CN103080278A - 用于为反应器供料以改质重质烃类原料的得自催化剂前体的催化剂制备反应器 - Google Patents
用于为反应器供料以改质重质烃类原料的得自催化剂前体的催化剂制备反应器 Download PDFInfo
- Publication number
- CN103080278A CN103080278A CN2011800391438A CN201180039143A CN103080278A CN 103080278 A CN103080278 A CN 103080278A CN 2011800391438 A CN2011800391438 A CN 2011800391438A CN 201180039143 A CN201180039143 A CN 201180039143A CN 103080278 A CN103080278 A CN 103080278A
- Authority
- CN
- China
- Prior art keywords
- catalyzer
- described method
- transition metal
- catalyst
- hydrotreatment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 239000012018 catalyst precursor Substances 0.000 title claims abstract description 30
- 239000003054 catalyst Substances 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 38
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 20
- 150000003624 transition metals Chemical group 0.000 claims abstract description 20
- 230000000737 periodic effect Effects 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims description 45
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 30
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 22
- 239000004215 Carbon black (E152) Substances 0.000 claims description 21
- 229930195733 hydrocarbon Natural products 0.000 claims description 21
- 150000002430 hydrocarbons Chemical class 0.000 claims description 21
- 239000002243 precursor Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 16
- 229910052742 iron Inorganic materials 0.000 claims description 13
- 229910052750 molybdenum Inorganic materials 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 125000001424 substituent group Chemical group 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910052720 vanadium Inorganic materials 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 4
- 239000003446 ligand Substances 0.000 claims description 4
- 125000005609 naphthenate group Chemical group 0.000 claims description 4
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 3
- -1 isonitrile compound Chemical class 0.000 claims description 3
- 125000002524 organometallic group Chemical group 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical group O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 150000004703 alkoxides Chemical class 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 claims description 2
- 229910000071 diazene Inorganic materials 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 150000004678 hydrides Chemical class 0.000 claims description 2
- 150000003949 imides Chemical class 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims description 2
- 238000002407 reforming Methods 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 229910052714 tellurium Inorganic materials 0.000 claims description 2
- 150000007944 thiolates Chemical class 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 5
- 238000012360 testing method Methods 0.000 description 22
- 239000000571 coke Substances 0.000 description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 18
- 239000003921 oil Substances 0.000 description 17
- 239000000203 mixture Substances 0.000 description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 10
- 235000016768 molybdenum Nutrition 0.000 description 10
- 239000005864 Sulphur Substances 0.000 description 9
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 8
