CN105540630B - A kind of preparation method of coal-ethylene glycol catalyst carrier - Google Patents
A kind of preparation method of coal-ethylene glycol catalyst carrier Download PDFInfo
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- CN105540630B CN105540630B CN201510904473.9A CN201510904473A CN105540630B CN 105540630 B CN105540630 B CN 105540630B CN 201510904473 A CN201510904473 A CN 201510904473A CN 105540630 B CN105540630 B CN 105540630B
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Substances OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000003054 catalyst Substances 0.000 title claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 17
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000011148 porous material Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 230000004913 activation Effects 0.000 claims abstract description 6
- 238000001994 activation Methods 0.000 claims abstract description 6
- 238000000227 grinding Methods 0.000 claims abstract description 4
- 238000004131 Bayer process Methods 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 9
- 239000003245 coal Substances 0.000 claims description 8
- 238000012216 screening Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 229910001648 diaspore Inorganic materials 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 4
- 230000001788 irregular Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000004033 plastic Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims 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 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 230000036541 health Effects 0.000 abstract description 2
- 238000007493 shaping process Methods 0.000 abstract description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 abstract 1
- 239000012752 auxiliary agent Substances 0.000 abstract 1
- 238000000465 moulding Methods 0.000 abstract 1
- 230000003213 activating effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 3
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011265 semifinished product Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/44—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water
- C01F7/441—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water by calcination
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/612—Surface area less than 10 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of preparation method of coal-ethylene glycol catalyst carrier, be the aluminium hydroxide that Bayer process is produced by being dried, grinding, fast de-, directed agents mixing, forming agent molding, shaping, health preserving, auxiliary agent heat treatment, drying, activation, inorganic agent process, the technical process such as be dried, screen, so as to prepare alpha active aluminium oxide, product specific surface of the present invention is little, pore volume is little, aperture is big, crystal structure is α types, can be used as kind of an effective carrier for coal-ethylene glycol catalyst.
Description
Technical Field
The invention relates to the field of inorganic materials, in particular to a preparation method of a catalyst carrier for preparing ethylene glycol from coal.
Background
Ethylene glycol is an important bulk chemical raw material, is mainly used for producing polyester, alkyd resin, glyoxal and the like, and can also be used as an antifreezing agent. In 2014, the apparent consumption of the ethylene glycol is 1210 ten thousand tons in China, the imported ethylene glycol is 845 ten thousand tons, the external dependence reaches 70 percent, and the demand is expected to reach 1800 ten thousand tons in 2020. The traditional ethylene glycol production must rely on petroleum ethylene as a raw material, and has important practical significance and long-term strategic significance for developing coal-made ethylene glycol due to the energy endowment characteristics of 'oil shortage, gas shortage and coal enrichment' in China. The preparation of ethylene glycol from coal is one of five novel coal chemical technologies which are mainly promoted in the twelve-five program of China.
In the preparation process of the coal-to-ethylene glycol catalyst, the property of the carrier has great influence on the activity and selectivity of the catalyst. On one hand, the surface property of the carrier obviously influences the dispersion degree of the active component on the surface of the carrier and the interaction degree of the active component and the carrier, thereby influencing the activity of the catalyst; on the other hand, the pore structure of the support affects the diffusion of reactants and products during the reaction, thereby affecting the activity and selectivity of the catalyst. Gamma-alumina is generally considered to be active, while alpha-alumina is classified as inert alumina, so that gamma-alumina is more applied than alpha-alumina in the catalytic fields of petrochemical industry, energy environment and the like, but alpha-alumina has an irreplaceable function for some catalytic reactions with special requirements.
Disclosure of Invention
The invention aims to provide a preparation method of a coal-to-ethylene glycol catalyst carrier, which can solve the technical problems.
A preparation method of a coal-to-ethylene glycol catalyst carrier comprises the following steps: drying and grinding, quick removing, mixing of a guiding agent, preparation of a forming agent, manufacture of mother balls, heat treatment, drying, activation, cleaning, drying and screening.
The water content of the ground aluminum hydroxide is lower than 0.2 percent, and the aluminum hydroxide is ground until the particle size D50 is 2.0 mu
m, particle size D97 was 4.0. mu.m.
The preparation method of the forming agent comprises the following steps: adding about 100 liters of water, slowly adding 10-12 kilograms of nitric acid into the mixture
And (3) uniformly adding 6-8 Kg of diaspore under stirring, continuously stirring for 10 minutes after the diaspore is added, adding 50 Kg of diaspore into a reaction kettle, adding 50 Kg of water, starting stirring, and uniformly adding 2Kg of ammonia water to obtain the aqueous ammonia.
The manufacturing method of the cue ball comprises the following steps: adding the forming agent into the aluminum hydroxide particles in the mixing cylinder to form
Semi-paste, placing into 12 mesh stainless steel net, twisting into irregular particles, sieving, placing into plastic bag, standing mother ball, and maintaining for 2-4 hr.
