CN116769510A - CS removal from liquid light hydrocarbon streams by reaction and distillation 2 Method for producing sulfur-containing compounds - Google Patents
CS removal from liquid light hydrocarbon streams by reaction and distillation 2 Method for producing sulfur-containing compounds Download PDFInfo
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- CN116769510A CN116769510A CN202310725700.6A CN202310725700A CN116769510A CN 116769510 A CN116769510 A CN 116769510A CN 202310725700 A CN202310725700 A CN 202310725700A CN 116769510 A CN116769510 A CN 116769510A
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- Prior art keywords
- sulfur
- salt
- light hydrocarbon
- way switching
- reaction
- Prior art date
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 155
- 239000011593 sulfur Substances 0.000 title claims abstract description 155
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 155
- 238000004821 distillation Methods 0.000 title claims abstract description 106
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 104
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 104
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 99
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 73
- 239000007788 liquid Substances 0.000 title claims abstract description 57
- 150000001875 compounds Chemical class 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 78
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 77
- 229910001868 water Inorganic materials 0.000 claims abstract description 74
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 68
- 230000003009 desulfurizing effect Effects 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 49
- 150000001412 amines Chemical class 0.000 claims abstract description 42
- 239000000463 material Substances 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 238000007789 sealing Methods 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims description 90
- 150000003463 sulfur Chemical class 0.000 claims description 88
- 230000008929 regeneration Effects 0.000 claims description 69
- 238000011069 regeneration method Methods 0.000 claims description 69
- 238000011084 recovery Methods 0.000 claims description 51
- 238000010926 purge Methods 0.000 claims description 40
- 239000002904 solvent Substances 0.000 claims description 33
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 18
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 14
- 238000000354 decomposition reaction Methods 0.000 claims description 10
- 150000003464 sulfur compounds Chemical class 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 8
- 239000007791 liquid phase Substances 0.000 claims description 6
- 239000012071 phase Substances 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 4
- 239000002608 ionic liquid Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 238000003303 reheating Methods 0.000 claims description 2
- -1 amine salt Chemical class 0.000 abstract description 28
- 239000003208 petroleum Substances 0.000 abstract description 15
- 239000010865 sewage Substances 0.000 abstract description 7
- 239000012159 carrier gas Substances 0.000 abstract description 5
- 238000005191 phase separation Methods 0.000 abstract description 4
- 239000007789 gas Substances 0.000 description 86
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 48
- 239000000243 solution Substances 0.000 description 34
- 238000006477 desulfuration reaction Methods 0.000 description 29
- 230000023556 desulfurization Effects 0.000 description 29
- 229910052757 nitrogen Inorganic materials 0.000 description 24
- 239000000047 product Substances 0.000 description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 18
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
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- 238000010438 heat treatment Methods 0.000 description 10
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- 229920000768 polyamine Polymers 0.000 description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 8
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- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 8
- CRSOQBOWXPBRES-UHFFFAOYSA-N neopentane Chemical compound CC(C)(C)C CRSOQBOWXPBRES-UHFFFAOYSA-N 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- 150000003568 thioethers Chemical class 0.000 description 8
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 7
- 239000003463 adsorbent Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 6
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- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 4
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 239000001273 butane Substances 0.000 description 4
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 4
- 229940043276 diisopropanolamine Drugs 0.000 description 4
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 4
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 150000007529 inorganic bases Chemical class 0.000 description 4
- 239000003915 liquefied petroleum gas Substances 0.000 description 4
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- KJRCEJOSASVSRA-UHFFFAOYSA-N propane-2-thiol Chemical compound CC(C)S KJRCEJOSASVSRA-UHFFFAOYSA-N 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 230000001172 regenerating effect Effects 0.000 description 4
- 150000003457 sulfones Chemical class 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000003444 phase transfer catalyst Substances 0.000 description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001299 aldehydes Chemical class 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
- 229910021529 ammonia Inorganic materials 0.000 description 2
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 2
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- 239000004202 carbamide Substances 0.000 description 2
- 150000003857 carboxamides Chemical class 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- 150000002019 disulfides Chemical class 0.000 description 2
- 239000012990 dithiocarbamate Substances 0.000 description 2
- 230000005674 electromagnetic induction Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
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- 239000004576 sand Substances 0.000 description 2
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- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 2
- SZUVGFMDDVSKSI-WIFOCOSTSA-N (1s,2s,3s,5r)-1-(carboxymethyl)-3,5-bis[(4-phenoxyphenyl)methyl-propylcarbamoyl]cyclopentane-1,2-dicarboxylic acid Chemical compound O=C([C@@H]1[C@@H]([C@](CC(O)=O)([C@H](C(=O)N(CCC)CC=2C=CC(OC=3C=CC=CC=3)=CC=2)C1)C(O)=O)C(O)=O)N(CCC)CC(C=C1)=CC=C1OC1=CC=CC=C1 SZUVGFMDDVSKSI-WIFOCOSTSA-N 0.000 description 1
- YZFQBIYIERZDBV-UHFFFAOYSA-N (2-ethylphenyl)methanediamine Chemical compound CCC1=CC=CC=C1C(N)N YZFQBIYIERZDBV-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical class [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
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- YNNGZCVDIREDDK-UHFFFAOYSA-N aminocarbamodithioic acid Chemical class NNC(S)=S YNNGZCVDIREDDK-UHFFFAOYSA-N 0.000 description 1
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- 229910052791 calcium Inorganic materials 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
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- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000000066 reactive distillation Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003335 secondary amines Chemical group 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
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- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention belongs to the technical field of petroleum processing and petrochemical industry, and relates to a method for removing CS from liquid light hydrocarbon material flow by utilizing reaction and distillation 2 And a method for producing a sulfur-containing compound. The method is characterized in that the sulfur-containing amine salt formed in the reaction process is reversibly transformed, the sulfur-containing amine salt is separated by a filter, and the sulfur-containing amine salt is thermally decomposed by high-temperature carrier gas to form organic amine and CS 2 The regenerated organic amine can be recycled, and the regenerated CS 2 Sealing and storing the mixture in cold water at low temperature. The method can greatly reduce the dosage of desulfurizing agent, and can solve the sewage problem generated by water phase separation and the problem of salt blockage in the pipelineThe whole process is more environment-friendly.
Description
Technical Field
The invention belongs to the technical field of petroleum processing and petrochemical industry, and relates to a method for removing CS from liquid light hydrocarbon material flow by utilizing reaction and distillation 2 A method for producing a sulfur-containing compound; in particular low CS is continuously obtained from light hydrocarbon streams rich in olefins by reaction, distillation and decomposition of sulfur-containing salts 2 And a process for producing a low sulfur liquid light hydrocarbon stream.
Background
Liquid light hydrocarbons (C3-C5) are mainly from atmospheric and vacuum devices, delayed coking, catalytic cracking, hydrocracking, catalytic reforming and head oil removal devices and hydrocarbon steam cracking devices in petrochemical industry. Wherein, the cracking carbon five is rich in olefin, components such as isoprene, piperylene, cyclopentadiene, valerene and the like can be obtained through distillation, and can be further processed as raw materials to form high molecular compounds such as plastics, polyesters, rubber and the like. With the deterioration of petroleum processing raw materials in recent years, the contents of sulfur, nitrogen and the like in petroleum processing products are gradually increased, and the existence of sulfur-containing compounds can obviously influence the stability of light hydrocarbon components (when the petroleum processing raw materials are rich in olefins) and cause corrosion to catalysts, auxiliary agents and metal equipment in subsequent processing technologies. The traditional removing modes of the sulfur-containing compounds in the hydrocarbon comprise hydrodesulfurization, adsorption desulfurization, oxidation desulfurization, complexation desulfurization, solvent desulfurization, biological desulfurization and the like. For C5 hydrocarbons (especially from cracking C5), the sulfur-containing component is CS 2 And secondly, the composition also contains a small amount of isopropyl mercaptan, dimethyl sulfide and the like. The common method for removing sulfur-containing components (mostly) in the carbon five comprises the following steps: adsorption desulfurization (solid adsorbent, activated carbon fiber, etc.), catalytic hydrolysis desulfurization (CS) 2 Forming COS and then H 2 S), liquid phase physical adsorption desulfurization and liquid phase solvent desulfurization.
