CN106914260A - Oil product hydrofining catalyst, preparation method and application thereof - Google Patents
Oil product hydrofining catalyst, preparation method and application thereof Download PDFInfo
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- CN106914260A CN106914260A CN201510982941.4A CN201510982941A CN106914260A CN 106914260 A CN106914260 A CN 106914260A CN 201510982941 A CN201510982941 A CN 201510982941A CN 106914260 A CN106914260 A CN 106914260A
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- Prior art keywords
- catalyst
- metal
- molybdenum
- hydrogenation catalyst
- carrier
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- 239000003054 catalyst Substances 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000003921 oil Substances 0.000 claims abstract description 44
- 229910052751 metal Inorganic materials 0.000 claims abstract description 41
- 239000002184 metal Substances 0.000 claims abstract description 41
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 38
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 26
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 19
- 239000011733 molybdenum Substances 0.000 claims abstract description 19
- 239000010941 cobalt Substances 0.000 claims abstract description 14
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000000694 effects Effects 0.000 claims abstract description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 11
- 239000011574 phosphorus Substances 0.000 claims abstract description 11
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052796 boron Inorganic materials 0.000 claims abstract description 10
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 10
- 239000010703 silicon Substances 0.000 claims abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000010949 copper Substances 0.000 claims abstract description 5
- 239000011701 zinc Substances 0.000 claims abstract description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 3
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 34
- 238000007670 refining Methods 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 11
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 229910052681 coesite Inorganic materials 0.000 claims description 9
- 229910052906 cristobalite Inorganic materials 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 239000002808 molecular sieve Substances 0.000 claims description 9
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052682 stishovite Inorganic materials 0.000 claims description 9
- 229910052905 tridymite Inorganic materials 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 8
- 229910000765 intermetallic Inorganic materials 0.000 claims description 8
- 238000004898 kneading Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 7
- 238000005470 impregnation Methods 0.000 claims description 7
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 7
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 7
- 229910001593 boehmite Inorganic materials 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000008139 complexing agent Substances 0.000 claims description 5
- 150000002736 metal compounds Chemical class 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims 2
- 239000003502 gasoline Substances 0.000 abstract description 28
- 229910052717 sulfur Inorganic materials 0.000 abstract description 12
- 239000011593 sulfur Substances 0.000 abstract description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 9
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 18
- 238000005516 engineering process Methods 0.000 description 14
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000001354 calcination Methods 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 5
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 5
- 239000011609 ammonium molybdate Substances 0.000 description 5
- 235000018660 ammonium molybdate Nutrition 0.000 description 5
- 229940010552 ammonium molybdate Drugs 0.000 description 5
- 239000000969 carrier Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 4
- 241000219782 Sesbania Species 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 150000001868 cobalt Chemical class 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 4
- 150000002815 nickel Chemical class 0.000 description 4
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 4
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 238000004523 catalytic cracking Methods 0.000 description 3
- HIYNGBUQYVBFLA-UHFFFAOYSA-D cobalt(2+);dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Co+2].[Co+2].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O HIYNGBUQYVBFLA-UHFFFAOYSA-D 0.000 description 3
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229940011182 cobalt acetate Drugs 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000005078 molybdenum compound Substances 0.000 description 2
- 150000002752 molybdenum compounds Chemical class 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229940078494 nickel acetate Drugs 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- -1 other forms Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- 241001120493 Arene Species 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 208000013586 Complex regional pain syndrome type 1 Diseases 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 229910003294 NiMo Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000012360 testing method 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- 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
- B01J35/615—100-500 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
- B01J35/635—0.5-1.0 ml/g
-
- 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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
-
- 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
- C10G2300/70—Catalyst aspects
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention relates to an oil product hydrofining catalyst, which comprises 10-35 wt% of active metal oxide, 0.1-5 wt% of auxiliary metal, 1-5 wt% of auxiliary and the balance of carrier, wherein the weight of the catalyst is 100%; wherein, the active metal is one or two of molybdenum and a combination selected from cobalt and nickel, the assistant metal is one or more of iron, zinc and copper, and the assistant is one or more of phosphorus, boron and silicon. The invention also relates to a preparation method and application of the catalyst. The prepared catalyst has the advantages of small active component scale, good dispersity, high catalyst activity and good stability, can basically and completely convert sulfur-containing compounds in the gasoline, simultaneously reserve aromatic hydrocarbon components in the gasoline, and reduce octane number loss in the gasoline hydrogenation process. Is suitable for the gasoline hydrogenation process with the V standard and higher standard requirements of the producing country.
