CN105934421A - Process for the dimerization/oligomerization of mixed butenes over an ion-exchange resin catalyst - Google Patents
Process for the dimerization/oligomerization of mixed butenes over an ion-exchange resin catalyst Download PDFInfo
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- CN105934421A CN105934421A CN201480064816.9A CN201480064816A CN105934421A CN 105934421 A CN105934421 A CN 105934421A CN 201480064816 A CN201480064816 A CN 201480064816A CN 105934421 A CN105934421 A CN 105934421A
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- Prior art keywords
- alkene
- carbon atoms
- mixed
- dimerization
- reactor
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- 238000000034 method Methods 0.000 title claims abstract description 94
- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 238000006471 dimerization reaction Methods 0.000 title claims abstract description 46
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 title claims abstract description 40
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 37
- 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 title claims abstract description 30
- 239000003456 ion exchange resin Substances 0.000 title claims abstract description 27
- 229920003303 ion-exchange polymer Polymers 0.000 title claims abstract description 27
- 230000008569 process Effects 0.000 title abstract description 22
- 150000001336 alkenes Chemical class 0.000 claims abstract description 129
- 239000000446 fuel Substances 0.000 claims abstract description 21
- -1 C12 Chemical class 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 15
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 48
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 46
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 41
- 239000003502 gasoline Substances 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 150000002430 hydrocarbons Chemical class 0.000 claims description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims description 8
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000003380 propellant Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 4
- 239000003921 oil Substances 0.000 claims description 4
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002283 diesel fuel Substances 0.000 claims description 2
- 239000000295 fuel oil Substances 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims 1
- 239000001273 butane Substances 0.000 claims 1
- 150000001721 carbon Chemical group 0.000 claims 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 230000001737 promoting effect Effects 0.000 claims 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 26
- 230000035945 sensitivity Effects 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 34
- 239000002994 raw material Substances 0.000 description 27
- 235000019441 ethanol Nutrition 0.000 description 18
- 229960004756 ethanol Drugs 0.000 description 16
- 150000002500 ions Chemical class 0.000 description 15
- 239000011347 resin Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- 229910021536 Zeolite Inorganic materials 0.000 description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 239000010457 zeolite Substances 0.000 description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 230000008901 benefit Effects 0.000 description 8
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 6
- 238000004231 fluid catalytic cracking Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229910000480 nickel oxide Inorganic materials 0.000 description 6
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000003623 enhancer Substances 0.000 description 5
- 239000012744 reinforcing agent Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000539 dimer Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 230000008450 motivation Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003729 cation exchange resin Substances 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 150000004696 coordination complex Chemical class 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000012508 resin bead Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- DFVOXRAAHOJJBN-UHFFFAOYSA-N 6-methylhept-1-ene Chemical compound CC(C)CCCC=C DFVOXRAAHOJJBN-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000007171 acid catalysis Methods 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000001282 iso-butane Substances 0.000 description 2
- 235000013847 iso-butane Nutrition 0.000 description 2
- 239000003915 liquefied petroleum gas Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- RGYAVZGBAJFMIZ-UHFFFAOYSA-N 2,3-dimethylhex-2-ene Chemical compound CCCC(C)=C(C)C RGYAVZGBAJFMIZ-UHFFFAOYSA-N 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000628997 Flos Species 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 125000004067 aliphatic alkene group Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 125000000746 allylic group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000003442 catalytic alkylation reaction Methods 0.000 description 1
- 229920001429 chelating resin Polymers 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
- 239000002131 composite material Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Natural products CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000447 dimerizing effect Effects 0.000 description 1
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
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- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 231100000003 human carcinogen Toxicity 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
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- 238000012545 processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 150000003458 sulfonic acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000271 synthetic detergent Substances 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- FLTJDUOFAQWHDF-UHFFFAOYSA-N trimethyl pentane Natural products CCCCC(C)(C)C FLTJDUOFAQWHDF-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/26—Catalytic processes with hydrides or organic compounds
- C07C2/28—Catalytic processes with hydrides or organic compounds with ion-exchange resins
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
- C10G50/02—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation of hydrocarbon oils for lubricating purposes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/10—Use of additives to fuels or fires for particular purposes for improving the octane number
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- C07C2531/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- C07C2531/08—Ion-exchange resins
- C07C2531/10—Ion-exchange resins sulfonated
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1088—Olefins
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/06—Gasoil
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/08—Jet fuel
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/10—Lubricating oil
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2200/00—Components of fuel compositions
- C10L2200/04—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
- C10L2230/22—Function and purpose of a components of a fuel or the composition as a whole for improving fuel economy or fuel efficiency
Abstract
Processes for the effective dimerization and oligomerization of a mixed butenes feed using an ion exchange resin based catalyst are provided. The dimerization and oligomerization processes produce highly branched C8 and C8+ olefins (e.g., C12, C16 and C20 olefins) which could be used as superior fuel blending component for higher energy contents, higher octane value, higher octane sensitivity and lower RVP.
Description
Technical field
A kind of method that the present invention relates to dimerizing olefins/oligomerization, particularly relates to a kind of one-stage process, under gentle reaction condition,
Using ion-exchange resin catalyst, raw material dimerization/oligomerization metaplasia is produced highly-branched alkene, described raw material comprise butylene same point is different
Structure body (mixed butene), described product comprises alkene and the alkene more than 8 carbon atoms of 8 carbon atoms.
