CN105712848B - A kind of methyl tertiary butyl ether(MTBE) desulfurizing agent and its application method - Google Patents
A kind of methyl tertiary butyl ether(MTBE) desulfurizing agent and its application method Download PDFInfo
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- CN105712848B CN105712848B CN201610169017.9A CN201610169017A CN105712848B CN 105712848 B CN105712848 B CN 105712848B CN 201610169017 A CN201610169017 A CN 201610169017A CN 105712848 B CN105712848 B CN 105712848B
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- mtbe
- tertiary butyl
- butyl ether
- methyl tertiary
- desulfurizing agent
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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 172
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 92
- 230000003009 desulfurizing effect Effects 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title description 30
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 57
- 239000011593 sulfur Substances 0.000 claims abstract description 57
- -1 styrene compound Chemical class 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 11
- 239000005864 Sulphur Substances 0.000 claims abstract description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006477 desulfuration reaction Methods 0.000 claims description 31
- 230000023556 desulfurization Effects 0.000 claims description 31
- 239000002994 raw material Substances 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 12
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 claims description 11
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 8
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 6
- KETWBQOXTBGBBN-UHFFFAOYSA-N hex-1-enylbenzene Chemical compound CCCCC=CC1=CC=CC=C1 KETWBQOXTBGBBN-UHFFFAOYSA-N 0.000 claims description 6
- 150000002469 indenes Chemical class 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- KHMYONNPZWOTKW-UHFFFAOYSA-N pent-1-enylbenzene Chemical compound CCCC=CC1=CC=CC=C1 KHMYONNPZWOTKW-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- LRTOHSLOFCWHRF-UHFFFAOYSA-N 1-methyl-1h-indene Chemical class C1=CC=C2C(C)C=CC2=C1 LRTOHSLOFCWHRF-UHFFFAOYSA-N 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- MRNOGRFKOQUFBC-UHFFFAOYSA-N 1-butyl-1h-indene Chemical class C1=CC=C2C(CCCC)C=CC2=C1 MRNOGRFKOQUFBC-UHFFFAOYSA-N 0.000 claims description 2
- IEKPDJDYFASRFB-UHFFFAOYSA-N 1-ethyl-1h-indene Chemical class C1=CC=C2C(CC)C=CC2=C1 IEKPDJDYFASRFB-UHFFFAOYSA-N 0.000 claims description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- RFRXIWQYSOIBDI-UHFFFAOYSA-N benzarone Chemical compound CCC=1OC2=CC=CC=C2C=1C(=O)C1=CC=C(O)C=C1 RFRXIWQYSOIBDI-UHFFFAOYSA-N 0.000 claims description 2
- 230000000536 complexating effect Effects 0.000 claims description 2
- AQEFLFZSWDEAIP-UHFFFAOYSA-N di-tert-butyl ether Chemical compound CC(C)(C)OC(C)(C)C AQEFLFZSWDEAIP-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims 1
- 239000002736 nonionic surfactant Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 23
- 238000004821 distillation Methods 0.000 abstract description 18
- 238000004523 catalytic cracking Methods 0.000 abstract description 10
- 239000003054 catalyst Substances 0.000 abstract description 8
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 206010027439 Metal poisoning Diseases 0.000 abstract description 2
- 208000010501 heavy metal poisoning Diseases 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002808 molecular sieve Substances 0.000 description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 5
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000002309 gasification Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 2
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 2
- 208000005374 Poisoning Diseases 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical group CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XIWDLKOACQAPJS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxymethanethiol Chemical compound CC(C)(C)OCS XIWDLKOACQAPJS-UHFFFAOYSA-N 0.000 description 1
- WHFHDVDXYKOSKI-UHFFFAOYSA-N 1-ethenyl-4-ethylbenzene Chemical compound CCC1=CC=C(C=C)C=C1 WHFHDVDXYKOSKI-UHFFFAOYSA-N 0.000 description 1
