CN105948793B - A kind of preparation method of light porous aluminum phosphate-mullite ceramic ball - Google Patents
A kind of preparation method of light porous aluminum phosphate-mullite ceramic ball Download PDFInfo
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- CN105948793B CN105948793B CN201610283659.1A CN201610283659A CN105948793B CN 105948793 B CN105948793 B CN 105948793B CN 201610283659 A CN201610283659 A CN 201610283659A CN 105948793 B CN105948793 B CN 105948793B
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- 229910052863 mullite Inorganic materials 0.000 title claims abstract description 33
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 30
- 239000000919 ceramic Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 46
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000004321 preservation Methods 0.000 claims abstract description 12
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims abstract description 6
- 239000004411 aluminium Substances 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims abstract description 6
- 238000007493 shaping process Methods 0.000 claims abstract description 5
- RGPUVZXXZFNFBF-UHFFFAOYSA-K diphosphonooxyalumanyl dihydrogen phosphate Chemical compound [Al+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O RGPUVZXXZFNFBF-UHFFFAOYSA-K 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 9
- 208000015924 Lithiasis Diseases 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 229940068984 polyvinyl alcohol Drugs 0.000 claims description 5
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 5
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 5
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- 235000013339 cereals Nutrition 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 4
- 238000007088 Archimedes method Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000010433 feldspar Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/02—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by adding chemical blowing agents
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- 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
- C04B35/16—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 silicates other than clay
- C04B35/18—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 silicates other than clay rich in aluminium oxide
- C04B35/185—Mullite 3Al2O3-2SiO2
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- 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
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/6303—Inorganic additives
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- 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
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
- C04B35/634—Polymers
- C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- 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
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
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Abstract
A kind of preparation method of light porous aluminum phosphate-mullite ceramic ball, it is characterised in that using following steps：（1）Mullite Powder, alumina powder, biphosphate aluminium powder, frit powder carries out dry-mixed in proportion；（2）It is granulated, shaping, cylindric green body is made；（3）After when 70 DEG C of dry base substrates 5 are small, green body is put into the alumina crucible that interior bottom is semicircle spherical shape, when heating to 150 DEG C and small heat preservation 2 under air atmosphere with the speed of 5 DEG C/min, 380 DEG C are heated to the speed of 10 20 DEG C/min and keep the temperature 1 hour again, when then heating to 680 DEG C and small heat preservation 2 with the speed of 1 DEG C/min, finally 1150 DEG C are heated to the speed of 5 DEG C/min and keep the temperature 2 hours, room temperature then is naturally cooled to, that is, light porous aluminum phosphate-mullite ceramic ball is made.
Description
Technical field
The present invention is to provide a kind of preparation methods of light porous aluminum phosphate-mullite ceramic ball, belong to special cermacis
Technical field of material.
Background technology
Porous alumionphosphate（AlPO4）- mullite（3Al2O3 .2SiO2) Ceramic Balls being widely used in the industrial production
It is general, catalyst carrier, chemical filler, heat preservation and refractory material etc. can be used as.As carrier of photocatalyst and other liquid phases
Catalytic reaction agent carrier and as in water during the adsorbent of noxious material, in order to ensure with efficient catalytic effect and
（Or）Adsorption efficiency often requires that porous ceramic ball in water in suspended state, this just needs to prepare a kind of light porous pottery
Porcelain ball.At present, then pass through mainly using " core " of the sphere made of the organic matter lost as spherical green body is easily burnt both at home and abroad
It is spherical organic " core " to burn till removing, so as to prepare a kind of suspensible porous ceramics hollow ball.The disadvantages of this method is：Shaping compared with
Difficulty, and during organic matter burns and loses, easily lead to ceramics cracking or destroy, reduce the yield rate of product；In addition, this work
Skill process is more complicated, and cost is higher, deficiency in economic performance, environment easy to pollute.In order to overcome above-mentioned problem, invention provides one
The preparation side of efficient, simple, safe and reliable, easily operated, the low-cost light porous aluminum phosphate-mullite ceramic ball of kind
Method.
