CN104884735A - 从含烃沉积物回收的含硫烃类的处理 - Google Patents
从含烃沉积物回收的含硫烃类的处理 Download PDFInfo
- Publication number
- CN104884735A CN104884735A CN201380069062.1A CN201380069062A CN104884735A CN 104884735 A CN104884735 A CN 104884735A CN 201380069062 A CN201380069062 A CN 201380069062A CN 104884735 A CN104884735 A CN 104884735A
- Authority
- CN
- China
- Prior art keywords
- oil
- mercaptan
- gas
- hydrogen sulfide
- poor
- 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
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 88
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 88
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims description 45
- 229910052717 sulfur Inorganic materials 0.000 title claims description 33
- 239000011593 sulfur Substances 0.000 title claims description 33
- 238000000034 method Methods 0.000 claims abstract description 109
- 239000007788 liquid Substances 0.000 claims abstract description 57
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 44
- 230000008569 process Effects 0.000 claims abstract description 42
- 239000002737 fuel gas Substances 0.000 claims abstract description 20
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003085 diluting agent Substances 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 58
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 54
- 239000000203 mixture Substances 0.000 claims description 54
- 239000004215 Carbon black (E152) Substances 0.000 claims description 49
- 239000003518 caustics Substances 0.000 claims description 38
- 238000010796 Steam-assisted gravity drainage Methods 0.000 claims description 19
- 239000003513 alkali Substances 0.000 claims description 18
- 238000012545 processing Methods 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 230000008929 regeneration Effects 0.000 claims description 8
- 238000011069 regeneration method Methods 0.000 claims description 8
- 239000003027 oil sand Substances 0.000 claims description 7
- 239000010426 asphalt Substances 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 4
