HU226818B1 - Process for the carbonylation of ethylene - Google Patents
Process for the carbonylation of ethylene Download PDFInfo
- Publication number
- HU226818B1 HU226818B1 HU0000772A HUP0000772A HU226818B1 HU 226818 B1 HU226818 B1 HU 226818B1 HU 0000772 A HU0000772 A HU 0000772A HU P0000772 A HUP0000772 A HU P0000772A HU 226818 B1 HU226818 B1 HU 226818B1
- Authority
- HU
- Hungary
- Prior art keywords
- ethylene
- carbon monoxide
- molar ratio
- process according
- palladium
- Prior art date
Links
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims description 59
- 239000005977 Ethylene Substances 0.000 title claims description 59
- 238000000034 method Methods 0.000 title claims description 21
- 238000005810 carbonylation reaction Methods 0.000 title description 9
- 230000006315 carbonylation Effects 0.000 title description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 48
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 48
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 30
- 239000003054 catalyst Substances 0.000 claims description 29
- 239000007791 liquid phase Substances 0.000 claims description 24
- 239000012071 phase Substances 0.000 claims description 19
- 229940117927 ethylene oxide Drugs 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 17
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 16
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 16
- 229940017219 methyl propionate Drugs 0.000 claims description 16
- 229910052763 palladium Inorganic materials 0.000 claims description 14
- 239000003446 ligand Substances 0.000 claims description 12
- -1 palladium ions Chemical class 0.000 claims description 11
- 150000001450 anions Chemical class 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 8
- 150000002941 palladium compounds Chemical class 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 125000000962 organic group Chemical group 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 125000005647 linker group Chemical group 0.000 claims description 4
- 125000004437 phosphorous atom Chemical group 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 230000005764 inhibitory process Effects 0.000 claims description 3
- 125000003107 substituted aryl group Chemical group 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 claims 2
- CURXFECNXOCIMI-UHFFFAOYSA-N ditert-butyl-[[3-(ditert-butylphosphanylmethyl)naphthalen-2-yl]methyl]phosphane Chemical compound C1=CC=C2C=C(CP(C(C)(C)C)C(C)(C)C)C(CP(C(C)(C)C)C(C)(C)C)=CC2=C1 CURXFECNXOCIMI-UHFFFAOYSA-N 0.000 claims 1
- 239000007789 gas Substances 0.000 description 24
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 150000007513 acids Chemical class 0.000 description 9
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 229940098779 methanesulfonic acid Drugs 0.000 description 5
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000003003 phosphines Chemical class 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- WMKGGPCROCCUDY-PHEQNACWSA-N dibenzylideneacetone Chemical compound C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 WMKGGPCROCCUDY-PHEQNACWSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 description 1
- MBDUIEKYVPVZJH-UHFFFAOYSA-N 1-ethylsulfonylethane Chemical compound CCS(=O)(=O)CC MBDUIEKYVPVZJH-UHFFFAOYSA-N 0.000 description 1
- XTDQDBVBDLYELW-UHFFFAOYSA-N 2,2,3-trimethylpentane Chemical compound CCC(C)C(C)(C)C XTDQDBVBDLYELW-UHFFFAOYSA-N 0.000 description 1
- HSXUNHYXJWDLDK-UHFFFAOYSA-N 2-hydroxypropane-1-sulfonic acid Chemical compound CC(O)CS(O)(=O)=O HSXUNHYXJWDLDK-UHFFFAOYSA-N 0.000 description 1
- XCJGLBWDZKLQCY-UHFFFAOYSA-N 2-methylpropane-2-sulfonic acid Chemical compound CC(C)(C)S(O)(=O)=O XCJGLBWDZKLQCY-UHFFFAOYSA-N 0.000 description 1
- INVGSXKPOIHXPB-UHFFFAOYSA-N C=C.[C-]#[O+] Chemical compound C=C.[C-]#[O+] INVGSXKPOIHXPB-UHFFFAOYSA-N 0.000 description 1