Background technology
Gasoline is still the main energy sources source of internal combustion engine, and internal combustion engine often comes conveying people and goods for providing power for motor.Evaluate
The index of gasoline performance is octane number.Modal octane number measuring method is research octane number (RON) (RON), and motor method is pungent
Alkane value (MON) and the mean value of anti-knock index (AKI) RON and MON.Antiknock gasoline can be used for multi-stage compression, higher
The engine of performance.Therefore, the motivation of research staff is that exploitation new method is to improve the octane number of gasoline.
Additionally, the fuel legislation of increasingly stringent more strengthens this motivation in the world.Fuel quality is kept to become challenge, simultaneously
Reduce its noxious emission.A kind of legislation demands in gasoline reduces being harmful to as material of discharge at present is aromatic hydrocarbons (e.g., benzene discharge).
Making laws according to limiting emission, the arene content in gasoline now must be reduced to 35% volume (U.S. is even as low as 25% volume).Virtue
Hydrocarbon compound has maximum contribution to RON, and therefore, legislation forces to reduce gasoline arene content will cause the notable of gasoline quality
Reduce, i.e. RON is not enough.Additionally, fuel providers is also it must be recognized that the Lei Shi vapour pressure (RVP) of fuel, a kind of being used for is weighed
The method of fuel vaporization speed.The RVP of fuel is the highest, and its evaporation rate is the fastest, and therewith, depletion of the ozone layer is the fastest.Combustion
Material RVP typically should be less than 14.7psi, and this is normal atmospheric pressure.RVP is the fuel measurement mode of particular importance,
Especially in summer, Environmental Protection Agency strictly supervises the gasoline RVP of retail shop.In summer, gasoline RVP does not surpasses
Cross 9.0psi.Owing to aromatic hydrocarbons has relatively low RVP, the reduction of the arene content in gasoline also results in the increasing of its RVP
Add.Therefore, present motivation is to find new method to retain the high-octane rating of gasoline, meets the framework of new Abgasgesetz simultaneously
With the low RVP of maintenance.
Decades ago, lead is used as gasoline additive to increase its octane number.But because of the ambient influnence that it is harmful, in most of states
Family, lead removes from gasoline concoction thing.Left and right in the past twenty years, in the case of without lead, a certain degree is
The raising of response octane number, the U.S. and the gasoline concoction sold the elsewhere methyl-tert butyl oxide (MTBE) of 15%,
MTBE is a kind of oxide, in order to reduces environmentally hazardous substance discharge, rises high-octane rating simultaneously.
Although MTBE has low RVP, but MTBE itself has been classified as pollutant and potential human carcinogen.Even worse
It is that many gasoline tanks leak, and due to highly-water-soluble and the low biological degradability of MTBE, MTBE has polluted
The underground water in a lot of regions.Therefore, in recent years in the gasoline that the U.S. sells, the use of MTBE is almost forbidden.
At present, plan is wheat or the grain ethanol of sugarcane fermentation for substitute MTBE.U.S. Patent number 4398920 (A)
Describe by the mediation fuel including ethanol, acetone and methyl alcohol fermented.In gasoline concoction thing, the use of ethanol has following several
The advantage of individual aspect, including toxicology known to high blending RON value and industrial quarters.But, the production of ethanol is expensive, and
And if only if during tax reduction, be only Economic Sustainability.Additionally, to meet the demand of transport service, produce sufficient amount of grain alcohol
Cereal as food can be had a negative impact.For further, compared with gasoline, ethanol has relatively low energy
Content.Ethanol contains the energy of about 76000BTU/ gallon, and gasoline contains the energy of about 13000BTU/ gallon.Ethanol is the most right
Water has high-affinity, can not directly mix with gasoline at oil plant ethanol, its only quilt before the final output of gasoline flow network
Add.Furthermore, ethanol is easily and gasoline component forms low-boiling azeotrope, and which results in pressure limit is 17～22psi,
Blending concentration range is Lei Shi vapour pressure higher under 10-15%.But, especially in summer months, vapor pressure is one and asks
Topic.Additionally, the ethanol of excessive concentrations (the ethanol volume of about 10%) is as causing NOxThe increase of discharge capacity.
Owing to alkylates has higher RON value, low RVP and the positive impact on discharge, alkylates is (as different pungent
Alkane and trimethylpentane) also it is the most desirable MTBE substitute.Alkylation is an oil refining process, and it refers to that catalytic alkylation is anti-
Should generate highly-branched alkane, this reaction refers in the presence of sulfuric acid and hydrofluoric acid, iso-butane and light olefin (propylene and butylene)
Reaction.From the perspective of environmental protection, sulfuric acid and hydrofluoric acid are strong acid.Due to its severe corrosive, substantial amounts of sulfuric acid and hydrofluoric acid exist
Routine operation, all there is excessive risk in process and the recovery course of conveying of accessory substance.The production of alkylates is not environment-protective process.This
Outward, compared with aforementioned octane number, alkylates has a motor octane number (MON), therefore its to have relatively low octane number sensitive
Degree.Based on the present and following high efficiency requirement, use that has determined octane number to have material highly sensitive to octane number as combustion
Material, spark ignition engine will have more preferable anti-knock properties and higher efficiency of combustion.
Generally speaking, it is contemplated that cost and environmental problem, and need to keep higher RON value and relatively low RVP, its
The production method of his octane enhancers is necessary.
