CN106311254B - A kind of residual oil hydrocatalyst and preparation method and method of hydrotreating - Google Patents
A kind of residual oil hydrocatalyst and preparation method and method of hydrotreating Download PDFInfo
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- CN106311254B CN106311254B CN201611007524.9A CN201611007524A CN106311254B CN 106311254 B CN106311254 B CN 106311254B CN 201611007524 A CN201611007524 A CN 201611007524A CN 106311254 B CN106311254 B CN 106311254B
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- nanotube
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- catalyst
- residual oil
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- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 86
- 239000002071 nanotube Substances 0.000 claims abstract description 69
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000012545 processing Methods 0.000 claims abstract description 27
- 238000001354 calcination Methods 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 23
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 23
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 23
- 230000008569 process Effects 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 238000005470 impregnation Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 26
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 16
- 239000003513 alkali Substances 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 238000007598 dipping method Methods 0.000 claims description 12
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 12
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 10
- 238000010306 acid treatment Methods 0.000 claims description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- 239000011592 zinc chloride Substances 0.000 claims description 8
- 235000005074 zinc chloride Nutrition 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 238000009413 insulation Methods 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 5
- 229940043237 diethanolamine Drugs 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 229920000609 methyl cellulose Polymers 0.000 claims description 4
- 239000001923 methylcellulose Substances 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 claims 1
- 229940005991 chloric acid Drugs 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 239000003921 oil Substances 0.000 abstract description 76
- 239000000295 fuel oil Substances 0.000 abstract description 14
- 239000003208 petroleum Substances 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 14
- 239000011148 porous material Substances 0.000 description 12
- 230000003252 repetitive effect Effects 0.000 description 11
- 239000007788 liquid Substances 0.000 description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 5
- 239000004411 aluminium Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000004939 coking Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910001593 boehmite Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000004523 catalytic cracking Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- -1 metals sulfide Chemical class 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- MKPXGEVFQSIKGE-UHFFFAOYSA-N [Mg].[Si] Chemical compound [Mg].[Si] MKPXGEVFQSIKGE-UHFFFAOYSA-N 0.000 description 1
- CKQGJVKHBSPKST-UHFFFAOYSA-N [Ni].P#[Mo] Chemical compound [Ni].P#[Mo] CKQGJVKHBSPKST-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 239000012053 oil suspension Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910021524 transition metal nanoparticle Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—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
- B01J23/83—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 rare earths or actinides
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
-
- 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
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
-
- 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
- C10G2300/70—Catalyst aspects
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of preparation method of residual oil hydrocatalyst, the described method includes：A1：Carbon nanotubes is pre-processed, obtains nanotube I；A2：Active carrier adhesion layer is generated on the surface of nanotube I, obtains nanotube II；A3：Two-part calcination processing is carried out to nanotube II, obtains nanotube III；A4：Two-part reactive metal impregnation processing is sequentially carried out to nanotube III, obtains nanotube IV；A5：Nanotube IV is subjected to water vapour air Mixture atmosphere high-temperature process and calcination processing, so as to obtain the residual oil hydrocatalyst.Additionally provide the residual hydrogenation method using the catalyst.The preparation method passes through the mutual collaboration of multiple technical characteristics so that obtained catalyst has many excellent properties, has a good application prospect in PETROLEUM PROCESSING field and industrial production potential, can be used in the hydrotreating of residual oil and heavy oil.
Description
Technical field
The present invention relates to a kind of catalyst and its preparation method and application, relates more particularly to a kind of residual oil hydrocatalyst
And preparation method and method of hydrotreating, belong to technical field of petrochemical industry.
Background technology
Utilized with the exploitation of decades industrialized high speed development and petroleum resources, at present in the world, oil
Increasingly heaviness, sulfur content are also higher and higher, and the notable consequence so produced is exactly to produce after heavy oil and PETROLEUM PROCESSING
Residual oil quantity is more and more, and proportion is higher and higher.
And in order to residual oil, heavy oil etc. are processed and integrated deep exploitation, it is essential to carry out hydrotreating to it
Means and method.And in order to realize the purpose, residual oil hydrocatalyst is the most key, also has to its performance higher and higher
It is required that and demand, such as usually require it there is higher Hydrogenation, demetalization performance etc..
At present, the research hotspot of residual oil hydrocatalyst and emphasis are concentrated mainly on two aspects：1st, carried for catalyst
The research of body, the carrier of residual oil hydrocatalyst is usually aluminium oxide at present；2nd, catalyst loads the research of activated metal, main
Concentrate in the species and dosage selection of metal.For the two emphasis, people have carried out substantial amounts of further investigation, and obtain
Many achievements, such as：
CN1362484A discloses a kind of preparation method of hydrogenation catalyst, which overcomes existing hydrogenation catalyst and is particularly
The defects of residual oil hydrocatalyst production cost is high.By adjusting the kneading mistake of the materials such as a water-aluminum hydroxide and metallic salt
Journey, and auxiliary agent is timely and appropriately introduced, promote metal dispersion, making the disposable kneading of all materials, extruded moulding is simultaneously into plastic
It is dry, then catalyst is made through steam-air high-temperature activation.Method for preparing catalyst using the present invention, is ensureing to be catalyzed
On the premise of agent activity, catalyst preparation cost can be made to reduce 40-50% compared with infusion process.