Description
Technical field
The present invention relates to a kind of for high-sulfur, the catalyst of rich aromatic type gasoline hydroprocessing technique and its preparation side
Method, belongs to oil-refining chemical field.
Background technology
Catalytic cracking (FCC) is the core technology of modern refineries secondary operation, is that oil plant obtains economy
A kind of important means of benefit, occupies very important status in petroleum refining industry.FCC techniques are by weight
Matter oil lighting, purpose product includes gasoline, diesel oil and liquefied gas.In China's catalytic cracking unit status more
Plus it is prominent, the main device of vehicle fuel is to provide, catalytically cracked gasoline accounts for China's motor petrol pond ratio and reaches
80%.
With increasingly stricter, the standard continuous improvement of motor petrol of environmental requirement, catalytic cracking production
Gasoline also exposes many problems, and mainly sulphur and olefin(e) centent is high.According to statistics in motor petrol 90% with
On sulphur and more than 98% alkene come from catalytically cracked gasoline.The sulfur content one of current catalytically cracked gasoline
As in 100~700mg/kg, olefin(e) centent is 20~50%, arene content 10~20%.
Therefore, the key of production clean gasoline is the quality upgrading for solving the problems, such as FCC gasoline, particularly FCC
The desulphurization problem of gasoline.It is more ripe to the treatment technology of cat naphtha in the prior art, typically adopt
The characteristics of using selective hydrogenation technology, selective hydrodesulfurization technology is that operating condition relaxes, and yield of gasoline is high
And hydrogen consumption is low.The main of current international most advanced level can be represented to be had：The Prime-G+ technologies of IFP and
The SCANfining technologies of ExxonMobil, the catalyst with high selectivity as core, using conventional fixation
Bed reactor, process is simple is easy to be reconstructed using existing apparatus；The CD Hydro/CD HDS of CDTech
Technology is optimized the process conditions of process using unique catalytic distillation technology, improves selectivity
And there is significant advantage at aspects such as operating condition, catalyst lifes.The domestic main RIPP with sinopec
Based on the technology developed with FRIPP, such as：The RSDS selective hydrogenations of OCT-M, RIPP of FRIPP
Desulfurization technology, RIDOS hydroisomerizings desulfurating and reducing olefinic hydrocarbon (octane value recovering) technology of RIPP, above-mentioned technology
All exist when in face of high-sulfur, catalytic gasoline raw material inferior not high enough different degrees of desulfurization degree, poor selectivity,
The problems such as loss of octane number is big.
CN102337153A discloses a kind of hydrotreating method of gasoline fraction oil, is related to catalytic gasoline
The hydrotreating method of raw material, the enrichment of sulfide in petrol is realized by sulfur separation system, isolates high-sulfur
The rich aromatic hydrocarbons extraction oil of content and the raffinate oil of high olefin content, then high-sulfur, rich aromatic component enter specific
Hydrodesulfurization unit carries out hydrodesulfurization reaction, realizes the removing of sulfide, and the olefin component of high content enters
Aromatisation device, produces high-octane aromatic hydrocarbons；Catalyst is hydroaromatization desulphurization catalyst.
Therefore, be high-sulfur, rich aromatic type gasoline component a kind of high desulfurization activity, inexpensive hydrofinishing are provided
Catalyst, solves high-sulfur, the processing problem of inferior patrol, and product meets state V and higher standard requirement,
Loss of octane number is reduced simultaneously, for enterprise's cost efficiency provides technical support.
The content of the invention
It is an object of the invention to provide a kind of oil hydrogenation catalyst for refining.
The present invention also aims to provide a kind of preparation method of oil hydrogenation catalyst for refining.
The present invention also aims to provide a kind of application of oil hydrogenation catalyst for refining.
