海北连生物科技有限公司生产)与分散乳胶(德国瓦克化学，
Figure PCTCN2021144043-appb-000019
)按1：1的质量比组成的混合物；
泡孔调节剂为羟乙基乙基纤维素醚(荷兰阿克苏诺贝尔公司)与羟乙基纤维素醚(美国赫尔克里斯公司)按1：1的质量比组成的混合物。
实施例15
本实施例的刚玉质微纳孔绝隔热耐火材料，主晶相为颗粒状的刚玉相，材料的化学组成中Al 2O 3的质量百分含量为98～99％，由基础料及以下占基础料总重量百分比的原料制成：制备制品所用原料的种类及配比基本同实施例14，区别仅在于此实施例技术方案中没有使用有机固化剂。
二、本发明的刚玉质微纳孔绝隔热耐火材料的制备方法的具体实施例
实施例16
本实施的制备方法，对实施例1中的刚玉质绝隔热耐火材料的制备进行说明，具体如下：
(1)基础料、添加剂、发泡组合物的制备
1)基础料的制备
将0.2吨Al(OH) 3、0.1吨水铝石、0.5吨γ-Al 2O 3、0.1吨硅藻土、0.1吨硅微粉倒入强制式搅拌机并干混15min得到基础料；
2)添加剂的制备
称取90kg膨润土、10kg韦兰胶、20kgAlF 3·3H 2O、20kgZnO、20kgV 2O 5、20kgLa 2O 3、20kgBaO、20kgTiC、20kgK 4TiO 4、40kgB 4C、20kgSb 2O 3倒入行星式搅拌机并干混5min得到添加剂；
3)发泡组合物的制备
称取2kg季铵型Gemini表面活性剂、2kg半环型Bola表面活性剂、40kg氧化铝凝胶、60kgAl 2O 3微粉、10kg醋酸乙烯酯与乙烯和高级脂肪酸共聚物、5kg醋酸乙烯酯与乙烯共聚物、2kg羟乙基乙基纤维素醚、1kg皂素，倒入行星式搅拌机并干混5min，得到均匀的发泡组合物；
(2)悬浮料浆、泡沫料浆的制备
1)悬浮料浆的制备
将基础料与添加剂倒入滚筒球磨机中，加2吨水，球磨混合2h，再超声震荡(超声功率2000W)4min后得均匀悬浮料浆(其中固体颗粒粒径为≦30μm)；球磨机中研磨球采用氧化铝球，大球
Figure PCTCN2021144043-appb-000020
中球
Figure PCTCN2021144043-appb-000021
小球
Figure PCTCN2021144043-appb-000022
的重量比为1：1：8，料/球重量比为1：0.8；
2)泡沫料浆的制备
将悬浮料浆注入搅拌机，先预搅拌1min(预搅拌过程中搅拌桨的线速度为5m/s)后把发泡组合物加入搅拌机，搅拌桨以线速度200m/s快速混合1min，得均匀的泡沫料浆。
(3)浇注、养护
将泡沫料浆注入橡胶模具，在空气温度和湿度分别为1℃、50％的环境中养护12h待其固化；
(4)干燥、烧制
将固化坯体脱模，利用二氧化碳超临界干燥法脱除坯体中水分，二氧化碳控制压力为9MPa，温度在42℃，超临界干燥时间为4h，得到干燥坯体；干燥坯体的含水率≦2wt％，耐压强度≧0.7MPa。
将干燥坯体装入电阻窑炉中烧成，从室温以1℃/min的升温速率升至500℃，再以5℃/min升温至1000℃，保温1.5h，再以1℃/min升温至1200～1230℃，保温10h，后以10℃/min降温至1100℃，并在1100℃保温1.5h，再以5℃/min降温至500℃，于500℃保温0.5h，最后以1℃/min降温至50℃，即得刚玉质微纳孔绝隔热耐火材料；
实施例17
本实施的制备方法，对实施例2中的刚玉质绝隔热耐火材料的制备进行说明，具体如下：
(1)基础料、添加剂、发泡物的制备
1)基础料的制备
将0.3吨工业Al(OH) 3、0.5吨烧结刚玉、0.05吨钾长石、0.15吨硅微粉倒入非重力搅 拌机并干混15min得基础料；
2)添加剂的制备
称取0.3kg酰胺型聚羧酸分散剂、0.2kg聚羧酸醚分散剂、50kg膨润土、3kg纤维素纤维、30kgMnO 2、30kgZnO、30kgV 2O 5、20kgTiC、20kgK 4TiO 4、20kgSb 2O 3倒入双锥混合机并干混5min得添加剂；
3)发泡组合物的制备
称取1kg聚醚型Dendrimer表面活性剂、29kg植物蛋白发泡剂、70kg污泥蛋白发泡剂、120kg氧化铝溶胶、80kg氧化硅溶胶、0.5kg可得然胶、0.5kg结冷胶、0.05kg羧甲基乙基纤维素醚、0.03kg羧甲基羟甲基纤维素醚、0.02kg羧甲基羟乙基纤维素醚，倒入双锥混合机并干混5min，得均匀的发泡组合物；
(2)悬浮料浆、泡沫料浆的制备
1)悬浮料浆的制备
将基础料与添加剂倒入滚筒球磨机中，加1.8吨水，球磨混合10h，再超声震荡(超声功率1500W)6min后得均匀悬浮料浆(其中固体颗粒粒径≦30μm)；球磨机中研磨球采用氧化铝球，大球
Figure PCTCN2021144043-appb-000023
中球
Figure PCTCN2021144043-appb-000024
小球
Figure PCTCN2021144043-appb-000025
的重量比为1：1：8，料/球重量比为1：0.9；
2)泡沫料浆的制备
将悬浮料浆注入搅拌机中，先预搅拌1min(预搅拌过程中搅拌桨的线速度为5m/s)后把发泡组合物加入搅拌机，搅拌桨以线速度为50m/s快速混合5min，得均匀泡沫料浆；
(3)浇注、养护
将泡沫料浆注入塑料模具，在空气温度和湿度分别为10℃、60％的环境中养护6h待其固化；
(4)干燥、烧制
将固化坯体脱模，利用二氧化碳超临界干燥法脱除坯体中的水分，二氧化碳的控制压力为9MPa，温度为42℃，超临界干燥时间为4h，得干燥坯体；干燥坯体的含水率≦2wt％，耐压强度≧0.74MPa。
将干燥坯体采用高温隧道窑烧成，先从室温以2℃/min的升温速率升至500℃，再以8℃/min升温至1000℃，保温1h，再以3℃/min升温至1280～1310℃，保温8h，后以10℃/min降温至1100℃，并在1100℃保温1h，再以6℃/min降温至500℃，于500℃保温0.5h，最后以2℃/min降温至50℃，即得刚玉质微纳孔绝隔热耐火材料。
实施例18
本实施的制备方法，对实施例3中的刚玉质绝隔热耐火材料的制备进行说明，具体如下：
(1)基础料、添加剂、发泡物的制备
1)基础料的制备
