CN102617120B - Method for producing beta''-aluminum oxide ceramic membrane - Google Patents
Method for producing beta''-aluminum oxide ceramic membrane Download PDFInfo
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- CN102617120B CN102617120B CN201210091286.XA CN201210091286A CN102617120B CN 102617120 B CN102617120 B CN 102617120B CN 201210091286 A CN201210091286 A CN 201210091286A CN 102617120 B CN102617120 B CN 102617120B
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- 238000004519 manufacturing process Methods 0.000 title abstract description 14
- 239000012528 membrane Substances 0.000 title abstract description 6
- 239000011224 oxide ceramic Substances 0.000 title abstract 4
- 229910052574 oxide ceramic Inorganic materials 0.000 title abstract 4
- 239000000843 powder Substances 0.000 claims abstract description 91
- 239000000919 ceramic Substances 0.000 claims abstract description 60
- 235000015895 biscuits Nutrition 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 35
- 238000005245 sintering Methods 0.000 claims abstract description 30
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 62
- 239000007788 liquid Substances 0.000 claims description 44
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 36
- 229910052782 aluminium Inorganic materials 0.000 claims description 36
- 239000004411 aluminium Substances 0.000 claims description 33
- 230000008569 process Effects 0.000 claims description 30
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 25
- 230000009257 reactivity Effects 0.000 claims description 25
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 25
- 230000032683 aging Effects 0.000 claims description 22
- 238000000465 moulding Methods 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 22
- 239000002243 precursor Substances 0.000 claims description 22
- 239000002002 slurry Substances 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 19
- VCNTUJWBXWAWEJ-UHFFFAOYSA-J aluminum;sodium;dicarbonate Chemical compound [Na+].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O VCNTUJWBXWAWEJ-UHFFFAOYSA-J 0.000 claims description 19
- 238000001694 spray drying Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 239000012752 auxiliary agent Substances 0.000 claims description 15
- 239000002131 composite material Substances 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 230000008859 change Effects 0.000 claims description 10
- 230000000694 effects Effects 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 9
- 229920003023 plastic Polymers 0.000 claims description 9
- 239000004033 plastic Substances 0.000 claims description 9
- 230000004888 barrier function Effects 0.000 claims description 8
- 238000000354 decomposition reaction Methods 0.000 claims description 8
- 230000029087 digestion Effects 0.000 claims description 8
- 238000004880 explosion Methods 0.000 claims description 8
- 239000006210 lotion Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000000643 oven drying Methods 0.000 claims description 8
- 238000007127 saponification reaction Methods 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 3
- 239000000243 solution Substances 0.000 description 49
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 19
- 229910052799 carbon Inorganic materials 0.000 description 19
- 239000011259 mixed solution Substances 0.000 description 14
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 12
- 230000008602 contraction Effects 0.000 description 12
- 238000001556 precipitation Methods 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- 239000013078 crystal Substances 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- 230000002902 bimodal effect Effects 0.000 description 7
- 238000007766 curtain coating Methods 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 7
- 229910001948 sodium oxide Inorganic materials 0.000 description 7
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 6
- 235000011613 Pinus brutia Nutrition 0.000 description 6
- 241000018646 Pinus brutia Species 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 6
- 238000004220 aggregation Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 6
- 239000003292 glue Substances 0.000 description 6
- 238000010298 pulverizing process Methods 0.000 description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000008279 sol Substances 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000001166 ammonium sulphate Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- -1 hydrogen aluminum oxide Chemical class 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention discloses a method for producing a beta''-aluminum oxide ceramic membrane. The method comprises the following steps of: plastifying beta''-aluminum oxide powder used as a raw material, forming ceramic biscuit, drying the ceramic biscuit under negative pressure at low temperature, and sintering the ceramic membrane. According to the method for producing the beta''-aluminum oxide ceramic membrane, the beta''-aluminum oxide powder is prepared and is used as the raw material, so that a beta''-aluminum oxide ceramic membrane product is high in batch stability, and is easy to produce.
Description
Technical field
The present invention relates to ionic conductivity ceramics material technology field, particularly a kind of β " preparation method of alumina-ceramic barrier film.
Background technology
Crystalline phase is β " alumina phase pottery is a kind of solid electrolyte barrier film of holding concurrently, and at the stupalith of sulphur sode cell special conduction sodium ion in service.Specific energy is high, the sulphur sode cell of long service life, and " these performances of alumina-ceramic depend on manufacturing process strongly to require pottery to have good performance and homogeneous structural, β.
Tradition prepare β, and " method of alumina ceramic envelope is to select Ultrafine Aluminium Oxide Particle; crystal formation is α type or α, γ mixed type; in advance the alumina powder through metering and the composition that need to add are mixed for a long time through mixer; compound is pressed into the biscuit pipe of desired size through shaping press, then through high-temperature calcination formation, contain the β " alumina ceramic envelope of alumina phase.The raw material using due to this production method is the aluminum oxide that contains q.s α phase through prior calcining, with the aluminum oxide of this crystal formation, generates contain β " sintering temperature (more than 1580 ℃) and extremely long sintering time that alumina-ceramic needs are high.The effective constituent Na making under long-time high temperature
2o is easy to vapor away, and this contains β " alumina-ceramic is harmful to generating with reaction sintering.Moreover, adopt this raw material also to have following deficiency: the one, the ultrafine powder of aluminum oxide and the composition adding can not reach desirable degree of mixing, have the dead angle of mixing inevitable, on ceramic impact, are exactly that crystalline phase is not single, β " alumina-ceramic dephasign is many, conductivity variation; The incorgruous growth of crystal, causes ceramic machinery intensity variation; The 2nd, this feedstock production process can only adopt compression moulding, can only production small size ceramic case, and large size shell is produced and is subject to certain restriction.Be not suitable with the production of high capacity cell.