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical compound OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000012546 transfer Methods 0.000 claims description 4
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims 4
- 239000006193 liquid solution Substances 0.000 claims 2
- AMRUKLMZDPPJNU-IOLLQWDPSA-N (2-hydroxy-3-octadecanoyloxypropyl) (5e,8e,11e,14e)-icosa-5,8,11,14-tetraenoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)COC(=O)CCC\C=C\C\C=C\C\C=C\C\C=C\CCCCC AMRUKLMZDPPJNU-IOLLQWDPSA-N 0.000 claims 1
- 238000004821 distillation Methods 0.000 claims 1
- 238000005194 fractionation Methods 0.000 claims 1
- 238000002203 pretreatment Methods 0.000 claims 1
- 239000003921 oil Substances 0.000 abstract description 58
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 27
- 239000000047 product Substances 0.000 description 18
- 239000005864 Sulphur Substances 0.000 description 13
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000006096 absorbing agent Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- -1 sulphur compound Chemical class 0.000 description 6
- 238000013461 design Methods 0.000 description 5
- 239000004058 oil shale Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000003350 kerosene Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
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- 230000000717 retained effect Effects 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 3
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- ZRKMQKLGEQPLNS-UHFFFAOYSA-N 1-Pentanethiol Chemical compound CCCCCS ZRKMQKLGEQPLNS-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- 238000010795 Steam Flooding Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229920003240 metallophthalocyanine polymer Polymers 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- KJRCEJOSASVSRA-UHFFFAOYSA-N propane-2-thiol Chemical compound CC(C)S KJRCEJOSASVSRA-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
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- 238000003756 stirring Methods 0.000 description 2