CN103182291A discloses a deep desulfurization adsorbent for cracking carbon five distillate oil, which adopts gamma-Al 2 O 3 Impregnating the carrier with group IA or group IIA metals such as zinc, copper, potassium, sodium, calcium, etc.; CN 111875469A discloses a method for ultra-deep removal of carbon disulfide in isoprene (carbon five), and the adsorbent contains porous silica powder and alkaline earth goldBelongs to oxide powder, pore-expanding agent and auxiliary agent; CN 104907104A discloses a method for removing CS at low temperature using a core-shell catalyst 2 The method prepares the active carbon nano particles which are used as the inner core and are coated with a layer of Fe 2 O 3 A low temperature desulfurization catalyst of the shell; CN109019535a discloses an active boron nitride absorber; CN 114026203a achieves removal of sulfur-containing species by grafting primary/secondary amine groups onto a solid inorganic support (e.g., silica, alumina, magnesia, titania, zirconia); jilin university (Xu Yang. Adsorption desulfurization study of sulfides in isoprene [ D ] ]University of Jilin, 2015.) CS using a adsorbent composed of activated carbon and molecular sieve and an adsorbent composed of activated carbon and zinc oxide 2 Desulfurizing; research of China university of Petroleum (Meng Ling rigid. Modified activated alumina adsorption removal of carbon disulfide from isoprene [ D ]]University of petroleum, 2020.) K is used 2 CO 3 /γ-Al 2 O 3 The breakthrough time was 158 hours and the breakthrough sulfur capacity was 0.72 for the adsorbent. When the adsorption method is adopted to carry out the adsorption desulfurization of the liquid carbon five light hydrocarbons, the desulfurization requirement of industrial products is difficult to be met due to the limited adsorption sulfur capacity of the solid; meanwhile, the harsh regeneration conditions and the deactivation of the regenerated adsorbent lead the industrialized multi-selective liquid phase solvent desulfurization of the carbon five light hydrocarbon desulfurization.
US 2,418,047 reacts hydrocarbon liquids with dimethylamine in aqueous solution to form aminodithiocarbamates to remove carbon disulphide. EP 0053571 A1 is modified with polyamines (e.g. tetraethylenepentamine) and CS-containing compounds 2 Is contacted with a solution of isoprene and pentane. WO 2015/026649 A1 uses a polyamine (tetraethylenepentamine or diethylenetriamine with quaternary ammonium salt as phase transfer catalyst. CN 105451861A uses a treatment composition of at least one phase transfer catalyst to remove carbon disulfide from a hydrocarbon stream. U.S. Pat. No. 4,98889 B2 discloses a combined treatment composition using a carbon disulfide removal agent and at least one phase transfer catalyst. The carbon disulfide removal agent comprises at least one polyamine molecule, H 2 N-(R1-NH)x-R 2 -(NH-R 3 )y-NH 2 . CN105112093A reacts the carbon-five raw material with desulfurizing agent at a certain temperature and pressure for a period of time, and then distilledThe top of the tower is divided into cracking carbon five without sulfur, and the desulfurizing agent comprises the following components: 3-8% of triethanolamine, 3-8% of acetonitrile, 3-8% of toluene, 3-8% of acetone, 8-12% of benzene, 25-35% of saturated ammonia water, 8-12% of butyronitrile, 8-12% of cyclohexane, 10-20% of aniline and 3-8% of 2-ethyltoluenediamine.
Better removal of low sulfur compounds and the like can be realized by adopting vulcanizing agents such as organic amine, polyamine, alcohol amine and the like, however, when the vulcanizing agents are combined with the sulfur compounds, the separation mode of the vulcanizing agents and hydrocarbons is not efficient; in US 2,418,047, EP 0053571A1, CN 105451861A and US 9981889 B2, CS 2 RNH (CS) RNH with organic amine and polyamine, and RH with isopropyl mercaptan 3 SCH(CH 3 ) 2 . Water is added into the system to separate sulfur-containing compounds from hydrocarbons, and the disulfide-containing compounds form dithiocarbamates which are transferred into a water phase under the assistance of phase transfer quaternary ammonium salt, so that separated isoprene is subjected to multiple water washing, and a large amount of sewage is formed; at the same time, the dithiocarbamate regeneration process can clog the lines, leading to process failure.
If the new method can be adopted to make sulfide react with vulcanizing agent, and the formed sulfur-containing species are effectively separated from hydrocarbon after the reaction, it is possible to solve the sewage problem and salt blockage problem generated by water phase separation, and the sulfide removal in light hydrocarbon is more effectively realized. Meanwhile, the formation of azeotrope can be avoided, and the high-purity light hydrocarbon product can be obtained.
Disclosure of Invention
Based on the above problems, the present invention provides a method for removing CS from a liquid light hydrocarbon stream by reaction and distillation 2 And a method for producing a sulfur-containing compound. The method is characterized in that the sulfur-containing amine salt formed in the reaction process is reversibly transformed, the sulfur-containing amine salt is separated by a filter, and the sulfur-containing amine salt is thermally decomposed by high-temperature carrier gas to form organic amine and CS 2 The regenerated organic amine can be recycled, and regeneratedPost CS 2 Sealing and storing the mixture in cold water at low temperature. The method can greatly reduce the dosage of the desulfurizing agent, can solve the sewage problem generated by water phase separation and the problem of pipeline blockage caused by salts, and is more environment-friendly.
The invention specifically provides the following technical scheme.
CS removal from liquid light hydrocarbon streams by reaction and distillation 2 And a method for producing a sulfur-containing compound, comprising the steps of:
step 1, mixing a sulfur-containing light hydrocarbon component with a desulfurizing agent, adding the mixture into a reactor, and reacting at a certain reaction temperature and a certain reaction pressure;
step 2, after the reaction is finished, the desulfurized components enter a distillation tower, and light hydrocarbon components with qualified sulfur content are obtained from the top of the distillation tower; step 3, circulating solution containing salt in the tower bottom material flows through a filtering and sulfur salt-containing regeneration system under the drive of a pump to form filtered circulating solution, and the filtered circulating solution returns to the distillation tower; meanwhile, after the purging regenerated gas enters a filtering and sulfur salt-containing regeneration system, regenerated decomposed gas is formed;
and 4, condensing the regenerated decomposed gas in an organic amine recovery tank, and discharging the condensed liquid organic amine at the bottom of the organic amine recovery tank for recycling. The condensed gaseous product is further sent to a cold water recovery tank. Discharging tail gas from the top of the cold water recovery tank, and sealing the enriched liquid sulfur-containing substances at the bottom of the cold water recovery tank
Further, in step 1, the hydrocarbon in the sulfur-containing light hydrocarbon component is a C3-C5 component, including liquefied petroleum gas, reformed topped oil, petroleum ether, cracked carbon five component, light petroleum oil, etc., and typically at least comprises one or more of propane, propylene, butane, butene, butadiene, n-pentane, isopentane, neopentane, cyclopentane, pentene, isopentene, pentadiene, isoprene, piperylene, cyclopentadiene, etc.; the sulfides in the sulfur-containing light hydrocarbon component generally include solubility H 2 S、COS，CS 2 Mercaptans, sulfides, disulfides, and the like.
In step 1, the desulfurizing agent may be an alcohol solvent, a sulfone solvent, an organic amine, a polyamine, an alcohol amine, an amide, a ketone solvent, an aldehyde solvent, an ether, ammonia, a water-soluble inorganic amine salt, or a water-soluble inorganic base, or may be a mixture of one or more solvents.
