CN1420857A - 通过烯烃羰基化来制备羧酸的方法 - Google Patents
通过烯烃羰基化来制备羧酸的方法 Download PDFInfo
- Publication number
- CN1420857A CN1420857A CN00810874A CN00810874A CN1420857A CN 1420857 A CN1420857 A CN 1420857A CN 00810874 A CN00810874 A CN 00810874A CN 00810874 A CN00810874 A CN 00810874A CN 1420857 A CN1420857 A CN 1420857A
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- CN
- China
- Prior art keywords
- carboxylic acid
- alkene
- alkyl
- rhodium
- preparing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 150000001735 carboxylic acids Chemical class 0.000 title abstract 2
- 230000006315 carbonylation Effects 0.000 title description 9
- 238000005810 carbonylation reaction Methods 0.000 title description 9
- 238000004519 manufacturing process Methods 0.000 title description 2
- 239000003054 catalyst Substances 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 28
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 25
- -1 nitrogenous heterocyclic compound Chemical class 0.000 claims abstract description 23
- 150000001336 alkenes Chemical class 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000010948 rhodium Substances 0.000 claims abstract description 20
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 14
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 150000003284 rhodium compounds Chemical class 0.000 claims abstract description 10
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 23
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 11
- 229910052736 halogen Inorganic materials 0.000 claims description 11
- 150000002367 halogens Chemical class 0.000 claims description 11
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000005516 engineering process Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 4
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 claims description 2
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 2
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 150000003217 pyrazoles Chemical class 0.000 claims description 2
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 abstract description 4
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 abstract 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 18
- 230000000694 effects Effects 0.000 description 9
- 235000019260 propionic acid Nutrition 0.000 description 9
- 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 9
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 8
