CN114855276A - Mullite single crystal material prepared from industrial silica-alumina gel waste at low temperature and preparation method thereof - Google Patents
Mullite single crystal material prepared from industrial silica-alumina gel waste at low temperature and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a mullite single crystal material prepared from industrial silica-alumina gel waste at a low temperature and a preparation method thereof, belonging to the technical field of mullite single crystal materials. The method for preparing the mullite single crystal material from the industrial alumino-silica gel waste at low temperature comprises the following steps: industrial silica-alumina gel waste, fluoride salt, fluxing agent and aluminum source supplement are taken as raw materials, water is added for ball milling and drying, and then calcination is carried out at the temperature of 600-800 ℃, so as to obtain the mullite single crystal material. The mullite single crystal material has high purity and low synthesis temperature; meanwhile, the invention provides a simple and feasible preparation method, effectively utilizes industrial waste residues, is energy-saving and environment-friendly, and has remarkable economic benefit.
Description
Technical Field
The invention relates to a mullite single crystal material prepared from industrial silica-alumina gel waste at a low temperature and a preparation method thereof, belonging to the technical field of mullite single crystal materials.
Background
The industrial silica-alumina gel waste is one of byproducts of the oil refining catalyst industry, belongs to chemical waste liquid, wherein the annual emission amount of the industrial silica-alumina gel waste reaches 3000 ten thousand tons, the resource utilization rate is low, and a large amount of the industrial silica-alumina gel waste is accumulated and buried, so that the industrial silica-alumina gel waste occupies fertile fields, pollutes water and soil resources, and even causes serious secondary disasters. The main chemical component of industrial silica-alumina gel waste is SiO 2 And Al 2 O 3 Belonging to useful mineral resources. Therefore, it is important to develop a sustainable method for recycling industrial silica alumina gel waste.
The mullite has a chemical composition of Al 2 (Al 2+x Si 2-2x )O 10-x And x is the number of oxygen atoms lost by unit cell (x is in the range of 0.2-0.9), belongs to an orthorhombic system, and the structure thereof is internally connected by sharing edges and sharing angle tops, the tetrahedrons form octahedral chains and tetrahedral double chains along the axial direction, and the crystal structure has higher growth rate along the axial crystallographic direction, so that the mullite crystal is highly anisotropic. Mullite single crystal material has high thermal stability, low thermal expansion, thermal conductivity, high creep and corrosion resistance, and appropriate strength and fracture toughness, making it the most potential material for applications requiring high temperature and corrosion resistance. In particular, the method has wide application scenes in the fields of aerospace, machinery, energy, electronics, environmental protection, chemical industry and the like. In addition, the mullite monocrystal material body has wide application in the fields of material reinforcement, toughening, refractoriness improvement, adsorption filtration and the like, is particularly suitable for reinforcing fibers of Fiber Reinforced Plastics (FRP), Fiber Reinforced Metals (FRM) and Fiber Reinforced Ceramics (FRC),is an important functional material in the field of materials. The mullite single crystal material is applied to various fields due to excellent chemical and physical properties, but the preparation is difficult, the popularization and the popularization of the mullite single crystal material are limited due to the uniqueness of a complex synthesis technology, the quantity of the mullite single crystal material is rare, and the price of the mullite single crystal material is high. If the industrial silica-alumina gel waste is subjected to landfill treatment, the environment is seriously polluted, and the time concept of energy conservation and emission reduction is not met, so that the development of high-added-value resource utilization of the industrial silica-alumina gel waste has very important significance.
For example, Chinese patent CN 201910187746.0 discloses a method for preparing mullite whisker from kaolin at low temperature, wherein the method uses kaolin as raw material, cryolite (Na) 3 AlF 6 ) And Al (OH) 3 The mullite whisker is prepared at 900 deg.c by regulating Si/Al ratio for molten salt medium, and the main material of the process is not industrial silica-alumina gel waste. The phase-change reaction temperature for preparing mullite by taking kaolin as a main raw material is more than 1000 ℃, so that the mullite whisker is prepared. For example, Chinese patent CN 201711172952.1 discloses a method for preparing a ceramic material for in-situ generation of mullite whiskers, which comprises the steps of taking coal gangue and high-alumina as raw materials, adding polycrystalline mullite fiber as seed crystal, chlorine fluoride and acid-activated potassium feldspar to prepare mullite whiskers at 1300-1500 ℃. The raw materials used in the two methods are not industrial silica-alumina gel wastes, but the industrial silica-alumina gel wastes are used as main raw materials, and the phase-change reaction temperature for preparing the mullite by adding a compound salt system is above 650 ℃, and generally above 700 ℃ is needed to prepare the mullite single crystal product.