将0.6吨Al(OH) 3、0.2吨勃姆石、20kg正丁醇铝、20kg异丙醇铝、10kg仲丁醇铝、60kg硅微粉、30kg正硅酸甲酯、30kg正硅酸乙酯、30kg甲基三甲氧基硅烷倒入强制式搅拌机并干混5min得基础料；
2)添加剂的制备
称取0.5kg酰亚胺型聚羧酸分散剂、0.5kg萘系分散剂、30kg海泡石、10kg壳聚糖、30kg MnO 2、30kg ZnO、20kg V 2O 5、20kg K 2Ti 6O 13、20kg K 4TiO 4、20kg Ni(NO 3) 2倒入V型混合机并干混5min得添加剂；
3)发泡组合物的制备
称取1kg羧酸盐型Gemini表面活性剂、50kg动物蛋白发泡剂、3kg可得然胶、2kg结冷胶、0.4kg磺酸乙基纤维素醚、0.2kg甲基纤维素醚，倒入V型混合机并干混5min，得均匀发泡组合物；
(2)悬浮料浆、泡沫料浆的制备
1)悬浮料浆的制备
将基础料与添加剂倒入滚筒球磨机中，加1.6吨水，球磨混合8h，再超声震荡(超声功率1500W)6min后得均匀悬浮料浆(其中固体颗粒粒径为≦30μm)；球磨机中研磨球采用氧化铝球，大球
Figure PCTCN2021144043-appb-000026
中球
Figure PCTCN2021144043-appb-000027
小球
Figure PCTCN2021144043-appb-000028
的重量比为1：1：8，料/球比为1：0.9；
2)泡沫料浆的制备
将悬浮料浆注入搅拌机，先预搅拌1min(预搅拌过程中搅拌桨的线速度为5m/s)后把发泡组合物及150kg硅铝溶胶加入搅拌机，搅拌桨以线速度为100m/s快速混合4min，得均匀的泡沫料浆；
(3)浇注、养护
将泡沫料浆注入不锈钢模具，在空气温度和湿度分别为20℃、70％的环境中养护2h待其固化；
(4)干燥、烧制
将固化后的坯体脱模，利用二氧化碳超临界干燥法脱除坯体中的水分，二氧化碳的控制压力为9MPa，干燥温度为42℃，超临界干燥时间为4h，得干燥坯体；干燥坯体的含水率≦2wt％，耐压强度≧0.76MPa。
将干燥坯体采用高温隧道窑烧成，先从室温以5℃/min的升温速率升至500℃，再以8℃/min升温至1000℃，保温1h，再以3℃/min升温至1370～1400℃，保温7h，后以10℃/min降温至1100℃，并在1100℃保温1h，再以6℃/min降温至500℃，于500℃保温0.5h，最后以2℃/min降温至50℃，即得刚玉质微纳孔绝隔热耐火材料。
实施例19
本实施的制备方法，对实施例4中的刚玉质绝隔热耐火材料的制备进行说明，具体如下：
(1)基础料、添加剂、发泡物的制备
1)基础料的制备
将0.4吨工业Al(OH) 3、0.45吨α-Al 2O 3、0.05吨煤矸石、0.05吨钠长石、0.05吨高岭土倒入行星式搅拌机并干混15min得到基础料；
2)添加剂的制备
称取1.5kg磺化蜜胺缩聚物、20kg凹凸棒、10kg聚合氯化铝、20kg Y 2O 3、20kg MgO、20kg V 2O 5、20kg金红石、20kg ZrSiO 4倒入三维混合机并干混5min得到添加剂；
3)发泡组合物的制备
称取1kg羧酸盐型Gemini表面活性剂、1kg半环型Bola表面活性剂、5kg刺槐豆胶、5kg刺槐树胶、1kg羧甲基乙基纤维素醚、1kg羟乙基乙基纤维素醚，倒入三维混合机并干混5min，得到均匀的发泡组合物；
(2)悬浮料浆、泡沫料浆的制备
1)悬浮料浆的制备
将基础料与添加剂倒入滚筒球磨机中，加1.4吨水，球磨混合8h，再超声震荡(超声功率1500W)6min后得均匀悬浮料浆(其中固体颗粒粒径为≦30μm)；球磨机中研磨球的材质为莫来石质，大球
Figure PCTCN2021144043-appb-000029
中球
Figure PCTCN2021144043-appb-000030
小球
Figure PCTCN2021144043-appb-000031
的重量比为1：1：8，料/球比为1：0.9；
2)泡沫料浆的制备
将悬浮料浆注入搅拌机中，先预搅拌1min(预搅拌过程中搅拌桨的线速度为5m/s)后把发泡组合物及120kg氧化铝溶胶加入搅拌机中，搅拌桨以线速度为130m/s快速混合3min， 得到均匀的泡沫料浆；
(3)浇注、养护
将泡沫料浆注入玻璃模具，在空气温度和湿度分别为25℃、80％的环境中养护1.5h待其固化；
(4)干燥、烧制
将固化后的坯体脱模，利用二氧化碳超临界干燥法脱除坯体中的水分，二氧化碳的控制压力为9MPa，温度在42℃，超临界干燥时间为4h，得到干燥坯体；干燥坯体的含水率≦2wt％，耐压强度≧0.8MPa。
将干燥坯体采用高温隧道窑烧成，先从室温以3℃/min的升温速率升至500℃，再以8℃/min升温至1000℃，保温1h，再以3℃/min升温至1430～1470℃，保温6h，后以10℃/min降温至1100℃，并在1100℃保温1h，再以6℃/min降温至500℃，于500℃保温0.5h，最后以2℃/min降温至50℃，即得刚玉质微纳孔绝隔热耐火材料。
实施例20
本实施的制备方法，对实施例5中的刚玉质微纳孔绝隔热耐火材料的制备进行说明，具体如下：
(1)基础料、添加剂、发泡物的制备
1)基础料的制备
将0.3吨工业氧化铝、0.2吨β-Al 2O 3、0.15吨γ-Al 2O 3、0.1吨δ-Al 2O 3、0.1吨χ-Al 2O 3、0.05吨蓝晶石、0.05吨高岭土、0.05吨钡长石倒入强制式搅拌机并干混15min得到基础料；
2)添加剂的制备
称取0.8kg聚酰胺型聚羧酸分散剂、1.2kg聚丙烯酸钠、10kg聚乙烯吡咯烷酮、10kg干酪素、20kg MnO 2、20kg SiF 4、10kg Cr 2O 3倒入行星式搅拌机并干混5min，得到均匀的添加剂；
3)发泡组合物的制备
称取1.1kg羧酸盐型Gemini表面活性剂、3.3kg十二醇聚氧乙烯醚羧酸钠、10kg氧化硅凝胶、10kg七铝酸十二钙、10kg铁铝酸四钙、20kg氧化铝凝胶、4kg乙烯与乙酸乙烯酯共聚物、4kg可得然胶、2kg结冷胶、2kg羧甲基羟丁基纤维素醚、2kg羟丙基羟丁基纤维素醚，倒入行星式搅拌机并干混5min，得均匀的发泡物；
(2)悬浮料浆、泡沫料浆的制备
1)悬浮料浆的制备
将基础料与添加剂倒入滚筒球磨机，加1.2吨水，球磨混合4h，再超声震荡(超声功率1500W)6min后得均匀悬浮料浆(其中固体颗粒粒径为≦44μm)；球磨机中研磨球的材质为氧化锆质，大球
