CN113694913B - Preparation method of hydrotreating catalyst - Google Patents
Preparation method of hydrotreating catalyst Download PDFInfo
- Publication number
- CN113694913B CN113694913B CN202010439515.7A CN202010439515A CN113694913B CN 113694913 B CN113694913 B CN 113694913B CN 202010439515 A CN202010439515 A CN 202010439515A CN 113694913 B CN113694913 B CN 113694913B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- drying
- active metal
- potassium
- carrier
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 34
- 239000002184 metal Substances 0.000 claims abstract description 34
- 238000001035 drying Methods 0.000 claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000000843 powder Substances 0.000 claims abstract description 24
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 21
- 239000000243 solution Substances 0.000 claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 239000002023 wood Substances 0.000 claims abstract description 13
- 239000002028 Biomass Substances 0.000 claims abstract description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011591 potassium Substances 0.000 claims abstract description 9
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 9
- 229920000642 polymer Polymers 0.000 claims abstract description 8
- 238000004898 kneading Methods 0.000 claims abstract description 7
- 238000010000 carbonizing Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 239000003929 acidic solution Substances 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims abstract description 4
- 238000003763 carbonization Methods 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- -1 aluminum ions Chemical class 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 229920000609 methyl cellulose Polymers 0.000 claims description 5
- 239000001923 methylcellulose Substances 0.000 claims description 5
- 235000010981 methylcellulose Nutrition 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 239000002699 waste material Substances 0.000 claims description 3
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 claims description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 2
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 2
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 2
- 239000011425 bamboo Substances 0.000 claims description 2
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 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
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 2
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 2
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 2
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 241001330002 Bambuseae Species 0.000 claims 1
- 239000000428 dust Substances 0.000 claims 1
- 235000013399 edible fruits Nutrition 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 9
- 238000006477 desulfuration reaction Methods 0.000 abstract description 5
- 230000023556 desulfurization Effects 0.000 abstract description 5
- 238000007598 dipping method Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 12
- 239000011257 shell material Substances 0.000 description 12
- 235000013162 Cocos nucifera Nutrition 0.000 description 11
- 244000060011 Cocos nucifera Species 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000002920 hazardous waste Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 241001494508 Arundo donax Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- AFTDTIZUABOECB-UHFFFAOYSA-N [Co].[Mo] Chemical compound [Co].[Mo] AFTDTIZUABOECB-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000005539 carbonized material Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- B01J35/613—
-
- B01J35/615—
-
- B01J35/635—
-
- B01J35/638—
-
- B01J35/695—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
- C10G2300/206—Asphaltenes
Abstract
The invention provides a preparation method of a hydrotreating catalyst. The method comprises the following steps: (1) Drying biomass raw materials, crushing the biomass raw materials into wood chips, kneading the wood chips with high polymers and potassium-containing inorganic matters, forming and heat treating; (2) Carbonizing the material obtained in the step (1), and then carrying out steam treatment; (3) repeating the step (2) for 1-5 times to obtain an intermediate; (4) washing the intermediate with water and drying to obtain a carbon carrier; (5) Adding catalyst powder containing hydrogenation active metal components into an acidic solution, adjusting the pH value, and filtering to obtain a solution containing the active metal components; (6) And (3) dipping the carbon carrier obtained in the step (4) in the solution obtained in the step (5), drying and roasting to obtain the hydrotreating catalyst. The method can effectively regulate and control the action relation between the carrier and the active metal, improve the surface acidity of the catalyst, and the obtained catalyst has a proper pore structure, and has higher efficiency of hydrodemetallization, desulfurization and deasphalting when being used for hydrotreating residual oil.
Description
Technical Field
The invention relates to a preparation method of a hydrotreating catalyst, in particular to a preparation method of a hydrotreating catalyst suitable for hydrotreating residual oil.
Background
At present, with the increasing strictness of environmental protection regulations, hydrogenation devices are more and more, the use amount of hydrogenation catalysts is more and more, and the estimated China residual oil hydrogenation catalysts reach 3 ten thousand tons/year. During the production of the catalyst, a large amount of catalyst powder is produced, and the powder contains a large amount of active metals such as molybdenum nickel or molybdenum cobalt. At present, most of powder materials are directly treated by hazardous waste manufacturers as hazardous waste solids, so that the production cost of the catalyst is increased. If the catalyst fines are directly incorporated back into the catalyst preparation process, catalyst performance may be affected. How to improve the recovery of catalyst powder becomes an important research direction for reducing the cost of the catalyst.
