CN1106374A - 1,3-丁二烯加氢甲酰化法 - Google Patents
1,3-丁二烯加氢甲酰化法 Download PDFInfo
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- CN1106374A CN1106374A CN94115656A CN94115656A CN1106374A CN 1106374 A CN1106374 A CN 1106374A CN 94115656 A CN94115656 A CN 94115656A CN 94115656 A CN94115656 A CN 94115656A CN 1106374 A CN1106374 A CN 1106374A
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- China
- Prior art keywords
- rhodium
- water
- reaction
- phosphine
- weight
- 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.)
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 230000020477 pH reduction Effects 0.000 title description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 18
- 239000000243 solution Substances 0.000 claims abstract description 18
- -1 carbon aldehydes Chemical class 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- 150000003284 rhodium compounds Chemical class 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 33
- 239000010948 rhodium Substances 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 20
- 229910052703 rhodium Inorganic materials 0.000 claims description 20
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 20
- 238000005984 hydrogenation reaction Methods 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 claims description 6
- 230000003165 hydrotropic effect Effects 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 125000001118 alkylidene group Chemical group 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000002877 alkyl aryl group Chemical group 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 150000001299 aldehydes Chemical class 0.000 description 16
- 238000007037 hydroformylation reaction Methods 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000012074 organic phase Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 9
- 238000005882 aldol condensation reaction Methods 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000007859 condensation product Substances 0.000 description 7
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical group C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000004014 plasticizer Substances 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 239000004902 Softening Agent Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000013543 active substance Substances 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 3