Figure PCTCN2021144043-appb-000032
中球
Figure PCTCN2021144043-appb-000033
小球
Figure PCTCN2021144043-appb-000034
的重量比为1.5：2：6.5，料/球比为1：1；
2)泡沫料浆的制备
将悬浮料浆注入搅拌机中，先预搅拌1min(预搅拌过程中搅拌桨的线速度为5m/s)后把发泡组合物加入搅拌机中，搅拌桨以线速度为150m/s快速混合2min，得均匀的泡沫料浆。
(3)浇注、养护
将泡沫料浆注入不锈钢模具，在空气温度和湿度分别为25℃、85％的环境中养护1.3h待其固化；
(4)干燥、烧制
将固化后的坯体脱模，采用冷冻干燥法脱除坯体中的水分，干燥温度为-85℃，干燥12h，得干燥坯体；干燥坯体的含水率≦2wt％，耐压强度≧0.9MPa。
将干燥坯体装入电阻窑炉中烧成，先从室温以3℃/min的升温速率升至500℃，再以10℃/min升温至1000℃，保温1h，再以3℃/min升温至1500～1540℃，保温5h，后以10℃/min降温至1100℃，并在1100℃保温1h，再以6℃/min降温至500℃，于500℃保温0.5h，最后以2℃/min降温至50℃，即得刚玉质微纳孔绝隔热耐火材料。
实施例21
本实施的制备方法，对实施例6中的刚玉质微纳孔绝隔热耐火材料的制备进行说明，具体如下：
(1)基础料、添加剂、发泡物的制备
1)基础料的制备
将0.5吨α-Al 2O 3、0.15吨κ-Al 2O 3、0.1吨θ-Al 2O 3、0.1吨η-Al 2O 3、0.06吨蓝晶石、0.03吨瓷石、0.06吨焦宝石倒入强制式搅拌机并干混15min得到基础料；
2)添加剂的制备
称取2kg氨基磺酸系分散剂、1kg腐殖酸钠、4kg纤维素纳米纤维、4kg聚乙二醇、2kg聚乙烯醇、10kgAlF 3·3H 2O、20kgBaO、10kgV 2O 5、20kgNi(NO 3) 2、10kgFe 3O 4倒入双锥混合机并干混5min，得到均匀的添加剂；
3)发泡组合物的制备
称取0.3kg羧酸盐型Gemini表面活性剂、3.6kg月桂酸酰胺丙基磺基甜菜碱、50kg硅铝凝胶、2kg鹿角菜胶、2kg魔芋胶、2kg丙烯酸酯聚合物、2kg醋酸乙烯酯与乙烯和丙烯酸酯共聚物、2kg乙烯与氯乙烯共聚物、2kg羟丙基羟丁基纤维素醚、4kg木质纤维素倒入双锥混合机并干混5min，得到均匀的发泡组合物；
(2)悬浮料浆、泡沫料浆的制备
1)悬浮料浆的制备
将基础料与添加剂倒入滚筒球磨机中，加1吨水，球磨混合4h，再超声震荡(超声功率1500W)6min后得均匀悬浮料浆(其中固体颗粒粒径为≦44μm)；球磨机中研磨球的材质为氧化锆质，大球
Figure PCTCN2021144043-appb-000035
中球
Figure PCTCN2021144043-appb-000036
小球
Figure PCTCN2021144043-appb-000037
的重量比为1.5：2：6.5，料/球重量比为1：1；
2)泡沫料浆的制备
将悬浮料浆注入搅拌机中，先预搅拌1min(预搅拌过程中搅拌桨的线速度为5m/s)后把发泡组合物加入搅拌机中，搅拌桨以线速度为170m/s快速混合2min，得到均匀的泡沫料浆。
(3)浇注、养护
将泡沫料浆注入不锈钢模具中，在空气温度和湿度分别为25℃、88％的环境中养护1h待其固化；
(4)干燥、烧制
将固化后的坯体脱模，采用冷冻干燥法脱除坯体中的水分，干燥温度为-85℃，干燥12h，得干燥坯体；干燥坯体的含水率≦2wt％，耐压强度≧0.9MPa。
将干燥坯体装入电阻窑炉中烧成，先从室温以3℃/min的升温速率升至500℃，再以10℃/min升温至1000℃，保温1h，再以3℃/min升温至1570～1600℃，保温4h，后以10℃/min降温至1100℃，并在1100℃保温1h，再以6℃/min降温至500℃，于500℃保温0.5h，最后以2℃/min降温至50℃，即得刚玉质微纳孔绝隔热耐火材料。
实施例22
本实施的制备方法，对实施例7中的刚玉质微纳孔绝隔热耐火材料的制备进行说明，具体如下：
(1)基础料、添加剂、发泡物的制备
1)基础料的制备
将0.03吨α-Al 2O 3、0.07吨烧结刚玉、0.85吨高铝矾土、0.05吨烧结莫来石倒入行星 式搅拌机并干混15min得到基础料；
2)添加剂的制备
称取2kg聚羧酸醚分散剂、2kg三聚氰胺甲醛缩聚物、2kg十六醇、2kg蔗糖、2kg糊精、10kg SrO、10kg WO 3、10kg Er 2O 3、15kg CoCl 2、10kg Ni(NO 3) 2、5kg Fe 3O 4倒入三维混合机并干混5min，得到均匀的添加剂；
3)发泡组合物的制备
称取0.2kg季铵型Gemini表面活性剂、3kgɑ-烯烃磺酸钠、20kg硅酸二钙、30kg二铝酸钙、8kg醋酸乙烯酯与乙烯和高级脂肪酸共聚物、4kg醋酸乙烯酯与乙烯和月桂酸乙烯酯共聚物、5kg羟丙基乙基纤维素醚、5kg丙基纤维素醚，倒入V型混合机并干混5min，得均匀的发泡组合物；
(2)悬浮料浆、泡沫料浆的制备
1)悬浮料浆的制备
将基础料与添加剂倒入滚筒球磨机中，加1吨水，球磨混合1.5h，再超声震荡(超声功率1000W)8min后得到均匀的悬浮料浆(其中固体颗粒粒径为≦44μm)；球磨机中研磨球的材质为锆刚玉质，大球
Figure PCTCN2021144043-appb-000038
中球
Figure PCTCN2021144043-appb-000039
小球
Figure PCTCN2021144043-appb-000040
的重量比为1.5：2：6.5，料/球比为1：1.1；
2)泡沫料浆的制备
将悬浮料浆注入搅拌机中，先预搅拌1min(预搅拌过程中搅拌桨的线速度为4m/s)后把发泡组合物加入搅拌机中，搅拌桨以线速度为200m/s快速混合1min，得到均匀的泡沫料浆。
(3)浇注、养护
将泡沫料浆注入铝合金模具中，在空气温度和湿度分别为25℃、92％的环境中养护0.8h待其固化；
(4)干燥、烧制
将固化后的坯体脱模，利用微波干燥法脱除坯体中的水分，微波频率为915MHz，微波干燥时间为2h，得干燥坯体；干燥坯体的含水率≦2wt％，耐压强度≧1.1MPa。