" alumina-ceramic is that the false body that burns obtains through soaking Na to patent: the β in CN1233082A, causes batches of materials ingredient stability poor in implementation process.Moreover when false burning body is a kind of porous material, after sintering, the intensity of ceramic body is influenced very large." the batch mixing lack of homogeneity of aluminum oxide and Alpha-alumina pressed powder directly affects ceramic performance to also have β.The false body outstanding problem that burns, one, do not add pore former and can form via material and be worth discussing.Two, first cooling use again after 1000 ℃ of above sintering of false burning body, very uneconomical in seeming now of energy scarcity.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of β, and " preparation method of alumina-ceramic barrier film, poor stability, the production that solves currently available technology existence is difficult to operation, is not suitable for the problem of scale production.
For reaching goal of the invention, " the preparation method of alumina-ceramic barrier film; " alumina powder is raw material to take β that the invention provides a kind of β, first carry out the plastics processing of alumina powder, carry out again biscuit of ceramics moulding, then biscuit of ceramics adopts negative pressure oven drying at low temperature, finally carries out the sintering of ceramic diaphragm.
Further, rate temperature change 1.0-3.0 ℃/min in described sintering process, heat up simultaneously and adopt four sections of constant temperature methods, make described biscuit of ceramics reach successively four constant temperature points, described four constant temperature points are respectively 500-600 ℃, 800-1000 ℃, 1250-1350 ℃, 200-300 ℃, and are 150 to 180min in the soaking time of each constant temperature point.
Further, the wall thickness of described biscuit of ceramics, shrinking percentage are controlled at respectively 2.5-4.0mm, 18-23%, and described negative pressure is-arrive-1atm of 3atm that the sintering of described ceramic diaphragm carries out in tunnel furnace simultaneously.
Further, described biscuit of ceramics moulding adopts curtain coating to build moulding.
Further, the fluidizer that described plastics processing adopts is aluminium colloidal sol.
Further, described biscuit of ceramics wall thickness is 3.0-3.5mm.
Further, described biscuit of ceramics shrinking percentage is 22-22.5%.
Further, described bake out temperature is 50-80 ℃.
Further, the temperature of described oven dry is 55-70 ℃.
Further, the rate temperature change of described ceramic diaphragm sintering is 2.0-2.5 ℃/min.
Further, described four constant temperature points are respectively 550-580 ℃, 900-950 ℃, 1280-1350 ℃, 260-280 ℃.
Further, described in the ceramic diaphragm that makes be polycrystal, grain-size 17-35um, crystal grain grating is bimodal distribution.
Further, described β " aluminum oxide is produced by the following method:
The first step, the sodium aluminate solution of preparation energy output presoma, this solution, containing NT150-350g/l, contains AO10-50g/l, temperature 20-45 ℃, viscosity 1-30MPa/s;
Second step, the decomposition of presoma; Toward described sodium aluminate solution, add a minute enzymolysis auxiliary agent, in presoma decomposition course, control the stirring velocity of the speed, flow and the equipment that add minute enzymolysis auxiliary agent well simultaneously, thereby make presoma slurries, and guarantee to comprise in the phase composite of presoma material thing aluminium carbonate sodium and high reactivity gel hydrogen aluminium, size of particles nano level; Then carry out the aging, separated of presoma slurries, and washing is to required alkali content;
The 3rd step, the oven dry of presoma; Before oven dry, the presoma lotion after washing is carried out to saponification processing, the amount that saponifying agent adds is the 20-80% of presoma butt quality;
The 4th step, the preparation of oxide of high activity aluminium powder form, carries out roasting to the precursor powder after drying; Precursor powder after drying is directly dropped into high-temperature zone, anxious heat, temperature 1100-1350 ℃, roasting time 30-150 minute; Chilling again after powder roasting completes, drop temperature 1100-1350 ℃; In roasting process, make powder produce explosion effect, make powder keep nanometer state simultaneously.
Further, described sodium aluminate solution is the two mixed solution of concentrated carbon mother liquid and seed precipitation solution.
Further, the NT concentration of described sodium aluminate solution is 200-280g/l.
Further, the content of the AO of described sodium aluminate solution is 30-40g/l.
Further, the temperature of described sodium aluminate solution is 30-40 ℃.
Further, the viscosity of described sodium aluminate solution is 5-20Mpa/s.
Further, the decomposer that described presoma decomposes use is with cone; The equipment length-to-diameter ratio 1-5 of described decomposer.
The equipment length-to-diameter ratio of the decomposer that further, described presoma decomposition is used is 3-4.