In recent years, activated carbon has received attention from researchers as a carrier for hydrodemetallization catalysts. The active carbon has the advantages of adjustable pore structure, large specific surface area, small effect with active metal and the like. US5374350 discloses a hydrodemetallization catalyst, wherein the carrier is activated carbon and is loaded with an active metal component, but the catalyst has lower mechanical strength and poor stability when being used for hydrotreating reaction. CN101862684a discloses a preparation method of an alumina-activated carbon composite carrier, which is obtained by kneading, molding and calcining alumina, activated carbon and an auxiliary agent. The hydrodesulfurization catalyst prepared by the composite carrier can remove dibenzothiophene in petroleum distillate oil. The composite carrier is not suitable for being used as a fixed bed residual oil hydrogenation catalyst carrier. CN103657736a discloses a composite catalyst carrier, its preparation and application, in which method, carbon and Al 2 O 3 The carrier is prepared by kneading and molding after the pore structure is formed, which is not beneficial to regulating and controlling the action relation between the activated carbon and the alumina and the pore structure and the surface property of the catalyst carrier. CN101371988A discloses a preparation method and application of a transition metal carbon material, and the preparation method is used for preparing a supported transition metal carbide catalyst, which is mainly applied to fuel cell electrode reaction and is not suitable for hydrogenation catalysts.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of a hydrotreating catalyst. The method can effectively regulate and control the action relation between the carrier and the active metal, improve the acidity of the catalyst surface, and the prepared catalyst has a proper pore structure, and has higher hydrodemetallization, desulfurization and deasphalting efficiency when being used for the hydrotreatment of residual oil.
The invention provides a preparation method of a hydrotreating catalyst, which comprises the following steps:
(1) Drying biomass raw materials, crushing the biomass raw materials into wood chips, mixing and kneading the wood chips with high polymers and potassium-containing inorganic matters, forming, and performing heat treatment;
(2) Carbonizing the material obtained in the step (1) firstly, and then performing steam treatment;
(3) Repeating the step (2) for 1-5 times to obtain an intermediate;
(4) Washing the intermediate obtained in the step (3) with water, and drying to obtain a carbon carrier;
(5) Adding catalyst powder containing hydrogenation active metal components into an acidic solution, then adjusting the pH value, and filtering to prepare a solution containing the active metal components;
(6) And (3) dipping the carbon carrier obtained in the step (4) into the solution containing the active metal component obtained in the step (5), and drying and roasting to obtain the hydrotreating catalyst.
In the step (1) of the invention, the biomass raw material can be one or more of wood, shell, starch and bamboo. In the step (1), the drying conditions are as follows: and drying at 100-250 ℃ for 4-8 hours. The particle size of the wood chips is 100-400 meshes, preferably 200-350 meshes.
In the step (1) of the invention, the polymer is one or more of cellulose and resin, preferably one or more of hydroxypropyl cellulose, methyl cellulose, phenolic resin and ethylene-vinyl acetate resin. The inorganic matter containing potassium is one or more of potassium carbonate, potassium hydroxide and potassium oxide.
In the step (1) of the invention, the mass ratio of the wood chips to the high polymer is 9~7: 1-3, wherein the addition of the potassium-containing inorganic matters satisfies the mass ratio of the addition of potassium elements to carbon-containing elements in the hydrotreating catalyst being 0.001-0.05.
The heat treatment conditions in the step (1) are as follows: treating at 150-300 ℃ for 0.5-1.0 h. Wherein the heating rate for heating to the temperature required by heat treatment is 50-100 ℃/h.
In the step (2) of the invention, the condition of the carbonization treatment is as follows: the temperature is 300-900 ℃, preferably 500-800 ℃ and the time is 1-4 h. The carbonization treatment is carried out under a protective gas, wherein the protective gas can be inert gas and/or nitrogen, and the inert gas is one or a mixture of more of argon and helium.