- 238000010977 unit operation Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 241001074085 Scophthalmus aquosus Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000010793 Steam injection (oil industry) Methods 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000029142 excretion Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
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- 239000013067 intermediate product Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
- E21B43/24—Enhanced recovery methods for obtaining hydrocarbons using heat, e.g. steam injection
-
- 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
- C10G19/00—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
- C10G19/08—Recovery of used refining agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1425—Regeneration of liquid absorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1456—Removing acid components
- B01D53/1468—Removing hydrogen sulfide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1456—Removing acid components
- B01D53/1481—Removing sulfur dioxide or sulfur trioxide
-
- 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
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
-
- 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
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
-
- 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
- C10G19/00—Refining hydrocarbon oils in the absence of hydrogen, by alkaline 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
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
- C10G21/12—Organic compounds only
- C10G21/14—Hydrocarbons
-
- 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
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/28—Recovery of used solvent
-
- 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
- C10G7/00—Distillation of hydrocarbon oils
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/20—Organic absorbents
- B01D2252/205—Other organic compounds not covered by B01D2252/00 - B01D2252/20494
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/24—Hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/304—Hydrogen sulfide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/306—Organic sulfur compounds, e.g. mercaptans
-
- 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
-
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Abstract
在用以处理从含烃沉积物原位回收液体烃类所获得的气体组份的方法中,使用贫油将硫醇和硫化氢彼此分离,且所述硫化氢进一步经加工以获得不含硫的燃料气产物。在处理所述气体组份后所获得的富油可与所述液体烃类一起用作稀释剂,或经加工以去除所述硫醇并将其转化成二硫化物油。
Description
技术领域
本发明涉及处理和加工从含烃地质材料获得的液体、半固体和气体烃类的方法和装置,所述含烃地质材料包括焦油砂、油砂、油砂岩和油页岩。具体而言,本发明涉及去除在从诸如蒸汽辅助重力泄油(SAGD)工艺等工艺获得的气体烃类中所发现的硫污染物的方法。
背景技术
本文中所使用的含烃沉积物应视为包括焦油砂、油砂、油砂岩、油页岩和具有在通常多孔的岩石类无机基质内所含的烃类的所有其它天然存在的地质材料。基质可为松散的、易碎的或坚硬的。
焦油砂是在(例如)加拿大(亚伯达)(Canada(Alberta))发现的天然存在的地质层。所述砂具有产生大量石油的潜力。焦油砂为多孔的,通常为松散的或易碎的,且通常含有大量粘土,且具有填充有业内常称为沥青的高粘度烃类的间隙。这些类焦油沥青材料中的大部分是在较轻(较低分子量)烃类已逸出或通过微生物的作用、水洗且可能地无机氧化降解后所保留的残余物。极广泛的焦油砂沉积物存在于沿亚大巴斯卡河(Athabasca River)的北亚伯达和其它地方。估计所述沉积物含有超过1.6万亿桶油的潜在产量。
油页岩与油砂和焦油砂有关;然而,基质是通常含有产油类的有机化合物(称为油母质)的细粒层压沉积岩。油页岩存在于全世界许多地方。特定而言,富含油母质的页岩存在于美国(United States)的怀俄明州(Wyoming)、科罗拉多州(Colorado)和犹他州(Utah),且估计含有超过5400亿桶潜在的石油。
可从焦油砂和油页岩回收的烃类可包含(但不限于)沥青、油母质、沥青质、石蜡、烷烃、芳香族烃、烯烃、萘类和二甲苯类。
在从含烃沉积物回收石油的已知技术中,高分子量的沥青或油母质材料可利用热从砂、砂岩或页岩驱出。例如,在蒸汽辅助重力泄油(SAGD)工艺中,在地层中钻两个平行的水平油井,一个油井高出另一个油井约4米到6米。上部油井注入蒸汽,且下部油井收集流出地层的经加热原油或沥青以及来自所注入蒸汽的冷凝的任何水。所述工艺的基础是所注入蒸汽形成在地层中垂直和水平生长的“蒸汽室”。来自蒸汽的热减小重质原油或沥青的粘度,此允许其向下流动到下部井眼中。蒸汽和气体由于其与下方重质原油相比密度低而上升,从而确保在下部生产井处不产生蒸汽。所释放的气体(其包括甲烷、二氧化碳且时常一些硫化氢)往往在蒸汽室中上升,填充石油所留下的空隙空间,并在一定程度上在蒸汽上方形成隔热覆盖层。石油和水是通过逆流的重力驱动排泄流动到下部井眼中。通过使用地下系统压力或通过利于移动具有悬浮固体的高粘度流体的泵(例如推进腔式泵)将冷凝水和原油或沥青回收至表面。
在从SAGD井去除后,从沥青分离所溶解和夹带的气体,且然后将沥青与中等分子量“载体”(称为稀释剂)组合,从而产生稀沥青(dilbit)。稀沥青是相比于原料沥青较轻且粘度较低的烃材料,且更易于经由管道输送到精炼厂。在精炼厂,将稀沥青加工成最终产物,且在一些情形下,将一部分中等产物返回至生产现场以用作稀释剂。
SAGD工艺在所获得的气体组份以及液体或半固体沥青方面存在严重的缺点。这些气体组份不仅包括烃类,而且包括不需要的含硫化合物,例如硫化氢(H2S)、硫醇(RSH)、羰基硫(COS)和二硫化碳(CS2)。生产现场通常利用从沥青初始分离的伴产气作为蒸汽产生器的燃料,然而,得自使用气体组份作为燃料的含硫燃烧产物系主要污染问题。防止硫空气污染的经济途径是在用作燃料之前从气体组份去除硫化合物。除SAGD工艺以外,存在可受益于本发明的从含烃沉积物回收烃类的其它工艺,例如周期蒸汽注入或“间歇热攻采油(Huff and Puff)”,其中将蒸汽注入生产井(经常垂直井)中一段时间,然后进行浸泡且然后产生石油;或蒸汽驱,其与SAGD类似,但利用一系列垂直井以注入蒸汽并回收石油;或水驱,其与蒸汽驱类似,但使用可回收并再注入的水;或气体再注入,其中将一些所产生的天然气压缩并再注入;或CO2注入,其中引入来自外部来源的CO2以注入储油层中;或原位热方法,其中将井的一部分埋在地下以向石油供热。