- QKOWWTNERDILGA-UHFFFAOYSA-J molybdenum(4+) octanoate Chemical compound C(CCCCCCC)(=O)[O-].[Mo+4].C(CCCCCCC)(=O)[O-].C(CCCCCCC)(=O)[O-].C(CCCCCCC)(=O)[O-] QKOWWTNERDILGA-UHFFFAOYSA-J 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 230000009466 transformation Effects 0.000 description 8
- 238000004088 simulation Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- VLXBWPOEOIIREY-UHFFFAOYSA-N dimethyl diselenide Natural products C[Se][Se]C VLXBWPOEOIIREY-UHFFFAOYSA-N 0.000 description 6
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000011733 molybdenum Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000003079 shale oil Substances 0.000 description 5
- 241000239290 Araneae Species 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 230000001186 cumulative effect Effects 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 4
- 238000000197 pyrolysis Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000011144 upstream manufacturing Methods 0.000 description 4
- OKLQFFLQJUXTAD-UHFFFAOYSA-L Cl[Mo](Cl)C1C=CC=C1 Chemical compound Cl[Mo](Cl)C1C=CC=C1 OKLQFFLQJUXTAD-UHFFFAOYSA-L 0.000 description 3
- 239000012075 bio-oil Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005204 segregation Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 235000019580 granularity Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- UVPKUTPZWFHAHY-UHFFFAOYSA-L 2-ethylhexanoate;nickel(2+) Chemical compound [Ni+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O UVPKUTPZWFHAHY-UHFFFAOYSA-L 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 229910017318 Mo—Ni Inorganic materials 0.000 description 1
- 229910003294 NiMo Inorganic materials 0.000 description 1
- UNRQTHVKJQUDDF-UHFFFAOYSA-M acetylpyruvate Chemical compound CC(=O)CC(=O)C([O-])=O UNRQTHVKJQUDDF-UHFFFAOYSA-M 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000003822 preparative gas chromatography Methods 0.000 description 1
- 125000002577 pseudohalo group Chemical group 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- XSCIEFUPKGHAAM-UHFFFAOYSA-N thiosilicic acid Chemical class O[Si](O)(O)S XSCIEFUPKGHAAM-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
-
- 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
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
-
- 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
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
- C10G49/04—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing nickel, cobalt, chromium, molybdenum, or tungsten metals, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/10—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 with moving solid particles
- C10G49/12—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 with moving solid particles suspended in the oil, e.g. slurries
-
- 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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
-
- 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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
-
- 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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/646—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of aromatic or heteroaromatic rings
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—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