In the step (2) of the invention, the conditions of the steam treatment are as follows: the temperature is 100-900 ℃ and the time is 0.5-3 h.
In the step (4), the water washing is performed by adopting a conventional means in the field, and the drying conditions are as follows: and drying at 100-200 ℃ for 3-8 hours.
The catalyst powder containing the hydrogenation active metal component in the step (5) of the invention can be derived from waste materials generated in the preparation process of the hydrogenation catalyst, wherein the hydrogenation active metal component contained in the hydrogenation catalyst is a component of metals of the VIB group and the VIII group, further, the VIB group is preferably molybdenum and/or tungsten, and the VIII group metal is preferably nickel and/or cobalt. The catalyst powder containing the hydrogenation active metal component also contains a carrier component, wherein the carrier component contains alumina, and the carrier component accounts for less than 85% of the mass of the catalyst powder. The acid solution is at least one solution of nitric acid, sulfuric acid, hydrochloric acid or citric acid, wherein the dosage of the acid solution is the minimum dosage for dissolving the catalyst powder.
In the step (5), the pH value is regulated to 3-7, and the mass concentration of aluminum ions in the solution containing the active metal component is controlled to be 5-20%.
In step (6) of the present invention, the impregnation may be performed by a conventional impregnation method such as saturated impregnation, supersaturated impregnation, etc., either by one-step impregnation or by stepwise impregnation.
In the step (6), the drying adopts microwave drying, and the drying conditions are as follows: drying for 1-4 hours at 100-200 ℃, wherein the microwave power is 2-8 kW. The roasting conditions are as follows: roasting for 2-5 h at 300-600 ℃ in an inert atmosphere.
In the invention, the hydrotreating catalyst takes the weight of the catalyst as a reference, the mass content of the VIB group metal in terms of oxide is 3% -15%, the mass content of the VIII group metal in terms of oxide is 0.2% -5%, and the mass content of the alumina is 2% -35%.
The hydrotreating catalyst prepared by the method of the invention is suitable as a hydrotreating catalyst, in particular a hydrodemetallization catalyst.
Compared with the prior art, the invention has the following advantages:
the method adopts the biomass raw material and the high polymer and the potassium salt as the carbonization raw material, which is easier to control the pore size distribution of the carrier and improve the specific surface area of the carrier. Simultaneously, the carbonization carrier is alternately treated by adopting the shielding gas and the water vapor, which is beneficial to reducing the adding amount of the potassium salt in the carrier and simultaneously beneficial to controlling the pore diameter of the carrier. The comprehensive coordination of the steps of the method can also effectively improve the acidity of the surface of the catalyst and improve the hydrotreating performance of the catalyst.
The method of the invention reasonably utilizes the catalyst powder, can effectively utilize the dangerous waste solids generated by the catalyst, improves the value of the product and reduces the production cost of the catalyst.
When the catalyst prepared by the invention is used for the residuum hydrotreatment process, compared with the existing catalyst containing a carbon carrier, the catalyst has higher hydrodemetallization, desulfurization and deasphalting efficiency and better activity and stability.
Detailed Description
The technical scheme and technical effects of the present invention will be further described with reference to the following examples, but are not limited thereto. Wherein the contents of the respective components in the catalyst powder containing the hydrogenation-active metal component used in all of the examples and comparative examples are as follows: 80% of aluminum oxide, 15% of molybdenum oxide and 5% of nickel oxide. In the invention, the weight percent is the mass fraction.
Example 1
Drying the coconut shell raw material at 130 ℃ for 5 hours, and then crushing the coconut shell raw material into 200-mesh coconut shell powder; weighing 1000g of coconut shell powder, methyl cellulose and potassium hydroxide according to the mass ratio of 7:3:0.5, kneading and molding; heating to 300 ℃ at a heating rate of 60 ℃/h, and then treating the molded product at 300 ℃ for 1h; then carbonizing for 2 hours under inert gas, wherein the carbonizing temperature is 700 ℃; carrying out steam treatment on the carbonized material for 1h at 700 ℃, and repeatedly carrying out the carbonization treatment and the steam treatment for 1 time, namely carrying out the carbonization treatment and the steam treatment for 2 times to obtain an intermediate; then carrying out water purification washing treatment on the obtained intermediate, and drying at 150 ℃ for 3 hours to obtain 200g of carbon carrier; adding 200g of catalyst powder containing hydrogenation active metal components into nitric acid, adjusting the pH value to 4.0, filtering to obtain a molybdenum-nickel-aluminum solution, and controlling the mass concentration of aluminum ions in the molybdenum-nickel-aluminum solution to be 14%; the molybdenum nickel aluminum solution is saturated and impregnated on the carbon carrier, and is dried for 4 hours at 150 ℃ by microwave with the microwave power of 3kW. Then, the catalyst was calcined at 450℃for 3 hours under a nitrogen atmosphere to prepare the hydrotreating catalyst A of the present invention.