Further, the alcoholic solvents generally include water-soluble organic alcohols (e.g., methanol, ethanol, propanol, glycol, etc.), polyethylene glycol, ethylene glycol, etc.
Further, sulfone-based solvents typically include sulfolane and its derivatives.
Further, organic amines include primary, secondary, tertiary amine organic compounds, common organic amines include diethylamine further, polyamines of the general formula: h 2 N-(R 1 -NH)x-R 2 -(NH-R 3 )y-NH 2 Wherein R is 1 、R 2 、R 3 Are identical or different and comprise H, aryl and C1-C4 alkyl; x and y are integers between 0 and 10.
Further, the alcohol amine typically includes ethanolamine (MEA), diethanolamine, triethanolamine, diglycolamine (DGA), diisopropanolamine (DIPA), triethanolamine (TEA), N-Methyldiethanolamine (MDEA), and the like.
Further, the amide generally includes formamide, acetamide, dimethylformamide, carboxamide, etc., in which case the desulfurizing agent may be a liquid or an aqueous solution.
Further, the water-soluble inorganic amine salts generally include ammonium formate, ammonium oxalate, urea, and the like.
Further, the water-soluble inorganic base generally includes NaOH, KOH, ca (OH) 2 Etc.
Further, in step 1, the reaction temperature of the sulfur-containing light hydrocarbon component and the desulfurizing agent is-20 to 300 ℃, preferably 0 to 100 ℃.
Further, in step 1, the reaction pressure of the sulfur-containing light hydrocarbon component and the desulfurizing agent should ensure that the hydrocarbon is in a liquid phase, and the reaction pressure is normal pressure for the carbon five component; for C3-C4 components pressures of 0.1-2.0MPa, preferably 0.2-1.5MPa, for C three and C four.
Further, in step 1, the contact time of the sulfur-containing light hydrocarbon component with the desulfurizing agent is 5 minutes to 24 hours, preferably 20 minutes to 6 hours.
Further, in step 1, the ratio of the desulfurizing agent to the sulfur-containing light hydrocarbon component is 1/10000 to 1/10 (V/V) (100 ppm to 100000 ppm), preferably 1/2000 to 1/100 (V/V) (500 ppm to 10000 ppm).
Further, in step 1, the reactor is one of a tank reactor, a tubular reactor, a reactor of a solid particle bed layer or a tower reactor.
Further, in the step 2, the distillation tower can obtain a product through the tower top or a side line according to the product requirement; an overhead condenser may be included or not, a break condenser may be included or not, and a reboiler may be included or not, and a stripper may be included or not when the product is obtained by side stripping.
Further, the materials enter the distillation tower from the reactor to be continuously fed or intermittently fed; depending on the reactor and distiller volumes, when intermittent feed is used, it is one of one distillation per reaction, one distillation multiple times per reaction, or concentrated distillation after multiple times per reaction.
Further, in step 2, the light hydrocarbon component with qualified sulfur content is the same as the hydrocarbon component in the sulfur-containing light hydrocarbon component, and is a C3-C5 component, including liquefied petroleum gas, reformed topped oil, petroleum ether, cracked carbon five component, light petroleum oil, and the like, and generally at least comprises one or more of propane, propylene, butane, butene, butadiene, n-pentane, isopentane, neopentane, cyclopentane, pentene, isopentene, pentadiene, isoprene, piperylene, and cyclopentadiene.
Further, the light hydrocarbon component with qualified sulfur content can be directly obtained as a product; when a small amount of water exists at the bottom of the distillation tower, part of the water and the light hydrocarbon component are distilled at the same time, at the moment, an external light hydrocarbon liquid separation tank is needed, after the light hydrocarbon component and the water are kept stand for layering, the light hydrocarbon component with qualified sulfur content and without water is obtained from the top, and a small amount of separation water can be recycled.
Further, in the step 3, the salt in the salt-containing circulating solution is derived from the salt generated by the reaction of sulfide in the sulfur-containing light hydrocarbon component and the desulfurizing agent; when the salt is a solution, the normal circulation is performed; when the salt contains solid particles, the salt is conveyed by a slurry pump.
Further, in step 3, the salt-containing circulating solution at the bottom of the distillation column is circulated, and the filtration and the operation of the sulfur salt-containing regeneration system are determined according to the formation conditions of the generated sulfur salt, and one of circulation and regeneration is performed during each distillation, circulation and regeneration are performed after each distillation, or circulation and regeneration are performed after a plurality of reactions and distillation.
Further, in step 3, the first distillation is initiated, and a certain amount of solvent is added into the distillation tower to improve the solubility of the sulfur-containing salt. The solvent can only dissolve sulfur-containing salt but not light hydrocarbon, such as water; can also dissolve sulfur-containing salt and light hydrocarbon, such as furfural and other organic compounds. The ratio of solvent to light hydrocarbon is 0-0.80, preferably 0-0.20.
Further, in step 3, the filtration and sulfur salt-containing regeneration system comprises a plurality of switching valves, 1 or more filtration and sulfur salt-containing regenerators.
Further, the switching valve is a multi-way valve, and comprises any one of a ten-way valve, an eight-way valve, a six-way valve, a four-way valve, a three-way valve and a two-way valve; wherein, a six-way switching valve can be replaced by two four-way switching valves, a four-way switching valve can be replaced by two three-way switching valves, and a three-way switching valve can be replaced by two-way switching valves.
Further, the plurality of filtering and sulfur salt-containing regenerators are equivalent, the types of the filtering and sulfur salt-containing regenerators can be the same or different, the filtering and sulfur salt-containing regenerators can be externally heated or not heated, and when externally heated, the heating mode can adopt direct heating (such as fuel combustion) and indirect heating (such as oil bath, sand bath, resistance furnace, heat radiation, electromagnetic induction, microwaves and the like). When unheated, should be able to withstand the high temperatures of the purge regeneration gas for long periods of time.
Further, in step 3, the structure of the filtration and sulfur salt-containing regeneration system comprises a plurality of three-way switching valves and two filtration and sulfur salt-containing regenerators which are independently and externally heated; the salt-containing circulating solution enters two filtering and sulfur salt-containing regenerators through a front three-way switching valve, then flows out through a rear three-way switching valve to form filtered circulating solution, and the purging regenerated gas enters the two filtering and sulfur salt-containing regenerators through the front three-way switching valve and then flows out through the rear three-way switching valve to form regenerated decomposed gas.
Further, in step 3, the filtration and sulfur salt-containing regeneration system comprises: the system comprises a plurality of three-way switching valves and an independent externally heated filtering and sulfur salt-containing regenerator, wherein a salt-containing circulating solution enters the filtering and sulfur salt-containing regenerator through a front three-way switching valve, then flows out through a rear three-way switching valve to form a filtered circulating solution, and a purging regenerated gas enters the filtering and sulfur salt-containing regenerator through the front three-way switching valve and then flows out through the rear three-way switching valve to form regenerated decomposed gas, and the front three-way switching valve and the rear three-way switching valve are connected through a bypass.
Further, in step 3, the filtration and sulfur salt-containing regeneration system comprises: a plurality of four-way switching valves and two equivalent filtering and sulfur salt-containing regenerators; the four interfaces of the front four-way switching valve are sequentially provided with a salt-containing circulating solution, a filtering and sulfur-containing salt regenerator, a purging regeneration gas, a filtering and sulfur-containing salt regenerator; the four interfaces of the rear four-way switching valve are sequentially provided with a regenerated decomposed gas, a filter and sulfur salt-containing regenerator, a filtered circulating liquid and a filter and sulfur salt-containing regenerator.