A kind of method producing octane enhancers is dimerization or the oligomerization generation high-octane rating hydrocarbon component of butylene, from mixing
Contained by the main compound that the dimerization of butylene or oligomerization produce is C8 and C12 alkene.In this C8 alkene, two isoolefines
Hydrocarbon (DIBs) is optimum.DIBs is a kind of non-oxide propellant composition, and this component has the advantage that and MTBE and alkane
Base compound is compared, and it has higher octane number, preferable anti-knock properties and higher energy content, compared with MTBE and ethanol,
It has relatively low Lei Shi vapour pressure.Also need to be mentioned that the highly-branched octene that the dimerization of butylene or oligomerization generate tends to have as follows
Advantage: the amount of same volume is being added to low octane value gasoline by (a), and it has much the same with MTBE pungent
Alkane value lifting capacity；B (), compared with MTBE and alkylates, it has higher octane number sensitivity, therefore now and
In following spark type ignition engine, it has preferable anti-knock properties and higher efficiency of combustion；(c) with MTBE phase
Ratio, its have higher can value and relatively low RVP.
Light aliphatic alkene dimerization reaction mechanism has a following two: acid-catalytic ionic mechanism and vanadium-catalytic ligand mechanism.Acid catalysis
Technique produces highly-branched alkene and metal complex catalyzed technique produces long linear alkene.Metal complex catalyzed technique generally uses
Nickel, cobalt and Ziegler-type catalyst etc..This technique typically uses butylene as raw material, generates long linear alkene, or is mainly
The head-tail of olefinic double bonds and head-head dimerization and oligomerization, metal complex catalyzed technique is widely studied；Therefore, this work
Skill is not subject of the present invention.
On the contrary, acid catalysis technique produces highly-branched alkene.The dimerization reaction of isobutene typically uses acid catalyst, including sulfonic acid
Derivative, zeolite and ion exchange resin.Sulfuric acid and hydrofluoric acid are commonly used for the dimerization reaction of catalyzing iso-butane alkene, but as above-mentioned,
This type of catalyst often has severe corrosive.
Nickel oxide catalyst is also used for the oligomerisation reaction technique of butylene.But, although its C8 alkene that can obtain 85% selects
Property, due to the formation of coke, this type of catalyst is just quickly eliminated.These loading type nickel-based catalysts also tend to for producing relatively
The dimer of few side chain or oligomer.
It is reported, be used for dimerization or the oligomerization of alkene at the 1970's zeolite based catalysts.Such as, DE2347235 A1
Report under 170 DEG C/40atm, use 5% ni-loaded catalyst, the reaction of 1-butene dimerization generate linear octenes, this reaction
Conversion ratio be 40.5%, selectivity is 81.8%.But, even if at 150 DEG C, the dimerization that the formation of coke also result in butylene is anti-
The low reaction activity answered and rapid deactivation.A small amount of hard coke be enough to the acid site stoping reactant to enter in zeolite.Use zeolite
Base catalyst, typically can crack.
Compared with inorganic acid catalyst, ion-exchange resin catalyst (ion) reduces the negative environmental consequences of acid waste water.This
Outward, ion-exchange resin catalyst has minimum corrosivity, and is easier to separate from product.Up to the present, amberlite
Fat catalyst is only applied to selective dimerization of isobutene reaction method and produces two isoalkene and isooctene, and this product is the pungent of practicality
Alkane value reinforcing agent.In other words, raw material is only limitted to isobutene (one of isomer of butylene), and this causes being substantially entirely formed two
Isoalkene.Other catalyst, such as nickel oxide and nickeliferous or the most nickeliferous zeolite based catalysts, exchange with than the ion of the present invention
Resin catalyst is compared, and has an inferior position of following several respects: activity, selectively with for mixing urging of light olefin dimerization
The agent life-span.
Therefore, it is necessary to efficiently production hydrocarbon is as RON reinforcing agent, this hydrocarbon and at present used MTBE,
Ethanol or alkylates have more advantage.Further, since ion-exchange resin catalyst has minimum corrosivity and is prone to
Separate from subsequent reactions product, therefore ion-exchange resin catalyst is necessary to for the method.Finally, due to other
The high production cost of octane enhancers such as ethanol, the motivation seeking to produce the inexpensive method of octane enhancers strengthens day by day.
Summary of the invention
The present invention be directed to prior art and provide a kind of method producing antiknock gasoline composition, to overcome other propellant compositions such as
The shortcoming of MTBE, ethanol and alkylates.Specifically, embodiments of the invention refer to a kind of method, and the method refers to adopt
C8 and C8+ alkene is produced with mixed olefins (butylene) raw material generation dimerization and oligomerization.The method process is as follows: in gentleness
Under the conditions of, the mixed olefins liquid feedstock at least containing two kinds of butylene isomers is introduced and is mounted with acid-exchange resin
The reactor of catalyst.
In one embodiment, mixed butene charging includes the isomer of all four butylene.In another embodiment, described
Mixed butene charging includes the isomer of at least two butylene, it is preferred that can comprise other C2-C5 alkene, as ethene,
Propylene and amylene.
In the reactor, mixed butene charging contacts with ion-exchange resin catalyst, and mixed butene is converted into higher olefins.
Under gentle reaction condition, the use of ion-exchange resin catalyst can prevent product cracking and catalysqt deactivation, and this is for adopting
With nickel oxide and zeolite based catalysts other industry oligomerization process for be an obvious advantage.
Additionally, under mild conditions, in butene dimerization and oligomerization, compared with using nickel oxide and zeolite based catalysts,
Use ion-exchange resin catalyst can generate more highly-branched C8 and C8+ olefin product particularly highly-branched octene,
It is very important RON reinforcing agent.In one embodiment, ion-exchange resin catalyst is a kind of sulfonic acid with hydrogen as form
Cation-exchanger.In another embodiment, a kind of polar compound such as butanol or water can be only added to catalyst with promotion
Learn reaction.