Example 2
The procedure is as in example 1, except that the coconut shell material is replaced with arundo donax; the carbonization treatment is carried out under nitrogen instead, and other conditions are unchanged, so that the hydrotreating catalyst B of the invention is prepared.
Example 3
The same as in example 1 except that 1000g of coconut shell powder, methyl cellulose and potassium hydroxide were weighed according to a mass ratio of 8:2:0.5, and carbonization treatment and steam treatment steps were performed three times in total, to prepare a carbon carrier, to prepare the hydrotreating catalyst C of the present invention.
Example 4
The same procedure as in example 1 was repeated except that the carbonization temperature was 800℃and the carbonization treatment and the steam treatment were performed four times in total to prepare a carbon support, thereby preparing the hydrotreating catalyst D of the present invention.
Example 5
The same as in example 1, except that the coconut shell raw material was replaced with starch, and 1000g of starch, phenolic resin and potassium carbonate were weighed in a mass ratio of 7:3:2; 200g of catalyst powder containing hydrogenation active metal components is added into nitric acid, the pH value is adjusted to 5.0, a molybdenum-nickel-aluminum solution is obtained by filtration, and the mass concentration of aluminum ions in the molybdenum-nickel-aluminum solution is controlled to be 6%, so that the hydrotreating catalyst E is prepared.
Comparative example 1
Mixing industrial pseudo-boehmite, 3wt% acetic acid and 2wt% sesbania powder, molding, drying at 130 ℃ for 3h, roasting at 850 ℃ for 3h to prepare an alumina carrier, impregnating the carrier with a solution containing active metals molybdenum and nickel, drying at 150 ℃ for 4h, and roasting at 450 ℃ for 3h to prepare the hydrotreating catalyst F.
Comparative example 2
Drying the coconut shell raw material at 130 ℃ for 5 hours, and then crushing the coconut shell raw material into 200-mesh coconut shell powder; weighing 1000g of coconut shell powder, adding an adhesive, kneading and forming; treating the formed product at 300 ℃ for 1h, and then carbonizing the formed product for 2h in a nitrogen atmosphere at 700 ℃; washing and drying to obtain 200g of carbon carrier; the molybdenum nickel solution was saturated impregnated on a carbon support, dried at 150 ℃ for 4 hours, and then calcined at 450 ℃ for 3 hours under nitrogen atmosphere to prepare a hydrotreating catalyst G.
Comparative example 3
Compared with example 1, a hydrotreating catalyst H was prepared without adding methyl cellulose.
Comparative example 4
Compared with example 1, the hydrotreating catalyst I was prepared by performing only one carbonization and one steam treatment.
Evaluation test
The catalysts obtained in the examples and comparative examples were evaluated on a 200mL fixed bed residuum hydrogenation apparatus, respectively, and the catalyst evaluation conditions and the feedstock properties are shown in Table 1, and the evaluation results are shown in Table 2.