To achieve the above object, the invention provides a kind of oil hydrogenation catalyst for refining, with catalyst weight
It is 100% meter, the catalyst is by the reactive metal oxides of 10~35wt%, the auxiliary agent gold of 0.1~5wt%
The carrier composition of category, the auxiliary agent of 1~5wt% and surplus；
Wherein, active metal is molybdenum and cobalt or for molybdenum and nickel or be molybdenum, cobalt and nickel, promoter metal
It it is one or more in iron, zinc and copper, auxiliary agent is one or more in phosphorus, boron and silicon.
Wherein, the active metal is molybdenum and nickel, and molybdenum oxide：The weight ratio of nickel oxide is 2~8:1.
Wherein, the active metal is molybdenum and cobalt, and molybdenum oxide：The weight ratio of cobalt oxide is 2~8:1.
Wherein, the active metal be molybdenum, cobalt and nickel, and nickel oxide and cobalt oxide weight summation with oxidation
The weight ratio of molybdenum is 1:2~8, wherein nickel oxide and cobalt oxide can be mixed with arbitrary proportion, preferred mass ratio
It is 1:1.
Wherein, the carrier is inorganic porous oxide material.
Wherein, the carrier is Al2O3、SiO2, one or more in molecular sieve and activated carbon.
Wherein, the catalyst is cylindrical, spherical or cloverleaf pattern.
Wherein, the specific surface area of the catalyst is 150~280m2/ g, pore volume is 0.4~0.7cm2/g。
To achieve the above object, present invention also offers a kind of preparation method of oil hydrogenation catalyst for refining,
Comprise the following steps：
Step one, first by boehmite, SiO2, one or more in molecular sieve and activated carbon with help
Agent mixing is squeezed, is subsequently adding containing sour deionized water, through kneading, extrusion, then in atmosphere 80~150 DEG C
Drying 6~8 hours, 400~700 DEG C are calcined 3~5 hours, and carrier is obtained；
Step 2, by active metallic compound and network containing one or more element in phosphorus, boron and silicon
Mixture deionized water dissolving, is subsequently adding the dissolving of promoter metal compound and is made metal co-impregnated solution, by step
Carrier obtained in one adds metal co-impregnated solution with saturation impregnation method, then 80~150 DEG C of drying in atmosphere
6~8 hours, 2~6h finished product catalyst is calcined at 200~500 DEG C.
To achieve the above object, present invention also offers a kind of preparation method of oil hydrogenation catalyst for refining,
Comprise the following steps：
Step one, by the complexing agent containing one or more element in phosphorus, boron and silicon, promoter metal chemical combination
Thing and boehmite, SiO2, one or more mixing in molecular sieve and activated carbon, be subsequently adding containing acid
Deionized water, through kneading, extrusion, then in atmosphere 80~150 DEG C dry 6~8 hours, 400~700
DEG C roasting 3~5 hours, be obtained carrier；
Step 2, metal co-impregnated solution is made of deionized water dissolving by active metallic compound, then by step
Carrier saturation impregnation method is added in metal co-impregnated solution obtained in one, then in atmosphere 80~150 DEG C
Drying 6~8 hours, is calcined 2~6h finished product catalyst at 200~500 DEG C.
To achieve the above object, present invention also offers a kind of method that oil hydrogenation is refined, used catalyst
It is above-mentioned oil hydrogenation catalyst for refining.
The refined method of the oil hydrogenation, using fixed bed reactors, reaction pressure be 1.5~3.0MPa,
Temperature is 210~300 DEG C, air speed is 1.5~5.0h-1, hydrogen-oil ratio is 150~450：1.
Catalyst of the invention is particularly suited for C6~C12, rich aromatic hydrocarbons midbarrel of the boiling range at 120~200 DEG C
Oil.
Heretofore described active metallic compound can be the soluble metallic salt or oxide of diversified forms,
Such as molybdenum compound has ammonium molybdate, molybdenum trioxide, and nickel salt includes ortho phosphorous acid nickel, can also include other shapes
The nickel salt of formula, such as nickel nitrate, basic nickel carbonate, nickel acetate；Cobalt salt includes ortho phosphorous acid cobalt, can be with
Cobalt salt including other forms, such as cobalt nitrate, basic cobaltous carbonate, cobalt acetate.
Heretofore described promoter metal compound can be the soluble metallic salt or oxide of diversified forms,
Such as zinc nitrate, zinc acetate and zinc oxide.