- WBEMJRFRGOAAJI-UHFFFAOYSA-N 3-(1-methyl-3,4-dihydronaphthalen-2-yl)pyridine Chemical compound C1CC2=CC=CC=C2C(C)=C1C1=CC=CN=C1 WBEMJRFRGOAAJI-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- 150000003797 alkaloid derivatives Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- SYWDWCWQXBUCOP-UHFFFAOYSA-N benzene;ethene Chemical group C=C.C1=CC=CC=C1 SYWDWCWQXBUCOP-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- SQHOHKQMTHROSF-UHFFFAOYSA-N but-1-en-2-ylbenzene Chemical group CCC(=C)C1=CC=CC=C1 SQHOHKQMTHROSF-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- YJSSCAJSFIGKSN-UHFFFAOYSA-N hex-1-en-2-ylbenzene Chemical group CCCCC(=C)C1=CC=CC=C1 YJSSCAJSFIGKSN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- PZKNFJIOIKQCPA-UHFFFAOYSA-N oxalic acid palladium Chemical compound [Pd].OC(=O)C(O)=O PZKNFJIOIKQCPA-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- ANGVCCXFJKHNDS-UHFFFAOYSA-N pent-1-en-2-ylbenzene Chemical group CCCC(=C)C1=CC=CC=C1 ANGVCCXFJKHNDS-UHFFFAOYSA-N 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 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 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000004246 zinc acetate Substances 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
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/46—Use of additives, e.g. for stabilisation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a kind of methyl tertiary butyl ether(MTBE) desulfurizing agent, the active component of the desulfurizing agent includes styrene compound, and the addition of the methyl tertiary butyl ether(MTBE) desulfurizing agent is 100~10000mg/kg of sulfur methyl tertiary butyl ether material quality.The methyl tertiary butyl ether(MTBE) desulfurizing agent addition of the present invention is seldom, add 100~10000mg/kg using existing catalytic distillation device just effectively can be reduced to below 10mg/kg by sulfur content for the sulphur in 120mg/kg methyl tertiary butyl ether(MTBE), even it is reduced to 2mg/kg, and be free of metallic element, the heavy metal poisoning of follow-up hydrogenation or catalytic cracking catalyst will not be caused, there is extensive prospects for commercial application.
Description
Technical field
The invention belongs to methyl tertiary butyl ether(MTBE) technical field of desulfurization, and in particular to a kind of methyl tertiary butyl ether(MTBE) desulfurizing agent and its
Application method.
Background technology
Methyl tertiary butyl ether(MTBE) (methyltert-butylether, MTBE) is unleaded production, high-octane rating, oxygenated gasoline
Preferable blend component, it has good intermiscibility with gasoline, can not only improve the efficiency of combustion and its capability of antidetonance of gasoline,
CO and other harmful substances (such as ozone, benzene, butadiene) discharge can also be reduced.MTBE can also be used as paraffin, oil product,
Spices, alkaloid, resin, the solvent of rubber, the reactant of organic synthesis, can also crack and prepare high-purity isobutene.State at present
Interior gasoline generally adds methyl tertiary butyl ether(MTBE) to improve the octane number of gasoline.But environmentally friendly new rule require that gasoline need to reach state IV or state
V standard, i.e. its sulfur content need to be less than 50mg/kg or 10mg/kg.The main production of domestic methyl tertiary butyl ether(MTBE) is at present
It is etherified and is separated using C4 and methanol is mixed in cationic ion-exchange resin is as the catalytic distillation tower of catalyst.Due to mixed
It is higher to close sulfur content in C4, and sulphur is relatively soluble in methyl tertiary butyl ether(MTBE), causes to usually contain 50 in methyl tert-butyl ether product
~200mg/kg sulfide, sulfide content is sometime up to 2000mg/kg in the methyl tertiary butyl ether(MTBE) of part manufacturer production, because
This methyl tertiary butyl ether(MTBE) must desulfurization can be used as preferable gasoline blend component.
Sulfide in methyl tertiary butyl ether(MTBE) is mainly disulphide and a small amount of mercaptan, thioether, thiophenic sulfur, in the prior art
Desulfurizing agent mainly has organic solvent extracting type, molecular sieve catalytic type and a sulfur enrichment agent type containing metallic element, but organic solvent
Addition is big, causes desulphurization cost high, molecular sieve catalyst cost is high and generating apparatus and complex operation, most sulfur enrichment agents contain again
There is metallic element, follow-up hydrogenation and catalytic cracking catalyst can be made to be poisoned, therefore use is limited to.