CN1626625A discloses a kind of residuum hydrogenating and metal-eliminating catalyst, which contains a kind of macroporous aluminium oxide and carry
The molybdenum and/or tungsten and cobalt and/or nickel of body and load on this carrier, are counted and on the basis of catalyst, the catalysis by oxide
Molybdenum and/or tungsten, the cobalt of 0.3-8 weight % and/or nickel, the carrier of aequum, the carrier that agent contains 0.5-15 weight % contain
There is a kind of halogen, on the basis of carrier total amount, which contains the aluminium oxide of 95-99 weight %, based on the element, 0.1-5 weights
The halogen of % is measured, its acid amount is less than 0.2 mM/gram.Since the carrier acid amount in catalyst is low, make its keep it is higher plus
While hydrogen metal removal activity, carbon deposition quantity is low.
CN101024186A discloses a kind of catalyst and its system for being used for inferior heavy oil or dreg-oil suspension bed hydrogenation cracking
Preparation Method, the catalyst are a kind of sulphided state transition metal nanoparticles being present in reversed phase micelle colloidal solution, anti-phase glue
The decentralized medium of beam colloidal solution is organic phase, and dispersed phase is the water phase wrapped up by surfactant, and sulphided state transition metal is received
Rice grain is stable in the presence of in water phase.Transition metal active component in dispersed phase be preferably Cu, Mn, Fe, Co, Ni, Cr, Mo,
W, the sulphided state particle of the element such as Zn, Sn, Pd, particle diameter is between 1nm-1000 μm.The catalyst can be dispersed in poor quality
In heavy oil, residual oil, and under certain reaction temperature and hydrogen atmosphere, pass through the inferior heavy oil containing catalyst or residual oil outstanding
Floating bed, which is hydrocracked, is converted into light-end products.On the premise of catalyst charge is reduced, effectively inhibit heavy oil or residual oil hangs
The generation of coke in floating bed hydrocracking process, improves the yield of light-end products.
CN102039138A discloses a kind of heavy oil, catalyst for hydrotreatment of residual oil and preparation method thereof, catalyst carrier
By being prepared by siliceous aluminium hydroxide prepared by crystal seed of clay alteration raw material, active metal component includes Section VIII and VIB
Metal, dioxide-containing silica is 0.1-45wt% in catalyst, then its preparation process adds first to prepare siliceous aluminium hydroxide
Suitable peptizing agent, additive shaping, by drying, roasting, obtain heavy oil, residual oil hydrocatalyst carrier, the residual hydrogenation
Catalyst carrier impregnates active hydrogenation metal component, and then dry, roasting obtains heavy oil, residual oil hydrocatalyst.The catalysis
Agent can significantly improve the physico-chemical property and performance of catalyst, particularly make during heavy oil or residual hydrocracking
Use performance.
CN103007981A discloses a kind of Resid Fcc Catalyst, the catalytic cracking catalyst by weight 100%
Meter, by the REUSY molecular sieves of 15-35%, 5-25% silicon magnesium glue, the MFI structure shape-selective molecular sieve of 0-5%, 15-25% a water
The clay composition of aluminium stone, the inorganic oxide binder of 2-10% and 20-60%；The catalytic cracking catalyst is due to big
Matrix specific surface area, suitable acidity and the function of passive metal nickel and vanadium, while there is excellent heavy oil conversion performance
Catalytic cracking coke yield can be reduced.
CN103055932A discloses a kind of catalyst for hydrotreatment of residual oil and preparation method thereof.The work that the catalyst uses
Property metal component be group VIII metal and vib metals, carrier is made of aluminium oxide and mesopore molecular sieve, its intermediary hole point
Son sieve accounts for the 4.5-9.5% of vehicle weight.In the catalyst carrier preparation process, using boehmite, alumina powder, mesoporous
Molecular sieve is raw material, adds suitable basic nitrogen compound, due to blending and agglomeration, make made of catalyst have compared with
Big specific surface area, larger aperture and suitable pore structure, reduces the diffusion limitation of reactant, is adapted to catalysis macromolecular to participate in
Reaction, while there is suitable acidity, and improve the abrasion resistance properties of catalyst, improving hydrodemetallization, depitching
Matter keeps desulphurizing activated while active.
CN104096584A discloses a kind of residual oil hydrocatalyst and preparation method thereof, and its preparation method is：1st, with oxygen
It is carrier to change aluminium and activated carbon kneading body, and activated carbon weight accounts for 5-35%, aluminium oxide 65-95% in carrier；2nd, in catalyst
Active component content is Ni based on 100% by the gross weight of catalyst2P is 1-14%, MoO3And/or WO3For 3-8%, and/or
CoO and/or NiO is 1-5%, remaining is carrier；3rd, pore volume 0.3-1ml/g；4th, it is 50-280m than surface2/g；By in oxygen
Change in aluminium and introduce a small amount of activated carbon, reduce Ni2Reaction in P active component generating process with aluminium oxide, while improve it
Dispersiveness, reaches and gives full play to Ni2The high activity of P and the carrier advantage of aluminum oxide-activated carbon kneading body, and then improve catalyst
Desulfurization, the impurity ability such as carbon residue.
