CN112675880A - Mo-Co bimetal supported catalyst and method thereof - Google Patents
Mo-Co bimetal supported catalyst and method thereof Download PDFInfo
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- CN112675880A CN112675880A CN202011572144.6A CN202011572144A CN112675880A CN 112675880 A CN112675880 A CN 112675880A CN 202011572144 A CN202011572144 A CN 202011572144A CN 112675880 A CN112675880 A CN 112675880A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 36
- 229910017313 Mo—Co Inorganic materials 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims description 12
- 239000002245 particle Substances 0.000 claims abstract description 16
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 11
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 8
- 150000003624 transition metals Chemical class 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 238000002156 mixing Methods 0.000 claims description 13
- 150000002751 molybdenum Chemical class 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 150000001868 cobalt Chemical class 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 239000011593 sulfur Substances 0.000 claims description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 7
- 239000011733 molybdenum Substances 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 6
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 6
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 4
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 4
- 239000011609 ammonium molybdate Substances 0.000 claims description 4
- 229940010552 ammonium molybdate Drugs 0.000 claims description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 235000015393 sodium molybdate Nutrition 0.000 claims description 3
- 239000011684 sodium molybdate Substances 0.000 claims description 3
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000001308 synthesis method Methods 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 7
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 8
- 239000000295 fuel oil Substances 0.000 abstract description 8
- 238000002360 preparation method Methods 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007841 coal based oil Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- VLXBWPOEOIIREY-UHFFFAOYSA-N dimethyl diselenide Natural products C[Se][Se]C VLXBWPOEOIIREY-UHFFFAOYSA-N 0.000 description 1
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Abstract
The Mo-Co bimetal supported catalyst comprises a carbonaceous particle carrier and active components of transition metals Mo and Co, wherein the specific surface of the carbonaceous particle carrier is 300-1500 m 2/g. The invention solves the problems of complex preparation process, high preparation cost and low hydrogenation activity of the existing heavy oil hydrogenation transition metal catalyst.
Description
Technical Field
The invention relates to the technical field of heavy oil hydrogenation, in particular to a Mo-Co bimetal supported catalyst and a method thereof.
Background
With the global trend of increasing the weight and deterioration of crude oil and the increasing dependence of domestic crude oil import, the development of hydrogenation technology for petroleum-based heavy oil and coal-based oil becomes a development trend in the refining and chemical field.
Most of the prior dispersed catalysts need to be additionally added with a vulcanizing agent for vulcanization to form an activated state, and the vulcanizing agent usually adopts hydrogen sulfide, industrial sulfur powder or DMDS, and the vulcanizing agents respectively have the defects of high toxicity, difficult dissolution, high cost and the like. In addition, the heavy oil suspension bed hydrogenation catalyst has the contradiction that the cost is low and the activity is high, in general, the Fe system dispersion type catalyst has low cost but low hydrogenation activity, and the transition metal oil-soluble catalysts such as Mo, Ni and Co have high reinforced activity but high cost due to the existence of organic ligands. The patent with application number 201310317514.5 discloses an oil-soluble auto-molybdenum sulfide catalyst, which comprises the steps of (1) putting a molybdenum source, water, sodium sulfide, a solvent and an inorganic acid in a container in sequence under the protection of nitrogen, uniformly mixing and stirring, cooling at 5-50 ℃, and reacting for 10-150 min; (2) adding alkylamine and carbon disulfide, stirring uniformly, heating to 60-200 ℃ and reacting for 3-10 h; (3) after the reaction is finished, fully cooling and filtering the product, fully washing the product with methanol, and drying the product to obtain the oil-soluble molybdenum sulfide catalyst; the hydrogenation activity of the catalyst is enhanced to a certain extent, but the defects of complex synthesis process and high cost still exist.
In general, the existing heavy oil hydrogenation catalyst has the conditions of complex preparation process, high preparation cost or low hydrogenation activity, so that the hydrogenation technology has the conditions of high device investment and operation cost, harsh reaction working conditions, high device operation difficulty and the like.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a Mo-Co bimetal supported catalyst and a method thereof, and solves the problems of complex preparation process, high preparation cost and low hydrogenation activity of the conventional suspended bed transition metal catalyst.
In order to achieve the purpose, the invention adopts the technical scheme that:
the Mo/Co bimetal supported catalyst comprises a carbonaceous particle carrier and active components of transition metals Mo and Co, wherein the specific surface of the carbonaceous particle carrier is 300-1500 m2/g, and a synthetic raw material contains alcohols.
The synthetic raw materials of the Mo/Co bimetallic supported catalyst mainly comprise molybdenum salt, cobalt salt, carbonaceous particles, a sulfur source and an acid solution.
A synthetic method of a Mo-Co bimetal supported catalyst comprises the following steps;
(1) dissolving molybdenum salt, a sulfur source and alcohols in water, and placing the solution in a reaction generating device for reaction for a certain time;
(2) adding the carbonaceous particles into a reaction generating device for fully mixing for a certain time;
(3) adding the acid solution and the cobalt salt into a reaction generating device together, and carrying out precipitation loading for a certain time under a certain pH environment to obtain the Mo/Co bimetallic supported catalyst.
The reaction time of the step (1) is 10-40min, the mixing time of the step (2) is 10-40min, and the precipitation load time of the step (3) is 20-80 min.
The molybdenum salt is any one or combination of more of ammonium molybdate, potassium molybdate and sodium molybdate, and the adding amount of the molybdenum salt is calculated according to the mass ratio of metal molybdenum to carbonaceous particles of 0.1-3: 100.
The sulfur source is any one or combination of sodium sulfide and hydrogen sulfide, and the molar ratio of elemental sulfur in the sulfur source to metal molybdenum in the molybdenum salt is 3-6: 1.
The alcohol comprises any one or more of polyethylene glycol, ethylene glycol, propanol and ethanol.
The adding amount of the alcohols is 0.1-1% of the mass of the water.
The step (1), the step (2) and the step (3) all need stirring and have heat tracing at 25-85 ℃.
The acid solution is any one or more of hydrochloric acid, nitric acid and sulfuric acid solution.
The pH environment is pH value of 1-4.
The adding amount of the cobalt salt is measured according to the molar ratio of the metal cobalt contained in the cobalt salt to the metal molybdenum in the molybdenum salt of 1:9-1: 2.
The invention has the beneficial effects that:
(1) the transition metal catalyst which is simple and convenient in synthesis method in the heavy oil hydrogenation field is provided, and the cost is relatively low;
(2) according to the characteristic that heavy oil hydrogenation is influenced by diffusion and mass transfer, a transition metal catalyst loaded on the outer surface is designed, and active carbon with large specific surface is adopted, so that the activity is high, the internal diffusion process is omitted, the reaction efficiency is improved, and the coke adsorption capacity is enhanced;
(3) the design of the bimetallic catalyst effectively improves the desulfurization level of the catalyst;
(4) provides favorable conditions for reducing the severity of heavy oil hydrogenation reaction.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
Adding 0.0185g of ammonium molybdate and 0.075g of sodium sulfide into a reaction device filled with 200g of deionized water, adding 0.2g of polyethylene glycol, starting stirring, heating to 25 ℃, and reacting for 10 min; the specific surface area is 300m2Adding 10 g/g of carbonaceous particles into a reaction device for fully mixing, and keeping the stirring operation and the reaction temperature at 25 ℃; after mixing well for 10min, the hydrochloric acid solution and 0.275g of cobalt nitrate were added to the reaction apparatus, and the pH was adjusted to 1, and the precipitation load was 80 min.
Example 2:
adding 0.745g of potassium molybdate and 0.638g of hydrogen sulfide into a reaction device filled with 200g of deionized water, adding 2g of ethylene glycol, starting stirring, heating to 85 ℃, and reacting for 40 min; the specific surface area is 1500m2Adding 10 g/g of carbonaceous particles into a reaction device for fully mixing, and keeping stirring operation and reaction temperature at 85 ℃; after mixing well for 40min, the sulfuric acid solution and 1.821g of cobalt nitrate were added to the reaction apparatus, the pH was adjusted to 3, and the precipitation load was 20 min.
Example 3:
adding 0.504g of sodium molybdate and 2.003g of sodium sulfide into a reaction device filled with 200g of deionized water, adding 1g of ethanol, starting stirring, heating to 40 ℃, and reacting for 30 min; the specific surface area is 600m2Adding 10 g/g of carbonaceous particles into a reaction device for fully mixing, and keeping stirring operation and reaction temperature at 40 ℃; after mixing well for 20min, the nitric acid solution and 3.637g were added to the reaction apparatus and the pH was adjusted to 4 and the precipitate was loaded for 60 min.
Example 4:
adding 0.185g of ammonium molybdate and 1.258g of sodium sulfide into a reaction device filled with 200g of deionized water, adding 1g of propanol, starting stirring, heating to 60 ℃, and reacting for 35 min; the specific surface area is 800m2Adding 10 g/g of carbonaceous particles into a reaction device for fully mixing, and keeping stirring operation and reaction temperature at 60 ℃; after mixing well for 25min, the nitric acid solution and 1.220g of cobalt nitrate were added to the reaction apparatus, the pH was adjusted to 1, and the precipitation load was 50 min.
Example 5
The catalysts prepared in examples 1 to 4 were used in a metal concentration of 200. mu.g.g-1The reaction mixture was added to Toledo vacuum residue, and after autoclave reaction was carried out at a reaction temperature of 450 ℃ and an initial hydrogen pressure of 9MPa for 60 minutes, the results are shown in Table 2.
TABLE 1 Toledo vacuum residua Properties and compositions
TABLE 2 distribution of the autoclave reaction products
The above description is only exemplary of the present invention and should not be taken as limiting the invention, as any modifications, equivalents, improvements and the like within the general concept of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The Mo-Co bimetal supported catalyst is characterized by comprising a carbonaceous particle carrier and active components of transition metals Mo and Co, wherein the specific surface of the carbonaceous particle carrier is 300-1500 m2/g, and a synthetic raw material contains alcohols.