Disclosure of Invention
The invention aims to provide a mullite single crystal material prepared by industrial silica alumina gel waste at low temperature, which has high purity and low synthesis temperature; meanwhile, the invention provides a simple and feasible preparation method, effectively utilizes industrial waste, is energy-saving and environment-friendly, and has remarkable economic benefit.
The method for preparing the mullite single crystal material from the industrial alumino-silica gel waste at low temperature comprises the following steps: the method comprises the steps of taking industrial silica-alumina gel waste, fluoride salt, a fluxing agent and an aluminum source supplement as raw materials, adding water, carrying out ball milling and drying, and then calcining at 600-800 ℃ to obtain the mullite single crystal material.
Preferably, the industrial silica alumina gel waste comprises the following components: al (Al) 2 O 3 、SiO 2 、MnO 2 、Na 2 O、SO 3 、CaO、MgO、GeO 2 。
Preferably, the fluoride salt is one or more of lithium fluoride, ammonium fluoride or cryolite.
Preferably, the fluxing agent is one or more of potassium sulfate, aluminum potassium sulfate or potassium chloride.
Preferably, the aluminum source supplement is one or two of aluminum sulfate or aluminum hydroxide.
Preferably, the molar ratio of the industrial silica alumina gel waste to the fluoride salt to the fluxing agent to the aluminum source supplement is 1 (0.5-0.8) to (0.9-1.3) to (1.2-1.5), and the molar content of the industrial silica alumina gel waste is based on the main component Al contained in the industrial silica alumina gel waste 2 O 3 And SiO 2 Is measured on a molar basis.
Preferably, the mass ratio of the grinding balls to the raw materials to the water is (2-2.5): (1-1.2): 1.5-3 during ball milling.
Preferably, the drying temperature is 110-130 ℃ and the drying time is 3-15 hours.
Preferably, the firing system in the firing step is: and keeping the temperature from room temperature to 600-800 ℃, keeping the temperature at 650 ℃ for 30-120 min, and keeping the temperature at the final firing temperature for 3-12 hours.
The temperature is raised from room temperature to 600-800 ℃ at a rate of 5 ℃/min, and the temperature is raised from 600-800 ℃ to the final firing temperature at a rate of 1-3 ℃/min.
Preferably, the present invention comprises the steps of:
according to the molar ratio of 1:0.5-0.8:0.9-1.3:1.2-1.5 of industrial silica-alumina gel waste, fluoride salt, fluxing agent and aluminum source supplement, in terms of corresponding weight percentage, 10-50% of industrial silica-alumina gel waste, 1-40% of fluoride salt, 10-70% of fluxing agent and 10-70% of aluminum source supplement are mixed, deionized water with the amount of 1.5-3 times of the mixed material is added, and the washing times are 3-8 times. Mixing and ball-milling the mixture in a ball mill for 6 to 10 hours; the evenly mixed raw materials are placed in a corundum crucible and dried for 8 to 12 hours at the temperature of 110-130 ℃, then are calcined at the temperature of 600 to 800 ℃ by a box-type resistance furnace, are kept warm for 6 to 12 hours, and then are cooled, washed and dried along with the furnace to obtain the mullite single crystal material.
The main chemical component of the industrial silica-alumina gel waste is Al 2 O 3 And SiO 2 Providing a silicon source and an aluminum source required by synthesizing the mullite monocrystal; MnO is also carried in industrial silica-alumina gel waste 2 、GeO 2 The beneficial single crystals of the oxide impurities such as MgO, CaO and the like are nucleated at low temperature and develop into complete crystal forms. Therefore, cheap industrial silica-alumina gel waste with rich sources can be used as a raw material, a part of aluminum source is added to adjust the silica-alumina ratio, and fluoride salt and fluxing agent are added to be used as a composite molten salt medium at a relatively low temperature<Preparing the high-purity mullite single crystal material at 800 ℃.