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000010517 secondary reaction Methods 0.000 description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 3
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 2
- QPRQEDXDYOZYLA-UHFFFAOYSA-N 2-methylbutan-1-ol Chemical compound CCC(C)CO QPRQEDXDYOZYLA-UHFFFAOYSA-N 0.000 description 2
- RCBGGJURENJHKV-UHFFFAOYSA-N 2-methylhept-1-ene Chemical compound CCCCCC(C)=C RCBGGJURENJHKV-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 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
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000005575 aldol reaction Methods 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- KSMVZQYAVGTKIV-UHFFFAOYSA-N decanal Chemical compound CCCCCCCCCC=O KSMVZQYAVGTKIV-UHFFFAOYSA-N 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Natural products O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- YWFDDXXMOPZFFM-UHFFFAOYSA-H rhodium(3+);trisulfate Chemical compound [Rh+3].[Rh+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O YWFDDXXMOPZFFM-UHFFFAOYSA-H 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RLPSARLYTKXVSE-UHFFFAOYSA-N 1-(1,3-thiazol-5-yl)ethanamine Chemical compound CC(N)C1=CN=CS1 RLPSARLYTKXVSE-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- YJLPJNLZCOKVAM-UHFFFAOYSA-N 2-ethylhexanoic acid;rhodium Chemical compound [Rh].CCCCC(CC)C(O)=O YJLPJNLZCOKVAM-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- KHBQMWCZKVMBLN-UHFFFAOYSA-N Benzenesulfonamide Chemical compound NS(=O)(=O)C1=CC=CC=C1 KHBQMWCZKVMBLN-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- IUVFPBKOOZTGMV-UHFFFAOYSA-N [Na].[Na].[Na].P Chemical compound [Na].[Na].[Na].P IUVFPBKOOZTGMV-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000003637 basic solution Substances 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
- 239000001273 butane Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000012259 ether extract Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 1
- FXHGMKSSBGDXIY-UHFFFAOYSA-N heptanal Chemical compound CCCCCCC=O FXHGMKSSBGDXIY-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical group CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-N methyl sulfate Chemical compound COS(O)(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 150000003112 potassium compounds Chemical class 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 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 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- 229910003450 rhodium oxide Inorganic materials 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- MWZNPHHDRLXXHO-UHFFFAOYSA-N rhodium;hydrate Chemical compound O.