Table 1 catalyst evaluation conditions and feedstock properties
| Project | |
| Reaction temperature, DEG C | 410 |
| The reaction pressure, the pressure of MPa, | 15 |
| hydrogen to oil volume ratio | 800 |
| Liquid hourly space velocity, h -1 | 1.0 |
| Run time, h | 2500 |
| Properties of the feedstock | |
| S，wt% | 3.8 |
| Ni，µg/g | 30.3 |
| V，µg/g | 74.4 |
| CCR，wt% | 12.4 |
| Asphaltene content, wt% | 3.5 |
TABLE 2 Properties of the catalysts obtained in examples and comparative examples and test evaluation results
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| Catalyst numbering | A | B | C | D | E | F | G | H | I |
| Specific surface area, m 2 /g | 174 | 162 | 153 | 143 | 143 | 145 | 98 | 89 | 160 |
| Pore volume, mL/g | 1.30 | 1.32 | 1.38 | 1.42 | 1.26 | 0.86 | 0.56 | 0.54 | 0.95 |
| Pore distribution, percent | |||||||||
| <100nm | 47 | 45 | 39 | 35 | 42 | 92 | 12 | 0 | 62 |
| 100-1000nm | 30 | 27 | 30 | 30 | 28 | 8 | 43 | 35 | 24 |
| >1000nm | 23 | 28 | 31 | 35 | 30 | 0 | 45 | 65 | 12 |
| Catalyst composition | |||||||||
| Al 2 O 3 ，wt% | 30 | 28 | 29 | 31 | 10 | 83 | 0 | 27 | 29 |
| MoO 3 ，wt% | 14.5 | 14.8 | 14.5 | 14.6 | 14.7 | 14. | 14.5 | 14.5 | 14.6 |
| NiO，wt% | 2.7 | 2.7 | 2.6 | 2.8 | 2.7 | 2.5 | 2.7 | 2.7 | 2.6 |
| Carbon carrier, wt% | Allowance of | Allowance of | Allowance of | Allowance of | Allowance of | 0 | Allowance of | Allowance of | Allowance of |
| Evaluation of test results | |||||||||
| Desulfurization rate, percent | 91.3 | 92.1 | 90.9 | 90.4 | 89.8 | 86.3 | 56.8 | 67.5 | 90.2 |
| Demetallization rate% | 92.5 | 92.3 | 91.2 | 92.0 | 91.8 | 85.3 | 84.2 | 85.8 | 88.5 |
| Asphaltene conversion% | 75.0 | 74.8 | 75.2 | 74.3 | 75.2 | 69.3 | 70.5 | 71.2 | 71.8 |
As can be seen from Table 2, when the hydrotreating catalyst prepared in the present invention is used for hydrotreating residuum, the hydrodemetallization rate, the desulfurization rate and the asphaltene conversion rate are all superior to those of the comparative example.
Claims (14)
1. A method of preparing a hydrotreating catalyst comprising:
(1) Drying biomass raw materials, crushing the biomass raw materials into wood chips, mixing and kneading the wood chips with high polymers and potassium-containing inorganic matters, forming, and performing heat treatment;
(2) Carbonizing the material obtained in the step (1) firstly, and then performing steam treatment;
(3) Repeating the step (2) for 1-5 times to obtain an intermediate;
(4) Washing the intermediate obtained in the step (3) with water, and drying to obtain a carbon carrier;
(5) Adding catalyst powder containing hydrogenation active metal components into an acidic solution, then adjusting the pH value, and filtering to prepare a solution containing the active metal components;
(6) Impregnating the carbon carrier obtained in the step (4) with the solution containing the active metal component obtained in the step (5), and drying and roasting to obtain a hydrotreating catalyst;
in the step (1), the high polymer is one or more of hydroxypropyl cellulose, methyl cellulose, phenolic resin and ethylene-vinyl acetate resin; the potassium-containing inorganic matter is one or more of potassium carbonate, potassium hydroxide and potassium oxide;
the conditions of the heat treatment in the step (1) are as follows: treating for 0.5-1.0 h at 150-300 ℃, and heating to the temperature required by heat treatment at a heating rate of 50-100 ℃/h;
in the step (1), the mass ratio of the wood chips to the high polymer is 9-7:1-3; the addition amount of the potassium-containing inorganic matters meets the mass ratio of the addition amount of potassium elements to carbon-containing elements in the hydrotreating catalyst being 0.001-0.05.
2. A method according to claim 1, characterized in that: in the step (1), the biomass raw material is one or more of wood, fruit shell and bamboo.
3. A method according to claim 1, characterized in that: in the step (1), the drying conditions are as follows: drying for 4-8 hours at 100-250 ℃; the granularity of the wood dust is 100-400 meshes.
4. A method according to claim 3, characterized in that: in the step (1), the particle size of the wood chips is 200-350 meshes.