The preparation method of the polyurethane rigid foam material reinforced by the high-purity mullite monocrystal material comprises the following steps:
uniformly stirring and mixing 0.01-15% of the prepared high-purity mullite monocrystal with polyether polyol 4110, a chain extender, a foaming agent, a catalyst, a foam stabilizer and the like according to a certain proportion to obtain a component A; the addition amounts of the chain extender, the foaming agent, the catalyst, the foam stabilizer and the like are respectively 1 to 15 percent, 5 to 35 percent, 0.1 to 10 percent of the total mass of reactants, the mixture is uniformly mixed to be used as a white material, and then the white material is stirred with 48.40g of PAPI-27 for 18s to be foamed, and the hard polyurethane material is obtained after cooling.
Preferably, the foaming agent is one or more of cyclopentane, 1, 1, 1, 3, 3-pentafluorobutane, 1, 1, 2-tetrafluoroethane, N-Azobisisobutyronitrile (AZDN), N-butane, 1, 1-dichloro-1-fluoroethane, propane-butane, water and Azodicarbonamide (AC).
Preferably, the catalyst is one or more of tris (dimethylaminopropyl) hexahydrotriazine, dimethylethanolamine, N, N, N '-pentamethyldiethylenetriamine, triethylenediamine, N, N-dimethylpiperazine, triethylenediamine, dimethylaminoethyl ether, pentamethyldiethylenetriamine, 2' -dimorpholinodiethyl ether, N, N-dimethylbenzylamine, dibutyltin dilaurate and triethanolamine.
Preferably, the foam stabilizer is one or more of silicone oil L-600, silicone oil SE-232, silicone oil CGY-5, silicone oil DC-193, silicone oil SC-154 and silicone oil SC-155.
The industrial silica-alumina gel waste and the composite molten salt generate synergistic effect, eutectic is formed at a lower temperature (800 ℃), and meanwhile, an ideal liquid phase environment is provided by a composite molten salt system to promote the growth of mullite single crystals. The oxide impurities of the industrial silica alumina gel waste can also assist the nucleation and uniform growth of the mullite monocrystal for the growth of the mullite monocrystal. The eutectic is formed under low temperature conditions, and the eutectic mainly comprises the following factors:
(1) the synergistic effect of the composite molten salt medium and the industrial alumino-silica gel waste is as follows:
the mixed molten salt medium and industrial silica-alumina gel waste can activate Al 2 O 3 And SiO 2 To assist the mullite reaction and provide an ideal liquid phase single crystal growth environment. In a liquid phase matrix of the composite molten salt, the composite molten salt medium and the industrial silica alumina gel waste act synergistically to promote the silica alumina gel to form mullite monocrystal at a lower temperature. The principle is that the composite molten salt medium and industrial silica-alumina gel waste form a eutectic liquid drop source, and F generated by fluoride salt is generated due to the reaction condition in a closed space - Attack Al continuously 3+ And Si 4+ To form gaseous AlAF and SiF 4 High proportion of SiF in the gas when the concentration of both is supersaturated 4 And AlAF gas molecules are precipitated in small droplets on the liquid-solid interface, causing the solution to chemically react with the vapor to form mullite crystals. Therefore, the fluorine ions generated in the sample containing the composite molten salt are easy to undergo a phase transition process with alumina and silica in the system. Because the liquid phase matrix of the composite molten salt medium accelerates the diffusion rate of the medium, the composite molten salt medium and the oxide in the industrial silica-alumina gel waste generate synergistic effect to accelerate SiO 2 Melting of (2), loweringLow generation of glass phase, low temperature activation of Al 2 O 3 Thereby promoting the low-temperature nucleation of the mullite.
