CN108940253B - Preparation method of water treatment active alumina ball - Google Patents
Preparation method of water treatment active alumina ball Download PDFInfo
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- CN108940253B CN108940253B CN201810678458.0A CN201810678458A CN108940253B CN 108940253 B CN108940253 B CN 108940253B CN 201810678458 A CN201810678458 A CN 201810678458A CN 108940253 B CN108940253 B CN 108940253B
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000243 solution Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910007541 Zn O Inorganic materials 0.000 claims abstract description 22
- FJMNNXLGOUYVHO-UHFFFAOYSA-N aluminum zinc Chemical compound [Al].[Zn] FJMNNXLGOUYVHO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011259 mixed solution Substances 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims abstract description 6
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 6
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001354 calcination Methods 0.000 claims abstract description 6
- URDDJSKMZSGLHS-UHFFFAOYSA-M ethanol;tetrabutylazanium;hydroxide Chemical compound [OH-].CCO.CCCC[N+](CCCC)(CCCC)CCCC URDDJSKMZSGLHS-UHFFFAOYSA-M 0.000 claims abstract description 6
- 238000001704 evaporation Methods 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000001632 sodium acetate Substances 0.000 claims abstract description 6
- 235000017281 sodium acetate Nutrition 0.000 claims abstract description 6
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004246 zinc acetate Substances 0.000 claims abstract description 6
- 238000004321 preservation Methods 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 239000002826 coolant Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 239000008399 tap water Substances 0.000 claims description 5
- 235000020679 tap water Nutrition 0.000 claims description 5
- 238000001179 sorption measurement Methods 0.000 abstract description 7
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 6
- 238000004140 cleaning Methods 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 3
- 238000013032 photocatalytic reaction Methods 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 239000008204 material by function Substances 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 238000002791 soaking Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000006115 defluorination reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B01J35/39—
-
- B01J35/51—
-
- B01J35/60—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
A preparation method of water treatment active alumina balls belongs to the field of environment purification functional materials; the preparation method comprises the following steps: 1) mixing ethanol, zinc acetate and aluminum isopropoxide in a flask, heating and preserving heat, then adding 15% tetrabutylammonium hydroxide ethanol solution, sodium acetate and tributyl phosphate into the flask, continuing heating and preserving heat, and evaporating the solution in the flask until the volume of the solution is remained 2/3 to obtain an aluminum-zinc mixed solution; 2) adding the activated alumina balls treated by phosphoric acid into the aluminum-zinc mixed solution, carrying out hydrothermal reaction, filtering the solid-liquid mixture after the reaction, and cleaning solid substances; 3) drying the cleaned solid matter, then calcining at high temperature, and cooling to obtain water treatment activated alumina balls; the Al-Zn-O surface bonding coating is prepared on the surface of the active alumina ball, so that pollutants in water can be removed in an adsorption mode, and adsorbed organic pollutants can be degraded through a photocatalytic reaction, so that the coating has continuous adsorption capacity.
Description
Technical Field
The invention belongs to the field of materials with an environment purification function, and particularly relates to a preparation method of water treatment active alumina balls.
Background
The activated alumina spheres are also known as clean water activated alumina and the alumina used in the catalyst is commonly referred to as activated alumina. It is a porous, high-dispersion solid material, has a large surface area, and its microporous surface possesses the characteristics required for catalytic action, such as adsorption property, defluorination property, drying property, surface activity and excellent thermal stability, so that it can be extensively used as domestic drying agent and catalyst carrier for chemical reaction. The modern water purifying active alumina is white spherical porous particle, and has homogeneous granularity, smooth surface, high mechanical strength, high hydroscopicity, no swelling, no cracking and other advantages. Besides being used as a drying agent, the adsorbent can also be used for adsorbing various organic pollutants. When the active alumina ball is saturated with adsorbed pollutant, the active alumina ball needs to be regenerated by heating, solvent soaking and other modes, and then can be used continuously. The adsorption-regeneration process causes interruption of the adsorption treatment process, which is not conducive to continuous treatment of the contaminants. To solve this problem, it is necessary to allow the adsorbed contaminants to decompose on the surface of the activated alumina spheres, thereby releasing the surface of the activated alumina spheres.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a preparation method of water treatment activated alumina balls. The active alumina ball has the activity of degrading organic pollutants by photocatalysis, and can remove various organic pollutants in water under illumination.
