CN108883360A - 用于烃的硫还原的化学方法 - Google Patents
用于烃的硫还原的化学方法 Download PDFInfo
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- CN108883360A CN108883360A CN201780022446.6A CN201780022446A CN108883360A CN 108883360 A CN108883360 A CN 108883360A CN 201780022446 A CN201780022446 A CN 201780022446A CN 108883360 A CN108883360 A CN 108883360A
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- reducing agent
- hydrocarbon
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Links
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 90
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 90
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 89
- 239000005864 Sulphur Substances 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims description 44
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title description 40
- 239000000126 substance Substances 0.000 title description 8
- -1 sulphur compound Chemical class 0.000 claims abstract description 86
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 49
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910010277 boron hydride Inorganic materials 0.000 claims abstract description 41
- 238000012545 processing Methods 0.000 claims abstract description 28
- 239000002250 absorbent Substances 0.000 claims abstract description 16
- 230000002745 absorbent Effects 0.000 claims abstract description 16
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 13
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 10
- 239000004927 clay Substances 0.000 claims abstract description 7
- 230000009467 reduction Effects 0.000 claims abstract description 7
- 239000007859 condensation product Substances 0.000 claims abstract description 6
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract 2
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 39
- 229910000085 borane Inorganic materials 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 26
- 239000007795 chemical reaction product Substances 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000003502 gasoline Substances 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 19
- 239000011593 sulfur Substances 0.000 claims description 19
- 229910052717 sulfur Inorganic materials 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 18
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 239000003610 charcoal Substances 0.000 claims description 15
- 239000003513 alkali Substances 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000002879 Lewis base Substances 0.000 claims description 9