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/50—Complexes comprising metals of Group V (VA or VB) as the central metal
- B01J2531/56—Vanadium
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/64—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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
-
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/27—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a liquid or molten state
-
- 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
- C10G2300/1011—Biomass
-
- 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
- C10G2300/107—Atmospheric residues having a boiling point of at least about 538 °C
-
- 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
- C10G2300/1077—Vacuum residues
-
- 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
- C10G2300/703—Activation
-
- 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
- C10G2300/708—Coking aspect, coke content and composition of deposits
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
本发明涉及一种在至少一个用于加氢转化重质烃类原料的加氢转化反应器中,以及在至少一个用于加氢处理重质烃类原料的加氢处理反应器中改质所述重质烃类原料的方法,所述方法包括制备两种或更多种催化剂,每种催化剂在至少一个特定的制备反应器中由一种或更多种催化剂前体制备,所述催化剂前体含有至少一种选自元素周期表的IIA、IIIB、IVB、VB、VIB、VIIB、VIII、IB或IIB族的过渡金属,每个制备反应器为一个或更多个加氢转化或加氢处理反应器供料,制备反应器中所含的每种催化剂专用于加氢转化或加氢处理所述原料。该方法允许在连续操作条件下获得更高品质的产品。
Description
本发明涉及一种改质重质烃类原料的方法,且特别是方法中所使用的反应器的催化剂供料。
由于原油价格上涨或原油短缺增加,对于寻找更好的开发这些较低品质原料和由此提取燃料值的方法有增长的需求。
已知的改善改质烃类原料的方法使用特定的操作条件(T°、P°、H2等)。
然而,仍然需要用于改质烃类原料的改进的方法。
本发明的第一个目的涉及一种改质重质烃类原料的方法,其在至少一个用于加氢转化所述重质烃类原料的加氢转化反应器中以及在至少一个用于加氢处理所述重质烃类原料的加氢处理反应器中进行,所述方法包括制备两种或更多种催化剂,每种催化剂在至少一个特定的制备反应器中由一种或更多种催化剂前体制备,所述催化剂前体含有至少一种选自元素周期表的IIA、IIIB、IVB、VB、VIB、VIIB、VIII、IB或IIB族的过渡金属,每个制备反应器为一个或更多个加氢转化或加氢处理反应器供料,制备反应器中所含的每种催化剂专用于所述原料的加氢转化或加氢处理。
这种方法允许在连续的操作条件下获得较好品质的产品。
专用于催化剂前体活化的制备反应器给予了更多的灵活性。因而,有利地,可以获得对反应段的反应器的连续进料,并且,所述催化剂制备反应器可将不同的催化系统供给到加氢转化反应器和加氢处理反应器。
加氢转化是指在氢气气氛下破坏烃分子中的化学键以减少或抑制焦炭和气体(C1-C4)的形成。化学键的破坏本身主要通过温度驱动,催化剂被用来促进氢结合进入产物。使用术语加氢转化以区分“氢化裂化”,所述氢化裂化中化学键的破坏主要由催化剂促进。
加氢转化工艺的催化剂基于来自IIA、IIIB、IVB、VB、VIB、VIIB、VIII、IB或IIB族的金属。
加氢处理是指在氢气气氛下从烃料流中去除杂质如硫、氮、氧、金属、CCR(康氏残碳)等。加氢处理的催化剂与加氢转化的相同,然而(由于其较高的活性)优选由VIII族金属促进的或未由VIII族金属促进的VB和VIB族的金属。
加氢转化优选地在加氢处理之前进行,虽然加氢处理可以先于加氢转化。
有利地,每个制备反应器可以用部分待处理原料供料。最终,液态烃可以被供入制备反应器以获得较低粘度的混合物,添加到待处理原料中或代替该原料。
制备反应器还可以被供入用于活化催化剂前体的硫化剂。硫化剂可以是例如DMSO(二甲亚砜)、DMDS(二甲二硫醚)、单质硫或H2S,可以是纯的或者在来自炼油厂来源的混合物,或任意合适的含硫化合物。根据加入到制备反应器的催化剂前体中的原料的组成,可以不必添加该硫化剂:那么,催化剂前体的硫化通过原料中所含的硫进行。
可在专用的容器中实现催化剂前体的活化(将前体转化为前体中所含的金属的活性硫物质)。
在可编程的运行条件下(温度、压力、硫化剂的浓度、停留时间)加热混合物。
为改善添加剂的分散性以及为限制起泡,可添加粉碎的固体或其它添加剂(分散剂等)(例如碎焦炭,2wt%,粒度300至500微米;氧化铝;硫代硅酸盐、碳酸钙的磺酸盐;以及任意其它合适的如US5594945中描述的那些添加剂)。
还可以向制备反应器中加入氢气。该添加有助于控制活性催化剂中非常活性的硫物质的活性,以减少或避免催化剂焦化。
有利地,每种专用催化剂在至少两个制备反应器中制备。然后可以连续地向加氢转化反应器或加氢处理反应器供给催化剂。
加氢处理和加氢转化的温度和压力条件可有利地非常相似或相同。
加氢转化的反应温度可以为360℃至480℃,优选400℃至440℃,在50巴至300巴的压力下,优选100巴至200巴。
加氢处理的反应温度可以为360℃至480℃,优选380℃至440℃,在50巴至300巴的压力下,优选100巴至200巴。
加氢处理和加氢转化反应器可以在上流或下流反应器中进行。这些反应器优选是完全搅拌反应器(CTSR)。
至少一种从催化剂制备反应器生成的油浆被供入每个反应器中。
所述油浆(由含有活性催化剂、氢气和可能的其它添加剂的原料,以及需要时另外的氢气组成)被加压并进入加氢转化反应器中和加氢处理反应器。
优选地,所述油浆在加压前被预热。
有利地,专用于加氢转化的催化剂含有一种处于活性状态的过渡金属,其选自VB、VIB、VIII族,且专用于加氢处理的催化剂含有两种处于活性状态的过渡金属,一种过渡金属选自VB、VIB、VIII族且另一种过渡金属选自VIII族。
对于加氢转化有活性的金属优选:Mo、Ni、Co、W、Cr、V、Fe。
专用于加氢转化的一种或更多种催化剂可包含V、Mo或Fe且专用于加氢处理的一种或更多种催化剂可包含如下组合:Mo-Ni,或Mo-V,或Fe-Ni。
有利地,专用于加氢转化的催化剂含有20ppm至700ppm的过渡金属(过渡金属相对于原料的重量比),优选250ppm至650ppm,最优选300ppm至600ppm。
