CN104370707B - The method of the thick product of purifying methyl tertiary butyl ether and the method for production methyl tertiary butyl ether - Google Patents
The method of the thick product of purifying methyl tertiary butyl ether and the method for production methyl tertiary butyl ether Download PDFInfo
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- CN104370707B CN104370707B CN201310354056.2A CN201310354056A CN104370707B CN 104370707 B CN104370707 B CN 104370707B CN 201310354056 A CN201310354056 A CN 201310354056A CN 104370707 B CN104370707 B CN 104370707B
- Authority
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- China
- Prior art keywords
- tertiary butyl
- butyl ether
- methyl tertiary
- sulphur
- hybrid
- Prior art date
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- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 title claims abstract description 278
- 238000000034 method Methods 0.000 title claims abstract description 129
- 238000004519 manufacturing process Methods 0.000 title abstract description 37
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 300
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 186
- 239000005864 Sulphur Substances 0.000 claims abstract description 141
- 238000004821 distillation Methods 0.000 claims abstract description 133
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 85
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 46
- 239000011593 sulfur Substances 0.000 claims abstract description 46
- 238000000605 extraction Methods 0.000 claims abstract description 36
- 238000005194 fractionation Methods 0.000 claims abstract description 27
- 238000010521 absorption reaction Methods 0.000 claims abstract description 18
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 52
- 230000003197 catalytic effect Effects 0.000 claims description 46
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 238000009835 boiling Methods 0.000 claims description 32
- 239000002904 solvent Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical class [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 claims description 10
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 10
- 229930195733 hydrocarbon Natural products 0.000 claims description 9
- 150000002430 hydrocarbons Chemical class 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 claims description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- -1 glycerin fatty acid ester Chemical class 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 229940120693 copper naphthenate Drugs 0.000 claims description 6
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 claims description 6
- 239000003350 kerosene Substances 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 238000009790 rate-determining step (RDS) Methods 0.000 claims description 6
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 claims description 6
- 241000220317 Rosa Species 0.000 claims description 5
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 5
- WDEQGLDWZMIMJM-UHFFFAOYSA-N benzyl 4-hydroxy-2-(hydroxymethyl)pyrrolidine-1-carboxylate Chemical compound OCC1CC(O)CN1C(=O)OCC1=CC=CC=C1 WDEQGLDWZMIMJM-UHFFFAOYSA-N 0.000 claims description 5
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 5
- 229960003280 cupric chloride Drugs 0.000 claims description 5
- 239000002283 diesel fuel Substances 0.000 claims description 5
- 239000011790 ferrous sulphate Substances 0.000 claims description 5
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 5
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 5
- UIEKYBOPAVTZKW-UHFFFAOYSA-L naphthalene-2-carboxylate;nickel(2+) Chemical compound [Ni+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 UIEKYBOPAVTZKW-UHFFFAOYSA-L 0.000 claims description 5
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000004246 zinc acetate Substances 0.000 claims description 5
- NKFIBMOQAPEKNZ-UHFFFAOYSA-N 5-amino-1h-indole-2-carboxylic acid Chemical compound NC1=CC=C2NC(C(O)=O)=CC2=C1 NKFIBMOQAPEKNZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910021590 Copper(II) bromide Inorganic materials 0.000 claims description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 claims description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 4
- GIWKOZXJDKMGQC-UHFFFAOYSA-L lead(2+);naphthalene-2-carboxylate Chemical compound [Pb+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 GIWKOZXJDKMGQC-UHFFFAOYSA-L 0.000 claims description 4
- PZKNFJIOIKQCPA-UHFFFAOYSA-N oxalic acid palladium Chemical compound [Pd].OC(=O)C(O)=O PZKNFJIOIKQCPA-UHFFFAOYSA-N 0.000 claims description 4
- RFLFDJSIZCCYIP-UHFFFAOYSA-L palladium(2+);sulfate Chemical compound [Pd+2].[O-]S([O-])(=O)=O RFLFDJSIZCCYIP-UHFFFAOYSA-L 0.000 claims description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 4
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- 229930195729 fatty acid Natural products 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000010687 lubricating oil Substances 0.000 claims description 3
- 239000003921 oil Substances 0.000 claims description 3
- 150000002895 organic esters Chemical class 0.000 claims description 3
- 229920001021 polysulfide Polymers 0.000 claims description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 2
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- MAHNFPMIPQKPPI-UHFFFAOYSA-N disulfur Chemical compound S=S MAHNFPMIPQKPPI-UHFFFAOYSA-N 0.000 claims description 2
- 239000003456 ion exchange resin Substances 0.000 claims description 2
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims description 2
- 229930192474 thiophene Natural products 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- 238000012423 maintenance Methods 0.000 abstract description 9
- 238000005265 energy consumption Methods 0.000 abstract description 8
- 230000007423 decrease Effects 0.000 abstract description 6
- 239000012467 final product Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 abstract 1
- XTFIVUDBNACUBN-UHFFFAOYSA-N 1,3,5-trinitro-1,3,5-triazinane Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)C1 XTFIVUDBNACUBN-UHFFFAOYSA-N 0.000 description 74
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 30
- 230000008569 process Effects 0.000 description 22
- 239000003502 gasoline Substances 0.000 description 21
- 238000007599 discharging Methods 0.000 description 17
- 239000003915 liquefied petroleum gas Substances 0.000 description 16
- 238000010533 azeotropic distillation Methods 0.000 description 11
- 238000006477 desulfuration reaction Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 7
- 230000023556 desulfurization Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-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
- 238000006266 etherification reaction Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000001577 simple distillation Methods 0.000 description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 230000019086 sulfide ion homeostasis Effects 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 125000000101 thioether group Chemical group 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000895 extractive distillation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 238000005732 thioetherification reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/40—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation
- C07C41/42—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
- C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention provides the method for the thick product of a kind of purifying methyl tertiary butyl ether and the method for production super low sulfur methyl tertiary butyl ether, the method comprises: the solution containing methyl tertiary butyl ether is carried out fractionation by distillation in a distillation column, and the described solution containing methyl tertiary butyl ether contains methyl alcohol, sulfide, hybrid C 4 and methyl tertiary butyl ether; Wherein, the method to be also included in fractionation by distillation and/or to contain in the solution of methyl tertiary butyl ether at fractionation by distillation process forward direction introduces sulphur pregnant solution, and the condition controlling distillation makes methyl alcohol and hybrid C 4 from overhead extraction, sulfide after being absorbed by described sulphur pregnant solution and not by the sulfide of described sulphur pregnant solution absorption from extraction at the bottom of tower, the logistics containing methyl tertiary butyl ether is from side take-off.Method of the present invention only needs to carry out single flash and is separated the MTBE getting final product production super low sulfur, reduces energy consumption, and decreases input and the maintenance cost of equipment, be very suitable for industrial applications.
Description
Technical field
The present invention relates to the method for the thick product of a kind of purifying methyl tertiary butyl ether and produce the method for methyl tertiary butyl ether.
Background technology
As everyone knows, methyl tertiary butyl ether (MTBE) is non-hydrocarbons blend component maximum in China's gasoline, can significantly improve quality of gasoline.But obviously containing sulfide in MTBE, generalized case is issued to 50-200mg/kg, and the sulphur content of the MTBE of part manufacturer production is sometimes especially up to 2000mg/kg.
Perform epoch of gasoline state II in China, sulphur content requires to be not more than 500mg/kg, because the sulphur content of in most cases MTBE is lower than 500mg/kg, is blended in gasoline and does not have negative impact for content of sulfur in gasoline; Performing the epoch of gasoline state III, as long as strengthen management and monitoring in LPG Desulfurization process, generally the sulphur content of MTBE can be controlled at about 150mg/kg or below, be blended in gasoline and there is some problems, but problem is not very large, can be dealt with reluctantly by adjustment; But along with GB is more and more stricter for the restriction of content of sulfur in gasoline, in the execution epoch of gasoline state IV or the epoch of state V, require that content of sulfur in gasoline reaches below 50mg/kg or below 10mg/kg respectively, by existing desulfurization technology, be difficult to the sulphur content of MTBE to be down to below 10mg/kg.This means, if do not taken measures, the problem only because of sulphur content is difficult to call in gasoline by following MTBE, and this not only directly can affect the production and supply of gasoline, also has influence on the Appropriate application of the resource of refinery's liquefied petroleum gas (LPG).