(2) The synergistic effect of oxide impurities in the industrial silica-alumina gel waste is as follows:
MnO in industrial silica alumina gel waste 2 Can promote liquid phase sintering reaction, reduce sintering temperature and inhibit SiO 2 Growth of quartz phase, promotion of nucleation and development of mullite phase, Mn during sintering 4+ The growth of mullite grains can be accelerated; meanwhile, a small amount of GeO exists in industrial silica-alumina gel waste 2 The MgO is used as a composite sintering aid, and the two are mixed to generate a synergistic effect, so that the effect is obvious, the sintering temperature is reduced, and the sintering promoting effect is good; in addition, CaO can promote the formation of mullite at a lower temperature and has a promoting effect on the nucleation and growth of mullite crystals. The single crystal synthesized by the method belongs to coarse interface growth, has strong anti-interference capability, smooth surface of the whisker, less crystal defects and more complete single crystals, and impurities mainly exist in the form of point defects, which can be fully proved by SEM.
The invention takes industrial alumino-silica gel waste as raw material to prepare the mullite single crystal material at low temperature (less than 800 ℃), and is a method with low energy consumption, low cost, high efficiency and environmental protection. The industrial silica-alumina gel waste has rich sources, the aim of recycling chemical waste is fulfilled by preparing the mullite single crystal material with low cost, the method has important significance for the industries of reinforcing and toughening refractory materials and materials, and particularly has wide application prospect in toughening ceramic matrix composite materials and inorganic material coatings by mullite whiskers. The method recycles the waste industrial silica-alumina gel waste to be changed into the high-purity mullite monocrystal material, accords with the development plan of the national fourteen-five cycle economy, not only has low price, but also changes waste into valuable, protects the environment, saves energy, and can bring good social benefit and economic benefit.
The high-purity mullite monocrystal material toughened polyurethane foam material prepared by the method has the advantages that the compression strength is greatly improved, the thermal insulation performance is excellent, and the heat conductivity coefficient, the apparent density, the water absorption and the like are all higher than the national standard. Therefore, the invention not only has higher environmental protection value, but also has strong practicability, higher economical efficiency and good social benefit.
Compared with the prior art, the invention has the following beneficial effects:
(1) the raw material main body used in the invention belongs to chemical waste, has wide source, solves the problems of large accumulation, occupation of precious land resources and the like by utilizing the chemical waste, and is green, energy-saving and environment-friendly;
(2) the high-purity mullite monocrystal prepared by the invention has the characteristics that the synthesis temperature is reduced by 800 ℃ compared with the traditional production process, the production process is simple, the yield is high, the effects of energy conservation and consumption reduction are achieved, and the high-valued application of industrial waste recovery is realized; the mullite whisker powder has good dispersibility and fluidity, and has the advantages of granularity meeting the nanometer-level requirement, uniform appearance and size and the like;
(3) the purity of the high-purity mullite monocrystal product prepared by the method reaches over 99.95 percent; the crystal whisker has high crystallinity, very smooth surface, no obvious defect, high size uniformity, average diameter of 0.3-0.4 mu m, average length of 9-12 mu m and length-diameter ratio of 28-33, and can be used as a high-quality reinforcing material for ceramic, military industry and rubber industry;
(4) the crystal whisker prepared by the method has high yield of over 99.91 percent, low cost and simple process, and is beneficial to industrial production.
Drawings
FIG. 1 is an SEM image of a mullite single crystal prepared without adding a complex molten salt system to a pure material;
FIG. 2 is an SEM image of mullite single crystal prepared by waste materials without adding a composite molten salt;
FIG. 3 is TEM and HRTEM images of a mullite single crystal obtained in example 1;
FIG. 4 is an SEM photograph of a mullite single crystal obtained in example 1;
FIG. 5 is an XRD pattern of a mullite single crystal obtained in example 1;
FIG. 6 is an infrared plot of the polyurethane foam without and with mullite whisker reinforcement obtained in example 1;
FIG. 7 is an SEM image of mullite whisker reinforced polyurethane foam obtained according to example 1;
wherein a is a polyurethane foam material before adding mullite whisker; b is polyurethane foam material reinforced by adding mullite whisker.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the practice of the invention.
The starting materials used in the examples are, unless otherwise specified, commercially available.
The specific steps not described in the examples are within the common knowledge of a person skilled in the art.
The preparation method for preparing the mullite single crystal material from the industrial alumino-silica gel waste at low temperature comprises the following steps:
industrial silica-alumina gel waste, fluxing agent, fluoride salt, aluminum source supplement and deionized water are mixed, sintered after ball milling, and subjected to synthesis reaction to obtain the mullite monocrystal material.