有利地,专用于加氢处理的催化剂中过渡金属的总含量为200ppm至1000ppm(过渡金属相对于原料的重量比),优选为250ppm至900ppm,最优选300ppm至500ppm。
对于每种催化剂可以使用不同的催化剂前体。催化剂前体可以选自环烷酸盐(naphtenates)、辛酸盐和氧化物。
例如,含Mo的前体将是环烷酸盐,含Ni的前体将是辛酸盐,如2-乙基己酸盐,以及含V的前体将是乙酰丙酮化物或乙酰丙酮酸盐。
可替代地,单金属催化剂的催化剂前体也可为式C1C2MLn的有机金属配位化合物,其中
-M是选自元素周期表的IIA、IIIB、IVB、VB、VIB、VIIB、VIII、IB或IIB族的过渡金属,
- -C1和-C2是以π键连接到M的单环或多环芳基烃配体,-C1和-C2是相同的或不同的,-C1或-C2各自包含0至5个取代基R,每个取代基R是相同的或不同的,R选自:
C3至C8,取代的或未取代的,单环或多环的环结构,其为部分不饱和的、不饱和的或者芳香族的,稠合或非稠合至配体-C1或-C2,
C3至C8,取代的或未取代的,部分不饱和的或不饱和的,直链的或支链的,脂环族烃基,
C1至C8,取代的或未取代的,直链的或支链的,饱和的烃基,-C1和-C2是独立的或经由至少一个取代基R连接,
- -L是σ键连接到M的配体,n是等于0至3的整数,每个-L是独立的单价配体。
稠环是与另一个环共同具有两个碳原子和一个化学键的环。
有利地,在式C1C2MLn中,每个C1或C2都是包含0至5个取代基R的C5-C8单环多烯配体,每个取代基R是相同的或不同的,R如上文所定义。
多烯是多不饱和的有机化合物,其含有一个或更多个交替的碳-碳双键和碳-碳单键的序列。
例如,每个C1或C2可以是取代的或未取代的环戊二烯。取代基可以与上述的取代基R相同。
有利地,有机金属配位化合物是由以下通式(II)表示的金属茂化合物
其中R取代的或未取代的环戊二烯基配体是π键连接到M的,且L配体是σ键连接到M的,且其中M、L、R和n如式(I)中的定义。
因此,金属茂化合物由两个环戊二烯阴离子(取代的或未取代的)连接到一个金属中心组成“夹心”结构。
有利地,在式(I)或(II)中,M选自元素周期表的IIA、IIB、IIIB、IVB、VB、VIB、VIIB或VIII族,优选地M选自Fe、V或Mo。
有利地,在式(I)或(II)中,配体-L选自:
·氢化物(-L=-H)
·卤化物(-L=-F、-Cl、-Br、-I)
“拟卤化物”(-L=-CN(氰化物))
·醇盐(-L=-OR)
硫醇盐(-L=-SR)
·酰胺(-L=-NR2)
磷化物(-L=-PR2)
·-L=-ER3或-EX3(E=Si、Ge、Sn;)
·烷基(-L=-CH2R或其它)
烯基(-L=-CHCHR)
炔基(-L=-CCR)
·酰基(-L=-COR)
·异腈化物(L=-CNR)
亚硝酰基(-L=-NO)
二氮烯(-L=-NNR)
酰亚胺(L==NR)
·-L=-PR3、-PX3、-AsR3、-SbR3和胺
·L=ER2(E=O、S、Se、Te)
其中X是卤素原子且R是C1-C8,优选C1-C6,直链或支链的烷基、烯基基团,或C3-C8的脂环族或芳香族基团。
催化剂前体根据催化剂前体的类型(辛酸盐、环烷酸盐、金属茂、氧化物等)在不同的浓度下以及在几种形式下添加:水溶性、油溶性或细粉状固体。
油溶性金属前体既可使用纯固体(金属茂化合物)也可使用烃中的溶液。
在纯的油溶性固体前体中,金属含量通过金属的原子量和前体分子的分子量而获知。从而,可计算出为了获得原料中给定的金属浓度而添加到原料中的前体的量。
以金属含量分析烃中油溶性前体溶液。从而可计算出为了获得原料中给定的金属浓度而添加到原料中的溶液的量。
根据本发明的方法可被用于改质包含至少0.25的H/C原子比的烃类原料。
因而,通过该方法可改质多种原料:常压和减压渣油、来自脱沥青的沥青、脱沥青油、减粘裂化流出物(热裂化)、页岩油、生物质前热解和前热液处理(biomass ex-pyrolysis and ex-hydrothermal treatment)、煤和(至少在理论上)来自延迟焦化装置的焦炭。
其它的原料也可以与石油残渣一起共处理:轮胎、聚合物、道路沥青。
上述原料的一般特性在下面的表1至10中给出(原料的数据表示粗原料的原始数据,工艺条件也可导致在其分析中很大的不同)。
对于某些原料,给出典型的模拟蒸馏结果。
该模拟蒸馏方法如下进行:
将烃引入气相色谱柱的柱中并随着沸点的增加进行分离。柱温增加。沸点从校准曲线中扣除,所述校准曲线利用已知的烃混合物在相同的运行条件下获得。
使用的柱是来自Analytical Controls的Simdis HT 750;长度=5m;膜=0.09μm;内径=0.53mm(AC partno.:24001.065)。可使用以下的校准混合物:
1.来自Analytical Controls的C5-C28混合物(AC partno.:59.50.101A),
2.来自Analytical Controls的C30-C120混合物(Ac partno.:59.50.100B)。
IP是指初始蒸馏点(Initial Point distillation):相应于整个色谱区间0.5%曲线区间的温度。
FP是指最终蒸馏点(Final Point distillation):相应于整个色谱区间99.5%曲线区间的温度。
表1a:页岩油典型的性质
性质 | 观测的值 | 单位 |
比重 | 900-1076 | kg/m3 |
°API | 7.9-25 | |
C | 78-86 | wt% |
H | 7.5-12 | wt% |
H/C | 1.2-1.7 | 原子比 |
O | 0.7-7.5 | wt% |
S | 0.5-7.5 | |
N | 0.1-2.5 | wt% |
砷化三氢 | 5.6-50 | ppm |
锑Sb | ||
烯烃(溴值) | 20-1260 | gBr2/100g |
表1b:页岩油典型的模拟蒸馏
页岩油富含杂质,某些杂质对催化剂有毒,如砷化三氢(AsH3)。砷化三氢是加氢工艺催化剂(NiMo、CoMo)最严重的毒物。可选的精炼页岩油的方法受砷化三氢存在的阻碍,所述砷化三氢使其催化功能中毒。在加氢处理过程中,砷化三氢沉积在催化剂上并被捕获为砷化镍。
在所描述的方法中,新制的催化剂被不断地加入使得催化剂中毒不影响其工艺性能或流出物品质。
表2a:常压和减压渣油典型的性质
表2b:常压和减压渣油典型的模拟蒸馏
表3a:沥青的典型性质
性质 | 观测的值 | 单位 |
脱沥青溶剂 | C3至C5 | - |
比重 | 1.1-1.2至固体 | t/m3 |
康氏碳 | 50 | wt% |
硫 | 6.5 | wt% |
表3b:沥青典型的模拟蒸馏
表4a:脱沥青油的典型性质
性质 | 观测的值 | 单位 |
脱沥青溶剂 | C3至C5 | - |
比重 | 0.970-1.025 | t/m3 |
康氏碳 | 7-22 | wt% |
硫 | 1-5 | wt% |
C7沥青质 | <0.05-3 | wt% |
表4b:脱沥青油的典型模拟蒸馏
表5a:减粘裂化渣油的典型性质:
性质 | 观测的值 | 单位 |
比重 | 995-1080 | kg/m3 |
康氏碳 | 22-33 | wt% |
表5b:减粘裂化渣油的典型模拟蒸馏:
表6:聚合物的典型性质:
表7:焦炭的典型性质:
表8:热解生物油的典型性质
表9:来自热解生物油的通常送去气化的油浆的典型性质
表10:生物油前热液转化的典型性质:
下面的附图和实施例将说明本发明。
图1表示根据本发明的方法的示意性实施方案。
图2表示实施例1的不同试验中的H2S产率(wt%)(反应时间:1小时;温度430℃)。
图3表示在实施例1的不同试验中500+馏分的液体中H/C的原子比(反应时间:1小时;温度430℃)。