Further, in step 3, the filtration and sulfur salt-containing regeneration system comprises: a plurality of four-way switching valves and a filtering and sulfur salt-containing regenerator; the four interfaces of the front four-way switching valve are sequentially provided with a salt-containing circulating solution, a filtering and sulfur-containing salt regenerator, a purging regeneration gas, a filtering and sulfur-containing salt regenerator; the four interfaces of the rear four-way switching valve are sequentially regenerated decomposed gas, a front four-way switching valve, filtered circulating liquid, filtered and a sulfur salt-containing regenerator.
Further, the filtration and sulfur salt regeneration system can also adopt a fractional step method, common filtration equipment is adopted, and the common filtration equipment such as a plate-and-frame filter press, a box filter press, a tubular filter, a rotary drum press filter and the like is adopted for collecting sulfur salt precipitate, and the collected sulfur salt precipitate is further decomposed on high temperature resistant equipment or is sold as a product.
Further, in step 3, the purging regeneration gas may be nitrogen, inert gas, steam or reducing gas (such as hydrogen), and when the purging regeneration gas is oxidizing gas (such as air or oxygen), the pipeline may be purged with inert gas (such as nitrogen) in advance.
Further, in step 3, the temperature of the purge regeneration gas is normal temperature or high temperature. When high-temperature purge gas is adopted, direct purge can be performed without reheating; the inlet temperature of the regenerated gas is higher than the decomposition temperature of the sulfur-containing salt, and the filtering and sulfur-containing salt regenerator is not damaged; the temperature is 30-1000deg.C, preferably 50-800deg.C, most preferably 60-600deg.C; the purge time is 10 minutes to 24 hours, preferably 20 minutes to 6 hours.
Further, in step 3, when the temperature of the purge regeneration gas is at normal temperature, a filtration and sulfur salt-containing regenerator capable of being independently heated should be selected. At this time, the temperature of the regenerator should be greater than the decomposition temperature of the sulfur-containing salt while ensuring that the filtration and sulfur-containing salt regenerator are not damaged; the temperature is 30-1000deg.C, preferably 50-800deg.C, most preferably 60-600deg.C; the purge time is 10 minutes to 24 hours, preferably 20 minutes to 6 hours.
In step 4, the organic amine recovery tank is a liquid product obtained after condensing the regenerated decomposed gas, and the temperature of the organic amine recovery tank is higher than the boiling point of sulfides in the sulfur-containing light hydrocarbon component under the pressure of the device and lower than the boiling point of the desulfurizing agent.
Further, in step 4, the cold water recovery tank is mainly used for capturing and liquid recovery of sulfur-containing compounds, and the temperature of the cold water recovery tank is lower than the boiling point of the recovered sulfur-containing compounds; when the density of the recovered sulfur-containing compound is higher than that of water (e.g. CS 2 ) The device can be directly stored at the bottom of a cold water recovery tank for sealing and can discharge regenerated tail gas at the top of the cold water recovery tank; . When the density of the recovered sulfur-containing compounds is less than that of water (mercaptan and thioether), the sulfur-containing compounds can be directly stored at the top of a cold water recovery tank for sealing; the regenerated tail gas is discharged through an externally added discharge pipe at the bottom of the cold water recovery tank.
Further, adding a solvent in the reactor or the distillation tower, wherein the solvent is water or an organic solvent, and the solvent comprises furfural, ionic liquid or a phase transfer agent and other reagents which are obviously dissolved in the sulfur-containing salt.
Compared with the prior art, the invention has the beneficial effects that.
Opposite to each otherThe sulfur-containing amine salt formed in the process is subjected to a reversible transformation. After the sulfur-containing compound forms sulfur-containing salt with the desulfurizing agent, the sulfur-containing compound is decomposed to obtain organic amine and sulfur-containing compound. Separating out the sulfur-containing amine salt by using a filter, and thermally decomposing the sulfur-containing amine salt at high temperature by using a carrier gas to form organic amine and CS 2 The method comprises the steps of carrying out a first treatment on the surface of the The regenerated organic amine can be recycled, and the regenerated CS 2 Sealing and storing the mixture in cold water at low temperature. In order to realize industrial continuous operation, filtration and regeneration can be alternately performed in situ. At this time, a filtration and sulfate-containing regeneration system can be constructed using a switching valve and a filter. The high temperature is achieved by either directly introducing a high temperature carrier gas or passing a normal temperature carrier gas through a heatable filter assembly. In order to save costs, when the reaction is operated batchwise, the filtration and regeneration processes can also be carried out stepwise. At this time, the sulfur-containing salt may be filtered and enriched by a conventional filtering apparatus, and then the enriched sulfur-containing salt may be separately subjected to thermal decomposition and recovery of the organic amine and the sulfur-containing compound. Unlike available patent, the said process can reduce desulfurizing agent amount greatly and solve the sewage problem caused by water phase separation and the problem of salt blocking pipeline.
Drawings
FIG. 1 removal of CS according to the present invention 2 And a process flow diagram of a sulfur-containing compound process.
FIG. 2 is a flow chart of the filtration and sulfur salt-containing regeneration system of the present invention.
The device comprises a sulfur-containing light hydrocarbon component 1, a desulfurizing agent 2, a reactor 3, a distillation tower 4, a salt-containing circulating solution 6,7 filtering and sulfur salt-containing regenerating system, a circulating solution after 8 filtering, a purging regenerated gas 9, a regenerating decomposed gas 10, an organic amine recovery tank 11, a cold water recovery tank 12, a tail gas 13, a liquid state of 14 enrichment, a liquid organic amine recovery liquid 15, a light hydrocarbon liquid separation tank 16, a light hydrocarbon component 17 free of moisture and qualified in sulfur content, separating water 18, a solvent 19, a front three-way switching valve 20, 24, 26 and 29, a rear three-way switching valve 21, 22, 27, 32, 33 and 36 filtering and sulfur salt-containing regenerator, a rear three-way switching valve 23, 25, 28 and 30, a front four-way switching valve 31 and 35, and a rear four-way switching valve 34 and 37.
Detailed description of the preferred embodiments
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
As shown in fig. 1 and 2, a method for removing CS from a liquid light hydrocarbon stream by reaction and distillation 2 And a method for producing a sulfur-containing compound, comprising the steps of:
step 1, mixing a sulfur-containing light hydrocarbon component 1 with a desulfurizing agent 2, adding the mixture into a reactor 3, and reacting at a certain reaction temperature and reaction pressure;
step 2, after the reaction is finished, the desulfurized component enters a distillation tower 4, and a light hydrocarbon component 5 with qualified sulfur content is obtained from the top of the distillation tower;
step 3, the salt-containing circulating solution 6 in the tower bottom material flows through a filtering and sulfur salt-containing regeneration system 7 under the drive of a pump to form a filtered circulating solution 8, and the filtered circulating solution returns to the distillation tower; meanwhile, after the purge regeneration gas 9 enters a filtering and sulfur salt-containing regeneration system 7 to be formed, a regenerated decomposition gas 10 is formed;
and 4, condensing the regenerated decomposed gas 10 in an organic amine recovery tank 11, introducing a gas product into a cold water recovery tank 12, and discharging the condensed liquid organic amine 15 at the bottom of the organic amine recovery tank 11 for recycling. The condensed gaseous product is further sent to a cold water recovery tank 12, tail gas 13 is discharged from the top of the cold water recovery tank 12, and an enriched liquid 14 is sealed at the bottom of the cold water recovery tank 12.
Further, in step 1, the hydrocarbon in the sulfur-containing light hydrocarbon component 1 is a C3-C5 component, including liquefied petroleum gas, reformed topped oil, petroleum ether, cracked carbon five component, light petroleum oil, etc., and typically at least comprises one or more of propane, propylene, butane, butene, butadiene, n-pentane, isopentane, neopentane, cyclopentane, pentene, isopentene, pentadiene, isoprene, piperylene, cyclopentadiene, etc.; the sulfides in sulfur-containing light hydrocarbon component 1 generally comprise solubility H 2 S、COS，CS 2 Mercaptans, sulfides, disulfides, and the like.