- 150000007527 lewis bases Chemical class 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000003345 natural gas Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 150000007942 carboxylates Chemical group 0.000 claims description 7
- 239000003915 liquefied petroleum gas Substances 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- 239000002737 fuel gas Substances 0.000 claims description 6
- 239000003350 kerosene Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- ZOCHARZZJNPSEU-UHFFFAOYSA-N diboron Chemical compound B#B ZOCHARZZJNPSEU-UHFFFAOYSA-N 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910021536 Zeolite Inorganic materials 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims 1
- 229910001948 sodium oxide Inorganic materials 0.000 claims 1
- 230000000670 limiting effect Effects 0.000 abstract description 29
- 239000003518 caustics Substances 0.000 abstract description 21
- 238000007670 refining Methods 0.000 abstract description 15
- 239000002516 radical scavenger Substances 0.000 abstract description 14
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 abstract description 11
- 229910000037 hydrogen sulfide Inorganic materials 0.000 abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052799 carbon Inorganic materials 0.000 abstract description 7
- 150000003464 sulfur compounds Chemical class 0.000 abstract description 5
- 150000003568 thioethers Chemical class 0.000 abstract description 4
- 150000003573 thiols Chemical class 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 34
- 230000000996 additive effect Effects 0.000 description 19
- 239000000654 additive Substances 0.000 description 18
- 239000012279 sodium borohydride Substances 0.000 description 16
- 229910000033 sodium borohydride Inorganic materials 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- 238000000926 separation method Methods 0.000 description 13
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 10
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 230000004087 circulation Effects 0.000 description 4
- LJSQFQKUNVCTIA-UHFFFAOYSA-N diethyl sulfide Chemical compound CCSCC LJSQFQKUNVCTIA-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052987 metal hydride Inorganic materials 0.000 description 3
- 150000004681 metal hydrides Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910000104 sodium hydride Inorganic materials 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N Glycolaldehyde Chemical compound OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
- 239000012280 lithium aluminium hydride Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- UORVGPXVDQYIDP-BJUDXGSMSA-N borane Chemical class [10BH3] UORVGPXVDQYIDP-BJUDXGSMSA-N 0.000 description 1
- SRSPILBBEHNEHD-UHFFFAOYSA-N boranylformonitrile Chemical compound BC#N SRSPILBBEHNEHD-UHFFFAOYSA-N 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000012864 cross contamination Methods 0.000 description 1
- KXRNYDKIPJKLTD-UHFFFAOYSA-N cyanoboron Chemical compound [B]C#N KXRNYDKIPJKLTD-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- VLXBWPOEOIIREY-UHFFFAOYSA-N dimethyl diselenide Natural products C[Se][Se]C VLXBWPOEOIIREY-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000002627 tracheal intubation Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical group [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
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
- C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
- C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
- C10G53/08—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one sorption step
-
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/005—Processes comprising at least two steps in series
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/11—Purification; Separation; Use of additives by absorption, i.e. purification or separation of gaseous hydrocarbons with the aid of liquids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/14858—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound with inorganic compounds not provided for before
-
- 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
- C10G21/16—Oxygen-containing 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
- 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
- C10G21/20—Nitrogen-containing 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
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/02—Non-metals
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Abstract
用高pH值水性还原剂诸如硼氢化物对烃流,并且在一个非限制性实施方案中对精炼馏出物进行处理,导致存在的硫化合物诸如二硫化物、硫醇和硫醚还原以产生易于除去的硫化物。所述处理将原始硫化合物转化为硫化氢或低分子量硫醇,所述低分子量硫醇能够用苛性碱溶液、硫化氢或硫醇清除剂、固体吸收剂诸如粘土或活性炭或者液体吸收剂诸如胺‑醛缩合物和/或水性醛从所述馏出物中萃取出来。
Description
技术领域
本发明涉及从烃流中除去硫化合物,并且更具体地说,在一个非限制性实施方案中,涉及使用还原剂从烃流中除去硫化合物的方法。
背景技术
通常具有有机硫分子的性质的硫在许多烃流和烃碳链长度为C1至C30的体积中是不想要的污染物,其中一些可用作含有具有C1-C12的烃分子的燃料或用于所述燃料中。
目前用于减少硫含量的添加剂仅适用于无机形式的硫(主要是硫化氢,H2S)或低分子量(C1-C4)硫醇。为了除去高分子量(C5+)硫醇、二硫化物、硫醚和其他硫化合物,文献建议需要氧化剂(例如过氧化物,例如过氧化氢)将硫物质转化为水溶性亚砜或砜,其可从烃中萃取出来。
美国未来的汽油规格要求将硫化合物减少到非常低的水平。水平足够低至汽油掺合物组分(例如含有硫化合物的丁烷)将使成品汽油不符合硫限制。精炼厂希望限制其资本支出并寻求建立额外加氢处理能力的替代方案,因此他们正寻求替代方法从馏出物中除去这些硫化合物。
希望使用目前使用的那些方法的替代方法从精炼馏出物流中除去硫化合物。
发明内容
在一个非限制性实施方案中提供了一种从含有硫化合物的烃流中除去硫化合物的方法,其中所述方法包括使烃流与有效与硫化合物反应以在处理的烃流中形成至少一种反应产物的量的还原剂接触;以及然后从处理的烃流中除去至少一种反应产物。硫化合物包括但不必限于具有式R-S-H的硫醇,其中R是直链或具支链C1至C4烷基;二硫化碳(CS2);羰基硫(COS);具有式R1-S-R2的二烷基硫化物,其中R1和R2独立地是直链或具支链C1至C4烷基;具有式R1-S-S-R2的二烷基二硫化物;以及其组合。烃流包含液体或气体烃,包括但不必限于C1至C12烷烃、C2至C12烯烃、液化石油气、天然气、燃料气、火炬气、石脑油、汽油、煤油以及其混合物。还原剂可包括但不必限于硼烷(BH3);二硼烷(B2H6);硼烷或二硼烷与路易斯碱的复合物,所述路易斯碱是选自由醚、二烷基硫化物、胺、醇以及其混合物组成的组;具有式M1BH4的无机硼氢化物盐,其中M1是选自由Li、Na和K组成的组,或具有式M2(BH4)2的无机硼氢化物盐,其中M2是选自由Mg、Ca和Zn组成的组;具有式M1BH3CN或具有式M2(BH3CN)2的氰基硼氢化物;具有式M1BR3 3H的有机硼氢化物并且R3独立地选自由直链或具支链C1至C3烷基和具有式R4C(O)O-的羧酸酯基团组成的组,并且R4是选自由直链或具支链C1至C9烷基组成的组;以及其组合。
在替代非限制性型式中,提供了处理的烃流,其包括选自由C1至C12烷烃、C2至C12烯烃、液化石油气、天然气、燃料气、火炬气、石脑油、汽油、煤油以及其混合物组成的组的液体或气体轻质烃,以及至少一种如上所定义的硫化合物,以及至少一种如上文所定义的还原剂,其中还原剂以有效与硫化合物反应形成至少一种反应产物的量存在。
在另一个非限制性实施方案中,所述方法在高pH值下实践,其中还原剂在水溶液中并且具有定义为约7至约14,或者7或更高的范围内的高pH值。在一个非限制性实施方案中,碱性pH水溶液含有硼氢化物,但是这些硼氢化物对酸具有反应性。较高的pH值通过形成氢气防止硼氢化物分解。
具体实施方式
已经发现,用还原剂、在非限制性实施方案中高pH值的硼氢化物水溶液处理烃、特别是精炼馏出物,导致存在的硫化合物(例如二硫化物、硫醇和硫醚)减少,以产生易于除去的硫化物。所述处理将原始硫化合物转化为硫化氢(H2S)或低分子量硫醇,所述低分子量硫醇能够用苛性碱溶液、硫化氢或硫醇清除剂或固体吸收剂(例如粘土或活性炭)或液体吸收剂(例如胺-醛缩合物和水性醛)从馏出物中萃取出。在一种预期的非限制性实践中,将硼氢化物溶液在从精炼厂生产单元到储罐的成品线管中注入馏出物中和/或能够注入储罐的再循环回路中。硼氢化物与馏出物的良好混合有利于反应,并且另外需要下游分离点以除去水溶液。分离器、离心机或甚至储罐底部都足以收集水性副产物。任选地使处理并脱水的烃通过随后的过滤或与固体或液体吸收剂(在非限制性实施方案中,粘土、炭、沸石、胺-醛缩合物等)接触,从而除去任何残留的硼氢化物和反应产物,从而产生能够满足所有销售规格的低硫含量馏出物。或者,也可使用萃取技术(例如接触塔或苛性碱洗涤单元)完成分离。
在另一个非限制性实施方案中,更具体地,将硼氢化物在苛性碱中的溶液注入含有有机硫化合物(例如二硫化物(R-S-S-R)、硫醚(R-S-R)、羰基硫(COS)或二硫化碳(CS2))的烃中。硼氢化物被认为将硫化合物还原为无机H2S或低分子量硫醇,其然后通过硼氢化物溶液中的苛性碱或者通过添加额外的H2S清除剂(包括但不必限于三嗪;金属羧酸盐,例如包括金属Zn、Cu和/或Fe的那些羧酸盐;氧化物、氢氧化物或碳酸盐)到馏出物中从烃中来除去。硫化氢清除剂应该是水性的或者配制在烃不溶性溶剂中,因此含硫反应产物能与烃分离。用于油/水分离的任何分离设备都能够用于本文所述的方法中。随后或最后的步骤可为处理的烃通过和/或与吸收剂接触,其用于除去任何残留的硼氢化物、硫化合物或H2S清除剂以产生硫含量大大降低的烃馏出物。
除硼氢化钠之外的其他还原剂包括但不必限于硼烷(BH3);与醚、硼烷和其他复合剂的硼烷复合物;氢化铝锂、氢化钠、氢化钙和其他金属氢化物可取代以上硼氢化物。金属氢化物(例如氢化铝锂、氢化钠和氢化钙)可能对空气太敏感并且在一些情形下对水分敏感以致于不能在应用中使用。在其他情况下,其可能是如此强的还原剂,以致于其会还原所处理的烯烃。催化剂(包括但不必限于路易斯酸(例如氯化铝、氯化铁、氯化锌))也可用于有利于硫化合物的还原。通过还原形成的硫化物可通过水相或其他不混溶相的简单重力分离或通过在吸收剂(粘土、沸石、炭)上使用固体吸收床(例如金属(锌、铁))来除去。或者,硫化物可通过与液体吸收剂(包括但不必限于胺-醛缩合物和/或水性醛等)接触来除去。处理可以分阶段或在单个过程中进行。例如,如果除了其他硫化合物之外烃还含有硫化氢,则可以首先用硫化氢清除剂对其进行处理以除去H2S,并且然后用硼氢化物处理以减少额外的硫化合物并且然后最后过滤或流经萃取过程以除去还原的硫产物。
合适的含硫化合物的精炼馏出物流包括但不必限于选自由以下组成的组的液体或气体烃:C1至C12烷烃(包括甲烷)、C2至C12烯烃、液化石油气、天然气、燃料气、火炬气、石脑油、汽油、煤油以及其混合物;对于柴油燃料可能高达C16。然而,预期本文所述的方法在油田应用中也是有效的,包括但不必限于从油田缩合物、天然气等中除去硫化合物。本文所述的方法也可有效地处理储存设施内或当其从储存设施中取出时的天然气液体(NGL)或液体石油气(LPG)。
可从精炼馏出物流中除去的硫化合物包括但不必限于具有式R-S-H的硫醇,其中R为直链或具支链C1至C4烷基;二硫化碳(CS2);羰基硫(COS);具有式R1-S-R2的二烷基硫化物,其中R1和R2独立地是直链或具支链C1至C4烷基;具有式R1-S-S-R2的二烷基二硫化物,其中R1和R2如前所定义。
更具体地,合适的还原剂包括但不必限于硼烷(BH3);二硼烷(B2H6);硼烷或二硼烷与路易斯碱的复合物,所述路易斯碱是选自由醚、二烷基硫化物,胺、醇以及其混合物组成的组;具有式M1BH4的无机硼氢化物盐,其中M1是选自由Li、Na和K组成的组,或具有式M2(BH4)2的无机硼氢化物盐,其中M2是选自由Mg、Ca或Zn组成的组;具有式M1BH3CN的氰基硼氢化物,其中M1如前所定义,或具有式M2(BH3CN)2的氰基硼氢化物,其中M2如前所定义;具有式M1BR3 3H的有机硼氢化物,其中M如前所定义,并且R3独立地选自由直链或具支链C1至C3烷基和具有式R4C(O)O-的羧酸酯基团组成的组并且R4是选自由直链或具支链C1至C9烷基组成的组;以及其组合。也就是说,在同一硼上能够存在R和R4C(O)O-的组合,使得所有R3都可为烷基,所有R3都可为R4C(O)O-,或者能够存在两者的组合。