The technical scheme adopted by the invention is as follows:
a preparation method of water treatment active alumina balls comprises the following process steps:
step 1, preparing an aluminum-zinc mixed solution:
(1) adding 255-310 mL of ethanol, 8-15 g of zinc acetate and 11-18 g of aluminum isopropoxide into a 500mL round-bottom flask in sequence, installing a spherical condenser tube, using tap water as a cooling medium, heating the solution to 68 ℃, and carrying out heat preservation and reflux for 50min at the temperature;
(2) adding 9-13 mL of 15% tetrabutylammonium hydroxide ethanol solution, 3-7 g of sodium acetate and 3.5-5.5 mL of tributyl phosphate into a round-bottom flask, and continuously carrying out heat preservation and reflux for 70min at 68 ℃;
(3) mounting the flask on a rotary evaporator, controlling the water bath temperature at 70 ℃, rotating the flask at a speed of 100rpm, and evaporating until 2/3 solution volume remains to obtain an aluminum-zinc mixed solution;
step 2, Al-Zn-O surface bonding:
(1) 20g of active alumina balls are soaked in 0.6mol/L phosphoric acid solution for 1 hour, then filtered, fully washed by distilled water and placed in an oven at 180 ℃ for 15 hours until being completely dried;
(2) transferring the aluminum-zinc mixed solution into a stainless steel high-pressure reaction kettle, adding 20g of activated alumina balls treated by phosphoric acid, sealing the reaction kettle, keeping the temperature of the solution in the reaction kettle at 150-170 ℃, keeping the pressure in the reaction kettle at no more than 2.8MPa, reacting for 50-70 h under the condition, and then cooling to room temperature;
(3) filtering the solid-liquid mixture in the reaction kettle, washing the obtained solid substance with ethanol, and then washing with deionized water to obtain Al-Zn-O surface bonding active alumina balls;
and 3, drying and heat treatment:
(1) drying the Al-Zn-O surface bonding active alumina ball at 220 ℃ for 18 h;
(2) and (3) placing the dried Al-Zn-O surface bonding active alumina ball in a program-controlled box type electric furnace, calcining for 3-7 h at 460-570 ℃, and cooling the electric furnace to obtain the water treatment active alumina ball.
The preparation method of the water treatment active alumina ball comprises the following steps:
in the step 2(1), the diameter of the activated alumina ball is 2-7 mm, and the specific surface area is 280-360 m2/g。
Compared with the prior art, the preparation method of the water treatment active alumina ball has the advantages that:
the Al-Zn-O surface bonding coating is prepared on the surface of the active alumina ball, and has strong bonding property with the active alumina ball, compact coating and good stability. The novel active alumina ball keeps the original porous characteristic, can remove pollutants in water in an adsorption mode, can degrade adsorbed organic pollutants through photocatalytic reaction, has continuous adsorption capacity, and does not need frequent regeneration to recover the adsorption surface. The active alumina ball can be used for removing organic pollutants in water for a long time, and has wide application in various water treatment and purification fields.
Detailed Description
In the following examples 1 to 3, the chemical materials were pure materials except for specific indications.
Example 1
A preparation method of water treatment active alumina balls comprises the following process steps:
step 1, preparing an aluminum-zinc mixed solution:
(1) adding 255mL of ethanol, 8g of zinc acetate and 11g of aluminum isopropoxide into a 500mL round-bottom flask in sequence, installing a spherical condenser pipe at the bottle mouth, using tap water as a cooling medium, heating the solution to 68 ℃, and carrying out heat preservation and reflux for 50 min;
(2) adding 9mL of 15% tetrabutylammonium hydroxide ethanol solution, 3g of sodium acetate and 3.5mL of tributyl phosphate into a round-bottom flask, and continuously carrying out heat preservation and reflux at 68 ℃ for 70 min;
(3) mounting the flask on a rotary evaporator, controlling the water bath temperature at 70 ℃, rotating the flask at a speed of 100rpm, and evaporating until 2/3 solution volume remains to obtain an aluminum-zinc mixed solution;
step 2, Al-Zn-O surface bonding:
(1) 20g of activated alumina spheres (diameter 2mm, specific surface area 360 m)2/g) soaking in 0.6mol/L phosphoric acid solution for 1h, then filtering, fully cleaning with distilled water, and placing in an oven at 180 ℃ for 15h until completely drying;
(2) transferring the aluminum-zinc mixed solution into a stainless steel high-pressure reaction kettle, adding 20g of activated alumina balls treated by phosphoric acid, sealing the reaction kettle, keeping the temperature of the solution in the reaction kettle at 150 ℃ and the pressure in the reaction kettle at 2.3MPa, reacting for 50h under the condition, and then cooling to room temperature;
(3) filtering the solid-liquid mixture in the reaction kettle, washing the obtained solid substance with ethanol, and then washing with deionized water to obtain Al-Zn-O surface bonding active alumina balls;
and 3, drying and heat treatment:
(1) drying the Al-Zn-O surface bonding active alumina ball in a constant-temperature electric heating drying oven at 220 ℃ for 18 h;
(2) and calcining the dried Al-Zn-O surface bonding active alumina ball in a program-controlled box type electric furnace at 460 ℃ for 7h, and cooling to obtain the water treatment active alumina ball.