5. A method according to claim 1, characterized in that: in the step (2), the condition of the carbonization treatment is as follows: the temperature is 300-900 ℃ and the time is 1-4 h; the carbonization treatment is carried out under a protective gas, wherein the protective gas is inert gas and/or nitrogen.
6. A method according to claim 1, characterized in that: in the step (2), the carbonization treatment temperature is 500-800 ℃.
7. A method according to claim 1, characterized in that: in the step (2), the conditions of the steam treatment are as follows: the temperature is 100-900 ℃ and the time is 0.5-3 h.
8. A method according to claim 1, characterized in that: in the step (4), the drying conditions are as follows: and drying at 100-200 ℃ for 3-8 hours.
9. A method according to claim 1, characterized in that: the catalyst powder containing the hydrogenation active metal component in the step (5) is derived from waste materials generated in the preparation process of the hydrogenation catalyst, wherein the hydrogenation active metal component contained in the hydrogenation catalyst is a component of metal of the VIB group and a component of metal of the VIII group, the VIB group is molybdenum and/or tungsten, and the metal of the VIII group is nickel and/or cobalt.
10. A method according to claim 1 or 9, characterized in that: in the step (5), the catalyst powder containing the hydrogenation active metal component also contains a carrier component, the carrier component contains alumina, and the carrier component accounts for less than 85% of the mass of the catalyst powder.
11. A method according to claim 1, characterized in that: in the step (5), the acidic solution is at least one solution of nitric acid, sulfuric acid, hydrochloric acid or citric acid.
12. A method according to claim 1, characterized in that: in the step (5), the pH value is regulated to 3-7, and the mass concentration of aluminum ions in the solution containing the active metal component is controlled to be 5-20%.
13. A method according to claim 1, characterized in that: in the step (6), the drying adopts microwave drying, and the drying conditions are as follows: drying for 1-4 hours at 100-200 ℃, wherein the microwave power is 2-8 kW; the roasting conditions are as follows: roasting for 2-5 h at 300-600 ℃.
14. A method according to claim 1, characterized in that: the obtained hydrotreating catalyst takes the weight of the catalyst as a reference, the mass content of the VIB group metal in terms of oxide is 3% -15%, the mass content of the VIII group metal in terms of oxide is 0.2% -5%, and the mass content of the alumina is 2% -35%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010439515.7A CN113694913B (en) | 2020-05-22 | 2020-05-22 | Preparation method of hydrotreating catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010439515.7A CN113694913B (en) | 2020-05-22 | 2020-05-22 | Preparation method of hydrotreating catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113694913A CN113694913A (en) | 2021-11-26 |
| CN113694913B true CN113694913B (en) | 2024-03-08 |
Family
ID=78646062
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010439515.7A Active CN113694913B (en) | 2020-05-22 | 2020-05-22 | Preparation method of hydrotreating catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113694913B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114029046B (en) * | 2021-12-20 | 2022-08-19 | 黑龙江大学 | Preparation method of composite hydrodesulfurization catalyst with lamellar carbon prepared from biomass as carrier |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012050411A1 (en) * | 2010-10-13 | 2012-04-19 | Université Abdelmalek Essaadi | Nanoporous carbonated materials prepared from the shell of the argan fruit |
| CN103769134A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Preparation method of catalyst for partial oxidation of isobutene to prepare methylacrolein |
| CN107303484A (en) * | 2016-04-21 | 2017-10-31 | 中国石油化工股份有限公司 | The preparation method and hydrotreating catalyst of a kind of siliceous macropore alumina supporter |
| CN107954423A (en) * | 2017-11-21 | 2018-04-24 | 福建省鑫森炭业股份有限公司 | A kind of high intensity activated carbon for precious metal catalyst agent carrier and preparation method thereof |
| CN108927146A (en) * | 2017-05-23 | 2018-12-04 | 中国石油天然气股份有限公司 | A kind of inferior heavy oil hydrogenation catalyst and preparation method thereof |
| CN109701537A (en) * | 2018-12-21 | 2019-05-03 | 胡平 | A kind of catalyst for pre-hydrogenation and its preparation method and application |