Chinese patent CN102491882 provides a kind of production method of low sulfur methyl tertiary butyl ether, by by sulfur-bearing
Methyl tertiary butyl ether(MTBE) again rectifying and before rectifying heating vaporization when add extraction take out sulphur solvent, its extract takes out sulphur solvent be selected from weight
In whole gasoline, catalytic hydrogenation heavy petrol, solvent naphtha, kerosene, diesel oil, aromatic hydrocarbons, heavy aromatics, butanol, octanol, furfural or sulfolane
One or more, dosage are 1~10% percent by volume of charging methyl tertiary butyl ether(MTBE).Specification only provides furfural conduct and takes out sulphur
The embodiment of solvent, remaining embodiment, which does not provide, specifically takes out sulphur solvent and desulfurized effect.Although the invention can be by methyl- tert
The sulfur content of butyl ether is reduced to below 10mg/kg, but the addition of its desulfurizing agent is big, account for methyl tertiary butyl ether(MTBE) raw material 1~
10% percent by volume, it is higher to be converted into mass ratio, more than 10000mg/kg~100000mg/kg, while increases a rectifying
Tower separating step, add energy consumption and equipment, running cost.
Chinese patent CN104370707 disclose it is a kind of production methyl tertiary butyl ether(MTBE) catalytic distillation separation in and/or
Sulfur enrichment agent is added before separated, its sulfur enrichment agent is cycloalkyl lead, cycloalkyl zinc, cycloalkyl copper, cycloalkyl nickel, cycloalkyl
Calcium, sulfonated phthalocyanine cobalt, poly- Cobalt Phthalocyanine, sulfonated phthalocyanine nickel, poly- Nickel Phthalocyanine, copper chloride, copper bromide, cupric iodide, cobalt chloride, vulcanization
One or more in cobalt, silver nitrate, palladium bichloride, palladium iodide, palladium sulfate, oxalic acid palladium, ferrous sulfate and zinc acetate, solvent are first
Evaporate the oil of organic oxygen-containing compound and initial boiling point more than 110 DEG C of hydrocarbon liquid, boiling point more than 110 DEG C o'clock more than 110 DEG C
One or more in product.But its advantageous effects is obtained by improving sulfur removal technology, and its sulfur enrichment agent for using
All contain heavy metal, and the high sulfur component of higher boiling containing desulfurizing agent subsequently needs to carry out hydrotreating or catalytic cracking processing,
Heavy metal easily causes follow-up hydrogenation or catalytic cracking catalyst to be poisoned, therefore influences follow-up hydrogenation or the processing energy of catalytic cracking
Power.
CN105130763A provides a kind of sulfur method of methyl tertiary butyl ether(MTBE), by methyl tertiary butyl ether(MTBE) from tower lower part
Desulfurizing tower is delivered to, column bottom temperature is 80~110 DEG C, and Fe-HMS molecular sieve catalysts, peroxide agent H are loaded in desulfurizing tower2O2From
Tower top enters, and tower top temperature is 50~70 DEG C.The MTBE total sulfur contents that this method obtains are below 10ppm, have reached state 5 and have marked
Standard, but this method uses Fe-HMS molecular sieve catalysts and peroxide agent H2O2As desulfurizing agent, regenerating molecular sieve equipment and operation
Complexity, while this method is carried out in desulfurizing tower, adds equipment and running cost.
Therefore, a kind of methyl tertiary butyl ether(MTBE) desulfurizing agent is researched and developed, a small amount of desulfurizing agent is added and is filled merely with existing catalytic distillation
Putting, which just can effectively reduce methyl tertiary butyl ether(MTBE) sulfur content, is extremely less than 10mg/kg, and desulfurizing agent is free of metallic element, after will not causing
Continuous hydrogenation or catalytic cracking catalyst poisoning just has great importance.