虽然有许多从含H2S气体去除并回收硫的可再生工艺,但硫醇的存在仍可造成严重的操作问题,因为这些工艺不能可靠地将其去除。事实上,RSH通常将以“脱硫(sweetened)”产物气体、再生空气排放及所产生硫结束。COS及CS2通常将能够穿过,且不被吸收或转化。RSH的强烈气味使得难以(如果不是不切实际)处置所产生的硫,且操作单元中的气味可能使其实际上不可操作。然而,H2S可容易地去除并转化成元素硫(S)。
因此,本发明涉及从气体组份去除有害的含硫化合物、特定而言RSH,留下H2S,然后可处理H2S以提供不含硫的气体燃料。
发明内容
本发明涉及避免与使用和/或加工从含烃沉积物获得的气体组份、尤其包括使用诸如SAGD工艺等工艺从油砂回收沥青的那些相关的问题。特定而言,本发明涉及处理从SAGD工艺获得的进料物流,此避免污染SAGD工艺中所获得的气体烃类的含硫硫醇化合物的有害效应。
更具体而言,本发明涉及用于处理从含烃沉积物获得的烃类的工艺,其中所述烃类包括液体烃类与含有硫化氢和硫醇的气体组份的混合物。首先将此混合物分离为液体或半固体烃相和主要包含被诸如硫化氢和硫醇等含硫化合物污染的烃燃料气的气相中。当使用原位SAGD工艺从油砂回收烃类时,液体或半固体烃类包含沥青。然后使经分离气体组份与贫油(轻质烃,例如煤油、石脑油等)接触,以使得硫醇被贫油吸收以形成含硫(sour)油或富油。将含有硫化氢的气体产物与富油分离,并加以处理以去除和/或转化硫化氢,来产生可在地上设施的其它地方用作燃烧产物的脱硫燃料气产物,具体而言生成用于SAGD工艺的蒸汽。
然后优选通过与贫油或等效烃混合以减小液体或半固体烃类的粘度来处理经分离液体烃类,使得其可经输送用于在精炼厂中加工。另一选择为,液体或半液体烃类可与富油或富油与贫油的混合物混合。在此替代方法中,含有硫醇的富油伴随液体烃类到达精炼厂,在精炼厂可对硫醇连同烃类一起进行加工以形成石油相关产物。在优选工艺方案中,使用SAGD工艺获得液体烃类与气体组份的混合物。当沥青是在SAGD工艺中所获得的液体或半固体烃时,稀释剂烃(即贫油、富油或两者的混合物)的添加导致形成稀沥青,然后可容易地将稀沥青从进行沥青的SAGD原位回收的区域输送到精炼厂操作。
可使用许多气液接触工艺处理在与贫油接触或利用其洗涤后获得的气体产物或低硫醇燃料气以去除硫化氢和/或将其转化成元素硫。在一个优选工艺中,使气体产物与碱溶液或苛性碱溶液在气液质量转移装置中接触,在其中硫化氢被苛性碱溶液吸收并转化以产生不含硫的燃料气,所述不含硫的燃料气可用于在其它工艺单元操作中燃烧。然后在生物反应器中使用空气处理废或富硫苛性碱溶液,在生物反应器中细菌在限氧条件下氧化经吸收的硫,以形成元素硫且同时再生苛性碱溶液用于循环返回以接触进入气体产物。
可用于产生不含硫的燃料气的其它硫化氢去除工艺包括采用克劳斯反应(Clausreaction)的那些。例如,可在使用二氧化硫(SO2)作为氧化剂的工艺中处理不含硫醇的气体产物,以通过经改良液相克劳斯反应将H2S转化成元素硫。所形成的元素硫可溶于反应溶液中,此消除高压设备中的循环固体。接着使元素硫结晶并使用经设计以处置固体的设备从所述工艺分离,而所述工艺的其余部分保持不含固体。
再一优选工艺(也称为氧化还原方法,例示并揭示于美国专利第4,238,462号和第5,160,714号中,其教示以引用的方式并入本文中)涉及气液质量转移操作,其中使液体催化剂调配物与含有硫化氢的气体产物接触,以优选地使用铁螯合物催化剂将硫化氢催化氧化成元素硫。通过在单独接触区中使反应溶液与所溶解的氧(优选呈环境空气形式)接触进行氧化来连续再生已用的多价金属螯合物混合物。在通过与(例如)催化性三价铁溶液接触来去除硫化氢的此一连续工艺中,使催化性溶液在吸收剂区(在其中H2S被催化性三价铁螯合物溶液吸收且溶液还原为二价铁)与氧化剂区(在其中将经还原二价铁氧化返回三价铁状态)之间连续循环。
不管最终转化硫化氢并从气体产物去除硫化氢使用何种工艺,本发明中的一个重要步骤是首先从气体组份去除硫醇,所述气体组份是初始从含烃沉积物获得的液体或半固体烃类分离。用于接触气体组份或对其洗涤以吸收硫醇的贫油可包括石脑油、煤油、中等烃类、汽油物流、喷射燃料、柴油和这些烃类的混合物。如所提及,使用贫油去除硫醇可使用吸收器完成,优选逆流气-液接触器,例如随机填充塔、结构化填充塔或泡罩盘塔。可实现的转移单元的数量(NTU)直接取决于所用塔的类型和所用贫油的类型。优选地,吸收器将在约30psig到70psig的压力范围及小于135°F的温度下操作。进给到吸收器的气体组份的硫醇含量不需维持或控制在特定水平下,然而优选含量为按体积计小于8500ppm。吸收器塔应经设计以将气体产物中的总硫醇浓度减小到经济上可行的低水平。优选的低水平将低到约2ppmv。
作为塔底产物从吸收器获得的富油可通过将其添加到沥青中以形成稀沥青来直接用作稀释剂烃。可希望对富油进行加工来去除硫醇,以获得循环或再生贫油用于反向循环以与气体组份接触和/或与从含烃沉积物回收的液体或半固体烃类混合。然而,在一些情形下,吸收器的设计可导致贫油对不可接受的水平的H2S的吸收,且在所述情形下需要汽提工艺来去除吸收硫化氢并生成基本上不含硫化氢的富油。