将干燥坯体装入高温隧道窑中烧成，先从室温以2℃/min的升温速率升至500℃，再以8℃/min升温至1000℃，保温1h，再以3℃/min升温至1630～1650℃，保温3h，后以10℃/min降温至1100℃，并在1100℃保温1h，再以6℃/min降温至500℃，于500℃保温0.5h，最后以2℃/min降温至50℃，即得刚玉质微纳孔绝隔热耐火材料。
实施例23
本实施的制备方法，对实施例8中的刚玉质微纳孔绝隔热耐火材料的制备进行说明，具体如下：
(1)基础料、添加剂、发泡物的制备
1)基础料的制备
将0.2吨α-Al 2O 3、0.7吨电熔刚玉、0.1吨木节土倒入强制式搅拌机并干混15min得到基础料；
2)添加剂的制备
称取3kg磺化蜜胺缩聚物、2kg柠檬酸钠、3kg纤维素纳米晶、1kg糊精、10kgEr 2O 3、10kgCeO 2、10kgK 4TiO 4、10kgSiC倒入行星式搅拌机并干混5min，得到均匀的添加剂；
3)发泡组合物的制备
称取0.2kg季铵型Gemini表面活性剂、2.4kg十二烷基二甲基甜菜碱表面活性剂、40kg磷酸铝、7kg丙烯酸酯与苯乙烯共聚物、6kg丙烯酸酯聚合物、2kg乙基纤维素醚、5kg羟甲基纤维素醚，倒入行星式搅拌机并干混5min，得到均匀的发泡组合物；
(2)悬浮料浆、泡沫料浆的制备
1)悬浮料浆的制备
将基础料与添加剂倒入滚筒球磨机中，加1吨水，球磨混合1h，再超声震荡(超声功率1000W)8min后得到均匀的悬浮料浆(其中固体颗粒粒径为≦44μm)；球磨机中研磨球的材质为氧化锆质，大球
Figure PCTCN2021144043-appb-000041
中球
Figure PCTCN2021144043-appb-000042
小球
Figure PCTCN2021144043-appb-000043
的重量比为1.5：2：6.5，料/球重量比为1：1.2；
2)泡沫料浆的制备
将悬浮料浆注入搅拌机中，先预搅拌1min(预搅拌过程中搅拌桨的线速度为4m/s)后把发泡组合物加入搅拌机中，搅拌桨以线速度为150m/s快速混合3min，得到均匀的泡沫料浆。
(3)浇注、养护
将泡沫料浆注入铝合金模具中，在空气温度和湿度分别为25℃、93％的环境中养护0.7h待其固化；
(4)干燥、烧制
将固化后的坯体脱模，利用微波干燥法脱除坯体中的水分，微波频率为2450MHz，微波干燥时间为1h，得干燥坯体；干燥坯体的含水率≦2wt％，耐压强度≧1.0MPa；
将干燥坯体装入微波窑炉中烧成，先从室温以5℃/min的升温速率升至500℃，再以30℃/min升温至1000℃，保温0.5h，再以30℃/min升温至1680～1700℃，保温1h，后以20℃/min降温至1100℃，并在1100℃保温0.5h，再以30℃/min降温至500℃，于500℃保温0.5h，最后以10℃/min降温至50℃，即得刚玉质微纳孔绝隔热耐火材料。
实施例24
本实施的制备方法，对实施例9中的刚玉质微纳孔绝隔热耐火材料的制备进行说明，具体如下：
(1)基础料、添加剂、发泡物的制备
1)基础料的制备
将0.15吨α-Al 2O 3、0.8吨电熔刚玉、0.05吨红柱石，倒入非重力搅拌机并干混15min得到基础料；
2)添加剂的制备
称取3kg聚羧酸醚分散剂、3kg萘系分散剂、1kg聚乙烯吡咯烷酮、2kg聚丙烯酸胺、5kg MgO、5kg SrO、10kg K 2Ti 6O 13、5kg Sb 2O 3、5kg Sb 2O 5，倒入三维混合机并干混5min，得到均匀的添加剂；
3)发泡组合物的制备
称取0.2kg硫酸盐型Gemini表面活性剂、1.6kg脂肪醇聚氧乙烯醚羧酸钠、30kg氧化铝凝胶、4kg乙烯与氯乙烯和月桂酸乙烯酯共聚物、4kg醋酸乙烯酯与高级脂肪酸乙烯酯共聚物、6kg醋酸乙烯酯均聚物、2kg羟丁基甲基纤维素醚、1kg水溶性纤维素醚、2kg淀粉醚，倒入双锥混合机并干混5min，得均匀的发泡组合物；
(2)悬浮料浆、泡沫料浆的制备
1)悬浮料浆的制备
将基础料与添加剂倒入滚筒球磨机中，加0.9吨水，球磨混合1h，再超声震荡(超声功率1000W)8min后得到均匀的悬浮料浆(其中固体颗粒粒径为≦44μm)；球磨机中研磨球的材质为氧化锆质，大球
Figure PCTCN2021144043-appb-000044
中球
Figure PCTCN2021144043-appb-000045
小球
Figure PCTCN2021144043-appb-000046
的重量比为1.5：2：6.5，料/球比为1：1.2；
2)泡沫料浆的制备
将悬浮料浆注入搅拌机中，先预搅拌1min(预搅拌过程中搅拌桨的线速度为4m/s)后把发泡组合物加入搅拌机中，搅拌桨以线速度为120m/s快速混合4min，得到均匀的泡沫料浆。
(3)浇注、养护
将泡沫料浆注入树脂模具中，在空气温度和湿度分别为27℃、95％的环境中养护0.6h待其固化；
(4)干燥、烧制
将固化后的坯体脱模，采用电源加热常压干燥法脱除其中的游离水，先以3℃/min升温至30℃并保温3h，再以2℃/min升温至50℃并保温2h，再以3℃/min升温至70℃并保温4h，再以5℃/min升温至90℃并保温4h，再5℃/min升温至110℃并保温12h，得干燥坯体；干燥坯体的含水率≦2wt％，耐压强度≧1.1MPa。
将干燥坯体装入梭式窑中烧成，先从室温以4℃/min的升温速率升至500℃，再以8℃/min升温至1000℃，保温1h，再以3℃/min升温至1700～1710℃，保温3h，后以10℃/min降温至1100℃，并在1100℃保温0.5h，再以6℃/min降温至500℃，于500℃保温0.5h，最后以2℃/min降温至50℃，即得刚玉质微纳孔绝隔热耐火材料。
实施例25
本实施的制备方法，对实施例10中的刚玉质微纳孔绝隔热耐火材料的制备进行说明，具体如下：
(1)基础料、添加剂、发泡物的制备
1)基础料的制备
将0.1吨α-Al 2O 3、0.85吨电熔刚玉、0.05吨硅线石，倒入非重力搅拌机并干混15min得到基础料；
2)添加剂的制备
称取2kg聚羧酸醚分散剂、5kg多聚磷酸钠、1kg韦兰胶、1kg纤维素纳米晶、5kg WO 3、5kg TiO 2、5kg Sb 2O 5，倒入双锥混合机并干混5min，得到均匀的添加剂；