图4表示利用两种油溶性铁催化剂前体(二茂铁(Fe-cene)和辛酸铁(Fe-octo))的500+馏分作为反应器温度函数的转化率。测试的条件(实施例2):反应时间=1小时;催化剂浓度=5000wppm金属。十字叉(x)表示出现焦炭形成的试验。
图5表示利用两种油溶性钼催化剂前体(二茂钼(Mo-cene)和辛酸钼(Mo-octo))的500+馏分作为反应器温度函数的转化。测试的条件(实施例3):反应时间=1小时;催化剂浓度=5000wppm金属。十字叉(x)表示出现焦炭形成的试验。
所表示的单元包括两个制备反应器10、20,其用于由催化剂前体制备催化剂。
每个制备反应器10、20专用于制备特定的催化剂,用于加氢转化(反应器10)或用于加氢处理(反应器20)。
每个制备反应器10、20分别用催化剂前体13、23供料,所述前体可以是下面几种形式:水溶性的、油溶性的或细粉状固体。
为了在每个制备反应器中活化催化剂前体13、23,可如图所示加入硫化剂15、25(DMDS、H2S、单质硫)。
还可以在制备反应器10、20中分别加入氢气H212、22。
每个制备反应器10、20还可以用待处理原料11、21供料。在那种情况下,原料中所含的硫可用于活化催化剂。
另外,还可以使用液态烃代替待处理原料,例如作为溶剂,并送入制备反应器10、20。
为改善催化剂前体在每个制备反应器中的分散性,可加入粉碎的固体或其它添加剂14、24(例如碎焦炭、2wt%,粒度300微米至500微米)。所述单元还包括加氢转化反应器40、加氢处理反应器50和分离段60。预热器30被置于加氢转化反应器40的上游,用于加热待处理原料。油浆31,来自制备反应器10,且由活性加氢转化催化剂以及待处理原料和/或其它烃类原料和最后其它添加剂组成,被输送至预热器30。
待处理原料还可以通过线路32部分或全部地供到预热器。然后,加热的油浆41被供入加氢转化反应器40。还可以从反应器40的上游加入补充的氢气42。
在加氢处理反应器50的上游,向离开加氢转化反应器40的流出物51加入制备反应器20中制备的加氢处理催化剂26。还可以在加氢处理反应器50的上游加入氢气52。
离开加氢处理反应器50的流出物56在分离段60分离。该分离段可以例如包括用于除去气体的闪蒸容器、常压分馏和减压分馏。
实施例
对减压渣油进行加氢转化和加氢处理。所测试的减压渣油表现出如下特性:
表11:测试的减压渣油的性质(阿拉伯重质减压渣油)
MCRT:微残碳量试验
所有的试验在500ml的搅拌间歇式反应器中,在恒定的压力下连续供应氢气而进行。操作条件为:总压力为15MPa,温度为420℃至450℃,H2流量设为100NL/h且搅拌速度为900rpm。
预热减压渣油以降低其粘度并使其转移至反应器中。催化剂前体(辛酸钼、辛酸镍、辛酸铁、二茂铁和/或二茂钼)和液态DMDS被加入反应器中的预热的减压渣油中,随后封闭反应器。然后加入氢气,并且升高温度,在250℃和320℃两个阶段各自保持十分钟。然后反应器的温度快速上升至操作值。
在试验结束时,反应器被冷却并减压。所有的气态和液态排出物被收集、称重并分析。
通过气相色谱法(Agilent G2891微型气相色谱仪)在线分析气体,且通过高温气相色谱法(ASTM D7169)分析反应产物以确定产率。
实施例1
在该试验系列中,催化金属的总(摩尔)含量保持恒定,但Ni/Mo比在0至0.5之间变化。对于该试验系列,操作温度固定在430℃1小时。
表12:在不同的试验中的催化金属的浓度(wppm,基于原料的重量)
对于该试验系列,钼和镍两者分别以辛酸盐的形式被加入原料,两者在常温下均为液态。
按推测,辛酸钼具有下式:C32H60MoO8。辛酸镍具有下式:C16H30NiO4。
300mL原料和适量的钼和镍基催化剂前体被送入反应器中(见表12)。260mol%的硫(相对于催化金属钼和镍的量)以DMDS的形式也被作为硫化剂送入反应器中。反应器用氢气加压并以5℃/分钟的升温速率加热至所需温度430℃。
所得产物的组成示出在表13中。
对于所有的试验,没有观测到焦炭的形成。
这些结果表示,适当选择的催化剂允许提高加氢转化产物的质量(特别是更多的加氢脱硫和塔底馏分中更高的氢含量)而不改变操作条件或转化率,且转化产物的比率没有明显改变。
结果还表明由于500+馏分的转化,在残余的500+中的金属(Mo、Ni、V)的浓度相对于原始的原料和催化金属的混合物增加。
表13:试验结果
(*)对应于蒸馏范围的范围。
实施例2(二茂铁)
已进行了试验系列以比较二茂铁和辛酸铁作为减压渣油加氢转化的活性催化相前体。
二茂铁具有下式:Cp2Fe(或(C5H5)2Fe)。
辛酸铁具有下式:C24H45FeO6。
使用与前面实施例中相同的减压渣油作为原料。其组成示出在表11中。
已在420℃至450℃范围内渐增的温度下进行了一系列不同的测试。
将300mL原料和铁基催化剂前体送入反应器中。对于每个催化剂前体,5000wppm的Fe以Cp2Fe或辛酸铁的形式加入到原料(wppm:基于原料的重量)。130mol%的硫(相比于铁)以DMDS的形式也送入反应器中作为硫化剂。反应器用氢气加压并以5℃/分钟的升温速率加热到需要的温度。
在渐增的温度下进行了数个试验,直到出现焦炭的产生。该温度被作为利用特定油浆相催化剂的加氢转化的最大许可温度。
结果示出在图4中。在该图中,转化率相对于温度作图。用十字叉表示发生焦炭形成的试验。
用辛酸铁作为前体,焦炭形成发生在425℃。在420℃观测到无焦炭形成的最大的500+转化率,为45w%。
用二茂铁作为前体,温度可升至435℃而没有焦炭形成。该温度下观测到的500+转化率为57w%。
该实施例示出了金属茂化合物作为前体以获得重质原料加氢转化的高加氢转化活性催化剂的潜能。
实施例3(二茂钼)
已进行试验以比较二氯化双(环戊二烯基)钼和辛酸钼作为减压渣油加氢转化的活性催化相前体。
二氯化双(环戊二烯基)钼具有下式:Cp2MoCl2(或(C5H5)2MoCl2)。
辛酸钼按照推测具有下式:C32H60MoO8。
使用与前面实施例中相同的减压渣油作为原料。其组成示出在表11中。
已在420℃至450℃范围内渐增的温度下进行了一系列不同的测试。
将300mL原料和钼基催化剂前体送入反应器中。对于每个催化剂前体,500wppm的Mo以Cp2MoCl2或辛酸钼的形式加入到原料(wppm:基于原料的重量)。260mol%的硫(相比于钼)以DMDS的形式也送入反应器中作为硫化剂。反应器用氢气加压并以5℃/分钟的升温速率加热到需要的温度。
已在渐增的温度下进行了数个试验,直到出现焦炭的产生。该温度被作为利用特定油浆相催化剂的加氢转化的最大许可温度。
结果示出在图5中。在该图中,转化率相对于温度作图。用十字叉表示发生焦炭形成的试验。
用辛酸钼作为前体,焦炭形成发生在440℃。在435℃观测到无焦炭形成的最大500+转化率,为52w%。
用二氯化双(环戊二烯基)钼作为前体,温度可升至450℃而没有焦炭形成。该温度下观测到的500+转化率为70w%。
二茂钼的使用使得比辛酸钼的使用适应更高的温度,因而导致更深度的转化并且没有焦炭的形成。
实施例4(空白试验)
进行常压渣油混合物不含任何催化剂的相同试验。该原料的组成给出在表14中。氢气流量被设为0Nl/h。原料在420.5℃的温度下处理30分钟。产生了大量的焦炭,其说明催化剂对抑制焦炭的效果。
表14:所测的减压渣油的性质(阿拉伯重质减压渣油)
MCRT:微残碳量试验
Claims (16)
1.一种改质重质烃类原料的方法,所述方法在至少一个用于加氢转化所述重质烃类原料的加氢转化反应器中以及在至少一个用于加氢处理所述重质烃类原料的加氢处理反应器中进行,所述方法包括制备两种或更多种催化剂,每种催化剂在至少一个特定的制备反应器中由一种或更多种催化剂前体制备,所述催化剂前体含有至少一种过渡金属,所述过渡金属选自元素周期表的IIA、IIIB、IVB、VB、VIB、VIIB、VIII、IB或IIB族,并且每个制备反应器为一个或更多个加氢转化或加氢处理反应器供料,制备反应器中所含的每种催化剂专用于所述原料的加氢转化或加氢处理。