Pretreating the industrial silica-alumina gel waste, and sequentially performing ball milling, drying and washing;
the ball: material preparation: the water mass ratio is 2:1: 1.5.
The rotating speed of the ball mill is 300 r/min.
The ball milling time was 6 hours.
The drying process required drying at 110 ℃ for 6 hours.
The firing system of the calcining procedure is from room temperature to 650 ℃ at 5 ℃/min, the temperature is preserved for 60min at 650 ℃, and then the temperature is raised to the final firing temperature at 3 ℃/min and the temperature is preserved for 5 h.
The mass ratio of the chemical components of the industrial silica-alumina gel waste is as follows:
TABLE 1 Mass ratio of chemical components of industrial alumino-silica gel waste
Comparative example 1
Synthesis of a conventional mullite single crystal material:
mixing Al 2 O 3 And SiO 2 Pure material is used as the raw material for synthesizing mullite monocrystal, and Al is used 2 O 3 /SiO 2 Mixing materials with the molar ratio of 1.5, and adding Al 2 O 3 And SiO 2 AlF 10% of the total mass 3 ·3H 2 And mixing the materials evenly, mixing the balls/materials according to the mass ratio of 7:5, ball-milling for 12 hours, sintering at 1350 ℃ in a box-type resistance furnace, and preserving heat for 8 hours to prepare the mullite monocrystal material.
The raw materials of the method are not industrial silica-alumina gel wastes, and the synergistic effect of the composite molten salt is avoided, so that the reaction temperature for preparing the mullite monocrystal is high, and the yield is 86.4%.
Comparative example 2
The mullite whisker prepared by the waste without adding the composite molten salt:
taking 18g of industrial silica-alumina gel waste and 22g of aluminum hydroxide, adding deionized water with the mass 1.5 times of that of the mixture, and mixing and ball-milling for 6 hours in a ball mill; and (3) placing the uniformly mixed raw materials into a ceramic crucible, drying for 12 hours at 110 ℃, calcining for 6 hours at 1300 ℃ by using a box-type resistance furnace, and then cooling along with the furnace to finally obtain the mullite whisker.
The raw materials of the method are industrial silica-alumina gel wastes, but the synergistic effect of the composite molten salt is not generated, the reaction temperature for preparing the mullite monocrystal is high, the yield is 75.4%, the average length of the mullite monocrystal is 0.71um, and the average width of the mullite monocrystal is 0.025 um.
Example 1
Taking 22g of industrial silica-alumina gel waste, 21g of aluminum hydroxide, 10g of aluminum sulfate, 7g of lithium fluoride, 2g of ammonium fluoride, 5g of cryolite, 17g of potassium sulfate, 6g of potassium chloride and 10g of potassium aluminum sulfate, uniformly mixing grinding balls, mixed raw materials and grinding solvent (water) according to the volume ratio of 2:1:1.5, carrying out ball milling for 6h at the rotating speed of 300r/min, and placing in a crucible to dry for 12h at 110 ℃; then placing the mullite monocrystal in a muffle furnace, heating to 600 ℃ at a heating rate of 5 ℃/min, heating to 735 ℃ at a heating rate of 2 ℃/min, calcining for 10h, cooling along with the furnace, finally washing with deionized water for 8 times, and drying to obtain the mullite monocrystal.
The polyurethane rigid foam material is enhanced by using a high-purity mullite monocrystal material:
uniformly stirring 0.1g of the prepared high-purity mullite monocrystal with 20g of polyether polyol 4110, 3g of silicone oil CGY-5, 0.2g of triethanolamine, 0.2g of organic tin and 15g of cyclopentane to obtain a white material, stirring the white material with 48.40g of PAPI-27 for 18s to foam the white material, and cooling to obtain the hard polyurethane material.