| CN109718797A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of preparation method of hydrotreating catalyst |
| CN109718798A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | The preparation method of hydrotreating catalyst |
| CN110975876A (en) * | 2019-12-31 | 2020-04-10 | 山东华安新材料有限公司 | Activated carbon supported chromium-based catalyst and preparation method and application thereof |
-
2020
- 2020-05-22 CN CN202010439515.7A patent/CN113694913B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012050411A1 (en) * | 2010-10-13 | 2012-04-19 | Université Abdelmalek Essaadi | Nanoporous carbonated materials prepared from the shell of the argan fruit |
| CN103769134A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Preparation method of catalyst for partial oxidation of isobutene to prepare methylacrolein |
| CN107303484A (en) * | 2016-04-21 | 2017-10-31 | 中国石油化工股份有限公司 | The preparation method and hydrotreating catalyst of a kind of siliceous macropore alumina supporter |
| CN108927146A (en) * | 2017-05-23 | 2018-12-04 | 中国石油天然气股份有限公司 | A kind of inferior heavy oil hydrogenation catalyst and preparation method thereof |
| CN109718797A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of preparation method of hydrotreating catalyst |
| CN109718798A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | The preparation method of hydrotreating catalyst |
| CN107954423A (en) * | 2017-11-21 | 2018-04-24 | 福建省鑫森炭业股份有限公司 | A kind of high intensity activated carbon for precious metal catalyst agent carrier and preparation method thereof |
| CN109701537A (en) * | 2018-12-21 | 2019-05-03 | 胡平 | A kind of catalyst for pre-hydrogenation and its preparation method and application |
| CN110975876A (en) * | 2019-12-31 | 2020-04-10 | 山东华安新材料有限公司 | Activated carbon supported chromium-based catalyst and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113694913A (en) | 2021-11-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109718797B (en) | Preparation method of hydrotreating catalyst | |
| CN109718798B (en) | Preparation method of hydrotreating catalyst | |
| CN113694913B (en) | Preparation method of hydrotreating catalyst | |
| CN114452978B (en) | Hydrogenation protection catalyst and preparation method and application thereof | |
| CN109652122B (en) | Deep hydrogenation denitrification method for inferior high-nitrogen heavy distillate oil | |
| CN106944137A (en) | The Application way of useless hydrogenation catalyst | |
| CN111378471B (en) | Method for removing metal impurities in residual oil by hydrogenation | |
| CN105709802B (en) | A kind of high metal dispersion degree hydrocracking catalyst and preparation method thereof | |
| CN109304214B (en) | Hydrocracking catalyst, and preparation method and application thereof | |
| CN112742425B (en) | Hydrogenation catalyst and preparation method thereof | |
| CN107670699B (en) | Heavy oil suspension bed hydrogenation catalyst adopting composite carrier | |
| CN105709805B (en) | A kind of chemical industry type hydrocracking catalyst and preparation method thereof | |
| CN109304213B (en) | Hydrocracking catalyst, and preparation method and application thereof | |
| US20230285944A1 (en) | Molybdenum Carbide Catalysts | |
| XIAO et al. | One-pot catalytic agroforestry waste cellulose to polyols over self-reducing bifunctional catalysts | |
| CN116060033B (en) | Paraffin hydrofining catalyst and preparation method and application thereof | |
| CN112547034A (en) | Residual oil hydrotreating catalyst and preparation method thereof | |
| JP3957122B2 (en) | Method for hydrotreating heavy hydrocarbon oils | |
| CN114130418B (en) | Method for regenerating hydrogenation catalyst | |
| CN116060033A (en) | Paraffin hydrofining catalyst and preparation method and application thereof | |
| CN111617789B (en) | Coal tar hydrogenation pretreatment catalyst and preparation method thereof | |
| CN111195522A (en) | Residual oil hydrodemetallization catalyst and preparation method thereof | |
| CN114602485B (en) | Preparation method of hydrotreating catalyst | |
| CN114130409B (en) | Regeneration method of hydrogenation catalyst | |
| CN113000074B (en) | Regeneration method of hydrogenation catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20231229 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Applicant after: CHINA PETROLEUM & CHEMICAL Corp. Applicant after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Applicant before: CHINA PETROLEUM & CHEMICAL Corp. Applicant before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |