CN101676367A - 改进的加氢处理方法 - Google Patents
改进的加氢处理方法 Download PDFInfo
- Publication number
- CN101676367A CN101676367A CN200910169029A CN200910169029A CN101676367A CN 101676367 A CN101676367 A CN 101676367A CN 200910169029 A CN200910169029 A CN 200910169029A CN 200910169029 A CN200910169029 A CN 200910169029A CN 101676367 A CN101676367 A CN 101676367A
- Authority
- CN
- China
- Prior art keywords
- hydrogen
- water
- gas
- flow
- air
- 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
- 238000000034 method Methods 0.000 title claims abstract description 38
- 230000008569 process Effects 0.000 title claims abstract description 14
- 239000007789 gas Substances 0.000 claims abstract description 81
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 71
- 239000001257 hydrogen Substances 0.000 claims abstract description 70
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 63
- 229910001868 water Inorganic materials 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 35
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 35
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 35
- 239000000446 fuel Substances 0.000 claims abstract description 33
- 239000011368 organic material Substances 0.000 claims abstract description 24
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 34
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 26
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 26
- 239000003054 catalyst Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000002994 raw material Substances 0.000 claims description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 17
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 13
- 239000001569 carbon dioxide Substances 0.000 claims description 12
- 239000005864 Sulphur Substances 0.000 claims description 10
- 235000011089 carbon dioxide Nutrition 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 239000011593 sulfur Substances 0.000 claims description 8
- 238000006477 desulfuration reaction Methods 0.000 claims description 5
- 230000023556 desulfurization Effects 0.000 claims description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 34
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 23
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 19
- 235000019198 oils Nutrition 0.000 description 19
- 238000005406 washing Methods 0.000 description 11
- 150000001412 amines Chemical class 0.000 description 10
- 150000002431 hydrogen Chemical class 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 241000196324 Embryophyta Species 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000002283 diesel fuel Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000002551 biofuel Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000005194 fractionation Methods 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 235000019484 Rapeseed oil Nutrition 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
- 235000015278 beef Nutrition 0.000 description 3