- 208000001408 Carbon monoxide poisoning Diseases 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- LIDMEVMARAKSDE-UHFFFAOYSA-N benzyl(ditert-butyl)phosphane Chemical compound CC(C)(C)P(C(C)(C)C)CC1=CC=CC=C1 LIDMEVMARAKSDE-UHFFFAOYSA-N 0.000 description 1
- 230000002051 biphasic effect Effects 0.000 description 1
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- SFCNPIUDAIFHRD-UHFFFAOYSA-N ditert-butyl-[[2-(ditert-butylphosphanylmethyl)phenyl]methyl]phosphane Chemical compound CC(C)(C)P(C(C)(C)C)CC1=CC=CC=C1CP(C(C)(C)C)C(C)(C)C SFCNPIUDAIFHRD-UHFFFAOYSA-N 0.000 description 1
- 210000003317 double-positive, alpha-beta immature T lymphocyte Anatomy 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- ZODDGFAZWTZOSI-UHFFFAOYSA-N nitric acid;sulfuric acid Chemical compound O[N+]([O-])=O.OS(O)(=O)=O ZODDGFAZWTZOSI-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 150000002835 noble gases Chemical class 0.000 description 1
- 229940078552 o-xylene Drugs 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- ANIDRZQDJXBHHM-UHFFFAOYSA-N pyridin-2-ylphosphane Chemical compound PC1=CC=CC=N1 ANIDRZQDJXBHHM-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 125000004953 trihalomethyl group Chemical group 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5027—Polyphosphines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
- C07C67/38—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by addition to an unsaturated carbon-to-carbon bond
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Steroid Compounds (AREA)
- Catalysts (AREA)
- Polyethers (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Claims (12)
- SZABADALMI IGÉNYPONTOK1. Eljárás etilén karbonilezésére folyékony fázisban, amelynek során (i) etilén tápáramból és szén-monoxid tápáramból gázfázist képezünk, (ii) a gázfázist a hidroxilcsoport-forrást tartalmazó folyékony fázisban egy palládiumot vagy palládiumvegyületet, egy kétfogú foszfinligandumot és egy anionforrást tartalmazó katalizátor-rendszerrel hozzuk érintkezésbe, és (iii) az etilént a hidroxilcsoport-forrás és a katalizátor-rendszer jelenlétében reagáltatjuk a szén-monoxiddal, azzal jellemezve, hogy az etilén tápáramból és a szén-monoxid tápáramból etilént és szén-monoxidot egymáshoz viszonyítva 1:1-nél nagyobb mólarányban tartalmazó gázfázist alakítunk ki a reaktorban, és az anionokat egy vagy több, vizes oldatban 4-nél kisebb pKa-értékű sav formájában juttatjuk be.
- 2. Az 1. igénypont szerinti eljárás, azzal jellemezve, hogy a gázfázisban az etilén és szén-monoxid egymáshoz viszonyított mólarányát legalább 3:1-re állítjuk.
- 3. A 2. igénypont szerinti eljárás, azzal jellemezve, hogy a gázfázisban az etilén és szén-monoxid egymáshoz viszonyított mólarányát legalább 5:1-re állítjuk.
- 4. Az 1. igénypont szerinti eljárás, azzal jellemezve, hogy a folyadékfázisban az etilén és szén-monoxid egymáshoz viszonyított mólarányát legalább 3:1-re állítjuk.
- 5. A 4. igénypont szerinti eljárás, azzal jellemezve, hogy a folyadékfázisban az etilén és szén-monoxid egymáshoz viszonyított mólarányát legalább 5:1-re állítjuk.
- 6. Az 1-5. igénypontok bármelyike szerinti eljárás, azzal jellemezve, hogy a reakciót 20-250 °C-on végezzük.
- 7. Az 1-6. igénypontok bármelyike szerinti eljárás, azzal jellemezve, hogy katalizátor-rendszerként (a) palládium vagy egy palládiumvegyület, (b) egy (I) általános képletű kétfogú foszfin - a képletbenR° tercier szénatomot jelent,R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11 és R12a megfelelő R° szénatomhoz szénatomon keresztül kapcsolódó, azonos vagy eltérő, adott esetben szubsztituált szerves csoportot jelent,L1 és L2 a megfelelő foszforatomot az X csoporttal összekapcsoló, azonos vagy eltérő, adott esetben szubsztituált rövid szénláncú alkiléncsoportot jelent, ésX adott esetben szubsztituált arilcsoportot tartalmazó kapcsoló csoportot jelent, amihez a foszforatomok hozzáférhető szomszédos szénatomokon keresztül kapcsolódnak, és (c) a palládiumionokkal lényegében nem koordinálódó, vizes oldatban 4-nél kisebb pKa-értékű savból származtatható anion kombinációját használjuk.