The content of the invention
The technology of the present invention provides a kind of efficient, simple, safe and reliable, easily operated, low-cost light porous phosphoric acid
The preparation method of aluminium-mullite ceramic ball, technical solution are：
A kind of preparation method of light porous aluminum phosphate-mullite ceramic ball, it is characterised in that using following steps：（1）
Mullite Powder, alumina powder, biphosphate aluminium powder, frit powder is 2 according to mass ratio：1：3.11：0.03 ratio
Example carries out dry-mixed；Wherein, the silica containing 50 wt% lithias, the sodium oxide molybdena of 30 wt% and 20 wt% in frit；（2）Add
Adding the poly-vinyl alcohol solution that concentration is 8 wt%, the additive amount of binding agent is the 5% of blank gross mass as binding agent；Then make
Grain, shaping, are made cylindric green body；（3）After when 70 DEG C of dry base substrates 5 are small, green body is put into interior bottom as semicircle spherical shape
In alumina crucible, when heating to 150 DEG C and small heat preservation 2 under air atmosphere with the speed of 5 DEG C/min, then with 10-
The speed of 20 DEG C/min heats to 380 DEG C and keeps the temperature 1 hour, is then heated to the speed of 1 DEG C/min
680 DEG C and keep the temperature 2 it is small when, finally heat to 1150 DEG C with the speed of 5 DEG C/min and keep the temperature 2 hours, it is then natural
Room temperature is cooled to, that is, light porous aluminum phosphate-mullite ceramic ball is made.
A kind of preparation method of the light porous aluminum phosphate-mullite ceramic ball, it is characterised in that：Step（1）In
Mullite Powder and oxide powder average grain diameter all for 0.6 micron, aluminium dihydrogen phosphate powder average particle size is 0.5 micron,
The average grain diameter of frit powder is 0.7 micron.
A kind of preparation method of the light porous aluminum phosphate-mullite ceramic ball, it is characterised in that：Step（2）In
Shaping refer to powder carry out dry-pressing formed, briquetting pressure 10-25MPa.
Description of the drawings
Fig. 1 is that light porous aluminum phosphate-mullite ceramic ball prepared by the technology of the present invention floats on photo in water；From
It can see in figure：Aluminum phosphate-mullite ceramic ball is floated in water, illustrates that the volume of aluminum phosphate-mullite ceramic ball is close
Degree is less than the density of water, i.e., the material that prepared by the technology of the present invention belongs to light porous ceramic material.
The principle of this technology invention is as follows：
It is fusible at a lower temperature for liquid using aluminium dihydrogen phosphate, the then property of solidifiable again at relatively high temperatures
It can so that green body is spontaneously formed in sintering process as sphere, and concrete principle is as follows：Aluminium dihydrogen phosphate be heated to 150 DEG C,
Keep the temperature 2 it is small when after, aluminium dihydrogen phosphate is changed into as liquid, be then heated rapidly to 380 DEG C and keep the temperature 1 it is small when, the purpose is to make
Various raw materials form a kind of very big viscous body of viscosity at such a temperature.The effect for adding in frit is on the one hand can to promote raw material
Melt as a kind of very big viscous body of viscosity, on the other hand can also increase surface tension so that viscous physical efficiency spontaneously form for
Sphere.It is heated slowly to during 680 DEG C, aluminium dihydrogen phosphate is gradually solidified as solid；In temperature-rise period, aluminium dihydrogen phosphate meeting
Be decomposed into aluminum phosphate, vapor and phosphorus pentoxide, the phosphorus pentoxide of generation can and carbonic acid reactive magnesium generation aluminum phosphate-not
Carry out stone, and vapor and carbon dioxide etc. play an important role of pore-forming, can thus prepare light porous aluminum phosphate-mullite pottery
Porcelain.