In step 1, the desulfurizing agent 2 may be an alcohol solvent, a sulfone solvent, an organic amine, a polyamine, an alcohol amine, an amide, a ketone solvent, an aldehyde solvent, an ether, ammonia, a water-soluble inorganic amine salt, or a water-soluble inorganic base, or may be a mixture of one or more solvents.
Further, the alcoholic solvents generally include water-soluble organic alcohols (e.g., methanol, ethanol, propanol, glycol, etc.), polyethylene glycol, ethylene glycol, etc.
Further, sulfone-based solvents typically include sulfolane and its derivatives.
Further, organic amines include primary, secondary, tertiary amine organic compounds, common organic amines include diethylamine further, polyamines of the general formula: h 2 N-(R 1 -NH)x-R 2 -(NH-R 3 )y-NH 2 Wherein R is 1 、R 2 、R 3 Are identical or different and comprise H, aryl and C1-C4 alkyl; x and y are integers between 0 and 10.
Further, the alcohol amine typically includes ethanolamine (MEA), diethanolamine, triethanolamine, diglycolamine (DGA), diisopropanolamine (DIPA), triethanolamine (TEA), N-Methyldiethanolamine (MDEA), and the like.
Further, the amide generally includes formamide, acetamide, dimethylformamide, carboxamide, etc., in which case the desulfurizing agent may be a liquid or an aqueous solution.
Further, the water-soluble inorganic amine salts generally include ammonium formate, ammonium oxalate, urea, and the like.
Further, the water-soluble inorganic base generally includes NaOH, KOH, ca (OH) 2 Etc.
Further, in step 1, the reaction temperature of the sulfur-containing light hydrocarbon component 1 and the desulfurizing agent 2 is-20 to 300 ℃, preferably 0 to 100 ℃.
Further, in the step 1, the reaction pressure of the sulfur-containing light hydrocarbon component 1 and the desulfurizing agent 2 should ensure that the hydrocarbon is in a liquid phase, and the reaction pressure is normal pressure for the carbon five component; for C3-C4 components pressures of 0.1-2.0MPa, preferably 0.2-1.5MPa, for C three and C four.
Further, the sulfur-containing light hydrocarbon component 1 and the desulfurizing agent 2 are fully contacted under the reaction temperature and the reaction pressure, so that the sulfur-containing component of the sulfur-containing light hydrocarbon component 1 is effectively removed, and the product requirement is met.
Further, in step 1, the contact time of the sulfur-containing light hydrocarbon component 1 with the desulfurizing agent 2 is 5 minutes to 24 hours, preferably 20 minutes to 6 hours.
Further, in step 1, the ratio of the desulfurizing agent 2 to the sulfur-containing light hydrocarbon component 1 is 1/10000 to 1/10 (V/V) (100 ppm to 100000 ppm), preferably 1/2000 to 1/100 (V/V) (500 ppm to 10000 ppm).
Further, in the step 1, the reactor 3 is one of a kettle type reactor, a tubular type reactor, a solid particle bed reactor or a tower type reactor, so that the sulfur-containing light hydrocarbon component 1 and the desulfurizing agent 2 are ensured to fully react in the reactor 3.
Further, in step 2, the distillation column 4 may obtain the product through the top of the column or through the side line according to the product requirement; an overhead condenser may be included or not, a break condenser may be included or not, and a reboiler may be included or not. When the product is obtained by side stripping, a stripper may or may not be included.
Further, the material from the reactor 3 into the distillation column 4 may be continuously fed or may be intermittently fed; depending on the reactor and distiller volumes, when intermittent feeding is used, it may be one distillation reaction, multiple distillation reactions, or concentrated distillation after multiple reactions.
Further, in step 2, the hydrocarbon component 5 with qualified sulfur content is the same as the hydrocarbon component in the sulfur-containing light hydrocarbon component 1, and is a C3-C5 component, including liquefied petroleum gas, reformed topped oil, petroleum ether, cracked carbon five component, light petroleum oil, and the like, and generally at least comprises one or more of propane, propylene, butane, butene, butadiene, n-pentane, isopentane, neopentane, cyclopentane, pentene, isopentene, pentadiene, isoprene, piperylene, and cyclopentadiene.
Further, the light hydrocarbon component 5 with qualified sulfur content can be directly obtained as a product; when a small amount of water exists at the bottom of the distillation tower, part of the water and the light hydrocarbon component are distilled at the same time, at the moment, a light hydrocarbon liquid separation tank 16 is required to be externally connected, after the light hydrocarbon component and the water are kept stand for layering, the light hydrocarbon component 17 with qualified sulfur content and without water is obtained from the top, and a small amount of separation water 18 can be recycled.
Further, in the step 3, the salt in the salt-containing circulating solution 6 is derived from the salt generated by the reaction of the sulfide in the sulfur-containing light hydrocarbon component 1 and the desulfurizing agent 2; when the salt is a solution, the normal circulation is performed; when the salt contains solid particles, the salt is conveyed by a slurry pump.
Further, in step 3, the operation of the salt-containing circulating solution 6 at the bottom of the distillation column and the filtration and sulfur salt-containing regeneration system 7 is determined according to the formation conditions of the generated sulfur salt, and the circulating and regeneration are performed during each distillation, after each distillation, or after a plurality of reactions and distillation.
Further, in step 3, the first distillation is initiated, and a certain amount of solvent is added into the distillation tower to improve the solubility of the sulfur-containing salt. The solvent may dissolve only the sulfur-containing salt and not the light hydrocarbon, such as water. The sulfur-containing salt and light hydrocarbon, such as furfural and other organic compounds, can be dissolved at the same time, and the ratio of the solvent to the light hydrocarbon is 0-0.80, preferably 0-0.20.
Further, in step 3, the filtration and sulfur salt-containing regeneration system 7 comprises a plurality of switching valves, 1 or more filtration and sulfur salt-containing regenerators.
Further, the switching valve is a multi-way valve, and comprises any one of a ten-way valve, an eight-way valve, a six-way valve, a four-way valve, a three-way valve and a two-way valve; wherein, a six-way switching valve can be replaced by two four-way switching valves, a four-way switching valve can be replaced by two three-way switching valves, and a three-way switching valve can be replaced by two-way switching valves.
Further, the plurality of filtering and sulfur salt-containing regenerators have equivalence, and the types can be the same or different; the filtering and sulfur salt-containing regenerator can be externally heated or unheated, and when externally heated, the heating mode can adopt direct heating (such as fuel combustion) and indirect heating (such as oil bath, sand bath, resistance furnace, heat radiation, electromagnetic induction, microwave and the like). When unheated, the high temperature of the purge regeneration gas 9 should be tolerated for a long period of time.
Further, in step 3, as shown in fig. 2-a, the structure of the filtering and sulfur salt-containing regeneration system 7 may include a plurality of three-way switching valves and two filtering and sulfur salt-containing regenerators independently and externally heated; the salt-containing circulating solution 6 enters two filtering and sulfur salt-containing regenerators 21 and 22 through a front three-way switching valve 20, then flows out through a rear three-way switching valve 23 to form filtered circulating solution 8, and the purging regenerated gas 9 enters the two filtering and sulfur salt-containing regenerators through a front three-way switching valve 24 and then flows out through a rear three-way switching valve 25 to form regenerated decomposed gas 10.