[Rh] MWZNPHHDRLXXHO-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000005621 tetraalkylammonium salts Chemical group 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/16—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxo-reaction combined with reduction
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/02—Monohydroxylic acyclic alcohols
- C07C31/125—Monohydroxylic acyclic alcohols containing five to twenty-two carbon atoms
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/822—Rhodium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/24—Phosphines
Abstract
使1,3-丁二烯在60~150℃、1~20兆帕和催化
剂水溶液存在下加氢甲酰化,催化剂含有至少一种水
溶性铑化合物和至少一种水溶性有机膦。在催化剂水溶液中将pH值维持在8~11,以提高生成正C5醛和正C5醛的二次反应产物的反应选择性。
Description
本发明涉及1,3-丁二烯加氢甲酰化的一种方法,目的在于得到2-丙基庚醇前体和其他有价值的产品。
与邻苯二甲酸酯化的有8~10个碳原子的一元伯醇大规模用作增塑剂,特别是用作聚氯乙烯的增塑剂。有较短碳链的醇产生有良好胶凝能力的增塑剂,但它的缺点是挥发性较高。作为邻苯二甲酸酯的较长链的醇导致增塑剂胶凝缓慢和低温稳定性较差。
邻苯二甲酸酯增塑剂的性质不仅由醇分子中碳链的长度而且由碳链的分支程度决定。有低分支程度的醇产生这样的酯增塑剂,这些酯增塑剂由于它们的低温柔软性高而特别受重视,所以分子中有8~10个碳原子基本上直链的醇作为醇组分变得越来越重要。使用它们的前题是,它们可大量地且廉价地得到。目前,2-乙基己醇是生产邻苯二甲酸酯的最重要的醇组分。但是,仍正在尽力寻找另外的原料作为制备有上述性质的醇的基础。
根据DE-C-2855421,将C9醇的邻苯二甲酸酯用作增塑料,它们通过C8烯烃的羰基合成反应、反应产物加氢以及醇与邻苯二甲酸酐酯化来得到。对这些原料烯烃提出了某些要求。它们应含有3~20%(重量)有异丁烷骨架的化合物和小于3%(重量)有季碳原子的化合物。90%(重量)以上的烯烃应为正辛烯、一甲基庚烯和二甲基已烯。最后,正辛烯和一甲基庚烯的总量与二甲基已烯的重量比应大于0.8。
以C10醇为基础的邻苯二甲酸是欧州专利申请书0366089的申请对象。C10醇以混合物的形式使用,它通过丁烯镏分的加氢甲酰化、生成的醛混合物的醇醛缩合以及随后加氢的方法来得到。
得到邻苯二甲酸二癸酯混合物的另一方法在欧州专利申请书0424767中有说明。这样的酯按以下多步法制备:丁烯混合物的二聚;生成的辛烯混合物的加氢甲酰化和加氢成为壬醇混合物;壬醇混合物脱氢生成壬烯混合物;壬烯混合物的加氢甲酰化和加氢成为癸醇混合物。
不论是原料不能充分得到和/或不能廉价得到,还是原料生成醇的转化过程与相当复杂的工艺过程连系在一起,不管怎样,已知的这些方法仍不能满足在经济和技术方面对工业规模上进行的加工提出的所有要求。
所以,本发明的目的是要开发这样一种方法:由廉价的原料出发,用技术上简单的方法生产所希望的醇类,如果需要的话,还生产其他有价值的产品。
本发明是一种1,3-丁二烯加氢甲酰化的方法,该法在温度为60~150℃、压力为1~20兆帕和催化剂水溶液存在下进行。该水溶液含有至少一种水溶性铑化合物和至少一种水溶性有机膦。该法特征在于:丁二烯在pH为8~11的水溶液中进行反应。
在通过软质石油和较高级的烃类热裂解来制备乙烯时,不可避免地生成相当大量的原料烯烃1,3-丁二烯。例如用选择性溶剂如乙腈、二甲基甲酰胺或N-甲基吡咯烷酮通过液-液萃取将1,3-丁二烯从裂解产物的C4镏分分离出来。此外,1,3-丁二烯很容易通过丁烷或丁烯脱氢得到。
为加氢甲酰化,使用目前的1,3-丁二烯商业产品,也就是纯度至少99.5%(重)的产品。其轭二烯的加氢甲酰化已经进行过多次,不仅在钴催化剂而且在铑催化剂作用下进行。例如Adkins和Williams说明了这种钴催化的反应(见J.Org.Chem.17,980(1952))。此种钴催化的反应产生中等产率的正-和异-戊醛的混合物,摩尔比为1∶1。
在铑催化剂存在下,1,3-丁二烯加氢甲酰化中可达到更有利的醛产率。铑与含三价磷原子的多齿配位体的络合化合物已证明是很有用的。基于这样的催化剂的方法例如在EP-B-33554中有说明。