Specific embodiment
Embodiment 1
Mullite Powder, alumina powder, biphosphate aluminium powder, frit powder is 2 according to mass ratio：1：3.11：
0.03 ratio carries out dry-mixed；Wherein, the titanium dioxide containing 50 wt% lithias, the sodium oxide molybdena of 30 wt% and 20 wt% in frit
Silicon；Controlling the average grain diameter of Mullite Powder and oxide powder, aluminium dihydrogen phosphate powder average particle size is micro- for 0.5 for 0.6 micron
Rice, the average grain diameter of frit powder is 0.7 micron；Addition concentration is the poly-vinyl alcohol solution of 8 wt% as binding agent, binding agent
Additive amount be the 5% of blank gross mass；Then it is granulated, is dry-pressing formed with 10MPa pressure, cylindric green body is made；At 70 DEG C
After when dry base substrate 5 is small, green body be put into interior bottom be semicircle spherical shape alumina crucible in, under air atmosphere with 5 DEG C/
When the speed of min heats to 150 DEG C and small heat preservation 2, then heat to 380 DEG C with the speed of 10 DEG C/min and protect
Warm 1 hour, when then heating to 680 DEG C and small heat preservation 2 with the speed of 1 DEG C/min, finally with the speed of 5 DEG C/min
Degree heats to 1150 DEG C and keeps the temperature 2 hours, then naturally cools to room temperature, i.e., and obtained light porous aluminum phosphate-not
Carry out feldspar ball.The bulk density that porous ceramic ball is measured with Archimedes method is 0.89 g/cm3, open pore rate is 35 %.With
The crystalline phase that XRD analysis measure Ceramic Balls is aluminum phosphate-mullite.
Embodiment 2
Mullite Powder, alumina powder, biphosphate aluminium powder, frit powder are 2 according to mass ratio：1：3.11：
0.03 ratio carries out dry-mixed；Wherein, the titanium dioxide containing 50 wt% lithias, the sodium oxide molybdena of 30 wt% and 20 wt% in frit
Silicon；Controlling the average grain diameter of Mullite Powder and oxide powder, aluminium dihydrogen phosphate powder average particle size is micro- for 0.5 for 0.6 micron
Rice, the average grain diameter of frit powder is 0.7 micron；Addition concentration is the poly-vinyl alcohol solution of 8 wt% as binding agent, binding agent
Additive amount be the 5% of blank gross mass；Then it is granulated, is dry-pressing formed with 20MPa pressure, cylindric green body is made；At 70 DEG C
After when dry base substrate 5 is small, green body be put into interior bottom be semicircle spherical shape alumina crucible in, under air atmosphere with 5 DEG C/
When the speed of min heats to 150 DEG C and small heat preservation 2, then heat to 380 DEG C with the speed of 15 DEG C/min and protect
Warm 1 hour, when then heating to 680 DEG C and small heat preservation 2 with the speed of 1 DEG C/min, finally with the speed of 5 DEG C/min
Degree heats to 1150 DEG C and keeps the temperature 2 hours, then naturally cools to room temperature, i.e., and obtained light porous aluminum phosphate-not
Carry out feldspar ball.The bulk density that porous ceramic ball is measured with Archimedes method is 0.90 g/cm3, open pore rate is 34 %.With
The crystalline phase that XRD analysis measure Ceramic Balls is aluminum phosphate-mullite.
Embodiment 3
Mullite Powder, alumina powder, biphosphate aluminium powder, frit powder are 2 according to mass ratio：1：3.11：
0.03 ratio carries out dry-mixed；Wherein, the titanium dioxide containing 50 wt% lithias, the sodium oxide molybdena of 30 wt% and 20 wt% in frit
Silicon；It is all 0.6 micron to control the average grain diameter of Mullite Powder and oxide powder, and aluminium dihydrogen phosphate powder average particle size is 0.5
Micron, the average grain diameter of frit powder is 0.7 micron；The poly-vinyl alcohol solution that addition concentration is 8 wt% is bonded as binding agent
The additive amount of agent is the 5% of blank gross mass；Then it is granulated, is dry-pressing formed with 25 MPa pressure, cylindric green body is made；70
After when DEG C dry base substrate 5 is small, green body is put into the alumina crucible that interior bottom is semicircle spherical shape, with 5 under air atmosphere
DEG C/speed of min heat to 150 DEG C and keep the temperature 2 it is small when, then heat to 380 DEG C simultaneously with the speed of 20 DEG C/min
1 hour is kept the temperature, when then heating to 680 DEG C and small heat preservation 2 with the speed of 1 DEG C/min, finally with 5 DEG C/min's
Speed heats to 1150 DEG C and keeps the temperature 2 hours, then naturally cools to room temperature, i.e., and obtained light porous aluminum phosphate-
Mullite ceramic ball.The bulk density that porous ceramic ball is measured with Archimedes method is 0.91g/cm3, open pore rate is 32 %.