According to current MTBE production technique, the sulphur content of MTBE product almost depends on form and the content thereof of sulphur in refining liquefied petrolium gas (LPG) (hybrid C 4) completely.Therefore, need desulfurization is carried out to meet the sulphur content requirement of gasoline standard for MTBE.
At present, had the much research prepared about high-purity MTBE, main purpose is to prepare high-purity MTBE, or prepares high-purity iso-butylene, but about the sulfur removal technology of MTBE or the research of production super low sulfur MTBE less.
Conventional method of producing low-sulfur MTBE, normally by the re-distillation again of the hybrid C 4 after liquefied petroleum gas (LPG) fractionation, is cut into light C4 and heavy C4, wherein, in light C4, iso-butylene content is higher, and sulphur content is lower, can be used as etherificate or alkylating raw material, the sulphur content of the MTBE obtained after etherificate is also lower; Containing most sulfide in heavy C4, mainly as the blending stock of liquefied petroleum gas (LPG).The shortcoming one of this technique is that the energy consumption of raw material fractionation by distillation is higher, and two is because the boiling point of the light C4 such as the sulfide boiling point in heavy C4 and iso-butylene is more or less the same, and cause being difficult to being separated thorough, the sulphur content of the MTBE that result obtains also is difficult to reach below 10mg/kg.
CN101643392A discloses " a kind of method of desulphurizing methyl tertiary butyl ether with high sulphur content ", and it adopts redistilled method, by high sulfur-bearing MTBE re-distillation, by improving stage number and increasing reflux ratio, reduces the sulphur content steamed in MTBE.The defect of the method is, need MTBE to carry out redistillation, although the vaporization heat of MTBE is relatively little, adopt the method for re-distillation, no doubt the purity of MTBE can be improved, also MTBE sulphur content can be made significantly to reduce, but higher yield will be obtained, still need tower tray to have more stage number, larger reflux ratio is needed at tower top in still-process, energy consumption can be very high undoubtedly, and the input of equipment and maintenance cost also higher, it is obviously reasonable not economically to consider.
Summary of the invention
As everyone knows, the production of current methyl tertiary butyl ether (MTBE) widely uses catalytic distillation technology, also part is had still to use traditional reaction distillation technique (technique of common production methyl tertiary butyl ether), no matter use which kind of production technique, all need by distillation for removing methanol and unreacted C4.As background technology introduction, prior art is in order to produce the MTBE of low sulfur content, generally in advance MTBE and hybrid C 4, methyl alcohol are carried out pre-separation, then the MTBE of the sulfide containing high-content is obtained, then the MTBE of the sulfide of high-content is contained by MTBE from tower top fractionation out by described in simple distillation or rectifying, most sulfide is made to residue at the bottom of still, thus produce the MTBE obtaining deep desulfuration, but the direct cost that this method be separated by second distillation carries out deep desulfuration is that energy consumption is high, and the input of equipment and maintenance cost are also higher.
And find in the present inventor's research, the sulfide in methyl tertiary butyl ether (MTBE) substantially all derives from: the oxidation products of thiomethyl alcohol, sulfur alcohol etc. in (1) liquefied petroleum gas (LPG); (2) the thioetherification product of the thiomethyl alcohol in liquefied petroleum gas (LPG), sulfur alcohol and butene reaction is as alkyl-tert-butyl thioether; (3) polysulfide produced in liquefied petroleum gas (LPG) treating process; The boiling point of these sulfocompounds, generally more than 100 DEG C, is significantly higher than MTBE.Therefore, the present inventor attempts to imagine the production realizing the MTBE of super low sulfur in the process of distillation for removing methanol and unreacted hybrid C 4, thus MTBE is carried out redistillation desulfurization by the method being also similar to CN101643392A without the need to employing.
Based on aforementioned imagination, the present inventor proposes following technical scheme " in the distillation tower of distillation for removing methanol and unreacted hybrid C 4; increase side take-off mouth; the condition then by reasonably controlling distillation makes MTBE can from the extraction of described side take-off mouth; and by this technical scheme proposition patent application, application number is " 201210229184.X ".
But in further research process, contriver finds, technique scheme is adopted still to there is technological deficiency, when in C4, sulphur content is higher, especially when in mixture containing the boiling point sulfide suitable with MTBE time, be sometimes separated comparatively difficult, although reduce side line MTBE yield, can obtain the MTBE product that sulphur content is less than 10mg/kg, but during by normal yield extraction, in MTBE, sulphur content is sometimes more than 10mg/kg.The present inventor finds, in the mixture containing unreacted C4, methyl alcohol and MTBE, injecting a small amount of described sulphur pregnant solution, when keeping higher MTBE yield, the sulphur content of the MTBE of catalytic distillation tower or azeotropic distillation column side take-off can be reduced further.
Therefore, on the basis of the above, the present inventor thinks the sulphur content of the MTBE logistics in order to reduce side take-off further, sulphur pregnant solution can be introduced in the mixture entering catalytic distillation tower or azeotropic distillation column, carrying out physics and/or chemical absorption by described sulphur pregnant solution and sulfide makes sulfide become heavy thus distillate from tower reactor, wherein, when for chemical absorption, described sulphur pregnant solution can be can generate more macromolecular material with sulfide generation complex reaction or hydrocarbyl reaction, and when for physical absorption, described sulphur pregnant solution can be organometallic compound and/or inorganic metal compound.
Based on aforementioned invention thinking, the invention provides the method for the thick product of a kind of purifying methyl tertiary butyl ether, the method comprises: the solution containing methyl tertiary butyl ether is carried out fractionation by distillation in a distillation column, and the described solution containing methyl tertiary butyl ether contains methyl alcohol, sulfide, hybrid C 4 and methyl tertiary butyl ether; Wherein, the method to be also included in fractionation by distillation and/or to contain in the solution of methyl tertiary butyl ether at fractionation by distillation process forward direction introduces sulphur pregnant solution, and the condition controlling distillation makes methyl alcohol and hybrid C 4 from overhead extraction, sulfide after being absorbed by described sulphur pregnant solution and not by the sulfide of described sulphur pregnant solution absorption from extraction at the bottom of tower, the logistics containing methyl tertiary butyl ether is from side take-off.
Simultaneously, for the method being prepared methyl tertiary butyl ether by reaction distillation (ordinary process) of prior art, in order to the methyl tertiary butyl ether of production super low sulfur, the invention provides a kind of method of producing super low sulfur methyl tertiary butyl ether, the method comprises: methyl alcohol and hybrid C 4, under being the condition of methyl tertiary butyl ether by methyl alcohol and isobutene conversion, are sent in reactor the solution prepared with catalyst exposure containing methyl tertiary butyl ether by (1); Wherein, contain sulfide in described methyl alcohol and/or hybrid C 4, the described solution containing methyl tertiary butyl ether contains methyl alcohol, hybrid C 4 and methyl tertiary butyl ether; (2) fractionation by distillation is carried out by the described solution feeding distillation tower containing methyl tertiary butyl ether; Wherein, sulphur pregnant solution is introduced in step (1) and/or step (2), and the condition of distillation in rate-determining steps (2) makes methyl alcohol and hybrid C 4 from overhead extraction, sulfide after being absorbed by described sulphur pregnant solution and not by the sulfide of described sulphur pregnant solution absorption from extraction at the bottom of tower, the logistics containing methyl tertiary butyl ether is from side take-off.