In one embodiment, the temperature of reactor maintains 30 160 DEG C, and pressure maintains 20 100bar, and liquid space-time
Speed (LHSV) maintains about 0.33hr-1。
Accompanying drawing explanation
Reference as detailed below and combines accompanying drawing, and complete disclosure and the advantage thereof of the present invention will be more readily understood, it is notable that attached
Figure only describes one embodiment of the present of invention, is therefore not limited to this scope.
Fig. 1 represents the fixed-bed process flow chart of the embodiment of the present invention.
Detailed description of the invention
As it has been described above, prior art includes a series of isobutene dimerization/oligomerization reaction method；But the method includes corresponding shortcoming,
Such as a kind of alkene (such as C8 alkene) is had high selectivity, and now there are other higher olefins minimal amount of.Particularly,
Prior art refers to the dimerization/oligomerizationization reaction of a kind of butylene isomer (such as isobutene).Additionally, some in this type of method
Method and technology is complicated, and needs multiple step to process feed stream.
Instant invention overcomes the deficiencies in the prior art and limitation, the present invention refers to a kind of method, and it is urged based on ion exchange resin
Agent, mixed olefins (particularly mixed butene) dimerization and oligomerization produce highly-branched C8 and C8+ alkene.More specifically
Saying, the present invention is a kind of single-stage (one way) method, and the method is carried out under mild conditions, has following high-conversion rate.For
Selective dimerisation/the oligomerization of isobutene in mixed olefins mixture, typical range of reaction temperature is 30-100 DEG C.For
The dimerization/oligomerization reaction of mixed butene, typical range of reaction temperature is 80 DEG C～180 DEG C.
Mixed olefins (butylene)
Mixed butene has four kinds of isomers, 1-butylene, the trans-butylene of 1-, the cis-butylene of 2-and isobutene.Or, other low-carbon (LC)s
Alkene, such as propylene and ethene, it is possible to as following charging.Additionally, " higher olefins " word refers to the work that this method part is formed
For the alkene of product, it has more carbon number than the alkene in the initial feed introduced in reactor.
Two isoalkene (DIBs) or isooctene
Two isoalkene include two kinds of isomers, 2,4,4-triethyl group-1-amylenes and 2,4,4-triethyl group-2-amylenes.
Oligomerization
The oligomerization of mixed butene includes the oligomerization of all butylene isomers, including the oligomerization (dimerization of isobutene
Change), also include the butylene isomer of other forms.
The dimerization of isobutene
Ion exchange resin
Ion exchange resin (ion) is typically the least plastic bead, and therefore, resin is the structure of a kind of polymer, at this
The ion being permanently fixed is connected in structure.In order to keep the electroneutral of resin, each fixed ion is neutralized by counter ion.This is anti-
Ion is mobile, can enter and leave resin bead.The ion of each entrance resin bead is taken by each ion leaving resin bead
In generation, then keep electroneutral.This is i.e. referred to as ion exchange.Only equivalent ionic just can be exchanged.Therefore resin contains sun
Ion exchange resin and two kinds of forms of resin anion (R.A.).In order to obtain the exchange of effective ion, between resin ion and the ion that need to remove
Must there is different affinity.Compared with the ion in resin, resin must be to the more compatibility of the ion in solution.
According to the present invention, ion exchange resin is broadly defined as an insoluble matrix ion comprising instability, this ion energy
Swap with surrounding medium and the not great physical change in recurring structure.The use of the suitable resin of the present invention includes but does not limits
Exchange in the Sulfonic acid cation with hydrogen as form.But need to know that if other ion exchange resin have similar function, it is possible to use
And it is applicable to aforesaid dimerization/oligomerization method.
C8 alkene
C8 alkene mixture of the present invention is mixed octene, i.e. the dimer of mixed butene.Octene has 72 kinds and divides together different
Structure body, wherein only some contains high-octane rating.There are the alkene of 2 types, i.e. side chain and line style (straight chain).Highly-branched
Alkene is highly important octane number reinforcing agent, and therefore the production of this type of octene is desirable.Some C8 alkene are high
Change, such as dimethyhexenes and trimethylpentene.C8 alkene may also be the straight chain that the present invention is not directed to, or less side chain.Also
Understanding, the method also can generate circulation product.
C8+ alkene
C8+ alkene represent containing carbon number be 12 or more than 12 mixed butene dimer, the method also can generate circulation produce
Product.
Dimerization/oligomerization reaction method
As described herein, embodiments of the invention provide a kind of high efficiency method, the method by mixed olefins produce highly-branched C8 and
C8+ alkene, particularly generates highly-branched alkene.Additionally, embodiments provide the method producing fuel composition, institute
State the oligomer that composite fuel includes being generated by mixed butene and/or other alkene.
Such as, in one embodiment of this invention, mixed olefin feedstock contacts with catalyst under the appropriate reaction conditions, preferably
Part one-stage process (one way) produces the product stream comprising oligomer.In one embodiment of this invention, unreacted alkene
Can be recycled and produce the product stream of so-called oligomer.In particular, mixed butenes feedstock is under the appropriate reaction conditions
Contact production with catalyst and comprise highly-branched C8 and the product of C8+ alkene, such as two isoalkene.Product can mix raw with propellant composition
Produce fuel composition.According to spirit of the invention, the propellant composition of fuel composition has chosen below: gasoline, diesel oil, jet
Fuel, aviation gasoline, fuel oil, bunker oil, or combinations thereof, or other suitable propellant compositions.Specific at some
Embodiment, including preferred embodiment, the fuel composition of synthesis contains the octane number of rising and the Lei Shi vapour pressure of reduction, does not contains
Other chemical substances that environment is had undesirable effect.