Example 2
Taking 23g of industrial silica-alumina gel waste, 24g of aluminum hydroxide, 8g of lithium fluoride, 5g of cryolite, 3g of ammonium fluoride, 17g of potassium sulfate, 10g of potassium chloride and 10g of potassium aluminum sulfate, uniformly mixing grinding balls, mixed raw materials and grinding solvent (water) according to the volume ratio of 2:1:1.5, carrying out ball milling for 6h at the rotating speed of 300r/min, and placing in a crucible to dry for 12h at 110 ℃; then placing the mullite monocrystal in a muffle furnace, heating to 600 ℃ at a heating rate of 5 ℃/min, heating to 800 ℃ at a heating rate of 2 ℃/min, calcining for 10h, cooling along with the furnace, finally washing with deionized water for 8 times, and drying to obtain the mullite monocrystal.
The polyurethane rigid foam material is enhanced by using a high-purity mullite monocrystal material:
uniformly stirring 0.2g of the prepared high-purity mullite monocrystal with 20g of polyether polyol 4110, 3g of silicone oil CGY-5, 0.2g of dimethylethanolamine, 0.2g of organic tin and 15g of 1, 1, 1, 3, 3-pentafluorobutane to obtain a white material, stirring the white material with 48.40g of PAPI-27 for 18s to foam the white material, and cooling to obtain the hard polyurethane material.
Example 3
Taking 20g of industrial silica-alumina gel waste, 34g of aluminum sulfate, 7g of lithium fluoride, 3g of cryolite, 2g of ammonium fluoride, 15g of potassium sulfate, 9g of potassium chloride and 10g of potassium aluminum sulfate, uniformly mixing grinding balls, mixed raw materials and grinding solvent (water) according to the volume ratio of 2:1:1.5, carrying out ball milling for 6h at the rotating speed of 300r/min, and placing in a crucible to dry for 12h at 110 ℃; then placing the mullite monocrystal in a muffle furnace, heating to 600 ℃ at a heating rate of 5 ℃/min, heating to 800 ℃ at a heating rate of 2 ℃/min, calcining for 10h, cooling along with the furnace, finally washing with deionized water for 8 times, and drying to obtain the mullite monocrystal.
The polyurethane rigid foam material is enhanced by using a high-purity mullite monocrystal material:
0.3g of the prepared high-purity mullite monocrystal, 20g of polyether polyol 4110, 3g of silicone oil L-600, 0.2g of N, N, N' -pentamethyldiethylenetriamine, 0.2g of organic tin, 15g of 1 and 1, 2-tetrafluoroethane are uniformly stirred to be used as a white material, then the white material is stirred with 48.40g of PAPI-27 for 18s to foam, and the hard polyurethane material is obtained after cooling.
Example 4
Taking 22g of industrial silica-alumina gel waste, 18g of aluminum hydroxide, 10g of aluminum sulfate, 10g of lithium fluoride, 5g of ammonium fluoride, 20g of potassium sulfate and 16g of aluminum potassium sulfate, uniformly mixing grinding balls, mixed raw materials and grinding solvent (water) according to the volume ratio of 2:1:1.5, then carrying out ball milling for 6h at the rotating speed of 300r/min, and placing in a crucible to dry for 12h at 110 ℃; then placing the mullite monocrystal in a muffle furnace, heating to 600 ℃ at a heating rate of 5 ℃/min, heating to 800 ℃ at a heating rate of 2 ℃/min, calcining for 10h, cooling along with the furnace, finally washing with deionized water for 8 times, and drying to obtain the mullite monocrystal.
The polyurethane rigid foam material is enhanced by using a high-purity mullite monocrystal material:
uniformly stirring 0.4g of the prepared high-purity mullite monocrystal, 20g of polyether polyol 4110, 3g of silicone oil SE-232, 0.2g of triethylene diamine, 0.2g of organic tin and 15g of N, N-Azobisisobutyronitrile (AZDN) to obtain a white material, stirring the white material and 48.40g of PAPI-27 for 18s to foam the white material, and cooling to obtain the hard polyurethane material.
Example 5
Taking 21g of industrial silica-alumina gel waste, 21g of aluminum hydroxide, 8g of aluminum sulfate, 9g of lithium fluoride, 5g of cryolite, 16g of potassium sulfate and 20g of potassium aluminum sulfate, uniformly mixing grinding balls, mixed raw materials and grinding solvent (water) according to the volume ratio of 2:1:1.5, then ball-milling for 6 hours at the rotating speed of 300r/min, and placing in a crucible to dry for 12 hours at 110 ℃; then placing the mullite monocrystal in a muffle furnace, heating to 600 ℃ at a heating rate of 5 ℃/min, heating to 760 ℃ at a heating rate of 2 ℃/min, calcining for 10h, cooling along with the furnace, finally washing with deionized water for 8 times, and drying to obtain the mullite monocrystal.