在本发明中,1,3-丁二烯的加氢甲酰化在非均匀的两相体系中进行。这一方法的原理例如在DE-C-2627354中有说明。该法的特征是存在有机相和水相,有机相含有原料烯烃和反应产物,而水相中溶有催化剂。使用的催化剂是用水溶性有机膦作为配位体的水溶性铑络合物。水溶性膦特别是包括三烷基膦、三芳基膦、三(烷基、芳基)膦和亚烷基二膦和芳基二膦,它们至少含有一个被磺酸基或羧基取代了的有机基团。它们的制备方法是已知的,例如参见DE-C-2627354和DD-A-259194。特别适用的化合物是三苯基膦单磺酸盐、三苯基膦二磺酸盐和三苯基膦三磺酸盐,它们可作为单个化合物使用,或作为2或3种磺酸盐组分的混合物使用。令人惊奇的是,按照新的步骤,通过在反应过程中维持水相的pH值为8~11,可成功地显著提高生成C5醛和C5醛的二次产物的反应选择性。在加氢甲酰化过程中产生的C5醛的二次产物包括作为分子间缩合产物的不饱和C10醛,它可被加氢生成2-丙基庚醇。另一种二次产物是1,6-已二醛分子内缩合产物,它脱水和加氢后产生环戊烷甲醛,加氢后生成环戊烷甲醇,这是一种有机合成的有价值的中间体。已证明pH值在8.5~9.5范围内时,反应特别有效。
表明本发明方法特点的这一pH值与反应过程中的水相有关,因此实质上与由铑和水溶性有机膦组成的催化剂溶液有关。pH值可用已知的方法测定,例如用氢电极。
可通过将碱性试剂加到通常起弱碱性到弱酸性反应的催化剂溶液中的方法来调节pH值。适用于调节pH值的化合物是碱金属氢氧化物、碱金属碳酸盐,此外还有氨或胺类。如果溶液的碱性超过了要维持的pH值范围,可将无机酸(如磷酸或硫酸)、多价无机酸的酸式盐(如碱金属硫酸氢盐)、或水溶性有机酸如甲酸、醋酸、丙酸加到溶液中,一直到达到所需的pH值。也已证明有效的是,使用能准确调节pH范围并能保证pH值在整个反应周期内恒定的缓冲溶液。视所需要的pH值而定,适用的缓冲混合物是例如硼砂-HCl、硼砂-NaOH、NaHCO3-NaOH、H3BO3/KCl-NaOH。
在碱性溶液中催化剂的活性不下降,虽然照本技术领域熟练的技术人员的看法,对于催化剂的活性来说,羰基氢化铑的存在是有决定性作用。pH值对于丁二烯反应的速度和转化率都没有任何影响。生成的C5和C10醛的总量仍大致相同。
随着pH值的增加,只有一次反应产物(C5醛)和二次反应产物(C10醛)的比向有利于C10醛的方向变动。但是,当使用的催化剂溶液的pH值为11或11以上时,二次反应产物的生成明显减少。
可将催化剂溶液预制后加到反应体系中。但是,也可在反应条件下,在反应混合物中,由铑或至少一种铑化合物和至少一种水溶性有机膦的水溶液制备这种催化剂溶液,并有同样好的结果。
除了细分散形式的金属铑外,所用的铑源还可以是水溶性铑盐,如氯化铑、硫酸铑、酯酸铑,或者也可以是难溶于水或不溶于水的化合物,如2-乙基己酸铑或氧化铑。不仅铑和铑化合物,而且水溶性膦都可以作为纯物质或作为两种或两种以上组分的混合物使用。
在催化剂水溶液中的铑浓度按催化剂水溶液计为20~2000ppmw,优选50~700ppmw。
每摩尔铑使用4~100摩尔水溶性膦形式的磷。膦/铑比大于15∶1可抑制支链的初次反应产物的生成,有利于二醛的生成。膦/铑比对C10醛的生成也有影响。磷:铑摩尔比小于30∶1时,只生成很少醇醛缩合产物。直链一元醛和它的分子内醇醛缩合产物的总量几乎不受P/Rh比的影响。
1,3-丁二烯的加氢甲酰化在60~150℃之间,优选在90~120℃之间进行。在所述的温度范围内较高的温度有利于生成二醛。在约120℃以上,C5醛及其分子内醇醛缩合产物的生成减少。
1,3-丁二烯的加氢甲酰化优选在压力为1~10兆帕下进行。在所述的压力范围内较低的压力有利于生成C5醛,但使转化速度下降。压力超过10兆帕促进醇醛缩合反应。
如果将相转移剂(水溶增溶剂)加到催化剂的碱性水溶液中,可显著提高丁二烯单位时间的转化率以及C5醛缩合生成C10醛的转化率。相转移剂可改变两液相间界面的物理性质,使有机反应物很容易转移到催化剂水相中。
作为水溶增溶剂的化合物是已知的,它们的亲水基团是离子(阴离子或阳离子)基团或非离子基团。阴离子化合物包括有8~20个碳原子的羧酸的钠盐、钾盐或铵盐,特别是有12~18个碳原子的饱和脂肪酸盐,此外还有硫酸烷基酯、苯磺酸烷基酯和苯磷酸烷基酯。阳离子型水溶增溶剂的例子是四烷基铵盐和N-烷基吡啶鎓盐。非离子型相转移剂在水溶液中不能离解成离子。它们包括烷基聚乙二醇、烷基苯基聚乙二醇、脂肪酸的链烷醇酰胺和三烷基氧化胺。最后,两性电解质如氨基羧酸、甜菜碱和磺基甜菜碱也可用作水溶增溶剂。
特别是,化学式[A-N(R1R2R3)]+E-的阳离子型水溶增溶剂已证明是很有用的,其中A为有6~25个碳原子的直链或支链烷基,R1、R2、R3是相同的或不同的,为有1~5个碳原子的直链或支链烷基,以及E为阴离子,特别是硫酸根、四氟硼酸根、醋酸根、甲硫酸根、苯磺酸根、烷基苯磺酸根、甲苯磺酸根、乳酸根或柠檬酸根。
用简单的相分离方法将加氢甲酰化时生成的反应混合物从催化剂中分离出来。催化剂水溶液,如果需要的话,经过再生和调节铑和/或膦的浓度之后可再使用。用蒸镏的方法将有机相分成本身可使用的或进一步加工后可使用的组分。C10醛镏分可直接加氢成2-丙基庚醇。C5醛最好转化成醇醛缩合混合物。反应在碱性催化剂作用下按常规的方式进行。使用的催化剂为碱金属碳酸盐或碱金属氢氧化物,特别是钠化合物或钾化合物和胺类,优选的是叔胺,如三乙胺、三正丙胺、三正丁胺。采用60~160℃(特别是80~130℃)和常压或高压(一直到1兆帕)。反应时间为几分钟到几小时,特别与催化剂的类型和反应温度有关。由于相当高的反应速度,正C5醛特别与它本身或与异C5醛二聚生成C10醛。相反,而有分支的C5醛彼此之间的缩合进行得完全不显著。异C10醛加氢得到相应的饱和醇。适用于这一反应的加氢催化剂是含镍、铬或铜的催化剂。通常,加氢反应温度为100~180℃,压力为1~10兆帕。蒸镏异C10醇的混合物,使它纯化。C10醇不管是直接由氢甲酰化阶段得到或是由C5醛的醇醛缩合反应得到,它们都非常适合作为邻苯二甲酸酯增塑剂的醇组分。邻苯二甲酸酯的制备是已知的[见Ullmann,Encyclopadie der Technischen Chemie [Encyclopaedia of Industrial Chemistry(1979),Vol.18,page 536 ff.]。合适的是使邻苯二甲酸酐与癸醇混合物按摩尔比1∶2进行一步反应。通过催化剂和/或通过提高反应温度可提高反应速度。为了使反应平衡向生成酯的方向移动,从反应混合物中除去生成的水是必要的。