Simultaneously, for the method being prepared methyl tertiary butyl ether by catalytic distillation of prior art, in order to the methyl tertiary butyl ether of production super low sulfur, the invention provides a kind of method of producing super low sulfur methyl tertiary butyl ether, the method comprises: (1) is under being the condition of methyl tertiary butyl ether by methyl alcohol and isobutene conversion, methyl alcohol and hybrid C 4 are sent in reactor and obtains mixture with catalyst exposure, in described methyl alcohol and/or hybrid C 4, contain sulfide; (2) contact in described mixture feeding catalytic distillation tower with catalyzer; Wherein, sulphur pregnant solution is introduced in step (1) and/or step (2), and the condition of catalytic distillation in rate-determining steps (2) makes methyl alcohol and hybrid C 4 from overhead extraction, sulfide after being absorbed by described sulphur pregnant solution and not by the sulfide of described sulphur pregnant solution absorption from extraction at the bottom of tower, the logistics containing methyl tertiary butyl ether is from side take-off.
Method of the present invention only needs to carry out single flash and is separated the thick product of methyl tertiary butyl ether of can purifying, and the methyl tertiary butyl ether MTBE(sulphur content that can obtain super low sulfur even can reach lower than 2mg/kg, the concrete sulphur content also depended in raw material), reduce energy consumption, and decrease input and the maintenance cost of equipment, be very suitable for industrial applications.
And on the basis of being prepared the method for methyl tertiary butyl ether by reaction distillation of prior art, in order to the methyl tertiary butyl ether of production super low sulfur, the present invention only needs the pre-separation operation of the operation of the reaction distillation to prior art (by MTBE and hybrid C 4, methyl alcohol carries out pre-separation, then the operation of the MTBE of the sulfide containing high-content is obtained) distillation tower that uses transforms, side take-off mouth is increased in its side, then the condition by reasonably controlling distillation can produce the methyl tertiary butyl ether obtaining super low sulfur, thus decrease the operation of the MTBE of the sulfide of redistillation high-content, effectively reduce input and the maintenance cost of equipment, and effectively saved energy consumption.
Simultaneously, on the basis of being prepared the method for methyl tertiary butyl ether by catalytic distillation of prior art, in order to the methyl tertiary butyl ether of production super low sulfur, catalytic distillation tower that the present invention only needs to use the operation of the catalytic distillation of prior art (realizes MTBE and hybrid C 4 by the product of pre-contact reaction and the further contact reacts of catalyzer in contact reacts process, methyl alcohol carries out pre-separation, then the operation of the MTBE of the sulfide containing high-content is obtained) transform, side take-off mouth is increased in its side, then the condition by reasonably controlling catalytic distillation can produce the methyl tertiary butyl ether obtaining super low sulfur, thus decrease the operation of the MTBE of the sulfide of redistillation high-content, effectively reduce input and the maintenance cost of equipment, and effectively saved energy consumption.
Simultaneously, from the angle of further deep desulfuration, be that " 201210229184.X " only adopts side line to be separated the method for MTBE compared to application number, method of the present invention is by introducing the sulphur pregnant solution of seldom amount, can realize containing lower sulfide in the MTBE of side take-off, even substantially not sulfur compound.As can be seen here, method of the present invention is very suitable for industrial application.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
Fig. 1 is the method being prepared methyl tertiary butyl ether by reaction distillation for prior art, according to the schematic flow sheet of the method for the production super low sulfur methyl tertiary butyl ether of one embodiment of the present invention;
Fig. 2 is the method being prepared methyl tertiary butyl ether by catalytic distillation for prior art, according to the schematic flow sheet of the method for the production super low sulfur methyl tertiary butyl ether of one embodiment of the present invention.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides the method for the thick product of a kind of purifying methyl tertiary butyl ether, the method comprises: the solution containing methyl tertiary butyl ether is carried out fractionation by distillation in a distillation column, and the described solution containing methyl tertiary butyl ether contains methyl alcohol, sulfide, hybrid C 4 and methyl tertiary butyl ether; Wherein, the method to be also included in fractionation by distillation and/or to contain in the solution of methyl tertiary butyl ether at fractionation by distillation process forward direction introduces sulphur pregnant solution, and the condition controlling distillation makes methyl alcohol and hybrid C 4 from overhead extraction, sulfide after being absorbed by described sulphur pregnant solution and not by the sulfide of described sulphur pregnant solution absorption from extraction at the bottom of tower, the logistics containing methyl tertiary butyl ether is from side take-off.
According to the method for the thick product of purifying methyl tertiary butyl ether of the present invention, the described solution containing methyl tertiary butyl ether generally refers to the solution of methyl alcohol, sulfide and methyl tertiary butyl ether containing most hybrid C 4, small part.Preferably the described solution containing methyl tertiary butyl ether is under being the condition of methyl tertiary butyl ether by methyl alcohol and isobutene conversion further, is obtained by methyl alcohol, hybrid C 4 and catalyst exposure, contains sulfide in described methyl alcohol and/or hybrid C 4.More specifically, the described solution containing methyl tertiary butyl ether is prepared as follows: with the liquefied gas after amine liquid and/or alkali lye desulfurization for liquefied gas raw material, through gas fractionation, the hybrid C 4 obtained containing iso-butylene is (general containing C4 alkane and C4 alkene, and the sulfide etc. of trace, preferred sulphur content is the hybrid C 4 that 0.5-1000mg/kg(specifically refers to relative to 1kg, sulphur content is 0.5-1000mg), iso-butylene content is 5-30 quality %), then under being the condition of methyl tertiary butyl ether by methyl alcohol and isobutene conversion, by methyl alcohol, described hybrid C 4 be the catalyst exposure of methyl tertiary butyl ether by methyl alcohol and isobutene conversion.
According to the method for the thick product of purifying methyl tertiary butyl ether of the present invention, more preferably described containing in the solution of methyl tertiary butyl ether, the content of methyl alcohol is 0.05-15 quality %, the content of hybrid C 4 is 50-90 quality %, in the content of element sulphur sulfide for 0.001-0.150 quality %, the content of methyl tertiary butyl ether is 5-49 quality %; And in element sulphur, described sulfur alcohol content is 0.0001-0.001 quality %, and dithiocarbonic anhydride content is 0.00005-0.0001 quality %, and single thioether content is 0.0001-0.100 quality %, polysulphide content is 0.0002-0.09 quality %, and thiophene content is 0.0001-0.001 quality %.
According to the method for the thick product of purifying methyl tertiary butyl ether of the present invention, the range of choices of the condition of described distillation is wider, can adjust accordingly according to the described character of solution containing methyl tertiary butyl ether and the position of side take-off, generally speaking, the condition of described distillation comprises: the column bottom temperature of distillation tower is 70-150 DEG C, the tower bottom pressure of distillation tower is 0.3-1.0MPa, and the stage number of distillation tower is 20-80, and trim the top of column is than being 1-12.
In the present invention, described distillation tower can be the various distillation towers of prior art, such as, typically comprise the distillation towers such as catalytic distillation tower.
Simultaneously, for the method being prepared methyl tertiary butyl ether by reaction distillation of prior art, in order to the methyl tertiary butyl ether of production super low sulfur, according to a kind of concrete embodiment of the present invention, according to flow process shown in Fig. 1, the invention provides a kind of method of producing super low sulfur methyl tertiary butyl ether, the method comprises:
(1) under being the condition of methyl tertiary butyl ether by methyl alcohol and isobutene conversion, methyl alcohol and hybrid C 4 are sent in reactor the solution prepared with catalyst exposure containing methyl tertiary butyl ether; Wherein, contain sulfide in described methyl alcohol and/or hybrid C 4, the described solution containing methyl tertiary butyl ether contains methyl alcohol, hybrid C 4 and methyl tertiary butyl ether; (2) fractionation by distillation is carried out by the described solution feeding distillation tower containing methyl tertiary butyl ether; Wherein, sulphur pregnant solution is introduced in step (1) and/or step (2), and the condition of distillation in rate-determining steps (2) makes methyl alcohol and hybrid C 4 (unreacted C4) from overhead extraction, sulfide after being absorbed by described sulphur pregnant solution and not by the sulfide of described sulphur pregnant solution absorption from extraction at the bottom of tower, the logistics containing methyl tertiary butyl ether is from side take-off.More particularly, the angle of slave unit, the technique of distilling compared to the on-catalytic of the production MTBE of prior art (is the technique of the aforesaid reaction distillation of the present invention, those skilled in the art are usually also referred to as the ordinary process producing MTBE), the method of aforementioned production super low sulfur methyl tertiary butyl ether of the present invention can keep reactor constant, the azeotropic distillation column of MTBE and unreacted C4 and methyl alcohol is separated by transformation, namely side take-off mouth is set in the side of azeotropic distillation column, then the operational condition of azeotropic distillation column is reasonably controlled, realize the side take-off of methyl tertiary butyl ether, thus achieve the methyl tertiary butyl ether that a step separation obtains super low sulfur.Object of the present invention can be realized by aforementioned transformation.