The polyurethane rigid foam material is enhanced by using a high-purity mullite monocrystal material:
uniformly stirring 0.5g of the prepared high-purity mullite monocrystal, 20g of polyether polyol 4110, 3g of silicone oil DC-193, 0.2g of triethylene diamine, 0.2g of organic tin and 15g of n-butane to obtain a white material, stirring the white material with 48.40g of PAPI-27 for 18s to foam the white material, and cooling to obtain the hard polyurethane material.
Example 6
Taking 21g of industrial silica-alumina gel waste, 20g of aluminum hydroxide, 10g of aluminum sulfate, 9g of ammonium fluoride, 5g of cryolite, 17g of potassium sulfate and 18g of aluminum potassium sulfate, uniformly mixing grinding balls, mixed raw materials and grinding solvent (water) according to the volume ratio of 2:1:1.5, ball-milling for 6 hours at the rotating speed of 300r/min, and drying for 12 hours at the temperature of 110 ℃ in a crucible; then placing the mullite monocrystal in a muffle furnace, heating to 600 ℃ at a heating rate of 5 ℃/min, heating to 770 ℃ at a heating rate of 2 ℃/min, calcining for 10h, cooling along with the furnace, finally washing with deionized water for 8 times, and drying to obtain the mullite monocrystal.
The polyurethane rigid foam material is enhanced by using a high-purity mullite monocrystal material:
0.6g of the prepared high-purity mullite monocrystal, 20g of polyether polyol 4110, 3g of silicone oil SC-154, 0.2g of pentamethyldiethylenetriamine, 0.2g of organic tin and 15g of 1, 1-dichloro-1-fluoroethane are uniformly stirred to be used as a white material, then the white material and 48.40g of PAPI-27 are stirred for 18s to foam, and the hard polyurethane material is obtained after cooling.
Example 7
Taking 21g of industrial silica-alumina gel waste, 30g of aluminum sulfate, 7g of lithium fluoride, 2g of ammonium fluoride, 5g of cryolite, 25g of potassium sulfate and 10g of aluminum potassium sulfate, uniformly mixing grinding balls, mixed raw materials and grinding solvent (water) according to the volume ratio of 2:1:1.5, ball-milling for 6 hours at the rotating speed of 300r/min, and drying for 12 hours at the temperature of 110 ℃ in a crucible; then placing the mullite powder in a muffle furnace, heating to 600 ℃ at the heating rate of 5 ℃/min, heating to 790 ℃ at the heating rate of 2 ℃/min, calcining for 10h, cooling along with the furnace, finally washing with deionized water for 8 times, and drying to obtain the mullite monocrystal.
The high-purity mullite monocrystal material reinforced polyurethane rigid foam material comprises the following components in percentage by weight:
uniformly stirring 1g of the prepared high-purity mullite monocrystal with 20g of polyether polyol 4110, 3g of silicone oil SC-155, 0.2g of N, N-dimethylbenzylamine, 0.2g of organic tin and 15g of propane and butane to obtain a white material, stirring the white material with 48.40g of PAPI-27 for 18s to foam the white material, and cooling to obtain the hard polyurethane material.
Application examples
In order to demonstrate the technical effect of the preparation method of the whisker/polyurethane foam material, the mullite whisker prepared in the step 1 in the embodiments 1 to 7 of the invention is subjected to performance detection.
Comparative application
In order to verify the technical effect brought by adding mullite whiskers in the process of preparing polyurethane, 7-group comparison experiments are carried out, application comparative examples 1-7 correspond to examples 1-7 respectively, and the only difference between the specific process applying the comparative examples 1-7 and the above examples 1-7 is as follows: and (3) adding no mullite whisker in the preparation process of the step (2), keeping other process conditions unchanged, and then carrying out performance detection on the obtained whisker/polyurethane foam material.