以下的实施例说明本发明,而不是把本发明限于所述的实施例。
在所有的实施例中以相同的方式进行这种试验。将含有16.4毫克铑(相当于410ppm铑的2-乙基已酸铑或硫酸铑)和不同数量的三(间-磺基苯基)膦三钠盐的40克催化剂水溶液在氩气保护下加到125毫升不锈钢高压釜中,若无其它说明,分别加入碳酸钠或硫酸来调节它的pH值。在110℃和10兆帕压力下用合成气(CO/H2体积比=1∶1)处理催化剂溶液90分钟。在每种情况下都将20克1,3-丁二烯加到预制过的催化剂中,用合成气调节到希望的反应压力,让混合物反应12小时。反应完全后,分离催化剂相和产物相。将催化剂相萃取三次,每次用15毫升乙醚。将产物相和醚萃取物合并,用硫酸钠干燥,并在铂-活性炭催化剂(10%(重量)铂)存在下,在140℃和20兆帕压力下加氢12小时。加氢产物用气相色谱法分析。
在实施例中,使用以下缩写:
正戊醇 n-P
2-甲基丁醇 2-MB
环戊烷甲醇 CPM
2-丙基庚醇 PH
实施例1
反应条件:120℃;20兆帕;水相/有机相(体积)=2∶1;CO/H2(体积)=1∶1,水相pH值:9。
实验 P:Rh n-P 2-MB CPM PH (n-P+PH)
摩尔 %(重) %(重) %(重) %(重) %(重)
1/1 15:1 45 4 7 9 54
1/2 30:1 48 5 9 10 58
1/3 40:1 48 4 8 13 61
1/4 60:1 38 4 7 20 58
1/5 80:1 42 3 8 18 60
实施例2
反应条件:120℃;20兆帕;P/Rh(摩尔)=60∶1;水相/有机相(体积)=2∶1;CO/H2(体积)=1∶1。
实验 pH n-P 2-MB CPM PH (n-P+PH)
%(重) %(重) %(重) %(重) %(重)
2/1 3 61 4 8 7 68
2/2 7 47 3 9 8 55
2/3 9 36 3 8 23 60
2/4 11 55 4 8 11 66
实施例3
反应条件:20兆帕;P/Rh(摩尔)=60∶1;水相/有机相(体积)=2∶1;CO/H2(体积)=1∶1,水相pH值:9。
实验 温度 n-P 2-MB CPM PH (n-P+PH)
%(重) %(重) %(重) %(重) %(重)
(℃)
3/1 100 31 2 5 27 58
3/2 120 36 3 8 23 59
3/3 140 29 3 8 7 36
实施例4
反应条件:120℃;P/Rh(摩尔)=60∶1;水相/有机相(体积)=2∶1;水相pH值:9。
实验 压力(兆帕) n-P 2-MB CPM PH (n-P+PH)
%(重) %(重) %(重) %(重) %(重)
4/1 4.0 57 2 12 8 65
4/2 6.0 67 4 10 10 77
4/3 8.0 55 3 9 13 68
4/4 12.0 49 4 8 18 67
4/5 16.0 28 2 6 23 51
4/6 20.0 36 3 8 23 59
4/7 26.0 52 3 8 15 67
实施例5
反应条件:100℃;5.5兆帕,P/Rh(摩尔)=60∶1;水相/有机相(体积)=2∶1;CO/H2(体积)=1∶1。
实验 pH n-P 2-MB CPM PH (n-P+PH)
%(重) %(重) %(重) %(重) %(重)
5/1 9 33 2 4 25 58
5/2 9 26 2 4 32 58
5/3 11 49 2 1 19 68
5/4 11 53 2 1 22 75
这些实验的结果表明,甚至在5兆帕左右的压力下,生成醇醛缩合产物2-丙基庚醛的反应选择性也是令人满意的。当从弱碱性区向更强的碱性区转变时,生成醇醛缩合产物的选择性下降。
实施例6
反应条件:100℃;5.5兆帕;P/Rh(摩尔)=60∶1;水相/有机相(体积)=2∶1;CO/H2(体积)=1∶1;水相pH值∶9(在实验6/2~6/4中用H3BO3/KCl-NaOH缓冲剂调节);DTAB:十二烷基三甲基溴化铵。
实验 表面 n-P 2-MB CPM PH (n-P+PH)
缓冲剂
活性剂 %(重) %(重) %(重) %(重) %(重)
6/1 DTAB - 24 2 8 20 44
6/2 - + 27 2 4 19 46
6/3 - + 32 2 5 18 50
6/4 DTAB + 22 3 7 29 51
结果表明,如果在加表面活性剂或缓冲剂混合物的情况下进行反应,生成直链C5醛及其醇醛缩合二次反应产物的反应选择性都下降。
以下实验说明当将表面活性剂加到催化剂溶液中时,单位时间的转化率增加。
压力降低/兆帕
反应时间/小时
不加表面活性剂 加表面活性剂
1 0.7 2.0
2 1.3 3.1
4 2.8 4.9
8 4.3 6.0
12 5.1 6.3
实施例7(对比实施例)
这一对比实施例表明,在本发明的反应条件下1-丁烯在加氢甲酰化中的反应与1,3-丁二烯完全不同。加氢反应产物主要是正戊醇,而且只含有很少数量的2-丙基庚醇。