The source of mixed olefins logistics can be different, and it can comprise separate sources former of any kind being applicable to the present invention
Material (feed stream).As, in some embodiments of the invention, mixed olefins logistics can be FCC apparatus or thermal cracking unit
The Liquid Residue that discharging, MTBE process, the Liquid Residue that TBA processes, liquefied petroleum gas (LPG) or combinations thereof.Enter one
Step understands that other sources understanding mixed olefins are attributed to the scope of the present invention.
According to disclosed embodiment, mixed olefins logistics includes the butene stream of mixing.In another embodiment, mixed olefins stream can
C3～C5 olefin feed stream for mixing.In other examples, mixed olefins stream can include polypropylene, n-butene, 2-
Butylene, isobutene, amylene, hexene, containing one or more in the alkene etc. more than 6 carbon atoms.For art
Technical staff, other suitably source and alkene kinds of mixed olefins stream are very apparent also in the limit of consideration of the present invention.
According to a preferred embodiment of the invention, the present invention use mixed butene charging (logistics/raw material) be one be at least to contain
The liquid of two kinds of mixtures, preferably 1-butylene, isobutene, the cis-butylene of 2-and the trans-butylene of 2-.These relative worths are relatively low
Mixed butenes feedstock is directly from refinery tail-gas.
Different butylene isomers has different activity in dimerization and oligomerization.Such as, isobutene is prone to by dimerization
Or oligomerization.Generate corresponding dimer conversely, for the cis-butylene of 2-butylene, especially 2-or oligomer is extremely difficult.
Therefore major part conventional method focus on the isomer selecting a kind of butylene there is dimerization, in this type specially
Adjusting process makes the isomer dimerization of a certain butylene.The limitation of this technique causes product stream mainly by a kind of alkene
Hydrocarbon types forms.It has been observed that generate, do not contain only two isoalkene also to comprise the product of other highly-branched higher olefins be preferable.
According to the present invention, this technique allows the isomer of all four butylene to realize effectively under relatively mild reaction conditions
Dimerization or oligomerization, this technique has the high selectivity of high conversion per pass and C8 alkene (with C12 alkene and a small amount of
The generation of C12+ alkene).
In one embodiment, the mixed butene being made up of the isomer of all four butylene of varying number will set forth herein
Case look back.But as the most above-mentioned, according to another embodiment of the present invention in, charging can include that at least two butylene is with point different
Structure body, and other C3-C5 alkene, such as ethene and propylene.
According to the present invention, Fig. 1 illustrates a kind of typical mixed butene dimerization and the system 100 of oligomerization.Fig. 1 is the most also
Represent a kind of typical technological process.Fig. 1 shows that the present invention uses fixed-bed process.This system 100 includes fixed bed reactors
The reactor 110 of form.The catalyst of the present invention is loaded into a certain region or region 112, and this region is positioned at the reactor of diagram
In 110.In an illustrated embodiment, this catalyst is positioned at the center of reactor 110.Reactor 110 be placed on as
In hot tank 120 shown in figure.
Reactant is delivered to reactor 110 in the following manner.The source (e.g., mixed butene feeds) of raw material is defined as flowing stock 130,
Source 130 for fluidly connect (e.g., by the way of mozzle 131 (such as pipeline)) to a storage container 140 so that
Raw material stores at storage container 140.As above-mentioned, raw material is typically liquid stream stock.
One valve is set in the duct or volume control device 145 controls to storage container 140 and the raw material of reactor 110
Flow.Further it is provided that raw material (mixed butene) is sent into reactor 110 with required flow rate by mode 150.Mode 150 is passed through
Pipeline 141 is connected with the container 140 stored, and is configured to effectively by required flow rate, raw material is delivered to reactor 110.
In one embodiment, liquid charging stock is pressed required speed (flow velocity) with the form of a kind of source of the gas (such as nitrogen) by which 150
Press-in raw material reaction device 110.Source of the gas 150 is connected to store container 140 by pipeline (such as, pipe), and this pipeline arranges one
Individual valve or be similar to the device of 155 and control to store the flow of the gas of container 140.
Valve 145 is positioned over a certain position, cuts off the fluid from source 130 to storage container 140 and flows；But, in storage
Deposit the gaseous mixture in container 140 (from source 150) and storage raw material allows to flow to reactor 110 by valve 145.Pipeline
151 entrances that can be located at valve 145 to 110.In pipeline 151, valve 153 is set to control reactor 110 entrance
Feed rate.
Before the entrance entering reactor 110, raw material is through heat-exchanger rig 160, and this heat-exchange device is positioned at valve 145 with anti-
Answer between device 110.Entering reactor 110 prior to raw material, to predetermined temperature (e.g., heat-exchanger rig 160 for adjusting the temperature of raw material
Specific temperature of reactor).By reactor 110 with after contacting with the catalyst in region 112, define and above-mentioned beg for
The olefin product of opinion, this product is delivered to pipeline 171 by the outlet of reactor 110 and introduces separator 170.Such as this paper institute
Stating, reactor 110 is single-stage reactor, passes at this reactor Central Plains stream single and contacts with catalyst to form product stream.
Conversion ratio can be described as one way conversion ratio.
The form of separator 170 is a kind of liquid/gas separator, and in this separator, high boiling olefin product is cooled and is collected
Flowing through pipeline 173 before becoming fluid sample, this fluid sample typically represents with 180.Unreacted raw material is from separator 170
Send to process further and/or reclaim by different outlets.Such as, unreacted raw material (such as, unreacted butylene)
Can be analyzed by on-line gas chromatography 190 by pipeline 175, or be emitted into floss hole 179 simply by pipeline/line 177.