Complexing agent used is material commonly used in the art in the present invention, can be phosphoric acid, citric acid etc..
The acid containing in sour deionized water used is material commonly used in the art in the present invention, can for nitric acid,
Acetic acid, phosphoric acid etc., the consumption of acid is the 2~6% of carrier quality.
Extrusion aid used is material commonly used in the art, such as sesbania powder in the present invention.
The beneficial effects of the invention are as follows：
Catalyst of the invention is based on the stable carrier of high-ratio surface, by introduce in active metal it is a kind of or
Liang Zhong B races metal, improves decentralization of the active metal on carrier, and then improve adding for catalyst
Hydrogen is desulphurizing activated, makes that the active component yardstick of catalyst is small, and good dispersion degree, catalyst activity is high, stabilization
Property good advantage, aromatic hydrocarbons group in gasoline can be retained while conversion that sulfur-containing compound in gasoline is substantially all
Point, reduce the loss of octane number during gasoline hydrogenation.
Specific embodiment
In order to be further detailed to the present invention, spy enumerates following examples, but the present invention and not only limits
In embodiment.
The invention provides a kind of oil hydrogenation catalyst for refining, counted with catalyst weight as 100%, it is described
Catalyst is by the oxide of active metal of 10~35wt%, the promoter metal of 0.1~5wt%, 1~5wt%
The carrier composition of auxiliary agent and surplus；
Wherein, active metal is molybdenum and cobalt or for molybdenum and nickel or be molybdenum, cobalt and nickel, promoter metal
It it is one or more in iron, zinc and copper, auxiliary agent is one or more in phosphorus, boron and silicon.
Wherein, molybdenum oxide：Cobalt oxide：The weight ratio of nickel oxide is 2~8:1.
Wherein, molybdenum oxide：Cobalt oxide：The weight ratio of nickel oxide is 2~8:1.
Wherein, the active metal be molybdenum, cobalt and nickel, and nickel oxide and cobalt oxide weight summation with oxidation
The weight ratio of molybdenum is 1:2~8, wherein nickel oxide and cobalt oxide can be mixed with arbitrary proportion, preferred mass ratio
It is 1:1.
Wherein, the carrier is inorganic porous oxide material.
Wherein, the carrier is Al2O3、SiO2, one or more in molecular sieve and activated carbon.
Wherein, the catalyst is cylindrical, spherical or cloverleaf pattern.
Wherein, the specific surface area of the catalyst is 150~280m2/ g, pore volume is 0.4~0.7cm2/g。
To achieve the above object, present invention also offers a kind of preparation method of oil hydrogenation catalyst for refining,
Comprise the following steps：
Step one, first by boehmite, SiO2, one or more in molecular sieve and activated carbon with help
Agent mixing is squeezed, is subsequently adding containing sour deionized water, through kneading, extrusion, then in atmosphere 80~150 DEG C
Drying 6~8 hours, 400~700 DEG C are calcined 3~5 hours, and carrier is obtained；
Step 2, by active metallic compound and network containing one or more element in phosphorus, boron and silicon
Mixture deionized water dissolving, is subsequently adding the dissolving of promoter metal compound and is made metal co-impregnated solution, by step
Carrier obtained in one adds metal co-impregnated solution with saturation impregnation method, then 80~150 DEG C of drying in atmosphere
6~8 hours, 2~6h finished product catalyst is calcined at 200~500 DEG C.
To achieve the above object, present invention also offers a kind of preparation method of oil hydrogenation catalyst for refining,
Comprise the following steps：
Step one, by the complexing agent containing one or more element in phosphorus, boron and silicon, promoter metal chemical combination
Thing and boehmite, SiO2, one or more mixing in molecular sieve and activated carbon, be subsequently adding containing acid
Deionized water, through kneading, extrusion, then in atmosphere 80~150 DEG C dry 6~8 hours, 400~700
DEG C roasting 3~5 hours, be obtained carrier；
Step 2, metal co-impregnated solution is made of deionized water dissolving by active metallic compound, then by step
Carrier saturation impregnation method is added in metal co-impregnated solution obtained in one, then in atmosphere 80~150 DEG C
Drying 6~8 hours, is calcined 2~6h finished product catalyst at 200~500 DEG C.
To achieve the above object, present invention also offers a kind of method that oil hydrogenation is refined, used catalyst
It is above-mentioned oil hydrogenation catalyst for refining.
The refined method of the oil hydrogenation, using fixed bed reactors, reaction pressure be 1.5~3.0MPa,
Temperature is 210~300 DEG C, air speed is 1.5~5.0h-1, hydrogen-oil ratio is 150~450：1.
Catalyst of the invention is particularly suited for C6~C12, rich aromatic hydrocarbons midbarrel of the boiling range at 120~200 DEG C
Oil.
Heretofore described active metallic compound can be the soluble metallic salt or oxide of diversified forms,
Such as molybdenum compound has ammonium molybdate, molybdenum trioxide, and nickel salt includes ortho phosphorous acid nickel, can also include other shapes
The nickel salt of formula, such as nickel nitrate, basic nickel carbonate, nickel acetate；Cobalt salt includes ortho phosphorous acid cobalt, can be with
Cobalt salt including other forms, such as cobalt nitrate, basic cobaltous carbonate, cobalt acetate.
Heretofore described promoter metal compound can be the soluble metallic salt or oxide of diversified forms,
Such as zinc nitrate, zinc acetate and zinc oxide.
Complexing agent used is material commonly used in the art in the present invention, can be phosphoric acid, citric acid etc..
The acid containing in sour deionized water used is material commonly used in the art in the present invention, can for nitric acid,
Acetic acid, phosphoric acid etc., the consumption of acid is the 2~6% of carrier quality.
Extrusion aid used is material commonly used in the art, such as sesbania powder in the present invention.
Embodiment 1
Aluminum oxide 500g powders are taken, sesbania powder 16g mixing is added, is then added to contain industrial nitric acid 21g
450ml water in, through kneading, extruded moulding, dry 8h at 120 DEG C, then through 500 DEG C of roasting 4h,
Catalyst carrier is obtained.Settled solution is configured with ammonium molybdate and nickel nitrate, phosphoric acid is added dropwise, on above-mentioned carrier
NiO, 15% MoO of load 3%3P with 1%2O5, then dried 10 hours at 120 DEG C,
450 DEG C of calcination process, the time is 3h, obtains catalyst.
Embodiment 2
The carrier of embodiment 2 is prepared according to the same method of embodiment 1, configures clear with ammonium molybdate and cobalt nitrate
Clear solution, is added dropwise phosphoric acid, the CoO in above-mentioned supported on carriers 3%, 15% MoO3P with 1%2O5,
Dried 10 hours at 120 DEG C, 450 DEG C of calcination process, the time is 3h, obtains catalyst.
Embodiment 3
The carrier of embodiment 3 is prepared according to the same method of embodiment 1, with molybdenum trioxide and cobalt nitrate, alkali
Formula nickelous carbonate, phosphoric acid configuration settled solution, in above-mentioned supported on carriers totally 3% CoO, NiO and 15%
MoO3Active component and 1% P2O5, dried 10 hours at 120 DEG C, 450 DEG C of calcination process,
Time is 3h, obtains catalyst.
Embodiment 4
The carrier of embodiment 4 is prepared according to the same method of embodiment 1, with molybdenum trioxide, basic nickel carbonate
Settled solution is configured with phosphoric acid, in the MoO of the NiO and 18% of above-mentioned supported on carriers 3%3Active component
And 1.5% P2O5, while adding promoter metal Zn elements, weigh a certain amount of zinc nitrate and be added to and match somebody with somebody
In the NiMo solution put, then on carrier, ZnO content accounts for catalyst weight 3% to stain, 120
Dried 10 hours at DEG C, 500 DEG C of calcination process, the time is 3h, obtains catalyst.
Embodiment 5
The carrier of embodiment 5 is prepared according to the same method of embodiment 1, with molybdenum trioxide, basic cobaltous carbonate
Settled solution is configured with phosphoric acid, in the MoO of the CoO and 20% of above-mentioned supported on carriers 4%3Active component
And 2.0% P2O5, while adding promoter metal Cu elements, weigh a certain amount of copper nitrate and be added to and match somebody with somebody
In the CoMo solution put, then impregnated on carrier, CuO contents account for catalyst weight 3%,
Dried 10 hours at 120 DEG C, 500 DEG C of calcination process, the time is 3h, obtains catalyst.
Embodiment 6
Aluminum oxide 475g powders are taken, zinc oxide 17g, sesbania powder 16g mixing is added, is then added to contain
Have in the 450ml water of industrial nitric acid 21g, through kneading, extruded moulding, 8h is dried at 120 DEG C, then
Through 500 DEG C of roasting 4h, catalyst carrier is obtained.Settled solution is configured with ammonium molybdate and nickel nitrate, phosphorus is added dropwise
Acid, in the MoO of the NiO and 15% of above-mentioned supported on carriers 3%3, 1% P2O5, then 120
Dried 10 hours at DEG C, 450 DEG C of calcination process, the time is 3h, obtains catalyst.
Embodiment 7
This example introduces the activity rating process of catalyst.
It is raw material to use rich arenes catalytic gasoline, and feedstock property is shown in Table 1.
The micro anti-evaluation experiment of the same terms is carried out to catalyst in embodiment and comparative example, is taken within every 24 hours
Sample analysis product sulphur, nitrogen content, research octane number (RON), analysis result are averaged and are shown in Table 2.Catalyst is filled
Fill out as follows with appreciation condition：
Evaluation device is 100ml fixed bed reactors, and reactor interlude can realize thermostatic control,
Evaluate catalyst and take length between 2-5mm, be seated in control of the reactor interlude beneficial to reaction temperature,
Upper-lower section φ 2, the filling of the inert ceramic balls of φ 3, N2Airtight qualified rear temperature programming vulcanization, 150 DEG C of dryings
2h, then with the speed elevated temperature cure of 20 DEG C/h, 280 DEG C of constant temperature 6h, vulcanization terminates rear swap-in feedstock oil.
Appreciation condition：Reaction pressure 2.0MPa, 240 DEG C of reaction temperature, raw material volume air speed 2.0h-1, hydrogen-oil ratio
200：1.
The catalyst activity of table 1 evaluates raw material oil nature
Comparative example
Comparative catalyst is from the CoMo/Al in patent CN101134909A2O3Selective hydrodesulfurization is urged
Agent A, catalyst uses proprietary metal impregnation technology, can be used for gasoline hydrodesulfurizationmethod treatment, can reduce
Total sulfur and mercaptans content in FCC gasoline cut, without a large amount of loss gasoline, moreover it is possible to minimize octane number
Decline.
The catalyst activity of embodiment 1-6 and comparative example is investigated with the appreciation condition of embodiment 7, is as a result shown
Using the catalyst of the inventive method preparation, hydrodesulfurization performance is more excellent compared with the catalyst in comparative example
It is different, catalyst desulfurizing performance is improve after addition promoter metal, and product loss of octane number is effectively reduced,
It is particularly well-suited to the hydrotreating production high standard gasoline component of high-sulfur, rich aromatic type gasoline cut.
Concrete outcome is shown in Table 2.
The embodiment 1-6 of table 2 is constituted and micro anti-evaluation result with the catalyst preparation of comparative example 1
Catalyst prepared by embodiment 4 carries out desulphurizing activated and long period study on the stability, and vulcanization terminates
Afterwards, catalyst evaluation test in 1000 hours is carried out.
Every 96 hours sampling analysis products sulphur, nitrogen content, analysis result statistics are shown in Table 3.From table 3
Hydrogenation catalyst of the present invention is in reaction pressure 2.0MPa, 240 DEG C of reaction temperature, raw material volume air speed 2.0h-1、
Hydrogen-oil ratio 200：1, during condition, still keep good Hydrogenation, Hydrogenation stabilization, so originally
Invention is there is provided the refined method for preparing catalyst of a kind of high activity, high stability poor quality gasoline hydrogenation.
The catalyst long period Activity evaluation of table 3
Certainly, the present invention can also have other various embodiments, without departing substantially from spirit of the invention and its essence
In the case of, those of ordinary skill in the art can make various corresponding changes and change according to the present invention
Shape, but these corresponding changes and deformation should all belong to the protection domain of the claims in the present invention.
Claims (12)
1. a kind of oil hydrogenation catalyst for refining, it is characterised in that counted with catalyst weight as 100%,
The catalyst by 10~35wt% reactive metal oxides, the promoter metal of 0.1~5wt%, 1~5wt%
Auxiliary agent and surplus carrier composition；
Wherein, active metal is molybdenum and cobalt or for molybdenum and nickel or be molybdenum, cobalt and nickel, promoter metal
It it is one or more in iron, zinc and copper, auxiliary agent is one or more in phosphorus, boron and silicon.
2. oil hydrogenation catalyst for refining according to claim 1, it is characterised in that the activity
Metal is molybdenum and nickel, and molybdenum oxide：The weight ratio of nickel oxide is 2~8:1.
3. oil hydrogenation catalyst for refining according to claim 1, it is characterised in that the activity
Metal is molybdenum and cobalt, and molybdenum oxide：The weight ratio of cobalt oxide is 2~8:1.
4. oil hydrogenation catalyst for refining according to claim 1, it is characterised in that the activity
Metal is molybdenum, cobalt and nickel, and the weight summation of nickel oxide and cobalt oxide and the weight ratio of molybdenum oxide are 1:2~8.
5. oil hydrogenation catalyst for refining according to claim 1, it is characterised in that the carrier
It is inorganic porous oxide material.
6. oil hydrogenation catalyst for refining according to claim 1, it is characterised in that the carrier
It is Al2O3、SiO2, one or more in molecular sieve and activated carbon.
7. oil hydrogenation catalyst for refining according to claim 1, it is characterised in that the catalysis
Agent is cylindrical, spherical or cloverleaf pattern.
8. oil hydrogenation catalyst for refining according to claim 1, it is characterised in that the catalysis
The specific surface area of agent is 150~280m2/ g, pore volume is 0.4~0.7cm2/g。
9. the preparation method of the oil hydrogenation catalyst for refining described in any one of claim 1~8, its feature
It is to comprise the following steps：
Step one, first by boehmite, SiO2, one or more in molecular sieve and activated carbon with help
Agent mixing is squeezed, is subsequently adding containing sour deionized water, through kneading, extrusion, then in atmosphere 80~150 DEG C
Drying 6~8 hours, 400~700 DEG C are calcined 3~5 hours, and carrier is obtained；
Step 2, by active metallic compound and network containing one or more element in phosphorus, boron and silicon
Mixture deionized water dissolving, is subsequently adding the dissolving of promoter metal compound and is made metal co-impregnated solution, by step
Carrier obtained in one adds metal co-impregnated solution with saturation impregnation method, then 80~150 DEG C of drying in atmosphere
6~8 hours, 2~6h finished product catalyst is calcined at 200~500 DEG C.
10. the preparation method of the oil hydrogenation catalyst for refining described in any one of claim 1~8, it is special
Levy and be, comprise the following steps：
Step one, by the complexing agent containing one or more element in phosphorus, boron and silicon, promoter metal chemical combination
Thing and boehmite, SiO2, one or more mixing in molecular sieve and activated carbon, be subsequently adding containing acid
Deionized water, through kneading, extrusion, then in atmosphere 80~150 DEG C dry 6~8 hours, 400~700
DEG C roasting 3~5 hours, be obtained carrier；
Step 2, metal co-impregnated solution is made of deionized water dissolving by active metallic compound, then by step
Carrier saturation impregnation method is added in metal co-impregnated solution obtained in one, then in atmosphere 80~150 DEG C
Drying 6~8 hours, is calcined 2~6h finished product catalyst at 200~500 DEG C.
The refined method of 11. a kind of oil hydrogenations, it is characterised in that used catalyst is claim 1~8
Oil hydrogenation catalyst for refining described in any one.
The refined method of 12. oil hydrogenations according to claim 11, it is characterised in that the method
Using fixed bed reactors, reaction pressure is 1.5~3.0MPa, temperature is 210~300 DEG C, air speed is
1.5~5.0h-1, hydrogen-oil ratio is 150~450：1.
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| CN111491727A (en) * | 2017-12-29 | 2020-08-04 | 韩华思路信株式会社 | Catalyst for hydrogenation reaction and preparation method thereof |
| CN116474785A (en) * | 2022-01-13 | 2023-07-25 | 中国石油化工股份有限公司 | Residual oil hydrogenation catalyst and synthesis method and application thereof |
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