Further, described minute enzymolysis auxiliary agent adopts liquid CO 2; While passing into liquid CO 2, the flow of liquid CO 2 is 1.0-2.5Kg/min, the CO2 pressure 3-6MPa of liquid, turn/min of the stirring velocity 15-30 of equipment.
Further, described minute enzymolysis auxiliary agent adopts high concentrations of gas CO2; While passing into high concentrations of gas CO2, CO2 gas temperature 20-40 ℃, CO2 gaseous tension 2-5Mpa, CO2 gas flow 50-120L/min, turn/min of equipment stirring velocity 8-20.
Further, described saponifying agent is organic amine.
Further, the amount that described saponifying agent adds is the 30%-50% of presoma butt quality.
What further, described oven dry adopted is spray-drying tower; The length-to-diameter ratio of described spray-drying tower is 1.25-1.4.
Further, the inlet temperature that described presoma is dried is 220 ℃-260 ℃.
Further, 160 ℃-175 ℃ of the temperature outs that described presoma is dried.
Further, described spray-dried powders granularity is controlled at d5070um-90um.
Further, described maturing temperature is 1250 ℃-1320 ℃.
Further, described roasting time 90-120 minute.
Further, the drop temperature of described roasting after completing is 1250 ℃-1320 ℃.
Further, described precursor powder is to adopt box-type furnace roasting.
Further, described presoma slurry package is containing high reactivity gel hydrogen aluminium and aluminium carbonate sodium and high-concentration alkali liquor.
Further, in the phase composite of described presoma material thing, the quality percentage composition of aluminium carbonate sodium phase is 20% to 30%, and remaining is high reactivity gel hydrogen aluminium phase.
Further, the precursor particle size 30nm-100nm making after described washing.
Further, described presoma slurries are aging at 40 ℃-75 ℃, digestion time 2-48 hour.
Further, described presoma after washing is containing sodium oxide 1%-30%.
β provided by the invention " preparation method of alumina-ceramic barrier film; change the way that original employing Alpha-alumina is raw material; by producing β " alumina powder also be take it as raw material, can make β, and " alumina-ceramic membrane manufacture batch stability is high, produce easy handling, goods cost is moderate, proper scale is produced, economic benefit is better.
Embodiment
Below in conjunction with embodiment, carry out more in depth to illustrate the β provided by the invention " preparation method of alumina-ceramic barrier film.
Example one
Select concentrated carbon mother liquid and seed precipitation solution mixed solution, can certainly adopt by allocating with soda ash again after liquid caustic soda dissolved hydrogen aluminum oxide output primary solution, or add soda ash allotment with the wrought aluminum acid sodium solution in metallurgical production alumina process, or the two mixed solution of concentrated carbon mother liquid and concentrated seed precipitation solution.Described concentrated carbon mother liquid is in advance by the carbon mother liquid in alumina producing flow process, through the indirect heating evaporation of vacuum, falls after part moisture, becomes the concentrated solution of band portion sodium bicarbonate.Then described concentrated carbon mother liquid and seed precipitation solution are mixed to form to sodium aluminate solution, in this mixed solution, require NT content 220g/l, AO content 33g/l, 36 ℃ of temperature, viscosity 5MPa/s.The qualified sodium aluminate solution of allotment is sent in a decomposer with cone, and decomposer equipment length-to-diameter ratio 3, then passes into and decomposes auxiliary agent liquid CO
2, can certainly adopt other minute enzymolysis auxiliary agent, for example liquor alumini chloridi, aluminic acid aluminum solutions, aluminum nitrate solution, ammoniumsulphate soln, ammonium chloride solution, sal volatile, sodium hydrogen carbonate solution, liquid CO
2, high concentration CO
2one or several combinations in gas.In presoma decomposition course, pass into liquid CO
2time, liquid CO
2flow be 1.5Kg/min, the CO of liquid
2pressure 3.2MPa, the turn/min of stirring velocity 20 of equipment, manufactures CO
2local superfluous environment, makes to decompose and is containing q.s HCO
3under-environment, carry out, the presoma slurries that make are comprised of high reactivity gel hydrogen aluminium and aluminium carbonate sodium and high-concentration alkali liquor, and guarantee that the phase composite of presoma material thing is aluminium carbonate sodium and high reactivity gel hydrogen aluminium, and in this presoma, high reactivity gel hydrogen aluminium and aluminium carbonate sodium phase composite ratio are 30: 70, the precursor particle size 90nm making.Then carry out aging, separated, the washing of presoma slurries.Presoma slurries are aging at 75 ℃, digestion time 18 hours.After making qualified presoma after aging, carry out centrifugation, obtain body of paste, and wash to required alkali content, presoma is containing sodium oxide 15%.Before oven dry, add organic amine to carry out saponification processing the presoma lotion after washing, can certainly adopt other saponifying agent, one or more in ammoniacal liquor, ammonium chloride, ammonium sulfate, ethanol, glycerol, methyl alcohol for example, saponifying agent add-on is presoma butt 30%, and presoma is dried and carried out in flash spray-drying tower simultaneously.Described spray-drying tower length-to-diameter ratio 1.25,220 ℃ of inlet temperatures are dried in spraying, and 160 ℃ of temperature outs, have a narrow range of temperature and make drying rate fast, and particle does not produce hard aggregation, the spray-dried powders granularity d of formation