As it can be seen, one or more valve can be arranged on pipeline 177.
Understand product (fluid sample 180) and can be further processed and/or be delivered to other devices.
As it has been described above, according to an embodiment, fixed bed reactors 110 at least have a region 112 loading solid ion exchange,
This catalyst is suitable to this specific invention.A kind of typical Solid-state Ion-exchange catalyst is solid Bronsted acid catalyst.Therefore,
Solid-state Ion-exchange catalyst is the type being applicable to the present invention, it is possible to react formation for being applicable to the dimerization/oligomerization of mixed olefins
The type of required highly-branched alkene (C8 and C8+ alkene).
Under the reaction condition of gentleness as herein described, this kind of catalyst will prevent product cracking, make catalyst be difficult to inactivate, institute
Problem of stating is frequently encountered by using the industrial oligomerization technique of nickel oxide and zeolite based catalysts.Additionally, with nickel oxide and
Zeolite based catalysts is compared, and under relatively mild reaction condition, ion-exchange resin catalyst can produce more highly-branched C8
With C8+ alkene.
In certain embodiments, the catalyst resin used is the sulfonic acid cation exchange resin with hydrogen as form.A kind of typical case
Strong-acid cation-exchange resin see following open case.A kind of polar compound can be added to the catalyst in reactor
On promote oligomeric/dimerization reaction.In one embodiment, accelerator raw material can be a kind of alcohol, such as butanol.In another embodiment,
Accelerator raw material can be made up of water.
The reaction of the present invention is there is under gentle reaction temperature.For the selective dimerisation of isobutene in mixed olefins/oligomeric instead
Should, its range of reaction temperature is 30 100 DEG C.Dimerization/oligomerization for mixed butene is reacted, and instead its range of reaction temperature is 80-
180℃.More specifically, in the reactor 110, under gentle reaction condition, with the production process phase using alkylates
Ratio, the reaction using ion-exchange resin catalyst to be non-corrosiveness and environmental protection.Such as, in one embodiment, reaction temperature is adjusted
To 30 DEG C of temperature to realize the high selectivity of isobutene dimerization.
Described system and technique are a kind of continuous production processes, and wherein feed stream delivers to reactor continuously.
The product of the present invention is with the form of a certain logistics, and this logistics mainly includes C8 alkene and C12 alkene and a small amount of C16
Alkene, C16+ alkene and cyclic compound.In the C8 alkene produced, preferably DIB, DIB is as octane number as previously mentioned
Reinforcing agent aspect has great superiority.
Reaction in the present invention is to C8, including DIB, i.e. and C12 alkene, there is higher selectivity.In the present embodiment, no
As being produced the technique of DIB, the mixed butene that value of the present invention is relatively low before this by the selective dimerisation of isobutene
Raw material produces DIB and other valuable, C8 and C8+ alkene of highly-branched.In other words, use aforesaid operating condition
And processing step, the mixed butene being used in this technique the most specifically realizes isobutene (e.g., raw material is not only containing isobutene) two
Poly-effect high selectivity, more precisely, mixed butenes feedstock not only produces DIB, also produce other desirable alkene (as
Highly-branched alkene).
The product of the present invention, i.e. has high-octane highly-branched C8 and C8+ alkene, is extremely valuable at fuel industry.
Under the gasoline management and control of foregoing increasingly stringent, highly-branched C8 and C8+ alkene can strengthen by non-oxide octane number as an alternative
Agent meets above-mentioned restriction.Specifically, highly-branched C8 and C8+ alkene can increase the octane number of fuel and reduce the Lei Shi of fuel
Vapour pressure, and do not produce the negative environmental consequences produced by MTBE and aromatic hydrocarbons.Therefore the technique of the present invention reached produce as follows
The purpose of product, this product not only includes highly-branched C8 alkene, also includes the highly-branched alkene producing other carbon numbers more than 8
Hydrocarbon.
C8 and the C8+ alkene produced by the present invention also can be as valuable raw material.Specifically, C8 and C8+ alkene produces
Product can be used for the quality raw materials of fluid catalytic cracking (FCC) technique, such as technique DCC (DCC) and high level
Fluid catalytic cracking (HSFCC), produce high technology require low-carbon alkene, such as ethene, propylene etc..A kind of containing big
The dimer of amount allylic hydrogen is the most active with the mixture of tripolymer, has proved to be the optimal charging of FCC technique, FCC
Technique is process based on HSFCC and DCC.Described C8 and C8+ product also can as the intermediate of following product,
Described product includes: synthetic detergent, plasticizer, agricultural chemicals, lubricating oil, additive, spices, medicine and other fine chemistry industry
Raw material.
Embodiment
Embodiments of the invention preferably can be illustrated by following example.But need to know that following example is only used as describing, not limit
In the present invention.
Testing as follows in pilot plant, this experiment has structure and the characteristic of system 100 in FIG.In example 13,
Feed stream is mixed butene (mixed olefins), and more clearly, the composition of mixed butene is: 1 butylene 21%；Isobutene 35%；
The trans-butylene of 2-19%；The cis-butylene of 2-25%.
Mixed butene can obtain from the different industrial source of any kind, and the mixed butene in current experiment comes from
Abdullah Hashim gas companies, and do not purify.Catalyst is a kind of ion exchange resin, more precisely, catalyst
Being a kind of business-like ion exchange resin, Products Trade number is 0008-3, from Kairui Chemical Co., Ltd..This typical case
Resin is a kind of macroporous strong-acid cation-exchange resin, and it is made up of opaque pearl, and is the sulfonic acid sun with hydrogen as form
Ion-exchanger.