Example 2
A preparation method of water treatment active alumina balls comprises the following process steps:
step 1, preparing an aluminum-zinc mixed solution:
(1) adding 280mL of ethanol, 12g of zinc acetate and 15g of aluminum isopropoxide into a 500mL round-bottom flask in sequence, installing a spherical condenser tube, taking tap water as a cooling medium, heating the solution to 68 ℃, and carrying out heat preservation and reflux for 50min at the temperature;
(2) adding 11mL of 15% tetrabutylammonium hydroxide ethanol solution, 5g of sodium acetate and 4.5mL of tributyl phosphate into a round-bottom flask, and continuously carrying out heat preservation and reflux at 68 ℃ for 70 min;
(3) mounting the flask on a rotary evaporator, controlling the water bath temperature at 70 ℃, rotating the flask at a speed of 100rpm, and evaporating until 2/3 solution volume remains to obtain an aluminum-zinc mixed solution;
step 2, Al-Zn-O surface bonding:
(1) 20g of activated alumina spheres (diameter 5mm, specific surface area 310 m)2Per gram) soaking in 0.6mol/L phosphoric acid solution for 1 hour, then filtering, fully cleaning with distilled water, and placing in an oven at 180 ℃ for 15 hours until completely drying;
(2) transferring the aluminum-zinc mixed solution into a stainless steel high-pressure reaction kettle, adding 20g of activated alumina balls treated by phosphoric acid, sealing the reaction kettle, keeping the temperature of the solution in the reaction kettle at 160 ℃, keeping the pressure in the reaction kettle at 2.5MPa, reacting for 60 hours under the condition, and then cooling to room temperature;
(3) filtering the solid-liquid mixture in the reaction kettle, washing the obtained solid substance with ethanol, and then washing with deionized water to obtain Al-Zn-O surface bonding active alumina balls;
and 3, drying and heat treatment:
(1) drying the Al-Zn-O surface bonding active alumina ball at 220 ℃ for 18 h;
(2) and (3) placing the dried Al-Zn-O surface bonding active alumina ball in a program control box type electric furnace, calcining for 5h at 510 ℃, and cooling the electric furnace to obtain the water treatment active alumina ball.
Example 3
A preparation method of water treatment active alumina balls comprises the following process steps:
step 1, preparing an aluminum-zinc mixed solution:
(1) adding 310mL of ethanol, 15g of zinc acetate and 18g of aluminum isopropoxide into a 500mL round-bottom flask in sequence, installing a spherical condenser tube, taking tap water as a cooling medium, heating the solution to 68 ℃, and carrying out heat preservation and reflux for 50min at the temperature;
(2) adding 13mL of 15% tetrabutylammonium hydroxide ethanol solution, 7g of sodium acetate and 5.5mL of tributyl phosphate into a round-bottom flask, and continuously carrying out heat preservation and reflux at 68 ℃ for 70 min;
(3) mounting the flask on a rotary evaporator, controlling the water bath temperature at 70 ℃, rotating the flask at a speed of 100rpm, and evaporating until 2/3 solution volume remains to obtain an aluminum-zinc mixed solution;
step 2, Al-Zn-O surface bonding:
(1) 20g of activated alumina spheres (diameter 7mm, specific surface area 280 m)2Per gram) soaking in 0.6mol/L phosphoric acid solution for 1 hour, then filtering, fully cleaning with distilled water, and placing in an oven at 180 ℃ for 15 hours until completely drying;
(2) transferring the aluminum-zinc mixed solution into a stainless steel high-pressure reaction kettle, adding 20g of activated alumina balls treated by phosphoric acid, sealing the reaction kettle, keeping the temperature of the solution in the reaction kettle at 170 ℃ and the pressure in the reaction kettle at 2.8MPa, reacting for 70h under the condition, and then cooling to room temperature;
(3) filtering the solid-liquid mixture in the reaction kettle, washing the obtained solid substance with ethanol, and then washing with deionized water to obtain Al-Zn-O surface bonding active alumina balls;
and 3, drying and heat treatment:
(1) drying the Al-Zn-O surface bonding active alumina ball at 220 ℃ for 18 h;
(2) and (3) placing the dried Al-Zn-O surface bonding active alumina ball in a program control box type electric furnace, calcining for 3h at 570 ℃, and cooling the electric furnace to obtain the water treatment active alumina ball.