- 230000008676 import Effects 0.000 description 3
- 230000005389 magnetism Effects 0.000 description 3
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 239000003760 tallow Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 235000013311 vegetables Nutrition 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000014121 butter Nutrition 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 235000019628 coolness Nutrition 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 description 2
- 150000002830 nitrogen compounds Chemical class 0.000 description 2
- 150000002898 organic sulfur compounds Chemical class 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 210000000582 semen Anatomy 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 206010000234 Abortion spontaneous Diseases 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001672694 Citrus reticulata Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- 208000005374 Poisoning Diseases 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000015241 bacon Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 208000015994 miscarriage Diseases 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 208000000995 spontaneous abortion Diseases 0.000 description 1
- PTISTKLWEJDJID-UHFFFAOYSA-N sulfanylidenemolybdenum Chemical compound [Mo]=S PTISTKLWEJDJID-UHFFFAOYSA-N 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000017105 transposition Effects 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
Classifications
-
- 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
- C10G49/007—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 in the presence of hydrogen from a special source or of a special composition or having been purified by a special treatment
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
- C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
-
- 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
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
-
- 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
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
- C10G3/45—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof
- C10G3/46—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof in combination with chromium, molybdenum, 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
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
- C10G3/52—Hydrogen in a special composition or from a special source
-
- 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
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/54—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed
-
- 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
- C10G45/24—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 with hydrogen-generating compounds
- C10G45/28—Organic compounds; Autofining
-
- 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
- C10G49/18—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 in the presence of hydrogen-generating compounds, e.g. ammonia, water, hydrogen sulfide