2.根据权利要求1所述的方法,其中每个制备反应器被供给一部分待改质的原料。
3.根据权利要求1或2所述的方法,其中每个制备反应器被供给硫化剂。
4.根据权利要求1至3中任一项所述的方法,其中每个制备反应器被供给氢气。
5.根据权利要求1至4中任一项的所述方法,其中每个制备反应器被供给分散剂。
6.根据权利要求1至5中任一项所述的方法,其中每种专用的催化剂在至少两个制备反应器中制备。
7.根据权利要求1至6中任一项所述的方法,其中专用于加氢转化的一种或更多种催化剂含有一种活性状态的选自VB、VIB、VIII族的过渡金属,专用于加氢处理的一种或更多种催化剂含有两种活性状态的过渡金属,一种过渡金属选自VB、VIB、VIII族且另一种过渡金属选自VIII族。
8.根据权利要求7所述的方法,其中专用于加氢转化的一种或更多种催化剂含有V、Mo或Fe,以及专用于加氢处理的一种或更多种催化剂含有Mo和Ni,或Mo和V,或Fe和Ni。
9.根据权利要求1至8中任一项所述的方法,其中专用于加氢转化的一种或更多种催化剂含有20ppm至700ppm的过渡金属,优选250ppm至650ppm,最优选300ppm至600ppm。
10.根据权利要求1至9中任一项所述的方法,其中专用于加氢处理的一种或更多种催化剂中过渡金属的总含量为200ppm至1000ppm,优选250ppm至900ppm,最优选300ppm至500ppm。
11.根据权利要求1至10中任一项所述的方法,其中催化剂前体选自环烷酸盐、辛酸盐、氧化物。
12.根据权利要求1至10中任一项所述的方法,其中单金属催化剂的前体为式为C1C2MLn(I)的有机金属配位化合物,其中
- M是选自元素周期表的IIA、IIIB、IVB、VB、VIB、VIIB、VIII、IB或IIB族的过渡金属,
--C1和-C2是以π键连接到M的单环或多环芳基烃配体,-C1和-C2是相同的或不同的,-C1或-C2各自包含0至5个取代基R,每个取代基R是相同的或不同的,R选自:
C3至C8,取代的或未取代的,单环或多环的环结构,其为部分不饱和的、不饱和的或者芳香族的,稠合或非稠合至配体-C1或-C2,
C3至C8,取代的或未取代的,部分不饱和的或不饱和的,直链的或支链的,脂环族烃基,
C1至C8,取代的或未取代的,直链的或支链的,饱和的烃基基团,
-C1和-C2是独立的或经由至少一个取代基R连接,
- -L是σ键连接到M的配体,n是等于0至3的整数,每个-L是独立的单价配体。
13.根据权利要求12所述的方法,其中所述有机金属配位化合物是由以下通式(II)表示的金属茂化合物
其中R取代的或未取代的环戊二烯基配体是π键连接到M的,且L配体是σ键连接到M的,且其中M、L、R和n如式(I)中的定义。
14.根据权利要求12或13所述的方法,其中-L选自氢化物(-L=-H)、卤化物(-L=-F、-Cl、-Br、-I)、氰化物(-L=-CN)、醇盐(-L=-OR)、硫醇盐(-L=-SR)、酰胺(-L=-NR2)、磷化物(-L=-PR2)、烷基(-L=-CH2R或其它)、烯基(-L=-CHCHR)、炔基(-L=-CCR)、酰基(-L=-COR)、异腈化物(L=-CNR)、亚硝酰(-L=-NO)、二氮烯(-L=-NNR)、酰亚胺(L==NR)、-L=-ER3或-EX3(E=Si、Ge、Sn;)、-L=-PR3、-PX3、-AsR3、-SbR3、胺,L=ER2(E=O、S、Se、Te),其中X是卤素原子,且R是C1-C8,优选C1-C6,直链或支链的烷基、烯基或C3-C8脂环族或芳香族基团。
15.根据权利要求12至14中任一项所述的方法,其中M选自元素周期表的IIA、IIB、IIIB、IVB、VB、VIB、VIIB或VIII族。
16.根据权利要求1至15中任一项所述的方法,其中所述烃类原料包含至少0.25的H/C原子比。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP10305744.4 | 2010-07-06 | ||
EP10305744A EP2404982A1 (en) | 2010-07-06 | 2010-07-06 | Catalyst preparation reactors from catalyst precursor used for feeding reactors to upgrade heavy hydrocarbonaceous feedstocks |
PCT/EP2011/061284 WO2012004246A2 (en) | 2010-07-06 | 2011-07-05 | Catalyst preparation reactors from catalyst precursor used for feeding reactors to upgrade heavy hydrocarbonaceous feedstocks. |
Publications (2)
Publication Number | Publication Date |
---|---|
CN103080278A true CN103080278A (zh) | 2013-05-01 |
CN103080278B CN103080278B (zh) | 2016-03-16 |
Family
ID=43415352
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201180039143.8A Expired - Fee Related CN103080278B (zh) | 2010-07-06 | 2011-07-05 | 用于为反应器供料以改质重质烃类原料的得自催化剂前体的催化剂制备反应器 |
Country Status (7)
Country | Link |
---|---|
US (1) | US9233363B2 (zh) |
EP (2) | EP2404982A1 (zh) |
JP (1) | JP5896536B2 (zh) |
KR (1) | KR101893424B1 (zh) |
CN (1) | CN103080278B (zh) |
AU (1) | AU2011275813B2 (zh) |
WO (1) | WO2012004246A2 (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111841630A (zh) * | 2020-06-24 | 2020-10-30 | 中国石油大学(华东) | 用于煤/重油加氢共炼的脂肪酸镍油溶性催化剂及其应用 |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR3015514B1 (fr) | 2013-12-23 | 2016-10-28 | Total Marketing Services | Procede ameliore de desaromatisation de coupes petrolieres |
US10610854B2 (en) * | 2014-11-06 | 2020-04-07 | Shell Oil Company | Self-activating hydroprocessing catalyst having enhanced activity and self-activation characteristics and its use for treating resid feedstocks |
IT201600080528A1 (it) * | 2016-08-01 | 2018-02-01 | Luigi Patron | Sistema di idroconversione di oli pesanti esente da coking in singolo stadio di reazione con riciclo mediante un reattore a catalizzatore disperso comprendente molibdeno, e relativo metodo di idroconversione |
WO2023156742A1 (fr) | 2022-02-17 | 2023-08-24 | Totalenergies Onetech | Procede de production d'une huile de biomasse stabilisee |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4592827A (en) * | 1983-01-28 | 1986-06-03 | Intevep, S.A. | Hydroconversion of heavy crudes with high metal and asphaltene content in the presence of soluble metallic compounds and water |
US4770764A (en) * | 1983-03-19 | 1988-09-13 | Asahi Kasei Kogyo Kabushiki Kaisha | Process for converting heavy hydrocarbon into more valuable product |
CN1373008A (zh) * | 2001-02-28 | 2002-10-09 | 北京燕山石油化工公司研究院 | 茂金属催化剂及其制备方法、应用和选择加氢方法 |
CN101014411A (zh) * | 2004-09-10 | 2007-08-08 | 切夫里昂美国公司 | 高活性浆液催化剂组合物 |
CN101242898A (zh) * | 2005-07-11 | 2008-08-13 | 俄罗斯科学院西伯利亚分院格·克·巴类斯考夫催化研究院 | 催化剂、其制备方法以及使用所述催化剂对烃进行异构化的方法 |
CN101370582A (zh) * | 2006-01-06 | 2009-02-18 | 上游技术革新有限公司 | 烃溶性双金属催化剂前体及其制备方法 |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5665636A (en) | 1979-10-31 | 1981-06-03 | Chiyoda Chem Eng & Constr Co Ltd | Metal-carrying fine particles catalyst and preparation thereof |
US4430442A (en) * | 1982-07-20 | 1984-02-07 | Exxon Research And Engineering Co. | Catalysts from molybdenum polysulfide precursors and their preparation |
JPS59172587A (ja) | 1983-05-16 | 1984-09-29 | Asahi Chem Ind Co Ltd | 重質炭化水素油の軽質化方法 |
US4824821A (en) * | 1983-08-29 | 1989-04-25 | Chevron Research Company | Dispersed group VIB metal sulfide catalyst promoted with Group VIII metal |
US4839326A (en) * | 1985-04-22 | 1989-06-13 | Exxon Research And Engineering Company | Promoted molybdenum and tungsten sulfide catalysts, their preparation and use |
US5578197A (en) * | 1989-05-09 | 1996-11-26 | Alberta Oil Sands Technology & Research Authority | Hydrocracking process involving colloidal catalyst formed in situ |
US5372705A (en) * | 1992-03-02 | 1994-12-13 | Texaco Inc. | Hydroprocessing of heavy hydrocarbonaceous feeds |
JPH0790282A (ja) * | 1993-09-27 | 1995-04-04 | Asahi Chem Ind Co Ltd | 重質油分解・水素化処理方法 |
US5620591A (en) * | 1994-12-22 | 1997-04-15 | Exxon Research & Engineering Company | Hydroconversion process with plug-flow molybdenum catalyst concentrate preparation |
US5594945A (en) | 1995-02-14 | 1997-01-14 | Bellsouth Corporation | Method of providing registration reminder message to a roaming pager upon entry into a new service area |
EP2811006A1 (en) | 2004-04-28 | 2014-12-10 | Headwaters Heavy Oil, LLC | Ebullated bed hydroprocessing methods and systems and methods of upgrading an existing ebullated bed system |
US8034232B2 (en) * | 2007-10-31 | 2011-10-11 | Headwaters Technology Innovation, Llc | Methods for increasing catalyst concentration in heavy oil and/or coal resid hydrocracker |
US7931797B2 (en) * | 2009-07-21 | 2011-04-26 | Chevron U.S.A. Inc. | Systems and methods for producing a crude product |
-
2010
- 2010-07-06 EP EP10305744A patent/EP2404982A1/en not_active Withdrawn
-
2011
- 2011-07-05 WO PCT/EP2011/061284 patent/WO2012004246A2/en active Application Filing
- 2011-07-05 EP EP11741539.8A patent/EP2591077B1/en not_active Not-in-force
- 2011-07-05 AU AU2011275813A patent/AU2011275813B2/en not_active Ceased
- 2011-07-05 CN CN201180039143.8A patent/CN103080278B/zh not_active Expired - Fee Related
- 2011-07-05 KR KR1020137003198A patent/KR101893424B1/ko active IP Right Grant
- 2011-07-05 US US13/808,469 patent/US9233363B2/en not_active Expired - Fee Related
- 2011-07-05 JP JP2013517353A patent/JP5896536B2/ja not_active Expired - Fee Related
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4592827A (en) * | 1983-01-28 | 1986-06-03 | Intevep, S.A. | Hydroconversion of heavy crudes with high metal and asphaltene content in the presence of soluble metallic compounds and water |
US4770764A (en) * | 1983-03-19 | 1988-09-13 | Asahi Kasei Kogyo Kabushiki Kaisha | Process for converting heavy hydrocarbon into more valuable product |
CN1373008A (zh) * | 2001-02-28 | 2002-10-09 | 北京燕山石油化工公司研究院 | 茂金属催化剂及其制备方法、应用和选择加氢方法 |
CN101014411A (zh) * | 2004-09-10 | 2007-08-08 | 切夫里昂美国公司 | 高活性浆液催化剂组合物 |
CN101242898A (zh) * | 2005-07-11 | 2008-08-13 | 俄罗斯科学院西伯利亚分院格·克·巴类斯考夫催化研究院 | 催化剂、其制备方法以及使用所述催化剂对烃进行异构化的方法 |
CN101370582A (zh) * | 2006-01-06 | 2009-02-18 | 上游技术革新有限公司 | 烃溶性双金属催化剂前体及其制备方法 |
Non-Patent Citations (2)
Title |
---|
E. WOLFRUM, ET AL.: "einfluß eisen-und schwefelhaltiger katalysatoren auf die hydrierende verflüssigung von braunkohle", 《COMMISSION OF THE EUROPEAN COMMUNITIES》 * |
E. WOLFRUM, ET AL.: "einfluß eisen-und schwefelhaltiger katalysatoren auf die hydrierende verflüssigung von braunkohle", 《COMMISSION OF THE EUROPEAN COMMUNITIES》, 31 December 1984 (1984-12-31), pages 1 - 16 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111841630A (zh) * | 2020-06-24 | 2020-10-30 | 中国石油大学(华东) | 用于煤/重油加氢共炼的脂肪酸镍油溶性催化剂及其应用 |
Also Published As
Publication number | Publication date |
---|---|
US9233363B2 (en) | 2016-01-12 |
KR20130091326A (ko) | 2013-08-16 |
AU2011275813B2 (en) | 2015-08-13 |
WO2012004246A2 (en) | 2012-01-12 |
CN103080278B (zh) | 2016-03-16 |
JP2013535517A (ja) | 2013-09-12 |
KR101893424B1 (ko) | 2018-08-31 |
WO2012004246A3 (en) | 2012-04-12 |
EP2591077A2 (en) | 2013-05-15 |
AU2011275813A1 (en) | 2013-01-31 |
EP2591077B1 (en) | 2016-08-31 |
EP2404982A1 (en) | 2012-01-11 |
US20130193035A1 (en) | 2013-08-01 |
JP5896536B2 (ja) | 2016-03-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN111032833B (zh) | 使用再循环级间产物多级提质烃热解焦油 | |
CN103080279B (zh) | 重质烃类原料的加氢转化方法 | |
CN103097026B (zh) | 低品质烃类原料的加氢转化方法 | |
ES2797954T3 (es) | Sistema catalítico y proceso para la hidroconversión de productos de petróleo pesado | |
KR102622236B1 (ko) | 기회 공급원료와 함께 사용된 업그레이드된 에뷸레이티드 베드 반응기 | |
GB1576039A (en) | Hydroconversion of an oil-coal mixture | |
BRPI0715219A2 (pt) | processo para a conversço de cargas de alimentaÇço | |
CN108699451B (zh) | 具有增加的转化产物的生产率的升级的沸腾床反应器 | |
JP2018168352A (ja) | ファウリングが少ない堆積物を伴う改良された沸騰床リアクター | |
CN103080278B (zh) | 用于为反应器供料以改质重质烃类原料的得自催化剂前体的催化剂制备反应器 | |
CN109563416B (zh) | 用于沸腾床升级以生产改进质量的减压渣油产物的双催化剂体系 | |
JPH0762355A (ja) | 炭素質生成を抑制した重質油の水素化処理法 | |
CN112745946B (zh) | 一种加工重质原料油的方法和系统 | |
RU2672254C1 (ru) | Способ комплексной переработки остатка атмосферной дистилляции газового конденсата и установка для его осуществления | |
JP2000256675A (ja) | 重質油の水素化脱硫方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160316 Termination date: 20210705 |
|
CF01 | Termination of patent right due to non-payment of annual fee |