TABLE 2 mullite monocrystals prepared without complex molten salt system
TABLE 3 mullite monocrystal preparation result without adding composite molten salt in waste
TABLE 4 preparation results of mullite single crystal
TABLE 5 comparison of the Performance indices of polyurethane rigid foams
The commercial polyurethane rigid foam material is a combined white material formed by polyether polyol 4110 and additives such as a catalyst, silicone oil, a foaming agent and the like, and then is stirred with black material PAPI-27 and the like to foam, and the mixture is cooled to obtain the commercial polyurethane rigid foam material.
Claims (7)
1. A method for preparing a mullite single crystal material from industrial alumino-silica gel waste at a low temperature is characterized by comprising the following steps: the method comprises the following steps: the method comprises the steps of taking industrial silica-alumina gel waste, fluoride salt, a fluxing agent and an aluminum source supplement as raw materials, adding water, carrying out ball milling and drying, and then calcining at 600-800 ℃ to obtain the mullite single crystal material.
2. The method for preparing the mullite monocrystal material from the industrial alumino-silica gel waste at the low temperature according to claim 1, wherein the method comprises the following steps: the industrial silica-alumina gel waste comprises the following components: al (Al) 2 O 3 、SiO 2 、MnO 2 、Na 2 O、SO 3 、CaO、MgO、GeO 2 。
3. The method for preparing the mullite monocrystal material from the industrial alumino-silica gel waste at the low temperature according to claim 1, wherein the method comprises the following steps: the fluoride salt is one or more of lithium fluoride, ammonium fluoride or cryolite.
4. The method for preparing the mullite monocrystal material from the industrial alumino-silica gel waste at the low temperature according to claim 1, wherein the method comprises the following steps: the fluxing agent is one or more of potassium sulfate, aluminum potassium sulfate or potassium chloride.
5. The method for preparing the mullite monocrystal material from the industrial alumino-silica gel waste at the low temperature according to claim 1, wherein the method comprises the following steps: the aluminum source supplement is one or two of aluminum sulfate or aluminum hydroxide.
6. The method for preparing the mullite monocrystal material from the industrial alumino-silica gel waste at the low temperature according to claim 1, wherein the method comprises the following steps: the molar ratio of the industrial silica-alumina gel waste, the fluoride salt, the fluxing agent and the aluminum source supplement is 1 (0.5-0.8), 0.9-1.3 and 1.2-1.5.
7. A mullite single crystal material is characterized in that: prepared by the process of any one of claims 1 to 6.
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| WO1992011219A1 (en) * | 1990-12-21 | 1992-07-09 | The Dow Chemical Company | Preparation and use of mullite whisker networks |
| CN101498049A (en) * | 2009-01-21 | 2009-08-05 | 景德镇陶瓷学院 | Method for preparing mullite crystal whisker by non-hydrolytic sol-gel process |
| CN102433583A (en) * | 2011-09-20 | 2012-05-02 | 陕西科技大学 | Preparation method of mullite whiskers |
| CN105274623A (en) * | 2015-10-27 | 2016-01-27 | 天津大学 | Method for in-situ growth of mullite whiskers by virtue of vacuum impregnation and freeze drying |
| CN108516814A (en) * | 2018-06-14 | 2018-09-11 | 哈尔滨工业大学 | A kind of method of low temperature preparation high strength mullite ceramics |
| CN109811415A (en) * | 2019-03-13 | 2019-05-28 | 成都理工大学 | A method of from kaolin low temperature preparation mullite crystal whisker |
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| WO1992011219A1 (en) * | 1990-12-21 | 1992-07-09 | The Dow Chemical Company | Preparation and use of mullite whisker networks |
| CN101498049A (en) * | 2009-01-21 | 2009-08-05 | 景德镇陶瓷学院 | Method for preparing mullite crystal whisker by non-hydrolytic sol-gel process |
| CN102433583A (en) * | 2011-09-20 | 2012-05-02 | 陕西科技大学 | Preparation method of mullite whiskers |
| CN105274623A (en) * | 2015-10-27 | 2016-01-27 | 天津大学 | Method for in-situ growth of mullite whiskers by virtue of vacuum impregnation and freeze drying |
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