- C10G49/20—Organic compounds
-
- 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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/14—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including at least two different refining steps in the absence of hydrogen
-
- 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
- C10G2300/1011—Biomass
- C10G2300/1014—Biomass of vegetal origin
-
- 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
- C10G2300/207—Acid gases, e.g. H2S, COS, SO2, HCN
-
- 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
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4081—Recycling aspects
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/44—Solvents
-
- 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
- C10G2300/80—Additives
- C10G2300/805—Water
- C10G2300/807—Steam
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及燃料加氢处理的方法，并且在该方法的操作期间共产生氢气，该方法能够在加氢处理阶段补充氢气，即减少补充氢气的需要。导入加氢处理阶段的烃燃料是含可再生有机材料的燃料，该有机材料在该方法的操作期间产生一氧化碳。然后通过水煤气变换阶段，在循环回路中一氧化碳转化成氢气。
Description
技术领域
本发明涉及燃料的加氢处理方法，并且在该方法的操作期间共产生氢气。更特别是，本发明涉及其中烃燃料包含可再生有机材料的加氢处理方法，所述可再生有机材料在该方法的操作期间产生一氧化碳。然后，通过水煤气变换阶段，在循环回路中一氧化碳转化成氢气。
背景技术
在油料的精制期间，利用加氢处理阶段除去杂质例如硫和氮。烃原料且尤其是重烃，例如油和柴油通常包含有机硫和氮化合物，该有机硫和氮化合物在后续阶段代表不期望的杂质，因为它们对催化剂活性的负面影响。此外，环境条例强制要求制备非常低硫水平的非常清洁的运输燃料，例如低达10ppm总硫的柴油燃料。因此，在后续加氢处理阶段被处理之前，在加氢处理期间使硫和氮杂质氢化成硫化氢和氨，其中取决于所使用的烃原料，其价值可通过分子重排例如通过加氢裂解而增加。
在加氢处理方法中所需的氢气一般通过将烃燃料与在该方法中产生的富含氢气的循环气体混合，在方法内部提供。另外的氢气可以补充气体的形式从外部来源提供，该补充气体可以与在加氢处理方法中产生的富含氢气的循环气体组合。补充氢气用于补偿在加氢处理期间消耗的氢气。在通过与例如加氢脱硫(HDS)或加氢脱氮(HDN)催化剂的一个或多个固定床接触通过加氢处理阶段之后，将烃原料例如硫和氮贫化的油料或柴油导入热分离器，由此分离头馏分和底部馏分。然后，在进入冷分离器之前，使头馏分冷却并与水混合，其中以富含氢气的气流形式分离头馏分。然后，将该富含氢气的流再循环至加氢处理阶段，同时分离含清洁燃料的底部馏分，并准备用作例如运输燃料。
US-A-2002/004533描述了将变换反应器和加氢处理器集成的方法，其中来自加氢处理方法的富含氢气的再循环流与由合成气的水煤气变换产生的氢气组合，该合成气用独立的方法产生。
US 3,694,344描述了一种方法，其中用于加氢处理阶段的一部分氢气得自制备氢气的独立方法，包括将天然气重整，以制备合成气，随后通过水煤气变换，进一步转化成富含氢气的气体。
US 3,413,214公开了液态烃的氢化方法，其中为了诱导从加氢处理步骤产生含一氧化碳的气体产物，将氧气加入液态烃。接着，除尽气体产物中的硫化氢，然后经过水煤气变换，将气体中的一氧化碳转化成氢气。从水煤气变换得到的富含氢气的流再循环至加氢处理阶段。该另外氢气的制备减少了对外部来源氢气，例如作为补充氢气的需求。
发明内容
现在，我们已经发现，通过将部分由可再生有机材料组成的烃燃料加氢处理，在气体中即在该方法的操作期间，原位产生一氧化碳是可能的，因此与先有技术方法相比，能够更简单并相当安全地产生另外的氢气。因此，可使用可再生有机材料形式的有高度吸引力的替代燃料，而不采用高度危害性溶液，例如从外部来源注入氧，这另外需要专用的和非常昂贵的单独设备用于其制备，或分开的和非常昂贵的设备用于供给另外的氢气，例如重整装置用于制备含一氧化碳和氢气的合成气。
附图说明
唯一的图显示根据本发明特定实施方案的方法简化图，包括加氢处理阶段、相关的氢气循环回路、变换阶段和水加入。
具体实施方式
因此，我们提供烃燃料的加氢处理方法，所述方法包括步骤：
(a)通过将含可再生有机材料的烃燃料与氢气流组合，形成原料；
(b)通过使所述原料与至少一个加氢处理催化剂的固定床接触，使步骤(a)的原料进入加氢处理阶段；
(c)使步骤(b)的至少一个催化剂固定床的流出物通过热分离器，并从所述热分离器分离头馏分和底部馏分；
(d)使步骤(c)的头馏分进入水煤气变换阶段；
(e)使步骤(d)的流出物通过冷分离器，并从所述冷分离器分离气态头馏分，该气态头馏分为富含氢气的循环气流形式；
(f)使步骤(e)的气态头馏分通过硫化氢回收装置，其中溶剂与所述气流接触，并从所述回收装置分离硫化氢和二氧化碳含量降低的气流，从所述回收装置分离含硫化氢和二氧化碳的溶剂；
(g)使步骤(f)中硫化氢和二氧化碳含量降低的气流返回至步骤(a)，
或
通过将所述气流分成至少两个流，并将这些流中至少一个返回至步骤(a)，和将这些流中至少一个返回至步骤(d)，来将步骤(f)中硫化氢和二氧化碳含量降低的一部分气流返回至步骤(a)。
优选，步骤(g)包括将所述气流分成两个流，并使这些流之一返回至步骤(a)，使这些流之一返回至步骤(d)。
当用于本文时，术语“可再生有机材料”定义为植物油、动物脂、塔尔油和衍生的材料例如脂肪酸烷基酯，尤其是脂肪酸甲酯(FAME)-也称为生物柴油或其组合。所有这些代表可再生源。植物油包括菜籽油、大豆油、玉米油、椰子油、棕榈油和棉籽油。动物脂包括咸肉油、黄油、猪油、奶油和牛油。