CN103861627A discloses a kind of catalyst of the hydrotreating for heavy hydrocarbon feedstocks, and the catalyst includes extremely
A kind of few element from group vib；At least one element from VIII group；Phosphorus, its amount are opposite in the weight by five phosphorous oxides
In the range of total catalyst quality meter 0.1-9%；Vanadium, its amount by vanadium pentoxide weight based on total catalyst quality
In the range of 0.25-7%；The oxide carrier of at least one porous refractory；The catalyst has following characteristics：0.3ml/g
Or more total pore volume；40% or less macropore volume of total pore volume, the macropore volume, which is defined as having, to be exceeded
The volume in the hole of the diameter of 50nm；The median diameter of the mesoporous of 5-36nm scopes, the mesoporous are defined as diameter in 3.6-50nm
The hole of scope；At least 120m2The BET surface area of/g.
CN104084222A discloses a kind of residual oil hydrocatalyst, using activated processing coal activated carbon and/or
The graphitization reaming semi-coke obtained through expanding treatment is as carrier, afterwards supported active metals sulfide conduct on the carrier
The Residual catalyst that active component obtains, residual oil hydrocatalyst of the present invention, active component are highly divided on carrier
Dissipate, there is suitable pore-size distribution and obvious L weak acid center in carrier structure in addition, be conducive to suppress coking.To heavy oil
Or during residual oil progress hydrogenation reaction, there is the carrying capacity of higher not only for impurity such as the metal in residual oil raw material, sulphur, it is closed
Suitable large aperture distribution is also beneficial to asphalitine macromolecular and the close of activated centre, diffusion and conversion, suppresses coking, so that
Catalyst has the metal removal rate and desulphurizing activated improved, in addition, the catalyst is in high temperature, high hydrogen partial pressure reaction bar
Being presented under part has stronger methanation resisting ability.
CN104492448A discloses a kind of preparation method of residual hydrogenation monolithic catalyst, includes the following steps：1st, will
Different amounts mixed powder is prepared the monolithic catalyst with three-dimensional through hole with dust technology, superfine fibre mixed pressuring plate and is carried
Body.2nd, carrier impregnation is dried, dried, roasted in certain density Tween-80 solution, carrier after processing is immersed in not
In molybdenum nickel phosphorus solution with metering molybdenum nickel proportioning, dry, dry, roasting obtained residual hydrogenation monolithic catalyst.This method
It is the synthetic catalyst in the presence of Un-structured carrier, the addition of fiber, introduces micron-sized duct, be conducive in residual oil
Gum asphalt micelle by reducing diffusional resistance and suppressing coking, solve reaction coking and cause the problem of catalyst inactivation.Can
Shorten downtime period, reduce industrial cost.Supported active metals amount is high, has higher hydrogenation activity.Other impurities are not introduced,
It is environmentally safe, it is environmentally protective.
WO2014151653A discloses a kind of activity and stability for having in the hydrodemetallization of heavy hydrocarbon and improving
Carbon monoxide-olefin polymeric, the carbon monoxide-olefin polymeric include：1st, carrier, the carrier include including spherical or made of substantially spherical grain
The aluminium oxide of the precipitation of son；And 2, at least one catalyst, metal of at least one catalyst selected from 6 race of periodic table,
The metal of 9 race of periodic table, metal, phosphorus and the combinations thereof of 10 race of periodic table；Wherein described carrier has about 0.8-
Total pore size volume in the range of 1.2cc/g, and the total pore size volume more than 8% has the diameter more than 350nm, and
40% or the total pore size volume of bigger there is diameter about in the range of 200-500nm, and at least 5% total pore space
Volume has the diameter more than 1500nm.
CN105983417A discloses a kind of residuum hydrogenating and metal-eliminating catalyst, using aluminium oxide as carrier, with VIII group and
Group vib metal is active component, and catalyst pore volume is 0.8-1.2ml/g, specific surface area 100-180m2/ g, catalyst have
Bimodal pore distribution, the aperture portion most probable pore size of catalyst are located at 10-40nm, and macroperforation most probable pore size is located at 60-
800nm.The preparation method of residuum hydrogenating and metal-eliminating catalyst is additionally provided at the same time, is included the following steps：Three hydration oxygen will be selected from
Change one or more among aluminium, boehmite, boehmite and amorphous hydroted alumina and peptizing agent, extrusion aid, organic
Thing solution is uniformly mixed, and is then molded, is dry, roasting, obtaining carrier；With the carrier obtained by the nickeliferous and solution of molybdenum dipping and do
Dry, roasting, is made final catalyst.
As described above, although numerous researchers have developed a variety of residual oil hydrocatalysts and preparation method and application
Method, but the necessity and demand for continuing research are still suffered from for new residual oil hydrocatalyst and its methods for making and using same,
This is also exactly where the power that the present invention is accomplished and starting point.
The content of the invention
In order to research and develop new residual oil hydrocatalyst and its preparation method and application method, the present inventor is paying greatly
After the creative experiments of amount are explored, the residual oil hydrocatalyst is invented by further investigation, and then complete the present invention.Tool
For body, the present invention relates to following aspects.
The first aspect, the present invention provides a kind of preparation method of residual oil hydrocatalyst, the preparation method includes
Following steps：
A1：Carbon nanotubes is pre-processed, obtains nanotube I；
A2：Active carrier adhesion layer is generated on the surface of nanotube I, obtains nanotube II；
A3：Two-part calcination processing is carried out to nanotube II, obtains nanotube III；
A4：Two-part reactive metal impregnation processing is sequentially carried out to nanotube III, obtains nanotube IV；
A5：Nanotube IV is subjected to water vapour-air Mixture atmosphere high-temperature process and calcination processing, so as to obtain the slag
Oil hydrogenation catalysts.