反应条件:100℃;5.5兆帕;P/Rh(摩尔)=60∶1;水相/有机相(体积)=2∶1;CO/H2(体积)=1∶1;水相pH值:9。
实验 n-P 2-MB PH
%(重) %(重) %(重)
7/1 91 4 1
7/2 93 4 0.4
Claims (9)
1、一种1,3-丁二烯加氢甲酰化的方法,该法在温度为60~150℃、压力为1~20兆帕和催化剂水溶液存在下进行,催化剂含有至少一种水溶性铑化合物和至少一种水溶性有机膦,该法的特征在于:在pH值为8~11的水溶液中使丁二烯反应。
2、根据权利要求1的方法,其中水溶液的pH值为8.5~9.5。
3、根据权利要求1或2的方法,其中用缓冲剂混合物调节pH值。
4、根据权利要求1~3中1项或多项的方法,其中反应在90~120℃下进行。
5、根据权利要求1~4中1项或多项的方法,其中反应在压力为1~10兆帕下进行。
6、根据权利要求1~5中1项或多项的方法,其中催化剂水溶液中铑的浓度按催化剂水溶液计为20~2000ppmw,优选50~700ppmw。
7、根据权利要求1~6中1项或多项的方法,其中在水溶液中每摩尔铑有4~100摩尔磷,优选有10~60摩尔磷存在。
8、根据权利要求1~7中1项或多项的方法,其中所使用的水溶性膦为含有至少一个磺酸基或至少一个羧基的三芳基膦、三烷基膦、三(烷基-芳基)膦、亚烷基二膦或芳基二膦。
9、根据权利要求1~8中1项或多项的方法,其中水溶液含有一种水溶增溶剂。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4330489A DE4330489A1 (de) | 1993-09-09 | 1993-09-09 | Verfahren zur Hydroformylierung von Butadien-1,3 |
DEP4330489.3 | 1993-09-09 |
Publications (1)
Publication Number | Publication Date |
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CN1106374A true CN1106374A (zh) | 1995-08-09 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN94115656A Pending CN1106374A (zh) | 1993-09-09 | 1994-09-05 | 1,3-丁二烯加氢甲酰化法 |
Country Status (14)
Country | Link |
---|---|
US (1) | US5434312A (zh) |
EP (1) | EP0643031B1 (zh) |
JP (1) | JP2609429B2 (zh) |
KR (1) | KR100335516B1 (zh) |
CN (1) | CN1106374A (zh) |
AU (1) | AU671763B2 (zh) |
BR (1) | BR9403438A (zh) |
CA (1) | CA2131337A1 (zh) |
DE (2) | DE4330489A1 (zh) |
ES (1) | ES2112457T3 (zh) |
PL (1) | PL177092B1 (zh) |
SG (1) | SG44824A1 (zh) |
TW (1) | TW289017B (zh) |
ZA (1) | ZA946773B (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100496736C (zh) * | 2007-05-31 | 2009-06-10 | 南京大学 | 一种用于双环戊二烯氢甲酰化制醛的水溶性配体铑配合物催化剂 |
Families Citing this family (15)
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---|---|---|---|---|
DE19532394A1 (de) * | 1995-09-02 | 1997-03-06 | Hoechst Ag | Verfahren zur Herstellung von Pentenalen |
US6187970B1 (en) * | 1996-04-24 | 2001-02-13 | Union Carbide Chemicals & Plastics Technology Corporation | Processes for producing 1,6-hexanediols |
US5886237A (en) * | 1996-04-24 | 1999-03-23 | Union Carbide Chemicals & Plastics Technology Corporation | Processes for producing alkenals and alkenols |
US6172269B1 (en) * | 1996-04-24 | 2001-01-09 | Union Carbide Chemicals & Plastics Technology Corporation | Processes for producing 1,6-hexanediols |
US5821389A (en) * | 1996-04-24 | 1998-10-13 | Union Carbide Chemicals & Technology Corporation | Processes for producing hydroxyaldehydes |