当用于本文时，术语“热分离器”和“冷分离器”定义为常规的分馏装置。
通过按照本发明的方法，处理含可再生有机材料的烃燃料，将原位产生的一氧化碳和水转化成CO2和H2是可能的，因此能够除去产生的CO和H2O，否则该CO和H2O可以抑制加氢处理装置中的催化剂活性，并且也因为对再循环气流中允许的杂质浓度的操作限制，而限制其催化能力。因此，可制备完全或部分基于再生源的柴油形式的有高度吸引力的可替代燃料，而没有被迫限制生产能力或采用非常高的吹扫速率，否则这是限制污染物例如一氧化碳的含量所必需的，而且其对于在硫化氢回收装置，例如胺洗涤装置中除去具有非常低的亲和力。
步骤(a)的氢气流是氢气循环气流、氢气补充气体或两者的组合。
在本发明的一个实施方案中，在烃燃料中可再生有机材料的含量为至少5％体积，优选至少20％体积，更优选至少50％体积。烃燃料中的其它组分可能是常规的化石石油柴油。烃燃料中可再生有机材料的水平在5％体积以上时，产生的一氧化碳达到使水煤气变换阶段的供应有利的水平。最优选，烃燃料包含至少75％体积的可再生有机材料，尤其是至少75％体积的生物柴油。
术语“加氢处理”包括一系列需要氢气存在的方法，即氢化、加氢裂解、芳烃加氢(HDA)、加氢脱硫(HDS)和加氢脱氮(HDN)。在本发明中，加氢处理步骤优选为加氢脱硫(HDS)和/或加氢脱氮(HDN)步骤。
加氢处理条件涉及在200-500℃之间的温度下和最高达200巴的压力下正常地操作。用于加氢处理步骤的催化剂优选常规使用的那些，例如负载在氧化铝上的混合的钴和/或镍和钼硫化物和负载在氧化铝或二氧化硅上的混合的镍和钨硫化物。其它合适的催化剂包括包含硫化钌的那些和使用新载体例如二氧化硅-氧化铝、碳或其它材料的催化剂。
在加氢处理阶段期间，可再生有机材料与氢气反应，形成在柴油沸程的烃、一氧化碳、二氧化碳、水、甲烷和丙烷的混合物。因为气相包含贵重的未反应的氢气，所以它通常在净化之后再循环至加氢处理阶段。照惯例，气体净化阶段包括通过胺洗涤装置的气体洗涤，该胺洗涤装置除去CO2和H2S，但对CO的除去具有低亲和力。因此，一氧化碳在循环气体回路中积聚，除非将显著量的吹扫用气体排出，并送去燃烧，或用于另一个处理装置。如果循环气体中的CO水平变得太高，那么加氢处理器中的催化剂活性降低，且氢分压降低。这也传送了可再生有机材料在烃燃料中的量必须保持低至5％体积的问题。因为吹扫用气体含高的氢气量，因此吹扫越高表示也需要越高流量的昂贵高纯度补充氢气。
通过本发明，用高含量的可再生有机材料使加氢处理器运行是可能的，且同时，在富含氢气的再循环流中获得提高含量的氢气，从而也减少通过外部来源加入非常昂贵的氢气的需要是可能的。
来自加氢处理阶段的流出物通过热分离器(分馏装置)，其中气态产物作为轻的头馏分分离。少量的硫化氢可能还存在于该流中，其对常规的水煤气变换催化剂有毒，其中一氧化碳与水可逆地反应，以产生氢气和二氧化碳。因此，优选水煤气变换阶段是含硫-变换(sour-shift)阶段，该阶段包含抗硫催化剂例如钴-钼催化剂。
或者，在使其通过常规水煤气变换阶段之前，可将来自热分离器的气态头馏分洗涤，以除去硫化氢。因此，本发明还包括使步骤(c)的气态头馏分通过硫化氢回收装置，其中溶剂与所述气流接触，并从所述回收装置分离硫化氢和二氧化碳含量降低的气流，从所述回收装置分离含硫化氢和二氧化碳的溶剂。然后，使气流进入水煤气变换阶段。当用于本文时，溶剂为对硫化氢具有亲合力的物质，例如胺。
水煤气变换阶段选自低水煤气变换、中水煤气变换、高水煤气变换及其组合。为了利用以下变换反应的放热性：CO+H2O＝H2+CO2，其中在低温下有利于氢气的产生，但另一方面反应速率慢，可连续进行高温和低温变换。在特定的实施方案中，其中已经从气体中除去硫化氢，水煤气变换是用例如铁-铜基催化剂，在350-500℃下进行的高温水煤气变换。
在变换阶段期间，为了确保至少化学计量量的一氧化碳和水，可在进行所述变换阶段之前，将流加入气流(步骤(c)中热分离器的头馏分)或所述硫化氢和二氧化碳含量降低的气流中。按该方式，因为促使反应向氢气侧进行，所以存在于气体中的所有一氧化碳均用于氢气产生的变换反应。
在水煤气变换阶段之后，氢气富集的气体在冷却并与水混合之后，通过冷分离器(分馏装置)。从该装置分离富含氢气的再循环流形式的气态头馏分，以及含无硫生物柴油的烃液流形式的底部馏分，并任选也分离含硫水流，该含硫水流含例如通过除去一些氨和硫化氢引起的硫酸氢铵。
优选，在其中溶剂为胺的洗涤装置中，将来自冷分离器的气态头馏分洗涤。因此，为了将任何留下的一氧化碳转化成二氧化碳，可将获得的硫化氢和二氧化碳含量降低的气态流出物流部分地再循环至水煤气变换转换器，或可以将它全部返回至加氢处理阶段。因此，通过将所述气流分成至少两个流，并将这些流中至少一个返回加氢处理阶段，将这些流中至少一个返回水煤气变换阶段，来将步骤(f)的硫化氢和二氧化碳含量降低的一部分气流返回步骤(d)(水煤气变换阶段)。
来自胺洗涤装置的气流现在代表纯化的气体流出物，用作加氢处理反应器的氢气再循环流，并任选用作在所述反应器的催化床之间的骤冷气。
不需要在常规的加氢处理条件下将水加入加氢处理装置。已知加氢处理催化剂的催化活性与负载在氧化铝、二氧化硅、二氧化钛、沸石Y或其组合上的以下物质的硫化物存在有关：VI-B和VIII族元素例如Co、Mo、Ni、W，尤其是Co-Mo、Ni-Mo和Ni-W的混合物。如果催化剂未完全硫化，那么其活性急剧地下降。由于硫化催化剂转回至它们的氧化状态，并伴随催化活性损失的风险，因此在加氢处理中通常避免水的存在。
我们也已经发现，常规的加氢处理催化剂能够在加氢处理阶段建立水煤气变换反应的接近热力学平衡，并且还通过将水加入加氢处理阶段，使水煤气变换反应的平衡甚至更多地向二氧化碳和氢气方向移动，而没有影响催化剂的加氢脱硫或加氢脱氮能力。
因此，在本发明的还另一个实施方案中，以所述烃燃料的0.1-10％重量的量，将水加入步骤(a)的原料中，和/或加入步骤(b)的一个或多个加氢处理催化剂的固定床。
加入加氢处理阶段的水量取决于烃燃料中的可再生有机材料含量。可再生有机材料的含量越高，加入的水量就越高。对于含最高达约20％体积的可再生有机材料的烃燃料，加入的水量优选在烃燃料的1-8％重量范围内，更优选在2-4％重量范围内。对于含100％可再生有机材料的烃燃料，加入的水量可以高达10％重量。
在贵重的氢气消耗下，不加水，原位形成的一氧化碳至少部分转化成甲烷。通过将水加入加氢处理阶段，甲烷形成被抑制，并因此减少相关的贵重的氢气消耗。此外，可能获得较低的CO/CO2比率，因此，由于在加氢处理器中存在一氧化碳，催化剂中毒的风险较小。也可以将水直接加入一个或多个加氢处理催化剂的固定床。