50for 80um.Alumina powder is the precursor powder after loose shape roasting oven dry in box stoving oven, and in roasting process, makes powder produce explosion effect, makes powder keep nanometer state.Precursor powder in baking operation process after drying directly drops into high-temperature zone, 1260 ℃ of temperature, anxious heat; Roasting time 80 minutes; After powder roasting completes, drop temperature is 1260 ℃, chilling; Obtain alumina powder, the further pulverization process of this powder obtains nano level high reactivity β " aluminum oxide, the alumina powder finally obtaining pine shape unit weight 0.15g/l, specific surface 25cm2/g, size of particles 45nm.The moulding of ceramic diaphragm body adopts curtain coating to build moulding.Before biscuit of ceramics moulding, first carry out the plastics processing of alumina powder, fluidizer aluminium colloidal sol, can certainly adopt other fluidizer, a kind of such as alumina gel, aluminium colloidal sol, polyvinyl alcohol, starch, resin, wood glue, glue etc.Biscuit of ceramics wall thickness 3.0mm, shrinking percentage 22%.Biscuit of ceramics employing-3atm negative pressure oven drying at low temperature, 55 ℃ of temperature, it is little that vacuum and low temperature oven dry can keep biscuit contraction to stablize geometry deformation.The sintering of ceramic diaphragm carries out in tunnel furnace, 2.0 ℃/min of rate temperature change, and make sintering temperature reach successively 550 ℃ of four constant temperature points, 900 ℃, 1350 ℃, 260 ℃.The selected desirable constant temperature point of sintering can make the density of stupalith improve, contraction is stablized, electrical property is good, batch geometrical variations is little, intensity is played stably.The ceramic body grain-size 35um making; The pottery making is polycrystal, and crystal grain grating is bimodal distribution.
Example two
Select concentrated carbon mother liquid and seed precipitation solution mixed solution, described concentrated carbon mother liquid is in advance by the carbon mother liquid in alumina producing flow process, through the indirect heating evaporation of vacuum, falls after part moisture, becomes the concentrated solution of band portion sodium bicarbonate.So described concentrated carbon mother liquid and seed precipitation solution are mixed to form to sodium aluminate solution, in this mixed solution, require NT content 260g/l, AO content 50g/l, 40 ℃ of temperature, viscosity 10MPa/s.The qualified sodium aluminate solution of allotment is sent in a decomposer with cone, and decomposer equipment length-to-diameter ratio 3.5, then passes into a minute enzymolysis auxiliary agent gas CO
2, while decomposing, pass into high concentrations of gas CO in presoma decomposition course
2time, CO
224 ℃ of gas temperatures, CO
2gaseous tension 2.5Mpa, CO
2gas flow 52L/min, turn/min of equipment stirring velocity 12, manufactures CO
2local superfluous environment, makes to decompose and is containing q.s HCO
3 -under environment, carry out, the presoma slurries that make are comprised of high reactivity gel hydrogen aluminium and aluminium carbonate sodium and high-concentration alkali liquor, and guarantee that the phase composite of presoma material thing is aluminium carbonate sodium and high reactivity gel hydrogen aluminium, and in this presoma, high reactivity gel hydrogen aluminium and aluminium carbonate sodium phase composite ratio are 23: 77, the precursor particle size 39nm making.Then carry out aging, separated, the washing of presoma slurries.Presoma slurries are aging at 45 ℃, digestion time 28 hours.After making qualified presoma after aging, carry out centrifugation, obtain body of paste, and wash to required alkali content, presoma is containing sodium oxide 20%.Before oven dry, add organic amine to carry out saponification processing the presoma lotion after washing, saponifying agent add-on is presoma butt 50%.Presoma is dried and is carried out in flash spray-drying tower, spray-drying tower length-to-diameter ratio 1.5, and 260 ℃ of inlet temperatures are dried in spraying, and 180 ℃ of temperature outs, have a narrow range of temperature and make drying rate fast, and particle does not produce hard aggregation, the spray-dried powders granularity d obtaining
5080um.Alumina powder is the precursor powder after loose shape roasting oven dry in box stoving oven, makes powder produce explosion effect simultaneously in roasting process, makes powder keep nanometer state.In operating process, precursor powder directly drops into high-temperature zone, 1350 ℃ of temperature, anxious heat; Roasting time 90 minutes; After powder roasting completes, drop temperature is 1350 ℃, chilling; Obtain alumina powder, the further pulverization process of this powder obtains nano level high reactivity β " aluminum oxide.The alumina powder pine shape unit weight 0.18g/l obtaining, the alumina powder specific surface 25cm obtaining
2/ g, the alumina powder size of particles 45nm obtaining.The moulding of ceramic diaphragm body adopts curtain coating to build moulding.Before biscuit of ceramics moulding, first carry out the plastics processing of alumina powder, fluidizer aluminium colloidal sol.Biscuit of ceramics wall thickness 3.2mm, shrinking percentage 20%.Biscuit of ceramics employing-2atm negative pressure oven drying at low temperature, temperature 50 C, it is little that vacuum and low temperature oven dry can keep biscuit contraction to stablize geometry deformation.Ceramic diaphragm sintering carries out in tunnel furnace, 1.0 ℃/min of rate temperature change; And make sintering temperature reach successively 560 ℃ of four constant temperature points, 920 ℃, 1280 ℃, 280 ℃.The selected desirable constant temperature point of sintering can make the density of stupalith improve, contraction is stablized, electrical property is good, batch geometrical variations is little, intensity is played stably.The ceramic body grain-size 21um making; The pottery making is polycrystal, and crystal grain grating is bimodal distribution.