Further, in step 3, as shown in fig. 2-B, in order to save costs and reduce the number of the filtering and sulfur salt-containing regenerators, the filtering and sulfur salt-containing regeneration system 7 includes: a plurality of three-way switching valves and an independent externally heated filtration and sulfur salt-containing regenerator; the salt-containing circulating solution 6 enters the filtering and sulfur-containing salt regenerator 27 through the front three-way switching valve 26, then flows out through the rear three-way switching valve 28 to form filtered circulating solution 8, the purging regenerated gas 9 enters the filtering and sulfur-containing salt regenerator 27 through the front three-way switching valve 29, then flows out through the rear three-way switching valve 30 to form regenerated decomposed gas 10, and the front three-way switching valves 26 and 29 and the rear three-way switching valves 28 and 30 are connected through bypasses.
Further, in step 3, as shown in FIG. 2-C, the filtration and sulfur salt-containing regeneration system 7 comprises: a plurality of four-way switching valves and two equivalent filtering and sulfur salt-containing regenerators; the four interfaces of the front four-way switching valve 31 are sequentially provided with a salt-containing circulating solution 6, a filtering and sulfur salt-containing regenerator 32, a purging regenerated gas 9 and a filtering and sulfur salt-containing regenerator 33; the four interfaces of the rear four-way switching valve 34 are sequentially provided with a regenerated decomposed gas 10, a filtered and sulfur salt-containing regenerator 32, a filtered circulating liquid 8 and a filtered and sulfur salt-containing regenerator 33; the four-way valve can be flexibly switched in situ according to the formation condition of sulfur-containing salt, so that the circulating process and the regeneration process of sulfur-containing materials at the bottom of the tower are simultaneously carried out.
Further, in step 3, as shown in fig. 2-D, when the number of the filtering and sulfur salt-containing regenerators is reduced in order to save costs, the filtering and sulfur salt-containing regenerating system 7 includes: a plurality of four-way switching valves and a filtering and sulfur salt-containing regenerator; the four interfaces of the front four-way switching valve 35 are sequentially provided with a salt-containing circulating solution 6, a filtering and sulfur salt-containing regenerator 36, a purging regenerated gas 9 and the filtering and sulfur salt-containing regenerator 36; the four interfaces of the rear four-way switching valve 37 are sequentially provided with a regenerated decomposed gas 10, a front four-way switching valve 35, a filtered circulating liquid 8 and a filtered and sulfate-containing regenerator 36; the four-way valve can be flexibly switched in situ according to the formation condition of sulfur-containing salt, and the circulation of the bottom distillate is not influenced in the regeneration process.
Further, the filtration and sulfur salt regeneration system 7 may also adopt a step method, and common filtration equipment including plate-and-frame filter press, chamber filter press, tubular filter, rotary drum press filter and other conventional filtration equipment is adopted to collect sulfur salt precipitate, and the collected sulfur salt precipitate is further decomposed on high temperature resistant equipment, or the collected sulfur salt precipitate is sold as a product.
Further, in step 3, the purging regeneration gas 9 may be nitrogen, inert gas, steam or reducing gas (such as hydrogen), and when the purging regeneration gas 9 is oxidizing gas (such as air or oxygen), the inert gas (such as nitrogen) may be used to purge the pipeline in advance, so as to avoid the danger of light hydrocarbon components contained in the pipeline.
Further, in step 3, the temperature of the purge regeneration gas 9 is normal temperature or high temperature. When high temperature purge gas is used, the regeneration gas inlet temperature should be greater than the decomposition temperature of the sulfur salt while ensuring that the filtration and sulfur salt regenerator are not damaged, at 30-1000 ℃, preferably 50-800 ℃, optimally 60-600 ℃; the purge time is 10 minutes to 24 hours, preferably 20 minutes to 6 hours.
Further, in step 3, when the temperature of the purge regeneration gas 9 is normal temperature, a filtration and sulfur salt-containing regenerator capable of being independently heated should be selected. At this point, the temperature of the filter and sulfur salt regenerator after heating should be greater than the decomposition temperature of the sulfur salt while ensuring that the filter and sulfur salt regenerator is not damaged, at a temperature of 30-1000 ℃, preferably 50-800 ℃, most preferably 60-600 ℃. The purge time is 10 minutes to 24 hours, preferably 20 minutes to 6 hours.
Further, in step 4, the regenerated decomposed gas 10 is a product which is remained on the filtering and sulfur-containing salt regenerator and decomposed by heating the purged regenerated gas 9, and is usually a hydrocarbon of the desulfurizing agent 2 and the sulfide in the sulfur-containing light hydrocarbon component 1 obtained after decomposition, and also comprises a decomposition product of the desulfurizing agent 2.
Further, in step 4, the organic amine recovery tank 11 is a liquid product obtained by condensing the regenerated decomposed gas 10, and the temperature of the organic amine recovery tank 11 is higher than the boiling point of sulfide in the sulfur-containing light hydrocarbon component 1 under the pressure of the device and lower than the boiling point of the desulfurizing agent 2, so that the liquid organic amine recovery liquid 15 is obtained through simple gas-liquid separation.
Further, in step 4, the cold water recovery tank 12 is mainly used for capturing and liquid recovery of the sulfur compounds 14, and the temperature of the cold water recovery tank 12 is lower than the boiling point of the recovered sulfur compounds 14, so that the recovered sulfur compounds 14 exist in a liquid manner; when the sulfur-containing compound 14 is recovered at a density greater than that of water (e.g., CS 2 ) Can be directly stored at the bottom of the cold water recovery tank 12 for sealing and the top of the cold water recovery tank 12 is discharged with the regenerated tail gas 13; when the density of the recovered sulfur compounds 14 is less than that of water (mercaptans and thioethers), the recovered sulfur compounds can be directly stored at the top of the cold water recovery tank 12 for sealing; the regeneration tail gas 13 is discharged through an additional discharge pipe at the bottom of the cold water recovery tank 12.
Further, in order to increase the solubility of the sulfur-containing salt produced by the desulfurization reaction, a small amount of solvent 19 is added to the reactor 3 or the distillation column 4.
Further, the solvent 19 is used for dissolving sulfur-containing salt produced by the sulfur-containing light hydrocarbon component 1 and the desulfurizing agent 2, and the contact between the sulfur-containing light hydrocarbon component 1 and the desulfurizing agent 2 is enhanced in the reactor 3; the distillation tower 4 is beneficial to the circulation at the bottom of the tower and prevents the pipeline from being blocked; the solvent 19 may be water or an organic solvent, including furfural, ionic liquid or phase transfer agent which is significantly soluble in sulfur-containing salts.
Comparative example 1.
30wt% of compound amine is selected as a desulfurizing agent, the desulfurizing agent and sulfur-containing isoprene with the sulfur content of 80mg/L are added into a closed reactor according to the volume ratio of the agent to the oil of 1:200 (V/V), the desulfurizing temperature is controlled to be 25 ℃, and the desulfurizing agent and the crude isoprene are fully contacted and reacted for 120 minutes. After desulfurization, the residual sulfur content in the isoprene solution was 9.02mg/L, and the basic nitrogen content was 90mg/L. At 25deg.C, washing with multiple stages of water, coalescing and filtering, and using water amount V each time H2O /V C5 =0.1. Washing with circulating waterAnd (3) washing with deionized water for 2 times for 13 times, so that the total nitrogen in the isoprene can be reduced to be less than 10mg/L.
Example 1.