3)发泡组合物的制备
称取0.2kg硫酸盐型Gemini表面活性剂、1kg十二烷基苯磺酸钠、20kg氧化铝凝胶、8kg乙烯与氯乙烯和月桂酸乙烯酯共聚物、4kg异丁烯与马来酸酐共聚物、4kg醋酸乙烯酯与乙烯和氯乙烯共聚物、1kg羧甲基羟丙基纤维素醚、1kg羟丙基羟丁基纤维素醚、2kg淀粉醚，倒入双锥混合机并干混5min，得到均匀的发泡组合物；
(2)悬浮料浆、泡沫料浆的制备
1)悬浮料浆的制备
将基础料与添加剂倒入滚筒球磨机中，加0.7吨水，球磨混合1h，再超声震荡(超声 功率1000W)8min后得到均匀的悬浮料浆(其中固体颗粒粒径为≦50μm)；球磨机中研磨球的材质为锆刚玉质，大球
Figure PCTCN2021144043-appb-000047
中球
Figure PCTCN2021144043-appb-000048
小球
Figure PCTCN2021144043-appb-000049
的重量比为1.5：2：6.5，料/球重量比为1：1.2；
2)泡沫料浆的制备
将悬浮料浆注入搅拌机中，先预搅拌1min(预搅拌过程中搅拌桨的线速度为4m/s)后把发泡组合物加入搅拌机中，搅拌桨以线速度为80m/s快速混合5min，得到均匀的泡沫料浆。
(3)浇注、养护
将泡沫料浆注入橡胶模具中，在空气温度和湿度分别为30℃、97％的环境中养护0.4h待其固化；
(4)干燥、烧制
将固化后的坯体脱模，采用电源加热常压干燥法脱除其中的游离水，即先以3℃/min升温至30℃并保温3h，再以2℃/min升温至50℃并保温2h，再以3℃/min升温至70℃并保温4h，再以5℃/min升温至90℃并保温4h，再5℃/min升温至110℃并保温12h，得干燥坯体；干燥坯体的含水率≦2wt％，耐压强度≧1.2MPa。
将干燥坯体装入梭式窑中烧成，先从室温以3℃/min的升温速率升至500℃，再以8℃/min升温至1000℃，保温1h，再以3℃/min升温至1700～1710℃，保温3h，后以10℃/min降温至1100℃，并在1100℃保温1h，再以6℃/min降温至500℃，于500℃保温0.5h，最后以2℃/min降温至50℃，即得刚玉质微纳孔绝隔热耐火材料。
实施例26
本实施的制备方法，对实施例11中的刚玉质微纳孔绝隔热耐火材料的制备进行说明，具体如下：
(1)基础料、添加剂、发泡物的制备
1)基础料的制备
将0.2吨α-Al 2O 3、0.8吨电熔刚玉，倒入非重力搅拌机并干混1min得到基础料；
2)添加剂的制备
称取4kg磺化蜜胺缩聚物、4kg三聚氰胺甲醛缩聚物、0.5kg干酪素、0.5kg聚乙烯吡咯烷酮、1kgY 2O 3、6kgTiO 2，倒入V型混合机并干混5min，得到均匀的添加剂；
3)发泡组合物的制备
称取0.2kg硫酸盐型Gemini表面活性剂、0.4kg十二烷基苯磺酸钠、10kg氧化硅凝胶、 4kg乙烯与氯乙烯和月桂酸乙烯酯共聚物、6kg醋酸乙烯与叔碳酸乙烯酯和丙烯酸酯共聚物、8kg醋酸乙烯与叔碳酸乙烯共聚物、0.5kg羟丁基甲基纤维素醚、1.5kg磺酸乙基纤维素醚，倒入双锥混合机并干混5min，得到均匀的发泡组合物；
(2)悬浮料浆、泡沫料浆的制备
1)悬浮料浆的制备
将基础料与添加剂倒入滚筒球磨机中，加0.4吨水，球磨混合0.6h，再超声震荡(超声功率1800W)5min后得到均匀的悬浮料浆(其中固体颗粒粒径为≦60μm)；球磨机中研磨球的材质为锆刚玉质，大球
Figure PCTCN2021144043-appb-000050
中球
Figure PCTCN2021144043-appb-000051
小球
Figure PCTCN2021144043-appb-000052
的重量比为1.5：2：6，料/球重量比为1：1.4；
2)泡沫料浆的制备
将悬浮料浆注入搅拌机中，先预搅拌1min(预搅拌过程中搅拌桨的线速度为4m/s)后把发泡组合物加入搅拌机中，搅拌桨以线速度为50m/s快速混合7min，得到均匀的泡沫料浆。
(3)浇注、养护
将泡沫料浆注入竹质模具中，在空气温度和湿度分别为30℃、99％的环境中养护0.3h待其固化；
(4)干燥、烧制
将固化后的坯体脱模，采用常压热风干燥法脱除其中的游离水，即先以3℃/min升温至30℃并保温3h，再以2℃/min升温至50℃并保温2h，再以3℃/min升温至70℃并保温4h，再以5℃/min升温至90℃并保温4h，再5℃/min升温至110℃并保温12h，得干燥坯体；干燥坯体的含水率≦2wt％，耐压强度≧1.3MPa。
将干燥坯体装入梭式窑中烧成，先从室温以1℃/min的升温速率升至500℃，再以10℃/min升温至1000℃，保温0.5h，再以8℃/min升温至1750～1760℃，保温2h，后以10℃/min降温至1100℃，并在1100℃保温0.5h，再以7℃/min降温至500℃，于500℃保温0.5h，最后以4℃/min降温至50℃，即得刚玉质微纳孔绝隔热耐火材料。
实施例27
本实施的制备方法，对实施例12中的刚玉质微纳孔绝隔热耐火材料的制备进行说明，具体如下：
(1)基础料、添加剂、发泡物的制备
1)基础料的制备
将0.2吨α-Al 2O 3、0.8吨电熔刚玉倒入非重力搅拌机，并干混15min得到基础料；
2)添加剂的制备
称取5kg三聚氰胺甲醛缩聚物、5kg木质素磺酸钠、0.05kgY 2O 3、0.05kgLa 2O 3，倒入三维混合机并干混5min，得到均匀的添加剂；
3)发泡组合物的制备
称取0.1kg聚酰胺型Dendrimer表面活性剂、1kg氧化铝凝胶、10kg魔芋胶粉、10kg海藻酸钠、0.5kg淀粉醚、0.5kg丙基纤维素醚倒入V型混合机，并干混5min，得到均匀的发泡组合物；
(2)悬浮料浆、泡沫料浆的制备
1)悬浮料浆的制备
将基础料与添加剂倒入滚筒球磨机中，加0.3吨水，球磨混合0.5h，再超声震荡(超声功率2000W)4min后得到均匀的悬浮料浆(其中固体颗粒粒径为≦74μm)；球磨机中研磨球采用碳化钨球，大球
Figure PCTCN2021144043-appb-000053
中球
Figure PCTCN2021144043-appb-000054
小球
Figure PCTCN2021144043-appb-000055