The content of the invention
First purpose of the present invention is to provide a kind of methyl tertiary butyl ether(MTBE) desulfurizing agent, to overcome skill of the prior art
Art defect, has that desulfurizing agent addition is few, just can be effectively merely with existing catalytic distillation device the characteristics of without metallic element
Sulfur content in methyl tertiary butyl ether(MTBE) is reduced to below 10mg/kg, or even is reduced to 2mg/kg.
Second object of the present invention is to provide a kind of application method of methyl tertiary butyl ether(MTBE) desulfurizing agent.
To solve above-mentioned technical problem, the present invention adopts the following technical scheme that：
A kind of methyl tertiary butyl ether(MTBE) desulfurizing agent, the active component of the desulfurizing agent include styrene compound, the benzene
Ethylene compounds are one kind or more in styrene, methyl styrene, ethyl styrene, propylstyrene and butylstyrene
Kind.
The methyl styrene is α-methylstyrene, o-methyl styrene, a methyl styrene and p-methylstyrene
In one or more mixtures.
The ethyl styrene is α-ethyl styrene, adjacent ethyl styrene, an ethyl styrene and p -ethyl-styrene
In one or more mixtures.
The propylstyrene is α-propylstyrene, adjacent propylstyrene, a propylstyrene and to propylstyrene
In one or more mixtures.
The butylstyrene is α-butylstyrene, adjacent butylstyrene, a butylstyrene and to butylstyrene
In one or more mixtures.
According to a preferred embodiment of the invention, the active component also includes indene compounds.
Further, the indene compounds are indenes, methyl indenes, ethyl indenes, propyl group indenes and one kind or more in butyl indenes
Kind.
According to a preferred embodiment of the invention, the active component also includes benzofuran, dicyclopentadiene and ring penta 2
One or more in alkene.
According to a preferred embodiment of the invention, the desulfurizing agent also includes one or more organic solvents, described organic molten
Agent is fraction oil of petroleum, aromatic hydrocarbons, solvent naphtha, phenol, alcohol, ether, ester and non-ionic surface active of the boiling point between 100~500 DEG C
One or more in agent.
According to the present invention, by percentage to the quality, the content of active component is 2~100% in the desulfurizing agent, described to have
The content of solvent is 0~98%.
The application method of the methyl tertiary butyl ether(MTBE) desulfurizing agent of the present invention, is comprised the technical steps that：
1) the methyl tertiary butyl ether(MTBE) desulfurizing agent is mixed at 5~150 DEG C with sulfur methyl tertiary butyl ether raw material, obtained
Mixed material.
2) mixed material described in step 1) isolates the high sulfur component of higher boiling through destilling tower or desulfurization rectifying column, obtains
The methyl tertiary butyl ether(MTBE) of super-low sulfur.
According to a preferred embodiment of the invention, the addition of the methyl tertiary butyl ether(MTBE) desulfurizing agent is the sulfur-containing methyl tert-butyl group
100~10000mg/kg of ether material quality.
Preferably, the methyl tertiary butyl ether(MTBE) desulfurizing agent and the sulfide reaction in sulfur methyl tertiary butyl ether raw material, network
Close and extraction part return afterwards recycles.
Compared with prior art, methyl tertiary butyl ether(MTBE) desulfurizing agent of the invention has following Advantageous feature：
1) methyl tertiary butyl ether(MTBE) desulfurizing agent of the invention is free of metallic element, therefore hydrogenation or catalytic cracking will not be caused to urge
The heavy metal poisoning of agent, so as to improve follow-up hydrogenation or catalytic cracking disposal ability.
2) methyl tertiary butyl ether(MTBE) desulfurizing agent addition of the invention is few, and 100~10000mg/kg of addition just can be by sulfur-bearing
The sulphur of 120mg/kg methyl tertiary butyl ether(MTBE) raw material is reduced to below 10mg/kg, minimum to be reduced to 2mg/kg.
3) methyl tertiary butyl ether(MTBE) desulfurizing agent of the invention may be directly applied to existing methyl tertiary butyl ether(MTBE) catalytic distillation dress
Put, need not increase desulfurization destilling tower separating step after catalytic distillation tower also can effectively reduce sulfur content to below 10mg/kg.
Brief description of the drawings
The MTBE desulfurization process schematic diagrames of Fig. 1 embodiments 9.