While embodiments of the invention have been shown and described, it will be understood that modifications and changes will occur to those skilled in the art in light of the foregoing description, and that all such modifications and changes are intended to be included within the scope of the present invention as claimed.
Claims (2)
1. The preparation method of the water treatment active alumina ball is characterized by comprising the following process steps:
step 1, preparing an aluminum-zinc mixed solution:
(1) adding 255-310 mL of ethanol, 8-15 g of zinc acetate and 11-18 g of aluminum isopropoxide into a 500mL round-bottom flask in sequence, installing a spherical condenser tube, using tap water as a cooling medium, heating the solution to 68 ℃, and carrying out heat preservation and reflux for 50min at the temperature;
(2) adding 9-13 mL of 15% tetrabutylammonium hydroxide ethanol solution, 3-7 g of sodium acetate and 3.5-5.5 mL of tributyl phosphate into a round-bottom flask, and continuously carrying out heat preservation and reflux for 70min at 68 ℃;
(3) mounting the flask on a rotary evaporator, controlling the water bath temperature at 70 ℃, rotating the flask at a speed of 100rpm, and evaporating until 2/3 solution volume remains to obtain an aluminum-zinc mixed solution;
step 2, Al-Zn-O surface bonding:
(1) 20g of active alumina balls are soaked in 0.6mol/L phosphoric acid solution for 1 hour, then filtered, fully washed by distilled water and placed in an oven at 180 ℃ for 15 hours until being completely dried;
(2) transferring the aluminum-zinc mixed solution into a stainless steel high-pressure reaction kettle, adding 20g of activated alumina balls treated by phosphoric acid, sealing the reaction kettle, keeping the temperature of the solution in the reaction kettle at 150-170 ℃, keeping the pressure in the reaction kettle at no more than 2.8MPa, reacting for 50-70 h under the condition, and then cooling to room temperature;
(3) filtering the solid-liquid mixture in the reaction kettle, washing the obtained solid substance with ethanol, and then washing with deionized water to obtain Al-Zn-O surface bonding active alumina balls;
and 3, drying and heat treatment:
(1) drying the Al-Zn-O surface bonding active alumina ball at 220 ℃ for 18 h;
(2) and (3) placing the dried Al-Zn-O surface bonding active alumina ball in a program-controlled box type electric furnace, calcining for 3-7 h at 460-570 ℃, and cooling the electric furnace to obtain the water treatment active alumina ball.
2. The method for preparing water treatment active alumina ball according to claim 1Characterized in that in the step 2(1), the diameter of the activated alumina ball is 2-7 mm, and the specific surface area is 280-360 m2/g。
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6492014B1 (en) * | 1999-04-01 | 2002-12-10 | The United States Of America As Represented By The Secretary Of The Navy | Mesoporous composite gels an aerogels |
| CN108067212A (en) * | 2017-12-19 | 2018-05-25 | 沈阳理工大学 | A kind of method for preparing the hollow ball-type aluminum titanium composite oxide material of macropore |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6492014B1 (en) * | 1999-04-01 | 2002-12-10 | The United States Of America As Represented By The Secretary Of The Navy | Mesoporous composite gels an aerogels |
| CN108067212A (en) * | 2017-12-19 | 2018-05-25 | 沈阳理工大学 | A kind of method for preparing the hollow ball-type aluminum titanium composite oxide material of macropore |
Non-Patent Citations (1)
| Title |
|---|
| Al-Zn复合Al2 O3 -C材料抗氧化性研究;谢娟娟等;《耐火材料》;20110228;第45卷(第1期);第6-10页 * |
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Effective date of registration: 20230704 Address after: 043300 North Section of Shanxi Aluminum Plant No. 9 Road, Hejin Aluminum Industrial Park, Yuncheng City, Shanxi Province (opposite Huaze Aluminum Electricity) Patentee after: SHANXI JUHUA NEW MATERIAL TECHNOLOGY Co.,Ltd. Address before: 110159 No. 6 Nanping Road, Hunnan New District, Shenyang, Liaoning Patentee before: SHENYANG LIGONG University |
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