的重量比为1.5：2：6，料/球重量比为1：1.5；
2)泡沫料浆的制备
将悬浮料浆注入搅拌机中，先预搅拌1min(预搅拌过程中搅拌桨的线速度为3m/s)后把发泡组合物加入搅拌机中，搅拌桨以线速度为20m/s快速混合10min，得到均匀的泡沫料浆。
(3)浇注、养护
将泡沫料浆注入入不锈钢模具中，在空气温度和湿度分别为35℃、99.9％的环境中养护0.2h待其固化；
(4)干燥、烧制
将固化后的坯体脱模，采用远红外干燥法脱除坯体的游离水，具体条件为：红外线波长选取2.5～30μm，干燥时间为1h，得干燥坯体。干燥坯体的含水率≦2wt％，耐压强度≧1.5MPa。将干燥坯体装入梭式窑炉中烧成，先从室温以1℃/min的升温速率升至500℃，再以10℃/min升温至1000℃，保温0.5h，再以10℃/min升温至1780～1800℃，保温1h，后以10℃/min降温至1100℃，并在1100℃保温0.5h，再以10℃/min降温至500℃，于500℃保温0.5h，最后以5℃/min降温至80℃，即得刚玉质微纳孔绝隔热耐火材料。
实施例28
本实施的制备方法，对实施例13中的刚玉质微纳孔绝隔热耐火材料的制备进行说明， 具体如下：
(1)基础料、添加剂、发泡物的制备
1)基础料的制备
将0.2吨α-Al 2O 3微粉、0.8吨电熔刚玉粉，倒入非重力搅拌机并干混15min得到基础料；
2)添加剂的制备
称取4kg聚酰胺型聚羧酸分散剂、4kg三聚氰胺甲醛缩聚物、6kg TiO 2，倒入三维混合机并干混5min，得到均匀的添加剂；
3)发泡组合物的制备：同实施例26。
(2)悬浮料浆、泡沫料浆的制备
1)悬浮料浆的制备
将基础料与添加剂倒入搅拌机中，并加入0.4吨的水，搅拌15min得悬浮料浆；
2)泡沫料浆的制备
将把发泡组合物加入到搅拌机中，然后搅拌桨以20m/s的线速度快速混合30min，得到均匀的泡沫料浆；
(3)浇注、养护
将泡沫料浆注入不锈钢模具中，在空气温度和湿度分别为30℃、95％的环境中养护0.5h使其固化，然后脱模得坯体；
(4)干燥、烧制
将固化后的坯体脱模，采用常压热风干燥法脱除其中的水分，在40℃～55℃干燥24h，得干燥坯体；干燥坯体的含水率≦2wt％，耐压强度≧1.0MPa。将干燥坯体装入梭式窑中烧成，烧成工艺同实施例26，即得刚玉质微纳孔绝隔热耐火材料。
实施例29
本实施的制备方法，对实施例14中的刚玉质微纳孔绝隔热耐火材料的制备进行说明，具体如下：
(1)基础料、添加剂、发泡物的制备
1)基础料的制备
将0.2吨α-Al 2O 3微粉、0.8吨电熔刚玉粉，倒入非重力搅拌机并干混15min得到基础料；
2)发泡组合物的制备
称取10kg植物蛋白发泡剂、9kg醋酸乙烯与叔碳酸乙烯酯和丙烯酸酯共聚物、9kg分散乳胶、1kg羟乙基乙基纤维素醚、1kg羟乙基纤维素醚，倒入双锥混合机并干混5min，得均匀的发泡组合物；
(2)悬浮料浆、泡沫料浆的制备
1)悬浮料浆的制备
将基础料与添加剂倒入搅拌机中，并加入0.4吨的水，搅拌20min得悬浮料浆；
2)泡沫料浆的制备
将把发泡组合物和5kg氧化铝溶胶加入到搅拌机中，然后搅拌桨以50m/s的线速度快速混合7min，得到均匀的泡沫料浆；
(3)浇注、养护
将泡沫料浆注入不锈钢模具中，在空气温度和湿度分别为30℃、95％的环境中养护0.5h使其固化，然后脱模得坯体；
(4)干燥、烧制
将固化后的坯体脱模，采用常压热风干燥法脱除其中的水分，在40℃～55℃干燥24h，得干燥坯体；干燥坯体的含水率≦2wt％，耐压强度≧1.2MPa。将干燥坯体装入电阻窑中烧成，烧成工艺同实施例26，即得刚玉质微纳孔绝隔热耐火材料。
实施例30
本实施例为实施例15中刚玉质微纳孔绝隔热耐火材料的制备方法，其制备工艺基本同实施例29，区别在于其在空气温度和湿度分别为30℃、95％的环境中养护5h才可固化脱模，且坯体采用常压热风干燥时，在40℃～55℃的环境中干燥了36h，干燥时间大大延长，坯体干燥后的耐压强度仅0.5MPa。
实施例31
(1)基础料、添加剂组合、发泡物的制备
1)基础料的制备
基础料的制备同实施例26。
2)发泡组合物及预制泡沫的制备
取15kg乙烯与氯乙烯和月桂酸乙烯酯共聚物(德国瓦克，
Figure PCTCN2021144043-appb-000056
)、3kg丙烯酸酯聚合物(美国国民淀粉，
Figure PCTCN2021144043-appb-000057
)、0.5kg乙基纤维素醚(荷兰阿克苏公司)、1.5kg羟丁基甲基纤维素醚与磺酸乙基纤维素醚(美国陶氏化学)，倒入双锥混合机干混5min，得均匀发泡组合物；称取10kg动物蛋白发泡剂用发泡机预制备成泡沫。
(2)悬浮料浆、泡沫料浆的制备
1)悬浮料浆的制备
将基础料与添加剂组合倒入搅拌机中，并加入0.38吨的水，搅拌20min得悬浮料浆。
2)泡沫料浆的制备
将把发泡组合物和5kg氧化铝溶胶(Al 2O 3含量≧20％)及预制泡沫加入到搅拌机，然后搅拌桨以50m/s线速度快速剪切混合7min，得均匀泡沫料浆。
(3)浇注、养护
将泡沫料浆注入不锈钢模具中，在空气温度和湿度分别为30℃、95％的环境中养护0.6h使其固化，然后脱模得坯体。
(4)干燥、烧制
将固化后的坯体脱模，采用常压热风干燥法脱除其中的水分，在40℃～55℃干燥24h，得干燥坯体；干燥坯体的含水率≦2wt％，耐压强度≧0.9MPa。将干燥坯体装入电阻窑中烧成，烧成工艺同实施例26，即得刚玉质微纳孔绝隔热耐火材料。
三、实验例
实验例1
分别对实施例1～15及31中的刚玉质微纳孔绝隔热耐火材料进行气孔结构测试，采用压汞法测定材料的平均孔径及孔径分布，其中实施例6所制材料的孔径分布图如图8所示；采用GB/T2998-2001测试式样的总气孔率，同时采用GB/T2997-2000测试式样的闭口气孔率。测试结果如表1所示。
表1 孔结构测试结果
样品 平均孔径(μm) 气孔率(％) 闭口气孔率(％)
实施例1 7.1 91.1～92 63.3～65
实施例2 30 89.2～90.3 33.2～34.5
实施例3 15.4 87.3～88.8 35.6～36.1
实施例4 11.3 83.4～85.5 38.7～39.1
实施例5 7.2 79.3～81.2 41.3～42.4