In the preparation method of the residual oil hydrocatalyst of the present invention, the step A1 includes the following steps：
A1-1：Carbon nanotubes is added in strong alkali aqueous solution such as KOH aqueous solutions or NaOH aqueous solutions, is sufficiently stirred processing
40-50 minutes, then filter, and fully washed 2-3 times with deionized water, obtain alkali process carbon nanotubes；
A1-2：The alkali process carbon nanotubes is added in concentrated acid such as the concentrated sulfuric acid, perchloric acid or concentrated nitric acid, is sufficiently stirred
Processing 20-30 minutes, is then filtered, and is fully washed 2-3 times with deionized water, obtains acid treatment carbon nanotubes；
A1-3：By the acid treatment carbon nanotubes at room temperature, with 6-10 DEG C/min of heating rate, preferably 8 DEG C/minute
The heating rate of clock, is warming up to 480-550 DEG C, and calcines 30-50 minutes at such a temperature, obtains nanotube I.
Wherein, in step A1-1, the molar concentration of the strong alkali aqueous solution is 4-5mol/L, may be, for example, 4mol/L,
4.5mol/L or 5mol/L, the dosage of the strong alkali aqueous solution do not have stringent restriction, as long as can be abundant by carbon nanotubes
Immersion, those skilled in the art can carry out suitable determine and selection.
The diameter and length of carbon nanotubes used in the step have no stringent particular determination, but preferably its is a diameter of
30-60nm, length are 10-20 μm, which can no longer be retouched in detail herein by multiple channel and commercially available
State.
Wherein, in step A1-2, the mass percent concentration of the concentrated acid is 60-80%, may be, for example, 60%,
70% or 80%；Likewise, the dosage of the concentrated acid is also without stringent restriction, as long as can fully soak carbon nanotubes i.e.
Can, those skilled in the art can carry out suitable determine and selection.
Wherein, in step A1-3, the heating rate is 6-10 DEG C/min, may be, for example, 6 DEG C/min, 8 DEG C/min
Or 10 DEG C/min, it is most preferably 8 DEG C/min；Be warming up to 480-550 DEG C with the heating rate, may be, for example, 480 DEG C, 500 DEG C,
520 DEG C, 540 DEG C or 550 DEG C.
In the preparation method of the residual oil hydrocatalyst of the present invention, the step A2 includes the following steps：
A2-1：It is 1 by molar ratio:The aluminum nitrate and zirconium nitrate of 0.2-0.3 is added in deionized water, makes aluminum nitrate mole
Concentration is 0.4-0.6mol/L, is sufficiently stirred, and water-bath aging to viscosity is 60-80Pas at 80 DEG C, and it is molten to obtain colloidal
Liquid；
A2-2：Zinc chloride is dissolved in deionized water, it is 1mol/L to make its molar concentration, obtains liquor zinci chloridi；Then
The colloidal solution, liquor zinci chloridi, methylcellulose and diethanol amine are added in reactor, at 120-130 DEG C
When sealing reaction 3-4 is small；
A2-3：After the completion of reaction, pressure release and cooled to room temperature, filtering, obtained solid is fully washed with deionized water
Wash 4-5 times, and be dried in vacuo completely, obtain the nanotube II.
Wherein, in step A2-2, the dosage of the colloidal solution and liquor zinci chloridi should cause the molar ratio of Al/Zn
For 2-3:1, it may be, for example, 2:1、2.5:1 or 3:1, it is most preferably 2.5:1；Methylcellulose and zinc chloride (i.e. liquor zinci chloridi
Contained zinc chloride) mass ratio be 0.1-0.2:1, it may be, for example, 0.1:1、0.15:1 or 0.2:1；Diethanol amine and chlorination
The molar ratio of zinc (zinc chloride i.e. contained by liquor zinci chloridi) is 0.5-0.8:1, it may be, for example, 0.5:1、0.6:1、0.7:1 or
0.8:1。
Wherein, in step A2-3, those skilled in the art can carry out vacuum drying drying temperature suitably to determine
And selection, it may be, for example, 60-100 DEG C, such as 60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C or 100 DEG C.
In the preparation method of the residual oil hydrocatalyst of the present invention, the step A3 includes the following steps：
A3-1：By the nanotube II since room temperature, 340-380 DEG C is warming up to 5 DEG C/min of heating rate, and
Insulation calcining 20-30 minutes at such a temperature, obtains calcining nanotube；
A3-2：With 10 DEG C/min of heating rate, 450-500 DEG C is continuously heating to, and by the calcining nanotube at this
At a temperature of insulation calcining 40-60 minutes, after cooled to room temperature, so as to obtain the nanotube III.
In the preparation method of the residual oil hydrocatalyst of the present invention, the step A4 includes the following steps：
A4-1：According to 1:1-1.5:The molar ratio of 1.4-1.8, nickel nitrate, acetic acid and thiocarbamide are added in deionized water,
The molar concentration for making nickel nitrate is 2mol/L, obtains nickel nitrate composite solution；Separately take lanthanum chloride and be dissolved into deionized water, make
Its molar concentration is 0.5-0.8mol/L, obtains lanthanum chloride solution；
A4-2：Using equi-volume impregnating, the nanotube III is impregnated in the nickel nitrate composite solution, is impregnated
It is then dry abundant when time is 3-4 small, obtain dipping nanotube；
A4-3：Using equi-volume impregnating, the dipping nanotube is impregnated in the lanthanum chloride solution, dip time
It is then dry abundant when being also 3-4 small, obtain nanotube IV.