The heat treatment method comprises the following steps: adding a proper amount of water into a reaction kettle, adding the well-cured master batch into the reaction kettle,
adding into the mixture 40cm away from the tank opening, covering the cover tightly, heating to 120 deg.C, maintaining the temperature for 1 hr, heating to 290 + -5 deg.C, controlling the pressure at 3 + -0.05 MPa, maintaining the temperature for 1 hr, naturally cooling for at least 10 hr, and cooling to normal pressure to discharge.
The drying and activating method comprises the following steps: drying the semi-finished product obtained by heat treatment, activating, and activating
The temperature is raised to 300 ℃, the temperature is preserved for 0.5 to 1 hour, then the temperature is gradually raised to 650 ℃ and 700 ℃, the temperature is preserved for 1 hour, and then the mixture is naturally cooled.
The drying screening method comprises the following steps: the temperature is kept at 180 ℃ and 200 ℃, and a machine or a device is adopted after drying for 2 hours
Manually screening, and ensuring the particle size to be 2-4 mm.
The specific surface area of the α -alumina prepared by the invention is less than 10m2Per g, pore volume less than 0.01cm2Per g, pore
The diameter is larger than 7nm, and the mass ratio of sodium is less than 0.001%.
The alpha-alumina prepared by the invention is used as a catalyst carrier for preparing ethylene glycol from coal.
The invention has the following beneficial effects:
1) the production process of the invention adopts aluminum hydroxide with the particle size D50 of 2.0 mu m and D97 of 4.0 mu m as raw materials to produce the active aluminum oxide, wherein 50 percent of aluminum hydroxide particles smaller than 2.0 mu m and 97 percent of aluminum hydroxide particles smaller than 4.0 mu m meet the requirements of crystal form transformation and specific physical and chemical properties.
2) And a specific guiding agent is adopted to provide guarantee for the crystal structure transformation of the alpha-alumina.
3) The physicochemical property of the alpha-alumina is ensured by adopting the process of drying and activating after heat treatment.
4) The specific surface area of the alpha-alumina is extremely small.
5) In the case where the pore volume of α -alumina is extremely small, the pore diameter is maximized.
Detailed Description
The invention is further illustrated, but is not to be construed as limited, by the following examples:
a preparation method of a coal-to-ethylene glycol catalyst carrier comprises the following preparation steps:
(1) and (3) drying: the aluminum hydroxide produced by the Bayer process has the moisture content of less than 0.2 percent.
(2) Grinding: the dried aluminum hydroxide was ground to a D50 of 2.0 μm and a D97 of 4.0. mu.m.
(3) Quick release: removing crystal water in the aluminum hydroxide at a high temperature of more than 800 ℃.
(4) And (3) mixing a guiding agent: the directing agent is mixed into the alumina.
(5) Preparing a forming agent: adding about 100 liters of water, slowly adding 10-12 kilograms of nitric acid, uniformly adding 6-8 kilograms of diaspore under stirring, and continuously stirring for 10 minutes after the addition is finished. Adding 50 Kg of ammonia water into a middle reaction kettle, adding 50 Kg of water, starting stirring, and uniformly adding 2Kg of ammonia water.
(6) Manufacturing a cue ball: adding the forming agent solution into aluminum hydroxide quick-release powder from a mixing tank to form a semi-paste, putting the semi-paste into a 12-mesh stainless steel net, forcibly twisting the semi-paste into irregular granular matters, dropping the granular matters under a screen, and putting the granular matters into a plastic bag.
(7) Putting the mother ball into a ball rolling machine, adding the quick-release powder and the forming agent for forming, and then shaping.
(8) Health preserving: the cue ball is kept still for 2 to 4 hours.
(9) And (3) heat treatment: half water is added into a reaction kettle, then the master batch is added into the reaction kettle, after the master batch is added into the reaction kettle and is 40cm away from a tank opening, a cover is tightly covered, the temperature can be raised, the temperature is raised to 120 ℃, the temperature is kept for 1 hour, the temperature is raised to 290 +/-5 ℃, the pressure is controlled to be 3 +/-0.05 MPa, and the temperature is kept for 1 hour. Naturally cooling for at least 10 hours, reducing the pressure to normal pressure, and discharging.
(10) Drying and activating: drying the obtained semi-finished product, activating, raising the activation temperature to 300 ℃, preserving heat for 0.5-1 hour, gradually raising the temperature to the process temperature (650 plus 700 ℃), preserving heat for 1 hour, and naturally cooling.
(11) And (4) cleaning, namely repeatedly cleaning by using ionized water.
(12) And (3) drying: the temperature was maintained at 180 ℃ and 200 ℃ for 2 hours.
(13) Screening: the particles are guaranteed to be 2-4mm by adopting a machine and manual screening.
(14) Packaging: and packaging according to the requirements of customers.