- 239000005977 Ethylene Substances 0.000 description 7
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 150000003818 basic metals Chemical class 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 3
- 229910052728 basic metal Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000001632 sodium acetate Substances 0.000 description 3
- 235000017281 sodium acetate Nutrition 0.000 description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- DJDDPYWQGDLLNW-UHFFFAOYSA-N [Rh].CCBBB.C(C)(=O)CC(C)=O Chemical compound [Rh].CCBBB.C(C)(=O)CC(C)=O DJDDPYWQGDLLNW-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- AQIIVEISJBBUCR-UHFFFAOYSA-N 4-(3-phenylpropyl)pyridine Chemical compound C=1C=NC=CC=1CCCC1=CC=CC=C1 AQIIVEISJBBUCR-UHFFFAOYSA-N 0.000 description 1
- DBOLXXRVIFGDTI-UHFFFAOYSA-N 4-benzylpyridine Chemical compound C=1C=NC=CC=1CC1=CC=CC=C1 DBOLXXRVIFGDTI-UHFFFAOYSA-N 0.000 description 1
- VJXRKZJMGVSXPX-UHFFFAOYSA-N 4-ethylpyridine Chemical compound CCC1=CC=NC=C1 VJXRKZJMGVSXPX-UHFFFAOYSA-N 0.000 description 1
- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 description 1
- BAJKMPPHSZTMOF-UHFFFAOYSA-N 4-tridecylpyridine Chemical compound CCCCCCCCCCCCCC1=CC=NC=C1 BAJKMPPHSZTMOF-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical group [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910001038 basic metal oxide Inorganic materials 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229960004424 carbon dioxide Drugs 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 230000021523 carboxylation Effects 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- NAVSKFYJNZQECG-UHFFFAOYSA-N nickel;propanoic acid Chemical compound [Ni].CCC(O)=O NAVSKFYJNZQECG-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- BWILYWWHXDGKQA-UHFFFAOYSA-M potassium propanoate Chemical compound [K+].CCC([O-])=O BWILYWWHXDGKQA-UHFFFAOYSA-M 0.000 description 1
- 239000004331 potassium propionate Substances 0.000 description 1
- 235000010332 potassium propionate Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- JXKPEJDQGNYQSM-UHFFFAOYSA-M sodium propionate Chemical compound [Na+].CCC([O-])=O JXKPEJDQGNYQSM-UHFFFAOYSA-M 0.000 description 1
- 239000004324 sodium propionate Substances 0.000 description 1
- 235000010334 sodium propionate Nutrition 0.000 description 1
- 229960003212 sodium propionate Drugs 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 150000003566 thiocarboxylic acids Chemical class 0.000 description 1
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical class SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0204—Ethers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/20—Carbonyls
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2234—Beta-dicarbonyl ligands, e.g. acetylacetonates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/14—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on a carbon-to-carbon unsaturated bond in organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
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Abstract
本发明公开了一种在水的存在下由烯烃和一氧化碳制备羧酸的方法,其中使用一种包含以下混合物的无卤催化剂体系:a)铑或铑化合物,b)至少一种含氮的杂环化合物,c)至少一种脂族C2-C20-羧酸的碱金属盐或碱土金属盐和d)至少一种具有结构式I的二醇醚,其中R1和R2独立地为C1-C20-烷基或R3CO,其中R3是氢或C1-C20-烷基,或R1和R2共同形成一个C1-C20-亚烷基链,且n为1-30。
Description
本发明涉及一种在水以及包含铑或铑化合物、含氮化合物、碱金属羧酸盐或碱土金属羧酸盐和二醇醚的混合物的无卤催化剂体系的存在下,在30-150℃和30-150巴的压力下,通过将烯烃与一氧化碳进行反应来制备羧酸或其酯的方法。
在Industrielle Organische Chemie,1994,第4版,VerlagChemie,pp.153-154中,Weissermel等人描述了利用Reppe工艺的烯烃羰基化,例如在催化剂存在下由乙烯、一氧化碳和水制备丙酸。所用的催化剂是在反应条件下转化成羰基镍的丙酸镍。高乙烯转化率仅在高压(200-240巴)下实现。这些反应条件需要合适反应器的昂贵建造费用和-由于产物在反应条件下的腐蚀性-建造用的特殊昂贵材料。
烯烃的羰基化可在约100巴的压力下使用贵金属催化剂进行。即,EP-A495547提出使用一种包含钯源和双齿膦配体的催化剂。但这些催化剂往往由于金属钯在短反应时间之后的沉淀而减活化;尤其是,所用的膦配体在所需的反应条件下不稳定。
DE-A2263442描述了在苯酚衍生物或苯硫酚衍生物或氟化羧酸、硫代羧酸或磺酸的存在下,烯烃在含铑或铱的无卤催化剂上的羰基化作用。但催化活性不令人满意。
WO98/37049公开了烯烃在30-100巴和100-270℃下在含镍的无卤催化剂体系上的羰基化作用,该催化剂体系包含至少一种附加金属以及一种叔或季氮、砷或磷化合物或含氮的杂环化合物。该催化剂体系即使在低水浓度下也具有活性,这样可制备出即使在反应器排出物中水含量也低于1%的羧酸。缺点是,季铵化合物在所需高温下不稳定且在反应过程中形成的四羰基镍具有高挥发性和毒性,因此需要进行昂贵的废气纯化。
EP-A759420描述了一种在30-200℃和30-200巴下,通过烯烃在包含铑化合物和至少一种杂环化合物的无卤催化剂体系上的羰基化来制备羧酸的方法,该方法可在二醇醚溶剂中进行。但该催化剂体系在低水浓度下活性低,并在这种状态下低选择性地得到羧酸。
本发明的一个目的是提供一种避免了上述缺点且即使在低水浓度下也以良好选择性和活性得到羧酸的用于烯烃羰基化的方法。
我们已经发现,该目的通过一种在水和无卤催化剂体系的存在下,由烯烃和一氧化碳制备羧酸的新的改进方法而实现,该催化剂体系包含以下物质的混合物:
a)铑或铑化合物,
b)至少一种含氮的杂环化合物,
c)至少一种脂族C2-C20-羧酸的碱金属盐或碱土金属盐和
d)至少一种具有结构式I的二醇醚,
其中R1和R2独立地为C1-C20-烷基或R3CO,其中R3是氢或C1-C20-烷基,或R1和R2共同形成一个C1-C20-亚烷基链,且n为1-30。
与EP759420中所述的催化剂体系相比,本发明方法能够明显提高活性和选择性,尤其是在最高100巴的低压和低水浓度下。另外,按照本发明使用的催化剂体系在反应条件下稳定。不会出现在工业规模工艺中特别不利的催化剂组分的沉积或分解。即使在0.5-2摩尔水/摩尔烯烃的低水浓度下,用于本发明方法的催化剂体系也具有活性,可以制备出即使在反应器排出物中水含量为0-5%,优选低于1%的羧酸,这明显简化了反应产物的处理。
这是特别惊人的,因为US-A3917677和EP-A55875报道了脂族羧酸的碱金属盐如乙酸钠对无卤羰基化催化剂的不利影响。即,USA3,917,677的实施例7指出,无卤铑/膦催化剂在烯烃烷氧基羰基化中的活性在乙酸钠的存在下急剧下降。EP-A55875的实施例9报道,无卤钯催化剂体系在乙酸钠存在下失去所有活性。
以乙烯转化成丙酸为例,以下反应式说明了本发明方法:
适用于本发明方法的起始原料是具有优选2-20,特别优选2-7个碳原子的脂族和环脂族烯烃。例子为乙烯、丙烯、异丁烯、1-丁烯、2-丁烯、以及戊烯和己烯的异构体、及环己烯,其中乙烯是优选的。
上述起始原料与水和一氧化碳(CO)进行反应,后者可以纯净形式或用惰性气体如氮气或氩气稀释使用。起始化合物烯烃和水的摩尔比可在宽限度内变化,但一般使用至少等摩尔量的水。但优选使用0.5-2摩尔,特别优选0.9-1.5摩尔的水/摩尔烯烃,以得到在反应器排出物中水含量为0-5%,特别优选0-1%的羧酸。
烯烃与一氧化碳的摩尔比也可极大地变化,一般为5∶1-1∶5,其中优选的摩尔比为0.5∶1-1.5∶1摩尔烯烃/摩尔一氧化碳。
在本发明的方法中,该无卤催化剂体系包含以下物质的混合物
a)铑或铑化合物,
b)至少一种含氮的杂环化合物,
c)至少一种脂族C2-C20-羧酸的碱金属盐或碱土金属盐和
其中R1和R2独立地为C1-C20-烷基或R3CO,其中R3是氢或C1-C20烷基,或R1和R2共同形成一个C1-C20-亚烷基链,且n为1-30。
本发明的催化剂体系优选无镍和镍化合物,且优选无膦。
为了能够形成催化活性的含铑组分,有利地将可溶性铑化合物如乙酸盐、丙酸盐、乙酰基丙酮化物、氧化物、氢氧化物或碳酸盐加入反应混合物中。其它的合适铑化合物是羰基化合物,尤其是乙酰基丙酮二羰基铑、二(丙酸二羰基铑)、二(乙酸二羰基铑)、Rh4(CO)12、Rh6(CO)16、阴离子[Rh12(CO)30]2-的盐或由给体配体如氮碱或由烯烃稳定化的金属化合物。根据溶解度,铑以在反应混合物中的溶解形式或悬浮液存在。活性催化剂组分a)的形成可通过向反应混合物中引入氢而加速。该催化剂组分的活化(预羰基化)也可在单独的反应空间中,通过与CO和水或与CO和氢在50-150℃和50-150巴的压力下反应来进行。催化剂组分a)的铑或铑化合物也可在有机或无机惰性载体,例如活性炭、石墨、氧化铝、氧化锆和氧化硅上使用。反应溶液的铑含量(以金属计算)一般为0.001-1%重量,优选0.01-0.5%重量。
合适的含氮的杂环化合物b)是吡啶、带有1-3个C1-C30-烷基、芳基或芳烷基作为取代基的吡啶、喹啉和异喹啉、嘧啶、哒嗪、吡嗪、吡唑、咪唑、噻唑和噁唑。优选的是未取代吡啶或被C1-C30-烷基、芳基或芳烷基单取代的吡啶,例如4-乙基吡啶、4-十三烷基吡啶、4-叔丁基吡啶、4-(苯基丙基)吡啶、4-丙基吡啶或4-苄基吡啶、和4,4’-三亚甲基二吡啶。含氮的杂环化合物在反应溶液中的存在量一般为1-50%重量,优选5-30%重量。
作为碱金属盐或碱土金属盐c)优选使用脂族C2-C20-羧酸,优选脂族C2-C10-羧酸如乙酸、丙酸或丁酸的锂、钠、钾、铷、铯、镁、钙、锶或钡,特别优选钠或钾盐。特别优选使用所要制备的羧酸的碱金属或碱土金属盐。因此,丙酸的制备优选使用丙酸盐,特别优选丙酸钠或钾进行。存在于反应溶液中的C2-C20-羧酸的碱金属或碱土金属盐的量一般为1-50%重量,优选5-30%重量。也可通过与相应羧酸的反应,由合适的前体例如由碱金属或碱土金属氢氧化物、碳酸氢盐、碳酸盐或氧化物现场制备碱金属或碱土金属盐c)。
所用的其它催化剂组分d)是至少一种具有结构式I的二醇醚:
其中R1和R2独立地为C1-C20-烷基或R3CO,其中R3是氢或C1-C20-烷基,或R1和R2共同形成一个C1-C20-亚烷基链,且n为1-30。其中R1和R2独立地为C1-C10-烷基,尤其是乙基、丙基、戊基或丁基,且n为2、3或4的化合物,例如二甘醇二乙基醚、二甘醇二甲基醚、二甘醇二丁基醚和三甘醇二乙基醚是优选的。存在于反应溶液中的具有结构式I的二醇醚的量一般为1-70%重量,优选5-50%重量。
该催化剂体系的第二催化剂组分b)与存在于第一组分a)的铑(以金属计算)的摩尔比为10∶1-10000∶1,优选50∶1-1500∶1。第三催化剂组分c),即Cx-Cy-羧酸的碱金属盐或碱土金属盐与铑(以金属计算)的摩尔比一般为10∶1-10000∶1,优选50∶1-1500∶1。该催化剂体系的催化剂组分d)与存在于第一组分a)中的铑(以金属计算)的摩尔比为20∶1-10000∶1,优选100∶1-3000∶1。
作为用于本发明方法的溶剂,优选的是在反应条件下为液体的起始原料和产物以及液体催化剂组分。但可以使用附加溶剂。根据组成,反应混合物可形成单相或可由两相组成。反应一般在30-150℃,优选90-120℃,和30-150巴,优选40-100巴的压力下进行。
起始化合物烯烃、水和催化剂体系可在反应之前在反应器中,根据需要在溶剂中进行混合。它们可随后加热至反应温度,且反应压力通过注入一氧化碳,或在使用短链烯烃时通过注入该烯烃与一氧化碳的混合物而设定。
反应一般在0.5-3小时之后完成。它可以在反应器如罐、泡罩塔、管式反应器或环流反应器中连续或间歇进行。
在一个优选实施方案中,为了分离工艺产物,将反应器排出物进行减压。将包含工艺产物以及可溶性或悬浮催化剂的反应器排出物液相进行蒸馏处理,这样,如果合适,在一个随后的精蒸馏之后分离出工艺产物。含催化剂的蒸馏底物返回至反应体系。同样,在蒸馏之前分离出的所有催化剂成分以及在蒸馏中作为低沸点物或作为侧流分离出的挥发性催化剂成分可在合适处理之后返回。
本发明方法能够在低水浓度、低温和中压下,以高空时产率高选择性地制备出工艺产物,同时避免挥发性的有毒过渡金属化合物作为催化剂组分。不会出现在工艺的工业规模反应中特别不利的催化剂组分的沉积或分解。本发明方法能够制备出在反应器排出物中水含量低于1%的羧酸,并因此可在制备和处理时实现显著的成本节约。
实施例
实施例1-6:丙酸制备的间歇实验
向配有磁力搅拌器棒的270毫升高压釜中装入表1所示量的丙酸、水和新催化剂体系。随后,除非表1另有所指,使用50%体积CO和50%体积乙烯的气体混合物来设定表1所示的起始压力,然后将反应溶液加热至表1所示的温度。在反应温度达到之后,表1规定的反应压力利用CO/乙烯气体混合物进行设定并通过注入其它量的CO/乙烯气体混合物来保持。1小时之后,将高压釜冷却至室温并排气,然后对反应产物进行气体分析检测。
按照本发明的实施例1-6的实验结果汇总于表1。空时产率(STYPA)计算为除以所用反应溶液的体积(100毫升)的丙酸产量。丙酸选择性(SPA)基于作为起始化合物的乙烯。水的转化率在表1中表示为CH2O。催化剂活性记录为周转频率(TOF)。在所有实施例中,所用的铑化合物(催化剂组分(a))是乙酰基丙酮二羰基铑(Rh(acac)(CO)2)。在表中,diglyme=二甘醇二甲基醚,PA=丙酸和DEGBDE=二甘醇二正丁基醚。所用的催化剂组分c)是丙酸钾,在表1中简称为KO2CEt。
对比例A-E
对比例A-E按照以上实施例1-6所述来进行,但催化剂组分(c)和(d)在实验A和B中省去。实验C在没有催化剂组分(d)的情况下进行,且实验D和E在没有催化剂组分(c)的情况下进行。对比实验的结果在表1中给出。对比实验表明,在没有一种或两种催化剂组分(c)和(d)的情况下,所得空时产率和选择性低于按照本发明的实施例1-6。
表1
1)起始压力30巴CO/乙烯气体混合物2)起始压力9.5巴CO3)起始压力4.5巴CO
No. | PA[g] | H2O[g] | 吡啶[g] | Rh[mmol] | 催化剂(c)[mmol] | 催化剂(d)[g] | p[巴] | T[℃] | STYPA[g/l/h] | SPA[%] | [H2O]排出物[%m/m] | CH2O[%] | TOF molPA/(molRh h) |
A1) | 80 | 10 | 10 | 0.43 | - | - | 100 | 100 | 89 | 86 | 6.0 | 34 | 280 |
B2) | 85 | 5 | 10 | 0.43 | - | - | 100 | 100 | 51 | 81 | 2.4 | 50 | 237 |
C1) | 77 | 5 | 10 | 0.43 | 250KO2CEt | - | 100 | 100 | <5 | 不能确定 | 5.1 | <1% | 不能确定 |
D2) | 45 | 5 | 10 | 0.43 | - | 50diglyme | 100 | 100 | 98 | 90 | 1.8 | 60 | 472 |
E2) | 45 | 5 | 10 | 0.43 | - | 50DEGDBE | 100 | 100 | 12 | 55 | 3 | 33 | 60 |
11) | 47 | 5 | 10 | 0.43 | 125KO2CEt | 34diglyme | 100 | 100 | 195 | 94 | <0.1 | >99 | 994 |
21) | 55 | 5 | 10 | 0.43 | 105KO2CEt | 28diglyme | 100 | 100 | 131 | 95 | 0.6 | 80 | 640 |
33) | 47 | 5 | 10 | 0.86 | 125KO2CEt | 34diglyme | 55 | 100 | 184 | 92 | 0.4 | 91 | 469 |
42) | 45 | 5 | 10 | 0.43 | 125KO2CEt | 50DEGDBE | 100 | 100 | 156 | 93 | <0.1 | >99 | 905 |
53) | 45 | 5 | 10 | 0.43 | 125KO2CEt | 50DEGDBE | 55 | 100 | 189 | 96 | 0.7 | 82 | 1055 |
63) | 46 | 10 | 10 | 0.43 | 125KO2CEt | 34diglyme | 55 | 110 | 300 | 95 | 1.84 | 77 | 1660 |
Claims (11)
1.一种在水的存在下由烯烃和一氧化碳制备羧酸的方法,其中使用一种包含以下混合物的无卤催化剂体系:
a)铑或铑化合物,
b)至少一种含氮的杂环化合物,
c)至少一种脂族C2-C20-羧酸的碱金属盐或碱土金属盐和
d)至少一种具有结构式I的二醇醚
其中R1和R2独立地为C1-C20-烷基或R3CO,其中R3是氢或C1-C20-烷基,或R1和R2共同形成一个C1-C20-亚烷基链,且n为1-30。
2.根据权利要求1所要求的制备羧酸的方法,其中所述催化剂体系的组分以1∶10∶10∶20-1∶10000∶10000∶10000的摩尔比a)∶b)∶c)∶d)存在。
3.根据权利要求1或2所要求的制备羧酸的方法,其中所述催化剂组分b)选自吡啶、带有1-3个C1-C30-烷基、芳基或芳烷基作为取代基的吡啶、喹啉和异喹啉、嘧啶、哒嗪、吡嗪、吡唑、咪唑、噻唑和噁唑。
4.根据权利要求1-3中任何一项所要求的制备羧酸的方法,其中所述催化剂组分c)是脂族C2-C20-羧酸的钠或钾盐。
5.根据权利要求1或2所要求的制备羧酸的方法,其中所用的催化剂组分d)是具有结构式I的二醇醚,其中R1和R2相同或不同并分别为C1-C20烷基,且n为2、3或4。
6.根据权利要求1-5中任何一项所要求的制备羧酸的方法,其中所述反应溶液包含0.5-2摩尔水/摩尔烯烃。
7.根据权利要求1-6中任何一项所要求的制备羧酸的方法,其中所述反应在30-150℃和30-150巴的压力下进行。
8.根据权利要求1-7中任何一项所要求的制备羧酸的方法,其中一氧化碳和烯烃按照摩尔比5∶1-1∶5使用。
9.根据权利要求1-7中任何一项所要求的制备羧酸的方法,其中所用的烯烃是乙烯。
10.一种在权利要求1-4中至少一项中定义的无卤催化剂体系,它适合进行用于在权利要求1-9中任何一项中定义的制备羧酸或其酯的工艺。
11.在权利要求1-5中任何一项中定义的催化剂体系在水的存在下,在由烯烃和一氧化碳制备羧酸中的应用。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE19936979.8 | 1999-08-05 | ||
DE19936979A DE19936979A1 (de) | 1999-08-05 | 1999-08-05 | Verfahren zur Herstellung von Carbonsäuren durch Carbonylierung von Olefinen |
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CN1420857A true CN1420857A (zh) | 2003-05-28 |
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CN00810874A Pending CN1420857A (zh) | 1999-08-05 | 2000-07-21 | 通过烯烃羰基化来制备羧酸的方法 |
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Country | Link |
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EP (1) | EP1200382A1 (zh) |
JP (1) | JP2003506422A (zh) |
KR (1) | KR20020019602A (zh) |
CN (1) | CN1420857A (zh) |
DE (1) | DE19936979A1 (zh) |
WO (1) | WO2001010807A1 (zh) |
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CN106795083A (zh) | 2014-10-17 | 2017-05-31 | 陶氏环球技术有限责任公司 | 用于羧酸的气相制造的催化剂 |
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Publication number | Priority date | Publication date | Assignee | Title |
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GB754877A (en) * | 1953-06-13 | 1956-08-15 | Basf Ag | Improvements in the production of carboxylic acids, their anhydrides and esters |
DE19530992A1 (de) * | 1995-08-23 | 1997-02-27 | Basf Ag | Verfahren zur Herstellung von Carbonsäuren durch Carbonylierung von Olefinen |
RU2134682C1 (ru) * | 1997-11-19 | 1999-08-20 | Институт структурной макрокинетики и проблем материаловедения РАН | Способ получения пропионовой кислоты |
-
1999
- 1999-08-05 DE DE19936979A patent/DE19936979A1/de not_active Withdrawn
-
2000
- 2000-07-21 CN CN00810874A patent/CN1420857A/zh active Pending
- 2000-07-21 KR KR1020027001509A patent/KR20020019602A/ko not_active Application Discontinuation
- 2000-07-21 EP EP00951426A patent/EP1200382A1/de not_active Withdrawn
- 2000-07-21 WO PCT/EP2000/007025 patent/WO2001010807A1/de not_active Application Discontinuation
- 2000-07-21 JP JP2001515277A patent/JP2003506422A/ja not_active Withdrawn
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KR20020019602A (ko) | 2002-03-12 |
DE19936979A1 (de) | 2001-02-08 |
JP2003506422A (ja) | 2003-02-18 |
EP1200382A1 (de) | 2002-05-02 |
WO2001010807A1 (de) | 2001-02-15 |
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