2. The Mo-Co bimetallic supported catalyst of claim 1, wherein the raw materials for the synthesis of the Mo/Co bimetallic supported catalyst mainly comprise molybdenum salt, cobalt salt, carbonaceous particles, sulfur source and acid solution.
3. The synthesis method of the Mo-Co bimetal supported catalyst based on claim 1, which is characterized by comprising the following steps;
(1) dissolving molybdenum salt, a sulfur source and alcohols in water, and placing the solution in a reaction generating device for reaction for a certain time;
(2) adding the carbonaceous particles into a reaction generating device for fully mixing for a certain time;
(3) adding the acid solution and the cobalt salt into a reaction generating device together, and carrying out precipitation loading for a certain time under a certain pH environment to obtain the Mo/Co bimetallic supported catalyst.
4. The method for synthesizing the Mo-Co bimetallic supported catalyst as claimed in claim 3, wherein the reaction time of the step (1) is 10-40min, the mixing time of the step (2) is 10-40min, and the precipitation loading time of the step (3) is 20-80 min.
5. The method for synthesizing the Mo-Co bimetal supported catalyst according to claim 3, wherein the molybdenum salt is any one or combination of ammonium molybdate, potassium molybdate and sodium molybdate, and the addition amount of the molybdenum salt is 0.1-3: 100 of the mass ratio of metal molybdenum to carbonaceous particles.
6. The method for synthesizing the Mo-Co bimetallic supported catalyst according to claim 3, wherein the sulfur source is any one or combination of sodium sulfide and hydrogen sulfide, and the molar ratio of elemental sulfur in the sulfur source to metal molybdenum in the molybdenum salt is 3-6: 1.
7. The method for synthesizing the Mo-Co bimetallic supported catalyst as in claim 3, wherein the alcohol comprises any one or more of polyethylene glycol, ethylene glycol, propanol and ethanol; the adding amount of the alcohols is 0.1-1% of the mass of the water.
8. The method for synthesizing the Mo-Co bimetal supported catalyst according to claim 3, wherein the step (1), the step (2) and the step (3) all need stirring and have heat tracing at 25-85 ℃.
9. The method for synthesizing the Mo-Co bimetallic supported catalyst according to claim 3, wherein the acid solution is any one or more of hydrochloric acid, nitric acid and sulfuric acid solution; the pH environment is pH value of 1-4.
10. The method for synthesizing the Mo-Co bimetallic supported catalyst as recited in claim 3, wherein the amount of the cobalt salt added is measured according to the molar ratio of the metal cobalt contained in the cobalt salt to the metal molybdenum in the molybdenum salt being 1:9-1: 2.
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| CN202011572144.6A CN112675880A (en) | 2020-12-27 | 2020-12-27 | Mo-Co bimetal supported catalyst and method thereof |
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| CN202011572144.6A CN112675880A (en) | 2020-12-27 | 2020-12-27 | Mo-Co bimetal supported catalyst and method thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4668376A (en) * | 1984-12-28 | 1987-05-26 | Exxon Research And Engineering Company | Supported, Mn sulfide promoted Mo and W sulfide hydroprocessing catalysts and uses thereof |
| US20140135411A1 (en) * | 2011-04-19 | 2014-05-15 | Saudi Basic Industries Corporation | Carbon supported cobalt and molybdenum catalyst |
| US20140142206A1 (en) * | 2011-07-08 | 2014-05-22 | Saudi Basic Industries Corporation | Carbon supported cobalt and molybdenum catalyst and use thereof for producing lower alcohols |
| CN105521799A (en) * | 2014-09-29 | 2016-04-27 | 中国石油化工股份有限公司 | Vulcanized hydrogenation catalyst, and preparation method and application thereof |
| CN109012702A (en) * | 2018-08-31 | 2018-12-18 | 西安向阳航天材料股份有限公司 | A kind of preparation method of presulfurization Hydrobon catalyst |
-
2020
- 2020-12-27 CN CN202011572144.6A patent/CN112675880A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4668376A (en) * | 1984-12-28 | 1987-05-26 | Exxon Research And Engineering Company | Supported, Mn sulfide promoted Mo and W sulfide hydroprocessing catalysts and uses thereof |
| US20140135411A1 (en) * | 2011-04-19 | 2014-05-15 | Saudi Basic Industries Corporation | Carbon supported cobalt and molybdenum catalyst |
| US20140142206A1 (en) * | 2011-07-08 | 2014-05-22 | Saudi Basic Industries Corporation | Carbon supported cobalt and molybdenum catalyst and use thereof for producing lower alcohols |
| CN105521799A (en) * | 2014-09-29 | 2016-04-27 | 中国石油化工股份有限公司 | Vulcanized hydrogenation catalyst, and preparation method and application thereof |
| CN109012702A (en) * | 2018-08-31 | 2018-12-18 | 西安向阳航天材料股份有限公司 | A kind of preparation method of presulfurization Hydrobon catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 陈冠荣等: "《化工百科全书》", 30 September 1994, 化学工业出版社 * |
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Application publication date: 20210420 |