难以实现硫醇和硫化氢从富油物流的分离。为促进H2S从富油的分离,汽提塔必须在显著高于吸收器的压力下运行,且需要回流冷凝器以及塔底再沸器。使用回流冷凝器和再沸器允许塔内足够的蒸气和液体流量,以允许几乎所有H2S在塔顶馏出物蒸气中离开。遗憾地,一些硫醇也与塔顶馏出物蒸气一起泄漏。由于此蒸气物流中的硫醇的量显著低于最初从液体烃类分离的含硫气体组份,因此可将此塔顶馏出物的一部分循环回吸收器的前部,在其中将其与含硫气体组份进料混合或掺和。
汽提塔的压力应经选择以使H2S的去除最大化。优选方法是在50psig到200psig之间运行汽提塔以实现可接受的分离。此需要进料泵或富油进料泵以使富油高于塔操作压力,包括管线和其它系统损耗。优选地,将富油进给到塔的下半部分中,所述塔优选为盘式蒸馏塔。使用塔底再沸器在塔内生成必需蒸气流量以去除H2S和随后一小部分硫醇。随着蒸气沿塔向上行进,其与富油和然后回流冷凝物接触,此进一步促进所要的分离。如所提及,由于分离并不十分有效,因此硫醇往往与塔顶馏出物蒸气一起泄漏。
从气体组份去除硫醇的替代方法是实施蒸馏工艺,其中使用来自塔顶回流冷凝器的液体和来自再沸器的蒸气来蒸馏贫油和气体组份。此替代方法消除组合上文所提及的吸收和汽提的需求。
离开洗涤工艺的富含硫醇且低硫化氢含量的石油可进一步经加工以去除并转化硫醇,或如所提及用作稀释剂以减小从含烃沉积物获得的液体或半固体烃类的粘度。如果这些液体或半固体烃类包含沥青,那么当与或不与贫油一起添加富油时,所得混合物称为稀沥青。为去除并转化富油中的硫醇,优选方法是使富油与苛性碱接触,由此将硫醇转化成硫醇盐并保留在苛性碱溶液中,从而形成再生贫油。最后进一步处理废苛性碱中的硫醇盐以经由氧化反应将硫醇盐转化成二硫化物油(DSO),然后可将其收集并在精炼厂利用液体烃类进一步加工。然后使再生苛性碱溶液循环以与新鲜或补充苛性碱混合来处理富油进料。
将硫醇转化(与提取相反)成二硫化物油的另一更优选工艺使用处理水溶液和氧化反应。二硫化物油保留在从所述工艺去除的经分离烃产物物流中。更具体而言,将含有硫醇的富油与含氧气体组合以形成进料物流。使此进料与包含水、碱金属氢氧化物、多价螯合金属催化剂的处理水溶液在接触器容器中接触,在所述接触器容器中使用催化剂和氧经由氧化反应将硫醇转化成二硫化物油。接触步骤形成产物混合物,将所述产物混合物引导到至少一个分离区,在所述分离区中从所述混合物分离含有二硫化物油的经升级烃物流。除上文所描述的贫油以外,也可使用此含有DSO的贫油物流,或作为上文所描述贫油的替代物。在用补充催化剂和/或处理溶液的其它成份补充后,必要时使处理水溶液再循环来处理富油进料。
处理水溶液中所用的催化剂组合物优选为液体螯合多价金属催化剂溶液。多价催化剂包括(但不限于)金属酞青素,其中金属阳离子是选自由锰(Mn)、铁(Fe)、钴(Co)、镍(Ni)、铜(Cu)、锌(Zn)、钌(Ru)、铑(Rh)、钯(Pd)、银(Ag)等组成的群组。催化剂浓度为约10ppm到约10,000ppm、优选约20ppm到约4000ppm。可在处理溶液的制备期间包括所选择的特定催化剂,和/或稍后在使用所述溶液的地方将其添加到所述溶液中。
烃进料与处理水溶液的接触可通过任何液-液混合装置(例如填充塔、泡罩盘、搅拌容器、塞流反应器、纤维-膜接触器等)来完成。优选地,使用实现快速的液-液质量转移而不会在获得烃与处理水溶液之间的迅速且干净的相分离方面造成困难的接触器实施接触。所述接触器经配置以造成极少搅动或不造成任何搅动并减少烃中水溶液的夹带。可采用两个或更多个与处理水溶液接触的阶段来实现更高程度的处理效率。
从下文所含有的优选实施例的详细说明,这些和其它实施例将变得更显而易见。
附图说明
图1示意性图解说明本发明的一个可能实施例的工艺流程图。
具体实施方式
本发明涉及去除气体组份中所存在的硫污染物、具体而言硫醇,所述气体组份是分离自从含烃沉积物、优选从油或焦油砂的原位SAGD加工获得的液体和/或半固体烃类。参照图1,将描述一个可能工艺流程方案,然而,所属领域的技术人员应了解可设计替代流程方案。从含烃沉积物获得液体和/或半固体烃类(在此处进一步简称为“液体烃类”)、气体组份和水的混合物,并将其递送到地上加工设施中的分离器2,在所述分离器中经由管线3去除气体组份并经由管线4去除液体烃类。可使经分离水(未显示)循环以使蒸汽重新用于SAGD工艺中或用作其它工艺用水。当从油砂产生时,所回收的液体烃类包含沥青。
将管线4中的液体烃类与作为稀释剂的贫油13在容器14中混合,以减小液体烃类的粘度,从而允许更容易输送到精炼厂用于加工成有用烃产物。当沥青为液体烃时,所得经稀释物流15称为稀沥青。贫油13可为任何烃或能够稀释液体烃类4的烃类的混合物,优选地其中硫含量较低。优选贫油包括石脑油、煤油、中等烃类、汽油物流、喷射燃料、煤油、柴油、石脑油和其混合物。贫油的一种可能选择是裂化石脑油,例如FCC石脑油或焦化石脑油,其在约35℃到约230℃的范围内沸腾。