Further, for the method being prepared methyl tertiary butyl ether by catalytic distillation of prior art, in order to the methyl tertiary butyl ether of production super low sulfur, according to a kind of concrete embodiment of the present invention, according to flow process shown in Fig. 2, the invention provides a kind of method of producing super low sulfur methyl tertiary butyl ether, the method comprises:
(1) under being the condition of methyl tertiary butyl ether by methyl alcohol and isobutene conversion, methyl alcohol and hybrid C 4 are sent in reactor and obtains mixture with catalyst exposure, in described methyl alcohol and/or hybrid C 4, contain sulfide; (2) contact in described mixture feeding catalytic distillation tower with catalyzer; Wherein, sulphur pregnant solution is introduced in step (1) and/or step (2), and the condition of catalytic distillation in rate-determining steps (2) makes methyl alcohol and hybrid C 4 (unreacted C4) from overhead extraction, sulfide after being absorbed by described sulphur pregnant solution and not by the sulfide of described sulphur pregnant solution absorption from extraction at the bottom of tower, the logistics containing methyl tertiary butyl ether is from side take-off.
More particularly, the angle of slave unit, the technique of MTBE is produced compared to the catalytic distillation of prior art, the method of aforementioned production super low sulfur methyl tertiary butyl ether of the present invention can keep pre-reactor constant, by transformation catalytic distillation tower, namely side take-off mouth is set in the side of catalytic distillation tower, then reasonably controls the operational condition of catalytic distillation tower, realize the side take-off of methyl tertiary butyl ether, thus achieve one step be separated obtain methyl tertiary butyl ether.Object of the present invention can be realized by aforementioned transformation.
In the present invention, in step (1) and/or step (2), introduce sulphur pregnant solution be included in step (1) and/or step (2) is carried out front and/or carries out middle introducing sulphur pregnant solution, such as when introducing sulphur pregnant solution in step (1), can before step (1) carries out, in methyl alcohol, MTBE and hybrid C 4 mixture, introduce sulphur pregnant solution, also can introduce sulphur pregnant solution in methyl alcohol and hybrid C 4 contact process; And when introducing sulphur pregnant solution in step (2), can before step (2) carry out, in the raw material (solution containing methyl tertiary butyl ether such as or described mixture) that step (2) uses, introduce sulphur pregnant solution, also can carry out introducing sulphur pregnant solution in process in step (2).
In the present invention, described sulphur pregnant solution is for absorbing described sulfide so that described sulfide is converted into heavy substance as far as possible, thus can as much as possible whole sulfide be distillated from tower reactor, wherein said absorption can be physical absorption and/or chemical absorption, when for chemical absorption, described sulphur pregnant solution can for generating high boiling sulfide with sulfide generation complex reaction, when for physical absorption, described sulphur pregnant solution can be the organometallic compound of boiling point higher than methyl tertiary butyl ether; The sulphur pregnant solution meeting aforementioned claim all can be used for the present invention, for the present invention, preferred described sulphur pregnant solution is boiling point higher than the organometallics of methyl tertiary butyl ether and/or mineral compound, wherein metallic element can be such as one or more in II A race metal, IV A race metal and transition metal, be more preferably in lead, calcium, zinc, copper, iron, cobalt, nickel, chromium, silver, palladium and platinum one or more, one or more more preferably in copper, iron, nickel, palladium, silver, zinc and cobalt.More preferably described sulphur pregnant solution is the sulfonated phthalocyanine compound of aforementioned metal, poly-phthalocyanine compound, vitriol, chlorate, Bromide, iodized salt, oxalate, nitrate, one or more in acetate and oxide compound, more specifically, described sulphur pregnant solution can be lead naphthenate, zinc naphthenate, copper naphthenate, nickel naphthenate, calcium naphthenate, sulfonated phthalocyanine cobalt, poly-Cobalt Phthalocyanine, sulfonated phthalocyanine nickel, poly-Nickel Phthalocyanine, cupric chloride, cobalt chloride, rose vitriol, one or more in ferrous sulfate and zinc acetate, be more preferably zinc naphthenate, copper naphthenate, nickel naphthenate, sulfonated phthalocyanine cobalt, poly-Cobalt Phthalocyanine, sulfonated phthalocyanine nickel, poly-Nickel Phthalocyanine, cupric chloride, cupric bromide, cupric iodide, cobalt chloride, rose vitriol, Silver Nitrate, Palladous chloride, palladium iodide, palladous sulfate, oxalic acid palladium, one or more in ferrous sulfate and zinc acetate.
Except above-mentioned preferred sulphur pregnant solution kind, sulphur pregnant solution of the present invention can also be that organic esters is as p-methyl tosylate, halogenated hydrocarbon compound etc.
According to the method for the thick product of purifying methyl tertiary butyl ether of the present invention, for the ease of operate continuously, preferably described sulphur pregnant solution is dissolved and introduce with solution or form of suspension in a solvent, simultaneously in order to make the solvent of the described sulphur pregnant solution of dissolving finally discharge at the bottom of tower, described solvent is preferably organic oxygen-containing compound more than 100 DEG C of the hydrocarbon liquid of initial boiling point more than 100 DEG C, boiling point and one or more in the oil product of initial boiling point more than 100 DEG C; Be preferably in methyl alcohol, alkane, aromatic hydrocarbons, organic aldehyde, organic ether, organic ester, Organic Alcohol, organic phenol, heavy petrol, kerosene, diesel oil and lubricating oil one or more; Be more preferably methyl alcohol, octane, octane-iso, benzene, toluene, heavy petrol, kerosene, diesel oil, lubricating oil, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, phenyl ether, glycerin fatty acid ester, furfural, glycerol, Diethylene Glycol, cresols, xylenol and 2, one or more in 6-ditertbutylparacresol, to be particularly preferably boiling point be kerosene, the boiling point of more than 140 DEG C to be diesel oil, the boiling point of more than 140 DEG C be in the glycerin fatty acid ester of more than 140 DEG C one or more.
According to the present invention, preferably in 1kg solvent, the sulphur content in described solvent, at below 200mg, preferably at below 50mg, particularly preferably in below 2mg, does not most preferably contain S-contained substance in described solvent completely.
According to the present invention, introduce with continuous print in a solvent to can be good at sulphur pregnant solution to dissolve, the content preferably described sulphur pregnant solution being dissolved sulphur pregnant solution in the solution or suspension obtained in a solvent is 0.001-30 % by weight, is preferably 0.01-10 % by weight.
In the present invention, described sulphur pregnant solution can adjust according to the content of described sulfide, for the present invention, preferably in the logistics containing methyl tertiary butyl ether of the side take-off of 1kg, the consumption of sulphur pregnant solution solution or suspension is 10-300000mg, be preferably 200-20000mg, more preferably 1000-8000mg.
According to the method for the thick product of purifying methyl tertiary butyl ether of the present invention and the method for production methyl tertiary butyl ether, in order to realize aforementioned invention object of the present invention, preferably the described boiling range from the logistics containing methyl tertiary butyl ether described in side take-off is generally higher than temperature t1 to less than or equal to 110 DEG C, described temperature t1 is that (generally speaking the boiling point of hybrid C 4 is subzero 11 DEG C to 4 DEG C above freezing for the greater in the boiling point of hybrid C 4 and the azeotropic point of hybrid C 4 and methyl alcohol, hybrid C 4 and the low azeotrope of the formation of methanol, the boiling point of low azeotrope is less than 0 DEG C), for the present invention, in order to make the described logistics containing methyl tertiary butyl ether better from side take-off, preferably the boiling range of the described logistics containing methyl tertiary butyl ether is 40-95 DEG C, be more preferably 48-75 DEG C.Obtain as needed high purity as more than 99.6 % by weight MTBE, then the boiling range needing further preferably side-stream is 50-62 DEG C, and air lift repurity is carried out in the MTBE logistics that can certainly go out pump-around stream.
Core of the present invention is to make sulfur compound be converted into heavy substance by introducing sulphur pregnant solution, and heat when then utilizing fractionation by distillation hybrid C 4 and methyl alcohol at the bottom of still, the position suitable at distillation tower arranges side take-off, makes MTBE from side take-off.Well achieve the purifying of the thick product of methyl tertiary butyl ether and the production of super low sulfur MTBE thus.As can be seen here, compared to the existing MTBE in order to produce low sulfur content, by MTBE prepared by simple distillation or rectifying or " extractive distillation " traditional technology, by MTBE from tower top fractionation out, most sulfide is made to residue at the bottom of still, thus production sulphur content is less than the method for the MTBE of 10mg/kg, the present invention has not only saved large energy, and decreases input and the maintenance cost of equipment.
In the present invention, extraction at the bottom of tower (or residual at the bottom of still), except most sulfide, also may have other high boiler material, and to this, those skilled in the art can know according to technical scheme of the present invention, and the present invention does not repeat them here.
According to the method for the thick product of purifying methyl tertiary butyl ether of the present invention and the method for production methyl tertiary butyl ether, in order to make the application of the super low sulfur methyl tertiary butyl ether obtained more extensive, preferably the described logistics containing methyl tertiary butyl ether makes from the position of side take-off, relative to the logistics containing methyl tertiary butyl ether of every kg, sulphur content at below 10mg, preferably at below 2mg.The described logistics containing methyl tertiary butyl ether meeting aforementioned claim may be used for the mediation of gasoline octane rating, and the content of sulfur in gasoline after being in harmonious proportion can meet the standard of gasoline state IV or state V, even can meet the standard of following requirements at the higher level.Thus, compared to prior art, method of the present invention can not only ensure in the execution epoch of gasoline state IV or the epoch of state V, methyl tertiary butyl ether MTBE can directly be blended into ensure the normal production and supply of gasoline in gasoline, and the resource of refinery's liquefied petroleum gas (LPG) can be made reasonably to be utilized.And method of the present invention, compared to prior art, energy consumption is low, and input and the maintenance cost of equipment reduce greatly, thus effectively can reduce the cost of production super low sulfur methyl tertiary butyl ether.
In the present invention, can need according to different the position selecting side take-off, generally speaking, due in a distillation column, reduce gradually to tower top temperature by the bottom of tower, therefore, the position of side take-off is higher, namely at the bottom of tower more away from, then in the methyl tertiary butyl ether that obtains of extraction, sulphur content is lower, and vice versa.In specific implementation process, can according to the sulphur content requirement to methyl tertiary butyl ether, from different lateral line dischargings, then according to the condition that the control of the location-appropriate of side take-off is distilled, object of the present invention can well be realized thus, and those skilled in the art are according to preceding solution of the present invention, readily understand and how to carry out the selection of side line position and the control of distillation condition.
As previously mentioned, the position of described side take-off can be selected according to needs, for the present invention, stage number preferably at the bottom of the lateral distance tower of described distillation tower or catalytic distillation tower is that the 1/5-4/5 place of column plate sum arranges at least one side take-off mouth, 2-5 side take-off mouth is preferably set, with realize described by the logistics containing methyl tertiary butyl ether from side take-off.In the methyl tertiary butyl ether that aforementioned side take-off position extraction obtains, sulphur content all can meet the requirements.Also can increase depending on requirement, then determine to open which side take-off mouth as requested, with by the logistics containing methyl tertiary butyl ether from side take-off.
In the present invention, if not otherwise specified, described stage number all refers to number of actual plates.
In the present invention, the condition of described distillation or catalytic distillation comprises: the column bottom temperature of distillation tower or catalytic distillation tower is 70-150 DEG C, the tower bottom pressure of distillation tower or catalytic distillation tower is 0.3-1.0MPa, and the number of actual plates of distillation tower or catalytic distillation tower is 20-80, and trim the top of column is than being 1-12.
Concrete, the solution containing methyl alcohol, hybrid C 4, sulfide and methyl tertiary butyl ether that operation (those skilled in the art are commonly referred to common MTBE production technique) for the reaction distillation be separated conventionally obtains, namely for the method according to following step production super low sulfur methyl tertiary butyl ether of the present invention: methyl alcohol and hybrid C 4, under being the condition of methyl tertiary butyl ether by methyl alcohol and isobutene conversion, are sent in reactor the solution prepared with catalyst exposure containing methyl tertiary butyl ether by (1); Wherein, contain sulfide in described methyl alcohol and/or hybrid C 4, the described solution containing methyl tertiary butyl ether contains methyl alcohol, hybrid C 4 and methyl tertiary butyl ether;
(2) fractionation by distillation is carried out by the described solution feeding distillation tower containing methyl tertiary butyl ether;
The condition of described distillation generally comprises: the column bottom temperature of distillation tower is 70-150 DEG C, and the tower bottom pressure of distillation tower is 0.3-1.0MPa, and the number of actual plates of distillation tower is 20-80, and trim the top of column is than being 1-12.
And for the solution containing methyl alcohol, hybrid C 4, sulfide and methyl tertiary butyl ether that the operation being separated catalytic distillation conventionally obtains, namely for the method according to following step production super low sulfur methyl tertiary butyl ether of the present invention: (1) is under being the condition of methyl tertiary butyl ether by methyl alcohol and isobutene conversion, methyl alcohol and hybrid C 4 are sent in reactor and obtains mixture with catalyst exposure, in described methyl alcohol and/or hybrid C 4, contain sulfide; (2) contact in described mixture feeding catalytic distillation tower with catalyzer;
Operational condition in described catalytic distillation tower generally comprises: the column bottom temperature of catalytic distillation tower is 70-150 DEG C, and the tower bottom pressure of catalytic distillation tower is 0.3-1.0MPa, and the number of actual plates of catalytic distillation tower is 20-80, and trim the top of column is than being 1-12.
In the present invention, described is that the range of choices of the condition of methyl tertiary butyl ether is wider by methyl alcohol and isobutene conversion, the condition of contact preparation methyl tertiary butyl ether specifically can be carried out in the reactor with reference to the method for the reaction distillation according to this area routine of prior art (technique of common production MTBE) or catalytic distillation, it generally comprises: temperature is 40-80 DEG C, methyl alcohol with in the mol ratio of the hybrid C 4 of iso-butylene for 0.8-1.5:1.
According to preceding solution of the present invention, the present invention is mainly the improvement to separating step, the method of step (1) is had no special requirements, therefore, in the present invention, the catalyzer that described catalyzer adopts this area routine to use, the present invention to this without particular requirement, in an exemplary embodiment of the present invention, the catalyst for etherification of use is acidic ion exchange resin, but does not get rid of the catalyzer using other type.
According to the method for production super low sulfur methyl tertiary butyl ether of the present invention, described hybrid C 4 is the hybrid C 4 containing sulfide that this area is commonly used, it generally refers to the propylene in petrochemical plant gas fractionation plant separation liquefied gas, the mixture of remaining C4 component after propane, it is generally containing C4 alkane and C4 alkene, and the sulfide etc. of trace, for the present invention, preferably described is the hybrid C 4 that 0.5-1000mg/kg(specifically refers to relative to 1kg containing the sulphur content in the hybrid C 4 of sulfide, sulphur content is 10-1000mg), iso-butylene content is 5-30 quality %.It also can be the C4 of liquefied gas after being separated after concentrated iso-butylene, and as the light C4 after separating heavy C4, the content of iso-butylene is generally 20-70 % by weight.