Wherein, in step A4-2 and A4-3, in dipping, dipping temperature is 50-55 DEG C；And drying therein is for example
Vacuum drying can be used, drying temperature can carry out appropriately selected, may be, for example, 80-100 DEG C, those skilled in the art can be closed
Suitable determines, is no longer described in detail herein.
In the preparation method of the residual oil hydrocatalyst of the present invention, the step A5 includes the following steps：
A5-1：Nanotube IV is subjected to water vapour-air Mixture atmosphere high-temperature process, treatment temperature is 300-400 DEG C, place
It is 60-90 minutes to manage the time, obtains pretreatment catalyst；
A5-2：The pretreatment catalyst is kept the temperature at 400-500 DEG C calcining 2-3 it is small when, then naturally cool to room
Temperature, that is, obtain the residual oil hydrocatalyst.
Wherein, in step A5-1, in water vapour-air Mixture atmosphere, water vapour volume content is 55-65%, optimal
Elect 60% as, the volume space velocity of mixed atmosphere is 300-350h-1。
Wherein, in step A5-2, insulation calcining heat is 400-500 DEG C, may be, for example, 400 DEG C, 450 DEG C or 500 DEG C；
Keep the temperature calcination time for 2-3 it is small when, may be, for example, 2 it is small when, 2.5 it is small when or 3 it is small when.
Second aspect, the present invention provide the residual oil hydrocatalyst according to obtained by above-mentioned preparation method.
Found by studying, the residual oil hydrocatalyst as the method obtains has excellent catalytic activity, such as residual oil
Conversion ratio, demetallization per, liquid oily yield and cyclical stability etc., so as to have a good application prospect in Residual cracking field
And industrial production potential.
3rd aspect, the present invention provides a kind of residual hydrogenation method using the residual oil hydrocatalyst.
More specifically, the method is specially：Residual oil, the catalyst and Cosan are added into high-pressure reactor,
Hydrogen is pressurized to 8-10MPa after being sufficiently displaced from, first reacted 40-60 minutes at 300-340 DEG C, then heat to 400-420 DEG C,
And react 40-50 minutes at such a temperature.
Wherein, the mass ratio of residual oil and catalyst is 600-1200:1, it may be, for example, 600:1、800:1、1000:1 or
1200:1；The mass ratio of residual oil and Cosan is 600-800:1, it may be, for example, 600:1、700:1 or 800:1.
As described above, the present invention provides a kind of residual oil hydrocatalyst and preparation method thereof and method of hydrotreating, it is described to urge
Agent has excellent multiple performance, so as to have a good application prospect and industrialized production and application in PETROLEUM PROCESSING field
Potentiality.
Embodiment
Below by specific embodiment, the present invention is described in detail, but the purposes of these exemplary embodiments and
Purpose is only used for enumerating the present invention, not forms any type of any restriction to the real protection scope of the present invention, more non-to incite somebody to action
Protection scope of the present invention is confined to this.
Embodiment 1：The preparation of residual oil hydrocatalyst
A1：Carbon nanotubes is pre-processed, obtains nanotube I, is specially：
A1-1：Carbon nanotubes (a diameter of 30-60nm, length are 10-20 μm) is added to appropriate molar concentration is
In the KOH aqueous solution of 4.5mol/L, processing 45 minutes is sufficiently stirred, is then filtered, and fully washed 2-3 times with deionized water,
Obtain alkali process carbon nanotubes；
A1-2：The alkali process carbon nanotubes is added in the concentrated nitric acid that appropriate mass percent concentration is 70%, filled
Divide stir process 25 minutes, then filter, and fully washed 2-3 times with deionized water, obtain acid treatment carbon nanotubes；
A1-3：By the acid treatment carbon nanotubes at room temperature, 520 DEG C are warming up to 8 DEG C/min of heating rate, and
Calcine 40 minutes at such a temperature, obtain nanotube I；
A2：Active carrier adhesion layer is generated on the surface of nanotube I, obtains nanotube II, is specially：
A2-1：It is 1 by molar ratio:0.25 aluminum nitrate and zirconium nitrate is added in deionized water, makes aluminum nitrate mole dense
Spend for 0.5mol/L, be sufficiently stirred, and water-bath aging to viscosity is 70Pas at 80 DEG C, obtains colloidal solution；
A2-2：Zinc chloride is dissolved in deionized water, it is 1mol/L to make its molar concentration, obtains liquor zinci chloridi；Then
The colloidal solution, liquor zinci chloridi, methylcellulose and diethanol amine are added in reactor, sealed at 125 DEG C
React 3.5 it is small when；
Wherein, the dosage of the colloidal solution and liquor zinci chloridi make it that the molar ratio of Al/Zn is 2.5:1st, methyl is fine
The mass ratio of dimension element and zinc chloride is 0.15:1 and the molar ratio of diethanol amine and zinc chloride be 0.65:1；
A2-3：After the completion of reaction, pressure release and cooled to room temperature, filtering, obtained solid is fully washed with deionized water
Wash 4-5 times, and be dried in vacuo completely at 80 DEG C, obtain the nanotube II；
A3：Two-part calcination processing is carried out to nanotube II, obtains nanotube III, is specially：
A3-1：By the nanotube II since room temperature, 360 DEG C are warming up to 5 DEG C/min of heating rate, and at this
At a temperature of insulation calcining 25 minutes, obtain calcining nanotube；
A3-2：With 10 DEG C/min of heating rate, 475 DEG C are continuously heating to, and by the calcining nanotube in the temperature