同样为了本申请的目的,术语“苛性碱”广泛地定义以意指强碱(碱性)物质,包括但不限于氢氧化钠(NaOH)、氢氧化钾(KOH)和氢氧化锂(LiOH);但也特别包括现在已知或以后发现可用于从精炼馏出物流体流中萃取或以其他方式除去硫化合物的任何化合物。然而,在另一个非限制性实施方案中,“苛性碱”定义为选自由氢氧化钠,氢氧化钾、氢氧化锂以及其组合组成的组。应当理解,在一个非限制性实施方案中为苛性碱液体的液体洗涤相不包含含有相对少量碱金属氢氧化物或烷醇胺、烷基胺和/或烷酰胺以调节液体的pH值的所有碱性液体。在本文所用的苛性碱液体中,苛性碱或碱性物质,在碱性金属氢氧化物用于碱性体系的情形下,基于用于处理精炼馏出物流的水,碱金属氢氧化物的量可为约50wt%或更少;或者约15wt%或更少;并且在另一个非限制性实施方案中,约12wt%或更少。许多合适的苛性碱溶液将具有高含量的KOH和/或NaOH。这些苛性碱溶液的密度比所处理的烃高得多,以改善两相的分离。苛性碱与烃之间的密度差提高了沉降速率并提供了更好的分离。还原剂与精炼馏出物流的接触可在pH值独立地为约7至约14或者pH值为约10至约13.5的水溶液中。在另一个非限制性实施方案中,含有还原剂的碱性水性体系的pH值可为9或更大;或者9.5或更大;并且不同的非限制性实施方案中10或更大。在另一个非限制性型式中,这些阈值可与先前给出的pH值范围一起用作合适的替代pH范围的替代阈值。如上所述,这些液体是水性的。幸运的是,虽然硼氢化物是强还原剂,但其可用于水溶液中。
应当理解,本文的还原剂不包括金属氢化物,例如氢化铝、NaH、LiH和CaH2,这是因为其通常对水和/或空气太敏感以致于不适用于本文所述的方法中。
在本文的方法的一些实施方案中,用还原剂处理精炼馏出物流。在非限制性实例中,通过添加硼氢化钠(NaBH4)作为添加剂,能够从精炼馏出物流中除去羰基硫(COS)。当COS气体存在于NaBH4溶液中时,COS将与NaBH4反应并且反应不可逆。反应可以说明如下:
O=C=S+H–→O=CH-S–或–O-CH=S (1)
反应产物是极性更大的物质,也就是水溶性更大的物质,并且可通过苛性碱水溶液洗涤掉。
所添加还原剂的有效量是与硫化合物有效结合起来和/或反应并至少部分将其转换为可除去的反应产物的任何量。在一个非限制性型式中,还原剂的有效量高达还原剂与硫化合物的化学计量比的两倍;或者,有效量在还原剂与硫化合物的化学计量比的约0.8至约1.8倍范围内。在另一个非限制性实施方案中,NaBH4或其他还原剂的有效量是独立地0.02:1至约50:1的NaBH4与COS的摩尔比,其是基于工艺流中硫化合物的量;或者,摩尔比在独立地约0.1:1至约40:1的范围内。关于本文中的范围使用的词语“独立地”意味着任何下阈值可以与任何上阈值一起使用以提供合适的替代范围。理论量是NaBH4与COS的1:1摩尔比,如反应(1)中所示。在一个非限制性实施方案中,NaBH4与COS的量超过1:1的摩尔比。
在一些情形下,还原剂溶液将与烃接触,并且其将为将存在的硫化合物转化为另一种形式的清除剂,并且其也将为从烃中萃取出形成的硫化合物(反应产物)的溶液。在其他不同的情形下,将用固体或液体吸收剂进行烃的第二次处理,以除去由硼氢化物形成的硫化合物(反应产物)。也就是说,在一些非限制性实施方案中,烃将简单地与还原剂(例如硼氢化物)溶液接触,并且其将是清除剂和吸收剂二者。在其他不同的非限制性实施方案中,处理的烃将通过固体/液体吸收剂以确保除去所有硫化合物(和清除剂)。关于剂量比率,如果将还原剂(例如硼氢化物)溶液简单地注入烃流中,则可以提供基于化学性质的ppm的清除剂与ppm的硫比率。然而,如果烃鼓泡通过还原剂(例如硼氢化物)溶液,则与迁移通过还原剂水溶液的相对少量的烃相比,塔中还原剂溶液的量将相对较大。
在将还原剂(在这种情形下为硼氢化物)溶液直接注入酸性烃中的非限制性情形下,一个非限制性ppm剂量范围将为每ppm待除去的硫独立地约0.5至约10ppm的硼氢化物;或者,每ppm待除去的硫独立地约1至约5ppm的硼氢化物。
在其中酸性烃鼓泡通过硼氢化物溶液的塔应用中,该比率将更高,这是因为仅有小气泡的烃向上迁移通过塔中的硼氢化物溶液。存在相对大体积的硼氢化物溶液,这是因为其填充接触塔,并且迁移远离通过硼氢化物溶液的小气泡的烃中仅存在相对少量的硫化合物。在后一种情形下,硼氢化物溶液与烃的比率范围可以为相对于酸性汽油独立地约95vol%的硼氢化物清除剂至低至5vol%的硼氢化物;或者,相对于酸性烃独立地约10vol%至约50vol%的硼氢化物溶液。应当理解,对于与硼氢化物不同的还原剂,由于不同的化学计量,这些剂量范围将是不同的。
通常,添加剂将以如下水平存在于处理的精炼馏出物流中:使得流中硫化合物的浓度降低至独立地约1或小于1、至约5ppm。在其他实施方案中,处理后的浓度为独立地约0.1至约100ppm。在一个非限制性实施方案中,在处理的烃中可以保留约1至约2ppm的硫,并且仍然可以满足汽油规格。在一个非限制性实施方案中,预期在烃流中处理的硫的最高含量将为约500ppm,并且可能希望将硫含量降低至小于1ppm。或者,预期的起始硫含量为100ppm或更低,其可以降低至3ppm或更低,并且在不同的非限制性型式中,起始硫含量可以为约50ppm或更低,其可以降低至5ppm或更低。
还原剂接触的温度范围仅受添加剂性质的限制。所处理的流不能太热以至于闪蒸掉添加剂中的水并留下固体硼氢化物。相反,所述流不能太冷以至于添加剂冷冻并且不与烃流混合。通常,预期相对较热将比相对较冷更好,这是因为动力学随着温度的升高而改善,但通常,温度也不能太高以至于溶剂(水)闪蒸掉。