In the present invention, the general extraction of tower top be hybrid C 4 and methyl alcohol (wherein, a hybrid C 4 part and methyl alcohol extraction as an azeotrope, a part directly extraction); As previously mentioned, extraction at the bottom of tower except being mainly sulfide also may containing other high boiling point bed materials as a small amount of alkene oligomerization thing and a small amount of methyl tertiary butyl ether, to this, those skilled in the art all can predict according to preceding solution of the present invention, and the present invention is no longer described in detail at this.What also need to stress is, in the present invention, the described of side take-off contains in the logistics of methyl tertiary butyl ether except mainly containing except methyl tertiary butyl ether, also may contain the applications as laminates C8 hydro carbons etc. of C5 hydro carbons, C6 hydro carbons, C7 hydro carbons and C4, these hydro carbons are the higher octane component of gasoline, and therefore the described logistics containing methyl tertiary butyl ether of side take-off can be directly used in the mediation of gasoline octane rating.
According to method of the present invention, any mode that the two can be made to be separated can be adopted from hybrid C 4 and the methyl alcohol of overhead extraction, such as, adopt conventional water-washing method to isolate methyl alcohol, thus obtain unreacted hybrid C 4.It is extremely low that method of the present invention is separated sulphur content the hybrid C 4 obtained from tower top, makes it directly to be suitable for as multiple use.
According to method of the present invention, if necessary, in order to improve the purity of producing the methyl tertiary butyl ether obtained further, air lift measure can be taked to improve the purity of methyl tertiary butyl ether at side line, here be noted that, the purity taking air lift measure to improve product is the technical scheme that those skilled in the art all understand, and therefore, the present invention is no longer described in detail at this.
Main improvement of the present invention is that the condition reasonably controlling distillation realizes side take-off, the various equipment used in process to production methyl tertiary butyl ether are all without particular requirement, the equipment of prior art all can be adopted to carry out, and need the backflow, water cooler, reboiler etc. used also all can to carry out with reference to prior art in process, the present invention no longer repeats at this.
Generally speaking, the present invention mainly improves from the method for two aspects to MTBE desulfurization: heat when 1, utilizing fractionation by distillation hybrid C 4 and methyl alcohol at the bottom of still, the position suitable at distillation tower arranges side line, make MTBE from side take-off, the preferred condition controlling distillation makes the logistics mainly containing MTBE from side take-off, and in this logistics, sulphur content is very low; 2, by introducing sulphur pregnant solution in step (1) and/or step (2), the sulfide entered in MTBE is reduced further, thus more low-sulfur or the MTBE without sulphur can be obtained, make most sulfide residue at the bottom of still, may enter hybrid C 4 on a small quantity, side line obtains the MTBE of deep desulfuration.Adopt method of the present invention, MTBE sweetening effectiveness is good, and the MTBE purity obtained improves, process and Product environment close friend.Compared to the method for prior art, save large energy, and decrease input and the maintenance cost of equipment.
In the present invention, except as otherwise noted, content of sulphur compounds refers to the content in element sulphur, and sulphur content refers to sulfur content.
In the present invention, boiling range measures by the regulation of GB/T6536-1997 " petroleum products Measurement of distilled process method ", and sulphur content adopts ZDS-2000 type Ultraluminescence sulfur determinator, and the regulation according to SH/T0689 measures, and ppm(by weight).Hydrocarbon composition in logistics adopts gas chromatography determination, mol%.And adopt GC-SCD to measure the composition of sulfide, according to sulphur content and sulfide composition, calculate the concentration of sulfide, quality %.
In the present invention, the yield of methyl tertiary butyl ether (MTBE) refers to the per-cent of MTBE and the MTBE actual output obtained from side line, %.(wherein, MTBE actual output refers to the MTBE theoretical yield calculated based on iso-butylene content, and in the present invention, MTBE theoretical yield refers to the amount sum of the MTBE that the amount of the MTBE remained at the bottom of tower and side line obtain).
Below by way of specific embodiment, the present invention will be described in detail, but thought of the present invention is not limited to embodiment.
Embodiment 1
According to the production of flow process shown in Fig. 1 super low sulfur methyl tertiary butyl ether, specifically carry out as follows:
Wherein, " 1 " is main reactor, and " 2 " are azeotropic distillation column, and " 3 " are pump;
(1) under being the condition of methyl tertiary butyl ether by methyl alcohol and isobutene conversion, methyl alcohol, hybrid C 4 are sent in main reactor 1 solution obtained with catalyst exposure containing methyl alcohol, hybrid C 4, sulfide and methyl tertiary butyl ether;
(2) the injecting mouth after main reactor, according to the 1000mg/kg(of MTBE theoretical yield namely relative to the MTBE theoretical yield of 1kg, the consumption of sulphur pregnant solution solution is 1000mg) ratio, adopt pump 3 to inject sulphur pregnant solution solution (to consist of: 80% aviation kerosene+15% sec-butyl acetate+5% copper naphthenate, sulphur content <2mg/kg) and containing methyl alcohol, hybrid C 4, send in azeotropic distillation column 2 after the solution mixing of sulfide and methyl tertiary butyl ether and carry out fractionation by distillation, the condition controlling distillation makes methyl alcohol and hybrid C 4 from overhead extraction, sulfide and the sulphur pregnant solution that is enriched sulfide are from extraction at the bottom of tower, logistics containing methyl tertiary butyl ether is from side line (line or two wires) extraction,
Wherein, the condition being methyl tertiary butyl ether by methyl alcohol and isobutene conversion comprises: control alfin (iso-butylene) mol ratio (i.e. methyl alcohol with in the mol ratio of the hybrid C 4 of iso-butylene) for 1.01-1.10 charging and enter methyltertiarvbutyl ether reactor, catalyzer is strongly acidic styrene's large hole cation exchanger resin (commercial goods: D-005), wherein, the hybrid C 4 of charging comes from catalytic cracking liquefied gas through refining and carrying out gas fractionation process distillation, wherein, sulphur content is 75.7mg/kg, C3 content 0.05 quality %, Trimethylmethane content 37.45 quality %, normal butane content 10.58 quality %, 1-butylene content 11.10 quality %, iso-butylene content is 21.30 quality %, maleic content 7.82 quality %, anti-butene content 11.25%, C5 and C5+ content 0.45 quality %, sulphur content <1.0mg/kg in the methyl alcohol of charging), the solution containing methyl alcohol, hybrid C 4 (unreacted C4), sulfide and methyl tertiary butyl ether obtained after main reactor 1, is all fed to azeotropic distillation column 2 together with the sulphur pregnant solution injected at the feed entrance point of the 18th block of column plate upwards counted from bottom.
Wherein, the number of actual plates of azeotropic distillation column is 55 pieces (theoretical plate numbers 36 pieces), and is offering two side lines from the 40th piece of column plate (line) of the truth of a matter and the position of the 15th piece of column plate (two wires); Control charging and reaction conditions constant, respectively from a line or two wires gas phase discharging and through cooling after collected specimens, wherein, tower top discharging is unreacted hybrid C 4 and methyl alcohol, discharging at the bottom of tower is the high boiling point bed material such as sulfide and the sulphur pregnant solution being enriched sulfide, and a line or two wires discharging are the logistics that target product contains methyl tertiary butyl ether MTBE;
During one line discharging, the processing condition of azeotropic distillation column: trim the top of column ratio is 2.8, tower top temperature is 44 DEG C, and tower top pressure is 0.48MPa, and temperature is 108 DEG C (to have reboiler) at the bottom of tower;
During the discharging of two wires, the processing condition of azeotropic distillation column: trim the top of column ratio is 3.1, tower top temperature is 43 DEG C, and tower top pressure is 0.49MPa, and temperature is 113 DEG C (to have reboiler) at the bottom of tower;
Wherein, discharging (or being called tower base stream) at the bottom of tower top discharging (or being called overhead stream), tower, and the forming of logistics containing methyl tertiary butyl ether MTBE obtained by a line, two wires, sulphur content and yield are respectively as shown in table 1, table 2.
Table 1
Table 2
Embodiment 2
According to the production of flow process shown in Fig. 2 super low sulfur methyl tertiary butyl ether, specifically carry out as follows:
Wherein " 1 " is main reactor, and " 2 " are catalytic distillation tower, and " 3 " are pump:
(1) under being the condition of methyl tertiary butyl ether by methyl alcohol and isobutene conversion, methyl alcohol, hybrid C 4 are sent in main reactor 1 solution obtained with catalyst exposure containing methyl alcohol, hybrid C 4, sulfide and methyl tertiary butyl ether;
(2) the injecting mouth after main reactor, according to the 8000mg/kg(of MTBE theoretical yield namely relative to the MTBE theoretical yield of 1kg, the consumption of sulphur pregnant solution solution is 8000mg) ratio, adopt pump 3 to inject sulphur pregnant solution solution (to consist of: 80 quality % derv fuel oil+15 quality % soybean oil+2.5 quality % zinc naphthenate+2.5 quality % cupric chlorides, sulphur content 5mg/kg) and containing methyl alcohol, hybrid C 4, send in catalytic distillation tower 2 after the solution mixing of sulfide and methyl tertiary butyl ether and carry out fractionation by distillation, the condition controlling catalytic distillation makes methyl alcohol and hybrid C 4 (unreacted C4) from overhead extraction, sulfide and the sulphur pregnant solution that is enriched sulfide are from extraction at the bottom of tower, logistics containing methyl tertiary butyl ether is from side line (line or two wires) extraction,
Wherein, etherification reaction condition comprises: control alfin (iso-butylene) mol ratio (i.e. methyl alcohol and in the mol ratio of the hybrid C 4 of iso-butylene) for 1.05-1.10 charging and enter methyltertiarvbutyl ether reactor, catalyzer is strongly acidic styrene's large hole cation exchanger resin (commercial goods: D-005), wherein (in the hybrid C 4 of charging, sulphur content is about 100mg/kg, C3 content 0.00 quality %, Trimethylmethane content 32.29 quality %, normal butane content 10.41 quality %, 1-butylene content 13.45 quality %, iso-butylene content is 23.70 quality %, 2-butylene content 20.10 quality %, C5 and C5+ content 0.62 quality %, sulphur content <0.5mg/kg in the methyl alcohol of charging), the solution containing methyl alcohol, hybrid C 4, sulfide and methyl tertiary butyl ether obtained after reaction, is all fed to catalytic distillation tower 2 together with the sulphur pregnant solution injected in the position of the 22nd block of column plate upwards counted from bottom.
Wherein, the number of actual plates of catalytic distillation tower is 55 pieces (theoretical plate numbers 36 pieces), and is offering two side lines from the 33rd piece of column plate (line) of the lower tower truth of a matter and the position of the 15th piece of column plate (two wires); Control charging and etherification reaction condition constant, respectively from a line or two wires discharging and collected specimens, wherein, tower top discharging is unreacted hybrid C 4 and methyl alcohol, discharging at the bottom of tower is the high boiling point bed material such as sulfide and the sulphur pregnant solution being enriched sulfide, and a line or two wires discharging are the logistics that target product contains methyl tertiary butyl ether MTBE;
During one line discharging, the processing condition of catalytic distillation tower: trim the top of column ratio is 3.1, tower top temperature is 43 DEG C, and tower top pressure is 0.49MPa, and temperature is 109 DEG C (to have reboiler) at the bottom of tower;
During the discharging of two wires, the processing condition of catalytic distillation tower: trim the top of column ratio is 3.3, tower top temperature is 45 DEG C, and tower top pressure is 0.51MPa, and temperature is 111 DEG C (to have reboiler) at the bottom of tower;
Wherein, discharging at the bottom of tower top discharging, tower (or being called tower base stream), and the forming of logistics containing methyl tertiary butyl ether MTBE obtained by a line, two wires, sulphur content and yield are respectively as shown in table 3, table 4.
Table 3
Table 4
From the result of embodiment 1 and embodiment 2, it is very low that the present invention adopts filling sulphur pregnant solution and the method for side take-off to produce the sulphur content of the methyl tertiary butyl ether obtained, and according to the position of side take-off, can select the sulphur content of MTBE to be down to very low, and the yield of MTBE is more than 99%; Sulfide enriched material (being enriched the sulphur pregnant solution of sulfide) at the bottom of tower, can use as oil fuel, also after simple distillation process removes heavy impurity, can reclaim organism further, or as the process such as hydrogenation, fcc raw material.As can be seen here, whole process does not have waste residue, environmental friendliness.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (25)
1. a method for the thick product of purifying methyl tertiary butyl ether, the method comprises:
Solution containing methyl tertiary butyl ether is carried out fractionation by distillation in a distillation column, and the described solution containing methyl tertiary butyl ether contains methyl alcohol, sulfide, hybrid C 4 and methyl tertiary butyl ether;
It is characterized in that, the method to be also included in fractionation by distillation and/or to contain in the solution of methyl tertiary butyl ether at fractionation by distillation process forward direction introduces sulphur pregnant solution, and the condition controlling distillation makes methyl alcohol and hybrid C 4 from overhead extraction, sulfide after being absorbed by described sulphur pregnant solution and not by the sulfide of described sulphur pregnant solution absorption from extraction at the bottom of tower, logistics containing methyl tertiary butyl ether is from side take-off, described sulphur pregnant solution is lead naphthenate, zinc naphthenate, copper naphthenate, nickel naphthenate, calcium naphthenate, sulfonated phthalocyanine cobalt, poly-Cobalt Phthalocyanine, sulfonated phthalocyanine nickel, poly-Nickel Phthalocyanine, cupric chloride, cupric bromide, cupric iodide, cobalt chloride, rose vitriol, Silver Nitrate, Palladous chloride, palladium iodide, palladous sulfate, oxalic acid palladium, one or more in ferrous sulfate and zinc acetate.
2. method according to claim 1, wherein, the described solution containing methyl tertiary butyl ether is under being the condition of methyl tertiary butyl ether by methyl alcohol and isobutene conversion, is obtained by methyl alcohol, hybrid C 4 and catalyst exposure, contains sulfide in described methyl alcohol and/or hybrid C 4.
3. method according to claim 1, wherein, described containing in the solution of methyl tertiary butyl ether, the content of methyl alcohol is 0.05-15 quality %, the content of hybrid C 4 is 50-90 quality %, in the content of element sulphur sulfide for 0.001-0.150 quality %, the content of methyl tertiary butyl ether is 5-49 quality %; And in element sulphur, described sulfur alcohol content is 0.0001-0.001 quality %, dithiocarbonic anhydride content is 0.00005-0.0001 quality %, single thioether content is 0.0001-0.100 quality %, polysulphide content is 0.0002-0.09 quality %, and thiophene content is 0.0001-0.001 quality %.
4. produce a method for methyl tertiary butyl ether, the method comprises:
(1) under being the condition of methyl tertiary butyl ether by methyl alcohol and isobutene conversion, methyl alcohol and hybrid C 4 are sent in reactor the solution prepared with catalyst exposure containing methyl tertiary butyl ether; Wherein, contain sulfide in described methyl alcohol and/or hybrid C 4, the described solution containing methyl tertiary butyl ether contains methyl alcohol, hybrid C 4 and methyl tertiary butyl ether;
(2) fractionation by distillation is carried out by the described solution feeding distillation tower containing methyl tertiary butyl ether;
It is characterized in that, sulphur pregnant solution is introduced in step (1) and/or step (2), and the condition of distillation in rate-determining steps (2) makes methyl alcohol and hybrid C 4 from overhead extraction, sulfide after being absorbed by described sulphur pregnant solution and not by the sulfide of described sulphur pregnant solution absorption from extraction at the bottom of tower, logistics containing methyl tertiary butyl ether is from side take-off, described sulphur pregnant solution is lead naphthenate, zinc naphthenate, copper naphthenate, nickel naphthenate, calcium naphthenate, sulfonated phthalocyanine cobalt, poly-Cobalt Phthalocyanine, sulfonated phthalocyanine nickel, poly-Nickel Phthalocyanine, cupric chloride, cupric bromide, cupric iodide, cobalt chloride, rose vitriol, Silver Nitrate, Palladous chloride, palladium iodide, palladous sulfate, oxalic acid palladium, one or more in ferrous sulfate and zinc acetate.
5. produce a method for methyl tertiary butyl ether, the method comprises:
(1) under being the condition of methyl tertiary butyl ether by methyl alcohol and isobutene conversion, methyl alcohol and hybrid C 4 are sent in reactor and obtains mixture with catalyst exposure, in described methyl alcohol and/or hybrid C 4, contain sulfide;
(2) contact in described mixture feeding catalytic distillation tower with catalyzer;
It is characterized in that, sulphur pregnant solution is introduced in step (1) and/or step (2), and the condition of catalytic distillation in rate-determining steps (2) makes methyl alcohol and hybrid C 4 from overhead extraction, sulfide after being absorbed by described sulphur pregnant solution and not by the sulfide of described sulphur pregnant solution absorption from extraction at the bottom of tower, logistics containing methyl tertiary butyl ether is from side take-off, described sulphur pregnant solution is lead naphthenate, zinc naphthenate, copper naphthenate, nickel naphthenate, calcium naphthenate, sulfonated phthalocyanine cobalt, poly-Cobalt Phthalocyanine, sulfonated phthalocyanine nickel, poly-Nickel Phthalocyanine, cupric chloride, cupric bromide, cupric iodide, cobalt chloride, rose vitriol, Silver Nitrate, Palladous chloride, palladium iodide, palladous sulfate, oxalic acid palladium, one or more in ferrous sulfate and zinc acetate.
6. according to the method in claim 1-5 described in any one, wherein, described sulphur pregnant solution dissolved and introduce with solution or form of suspension in a solvent, described solvent is organic oxygen-containing compound more than 110 DEG C of the hydrocarbon liquid of initial boiling point more than 110 DEG C, boiling point and one or more in the oil product of initial boiling point more than 110 DEG C.
7. method according to claim 6, wherein, described solvent is one or more in alkane, aromatic hydrocarbons, organic aldehyde, organic ether, organic ester, Organic Alcohol, organic phenol, heavy petrol, kerosene, diesel oil and lubricating oil.
8. method according to claim 6, wherein, described solvent to be boiling point be kerosene, the boiling point of more than 140 DEG C the be diesel oil of more than 140 DEG C and boiling point are one or more in the glycerin fatty acid ester of more than 140 DEG C.
9. method according to claim 6, wherein, in 1kg solvent, the sulphur content in described solvent is at below 200mg.
10. method according to claim 9, wherein, in 1kg solvent, the sulphur content in described solvent is at below 50mg.
11. methods according to claim 10, wherein, in 1kg solvent, the sulphur content in described solvent is at below 2mg.
12. methods according to claim 6, wherein, the content described sulphur pregnant solution being dissolved sulphur pregnant solution in the solution or suspension obtained in a solvent is 0.001-30 % by weight.
13. methods according to claim 12, wherein, the content described sulphur pregnant solution being dissolved sulphur pregnant solution in the solution or suspension obtained in a solvent is 0.01-10 % by weight.
14. methods according to claim 6, wherein, in the logistics containing methyl tertiary butyl ether of the side take-off of 1kg, the consumption of sulphur pregnant solution solution or suspension is 10-300000mg.
15. methods according to claim 14, wherein, in the logistics containing methyl tertiary butyl ether of the side take-off of 1kg, the consumption of sulphur pregnant solution solution or suspension is 200-20000mg.
16. according to the method in claim 1-5 described in any one, wherein, be higher than temperature t1 to less than or equal to 110 DEG C from the boiling range of logistics containing methyl tertiary butyl ether described in side take-off, described temperature t1 is the greater in the boiling point of hybrid C 4 and the azeotropic point of hybrid C 4 and methyl alcohol.
17. methods according to claim 16 wherein, are 40-95 DEG C from the boiling range of the logistics containing methyl tertiary butyl ether described in side take-off.
18. according to the method in claim 1-5 described in any one, and wherein, the described logistics containing methyl tertiary butyl ether makes from the position of side take-off, and relative to the logistics containing methyl tertiary butyl ether of every kg, sulphur content is at below 10mg.
19. methods according to claim 18, wherein, the described logistics containing methyl tertiary butyl ether makes from the position of side take-off, and relative to the logistics containing methyl tertiary butyl ether of every kg, sulphur content is at below 5mg.
20. according to the method in claim 1-5 described in any one, wherein, stage number at the bottom of the lateral distance tower of distillation tower or catalytic distillation tower is that the 1/5-4/5 place of column plate sum arranges at least one side take-off mouth, with realize described by the logistics containing methyl tertiary butyl ether from side take-off.
21. methods according to claim 20, wherein, stage number at the bottom of the lateral distance tower of distillation tower or catalytic distillation tower is that the 1/5-4/5 place of column plate sum arranges 2-5 side take-off mouth, with realize described by the logistics containing methyl tertiary butyl ether from side take-off.
22. according to the method in claim 1-5 described in any one, wherein, the condition of distillation or catalytic distillation comprises: the column bottom temperature of distillation tower or catalytic distillation tower is 70-150 DEG C, the tower bottom pressure of distillation tower or catalytic distillation tower is 0.3-1.0MPa, the stage number of distillation tower or catalytic distillation tower is 20-80, and trim the top of column is than being 1-12.
23. according to the method in claim 2,4 or 5 described in any one, and wherein, the described condition being methyl tertiary butyl ether by methyl alcohol and isobutene conversion comprises: temperature is 40-80 DEG C, and the mol ratio of the iso-butylene in methyl alcohol and hybrid C 4 is 0.8-1.5:1.
24. according to the method in claim 2,4 or 5 described in any one, and wherein, described catalyzer is acidic ion exchange resin.
25. according to the method in claim 1-5 described in any one, and wherein, containing sulfide in described hybrid C 4, be 10-1000mg/kg containing the sulphur content in the hybrid C 4 of sulfide, iso-butylene content is 5-30 quality %.
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| CN1153164A (en) * | 1995-12-26 | 1997-07-02 | 北京燕山石油化工公司合成橡胶厂 | Process for preparing chemical industry type methyl t-butyl ether |
| CN202822829U (en) * | 2012-10-15 | 2013-03-27 | 山东济炼石化工程有限公司 | Device for lowering sulfur content in MTBE (Methyl Tert-butyl Ether) |
| CN103145534A (en) * | 2013-03-26 | 2013-06-12 | 南开大学 | Method for deeply removing sulfides in gasoline additive, namely methyl tert-butyl ether |
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| CN1153164A (en) * | 1995-12-26 | 1997-07-02 | 北京燕山石油化工公司合成橡胶厂 | Process for preparing chemical industry type methyl t-butyl ether |
| CN202822829U (en) * | 2012-10-15 | 2013-03-27 | 山东济炼石化工程有限公司 | Device for lowering sulfur content in MTBE (Methyl Tert-butyl Ether) |
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Denomination of invention: Methyl tert-butyl ether crude product purification method and methyl tert-butyl ether production method Effective date of registration: 20170123 Granted publication date: 20160330 Pledgee: Haidian Beijing science and technology enterprise financing Company limited by guarantee Pledgor: BEIJING ENERGY ENGINEERING TECHNOLOGIES Co.,Ltd. Registration number: 2017990000063 |
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Denomination of invention: Methyl tert-butyl ether crude product purification method and methyl tert-butyl ether production method Effective date of registration: 20180205 Granted publication date: 20160330 Pledgee: Haidian Beijing science and technology enterprise financing Company limited by guarantee Pledgor: BEIJING ENERGY ENGINEERING TECHNOLOGIES Co.,Ltd. Registration number: 2018990000128 |
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Denomination of invention: Method for purifying crude methyl tert butyl ether product and method for producing methyl tert butyl ether Effective date of registration: 20220428 Granted publication date: 20160330 Pledgee: Haidian Beijing science and technology enterprise financing Company limited by guarantee Pledgor: BEIJING ENERGY ENGINEERING TECHNOLOGIES Co.,Ltd. Registration number: Y2022110000108 |
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