实施例6 2.7 75.6～76 45.6～46.7
实施例7 0.1 78～79.5 49.9～51.3
实施例8 1.2 72.1～73.7 41.2～43.5
实施例9 1.8 66.4～67.5 35.7～36.1
实施例10 2.4 55.9～56.7 28.5～31.2
实施例11 4.3 50.3～53.2 23.3～24.5
实施例12 5.8 45～47.4 20～21.3
实施例13 6.0 52.3～54.7 18.2～19.3
实施例14 8.0 48.4～49.3 21.2～22.4
实施例15 36 47.8～50.2 13.2～14.5
实施例31 14.5 49.7～51.5 20.4～21.5
实验例2
对实施例1～15及31中的刚玉质微纳孔绝隔热耐火材料进行性能测试，具体测试方法为：根据中国国家标准GB/T2998-2001对材料的体积密度进行测试；耐压强度按照GB/T 3997.2-1998进行测试；重烧线变化率按照GB/T 3997.1-1998进行测试；热导率按照YB/T4130-2005进行测试，测试结果如表2所示。
表2 性能测试结果
Figure PCTCN2021144043-appb-000058
Figure PCTCN2021144043-appb-000059
由表1和表2可知，本发明的刚玉质微纳孔绝隔热耐火材料具有较好的微纳米尺寸孔径、超低导热、高强度的优点，可以满足不同的需求。
对比实施例1～2及15～16可以看出，在所制试样密度相差不大的情况下，分散剂的引入可使用水量显著减少；对比实施例4～5可以看出，红外遮光剂的引入显著减小了试样的高温热导率；对比实施例5～7可以看出，随着泡孔调节剂量的增多，试样的气孔孔径有效减小，且平均孔径的减小使试样的强度显著增强、热导率降低；对比实施例7～13可以看出，随着有机固化剂引入量的增多，干燥后试样坯体的强度逐渐增大；对比实施例6～7及21～22可以看出，随着搅拌速度的增大，试样的平均孔径逐渐减小。对比实施例11和13、及26和28可以看出，烧结助剂的引入使烧后试样的密度增大、强度升高；对比实施例11和14、及26和29可以看出，基础原料经过球磨后，试样烧结后的结合性更好，致密度增大，强度升高。对比实施例14和15，及29和30可以看出，没有添加有机固化剂时，坯体所需养护时间大大延长，才可以脱模，且坯体干燥后的强度大大降低，烧后试样的气孔孔径明显增大，体积密度和热导率显著升高，总气孔率和闭口气孔率及强度均明显下降。对比实施例14和31可以看出，当对发泡剂采用预发泡时，泡沫料浆的搅拌时间缩短，但坯体的养护时间延长，坯体干燥后强度减弱，烧后制品气孔的平均孔径增大，气孔率和高温热导率升高，体积密度和强度下降。
本发明在体积密度、气孔率、闭口气孔率、气孔孔径、耐压强度、热导率方面可实现可控可调，而且通过在刚玉质绝隔热耐火材料中微纳米尺寸气孔结构的构筑，可在保证材料气孔率及体积密度与现有技术相近的情况下，表现出更加优异的力学和绝隔热性能，在实际工程及技术应用中具有更好的实践意义，使其非常适用于冶金、石化、建材、陶瓷、机械等行业用工业窑炉的热面衬里、背衬及填充密封与隔热材料，还可适用于发动机引擎隔热部件及军工和航空航天等领域。

Claims (16)

  1. 一种刚玉质微纳孔绝隔热耐火材料，其特征在于，所述刚玉质微纳孔绝隔热耐火材料由基础料、添加料和水制成；制品的化学组成中Al 2O 3的含量为75～99.9％，或者为85～99.9％，或者为90～99.9％，或者为98～99.9％，或者为98～99.9％，或者为99～99.9％；
    所述基础料由以下质量分数的组分组成：氧化铝质原料10～100％，铝硅质原料0～90％，和二氧化硅质原料0～20％，上述三种基础原料质量百分比之和为100％；
    所述添加料至少包括发泡组合物，使用或不使用添加剂；所述发泡料由发泡剂、无机固化剂、有机固化剂和泡孔调节剂组成，以基础料的质量为基准，发泡剂、无机固化剂、有机固化剂、泡孔调节剂的添加质量分别为0.01～10％、0.1～20％、0.1～2％、0.01～1％；使用添加剂时，所述添加剂选自分散剂、悬浮剂、烧结助剂、红外遮光剂中的一种或两种以上组合，以基础料的质量为基准，烧结助剂和红外遮光剂的添加质量均不大于10％；
    所述水的质量为基础料质量的20～200％或30～200％。
  2. 根据权利要求1所述的刚玉质微纳孔绝隔热耐火材料，其特征在于，所述刚玉质微纳孔绝隔热耐火材料的平均孔径为0.1～30μm，总气孔率为30～92％，闭口型气孔率为15～65％，体积密度为0.3～2.0g/cm 3，常温耐压强度为2～190MPa，常温热导率为0.03～0.18W/(m·K)，350℃时的热导率为0.04～0.26W/(m·K)，1100℃时的热导率为0.05～0.35W/(m·K)。
  3. 根据权利要求1所述的刚玉质微纳孔绝隔热耐火材料，其特征在于，所述氧化铝质原料为工业氧化铝、工业Al(OH) 3、β-Al 2O 3、γ-Al 2O 3、δ-Al 2O 3、χ-Al 2O 3、κ-Al 2O 3、ρ-Al 2O 3、θ-Al 2O 3、η-Al 2O 3、α-Al 2O 3、电熔刚玉、烧结刚玉、板状刚玉、氢氧化铝、勃姆石、水铝石、正丁醇铝、异丙醇铝、仲丁醇铝、六水合氯化铝、九水合硝酸铝中的一种或多种；所述氧化铝质原料中Al 2O 3的质量百分含量为65～99.9％；
    所述铝硅质原料为烧结莫来石、电熔莫来石、高岭土、铝矾土、铝硅系均质料、煤矸石、蓝晶石、红柱石、硅线石、叶蜡石、钾长石、钠长石、钙长石、钡长石、瓷石、碱石、云母、锂辉石、珍珠岩、蒙脱石、伊利石、埃洛石、迪开石、焦宝石、黏土、膨润土、广西白土、苏州土、木节土、粉煤灰、漂珠中的一种或多种；所述铝硅质原料中Al 2O 3的质量百分含量为18～90％，SiO 2的质量百分含量为8～75％；
    所述二氧化硅质原料为α-石英、β-石英、α-鳞石英、β-鳞石英、α-方石英、β-方石英、脉石英、砂岩、石英岩、燧石、胶结硅石、河砂、海砂、白炭黑、硅藻土、硅微粉、稻壳、碳化稻壳、稻壳灰、正硅酸甲酯、正硅酸乙酯、甲基三甲氧基硅烷中的一种或多种；所述二氧化硅质原料中SiO 2的质量百分含量为28～99％。