In this is tested, the catalyst having 30 milliliters is loaded the region 112 in reactor 110, liquid air speed per hour (LHSV)
Close to 0.33hr-1, reaction condition is listed in table 1.
In example 1, the operation pressure of reactor is about 20bar, and operation temperature is about 150 DEG C.Mixed butene feeds by whole fourths
The isomer composition of alkene, each constituent content is as follows: the cis-butylene of 2-(25%), 1-butylene (21%), isobutene (35%), 2-
Trans-butylene (19%).Except as otherwise noted, referred herein to all percentages be mass percent.The result of example 1 is listed in table 1.
Table 1-example 1
In example 2, the operation pressure of reactor is about 20bar, and operation temperature is about 160 DEG C.Mixed butene feeds by whole fourths
The isomer composition of alkene, each constituent content is as follows: the cis-butylene of 2-(25%), 1-butylene (21%), isobutene (35%), 2-
Trans-butylene (19%).Test period is about 1020mins.The result of example 2 is listed in table 2.
Table 2-example 2
In example 3, the operation pressure of reactor is about 20bar, and operation temperature is about 150 DEG C.Mixed butene feeds by whole fourths
The isomer composition of alkene, each constituent content is as follows: the cis-butylene of 2-(25%), 1-butylene (21%), isobutene (35%), 2-
Trans-butylene (19%).The charging of a kind of water accelerator is increased injecting reactor with the speed of 0.01g/min.Test period is about
480mins.The result of example 3 is listed in table 3.
Table 3-example 3
The average conversion per pass of the mixed butene of the present invention is 84.5% (example 3), and the now selectivity of C8～C12 alkene is
94% (example 1).The conversion per pass of the present invention is anti-apparently higher than the pure isobutene dimerization reported in document and 1-butene dimerization
Should.Conversion ratio as herein described is the most conservative.According to gas-chromatography (GC), reactor is imported and exported the analysis of butylene, spy
Determining in embodiment 3, the conversion per pass of butylene is higher than 90%.
Therefore, it is known that the present invention describes a kind of single stage process (one way conversion), and this technique is mixed butene generation dimerization/oligomerization
(not being the selective technique of a kind of a kind of olefin product of main production, be not a kind of alcohol that produces, the adjoint alkene that produces is made in reaction
Hydration step for portioned product stream).As described herein, the technique of the present invention and system refer to make spent ion exchange resin for urging
Agent, the dimerization of four kinds of propylene isomer (including n-butene, cis-2-alkene, isobutene and trans-2-alkene) participations jointly/low
Poly-reaction, described technique and system realize in single-stage reactor.
With traditional dimerization/oligomerization metallization processes, the technique that the present invention relates to and system, there is many advantages.These advantages include but not
It is limited to: (1) provides a kind of new non-oxide octane enhancers, i.e. highly-branched C8 and C8+ alkene, to meet day by day
Strict regulation and the requirement of minimizing Aromatic Hydrocarbon in Gasoline；(2) relatively low mixed butene is stablized；(3) by circulation profit
The butylene of low value, increase valuable low-carbon alkene ethene and the yield of propylene, low-carbon alkene is the high-quality of cracking reaction
Raw material (C8～C16 alkene)
Although the present invention is illustrated by specific embodiment, for those skilled in the art, it is clear that also have many changes
And amendment.Therefore, described embodiment is only used as explanation in all respects, is not limited to this.Therefore the scope of the present invention is by institute
Attached claim explanation rather than preceding description.Certain meaning and scope are equal to claim changed all by
It is included in.
Claims (16)
1. the dimerization/oligomerization mixed olefin feedstock containing mixed olefins is with a method for preparation mixing higher olefins, and described method includes as follows
Step:
Under oligomerization conditions, mixed olefin feedstock is introduced in reactor；
In reactor, mixed olefin feedstock contacts with ion-exchange resin catalyst and mixed olefins changes into mixing higher olefins；With
The product stream produced includes coming the mixing higher olefins of autoreactor；
Wherein, described hydrocarbon material at least includes the alkene that two distinct types of carbon number is 2～5, described mixing high-carbon
Alkene includes: (1) alkene containing 8 carbon atoms, (2) are containing the alkene having more than 8 carbon atoms.
Method the most according to claim 1, wherein said mixed olefin feedstock at least includes the isomer of two kinds of butylene.
Method the most according to claim 2, wherein said mixed olefin feedstock includes the isomer of all 4 kinds of butane.
Method the most according to claim 1, wherein said ion-exchange resin catalyst includes that the Sulfonic acid cation of a Hydrogen is handed over
Change agent.
Method the most according to claim 1, wherein said mixing higher olefins includes containing 8 carbon atoms with former more than 8 carbon
The alkene of son.
Method the most according to claim 5, wherein said mixing higher olefins includes two isoalkene (DIB).
Method the most according to claim 5, wherein said mixing higher olefins include at least 50wt% containing 8 carbon atoms
The alkene containing 12 carbon atoms of alkene and at least 20wt%.
Method the most according to claim 5, the wherein said alkene containing 12 or more carbon number includes: (a) contains 12
The alkene of individual carbon atom, (b) alkene containing 16 carbon atoms；(c) alkene containing 20 carbon atoms.
Method the most according to claim 5, the alkene containing 8 carbon atoms of the portioned product wherein generated as reaction includes
Highly-branched alkene containing diethyl and triethyl group amylene.