除了已经描述的添加剂之外,本文使用的添加剂可包括已知可用于硫化合物除去方法的其他化合物,例如分散剂、消泡剂等。与添加剂减少或除去硫化合物的能力不具有不需要的相互作用的任何化合物可与本文所述的方法和组合物的至少一些实施方案一起使用。如果正在处理气体,则可特别使用消泡剂。另外,如果使用的分离步骤涉及沉降在储罐中,则可使用反乳化剂。例如,可存在一些通过水相与烃相的接触产生的乳液。反乳化剂有助于使水与烃分离。
为了减少处理的精炼馏出物流的硫含量,需要分离步骤。分离能利用固体吸收剂(例如炭、粘土和沸石),或者分离能利用苛性碱溶液或水进行萃取。萃取溶剂可任选地是硼氢化物添加剂的一部分(即硼氢化物可配制于苛性碱(如实验室测试中使用的贝克休斯添加剂C(Baker Hughes Additive C)添加剂)中),或者其可以存在于接触塔、沉降罐、水/苛性碱洗涤容器等中。小粒径吸收剂(粉末炭对炭丸粒)在吸收剂中是有利的。合适的粉末可具有等于或小于0.075mm的粒径,合适的颗粒大小可具有1.2-1.4mm的粒径,并且合适的丸粒可具有4mm的最小大小。萃取溶剂的唯一必要条件是其应具有中性或碱性(即等于或大于7.0)的pH值。酸分解硼氢化物,因此酸性pH值会导致过程中氢气产生的一些问题。合适的粘土包括但不必限于绿坡缕石、蒙脱石、膨润土等。
如上所述,从处理的精炼馏出物流中除去反应产物可包括相关领域技术人员已知的任何方法,例如通过使用粘土和/或炭。使用炭(例如活性炭、炭粉、颗粒炭、其他微粒炭)是分离步骤的考虑因素,这是因为已发现当用本文所述的还原剂处理烃时,能除去更多硫。不限于任何特定的解释,这可能是因为还原剂使存在的硫化合物改性,使得其通过吸收于炭介质上而更好地除去。在本方法中,硫化合物在与炭接触之前被改性,并且结果是,即使改性的炭能吸收更多的与本文所述的还原剂一起产生的硫物质。所需的吸收剂的量将根据被除去的硫化合物的类型而变化。例如,具有大“R”基团(即烷基)的一些硫化合物将比具有小“R”基团的硫化合物在炭上占据更多的空间。吸收剂的总容量将取决于所处理的烃精炼馏出物流中存在的每种硫化合物的量。
关于可选的液体吸收剂以除去通过用苛性碱/硼氢化物溶液处理形成的反应产物,合适的胺-醛缩合物包括但不必限于单乙醇胺(MEA)三嗪、甲胺(MA)三嗪。合适的醛水溶液包括但不必限于乙二醛、乙醇醛、戊二醛等。液体吸收剂的量的范围可为独立地约1至约90体积%的所处理的烃;或者,独立地约10至约50体积%的所处理的烃。下面报道的实施例52-60使用10体积%的液体吸收剂至90%的烃,其适合较窄的范围。烃与恰好苛性碱溶液良好接触,但萃取烃中形成的反应产物的能力是有限的。如果仅使用苛性碱溶液,则这导致添加剂的高替代率。当苛性碱/烃溶液分离时,反应产物(例如硫醇离子)可留在处理的烃中。应该注意的是,并非所有液体吸收剂都起作用。已经尝试过无机氧化剂(例如氯化铁)和简单的中和胺(例如甲基二乙醇胺),且其不起作用。
本文所述的方法还具有除去当前清除剂不能除去的高级硫醇的潜力。因此,使用该方法能够处理较高沸点馏分以除去这些腐蚀性物质。
提供以下实施例以说明本方法。这些实施例不是为了限制本方法的范围,并且其也不应该如此解释。除非另有说明,否则量为重量份或重量百分比。
硫清除剂测试程序
1.)投用从精炼厂新鲜接收的轻质原石脑油(LVN)与额外的硫(S)化合物。这些硫化合物包括1-丁硫醇、二甲基二硫化物、二乙基硫化物和二硫化碳。
a.使用适当大小的注射器将所需的S化合物以达到目标ppm水平(即100-1,000+ppm)所需的剂量直接注入测量体积的LVN样品中。
b.注射器(即10uL-1mL)应到达LVN样品表面以下,以限制在转移期间逃逸到容器顶部空间中。
c.针对每种S化合物使用不同的清洁注射器/微型分配器/插管,以避免交叉污染的潜能。
d.容器(例如带有螺旋盖的1L透明玻璃瓶)应靠近顶部填充,以限制更多挥发性S化合物放出至气相。
e.为确保均匀混合,将带盖的瓶置于220rpm的轨道振荡器上的水平位置,持续30秒。
2.)使用适当大小的注射器,向空的(例如6oz.(0.18L)有刻度的投药瓶)投用所需的化学添加剂。
a.在这种情形下,贝克休斯添加剂C(12.5wt.%的硼氢化钠)或贝克休斯添加剂A(45wt.%的氢氧化钾)
b.向投用瓶填充LVN至标记(例如100mL)以达到目标处理率(即,ppm v/v)
3.)充分混合以确保化学添加剂与LVN中的S化合物接触。
a.将带盖的瓶放置在设定于220rpm下的轨道振荡器上的水平位置达2小时。
b.此时,如果要过滤样品,则立即进入4号步骤,否则进行到3c号步骤,然后到5号步骤。
c.充分混合后,使样品静置过夜(约16小时),以使任何水性反应产物潜在沉降出。
4.)使过滤的样品重力迁移通过活性炭。
a.w/w比率1:3.2炭:LVN。
b.在漏斗(例如100mm粉末漏斗)底部中放入少量清洁玻璃棉(0.7-0.8克)以将粉末炭保持在适当位置。
c.向漏斗中称重25克炭。
d.通过炭过滤器缓慢且均匀地倒入LVN。
e.将过滤的LVN收集到较小的瓶(例如2oz.(59mL)带螺旋盖的透明玻璃瓶)中,直至填充到顶部,以限制顶部空间。
5.)然后测试标记的样品瓶的总硫的重量百分比(或ppm)和/或硫形态。
a.不要搅动/重新混合样品瓶。
b.从样品的上部抽取用于测试的等分试样,并且不应扰乱任何水性底部。
c.通过能量分散X射线荧光(ED-XRF)测定的总硫(即,油中的硫)(即,使用ASTMD4294方法)。
d.通过气相色谱-硫选择性检测(GC-SSD)测定硫形态(即,使用ASTM D5623方法)。
实施例1-23
使用上述硫清除剂测试程序来测量命名为添加剂C的硼氢化钠添加剂的影响,所述添加剂C为40wt%的NaOH水溶液中的12wt%的硼氢化钠。结果在表I中给出。缩写在下表I中给出。
表I-实施例1-23
添加剂C添加剂对硫除去的效应
添加剂A=45%KOH水溶液
添加剂B=辛酸锌
添加剂C=40%NaOH水溶液中的12%硼氢化钠
添加剂D=水中的50%氯化铝氢氧化物
添加剂E=水中的31%聚氯化铝