经分离气体组份3包含烃燃料气和硫污染物,例如硫醇、硫化氢、羰基硫和二硫化碳。此硫污染燃料气在容器40中进一步加工,以优于硫化氢选择性地提取或吸收硫醇。此是使用组成可与用于稀释液体烃类的贫油13相同或与其不同的贫油6来完成。接触容器40可为气液吸收塔、紧接着汽提分馏器的组合,或可为使用再沸和回流以实现硫醇从硫化氢的所要分离的蒸馏塔。除贫油6以外也可使用下文中更充分描述的循环贫油8。经由管线7去除含有硫醇的富油,在管线7中可将其全部或一部分用作稀释剂16以减小处理工艺14中的液体烃类的粘度。在此一情形下,将硫醇与稀释剂烃类和液体烃类一起输送到精炼厂,在精炼厂使用已知加工技术从烃类最终去除硫醇。
另一选择为,富油7的全部或一部分可进一步原位加工以在工艺17中去除硫醇并将其转化成二硫化物油,从而产生可在接触器40中用于从气体组份吸收硫醇的再生或循环贫油。工艺17优选涉及使富油7与苛性碱溶液18接触,由此将硫醇转化成硫醇盐,硫醇盐保留于苛性碱溶液中。从经由管线8去除的再生贫油分离废苛性碱。将经分离废苛性碱20与经由管线19的含氧气体(例如空气)在容器25中混合,在容器25中在催化剂的存在下发生氧化反应以将硫醇盐转化成二硫化物油(DS0)并形成再生苛性碱溶液。将DSO从再生苛性碱溶液分离,并经由管线27去除用于进一步加工或混合返回稀沥青中。可使经由管线26去除的再生苛性碱循环,并与管线18中的苛性碱混合。
将硫醇减少但富含硫化氢的燃料气经由管线5从工艺40去除,并运送到工艺10,在工艺10中将硫化氢转化成元素硫,经由管线12去除元素硫。可使用许多不同工艺转化并去除硫化氢,以产生不含硫的燃料气,经由管线11去除所述不含硫的燃料气。一种所述工艺涉及使用液-气接触器,在所述液气接触器中使苛性碱溶液与燃料气和硫化氢接触以提取硫化氢。然后在生物反应器中加工含硫或废苛性碱以产生再生苛性碱溶液,可使所述再生苛性碱溶液循环并向其添加新鲜的补充苛性碱来处理燃料气和硫化氢。另一选择为,工艺10可利用克劳斯反应或经改良克劳斯反应,在所述反应中硫化氢被吸收于烃中且使用二氧化硫(SO2)作为氧化剂以将入口H2S转化成元素硫。元素硫可溶于所得烃和水溶液中,此消除高压设备中的循环固体。接着使硫结晶并使用经设计以处置固体的设备从所述工艺分离,而所述工艺的其余部分保持不含固体。
从燃料气去除硫化氢的第三且优选工艺涉及使H2S污染的燃料气与液体氧化还原催化剂溶液9和空气30接触以产生不含硫的燃料气11和元素硫12。不管使用何种工艺,不含硫的燃料气最优选用作燃烧气体以原位加热另一单元操作,最具体而言以生成用于从含烃沉积物原位回收液体烃类的蒸汽。
如本文所用,硫醇化合物包括甲基硫醇、乙基硫醇、正丙基硫醇、异丙基硫醇、正丁基硫醇、硫苯酚和较高分子量硫醇。硫醇化合物常由符号RSH代表,其中R是正或具支链烷基或芳基。可存在于气体物流中且可通过本发明的氧化工艺转化成二硫化物的硫醇的具体类型将包括甲基硫醇、乙基硫醇、丙基硫醇、丁基硫醇、戊基硫醇等。
从富油去除硫醇的处理工艺17优选使用含有碱金属氢氧化物的处理水溶液。基于富油的重量,富油的硫醇水平可在约10wppm到约10,000wppm的范围内。尽管以上说明涉及在不存在氧的情况下使用两相处理溶液的处理工艺,但另一方法可使用处理水溶液以及所添加的使得烃进料中的硫醇氧化成保留在烃相中的二硫化物油的含氧气体。处理溶液可通过将金属酞青素催化剂添加到碱金属氢氧化物的水溶液中来制备。
具体实施例的上述说明将如此充分地揭示本发明的一般特性,以致于其它人可在不背离一般概念的情况下通过运用现有知识容易地修改和/或调适所述具体实施例以用于各种应用,且因此所述调适和修改打算涵盖在所揭示实施例的等效物的含义和范围内。应了解,本文中的措辞或术语是出于描述而非限制的目的。
用于实施各种所揭示功能的手段、材料和步骤可在不背离本发明的情况下采取各种替代形式。因此,表述“用以……的手段”和“用于……的手段”或在以上说明书或下文权利要求书中可发现的且接着为功能描述的任何方法步骤语言打算定义并涵盖现在或将来可能存在且实施所列举功能的任何结构、物理、化学或电元件或结构或任何方法步骤,无论是否精确地等效于以上说明书中所揭示的实施例,即,可使用用于实施相同功能的其它手段或步骤;且在所附权利要求书的各项中打算以其最宽泛解释给出所述表述。
Claims (19)
1.一种处理从含烃沉积物获得的烃类的方法,其包含
a)提供从含烃沉积物获得的液体烃类与气体组份的混合物,其中所述气体组份包含硫化氢和硫醇;
b)从所述气体组份分离所述液体烃类;
c)使所述气体组份与贫油接触,由此使所述硫醇被所述贫油吸收以形成富油;
d)从所述富油分离含有所述硫化氢的气体产物;
e)处理所述气体产物以去除所述硫化氢以产生贫燃料气;以及
f)在输送到精炼厂用于加工之前处理在步骤b)中所获得的所述液体烃类以减小粘度。
2.根据权利要求1所述的方法,其中使用SAGD工艺获得液体烃类与气体组份的所述混合物。
3.根据权利要求1所述的方法,其中所述液体烃类包含沥青。
4.根据权利要求1所述的方法,其中步骤f)中的液体烃类的所述处理包含将所述液体烃类与稀释剂烃混合。
5.根据权利要求1所述的方法,其中步骤f)中的液体烃类的所述处理包含将所述液体烃类与来自步骤d)的所述富油混合。
6.根据权利要求1所述的方法,其中步骤f)中的液体烃类的所述处理包含将所述液体烃类与稀释剂烃和来自步骤d)的所述富油混合。
7.根据权利要求1所述的方法,其中来自步骤d)的所述气体产物的所述处理包含使所述气体产物与液体溶液在气-液接触器中接触以将所述硫化氢转化成元素硫。
8.根据权利要求1所述的方法,其中来自步骤d)的所述气体产物的所述处理包含使所述气体产物与液体溶液在气-液接触器中接触,接着进行氧化反应以将所述硫化氢转化成元素硫。
9.根据权利要求1所述的方法,其中使来自步骤d)的所述富油与苛性碱接触来去除所述硫醇以形成再生贫油,由此将所述硫醇转化成硫醇盐,并转移到所述苛性碱中以形成废苛性碱。
10.根据权利要求9所述的方法,其中在步骤c)中使所述再生贫油与所述气体组份接触以自所述气体组份去除所述硫醇。
11.根据权利要求9所述的方法,其中在步骤f)中将所述再生贫油添加到所述液体烃类以减小所述液体烃类的粘度。
12.根据权利要求9所述的方法,其进一步包含通过以下方式再生所述废苛性碱:
a)将所述废苛性碱与含氧气体混合;
b)使用催化剂氧化所述废苛性碱以形成再生苛性碱,由此将所述废苛性碱中的所述硫醇盐氧化成二硫化物油;以及
c)从所述二硫化物油分离所述再生苛性碱,并循环所述再生苛性碱用于与来自根据权利要求1所述的步骤d)的所述富油接触。
13.根据权利要求1所述的方法,其中步骤c)中的所述接触包含使所述气体组份在蒸馏塔中与所述贫油接触并蒸馏以形成富油塔底馏出物和包含燃料气和硫化氢的低硫醇气体塔顶馏出物。
14.根据权利要求1所述的方法,其中步骤c)中的所述接触包含使所述气体组份在逆流液-气低压吸收塔中与所述贫油接触。
15.根据权利要求14所述的方法,其进一步包含分馏以从所述富油去除残余硫化氢。
16.一种处理使用SADG工艺自油砂原位获得的烃类的方法,其包含
a)从气体组份分离沥青,其中所述气体组份包含烃类、硫化氢和硫醇;
b)将所述沥青与足量的烃稀释剂混合以形成稀沥青;
c)使来自步骤a)的所述经分离气体组份与贫油在逆流液-气塔中接触,由此将所述硫醇吸收到所述贫油中以形成富油,且其中回收低硫醇气体产物;以及
e)利用液体氧化还原催化剂水溶液处理所述低硫醇气体产物,以将所述硫化氢氧化成元素硫并产生不含硫的燃料气。
17.根据权利要求16所述的方法,其中将所述富油与所述沥青混合,以形成所述稀沥青。
18.根据权利要求16所述的方法,其中利用苛性碱处理所述富油来去除所述硫醇,以形成经循环并用于步骤c)中的再生贫油。
19.根据权利要求18所述的方法,其中将含有从所述富油去除的所述硫醇的废苛性碱与含氧气体混合,然后使用催化剂进行氧化以形成再生苛性碱,由此将所述废苛性碱中的硫醇盐氧化成二硫化物油,将所述二硫化物油从所述再生苛性碱分离,且其中使所述再生苛性碱循环用于处理所述富油。
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CN110573232A (zh) * | 2017-05-12 | 2019-12-13 | 株式会社可乐丽 | 含硫化合物去除装置和含硫化合物去除方法 |
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BR112015012595B1 (pt) | 2021-08-31 |
CN104884735B (zh) | 2017-05-10 |
TW201435075A (zh) | 2014-09-16 |
BR112015012595A2 (pt) | 2017-07-11 |
US8815083B2 (en) | 2014-08-26 |
RU2015125643A (ru) | 2017-01-10 |
JP6186005B2 (ja) | 2017-08-23 |
TWI509062B (zh) | 2015-11-21 |
HK1210247A1 (zh) | 2016-04-15 |
JP2016507595A (ja) | 2016-03-10 |
RU2612808C2 (ru) | 2017-03-13 |
EP2925960A1 (en) | 2015-10-07 |
US20140144811A1 (en) | 2014-05-29 |
WO2014085559A1 (en) | 2014-06-05 |
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