US5817883A (en) * | 1996-04-24 | 1998-10-06 | Union Carbide Chemicals & Plastics Technology Corporation | Processes for producing hydroxyaldehydes |
US5962680A (en) * | 1997-04-15 | 1999-10-05 | Union Carbide Chemicals & Plastics Technology Corporation | Processes for producing epsilon caprolactams |
US5925754A (en) * | 1997-04-15 | 1999-07-20 | Union Carbide Chemicals & Plastics Technology Corporation | Epsilon caprolactam compositions |
US5886236A (en) * | 1997-04-15 | 1999-03-23 | Union Carbide Chemicals & Plastics Technology Corporation | Process for producing aldehyde acid salts |
DE102004029732A1 (de) | 2004-06-21 | 2006-01-19 | Basf Ag | Hilfsmittel enthaltend Cyclohexanpolycarbonsäurederivate |
BRPI0922742A2 (pt) * | 2008-12-05 | 2016-01-05 | Basf Se | adesivo ou selante, processo para preparar um adesivo ou selante, e, uso do adesivo ou selante. |
US20120220678A1 (en) | 2009-11-03 | 2012-08-30 | Christof Mehler | Thermoplastic compositions having improved flowability |
PL2576674T3 (pl) | 2010-06-01 | 2015-02-27 | Basf Se | Sposób wytwarzania spienialnych kompozycji polimerów styrenowych |
EP2716623A1 (de) | 2012-10-05 | 2014-04-09 | Basf Se | Verfahren zur Herstellung von Cyclohexanpolycarbonsäure-Derivaten mit geringem Nebenproduktanteil |
US20220177405A1 (en) | 2019-02-25 | 2022-06-09 | Basf Se | Method for processing benzene polycarboxylic acid esters and use of same to produce cyclohexane polycarboxylic acid esters |
Family Cites Families (10)
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US4248802A (en) * | 1975-06-20 | 1981-02-03 | Rhone-Poulenc Industries | Catalytic hydroformylation of olefins |
EP0033554B1 (en) * | 1980-02-04 | 1983-11-09 | Shell Internationale Researchmaatschappij B.V. | A process for the hydroformylation of conjugated dienes |
US4426542A (en) * | 1981-04-22 | 1984-01-17 | Monsanto Company | Synthesis of plasticizer and detergent alcohols |
DE3412335A1 (de) * | 1984-04-03 | 1985-10-10 | Ruhrchemie Ag, 4200 Oberhausen | Verfahren zur herstellung von aldehyden |
FR2571725B1 (fr) * | 1984-10-16 | 1987-09-18 | Rhone Poulenc Chim Base | Complexes rhodies, dinucleaires et hydrosolubles et leur utilisation comme catalyseur d'hydroformylation |
DE3534314A1 (de) * | 1985-09-26 | 1987-04-02 | Ruhrchemie Ag | Verfahren zur herstellung von aldehyden |
US4969953A (en) * | 1988-10-25 | 1990-11-13 | Mitsubishi Kasei Corporation | Alcohol mixture for plasticizer and method for producing the same |