  4. 根据权利要求1所述的刚玉质微纳孔绝隔热耐火材料，其特征在于，以基础料的质量为基准，分散剂的添加质量不大于1％，悬浮剂的添加质量均不大于10％；所述分散剂为聚羧酸类分散剂、聚羧酸醚分散剂、磺化蜜胺缩聚物、萘系分散剂、木质素磺酸盐类分散剂、氨基磺酸系分散剂、乙二胺四乙酸钠、三聚氰胺甲醛缩聚物、多聚磷酸钠、聚丙烯酸钠、柠檬酸钠、腐殖酸钠、磷酸钠、碳酸钠中的一种或多种；
    所述悬浮剂为膨润土、海泡石、凹凸棒、聚合氯化铝、聚合硫酸铝、壳聚糖、韦兰胶、琼脂、聚乙二醇、聚乙烯醇、聚丙烯酰胺、聚丙烯酸胺、聚乙烯吡咯烷酮、干酪素、十六醇、蔗糖、糊精、微晶纤维素、纤维素纤维、纤维素纳米纤维、纤维素纳米晶、可溶性淀粉中的一种或多种。
  5. 根据权利要求1所述的刚玉质微纳孔绝隔热耐火材料，其特征在于，所述烧结助剂为ZnO、Fe 2O 3、V 2O 5、SiF 4、AlF 3、AlF 3·3H 2O、MnO 2、CuO、CuSO 4、CaO、MgO、SrO、BaO、WO 3、Er 2O 3、Cr 2O 3、La 2O 3、YbO、Y 2O 3、CeO 2中的一种或多种。
  6. 根据权利要求1所述的刚玉质微纳孔绝隔热耐火材料，其特征在于，所述红外遮光剂为金红石、TiO 2、TiC、K 4TiO 4、K 2Ti 6O 13、Sb 2O 3、Sb 2O 5、ZrO 2、CoO、CoCl 2、Co(NO 3) 2、NiCl 2、Ni(NO 3) 2、ZrSiO 4、Fe 3O 4、B 4C、SiC中的一种或多种。
  7. 根据权利要求1所述的刚玉质微纳孔绝隔热耐火材料，其特征在于，所述发泡剂为表面活性剂和/或蛋白质型发泡剂，发泡倍数为8～60倍；所述表面活性剂选自阳离子型表面活性剂、阴离子型表面活性剂、非离子型表面活性剂、两性表面活性剂、Gemini型表面活性剂、Bola型表面活性剂、Dendrimer型表面活性剂中的一种或多种；所述蛋白质型发泡剂为动物蛋白发泡剂、植物蛋白发泡剂和/或污泥蛋白发泡剂。
  8. 根据权利要求1所述的刚玉质微纳孔绝隔热耐火材料，其特征在于，所述无机固化剂为氧化铝溶胶、硅铝溶胶、氧化硅溶胶、氧化铝凝胶、硅铝凝胶、氧化硅凝胶、Al 2O 3微粉、SiO 2微粉、硅酸二钙、二铝酸钙、硅酸三钙、铝酸三钙、铝酸一钙、磷酸铝、七铝酸十二钙、水玻璃、铁铝酸四钙、软质结合黏土中的一种或多种；
    所述有机固化剂选自水溶性聚合物树脂、低甲氧基果胶、鹿角菜胶、卡拉胶、羟丙基瓜尔胶、刺槐树胶、刺槐豆胶、结冷胶、可得然胶、海藻酸盐、魔芋胶、分散乳胶中的一种或两种以上组合；所述水溶性聚合物树脂选自醋酸乙烯酯与乙烯共聚物、醋酸乙烯酯均聚物、丙烯酸酯聚合物、乙烯与乙酸乙烯酯共聚物、乙烯与氯乙烯共聚物、醋酸乙烯酯与叔碳酸乙烯酯共聚物、醋酸乙烯与叔碳酸乙烯共聚物、丙烯酸酯与苯乙烯共聚物、醋酸乙烯酯与高级脂肪酸乙烯酯共聚物、醋酸乙烯酯与乙烯和氯乙烯共聚物、醋酸乙烯酯与乙烯 和丙烯酸酯共聚物、异丁烯与马来酸酐共聚物、乙烯与氯乙烯和月桂酸乙烯酯共聚物、醋酸乙烯酯与乙烯和高级脂肪酸共聚物、醋酸乙烯酯与丙烯酸酯及高级脂肪酸乙烯酯共聚物、醋酸乙烯酯与乙烯和月桂酸乙烯酯共聚物、醋酸乙烯与叔碳酸乙烯酯和丙烯酸酯共聚物中的一种或两种以上组合。
  9. 根据权利要求1所述的刚玉质微纳孔绝隔热耐火材料，其特征在于，所述泡孔调节剂选自纤维素醚、淀粉醚、木质纤维素、皂素中的一种或两种以上组合。
  10. 根据权利要求9所述的刚玉质微纳孔绝隔热耐火材料，其特征在于，所述纤维素醚选自水溶性纤维素醚、甲基纤维素醚、羧甲基纤维素醚、羧甲基甲基纤维素醚、羧甲基乙基纤维素醚、羧甲基羟甲基纤维素醚、羧甲基羟乙基纤维素醚、羧甲基羟丙基纤维素醚、羧甲基羟丁基纤维素醚、羟甲基纤维素醚、羟乙基纤维素醚、羟乙基甲基纤维素醚、羟乙基乙基纤维素醚、乙基纤维素醚、乙基甲基纤维素醚、丙基纤维素醚、羟丙基纤维素醚、羟丙基甲基纤维素醚、羟丙基乙基纤维素醚、羟丙基羟丁基纤维素醚、羟丁基甲基纤维素醚、磺酸乙基纤维素醚中的一种或两种以上组合。
  11. 如权利要求1～10中任一项所述的刚玉质微纳孔绝隔热耐火材料的制备方法，其特征在于，包括以下步骤：
    (1)使用添加剂时，将基础料、添加剂在水中分散成悬浮料浆；不使用添加剂时，将基础料、在水中分散成悬浮料浆；
    (2)将发泡剂、无机固化剂、有机固化剂、泡孔调节剂与悬浮料浆进行搅拌发泡，制得泡沫浆料；
    (3)将泡沫料浆注入模具中养护，脱模后得到坯体；坯体干燥后在1200～1800℃的温度下烧结。
  12. 根据权利要求11所述的刚玉质微纳孔绝隔热耐火材料的制备方法，其特征在于，步骤(1)中，所述悬浮料浆中固体颗粒的平均粒径不高于1mm，或不高于74μm，或不高于50μm，或不高于44μm，或不高于30μm。
  13. 根据权利要求11所述的刚玉质微纳孔绝隔热耐火材料的制备方法，其特征在于，步骤(2)中，搅拌发泡采用搅拌桨高速搅拌剪切发泡，搅拌桨外缘的线速度为20～200m/s，或50～200m/s，或80～200m/s，或100～200m/s，或150～200m/s，或180～200m/s。
  14. 根据权利要求11所述的刚玉质微纳孔绝隔热耐火材料的制备方法，其特征在于，步骤(3)中，养护环境的空气温度为1～35℃，湿度为50～99.9％；养护时间为0.2～12h。
  15. 根据权利要求11所述的刚玉质微纳孔绝隔热耐火材料的制备方法，其特征在于， 步骤(3)中，坯体干燥选自常压干燥、超临界干燥、冷冻干燥、真空干燥、红外干燥、微波干燥中的一种或两组以上的组合；坯体干燥至坯体含水率≦3wt％；干燥后坯体的耐压强度≧0.7MPa。
  16. 根据权利要求11～16中任一项所述的刚玉质微纳孔绝隔热耐火材料的制备方法，其特征在于，步骤(3)中，烧结制度为：从室温以1～5℃/min升温至500℃，再以5～30℃/min升温至1000℃，保温0.5～1.5h，再以1～30℃/min升温至1200～1800℃，保温1～10h，后以10～20℃/min降温至1100℃，并在1100℃保温0.5～1.5h，再以5～30℃/min降温至500℃，于500℃保温0.5h，最后以1～10℃/min降温至50～80℃。
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