Fig. 2 desulfurizing agents after catalytic distillation tower feed exchanger with MTBE mixing desulfurization process schematic diagrames.
Fig. 3 desulfurizing agents are introduced into catalytic reactor after being well mixed before catalytic reactor with methanol and mixing C4, so
Enter catalytic distillation tower desulfurization process schematic diagram afterwards.
The MTBE desulfurization process schematic diagrames of Fig. 4 embodiments 10.
Wherein：1- catalytic reactors, 2- catalytic distillation towers, 3- desulfurizing agents measuring pump, 4- desulfurizing agents tank, 5- catalytic distillation towers
Feed exchanger, 6- desulfurization destilling tower, 7- desulfurizing agents part pipeloop.
Embodiment
Below by way of specific embodiment, the present invention is described in further details.It should be understood that following examples are only used for
The bright present invention is not for restriction the scope of the present invention.
Methyl tertiary butyl ether(MTBE) raw material M1 (Shanghai Petrochemicals Company Ltd, sulfur content 120mg/kg), methyl tertiary butyl ether(MTBE) are former
Expect M2 (Anhui haydite oil Chemical Co., Ltd., sulfur content 252mg/kg), other components are commercially available.
Mixed methyl styrene used in following examples is：α-methylstyrene：O-methyl styrene：Between methyl
Styrene and：P-methylstyrene=1:3:3:3, mixing ethyl styrene is：Adjacent ethyl styrene：Between ethyl styrene：It is right
Ethyl styrene=3:2:5.
Involved degree in following examples, is mass percentage content in addition to especially indicating.
Methyl tertiary butyl ether(MTBE) desulfurization agent prescription：
MTBE desulfurization agent prescriptions are as described in Table 1：
Table 1, MTBE desulfurization agent prescriptions
Methyl tertiary butyl ether(MTBE) desulfurizing agent test method：
1) MTBE raw material M1 or M2 is mixed with desulfurizing agent with certain proportion, continuous equilibrium gasification is injected by measuring pump and steamed
Distillation unit flashes, and it is 90 DEG C to control bottom temperature, collects materials at bottom of tower and overhead F1；
2) overhead F1 and desulfurizing agent are mixed according to a certain percentage, dodged again through continuous equilibrium gasification distilling apparatus
Steam, it is 90 DEG C to control bottom temperature, collects materials at bottom of tower and overhead F2；
3) overhead F2 and desulfurizing agent are mixed according to a certain percentage, and again through continuous equilibrium gasification distilling apparatus
Flash distillation, it is 90 DEG C to control bottom temperature, collects materials at bottom of tower and overhead F3；
4) sulfur-bearing MTBE raw materials and overhead F3 sulfur content are analyzed by gas chromatographicanalyzer.
Embodiment 1
The desulfurizing agent 500mg/kg of addition formula 1 tries into MTBE raw materials M1 according to above-mentioned methyl tertiary butyl ether(MTBE) desulfurizing agent
Proved recipe method desulfurization, analyze the sulfur content in overhead F3.
Embodiment 2
The desulfurizing agent 240mg/kg of addition formula 2 tries into MTBE raw materials M1 according to above-mentioned methyl tertiary butyl ether(MTBE) desulfurizing agent
Proved recipe method desulfurization, analyze the sulfur content in overhead F3.
Embodiment 3
The desulfurizing agent 500mg/kg of addition formula 3 tries into MTBE raw materials M1 according to above-mentioned methyl tertiary butyl ether(MTBE) desulfurizing agent
Proved recipe method desulfurization, analyze the sulfur content in overhead F3.
Embodiment 4
The desulfurizing agent 650mg/kg of addition formula 4 tries into MTBE raw materials M1 according to above-mentioned methyl tertiary butyl ether(MTBE) desulfurizing agent
Proved recipe method desulfurization, analyze the sulfur content in overhead F3.
Embodiment 5
The desulfurizing agent 3000mg/kg of addition formula 5 tries into MTBE raw materials M1 according to above-mentioned methyl tertiary butyl ether(MTBE) desulfurizing agent
Proved recipe method desulfurization, analyze the sulfur content in overhead F3.