IT1229512B (it) * | 1989-01-27 | 1991-09-03 | Eniricerche Spa | Procedimento per la idroformilazione catalitica di.olefine |
DE4210028A1 (de) * | 1992-03-27 | 1993-09-30 | Hoechst Ag | Decyclalkoholgemische, daraus erhältliche Phthalsäureester und ihre Verwendung als Weichmacher |
US5312996A (en) * | 1992-06-29 | 1994-05-17 | Union Carbide Chemicals & Plastics Technology Corporation | Hydroformylation process for producing 1,6-hexanedials |
-
1993
- 1993-09-09 DE DE4330489A patent/DE4330489A1/de not_active Withdrawn
-
1994
- 1994-06-30 TW TW083105928A patent/TW289017B/zh active
- 1994-08-31 EP EP94113600A patent/EP0643031B1/de not_active Expired - Lifetime
- 1994-08-31 DE DE59404520T patent/DE59404520D1/de not_active Expired - Fee Related
- 1994-08-31 ES ES94113600T patent/ES2112457T3/es not_active Expired - Lifetime
- 1994-08-31 SG SG1996008273A patent/SG44824A1/en unknown
- 1994-09-01 CA CA002131337A patent/CA2131337A1/en not_active Abandoned
- 1994-09-01 PL PL94304861A patent/PL177092B1/pl unknown
- 1994-09-02 ZA ZA946773A patent/ZA946773B/xx unknown
- 1994-09-02 KR KR1019940022057A patent/KR100335516B1/ko not_active IP Right Cessation
- 1994-09-02 JP JP6210067A patent/JP2609429B2/ja not_active Expired - Lifetime
- 1994-09-02 US US08/300,169 patent/US5434312A/en not_active Expired - Fee Related
- 1994-09-05 CN CN94115656A patent/CN1106374A/zh active Pending
- 1994-09-05 AU AU71660/94A patent/AU671763B2/en not_active Ceased
- 1994-09-05 BR BR9403438A patent/BR9403438A/pt not_active IP Right Cessation
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100496736C (zh) * | 2007-05-31 | 2009-06-10 | 南京大学 | 一种用于双环戊二烯氢甲酰化制醛的水溶性配体铑配合物催化剂 |
Also Published As
Publication number | Publication date |
---|---|
KR100335516B1 (ko) | 2002-11-13 |
JPH07173094A (ja) | 1995-07-11 |
EP0643031B1 (de) | 1997-11-05 |
CA2131337A1 (en) | 1995-03-10 |
SG44824A1 (en) | 1997-12-19 |
JP2609429B2 (ja) | 1997-05-14 |
KR950008459A (ko) | 1995-04-17 |
PL304861A1 (en) | 1995-03-20 |
BR9403438A (pt) | 1995-05-09 |
ES2112457T3 (es) | 1998-04-01 |
US5434312A (en) | 1995-07-18 |
ZA946773B (en) | 1995-04-03 |
PL177092B1 (pl) | 1999-09-30 |
EP0643031A1 (de) | 1995-03-15 |
AU7166094A (en) | 1995-03-23 |
TW289017B (zh) | 1996-10-21 |
DE59404520D1 (de) | 1997-12-11 |
DE4330489A1 (de) | 1995-03-16 |
AU671763B2 (en) | 1996-09-05 |
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