It is lower insulation calcining 50 minutes, after cooled to room temperature, so as to obtain the nanotube III；
A4：Two-part reactive metal impregnation processing is sequentially carried out to nanotube III, obtains nanotube IV, is specially：
A4-1：According to 1:1.2:1.6 molar ratio, nickel nitrate, acetic acid and thiocarbamide are added in deionized water, make nitric acid
The molar concentration of nickel is 2mol/L, obtains nickel nitrate composite solution；Separately take lanthanum chloride and be dissolved into deionized water, make its mole
Concentration is 0.65mol/L, obtains lanthanum chloride solution；
A4-2：Using equi-volume impregnating, the nanotube III is impregnated in the nickel nitrate composite solution, is impregnated
When time is 3.5 small, dipping temperature is 52 DEG C, is then dried in vacuo fully at 90 DEG C, obtains dipping nanotube；
A4-3：Using equi-volume impregnating, the dipping nanotube is impregnated in the lanthanum chloride solution, dip time
When being also 3.5 small, dipping temperature is 52 DEG C, is then dried in vacuo fully at 90 DEG C, obtains nanotube IV；
A5：Nanotube IV is subjected to water vapour-air Mixture atmosphere high-temperature process and calcination processing, so as to obtain the slag
Oil hydrogenation catalysts, are specially：
A5-1：Nanotube IV is subjected to water vapour-air Mixture atmosphere high-temperature process, treatment temperature is 350 DEG C, during processing
Between be 75 minutes, obtain pretreatment catalyst；
Wherein, in water vapour-air Mixture atmosphere, water vapour volume content is 60%, and the volume space velocity of mixed atmosphere is
325h-1；
A5-2：The pretreatment catalyst is kept the temperature to calcining 150 minutes at 450 DEG C, then cooled to room temperature, i.e.,
The residual oil hydrocatalyst is obtained, is named as C1.
Embodiment 2-5：The preparation of residual oil hydrocatalyst
Except the heating rate in step A1-3 is replaced with 6 DEG C/min, 10 DEG C/min, 7 DEG C/minute by 8 DEG C/min respectively
Clock and 9 DEG C/min are outer, other operations are identical, so that repetitive operation embodiment 1.Used heating rate and
To catalyst name see the table below shown in 1.
Table 1
Embodiment 6-9：The preparation of residual oil hydrocatalyst
Except respectively by the molar ratio of Al/Zn in step A2-2 by 2.5:1 replaces with outside the ratio in table 3 below, other operations
It is identical, so that repetitive operation embodiment 1.Used heating rate and obtained catalyst name see the table below in 2
It is shown.
Table 2
Embodiment 10-11：The preparation of residual oil hydrocatalyst
Except the water vapour volume content in water vapour in step A5-1-air Mixture atmosphere is changed into by 60% respectively
Outside 55% and 65%, other operations are identical, so that repetitive operation embodiment 1.Used heating rate and obtain
Catalyst name see the table below shown in 3.
Table 3
Comparative example 1-3：The preparation of residual oil hydrocatalyst
Comparative example 1：In addition to step A1-1 is dispensed, other operations are constant (not to be carried out alkali process, directly carries out step
A1-2 and A1-3), repetitive operation embodiment 1, by gained catalyst is named as D1.
Comparative example 2：In addition to step A1-2 is dispensed, other operations are constant (not to be carried out acid treatment, only carries out step
A1-1 and A1-3), repetitive operation embodiment 1, by gained catalyst is named as D2.
Comparative example 3：In addition to step A1-3 is dispensed, other operations are constant (not to be carried out calcination processing, only carries out step
A1-1 and A1-2), repetitive operation embodiment 1, by gained catalyst is named as D3.
Comparative example 4-5：The preparation of residual oil hydrocatalyst
Comparative example 4：In addition to the zirconium nitrate in step A2-1 is omitted, other operations are constant, repetitive operation reality
Example 1 is applied, gained catalyst is named as D4.
Comparative example 5：In addition to step A2 is omitted, other operations are constant (not to be generated on the surface of nanotube I
Active carrier adhesion layer), repetitive operation embodiment 1, outer D5 is named by gained catalyst.
Comparative example 6-7：The preparation of residual oil hydrocatalyst
Comparative example 6：Except by the heating rate in step A3-1 by 5 DEG C/min of 10 DEG C/min be revised as in step A3-2
Outside, it is other to operate constant (i.e. heating rate is 5 DEG C/min in two steps), repetitive operation embodiment 1, by institute
Obtain catalyst and be named as D6.
Comparative example 7：Except by the heating rate in step A3-2 by 10 DEG C/min of 5 DEG C/min be revised as in step A3-1
Outside, it is other to operate constant (i.e. heating rate is 10 DEG C/min in two steps), repetitive operation embodiment 1, by institute
Obtain catalyst and be named as D7.
Comparative example 8：The preparation of residual oil hydrocatalyst
Step A4 is varied to：
A4-1：According to 1:1.2:1.6 molar ratio, nickel nitrate, acetic acid and thiocarbamide are added in deionized water, make nitric acid
The molar concentration of nickel is 2mol/L, while also adds lanthanum chloride, and it is 0.65mol/L to make its molar concentration, obtains mixed solution；
A4-2：Using equi-volume impregnating, the nanotube III is impregnated in the mixed solution, dip time is
3.5 it is small when, dipping temperature is 52 DEG C, is then dried in vacuo at 90 DEG C abundant, obtains nanotube IV；
The step impregnation in step A4 is namely revised as one-dip, and other operations are constant, repeat embodiment
1, obtained catalyst is named as D8.