30wt% of complex amine is selected as a desulfurizing agent. Desulfurizing agent and sulfur-containing isoprene with sulfur content of 80mg/L are added into a closed reactor according to the volume ratio of agent oil of 1:200 (V/V). At the beginning of the reaction, the desulfurization temperature is controlled to 25 ℃, and the desulfurizing agent and the crude isoprene are fully contacted and reacted for 120 minutes. After desulfurization, the residual sulfur content in the purified isoprene solution was 8.98mg/kg, and the basic nitrogen content was about 95mg/kg. After each reaction, the produced isoprene-containing mixture is pumped into a distillation tower at one time, and refined isoprene is further obtained by distillation. After distillation, the total nitrogen content of the light hydrocarbon product at the top of the tower is less than 10mg/L. In the distillation process, a circulating pump is opened to circulate the tower bottom materials. The bottom reaction material path is: the materials at the bottom of the distillation tower enter a switching valve, and after passing through a first filter, the filtered circulating liquid returns to the distillation tower. In the process of re-distillation, after the material at the bottom of the distillation tower is introduced into another filter through a switching valve, the filtered circulating liquid is returned to the distillation tower. At this time, the first filter is regenerated. The regenerated gas is nitrogen at normal temperature, and a heating component is arranged outside the filter. The regenerated gas material is as follows: the regenerated gas enters a filter to be regenerated to form regenerated tail gas. During regeneration, the temperature of the heated regenerated gas can be controlled at 350 ℃ and the regeneration time is 2 hours. The regenerated tail gas is condensed to 80 ℃ by heat exchange in an organic amine recovery tank. The gas component enters a cold water recovery tank to be further cooled to 20 ℃, and tail gas without sulfur and nitrogen is slowly discharged in water through bubbling.
Example 2.
30wt% of complex amine is selected as a desulfurizing agent. Desulfurizing agent and sulfur-containing isoprene with sulfur content of 80mg/L are added into a closed reactor according to the volume ratio of agent oil of 1:200 (V/V). At the beginning of the reaction, the desulfurization temperature is controlled to 25 ℃, and the desulfurizing agent and the crude isoprene are fully contacted and reacted for 120 minutes. After desulfurization, the residual sulfur content in the purified isoprene solution was 8.90mg/kg, and the basic nitrogen content was about 95mg/kg. After each reaction, the produced isoprene-containing mixture is pumped into a distillation tower at one time, and refined isoprene is further obtained by distillation. The first distillation was initiated by adding water in an amount of 0.20% by volume of isoprene to the distillation column. After distillation, the total nitrogen content of the light hydrocarbon product at the top of the tower is less than 10mg/L. In the distillation process, a circulating pump is opened to circulate the tower bottom materials. The bottom reaction material path is: the materials at the bottom of the distillation tower enter a switching valve, and after the materials pass through a filter, the filtered circulating liquid returns to the distillation tower. After 5 times of reaction and distillation, the salt on the filter is heated and decomposed for regeneration under the nitrogen flow. The method comprises the following steps: and blocking the materials at the bottom of the distillation tower and the filtered circulating liquid by a switching valve. The filter is regenerated. The regenerated gas is nitrogen at normal temperature, and a heating component is arranged outside the filter. The regenerated gas material is as follows: the regenerated gas enters a filter to be regenerated to form regenerated tail gas. During regeneration, the temperature of the heated regenerated gas can be controlled at 350 ℃ and the regeneration time is 2 hours. The regenerated tail gas is condensed to 80 ℃ by heat exchange in an organic amine recovery tank. The gas component enters a cold water recovery tank to be further cooled to 20 ℃, and tail gas without sulfur and nitrogen is slowly discharged in water through bubbling. After regeneration, the material at the bottom of the distillation column and the filtered circulating liquid are connected through a switching valve, a regeneration pipeline is blocked, and the circulation of the material at the bottom of the distillation column is continued.
Example 3.
30wt% of complex amine is selected as a desulfurizing agent. Desulfurizing agent and sulfur-containing isoprene with sulfur content of 80mg/L are added into a closed reactor according to the volume ratio of the agent to the oil of 1:100 (V/V). At the beginning of the reaction, the desulfurizing temperature is controlled to 25 ℃, and the desulfurizing agent and the crude isoprene are fully contacted and reacted for 180 minutes. After desulfurization, the residual sulfur content of the purified isoprene solution was 7.79mg/kg, and the basic nitrogen content was about 125mg/kg. After each reaction, the resultant isoprene-containing mixture was continuously pumped into a distillation column, and refined isoprene was further obtained by distillation. The first distillation was initiated by adding 0.20 volume total of isoprene in the distillation column. After distillation, the total nitrogen content of the light hydrocarbon product at the top of the tower is less than 10mg/L. In the distillation process, a circulating pump is opened, so that the material at the bottom of the distillation column is continuously circulated back to the distillation column through a filter. The four-way valve and two equivalent filters and regenerators are adopted to ensure the continuity of the tower bottom material circulation and regeneration process. The method comprises the following steps: the material at the bottom of the distillation tower flows through one of the filters through the four-way valve, and the filtered solution enters the bottom of the distillation tower for circulation. The regenerated gas flows through the other path of the filter regenerator through the four-way valve, and the formed regenerated tail gas enters a subsequent regenerated gas treatment device. When a significant blockage of the salt in the filter occurs, the four-way valve is switched as required so that the process is continuous. The regeneration gas is nitrogen at 300 ℃ and the regeneration time is 4 hours. The regenerated tail gas is condensed to 60 ℃ by heat exchange in an organic amine recovery tank. The gas component enters a cold water recovery tank to be further cooled to 20 ℃, and the tail gas is slowly bubbled in water to be discharged.
Example 4.
30wt% of compound amine is selected as a desulfurizing agent, and the desulfurizing agent and sulfur-containing isoprene with the sulfur content of 80mg/L are added into a closed reactor according to the volume ratio of agent oil of 1:100 (V/V); at the beginning of the reaction, the desulfurizing temperature is controlled to 25 ℃, and the desulfurizing agent and the crude isoprene are fully contacted and reacted for 180 minutes. After desulfurization, the residual sulfur content of the purified isoprene solution was 7.79mg/kg, and the basic nitrogen content was about 125mg/kg. After each reaction, the produced isoprene-containing mixture is pumped into a distillation tower at one time, and refined isoprene is further obtained by distillation. And (3) adding water with the total volume of 0.20 of the isoprene into the distillation tower at the beginning of the first distillation, wherein the total nitrogen content of a light hydrocarbon product at the top of the tower is less than 10mg/L after distillation, and in the distillation process, a circulating pump is started to enable materials at the bottom of the distillation tower to continuously circulate back to the distillation tower through a filter, and after 5 times of reaction and distillation are completed, the salt on the filter is heated and decomposed for regeneration. The method comprises the following steps: the four-way valve is rotated, so that materials at the bottom of the distillation column are continuously recycled to the distillation column without passing through a filter, regenerated gas passes through the filter regenerator through the four-way valve, the formed regenerated tail gas enters a subsequent regenerated gas treatment device, the regenerated gas is steam at 350 ℃, the regeneration time is 4 hours, the formed regenerated tail gas enters an organic amine recovery tank, the regenerated tail gas is condensed to 120 ℃ through heat exchange, gas phase components enter a cold water recovery tank, the temperature is further reduced to 20 ℃, and excessive condensed water in the cold water recovery tank can be discharged as required.
Table 1 light hydrocarbon desulfurization conditions and effects of examples 1-4 and comparative examples.
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By comparing the example 1 with the comparative example, it was found that the light hydrocarbon component with qualified nitrogen content could be directly obtained by distillation, no sewage was discharged during distillation, and the qualified nitrogen content product could be obtained by washing 15 times in the comparative case. The total sewage discharge amount can be reduced by about 2.5 times of the volume of the single reaction raw material after 10 times of reaction, distillation and regeneration processes. At the same time, the sulfur-containing salt formed in the reaction can be decomposed in the heated filter and subjected to organic amine recovery and CS 2 Capture, so that the reaction can proceed continuously.
The desulfurization method of embodiment 2 is the same as that of embodiment 1, but deionized water with a water-oil volume ratio of 0.20 is added in the beginning of distillation, the addition of water increases the solubility of sulfur-containing salt, improves the circulation performance of the bottom liquid, makes the regeneration process not too frequent, and can make the reaction continuously proceed through decomposing and regenerating the sulfur-containing salt.