- 8. A 7. igénypont szerinti eljárás, azzal jellemezve, hogy olyan (I) általános képletű vegyületeket használunk, amelyekben R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11 és R12 adott esetben szubsztituált rövid szénláncú alkilcsoportot jelent.
- 9. A 7. vagy 8. igénypont szerinti eljárás, azzal jellemezve, hogy olyan (I) általános képletű vegyületeket használunk, amelyekben R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11 és R12 a hozzájuk kapcsolódó megfelelő R° szénatomokkal együtt legalább a terc-butil-csoportéval azonos térbeli gátlást kifejtő csoportokat alkotnak.
- 10. A 7-9. igénypontok bármelyike szerinti eljárás, azzal jellemezve, hogy olyan (I) általános képletű vegyületeket használunk, amelyekben L1 és L2 metiléncsoportot jelent.
- 11. A 7. igénypont szerinti eljárás, azzal jellemezve, hogy kétfogú ligandumként a,a’-bisz(terc-butil-foszfino)-o-xilolt, a,a’-bisz(di-neopentil-foszfino)-o-xilolt vagy 2,3-bisz(di-terc-butil-foszfino-metil)-naftalint használunk.
- 12. Az 1-11. igénypontok bármelyike szerinti eljárás, azzal jellemezve, hogy metil-propionát előállítására hidroxilcsoport-forrásként metanolt használunk, és a folyadékfázis részeként egy oldószert alkalmazunk.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GBGB9705699.8A GB9705699D0 (en) | 1997-03-19 | 1997-03-19 | Process for the carbonylation of ethylene |
| PCT/GB1998/000629 WO1998041495A1 (en) | 1997-03-19 | 1998-02-27 | Process for the carbonylation of ethylene |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| HUP0000772A2 HUP0000772A2 (en) | 2000-07-28 |
| HUP0000772A3 HUP0000772A3 (en) | 2000-11-28 |
| HU226818B1 true HU226818B1 (en) | 2009-11-30 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| HU0000772A HU226818B1 (en) | 1997-03-19 | 1998-02-27 | Process for the carbonylation of ethylene |
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| US (1) | US6284919B1 (hu) |
| EP (1) | EP0970038B2 (hu) |
| JP (1) | JP4143133B2 (hu) |
| KR (1) | KR100540952B1 (hu) |
| CN (1) | CN1245371C (hu) |
| AT (1) | ATE215928T1 (hu) |
| AU (1) | AU737772C (hu) |
| BR (1) | BR9808354A (hu) |
| CA (1) | CA2282515C (hu) |
| CZ (1) | CZ295078B6 (hu) |
| DE (1) | DE69804776T3 (hu) |
| ES (1) | ES2172114T5 (hu) |
| GB (1) | GB9705699D0 (hu) |
| HU (1) | HU226818B1 (hu) |
| ID (1) | ID24681A (hu) |
| MY (1) | MY124656A (hu) |
| PT (1) | PT970038E (hu) |
| TW (1) | TW552257B (hu) |
| WO (1) | WO1998041495A1 (hu) |
| ZA (1) | ZA981982B (hu) |
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| US6489506B2 (en) * | 1997-03-19 | 2002-12-03 | Lucite International Uk Limited | Process for the palladium and phosphine ligand catalyzed carbonylation of ethylene |
| GB9918229D0 (en) * | 1999-08-04 | 1999-10-06 | Ici Plc | Improvements relating to metal-compound catalysed processes |
| JP2002019268A (ja) * | 2000-07-03 | 2002-01-23 | Nippon Aerosil Co Ltd | インクジェット記録媒体のインク吸収層形成用超微粒セラミック粉末凝集体分散水 |
| TWI301481B (en) * | 2002-08-10 | 2008-10-01 | Lucite Int Uk Ltd | A catalyst system |