Comparative example 9：The preparation of residual oil hydrocatalyst
In addition to step A5-1 is omitted, other operations are constant (not to carry out water vapour-air Mixture atmosphere high temperature
Processing), repetitive operation embodiment 1, by gained catalyst is named as D9.
Residual hydrogenation test method
The residual oil hydrocatalyst obtained to above-described embodiment and multiple comparative examples carries out residual hydrogenation experiment, concrete operations
It is as follows：Residual oil, catalyst and Cosan are added into high-pressure reactor, hydrogen is pressurized to 9MPa after being sufficiently displaced from, first at 320 DEG C
Lower reaction 50 minutes, then heats to 410 DEG C, and reacts 45 minutes at such a temperature.Wherein, the mass ratio of residual oil and catalyst
For 900:1, the mass ratio of residual oil and Cosan is 700:1.
Wherein, used residual oil comes from Daqing petrochemical company, its physical property is as shown in table 4 below.
Table 4：Residual oil property
Above-mentioned residual hydrogenation experiment is carried out to different catalyst, after reaction, measures and calculates multiple performance indicators,
Wherein liquid oil refers to the liquid oil that boiling point is less than 520 DEG C：
Bottoms conversion (%)=(gained liquid oil (containing gas)/feed residue) × 100%；
Tenor in demetallization per (%)=(tenor in tenor-liquid oil in residual oil)/residual oil ×
100%；
Sulfur content × 100% in desulfurization degree (%)=(sulfur content in sulfur content-liquid oil in residual oil)/residual oil；
Liquid oily yield (%)=(gained liquid oil/feed residue) × 100%.
The catalyst performance data of embodiment and all comparative examples synthesis is listed in table 5 below.
Table 5
Wherein, " D1/D2/D3 " represents its numerical order answered, such as is with demetallization per " 92.1/91.7/91.1 "
Example, the demetallization per (%) that the demetallization per (%) for representing D1 is 92.1, D2 is 91.7, and the demetallization per (%) of D3 is
91.1, other performance and " D6/D7 " also have identical correspondence, no longer repeat one by one.
From the data of upper table 5：1st, for the heating rate in step A1-3, the technical characteristic is extremely important,
Final performance can be significantly affected, wherein 8 DEG C/min are most preferred heating rate, deviates that the value is bigger, then performance reduces
It is more obvious.Reason be probably under the heating rate, can be to the hole that is formed in carbon nanotubes after alkali process and acid treatment
Footpath carries out best sintering and shaping, so as to obtain optimal specific surface area and the suitable aperture point most beneficial for hydrogenation reaction
Cloth；It can also be seen that for identical deviation value, property when performance during higher than 8 DEG C/min will slightly be weaker than less than 8 DEG C/min
Energy (such as seeing the contrast of C2 and C3)；2nd, for Al/Zn molar ratios in step A2-2,2.5:1 is most preferred molar ratio,
The catalyst with optimal performance can be obtained at this time, and it is bigger to deviate the value, then performance reduces more notable；It can also be seen that
For identical deviation value, higher than 2.5:Performance when 1 will slightly be weaker than less than 2.5:Performance when 1 (such as is shown in pair of C6 and C7
Than)；3rd, it is most preferably 60% for the water vapour volume content in water vapour in step A5-1-air Mixture atmosphere；4、
When omitting A1-1, A1-2 or A1-3 respectively, performance is caused to decrease, especially liquid oily yield reduces very bright
Aobvious, this should be due to fail to form suitable aperture, and then lead to not to obtain best specific surface area and pore-size distribution and have
Close；5th, when the zirconium nitrate in step A2-1 is omitted, each performance equally has significant reduction, this proves zirconium nitrate
In the presence of significant improve and synergy can be played together with other active ingredients；6th, when there is no during step A2, each individual character
The most notable, the presence of active carrier adhesion layer in this proof nanotube surface can be reduced, not only plays the work of active carrier
With, and due to the presence of wherein active ingredient such as zr element, so as to generate significant association together with impregnating metal
Same effect；7th, by D6-D7 data as it can be seen that the different heating rates in step A3-1 also significantly affect final various performances；
8 and by D8 and D9 data as it can be seen that step impregnation and water vapour-air Mixture atmosphere high-temperature process (are conducive to impurity in aperture
Remove activation with active metal etc.) equally significantly affect final performance.
In conclusion in the preparation method of the residual oil hydrocatalyst of the present invention, pass through many technologies in multiple steps
The mutual collaboration and combination of feature, so as to obtain the catalyst of excellent performance.
The cyclical stability test of residual oil hydrocatalyst
By taking the best C1 of performance as an example, the cyclical stability of its residual hydrogenation ability has been investigated, that is, has been repeated above-mentioned
Identical residual hydrogenation experiment, respectively after recycling 10 times, 30 times and 80 times, measures its each performance data, the result is shown under
Table 6, in order to more directly be contrasted, the performance data of first time is also together listed.
Table 6
By upper table 6 as it can be seen that the catalyst of the present invention has excellent cyclical stability, after recycling 80 times, still have
There is very high each index performance, show excellent long-time stability.
In conclusion the preparation method that the present invention is mutually cooperateed with by unique multiple technical characteristics, and obtain having all
The residual oil hydrocatalyst of more excellent properties, has a good application prospect and industrial production potential in PETROLEUM PROCESSING field,
It can be used in the hydrotreating of residual oil and heavy oil.
It should be appreciated that the purposes of these embodiments is merely to illustrate the present invention and is not intended to the protection model of the limitation present invention
Enclose.In addition, it should also be understood that, after the technology contents of the present invention have been read, those skilled in the art can make the present invention each
Kind change, modification and/or variation, all these equivalent forms equally fall within the guarantor that the application the appended claims are limited
Within the scope of shield.
Claims (5)
1. a kind of preparation method of residual oil hydrocatalyst, the preparation method include the following steps：
A1：Carbon nanotubes is pre-processed, obtains nanotube I；
A2：Active carrier adhesion layer is generated on the surface of nanotube I, obtains nanotube II；
A3：Two-part calcination processing is carried out to nanotube II, obtains nanotube III；
A4：Two-part reactive metal impregnation processing is sequentially carried out to nanotube III, obtains nanotube IV；
A5：Nanotube IV is subjected to water vapour-air Mixture atmosphere high-temperature process and calcination processing, is added so as to obtain the residual oil
Hydrogen catalyst；
The step A1 includes the following steps：
A1-1：Carbon nanotubes is added in strong alkali aqueous solution, be sufficiently stirred processing 40-50 minutes, then filter, and spend from
Sub- water fully washs 2-3 times, obtains alkali process carbon nanotubes；
A1-2：The alkali process carbon nanotubes is added in concentrated acid, processing 20-30 minutes is sufficiently stirred, then filters, be used in combination
Deionized water is fully washed 2-3 times, obtains acid treatment carbon nanotubes；
A1-3：By the acid treatment carbon nanotubes at room temperature, with 8 DEG C/min of heating rate, it is warming up to 480-550 DEG C, and
Calcine 30-50 minutes at such a temperature, obtain nanotube I；
The step A2 includes the following steps：
A2-1：It is 1 by molar ratio:The aluminum nitrate and zirconium nitrate of 0.2-0.3 is added in deionized water, makes aluminum nitrate molar concentration
For 0.4-0.6mol/L, it is sufficiently stirred, and water-bath aging to viscosity is 60-80Pas at 80 DEG C, obtains colloidal solution；
A2-2：Zinc chloride is dissolved in deionized water, it is 1mol/L to make its molar concentration, obtains liquor zinci chloridi；Then by institute
State colloidal solution, liquor zinci chloridi, methylcellulose and diethanol amine to be added in reactor, sealed at 120-130 DEG C
When reaction 3-4 is small；
A2-3：After the completion of reaction, pressure release and cooled to room temperature, filtering, 4-5 is fully washed by obtained solid with deionized water
It is secondary, and be dried in vacuo completely, obtain the nanotube II；
In step A2-2, the dosage of the colloidal solution and liquor zinci chloridi should make it that the molar ratio of Al/Zn is 2.5:1；
The step A3 includes the following steps：
A3-1：By the nanotube II since room temperature, 340-380 DEG C is warming up to 5 DEG C/min of heating rate, and at this
At a temperature of insulation calcining 20-30 minute, obtain calcine nanotube；
A3-2：With 10 DEG C/min of heating rate, 450-500 DEG C is continuously heating to, and by the calcining nanotube in the temperature
It is lower insulation calcining 40-60 minutes, after cooled to room temperature, so as to obtain the nanotube III；
The step A4 includes the following steps：
A4-1：According to 1:1-1.5:The molar ratio of 1.4-1.8, nickel nitrate, acetic acid and thiocarbamide are added in deionized water, make nitre
The molar concentration of sour nickel is 2mol/L, obtains nickel nitrate composite solution；Separately take lanthanum chloride and be dissolved into deionized water, it is rubbed
Your concentration is 0.5-0.8mol/L, obtains lanthanum chloride solution；
A4-2：Using equi-volume impregnating, the nanotube III is impregnated in the nickel nitrate composite solution, dip time
For 3-4 it is small when, it is then dry abundant, obtain dipping nanotube；
A4-3：Using equi-volume impregnating, the dipping nanotube is impregnated in the lanthanum chloride solution, dip time is also
It is then dry abundant when 3-4 is small, obtain nanotube IV；
The step A5 includes the following steps：
A5-1：Nanotube IV is subjected to water vapour-air Mixture atmosphere high-temperature process, treatment temperature is 300-400 DEG C, during processing
Between be 60-90 minutes, obtain pretreatment catalyst；
A5-2：The pretreatment catalyst is kept the temperature at 400-500 DEG C calcining 2-3 it is small when, then cooled to room temperature, i.e.,
Obtain the residual oil hydrocatalyst；
In step A5-1, in water vapour-air Mixture atmosphere, water vapour volume content is 60%.
2. preparation method according to claim 1, it is characterised in that：In step A1-1, the strong alkali aqueous solution is KOH
Aqueous solution or NaOH aqueous solutions.
3. preparation method according to claim 1, it is characterised in that：In step A1-2, the concentrated acid is the concentrated sulfuric acid, height
Chloric acid or concentrated nitric acid.
4. the residual oil hydrocatalyst being prepared according to any one of the claim 1-3 preparation methods.
A kind of 5. residual hydrogenation method, it is characterised in that：Residual hydrogenation described in the residual hydrogenation method usage right requirement 4
Catalyst.
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