Method the most according to claim 1, the operating temperature range of wherein said reactor maintains 30-80 DEG C.
11. methods according to claim 1, wherein further comprise the steps of: and are drawn by a kind of catalyst promoting agent containing polar compound
Enter reactor.
12. methods according to claim 11, wherein said accelerator is at least the one in water and butanol.
13. 1 kinds use the method that butene dimerization/oligomerization system produces fuel composition, said method comprising the steps of:
Under the conditions of dimerization, the mixed butene stream comprising mixed butene being introduced reactor, described reactor belongs to dimerization/oligomerization
A part for system.
In the reactor, mixed butene stream contacts with ion-exchange resin catalyst, mixed butene is changed into one and comprises mixed olefins
Product stream, described product stream includes the highly-branched alkene containing 8 carbon atoms and containing having more than the alkene of 8 carbon atoms；With
Described product stream is combined with propellant composition the described fuel composition of production；
Wherein said mixed butene includes n-butene, cis-2-butene, isobutene and trans-2 butylene；With
Wherein said propellant composition includes gasoline, diesel oil, jet fuel, aviation gasoline, fuel oil, bunker oil, or combinations thereof.
14. methods according to claim 13, wherein said mixing higher olefins includes that the alkene containing 8 carbon atoms such as two is different
Alkene (DIB), and containing having more than the alkene of 8 carbon atoms.
15. methods according to claim 14, wherein said mixed olefins includes the alkene containing 8 carbon atoms of at least 50wt%
Hydrocarbon and at least 20wt% contain the alkene having more than 8 carbon atoms.
16. methods according to claim 14, wherein said include containing the alkene having more than 8 carbon atoms: (a) contains 12 carbon
The alkene of atom, (b) alkene containing 16 carbon atoms；(c) alkene containing 20 carbon atoms.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US14/092,601 | 2013-11-27 | ||
| US14/092,601 US20150148572A1 (en) | 2013-11-27 | 2013-11-27 | Process for the Dimerization/Oligomerization of Mixed Butenes Over an Ion-Exchange Resin Catalyst |
| PCT/US2014/066736 WO2015080951A1 (en) | 2013-11-27 | 2014-11-21 | Process for the dimerization/oligomerization of mixed butenes over an ion-exchange resin catalyst |
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| CN105934421A true CN105934421A (en) | 2016-09-07 |
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| CN201480064816.9A Pending CN105934421A (en) | 2013-11-27 | 2014-11-21 | Process for the dimerization/oligomerization of mixed butenes over an ion-exchange resin catalyst |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20150148572A1 (en) |
| EP (1) | EP3074370A1 (en) |
| JP (1) | JP2017501131A (en) |
| KR (1) | KR20160108320A (en) |
| CN (1) | CN105934421A (en) |
| WO (1) | WO2015080951A1 (en) |
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| US10472580B2 (en) | 2016-11-21 | 2019-11-12 | Saudi Arabian Oil Company | Process and system for conversion of crude oil to petrochemicals and fuel products integrating steam cracking and conversion of naphtha into chemical rich reformate |
| EP3541894B1 (en) | 2016-11-21 | 2024-01-10 | Saudi Arabian Oil Company | Process for conversion of crude oil to petrochemicals and fuel products integrating steam cracking, fluid catalytic cracking, and conversion of naphtha into chemical rich reformate |
| US20180142167A1 (en) | 2016-11-21 | 2018-05-24 | Saudi Arabian Oil Company | Process and system for conversion of crude oil to chemicals and fuel products integrating steam cracking and fluid catalytic cracking |
| US10619112B2 (en) | 2016-11-21 | 2020-04-14 | Saudi Arabian Oil Company | Process and system for conversion of crude oil to petrochemicals and fuel products integrating vacuum gas oil hydrotreating and steam cracking |
| US10487275B2 (en) | 2016-11-21 | 2019-11-26 | Saudi Arabian Oil Company | Process and system for conversion of crude oil to petrochemicals and fuel products integrating vacuum residue conditioning and base oil production |
| US10487276B2 (en) | 2016-11-21 | 2019-11-26 | Saudi Arabian Oil Company | Process and system for conversion of crude oil to petrochemicals and fuel products integrating vacuum residue hydroprocessing |
| US10407630B2 (en) | 2016-11-21 | 2019-09-10 | Saudi Arabian Oil Company | Process and system for conversion of crude oil to petrochemicals and fuel products integrating solvent deasphalting of vacuum residue |
| US10472579B2 (en) | 2016-11-21 | 2019-11-12 | Saudi Arabian Oil Company | Process and system for conversion of crude oil to petrochemicals and fuel products integrating vacuum gas oil hydrocracking and steam cracking |
| US10472574B2 (en) | 2016-11-21 | 2019-11-12 | Saudi Arabian Oil Company | Process and system for conversion of crude oil to petrochemicals and fuel products integrating delayed coking of vacuum residue |
| CN111377789B (en) * | 2018-12-29 | 2023-01-13 | 中国石油化工股份有限公司 | Method for reducing 1-butene loss in raffinate carbon four-selective polymerization process |
| WO2021163352A1 (en) | 2020-02-11 | 2021-08-19 | Saudi Arabian Oil Company | Processes and systems for petrochemical production integrating deep hydrogenation of distillates |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2017501131A (en) | 2017-01-12 |
| WO2015080951A1 (en) | 2015-06-04 |
| KR20160108320A (en) | 2016-09-19 |
| EP3074370A1 (en) | 2016-10-05 |
| US20150148572A1 (en) | 2015-05-28 |
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