Performance advantages of the invention
| Item | The invention | HG/T3297 |
| Crystal structure | Model α | Without requirement |
| Specific surface area/(m)2/g） | Maximum 10 | Not less than 200 (minimum) |
| Pore volume/(cm)2/g) | Maximum 0.007 | Not less than 0.35 (minimum) |
| Pore size nm | Minimum 7.0 | Without requirement |
The above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, but not intended to limit the scope of the present invention, and all equivalent technical solutions also belong to the scope of the present invention, and the scope of the present invention should be defined by the claims.
Claims (3)
1. The preparation method of the catalyst carrier for preparing the ethylene glycol from the coal is characterized by comprising the following steps of: drying and grinding, quick removing, mixing of a guiding agent, preparation of a forming agent, preparation of mother balls, heat treatment, drying, activation, cleaning, drying and screening; wherein,
aluminum hydroxide produced by a Bayer process is taken as a raw material;
the dried and ground aluminum hydroxide has the moisture content of less than 0.2 percent and is ground until the particle size D50 is 2.0 mu m and the particle size D97 is 4.0 mu m;
the preparation method of the forming agent comprises the following steps: adding about 100 liters of water, slowly adding 10-12 kilograms of nitric acid, uniformly adding 6-8 kilograms of diaspore under stirring, continuously stirring for 10 minutes after the addition is finished, adding 50 kilograms of nitric acid into a reaction kettle, adding 50 kilograms of nitric acid, starting stirring, and uniformly adding 2 kilograms of ammonia water to prepare the catalyst;
the manufacturing method of the cue ball comprises the following steps: adding a forming agent into aluminum hydroxide particles in a mixing cylinder to form a semi-paste, placing the semi-paste into a 12-mesh stainless steel net, twisting the semi-paste into irregular granular substances, dropping the irregular granular substances into a sieve, placing the sieve into a plastic bag, and standing and curing mother balls for 2-4 hours;
the heat treatment method comprises the following steps: adding a proper amount of water into a reaction kettle, adding the cured master batch into the reaction kettle, adding the master batch into the reaction kettle 40cm away from a tank opening, covering a cover tightly, heating to 120 ℃, keeping the temperature for 1 hour, heating to 290 +/-5 ℃, controlling the pressure to be 3 +/-0.05 MPa, keeping the temperature for 1 hour, naturally cooling for at least 10 hours, reducing the pressure to normal pressure, and starting discharging;
the specific surface area of the finally prepared α -alumina is less than 10m2Per g, pore volume less than 0.01cm3The pore diameter is more than 7nm, and the mass ratio of sodium is less than 0.001%.
2. The preparation method of the catalyst carrier for ethylene glycol prepared from coal as claimed in claim 1, wherein the activation method comprises the following steps: the activation temperature is raised to 300 ℃, the temperature is kept for 0.5 to 1 hour, then the temperature is gradually raised to 650-700 ℃, the temperature is kept for 1 hour, and then the mixture is naturally cooled.
3. The preparation method of the catalyst carrier for ethylene glycol production from coal as claimed in claim 1, wherein the drying and screening method comprises the following steps: the temperature is kept at 180 ℃ and 200 ℃, and after drying for 2 hours, a machine or a manual screening is adopted, and the particle size is ensured to be 2-4 mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510904473.9A CN105540630B (en) | 2015-12-09 | 2015-12-09 | A kind of preparation method of coal-ethylene glycol catalyst carrier |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510904473.9A CN105540630B (en) | 2015-12-09 | 2015-12-09 | A kind of preparation method of coal-ethylene glycol catalyst carrier |
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| Publication Number | Publication Date |
|---|---|
| CN105540630A CN105540630A (en) | 2016-05-04 |
| CN105540630B true CN105540630B (en) | 2017-03-29 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1258567A (en) * | 1998-12-30 | 2000-07-05 | 中国石油化工集团公司 | Macroporous Alpha-alumina and its preparation and application |
| CN1307929A (en) * | 2000-12-25 | 2001-08-15 | 化学工业部天津化工研究设计院 | Preparation process of alumina adsorbant |
| CN103818939A (en) * | 2014-01-14 | 2014-05-28 | 淄博贝格工贸有限公司 | Aluminum oxide specially used for hydrogen peroxide fluidized bed and production technology for aluminum oxide |
-
2015
- 2015-12-09 CN CN201510904473.9A patent/CN105540630B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1258567A (en) * | 1998-12-30 | 2000-07-05 | 中国石油化工集团公司 | Macroporous Alpha-alumina and its preparation and application |
| CN1307929A (en) * | 2000-12-25 | 2001-08-15 | 化学工业部天津化工研究设计院 | Preparation process of alumina adsorbant |
| CN103818939A (en) * | 2014-01-14 | 2014-05-28 | 淄博贝格工贸有限公司 | Aluminum oxide specially used for hydrogen peroxide fluidized bed and production technology for aluminum oxide |
Non-Patent Citations (1)
| Title |
|---|
| CO经草酸二乙酯合成乙二醇催化剂研究;贺黎明;《中国博士学位论文全文数据库 工程科技I辑》;20120615(第6期);第B016-36页 * |
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