此外，通过简单地加入水，通过加氢处理阶段的烃燃料中可再生有机材料，优选生物柴油的量可以显著地增加，例如从约5％体积的可再生有机材料增加至10％体积或20％体积或甚至更多，例如30％体积或甚至100％体积的生物柴油。仅在可再生有机材料在原料中的水平最高达约5％体积时，才可能不变换和/或加入水来操作加氢处理方法。烃燃料中的其它组分可为常规的油馏分，例如轻瓦斯油、轻循环油、焦化瓦斯油或真空瓦斯油(VGO)。
在本发明的还另一个实施方案中，将水加入原料中，也加入一个或多个加氢处理催化剂的固定床。
在与氢气再循环流2混合形成流3之后，将含可再生有机材料的原料流1预热(未显示)，并导入加氢处理反应器10。将流3进一步加热(未显示)，并送至加氢处理反应器10的至少一个催化床11。从反应器10分离流出物4，该流出物4含产物柴油、硫化氢、氨、二氧化碳、一氧化碳、水和其它轻质烃，然后通过流产生或进料预热，经热交换器12冷却。然后将冷却的流出物导入热分离器(分馏装置)13，在此分离底部馏分5，同时作为头馏分6回收较轻的组分，该较轻的组分含一氧化碳、二氧化碳、硫化氢、氨、水和其它轻质烃。该头馏分经通过含硫水煤气变换转换器14被送至氢气回收装置，该转换器14其中安排含硫变换催化剂15的固定床。在含硫变换阶段上游加入流7，以确保一氧化碳完全反应成氢气。通过流产生或过程交换(未显示)，将来自变换转换器的流出物8冷却，并导入冷分离器(分馏装置)16。从冷分离器分离富含氢气的头馏分并通过胺洗涤装置18。将来自胺洗涤装置18的纯化气体流出物2部分地用作加氢处理反应器10的氢气再循环流，并任选用作催化床11之间的骤冷气。使流2的一部分作为流19再循环至水煤气变换转换器14，以确保完全除去一氧化碳。将水作为流21加入烃原料3，和作为流22、23加入加氢处理催化剂11的一个或多个固定床。然后，使底部馏分9从含产物柴油的冷分离器16分离，进一步用作清洁的可再生运输燃料。
实施例1
原料A(表1)是20％体积的菜籽油和80％体积的真空瓦斯油的混合物。将纯真空瓦斯油表示为原料B。使用105ml的加氢处理催化剂(浸渍在氧化铝载体上的Ni和Mo)，将原料A在直流式中试设备中加氢处理。原料A的流量为105ml/小时，对应于1hr-1的LHSV。将80巴压力下的100％氢气(不再循环)与73.5 Nl/小时速率的液流共进料，对应于700 Nl/l的H2/油比率。将反应器的温度维持在350℃。从液体流出物取产物样品。从反应器排出的气体通过气相色谱法分析。
表1
基于油和氢气的流量、液体产物分析和出口气体组成，制作表2，其显示产率(表达为(g产物/g液体进料)×100％)和基于体积的气体组成。
表2
可以从表2观察到，与处理不含或仅含痕量氧的纯烃原料相比，当处理原料B时，主要的区别是在气相产物中出现CO、CO2和H2O，以及增加产率的CH4和C3H8。C3H8产率的增加在实验误差范围内，与菜籽油中甘油三酸酯的完全转化一致。在该实施例和以下实施例中测量的HDS转化率均为约96-97％。
该实施例显示，当处理含氧的原料例如植物油和/或动物脂时，形成相当量的CO、CO2和H2O。而且，CH4的高产率表明，形成的CO部分转化成CH4，因此消耗贵重的氢气。
对于理想气体混合物，可将水煤气变换反应的平衡常数KP写为：
KP＝(yCO2yH2)/(yCO yH2O)，
其中yX表示化合物X(X＝CO2、H2、CO2、H2O)的体积气相浓度。在350℃下，KP的理论值是20.7。从实验数据计算得到17.6的值，非常接近理论平衡值。因此该实施例也显示，加氢处理催化剂在建立水煤气变换反应的热力学平衡中有效。
实施例2
使用与在实施例1中相同的催化剂和条件(温度＝350℃、压力＝80巴(barg)、LHSV＝1hr-1、H2/油＝700Nl/l)，处理实施例1的原料A，然而，在它进入反应器之前将H2O加入进料中。分别用2.1g H2O/小时和4.2g H2O/小时进行两个实验。这些水流量对应于原料A的2.0％体积和4.0％体积的质量流量。结果显示于表3，产率基于新鲜原料(H2O除外)的流量计算。
表3
在这些试验中，硫和氮的转化率与在实施例1中所观察到的相似。对于用原料A，有或没有水注入的所有实验，在实施例1和实施例2中CO、CO2和CH4的总摩尔产率在5％内恒定。这证明，由菜籽油脱羧基形成的CO和CO2将仅反应形成CH4，而不形成任何其它化合物。当注入H2O时，CH4的产率下降，意味着较少的CO和CO2转化成CH4。CH4的形成和有关的氢气消耗没有吸引力，该实施例显示其可以通过注入H2O来抑制。
此外，H2O的注入也使水煤气变换反应的平衡向CO2和H2方向移动。从表3可见，水煤气变换反应的KP观测值(16.3和16.9)接近热力学平衡值(20.7)，并接近实施例1中的观测值(17.6)，意味着在建立水煤气变换反应的平衡中，催化剂仍然有效，在将H2O加入进料的情况下同样如此。因此，CO/CO2摩尔比从不加入H2O时的1.5(实施例1)减少至0.77(加入2.1g H2O/小时)和0.49(加入4.2g H2O/小时)。而且，出口气体中CO的绝对水平从0.48％体积减少至0.37％体积(加入2.1g H2O/小时)和0.29％体积(加入4.2g H2O/小时)。当流出气体再循环至反应器的入口时，CO和CO2将在循环气体回路中积聚，如果没采取预防该情况的措施的话。因为CO和CO2可抑制催化剂活性，因此最好例如通过胺洗涤步骤，从处理气体中除去CO2。胺洗涤不除去CO，但该实施例证明，通过注入H2O，可以实现在处理气体中较低的CO水平，而无需另外的氢气消耗。
当较高量的H2O存在于反应器时，水煤气变换反应向CO2和H2方向移动。另外，CO至CH4的甲烷化反应被抑制。与其中在无H2O存在的情况下处理原料A的实施例1(H2消耗148 Nl/l)比较，当注入H2O时，这些作用导致较低的氢气消耗(141和140 Nl/l)。因此，本发明实施例证明，通过注入H2O，可以降低总的氢气消耗。
Claims (9)
1.一种用于烃燃料加氢处理的方法，所述方法包括步骤：
(a)通过将含可再生有机材料的烃燃料与氢气流组合，形成原料；
(b)通过使所述原料与至少一个加氢处理催化剂的固定床接触，使步骤(a)的原料进入加氢处理阶段；
(c)使步骤(b)的至少一个催化剂固定床的流出物通过热分离器，并从所述热分离器分离头馏分和底部馏分；
(d)使步骤(c)的头馏分进入水煤气变换阶段；
(e)使步骤(d)的流出物通过冷分离器，并从所述冷分离器分离气态头馏分，该气态头馏分为富含氢气的循环气流形式；
(f)使步骤(e)的气态头馏分通过硫化氢回收装置，其中溶剂与所述气流接触，并从所述回收装置分离硫化氢和二氧化碳含量降低的气流，从所述回收装置分离含硫化氢和二氧化碳的溶剂；
(g)使步骤(f)中硫化氢和二氧化碳含量降低的气流返回至步骤(a)，或
通过将所述气流分成至少两个流，并将这些流中至少一个返回至步骤(a)，和将这些流中至少一个返回至步骤(d)，来将步骤(f)中硫化氢和二氧化碳含量降低的一部分气流返回至步骤(a)。
2.权利要求1的方法，其中步骤(a)的氢气流是氢气循环气流、氢气补充气体或两者的组合。