Embodiment 6
The desulfurizing agent 700mg/kg of addition formula 6 tries into MTBE raw materials M1 according to above-mentioned methyl tertiary butyl ether(MTBE) desulfurizing agent
Proved recipe method desulfurization, analyze the sulfur content in overhead F3.
Embodiment 7
The desulfurizing agent 800mg/kg of addition formula 7 tries into MTBE raw materials M2 according to above-mentioned methyl tertiary butyl ether(MTBE) desulfurizing agent
Proved recipe method desulfurization, analyze the sulfur content in overhead F3.
Embodiment 8
The desulfurizing agent 800mg/kg of addition formula 8 tries into MTBE raw materials M2 according to above-mentioned methyl tertiary butyl ether(MTBE) desulfurizing agent
Proved recipe method desulfurization, analyze the sulfur content in overhead F3.
Comparative example 1
50000mg/kg mixed xylenes is added into MTBE raw materials M1, is tested according to above-mentioned methyl tertiary butyl ether(MTBE) desulfurizing agent
Method desulfurization, analyze the sulfur content in overhead F3.
Comparative example 2
50000mg/kg mixing trimethylbenzene is added into MTBE raw materials M1, is tested according to above-mentioned methyl tertiary butyl ether(MTBE) desulfurizing agent
Method desulfurization, analyze the sulfur content in overhead F3.
Comparative example 3
Add 100000mg/kg and reform heavy aromatics into MTBE raw materials M1, tried according to above-mentioned methyl tertiary butyl ether(MTBE) desulfurizing agent
Proved recipe method desulfurization, analyze the sulfur content in overhead F3.
Comparative example 4
10000mg/kg furfurals are added into MTBE raw materials M1, are taken off according to above-mentioned methyl tertiary butyl ether(MTBE) desulfurizing agent test method
Sulphur, analyze the sulfur content in overhead F3.
The sulfur content in embodiment 1-8 and comparative example 1-4 overheads F3 is analyzed, as a result as shown in table 2.
Analysis of sulfur content result in table 2, overhead F3
It can be seen from the result of table 2 methyl tertiary butyl ether(MTBE) raw material can be significantly reduced compared to comparative example 1-4, the present invention
In sulfur content to below 10mg/kg, most low energy be reduced to 2mg/kg, meet environmentally friendly new rule and require what content of sulfur in gasoline need to reach
National V emission standard, and the addition of desulfurizing agent is considerably reduced, while the desulfurizing agent of the present invention is free of metallic element, is subsequently containing
Hydrogenation or catalytic cracking catalysis will not be caused in hydrotreating or the catalytic cracking processing of the high sulfur component of higher boiling of desulfurizing agent
The poisoning of agent.
Embodiment 9：Commercial Application
100,000 tons/year of MTBE process units of certain company, MTBE desulfurization is carried out to it.Desulfurizing agent forms：Indenes 10%, methyl
Indenes 20%, mixed methyl styrene 15%, mix ethyl styrene 4%, dihydronaphthalene 6%, naphthalene 5%, methyl naphthalene 5%, heavy aromatics
Solvent naphtha 35%.
Concrete technology is：Added before catalytic distillation tower feed exchanger relative to the desulfurization that product MTBE is 600mg/kg
Agent, MTBE products, desulfurizing agent and sulfide reaction, the complexing in methyl tertiary butyl ether(MTBE) raw material are extracted out from the bottom side line gas phase of tower
Return and recycle with part after extraction, technological process is as shown in Figure 1.
Analyze after testing, the MTBE products sulfur content for being not added with desulfurizing agent is 120mg/kg, after with the addition of desulfurizing agent
MTBE products sulfur content is 5mg/kg, illustrates that a small amount of desulfurizing agent of the invention is only added in catalytic distillation device can just show
The sulfur content in ground reduction methyl tertiary butyl ether(MTBE) is write to below 10mg/kg, meets state's V standards.
Embodiment 10：Commercial Application
120,000 tons/year of MTBE process units of certain company, there is desulfurization destilling tower, MTBE desulfurization is carried out to it.Desulfurizing agent group
Turn into：Methyl indenes 10%, mixed methyl styrene 40%, mix ethyl styrene 20%, octanol 10%, solvent naphtha 15%, first
Base naphthalene 5%.
Concrete technology is：After catalytic distillation tower add relative to product MTBE be 500mg/kg desulfurizing agent, with containing
Enter desulfurization destilling tower after sulfidomethyl tertbutyl ether is well mixed, MTBE products, technique stream are extracted out from the bottom side line gas phase of tower
Journey is as shown in Figure 4.
Analyze after testing, the MTBE products sulfur content for not carrying out desulfurization process is 120mg/kg, after with the addition of desulfurizing agent
MTBE products sulfur content is 2mg/kg, and illustrating to add a small amount of desulfurizing agent of the invention in desulfurization tower process being capable of strong methyl- tert
Sulfur content in butyl ether is reduced to 2mg/kg, meets state's V standards.
The specific embodiment of the present invention is described in detail above, but it is only used as example, and the present invention is not intended to limit
In particular embodiments described above.The MTBE desulfurizing agents of the present invention can also be after catalytic distillation tower feed exchanger and first
Enter catalytic distillation tower (as shown in Figure 2) after the mixing of base tertbutyl ether mixed material, or before catalytic reactor with methanol and
Enter catalytic reactor after mixing C4 is well mixed, subsequently into catalytic distillation tower (as shown in Figure 3).For people in the art
For member, any equivalent modifications carried out to the practicality and replacement are also all among scope of the invention.Therefore, this is not being departed from
The impartial conversion made under the spirit and scope of invention and modification, all should be contained within the scope of the invention.
Claims (8)
1. a kind of application of active component including styrene compound as methyl tertiary butyl ether(MTBE) desulfurizing agent, its feature exist
In the styrene compound is in styrene, methyl styrene, ethyl styrene, propylstyrene and butylstyrene
One or more.
2. application as claimed in claim 1, it is characterised in that the active component also includes indene compounds；The indene
Compound is the one or more in indenes, methyl indenes, ethyl indenes, propyl group indenes and butyl indenes.
3. application as claimed in claim 1, it is characterised in that the active component also includes benzofuran, dicyclopentadiene
And the one or more in cyclopentadiene.
4. application as claimed in claim 1, it is characterised in that the methyl tertiary butyl ether(MTBE) desulfurizing agent also includes one or more
Organic solvent, the organic solvent be fraction oil of petroleum of the boiling point between 100~500 DEG C, aromatic hydrocarbons, solvent naphtha, phenol, alcohol, ether,
One or more in ester and nonionic surfactant.
5. application as claimed in claim 4, it is characterised in that by percentage to the quality, the methyl tertiary butyl ether(MTBE) desulfurizing agent
Described in the content of active component be 2~100%, the content of the organic solvent is 0~98%.
6. such as application according to any one of claims 1 to 5, it is characterised in that comprise the technical steps that：
1) the methyl tertiary butyl ether(MTBE) desulfurizing agent is mixed at 5~150 DEG C with sulfur methyl tertiary butyl ether raw material, mixed
Material；
2) mixed material described in step 1) isolates the high sulfur component of higher boiling through destilling tower or desulfurization rectifying column, obtains ultralow
The methyl tertiary butyl ether(MTBE) of sulphur.
7. application as claimed in claim 6, it is characterised in that the addition of the methyl tertiary butyl ether(MTBE) desulfurizing agent is sulfur-bearing first
100~10000mg/kg of base tertbutyl ether material quality.
8. application as claimed in claim 6, it is characterised in that the methyl tertiary butyl ether(MTBE) desulfurizing agent and the sulfur-containing methyl tert-butyl group
Part, which returns, after sulfide reaction, complexing and extraction in ether raw material recycles.
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| CN101514137B (en) * | 2008-02-20 | 2012-11-14 | 中国石油化工股份有限公司 | Method for removing trace sulfur in styrene by catalytic rectification |
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| CN102557888B (en) * | 2011-12-23 | 2014-04-02 | 中国石油大学(北京) | Method for deeply desulfurizing methyl tertiary butyl ether |
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