| JP2007516197A (ja) | 2003-07-03 | 2007-06-21 | ルーサイト インターナショナル ユーケー リミテッド | エチレン性不飽和化合物のヒドロホルミル化方法 |
| EP1656336B1 (en) * | 2003-07-25 | 2007-08-15 | DSM IP Assets B.V. | Process for the carbonylation of conjugated dienes using a palladium catalyst system |
| GB0403592D0 (en) * | 2004-02-18 | 2004-03-24 | Lucite Int Uk Ltd | A catalyst system |
| GB0411951D0 (en) * | 2004-05-28 | 2004-06-30 | Lucite Int Uk Ltd | Carbonylation of ester |
| GB0516556D0 (en) | 2005-08-12 | 2005-09-21 | Lucite Int Uk Ltd | Improved catalyst system |
| KR101633325B1 (ko) * | 2005-11-17 | 2016-06-24 | 루사이트 인터내셔널 유케이 리미티드 | 에틸렌성 불포화 화합물의 카르보닐화 |
| GB0607494D0 (en) | 2006-04-13 | 2006-05-24 | Lucite Int Uk Ltd | Metal complexes |
| WO2008065448A1 (en) | 2006-12-02 | 2008-06-05 | Lucite International Uk Limited | Novel carbonylation ligands and their use in the carbonylation of ethylenically unsaturated compounds |
| GB0625518D0 (en) * | 2006-12-21 | 2007-01-31 | Lucite Int Uk Ltd | Carbonylation of conjugated dienes |
| EP2025660A3 (en) * | 2007-08-14 | 2009-03-04 | Rohm and Haas Company | Processes for producing ethylene and carbon monoxide mixtures from ethane |
| JP5058915B2 (ja) * | 2007-09-20 | 2012-10-24 | ローム アンド ハース カンパニー | エタンからエチレン及び一酸化炭素の混合物を製造するための触媒プロセス |
| GB0812297D0 (en) | 2008-07-04 | 2008-08-13 | Lucite Int Uk Ltd | Novel carbonylation ligand sand thier use of in the carbonylation of ethylenically unsaturated compounds |
| EP2165997A1 (en) * | 2008-09-18 | 2010-03-24 | Rohm and Haas Company | Improved process for the oxidative dehydrogenation of ethane |
| GB0921876D0 (en) * | 2009-12-15 | 2010-01-27 | Lucite Int Uk Ltd | Improved carbonylation process |
| GB0921875D0 (en) | 2009-12-15 | 2010-01-27 | Lucite Int Uk Ltd | A continuous process for the carbonylation of ethylene |
| GB201000078D0 (en) * | 2010-01-05 | 2010-02-17 | Lucite Int Uk Ltd | Process for the carbonylation of ethylenically unsaturated compounds, novel carbonylation ligands and catalyst systems incorporatng such ligands |
| DE102010002809A1 (de) | 2010-03-12 | 2011-11-17 | Evonik Degussa Gmbh | Verfahren zur Herstellung von linearen alpha,omega-Dicarbonsäurediestern |
| BR112014004595A2 (pt) * | 2011-09-01 | 2017-03-21 | Dsm Ip Assets Bv | processo para a carbonilação de alquenos opcionalmente funcionalizados |
| GB201122054D0 (en) * | 2011-12-21 | 2012-02-01 | Lucite Int Uk Ltd | A continuous process for the carbonylation of ethylene |
| US9273020B2 (en) * | 2012-05-02 | 2016-03-01 | Haldor Topsoe A/S | Process for the production of chemical compounds from carbon dioxide |
| CN105636928B (zh) | 2013-09-30 | 2018-11-27 | 陶氏环球技术有限责任公司 | 链烷酸烷基酯的气相生产 |
| ES2709386T3 (es) | 2014-06-24 | 2019-04-16 | Dow Global Technologies Llc | Proceso para producir agentes coalescentes con contenidos bajos de COV |
| TW201634430A (zh) * | 2015-03-26 | 2016-10-01 | 陶氏全球科技責任有限公司 | 烷酸烷酯之氣相產生 |
| CN108003022B (zh) * | 2016-11-02 | 2020-01-07 | 中国科学院大连化学物理研究所 | 一种制备酯类化合物的方法 |
| CN108003024B (zh) * | 2016-11-02 | 2019-10-18 | 中国科学院大连化学物理研究所 | 一种丙酸甲酯的制备方法 |
| CN108003023B (zh) * | 2016-11-02 | 2019-10-18 | 中国科学院大连化学物理研究所 | 一种制备丙酸甲酯的方法 |
| CN111087306B (zh) | 2019-12-27 | 2021-08-03 | 南京诚志清洁能源有限公司 | 芳基双齿膦配体组合催化制备有机羧酸酯的方法 |
| CN114618521B (zh) * | 2020-12-11 | 2023-05-09 | 中国科学院大连化学物理研究所 | 一种负载型双金属核壳结构催化剂制备丙酸甲酯的方法 |
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| US4269781A (en) * | 1980-02-08 | 1981-05-26 | Celanese Corporation | Dimeric carbonylation of 1,3-butadiene |
| KR880007426A (ko) * | 1986-12-24 | 1988-08-27 | 오노 알버어스 | 팔라듐 촉매를 사용한 올레핀형 불포화 화합물의 카르보닐화 방법 |
| GB8917579D0 (en) * | 1989-08-01 | 1989-09-13 | Shell Int Research | Preparation of alkyl propionates |
| EP0495547B1 (en) † | 1991-01-15 | 1996-04-24 | Shell Internationale Researchmaatschappij B.V. | Carbonylation of olefins |
| SG49630A1 (en) * | 1992-04-08 | 1998-06-15 | Shell Int Research | Carbonylation process using palladium phosphine catalyst |
| GB9425911D0 (en) * | 1994-12-22 | 1995-02-22 | Ici Plc | Process for the carbonylation of olefins and catalyst system for use therein |
| ZA965990B (en) † | 1995-07-17 | 1997-02-24 | Shell Int Research | Process for the continuous carbonylation of olefins. |
-
1997
- 1997-03-19 GB GBGB9705699.8A patent/GB9705699D0/en active Pending
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1998
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- 1998-02-27 CZ CZ19993269A patent/CZ295078B6/cs not_active IP Right Cessation
- 1998-02-27 AU AU66286/98A patent/AU737772C/en not_active Expired
- 1998-02-27 PT PT98908202T patent/PT970038E/pt unknown
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- 1998-02-27 EP EP98908202A patent/EP0970038B2/en not_active Expired - Lifetime
- 1998-02-27 BR BR9808354-6A patent/BR9808354A/pt not_active Application Discontinuation
- 1998-02-27 KR KR1019997008531A patent/KR100540952B1/ko not_active IP Right Cessation
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Also Published As
| Publication number | Publication date |
|---|---|
| AU737772B2 (en) | 2001-08-30 |
| AU737772C (en) | 2005-08-18 |
| EP0970038A1 (en) | 2000-01-12 |
| US6284919B1 (en) | 2001-09-04 |
| TW552257B (en) | 2003-09-11 |
| DE69804776D1 (de) | 2002-05-16 |
| PT970038E (pt) | 2002-07-31 |
| CN1250434A (zh) | 2000-04-12 |
| HUP0000772A3 (en) | 2000-11-28 |
| CN1245371C (zh) | 2006-03-15 |
| ID24681A (id) | 2000-07-27 |
| EP0970038B1 (en) | 2002-04-10 |
| DE69804776T3 (de) | 2006-03-23 |
| DE69804776T2 (de) | 2002-09-26 |
| JP4143133B2 (ja) | 2008-09-03 |
| BR9808354A (pt) | 2000-05-23 |
| KR20000076427A (ko) | 2000-12-26 |
| WO1998041495A1 (en) | 1998-09-24 |
| CA2282515A1 (en) | 1998-09-24 |
| MY124656A (en) | 2006-06-30 |
| EP0970038B2 (en) | 2005-09-07 |
| ES2172114T5 (es) | 2006-04-01 |
| CZ295078B6 (cs) | 2005-05-18 |
| ATE215928T1 (de) | 2002-04-15 |
| KR100540952B1 (ko) | 2006-01-12 |
| ES2172114T3 (es) | 2002-09-16 |
| HUP0000772A2 (en) | 2000-07-28 |
| CA2282515C (en) | 2007-05-01 |
| JP2001517218A (ja) | 2001-10-02 |
| AU6628698A (en) | 1998-10-12 |
| GB9705699D0 (en) | 1997-05-07 |
| ZA981982B (en) | 1998-09-21 |
| CZ326999A3 (cs) | 2000-01-12 |
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