Example three
Select concentrated carbon mother liquid and concentrated seed precipitation solution mixed solution.Described concentrated carbon mother liquid is in advance by the carbon mother liquid in alumina producing flow process, through the indirect heating evaporation of vacuum, falls after part moisture, becomes the concentrated solution of band portion sodium bicarbonate.Then described concentrated carbon mother liquid and concentrated seed precipitation solution are mixed to form to sodium aluminate solution, in this mixed solution, require NT content 260g/l, AO content 35g/l, 40 ℃ of temperature, viscosity 15MPa/s.The qualified sodium aluminate solution of allotment is sent in a decomposer with cone, and decomposer equipment length-to-diameter ratio 3, then passes into and decomposes auxiliary agent liquid CO
2, liquid CO
2flow be 1.5Kg/min, the CO of liquid
2pressure 3MPa, the turn/min of stirring velocity 15 of equipment, manufactures CO
2local superfluous environment, makes to decompose and is containing q.s HCO
3under-environment, carry out, the presoma slurries that make are comprised of high reactivity gel hydrogen aluminium and aluminium carbonate sodium and high-concentration alkali liquor, and guarantee that the phase composite of presoma material thing is aluminium carbonate sodium and high reactivity gel hydrogen aluminium, and in this presoma, high reactivity gel hydrogen aluminium and aluminium carbonate sodium phase composite ratio are 20: 80, the precursor particle size 80nm making.Then carry out aging, separated, the washing of presoma slurries.Presoma slurries are aging at 75 ℃, digestion time 28 hours.After aging, the presoma making is carried out to centrifugation, obtain body of paste, and wash to required alkali content, presoma is containing sodium oxide 15%.Before oven dry, add organic amine to carry out saponification processing the presoma lotion after washing, add-on is presoma butt 30%, presoma is dried and is carried out in flash spray-drying tower simultaneously.Described spray-drying tower length-to-diameter ratio 1.25,220 ℃ of inlet temperatures are dried in spraying, and 160 ℃ of temperature outs, have a narrow range of temperature and make drying rate fast, and particle does not produce hard aggregation, the spray-dried powders granularity d of formation
50for 70um.Alumina powder is the precursor powder after loose shape roasting oven dry in box stoving oven, and in roasting process, makes powder produce explosion effect, makes powder keep nanometer state.In baking operation process, precursor powder directly drops into high-temperature zone, 1250 ℃ of temperature, anxious heat; Roasting time 90 minutes; After powder roasting completes, drop temperature is 1250 ℃, chilling; Obtain alumina powder, the further pulverization process of this powder obtains nano level high reactivity β " aluminum oxide, the alumina powder finally obtaining pine shape unit weight 0.15g/l, specific surface 25cm2/g, size of particles 45nm.The moulding of ceramic diaphragm body adopts curtain coating to build moulding.Before biscuit of ceramics moulding, first carry out the plastics processing of alumina powder, fluidizer aluminium colloidal sol, can certainly adopt other fluidizer, a kind of such as alumina gel, aluminium colloidal sol, polyvinyl alcohol, starch, resin, wood glue, glue etc.Biscuit of ceramics wall thickness 3.0mm, shrinking percentage 22%.Biscuit of ceramics employing-3atm negative pressure oven drying at low temperature, 55 ℃ of temperature, it is little that vacuum and low temperature oven dry can keep biscuit contraction to stablize geometry deformation.The sintering of ceramic diaphragm carries out in tunnel furnace, 2.0 ℃/min of rate temperature change, and make sintering temperature reach successively 550 ℃ of four constant temperature points, 900 ℃, 1350 ℃, 260 ℃.The selected desirable constant temperature point of sintering can make the density of stupalith improve, contraction is stablized, electrical property is good, batch geometrical variations is little, intensity is played stably.The ceramic body grain-size 25um making; The pottery making is polycrystal, and crystal grain grating is bimodal distribution.