The crystalline phase that Ceramic Balls are measured with XRD analysis is aluminum phosphate-mullite.
Claims (2)
1. a kind of preparation method of light porous aluminum phosphate-mullite ceramic ball, it is characterised in that using following steps：（1）
Mullite Powder, alumina powder, biphosphate aluminium powder, frit powder are 2 according to mass ratio：1：3.11：0.03 ratio
It carries out dry-mixed；Wherein, the silica containing 50 wt% lithias, the sodium oxide molybdena of 30 wt% and 20 wt% in frit；Control is not
Carry out the average grain diameter of stone powder and alumina powder for 0.6 micron, aluminium dihydrogen phosphate powder average particle size is 0.5 micron, frit
The average grain diameter of powder is 0.7 micron；（2）As binding agent, binding agent adds the poly-vinyl alcohol solution that addition concentration is 8 wt%
Dosage is the 5% of blank gross mass；Then it is granulated, is molded, cylindric green body is made；（3）After when 70 DEG C of dry base substrates 5 are small,
Green body is put into the alumina crucible that interior bottom is semicircle spherical shape, with the speed heat temperature raising of 5 DEG C/min under air atmosphere
It when to 150 DEG C and heat preservation 2 is small, then heats to 380 DEG C with the speed of 10-20 DEG C/min and keeps the temperature 1 hour, then
When heating to 680 DEG C and small heat preservation 2 with the speed of 1 DEG C/min, finally heated to the speed of 5 DEG C/min
1150 DEG C and 2 hours of heat preservation, room temperature is then naturally cooled to, that is, light porous aluminum phosphate-mullite ceramic ball is made.
2. a kind of preparation method of light porous aluminum phosphate-mullite ceramic ball as described in claim 1, it is characterised in that：
Step（2）In shaping refer to powder carry out dry-pressing formed, briquetting pressure 10-25MPa.
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| CN1091764A (en) * | 1993-02-19 | 1994-09-07 | 胡小弟 | The high temperature compound binding agent |
| CN102503510A (en) * | 2011-11-03 | 2012-06-20 | 杭州中亚新材料科技有限公司 | Production process for firing alumina foamed ceramic filter board in roller kiln |
| CN103396150A (en) * | 2013-07-30 | 2013-11-20 | 河南煤业化工集团研究院有限责任公司 | Method for preparing foam ceramic self-insulation wall material by utilizing solid wastes |
| CN103467123A (en) * | 2013-09-02 | 2013-12-25 | 安徽瑞泰新材料科技有限公司 | Silicon-rich mullite lightweight aggregate and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1091764A (en) * | 1993-02-19 | 1994-09-07 | 胡小弟 | The high temperature compound binding agent |
| CN102503510A (en) * | 2011-11-03 | 2012-06-20 | 杭州中亚新材料科技有限公司 | Production process for firing alumina foamed ceramic filter board in roller kiln |
| CN103396150A (en) * | 2013-07-30 | 2013-11-20 | 河南煤业化工集团研究院有限责任公司 | Method for preparing foam ceramic self-insulation wall material by utilizing solid wastes |
| CN103467123A (en) * | 2013-09-02 | 2013-12-25 | 安徽瑞泰新材料科技有限公司 | Silicon-rich mullite lightweight aggregate and preparation method thereof |
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