3.权利要求1或2的方法，其中所述烃燃料中可再生有机材料的含量为至少5％体积。
4.权利要求1-3中任一项的方法，其中所述加氢处理步骤是加氢脱硫(HDS)和/或加氢脱氮(HDN)步骤。
5.权利要求1-4中任一项的方法，其中所述水煤气变换阶段是含硫-变换阶段。
6.权利要求1的方法，所述方法还包括使步骤(c)的所述气态头馏分通过硫化氢回收装置，其中溶剂与所述气流接触，并从所述回收装置分离硫化氢和二氧化碳含量降低的气流，并从所述回收装置分离含硫化氢和二氧化碳的溶剂。
7.权利要求1-6中任一项的方法，其中所述水煤气变换阶段选自低水煤气变换、中水煤气变换、高水煤气变换及其组合。
8.权利要求1-7中任一项的方法，其中在进行所述水煤气变换阶段之前，将流加入步骤(c)的所述头馏分或所述硫化氢和二氧化碳含量降低的气流中。
9.权利要求1-8中任一项的方法，其中以所述烃燃料的0.1-10％重量的量，将水加入步骤(a)的原料中，和/或加入步骤(b)的一个或多个加氢处理催化剂的固定床中。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DKPA200801268 | 2008-09-10 | ||
| DKPA200801268 | 2008-09-10 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101676367A true CN101676367A (zh) | 2010-03-24 |
| CN101676367B CN101676367B (zh) | 2013-11-27 |
Family
ID=41582100
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009101690291A Expired - Fee Related CN101676367B (zh) | 2008-09-10 | 2009-09-04 | 改进的加氢处理方法 |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US8043600B2 (zh) |
| EP (1) | EP2165971B1 (zh) |
| KR (1) | KR101430508B1 (zh) |
| CN (1) | CN101676367B (zh) |
| AR (1) | AR073557A1 (zh) |
| AU (1) | AU2009213001B2 (zh) |
| BR (1) | BRPI0903362B1 (zh) |
| CA (1) | CA2678283C (zh) |
| ES (1) | ES2602332T3 (zh) |
| MX (1) | MX2009009618A (zh) |
| PT (1) | PT2165971T (zh) |
| RU (1) | RU2517185C2 (zh) |
| ZA (1) | ZA200906218B (zh) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102433153A (zh) * | 2011-10-21 | 2012-05-02 | 华东理工大学 | 一种生物油的精制方法 |
| WO2018058954A1 (zh) * | 2016-09-30 | 2018-04-05 | 南京康鑫成生物科技有限公司 | 一种废油脂直接制备正异构烷烃的方法 |
| CN115243997A (zh) * | 2020-03-13 | 2022-10-25 | 托普索公司 | 以减少的co2足迹和改善的氢集成生产烃的方法和设备 |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0919385D0 (en) * | 2009-11-05 | 2009-12-23 | Johnson Matthey Plc | Process |
| AU2011352020A1 (en) * | 2010-12-30 | 2013-06-27 | Kior Inc. | Production of renewable biofuels |
| FI126203B (fi) * | 2011-07-06 | 2016-08-15 | Upm Kymmene Corp | Menetelmä hiilivetykomponenttien valmistamiseksi |
| FR2994191B1 (fr) * | 2012-08-02 | 2015-06-05 | IFP Energies Nouvelles | Procede d'hydrotraitement et d'hydroisomerisation de charges issues de la biomasse dans lequel l'effluent a hydrotraiter et le flux d'hydrogene contiennent une teneur limitee en monoxyde de carbone |
| US20140336428A1 (en) * | 2013-05-10 | 2014-11-13 | Uop Llc | Recycle gas scrubbing using ionic liquids |
| US9752085B2 (en) | 2013-06-20 | 2017-09-05 | Uop Llc | Process and apparatus for producing diesel from a hydrocarbon stream |
| US8999256B2 (en) | 2013-06-20 | 2015-04-07 | Uop Llc | Process and apparatus for producing diesel from a hydrocarbon stream |
| TW201602336A (zh) | 2014-06-09 | 2016-01-16 | Ｗ Ｒ 康格雷氏公司 | 天然油及脂之催化脫氧方法 |
| US9617484B2 (en) | 2014-06-09 | 2017-04-11 | Uop Llc | Methods and apparatuses for hydrotreating hydrocarbons |
| DK201600005A1 (en) * | 2016-01-06 | 2016-12-19 | Haldor Topsoe As | Process for production of a hydrogen rich gas |