CS2=二硫化碳
C4SH-正丁基硫醇
DES=二乙基硫化物
DMDS=二甲基二硫化物
表II-实施例24-42
炭过滤用于除去所存在/由添加剂C形成的S物质
*此结果与其他数据不一致。需要重新运行以确认结果。
表III-实施例43-51
用以除去S物质的常见过滤介质的比较
注意:名称“WTX”、“CPG LF”、“BG HHH”、“OLC”和“Centaur HSV”是公司的商品名或商标。
实施例52-60
反应产物的液体吸收剂
在这些实验中,将10ml市售的硼氢化钠水溶液添加到具有90ml酸性汽油的分液漏斗中。用手振荡混合物100次,并且然后使其分离。对顶部烃相取样并通过ASTM D 4952-02(也称为刮涂测试)测试活性硫化合物,并且还通过ASTM D3227分析总硫醇含量。刮涂测试是工业中用于评价烃对铜等金属的腐蚀性的常见方法,并且是烃的常见规格。客户将进行测试,并且如果烃未通过测试,他们将知道其含有活性或腐蚀性硫化合物,例如,在将烃放入管道之前必须对所述化合物进行处理。用硼氢化物溶液洗涤汽油后,再次用10ml 48%MEA三嗪于水中的活性溶液洗涤相同的汽油(用手振荡100次)。使烃相分离,并且然后取样并通过刮涂测试和ASTM D3227分析。结果示于表IV中。
表IV
实施例52-56-硼氢化钠+MEA三嗪
在第二组实验中,再使用来自上述实施例52-56的硼氢化物和MEA三嗪溶液并与新鲜酸性汽油一起振荡以观察可以进行多少个循环并仍然通过刮涂测试。因此,将从上述测试分离的相同硼氢化物溶液与新鲜酸性汽油一起振荡,使其分离,取样并通过刮涂测试和ASTM D3227进行测试。如果汽油未通过刮涂测试,则将其仅与MEA三嗪溶液第二次振荡,使其分离,取样并通过刮涂测试和硫醇含量测试。重复使用废硼氢化物和MEA三嗪的循环,直到不再获得失败的刮涂测试为止。结果提供于表V中。
表V
实施例57-60-硼氢化钠+MEA三嗪续
表V中的测试显示,虽然硼氢化物溶液确实减少了汽油中的活性硫含量,但其留下了足够的硫化合物,以致于处理的汽油不能通过刮涂测试。用如MEA三嗪溶液等液体吸附剂洗涤除去硼氢化物洗涤留下的硫化合物,并使汽油通过测试。废清除剂和吸收剂能够再使用多个循环,这显著提高了任何处理的经济性。
在前述说明书中,已经参考本发明的具体实施方案描述了本发明,并且已经展现可有效提供用于从含有硫化合物的精炼馏出物流中除去硫化合物的构型、方法和组合物,例如如表I、II、和III的结果所展现。然而,显而易见的是,在不脱离如所附权利要求中阐述的本发明的更宽范围的情况下,能够对其进行各种修改和改变。因此,说明书应被视为说明性的而非限制性的。例如,预期精炼馏出物流的类型、还原剂、反应产物、硫化合物的量和比率、处理程序、反应参数、固体吸收剂、液体吸收剂和预期落入所要求保护的参数内、但在特定方法中未具体识别或尝试的其他组分和/或条件在本发明的范围内。此外,预期所述方法可以在一定程度上从一种应用变为另一种应用并且仍然实现本文所述的方法的所述目的和目标。
本发明可以适当地包含所公开的要素,由所公开的要素组成或基本上由所公开的要素组成,并且可以在没有未公开的要素的情况下实践。例如,可提供从含有硫化合物的烃流中除去硫化合物的方法,其中该方法包括以下、基本上由以下组成或由以下组成:使烃流与有效与硫化合物反应的量的还原剂接触以在处理的烃流中形成至少一种反应产物,并且从处理的烃流除去所述至少一种反应产物,其中硫化合物、还原剂和烃流如本文所定义。
在另一种非限制性情况下,可提供处理的烃流,其包含以下、基本上由以下组成或由以下组成:选自由C1至C12烷烃、C2至C12烯烃、液化石油气、天然气、燃料气、火炬气、石脑油、汽油、煤油以及其混合物组成的组的液体或轻质烃;至少一种选自由以下组成的组的硫化合物:具有式R-S-H的硫醇,其中R是直链或具支链C1至C4烷基,二硫化碳(CS2),羰基硫(COS),具有式R1-S-R2的二烷基硫化物,其中R1和R2独立地为直链或具支链C1至C4烷基,具有式R1-S-S-R2的二烷基二硫化物,其中R1和R2如前所定义,以及其组合;和至少一种选自由以下组成的组的还原剂:硼烷(BH3)、二硼烷(B2H6)、硼烷或二硼烷与路易斯碱的复合物,所述路易斯碱是选自由醚、二烷基硫化物、胺、醇及其混合物组成的组;具有式M1BH4的无机硼氢化物盐,其中M1是选自由Li、Na和K组成的组,或具有式M2(BH4)2的无机硼氢化物盐,其中M2是选自由Mg、Ca和Zn组成的组;具有式M1BH3CN的氰基硼氢化物,其中M1如前所定义,或具有式M2(BH3CN)2的氰基硼氢化物,其中M2如前所定义;具有式M1BR3 3H的有机硼氢化物,其中M如前所定义,并且R3独立地选自由直链或具支链C1至C3烷基和具有式R4C(O)O-的羧酸酯基团组成的组,并且其中R4是选自由直链或具支链C1至C9烷基组成的组;以及其组合;其中还原剂以有效与硫化合物反应形成至少一种反应产物的量存在。
如本文所用,术语“包含”、“包括”、“含有”、“特征在于”和其语法等同物是不排除额外、未列举的要素或方法动作的包括性的或开放式的术语,但也包括更具限制性的术语“由...组成”和“基本上由......组成”和其语法等同物。如本文所用,关于材料、结构、特征或方法动作的术语“可”指示预期用于实现本公开的实施方案,并且所述术语优先于更具限制性的术语“是”,以避免应该或必须排除与其组合使用的其他相容材料、结构、特征和方法的任何暗示。
如本文所用,单数形式“一(a、an)”和“所述”旨在也包括复数形式,除非上下文另有明确说明。
如本文所用,术语“和/或”包括一个或多个相关所列项目的任何和所有组合。
如本文所用,有关系的术语,例如“第一”、“第二”、“顶部”、“底部”、“上部”、“下部”、“上方”、“下方”等用于清楚和方便理解本公开内容并且不暗示或取决于任何特定的偏好、取向或顺序,除非上下文另有明确说明。
如本文中所用,术语“基本上”在参照给定的参数、性质或条件时在一定程度上意指并包括本领域的普通技术人员将理解,给定的参数、性质或条件满足一定程度的变化,例如在可接受的制造公差范围内。举例来说,取决于基本上满足的特定参数、性质或条件,参数、性质或条件可为至少90.0%满足、至少95.0%满足、至少99.0%满足或甚至至少99.9%满足。
如本文所用,在参照给定参数时术语“约”包括所述值并且具有由上下文指示的含义(例如,其包括与给定参数的测量相关的误差程度)。
Claims (12)
1.一种从含有硫化合物的烃流中除去所述硫化合物的方法,所述方法的特征在于包括:
使所述烃流与有效与所述硫化合物反应以在处理的烃流中形成至少一种反应产物的量的还原剂接触;以及
从所述处理的烃流中除去所述至少一种反应产物;其中:
所述硫化合物是选自由以下组成的组:具有式R-S-H的硫醇,其中R是直链或具支链C1至C4烷基;二硫化碳(CS2);羰基硫(COS);具有式R1-S-R2的二烷基硫化物,其中R1和R2独立地是直链或具支链C1至C4烷基;具有式R1-S-S-R2的二烷基二硫化物;以及其组合;
其中所述烃流包括选自由以下组成的组的液体或气体烃:C1至C12烷烃、C2至C12烯烃、液化石油气、天然气、燃料气、火炬气、石脑油、汽油、煤油以及其混合物;并且
其中所述还原剂选自由以下组成的组:
硼烷(BH3);
二硼烷(B2H6);
硼烷或二硼烷与路易斯碱的复合物,所述路易斯碱选自由醚、二烷基硫化物、胺、醇以及其混合物组成的组;
具有式M1BH4的无机硼氢化物盐,其中M1是选自由Li、Na和K组成的组,或具有式M2(BH4)2的无机硼氢化物盐,其中M2是选自由Mg、Ca和Zn组成的组;
具有式M1BH3CN或具有式M2(BH3CN)2的氰基硼氢化物;
具有式M1BR3 3H的有机硼氢化物并且R3独立地选自由直链或具支链C1至C3烷基和具有式R4C(O)O-的羧酸酯基团组成的组,并且其中R4选自由直链或具支链C1至C9烷基组成的组;以及
其组合。
2.如权利要求1所述的方法,其中在所述烃流与所述还原剂的接触中,所述还原剂是水性的并且pH值在7到14的范围内。
3.如权利要求2所述的方法,其中所述烃流与所述还原剂的接触是在选自由氢氧化钠、氢氧化钾以及其组合组成的组的碱存在下进行。
4.如权利要求1、2或3所述的方法,其中所述还原剂的所述有效量高达所述还原剂与所述硫化合物的化学计量比的两倍。
5.如权利要求1、2或3所述的方法,其中从所述烃流中除去所述至少一种反应产物包括选自由以下组成的组的程序:
使所述处理的烃流通过含有选自由粘土、炭、沸石以及其组合组成的组的固体吸收剂的床;以及
用选自由胺-醛缩合物、水性醛以及其组合组成的组的液体吸收剂洗涤所述处理的烃流。
6.如权利要求1、2或3所述的方法,其中所述还原剂在水溶液中。
7.如权利要求1、2或3所述的方法,其中所述烃流中的烃的范围为C1-C12。
8.一种处理的烃流,其特征在于包含:
选自由以下组成的组的液体或气体轻质烃:C1至C12烷烃、C2至C12烯烃、液化石油气、天然气、燃料气、火炬气、石脑油、汽油、煤油以及其混合物;
至少一种选自由以下组成的组的硫化合物:具有式R-S-H的硫醇,其中R是直链或具支链C1至C4烷基;二硫化碳(CS2);羰基硫(COS);具有式R1-S-R2的二烷基硫化物,其中R1和R2独立地是直链或具支链C1至C4烷基;具有式R1-S-S-R2的二烷基二硫化物,其中R1和R2是如前文所定义;以及其组合;以及
至少一种选自由以下组成的组的还原剂:
硼烷(BH3);
二硼烷(B2H6);
硼烷或二硼烷与路易斯碱的复合物,所述路易斯碱选自由醚、二烷基硫化物、胺、醇以及其混合物组成的组;
具有式M1BH4的无机硼氢化物盐,其中M1是选自由Li、Na和K组成的组,或具有式M2(BH4)2的无机硼氢化物盐,其中M2是选自由Mg、Ca和Zn组成的组;
具有式M1BH3CN或具有式M2(BH3CN)2的氰基硼氢化物;
具有式M1BR3 3H的有机硼氢化物并且R3独立地选自由直链或具支链C1至C3烷基和具有式R4C(O)O-的羧酸酯基团组成的组,并且其中R4选自由直链或具支链C1至C9烷基组成的组;以及
其组合;
其中所述还原剂以有效与所述硫化合物反应形成至少一种反应产物的量存在。
9.如权利要求8所述的处理的烃流,其中在所述烃流与所述还原剂的接触中,所述还原剂是水性的并且pH值在7到14的范围内。
10.如权利要求9所述的处理的烃流,其中所述烃流与所述还原剂的接触是在选自由氢氧化钠、氢氧化钾以及其组合组成的组的碱存在下进行。
11.如权利要求8、9或10所述的处理的烃流,其中所述还原剂的所述有效量高达所述还原剂与所述硫化合物的化学计量比的两倍。
12.如权利要求8、9或10所述的处理的烃流,其中所述烃流中的烃的范围为C1-C12。
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- 2017-03-28 CN CN201780022446.6A patent/CN108883360B/zh not_active Expired - Fee Related
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CA3020539C (en) | 2020-04-28 |
CA3020539A1 (en) | 2017-10-19 |
EP3442683A4 (en) | 2019-11-13 |
EP3442683A1 (en) | 2019-02-20 |
US20170298281A1 (en) | 2017-10-19 |
US10414989B2 (en) | 2019-09-17 |
ES2942714T3 (es) | 2023-06-06 |
PT3442683T (pt) | 2023-05-12 |
CN108883360B (zh) | 2021-05-25 |
WO2017180320A1 (en) | 2017-10-19 |
EP3442683B1 (en) | 2023-03-15 |
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