Example four
Select the wrought aluminum acid sodium solution in metallurgical production alumina process to add soda ash allotment, then described concentrated carbon mother liquid and allotment are formed to sodium aluminate solution mixed solution, in this mixed solution, require NT content 280g/l, AO content 45g/l, 40 ℃ of temperature, viscosity 9MPa/s.The qualified sodium aluminate solution of allotment is sent in a decomposer with cone, and decomposer equipment length-to-diameter ratio 3.5, then passes into a minute enzymolysis auxiliary agent high concentration CO
2gas, passes into CO
240 ℃ of gas temperatures, pressure 2Mpa, flow 120L/min, turn/min of equipment stirring velocity 20, manufactures CO
2local superfluous environment, makes to decompose and is containing q.s HCO
3under-environment, carry out, the presoma slurries that make are comprised of high reactivity gel hydrogen aluminium and aluminium carbonate sodium and high-concentration alkali liquor, and guarantee that the phase composite of presoma material thing is aluminium carbonate sodium and high reactivity gel hydrogen aluminium, and in this presoma, high reactivity gel hydrogen aluminium and aluminium carbonate sodium phase composite ratio are 25: 75, the precursor particle size 60nm making.Then carry out aging, separated, the washing of presoma slurries.Presoma slurries are aging at 45 ℃, digestion time 38 hours.After aging, the presoma making is carried out to centrifugation, obtain body of paste, and wash to required alkali content, presoma is containing sodium oxide 22%.Before oven dry, add organic amine to carry out saponification processing qualified presoma lotion, saponifying agent add-on is presoma butt 30%, presoma is dried and is carried out in flash spray-drying tower simultaneously.Described spray-drying tower length-to-diameter ratio 1.25,220 ℃ of inlet temperatures are dried in spraying, and 160 ℃ of temperature outs, have a narrow range of temperature and make drying rate fast, and particle does not produce hard aggregation, the spray-dried powders granularity d of formation
50for 70um.Alumina powder is the precursor powder after loose shape roasting oven dry in box stoving oven, and in roasting process, makes powder produce explosion effect, makes powder keep nanometer state.In baking operation process, precursor powder directly drops into high-temperature zone, 1250 ℃ of temperature, anxious heat; Roasting time 90 minutes; After powder roasting completes, drop temperature is 1250 ℃, chilling; Obtain alumina powder, the further pulverization process of this powder obtains nano level high reactivity β " aluminum oxide, the alumina powder finally obtaining pine shape unit weight 0.15g/l, specific surface 25cm
2/ g, size of particles 45nm.The moulding of ceramic diaphragm body adopts curtain coating to build moulding.Before biscuit of ceramics moulding, first carry out the plastics processing of alumina powder, fluidizer aluminium colloidal sol, can certainly adopt other fluidizer, a kind of such as alumina gel, aluminium colloidal sol, polyvinyl alcohol, starch, resin, wood glue, glue etc.Biscuit of ceramics wall thickness 3.0mm, shrinking percentage 22%.Biscuit of ceramics employing-1.5atm negative pressure oven drying at low temperature, 55 ℃ of temperature, it is little that vacuum and low temperature oven dry can keep biscuit contraction to stablize geometry deformation.The sintering of ceramic diaphragm carries out in tunnel furnace, 2.0 ℃/min of rate temperature change, and make sintering temperature reach successively 550 ℃ of four constant temperature points, 900 ℃, 1350 ℃, 260 ℃.The selected desirable constant temperature point of sintering can make the density of stupalith improve, contraction is stablized, electrical property is good, batch geometrical variations is little, intensity is played stably.The ceramic body grain-size 28um making; The pottery making is polycrystal, and crystal grain grating is bimodal distribution.
Example five
Select concentrated carbon mother liquid and seed precipitation solution mixed solution, it is in advance carbon mother liquid in alumina producing flow process to be fallen to part moisture content through the indirect heating evaporation of vacuum, become after band portion sodium bicarbonate concentrated solution, mix by design proportion with seed precipitation solution, in mixed solution, require sodium aluminate solution to contain N
t260g/l; Require sodium aluminate solution containing AO50g/l; Require 40 ℃ of sodium aluminate solution liquid temps; Require sodium aluminate solution fluid viscosity 10Mpa/s.Containing the high alkaline solution of aluminium, send into one and decompose auxiliary agent liquid CO with passing into after in the decomposer of cone allotment is qualified
2decompose decomposer equipment length-to-diameter ratio 3.5, simultaneously liquid CO
2flow be 1.8Kg/min, the CO of liquid
2pressure 3.2MPa, the turn/min of stirring velocity 20 of equipment,, manufacture CO
2local superfluous environment, makes to decompose and is containing q.s HCO
3 -under environment, carry out.Guarantee that the phase composite of presoma material thing is the mixture of aluminium carbonate sodium and high reactivity gel hydrogen aluminium, size of particles nano level.Then carry out the aging of presoma slurries, aging temperature is 65 ℃, and digestion time 20 hours is carried out centrifugation by the presoma making after aging, obtains body of paste, and washing is to required alkali content, and presoma is containing sodium oxide 20%.Before oven dry, add organic amine to carry out saponification processing the body lotion that drives through washing.Saponifying agent add-on is presoma butt 50%; Presoma is dried and is carried out in flash spray-drying tower.Spray-drying tower length is through than 1.5; 260 ℃ of inlet temperatures are dried in spraying; 180 ℃ of temperature outs; Have a narrow range of temperature and make drying rate fast, particle does not produce hard aggregation.Spray-dried powders granularity d
5080um.Alumina powder is the precursor powder after loose shape roasting oven dry in box stoving oven, and in roasting process, makes powder produce explosion effect, makes powder keep nanometer state.In operating process, precursor powder directly drops into high-temperature zone, 1350 ℃ of temperature, anxious heat; Roasting time 90 minutes; After powder roasting completes, drop temperature is 1350 ℃, chilling; Obtain alumina powder, the further pulverization process of this powder obtains nano level high reactivity β " Al
2o
3.The alumina powder pine shape unit weight 0.18g/l obtaining, specific surface 25cm2/g, size of particles 45nm.The moulding of ceramic diaphragm body adopts curtain coating to build moulding.Before biscuit of ceramics moulding, first carry out the plastics processing of alumina powder, fluidizer aluminium colloidal sol.Biscuit of ceramics wall thickness 3.2mm, shrinking percentage 20%, biscuit of ceramics employing-2.5atm negative-pressure vacuum oven drying at low temperature, temperature 50 C.It is little that vacuum and low temperature oven dry can keep biscuit contraction to stablize geometry deformation.Ceramic diaphragm sintering carries out in tunnel furnace, 1.0 ℃/min of rate temperature change, and make sintering temperature reach successively 560 ℃ of four constant temperature points, 920 ℃, 1280 ℃, 280 ℃.The selected desirable constant temperature point of sintering can make the density of stupalith improve, contraction is stablized, electrical property is good, batch geometrical variations is little, intensity is played stably.The ceramic body grain-size 21um making; The pottery making is polycrystal, and crystal grain grating is bimodal distribution.
Example six
Select concentrated carbon mother liquid and seed precipitation solution mixed solution, it is in advance the carbon mother liquid in alumina producing flow process to be fallen after part moisture content through the indirect heating evaporation of vacuum, become band portion sodium bicarbonate concentrated solution, then mix by design proportion with seed precipitation solution, in mixed solution, require sodium aluminate solution to contain N
t200g/l; Require sodium aluminate solution containing AO30g/l; Require 30 ℃ of sodium aluminate solution liquid temps; Require sodium aluminate solution fluid viscosity 5Mpa/s.Containing the high alkaline solution of aluminium, send into one and decompose with passing into a minute enzymolysis auxiliary agent after in the decomposer of cone allotment is qualified.Decomposer equipment length-to-diameter ratio 3.In presoma decomposition course, pass into and decompose auxiliary agent liquid CO
2, the flow of liquid CO 2 is 1.8Kg/min, the CO of liquid
2pressure 3.1MPa, the turn/min of stirring velocity 20 of equipment, manufactures CO
2local superfluous environment, makes to decompose and is containing q.s HCO
3 -under environment, carry out.Guarantee that the phase composite of presoma material thing is the mixture of aluminium carbonate sodium and high reactivity gel hydrogen aluminium, size of particles nano level.Then carry out the aging of presoma slurries, aging temperature is at 70 ℃, and digestion time 22 hours is carried out centrifugation by the presoma making after aging, obtains body of paste, and washing is to required alkali content, and presoma is containing sodium oxide 21%.Before oven dry, add organic amine to carry out saponification processing qualified presoma lotion, saponifying agent add-on is presoma butt 30%.Presoma is dried and is carried out in flash spray-drying tower, and spray-drying tower length, through than 1.25, is sprayed and dried 220 ℃ of inlet temperatures, and 160 ℃ of temperature outs, have a narrow range of temperature and make drying rate fast, and particle does not produce hard aggregation.Spray-dried powders granularity d
5070um.Alumina powder is the precursor powder after loose shape roasting oven dry in box stoving oven, and in roasting process, makes powder produce explosion effect, makes powder keep nanometer state.In operating process, precursor powder directly drops into high-temperature zone, 1250 ℃ of temperature, anxious heat; Roasting time 90 minutes; After powder roasting completes, drop temperature is 1250 ℃, chilling; Obtain aluminum oxide powder last, the further pulverization process of this powder obtains nano level high reactivity β " Al
2o
3, the alumina powder pine shape unit weight 0.15g/l obtaining, specific surface 25cm
2/ g, size of particles 45nm.The moulding of ceramic diaphragm body adopts curtain coating to build moulding.Before biscuit of ceramics moulding, first carry out the plastics processing of alumina powder, fluidizer aluminium colloidal sol.Biscuit of ceramics wall thickness 3.0mm, shrinking percentage 22%.Biscuit of ceramics employing-2.6atm negative-pressure vacuum oven drying at low temperature, 55 ℃ of temperature, it is little that vacuum and low temperature oven dry can keep biscuit contraction to stablize geometry deformation.Ceramic diaphragm sintering carries out in tunnel furnace, 2.0 ℃/min of rate temperature change, and make sintering temperature reach successively 550 ℃ of four constant temperature points, 900 ℃, 1350 ℃, 260 ℃.The selected desirable constant temperature point of sintering can make the density of stupalith improve, contraction is stablized, electrical property is good, batch geometrical variations is little, intensity is played stably.The ceramic body grain-size 32um making; The pottery making is polycrystal, and crystal grain grating is bimodal distribution.
It should be noted last that, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although the present invention is had been described in detail with reference to example, those of ordinary skill in the art is to be understood that, can modify or be equal to replacement technical scheme of the present invention, and not departing from the spirit and scope of technical solution of the present invention, it all should be encompassed in the middle of claim scope of the present invention.
Claims (10)
1. β " preparation method for aluminum oxide, is characterized in that:
The first step, the sodium aluminate solution of preparation energy output presoma, this solution is containing N
t150-350g/L, containing AO10-50g/L, temperature 20-45 ℃, viscosity 1-30mPas;
Second step, the decomposition of presoma; Toward described sodium aluminate solution, add a minute enzymolysis auxiliary agent, in presoma decomposition course, control the stirring velocity of the speed, flow and the equipment that add minute enzymolysis auxiliary agent well simultaneously, thereby make presoma slurries, and guarantee to comprise in the phase composite of presoma material thing aluminium carbonate sodium and high reactivity gel hydrogen aluminium, size of particles nano level; Then carry out the aging, separated of presoma slurries, and washing is to required alkali content;
The 3rd step, the oven dry of presoma; Before oven dry, add organic amine to carry out saponification processing the presoma lotion after washing, the add-on of described organic amine is the 20-80% of presoma butt quality;
The 4th step, the preparation of oxide of high activity aluminium powder form, carries out roasting to the precursor powder after drying; Precursor powder after drying is directly dropped into high-temperature zone, anxious heat, temperature 1100-1350 ℃, roasting time 30-150 minute; Chilling again after powder roasting completes, drop temperature 1100-1350 ℃; In roasting process, make powder produce explosion effect, make powder keep nanometer state simultaneously.
2. preparation method as claimed in claim 1, is characterized in that: described presoma decomposes the decomposer of use with cone; The equipment length-to-diameter ratio 1-5 of described decomposer.
3. preparation method as claimed in claim 1, is characterized in that: within described minute, enzymolysis auxiliary agent adopts liquid CO
2; Pass into liquid CO
2time, liquid CO
2flow be 1.0-2.5Kg/min, the CO of liquid
2pressure 3-6MPa, turn/min of the stirring velocity 15-30 of equipment.
4. preparation method as claimed in claim 1, is characterized in that: what described oven dry adopted is spray-drying tower; The length-to-diameter ratio of described spray-drying tower is 1.25-1.4.
5. preparation method as claimed in claim 4, is characterized in that: the inlet temperature that described presoma is dried is 220 ℃-260 ℃.
6. preparation method as claimed in claim 4, is characterized in that: 160 ℃-175 ℃ of the temperature outs that described presoma is dried.
7. preparation method as claimed in claim 1, is characterized in that: in the phase composite of described presoma material thing, the quality percentage composition of aluminium carbonate sodium phase is 20% to 30%, and remaining is high reactivity gel hydrogen aluminium phase.
8. preparation method as claimed in claim 1, is characterized in that: described presoma slurries are aging at 40 ℃-75 ℃, digestion time 2-48 hour.
9. a β " the preparation method of alumina-ceramic barrier film; " aluminum oxide is raw material to the β described in claim 8 any one to take claim 1, it is characterized in that: first described alumina powder is carried out to plastics processing, carry out again biscuit of ceramics moulding, then biscuit of ceramics adopts negative pressure oven drying at low temperature, finally carries out the sintering of ceramic diaphragm.
10. preparation method as claimed in claim 9, it is characterized in that: rate temperature change 1.0-3.0 ℃/min in described sintering process, heat up simultaneously and adopt four sections of constant temperature methods, make described biscuit of ceramics reach successively four constant temperature points, described four constant temperature points are respectively 500-600 ℃, 800-1000 ℃, 1250-1350 ℃, 200-300 ℃, and are 150 to 180min in the soaking time of each constant temperature point.
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Citations (4)
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|---|---|---|---|---|
| US4732741A (en) * | 1985-05-24 | 1988-03-22 | Lilliwyte Societe Anonyme | Method of making beta"-alumina |
| CN101462868A (en) * | 2009-01-05 | 2009-06-24 | 中国科学院上海硅酸盐研究所 | Method for preparing beta-alumina ceramic membrane |
| CN101558025A (en) * | 2006-12-11 | 2009-10-14 | 康宁股份有限公司 | Alpha-alumina inorganic membrane support and method of making the same |
| CN101905121A (en) * | 2010-08-26 | 2010-12-08 | 南京工业大学 | Preparation method of alumina-based ceramic hollow fiber membrane |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4732741A (en) * | 1985-05-24 | 1988-03-22 | Lilliwyte Societe Anonyme | Method of making beta"-alumina |
| CN101558025A (en) * | 2006-12-11 | 2009-10-14 | 康宁股份有限公司 | Alpha-alumina inorganic membrane support and method of making the same |
| CN101462868A (en) * | 2009-01-05 | 2009-06-24 | 中国科学院上海硅酸盐研究所 | Method for preparing beta-alumina ceramic membrane |
| CN101905121A (en) * | 2010-08-26 | 2010-12-08 | 南京工业大学 | Preparation method of alumina-based ceramic hollow fiber membrane |
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Effective date of registration: 20160531 Address after: Nam Dinh Town, Zhangdian city of Zibo province Shandong 255051 five km road No. 1 Patentee after: China Aluminum Shandong Co., Ltd. Address before: 100082 Beijing, Xizhimen, North Street, No. 62, No. Patentee before: Aluminum Corporation of China Limited |