| US20210403814A1 (en) * | 2020-06-29 | 2021-12-30 | Uop Llc | Integrated process for hydrotreating a renewable feedstock with improved carbon monoxide management |
| BR102021015852A2 (pt) | 2021-08-11 | 2023-02-14 | Petróleo Brasileiro S.A. - Petrobras | Processo para produção integrada de h2 e querosene de aviação a partir de matéria-prima renovável |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3413214A (en) * | 1965-12-20 | 1968-11-26 | Cities Service Res & Dev Co | Hydrogenation process |
| US3552924A (en) | 1966-08-15 | 1971-01-05 | Phillips Petroleum Co | Hydrogen manufacture |
| US3694344A (en) | 1970-09-24 | 1972-09-26 | William H Munro | Hydroprocessing of hydrocarbons |
| US3708569A (en) * | 1970-12-17 | 1973-01-02 | Cities Service Res & Dev Co | Burning unconverted h-oil residual |
| JP2966985B2 (ja) * | 1991-10-09 | 1999-10-25 | 出光興産株式会社 | 重質炭化水素油の接触水素化処理方法 |
| US5447621A (en) * | 1994-01-27 | 1995-09-05 | The M. W. Kellogg Company | Integrated process for upgrading middle distillate production |
| US6294079B1 (en) * | 1999-10-21 | 2001-09-25 | Uop Llc | High severity, low conversion hydrocracking process |
| WO2001056922A1 (en) | 2000-02-01 | 2001-08-09 | Texaco Development Corporation | Integration of shift reactors and hydrotreaters |
| US7422679B2 (en) * | 2002-05-28 | 2008-09-09 | Exxonmobil Research And Engineering Company | Low CO for increased naphtha desulfurization |
| BRPI0500591A (pt) | 2005-02-18 | 2006-10-03 | Petroleo Brasileiro Sa | processo para a hidroconversão de óleos vegetais |
| CA2614020C (en) * | 2005-07-04 | 2014-02-11 | Neste Oil Oyj | Process for the manufacture of diesel range hydrocarbons |
| CN100526432C (zh) * | 2006-01-19 | 2009-08-12 | 中国石油化工股份有限公司 | 控制加氢装置循环氢中硫化氢浓度的方法 |
| FR2904324B1 (fr) * | 2006-07-27 | 2012-09-07 | Total France | Procede d'hydrotraitement d'une charge gazole, reacteur d'hydrotraitement pour la mise en oeuvre dudit procede, et unite d'hydroraffinage correspondante. |
| EP1911734A1 (en) | 2006-10-06 | 2008-04-16 | Bp Oil International Limited | Process for hydrogenation of carboxylic acids and derivatives to hydrocarbons |
| FR2910485B1 (fr) * | 2006-12-22 | 2009-03-06 | Inst Francais Du Petrole | Procedes d'hydrotraitement d'un melange constitue d'huiles d'origine animale ou vegetale et de coupes petrolieres avec stripage intermediaire |
-
2009
- 2009-07-29 ES ES09009780.9T patent/ES2602332T3/es active Active
- 2009-07-29 PT PT90097809T patent/PT2165971T/pt unknown
- 2009-07-29 EP EP09009780.9A patent/EP2165971B1/en not_active Not-in-force
- 2009-08-11 US US12/539,491 patent/US8043600B2/en not_active Expired - Fee Related
- 2009-09-04 CN CN2009101690291A patent/CN101676367B/zh not_active Expired - Fee Related
- 2009-09-04 BR BRPI0903362-9A patent/BRPI0903362B1/pt not_active IP Right Cessation
- 2009-09-08 ZA ZA200906218A patent/ZA200906218B/en unknown
- 2009-09-08 KR KR1020090084620A patent/KR101430508B1/ko active IP Right Grant
- 2009-09-08 AU AU2009213001A patent/AU2009213001B2/en not_active Ceased