The desulfurization modes of the embodiment 3 and the embodiment 2 are the same, but in the process of distilling the furfural solution with the initial additive oil volume ratio of 0.20, the addition of the furfural also increases the solubility of sulfur-containing salt, improves the circulation performance of the bottom liquid, and the materials after the reaction desulfurization can be continuously pumped into a distillation tower.
In embodiment 4, sulfur-containing species in raw materials are relatively complex in desulfurization of cracked carbon five, a high-content desulfurizing agent is adopted for reaction, deionized water with the water-oil volume ratio of 0.20 is added in the initial distillation, the solubility of sulfur-containing salt is increased by adding water, the circulation performance of bottom liquid is improved, nitrogen can be adopted in the regeneration atmosphere, superheated steam can be adopted, even if the raw materials are relatively complex, the sulfur-containing salt can still be regenerated, the reactive distillation process is continuously carried out, and a small amount of condensed water formed after the condensation of regenerated gas can be discharged from a cold water recovery tank.
Compared with the traditional reaction water washing process, the invention can reversibly decompose the sulfur-containing amine salt formed in the reaction process instead of dissolving and storing the sulfur-containing amine salt by water; separating out sulfur-containing amine salt by using a filter, and thermally decomposing the sulfur-containing amine salt to form organic amine and CS by using high-temperature regenerated gas 2 The regenerated organic amine can be recycled. Unlike available patent, the said process can reduce desulfurizing agent amount, and has the advantages of saving in power, reducing emission and raising efficiency.
Claims (10)
1. CS removal from liquid light hydrocarbon streams by reaction and distillation 2 And a method for producing a sulfur-containing compound, characterized by comprising the steps of:
step 1, mixing a sulfur-containing light hydrocarbon component with a desulfurizing agent, adding the mixture into a reactor, and reacting at a certain reaction temperature and a certain reaction pressure;
step 2, after the reaction is finished, the desulfurized components enter a distillation tower, and light hydrocarbon components with qualified sulfur content are obtained from the top of the distillation tower;
step 3, circulating solution containing salt in the tower bottom material flows through a filtering and sulfur salt-containing regeneration system under the drive of a pump to form filtered circulating solution, and the filtered circulating solution returns to the distillation tower; meanwhile, after the purging regenerated gas enters a filtering and sulfur salt-containing regeneration system to be formed, regenerated decomposed gas is formed;
step 4, condensing the regenerated decomposed gas in an organic amine recovery tank, feeding a gas product to a cold water recovery tank, discharging tail gas from the top of the cold water recovery tank, and sealing the enriched liquid at the bottom of the cold water recovery tank; the liquid organic amine recovery liquid is discharged from the bottom of the organic amine recovery tank.
2. The method according to claim 1CS removal from liquid light hydrocarbon streams using reaction and distillation 2 And a sulfur-containing compound method, characterized in that in the step 1, the reaction temperature of the sulfur-containing light hydrocarbon component and the desulfurizing agent is-20-300 ℃, the reaction pressure of the sulfur-containing light hydrocarbon component and the desulfurizing agent is ensured to be liquid phase, the ratio of the desulfurizing agent to the sulfur-containing light hydrocarbon component is 1/10000-1/10 (V/V), and the contact time of the sulfur-containing light hydrocarbon component and the desulfurizing agent is 5 minutes-24 hours.
3. Removal of CS from a liquid light hydrocarbon stream using reaction and distillation according to claim 1 2 And a method for producing a sulfur-containing compound, characterized by connecting a light hydrocarbon liquid separation tank externally when a small amount of water is present at the bottom of the distillation column.
4. Removal of CS from a liquid light hydrocarbon stream using reaction and distillation according to claim 1 2 And a sulfur compound process, wherein in step 3, the filtration and sulfur salt regeneration system comprises a plurality of switching valves, 1 or more filtration and sulfur salt regenerators.
5. Removal of CS from a liquid light hydrocarbon stream using reaction and distillation according to claim 4 2 And a method for producing sulfur-containing compounds, wherein the structure of the filtration and sulfur-containing salt regeneration system comprises: a plurality of three-way switching valves and two filtering and sulfur salt-containing regenerators independently and externally heated; the salt-containing circulating solution enters two filtering and sulfur salt-containing regenerators through a front three-way switching valve, then flows out through a rear three-way switching valve to form filtered circulating solution, and the purging regenerated gas enters the two filtering and sulfur salt-containing regenerators through the front three-way switching valve and then flows out through the rear three-way switching valve to form regenerated decomposed gas.
6. Removal of CS from a liquid light hydrocarbon stream using reaction and distillation according to claim 4 2 And a method for the production of sulfur-containing compounds, wherein the filtration and sulfur salt regeneration system comprises: multiple three-way switching valves and an independently externally heated filter and sulfur-containing filterA salt regenerator; the salt-containing circulating solution enters the filtering and sulfur salt-containing regenerator through the front three-way switching valve, then flows out through the rear three-way switching valve to form filtered circulating solution, and the purging regenerated gas enters the filtering and sulfur salt-containing regenerator through the front three-way switching valve and then flows out through the rear three-way switching valve to form regenerated decomposed gas, and the front three-way switching valve and the rear three-way switching valve are connected through a bypass.
7. Removal of CS from a liquid light hydrocarbon stream using reaction and distillation according to claim 4 2 And a method for the production of sulfur-containing compounds, wherein the filtration and sulfur salt regeneration system comprises: a plurality of four-way switching valves and two equivalent filtering and sulfur salt-containing regenerators; the four interfaces of the front four-way switching valve are sequentially provided with a salt-containing circulating solution, a filtering and sulfur-containing salt regenerator, a purging regeneration gas, a filtering and sulfur-containing salt regenerator; the four interfaces of the rear four-way switching valve are sequentially provided with a regenerated decomposed gas, a filter and sulfur salt-containing regenerator, a filtered circulating liquid and a filter and sulfur salt-containing regenerator.
8. Removal of CS from a liquid light hydrocarbon stream using reaction and distillation according to claim 4 2 And a method for the production of sulfur-containing compounds, wherein the filtration and sulfur salt regeneration system comprises: a plurality of four-way switching valves and a filtering and sulfur salt-containing regenerator; the four interfaces of the front four-way switching valve are sequentially provided with a salt-containing circulating solution, a filtering and sulfur-containing salt regenerator, a purging regeneration gas, a filtering and sulfur-containing salt regenerator; the four interfaces of the rear four-way switching valve are sequentially regenerated decomposed gas, a front four-way switching valve, filtered circulating liquid, filtered and a sulfur salt-containing regenerator.
9. Removal of CS from a liquid light hydrocarbon stream using reaction and distillation according to claim 1 2 And a sulfur-containing compound method, characterized in that in the step 3, the temperature of the purge regeneration gas is normal temperature or high temperature; when high-temperature purge gas is adopted, the purge can be directly performed without reheating, the inlet temperature of the regenerated gas is higher than the decomposition temperature of sulfur-containing salt, and meanwhileEnsuring that the filtering and sulfur salt-containing regenerator is not damaged, wherein the temperature is 30-1000 ℃, and the purging time is 10 minutes-24 hours; when the temperature of the purging regenerated gas is normal temperature, an independently heatable filter and sulfur salt regenerator is selected, the temperature of the regenerator is higher than the decomposition temperature of the sulfur salt, and meanwhile, the filter and sulfur salt regenerator is not damaged, the temperature is 30-1000 ℃, and the purging time is 10 minutes-24 hours.
10. The method for removing CS2 and sulfur compounds from a liquid light hydrocarbon stream by reaction and distillation according to claim 1, wherein a solvent is added to the reactor or the distillation column, the solvent is water or an organic solvent, and the solvent to light hydrocarbon ratio is 0-0.80, including a reagent such as furfural, ionic liquid or a phase transfer agent which dissolves sulfur-containing salt significantly.
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