- 2009-09-09 AR ARP090103449A patent/AR073557A1/es not_active Application Discontinuation
- 2009-09-09 RU RU2009133698/04A patent/RU2517185C2/ru active
- 2009-09-09 CA CA2678283A patent/CA2678283C/en not_active Expired - Fee Related
- 2009-09-09 MX MX2009009618A patent/MX2009009618A/es active IP Right Grant
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102433153A (zh) * | 2011-10-21 | 2012-05-02 | 华东理工大学 | 一种生物油的精制方法 |
| WO2018058954A1 (zh) * | 2016-09-30 | 2018-04-05 | 南京康鑫成生物科技有限公司 | 一种废油脂直接制备正异构烷烃的方法 |
| CN115243997A (zh) * | 2020-03-13 | 2022-10-25 | 托普索公司 | 以减少的co2足迹和改善的氢集成生产烃的方法和设备 |
Also Published As
| Publication number | Publication date |
|---|---|
| AR073557A1 (es) | 2010-11-17 |
| EP2165971A3 (en) | 2012-09-19 |
| EP2165971A2 (en) | 2010-03-24 |
| RU2009133698A (ru) | 2011-03-20 |
| RU2517185C2 (ru) | 2014-05-27 |
| ZA200906218B (en) | 2010-06-30 |
| AU2009213001B2 (en) | 2013-08-29 |
| PT2165971T (pt) | 2016-11-16 |
| EP2165971B1 (en) | 2016-09-07 |
| BRPI0903362B1 (pt) | 2017-06-20 |
| ES2602332T3 (es) | 2017-02-20 |
| CA2678283C (en) | 2015-01-27 |
| US20100061927A1 (en) | 2010-03-11 |
| BRPI0903362A2 (pt) | 2011-05-31 |
| US8043600B2 (en) | 2011-10-25 |
| CA2678283A1 (en) | 2010-03-10 |
| MX2009009618A (es) | 2010-03-09 |
| AU2009213001A1 (en) | 2010-03-25 |
| KR101430508B1 (ko) | 2014-08-18 |
| CN101676367B (zh) | 2013-11-27 |
| KR20100030595A (ko) | 2010-03-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101676367B (zh) | 改进的加氢处理方法 | |
| Basile et al. | Methanol: science and engineering | |
| CN101210198B (zh) | 一种生产优质柴油和优质重整原料的加氢方法 | |
| CN102159671B (zh) | 烃油的制造方法 | |
| CA2728813C (en) | A process for producing paraffinic hydrocarbons | |
| CN101778928A (zh) | 通过植物油加氢处理制成的具有高乙烯、丙烯和聚合物收率的蒸汽裂化原料的生产 | |
| WO2009007061A1 (en) | Process to produce a methane rich gas mixture from gasification derived sulphur containing synthesis gases | |
| CN101684415A (zh) | 一种低成本最大量生产化工原料的加氢裂化方法 | |
| CN101448924B (zh) | 加氢精制方法 | |
| WO2010049075A2 (en) | Improved hydrotreatment of renewable organic material | |
| US8962905B2 (en) | Process for the continuous hydrogenation of triglyceride containing raw materials using a nickel and molybdenum-based catalyst | |
| BR102021013284A2 (pt) | Processo de hidrorrefinamento de matérias-primas biológicas | |
| CN105001899A (zh) | 清洁煤基合成制蜡的方法 | |
| WO2010143980A1 (en) | A process for integration of a methanol plant and an oil hydroprocessing plant | |
| US11248182B1 (en) | Reduction of SOx and NOx emissions from renewable diesel plants | |
| US20230416614A1 (en) | Process for treating offgas from hydrotreating of renewable feedstocks | |
| KR20220030946A (ko) | 저압 분리기로부터의 액체 재순환이 있는 옥시게네이트 공급원료의 수소화처리 | |
| AU2022375041A1 (en) | A process for hydrotreatment of aromatic nitrogen compounds | |
| CN101337656A (zh) | 焦炉煤气转化氢气,和在焦炉煤气转化油中的应用技术 |
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: 20131127 Termination date: 20210904 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |