JPH0154332B2 - - Google Patents
Info
- Publication number
- JPH0154332B2 JPH0154332B2 JP56140078A JP14007881A JPH0154332B2 JP H0154332 B2 JPH0154332 B2 JP H0154332B2 JP 56140078 A JP56140078 A JP 56140078A JP 14007881 A JP14007881 A JP 14007881A JP H0154332 B2 JPH0154332 B2 JP H0154332B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- acid
- chloride
- palladium
- organic acid
- 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.)
- Expired
Links
- 239000003054 catalyst Substances 0.000 claims description 81
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 32
- -1 organic acid halide Chemical class 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 21
- 238000006606 decarbonylation reaction Methods 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 16
- 229910052763 palladium Inorganic materials 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- 229910052703 rhodium Inorganic materials 0.000 claims description 9
- 239000010948 rhodium Substances 0.000 claims description 9
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 6
- 150000007513 acids Chemical class 0.000 claims description 6
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 150000002823 nitrates Chemical class 0.000 claims description 4
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 239000011159 matrix material Substances 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 23
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 23
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 16
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- 238000003756 stirring Methods 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 12
- 239000000377 silicon dioxide Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 8
- 230000006324 decarbonylation Effects 0.000 description 7
- 150000002736 metal compounds Chemical class 0.000 description 7
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 6
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 4
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 2
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- 229960003280 cupric chloride Drugs 0.000 description 2
- IPIVAXLHTVNRBS-UHFFFAOYSA-N decanoyl chloride Chemical compound CCCCCCCCCC(Cl)=O IPIVAXLHTVNRBS-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- VNVXHHXFIDRQDE-UHFFFAOYSA-N octanoyl bromide Chemical compound CCCCCCCC(Br)=O VNVXHHXFIDRQDE-UHFFFAOYSA-N 0.000 description 2
- XGISHOFUAFNYQF-UHFFFAOYSA-N pentanoyl chloride Chemical compound CCCCC(Cl)=O XGISHOFUAFNYQF-UHFFFAOYSA-N 0.000 description 2
- IFXDDAVRUDKPBW-UHFFFAOYSA-N phenyl acetate;hydrochloride Chemical compound Cl.CC(=O)OC1=CC=CC=C1 IFXDDAVRUDKPBW-UHFFFAOYSA-N 0.000 description 2
- 239000005297 pyrex Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 150000003284 rhodium compounds Chemical class 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- RXNOYRCWKRFNIM-UHFFFAOYSA-N 2-carbonochloridoylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(Cl)=O RXNOYRCWKRFNIM-UHFFFAOYSA-N 0.000 description 1
- XKXQFMHLDGIWSC-UHFFFAOYSA-N 2-phenylpropanoyl bromide Chemical compound BrC(=O)C(C)C1=CC=CC=C1 XKXQFMHLDGIWSC-UHFFFAOYSA-N 0.000 description 1
- FOTITZRWZUAVPH-UHFFFAOYSA-N 2-phenylpropanoyl chloride Chemical compound ClC(=O)C(C)C1=CC=CC=C1 FOTITZRWZUAVPH-UHFFFAOYSA-N 0.000 description 1
- COGRXLLCNAFTEM-UHFFFAOYSA-N 2-phenylpropanoyl iodide Chemical compound C(C)(C1=CC=CC=C1)C(=O)I COGRXLLCNAFTEM-UHFFFAOYSA-N 0.000 description 1
- RKIDDEGICSMIJA-UHFFFAOYSA-N 4-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=C(Cl)C=C1 RKIDDEGICSMIJA-UHFFFAOYSA-N 0.000 description 1
- HPFMWXQXAHHFAA-UHFFFAOYSA-N 5-chlorobenzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC(Cl)=CC(C(Cl)=O)=C1 HPFMWXQXAHHFAA-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- PEKQDCBFCZDABW-UHFFFAOYSA-N I.CC(=O)OC1=CC=CC=C1 Chemical compound I.CC(=O)OC1=CC=CC=C1 PEKQDCBFCZDABW-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- FXXACINHVKSMDR-UHFFFAOYSA-N acetyl bromide Chemical compound CC(Br)=O FXXACINHVKSMDR-UHFFFAOYSA-N 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- LEKJTGQWLAUGQA-UHFFFAOYSA-N acetyl iodide Chemical compound CC(I)=O LEKJTGQWLAUGQA-UHFFFAOYSA-N 0.000 description 1
- PWAXUOGZOSVGBO-UHFFFAOYSA-N adipoyl chloride Chemical compound ClC(=O)CCCCC(Cl)=O PWAXUOGZOSVGBO-UHFFFAOYSA-N 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- FNGBYWBFWZVPPV-UHFFFAOYSA-N benzene-1,2,4,5-tetracarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=C(C(Cl)=O)C=C1C(Cl)=O FNGBYWBFWZVPPV-UHFFFAOYSA-N 0.000 description 1
- CJPIDIRJSIUWRJ-UHFFFAOYSA-N benzene-1,2,4-tricarbonyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C(C(Cl)=O)=C1 CJPIDIRJSIUWRJ-UHFFFAOYSA-N 0.000 description 1
- MDUYJUQASRFAOG-UHFFFAOYSA-N benzene-1,2-dicarbonyl bromide Chemical compound BrC(=O)C1=CC=CC=C1C(Br)=O MDUYJUQASRFAOG-UHFFFAOYSA-N 0.000 description 1
- SGQNRMORXLDASA-UHFFFAOYSA-N benzene-1,2-dicarbonyl iodide Chemical compound IC(=O)C1=CC=CC=C1C(I)=O SGQNRMORXLDASA-UHFFFAOYSA-N 0.000 description 1
- WSSOFJVBBYXRNR-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl bromide Chemical compound BrC(=O)C1=CC(C(Br)=O)=CC(C(Br)=O)=C1 WSSOFJVBBYXRNR-UHFFFAOYSA-N 0.000 description 1
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 description 1
- KQVAMRBJDWJIBJ-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl iodide Chemical compound IC(=O)C1=CC(C(I)=O)=CC(C(I)=O)=C1 KQVAMRBJDWJIBJ-UHFFFAOYSA-N 0.000 description 1
- YAZXITQPRUBWGP-UHFFFAOYSA-N benzene-1,3-dicarbonyl bromide Chemical compound BrC(=O)C1=CC=CC(C(Br)=O)=C1 YAZXITQPRUBWGP-UHFFFAOYSA-N 0.000 description 1
- KRJYMHQSKZCAEL-UHFFFAOYSA-N benzene-1,3-dicarbonyl iodide Chemical compound IC(=O)C1=CC=CC(C(I)=O)=C1 KRJYMHQSKZCAEL-UHFFFAOYSA-N 0.000 description 1
- PIVFDRVXTFJSIW-UHFFFAOYSA-N benzene-1,4-dicarbonyl bromide Chemical compound BrC(=O)C1=CC=C(C(Br)=O)C=C1 PIVFDRVXTFJSIW-UHFFFAOYSA-N 0.000 description 1
- UTVSIMFHBHNACC-UHFFFAOYSA-N benzene-1,4-dicarbonyl iodide Chemical compound IC(=O)C1=CC=C(C(I)=O)C=C1 UTVSIMFHBHNACC-UHFFFAOYSA-N 0.000 description 1
- AQIHMSVIAGNIDM-UHFFFAOYSA-N benzoyl bromide Chemical compound BrC(=O)C1=CC=CC=C1 AQIHMSVIAGNIDM-UHFFFAOYSA-N 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- WPCXDBCEDWUSOU-UHFFFAOYSA-N benzoyl iodide Chemical compound IC(=O)C1=CC=CC=C1 WPCXDBCEDWUSOU-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- QAWBXZYPFCFQLA-UHFFFAOYSA-N butanoyl bromide Chemical compound CCCC(Br)=O QAWBXZYPFCFQLA-UHFFFAOYSA-N 0.000 description 1
- ZEEDSWFDNIDARI-UHFFFAOYSA-N butanoyl iodide Chemical compound CCCC(I)=O ZEEDSWFDNIDARI-UHFFFAOYSA-N 0.000 description 1
- DVECBJCOGJRVPX-UHFFFAOYSA-N butyryl chloride Chemical compound CCCC(Cl)=O DVECBJCOGJRVPX-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- BZRRQSJJPUGBAA-UHFFFAOYSA-L cobalt(ii) bromide Chemical compound Br[Co]Br BZRRQSJJPUGBAA-UHFFFAOYSA-L 0.000 description 1
- 230000001609 comparable effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- YQAGVUODRGLPSR-UHFFFAOYSA-N decanedioyl dibromide Chemical compound BrC(=O)CCCCCCCCC(Br)=O YQAGVUODRGLPSR-UHFFFAOYSA-N 0.000 description 1
- WMPOZLHMGVKUEJ-UHFFFAOYSA-N decanedioyl dichloride Chemical compound ClC(=O)CCCCCCCCC(Cl)=O WMPOZLHMGVKUEJ-UHFFFAOYSA-N 0.000 description 1
- HKWLPLLFJNQXFJ-UHFFFAOYSA-N dodecanoyl bromide Chemical compound CCCCCCCCCCCC(Br)=O HKWLPLLFJNQXFJ-UHFFFAOYSA-N 0.000 description 1
- NQGIJDNPUZEBRU-UHFFFAOYSA-N dodecanoyl chloride Chemical compound CCCCCCCCCCCC(Cl)=O NQGIJDNPUZEBRU-UHFFFAOYSA-N 0.000 description 1
- XRXYPKAFOXNLBL-UHFFFAOYSA-N dodecanoyl iodide Chemical compound CCCCCCCCCCCC(I)=O XRXYPKAFOXNLBL-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229960001781 ferrous sulfate Drugs 0.000 description 1
- 229940107029 ferrous sulfate,dried Drugs 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- YVHINPHWBQIAEH-UHFFFAOYSA-N heptanedioyl dibromide Chemical compound BrC(=O)CCCCCC(Br)=O YVHINPHWBQIAEH-UHFFFAOYSA-N 0.000 description 1
- LVIMBOHJGMDKEJ-UHFFFAOYSA-N heptanedioyl dichloride Chemical compound ClC(=O)CCCCCC(Cl)=O LVIMBOHJGMDKEJ-UHFFFAOYSA-N 0.000 description 1
- UJGPNLWJDSIACI-UHFFFAOYSA-N hexanedioyl dibromide Chemical compound BrC(=O)CCCCC(Br)=O UJGPNLWJDSIACI-UHFFFAOYSA-N 0.000 description 1
- WLDRPCCNZOIMIR-UHFFFAOYSA-N hexanedioyl diiodide Chemical compound IC(=O)CCCCC(I)=O WLDRPCCNZOIMIR-UHFFFAOYSA-N 0.000 description 1
- YWGHUJQYGPDNKT-UHFFFAOYSA-N hexanoyl chloride Chemical compound CCCCCC(Cl)=O YWGHUJQYGPDNKT-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- RTQIXXGJUAQHLB-UHFFFAOYSA-N nonanoyl bromide Chemical compound CCCCCCCCC(Br)=O RTQIXXGJUAQHLB-UHFFFAOYSA-N 0.000 description 1
- NTQYXUJLILNTFH-UHFFFAOYSA-N nonanoyl chloride Chemical compound CCCCCCCCC(Cl)=O NTQYXUJLILNTFH-UHFFFAOYSA-N 0.000 description 1
- CVUJUGBBRBWFBL-UHFFFAOYSA-N nonanoyl iodide Chemical compound C(CCCCCCCC)(=O)I CVUJUGBBRBWFBL-UHFFFAOYSA-N 0.000 description 1
- FVENDMFTYXWGLT-UHFFFAOYSA-N octanedioyl dibromide Chemical compound BrC(=O)CCCCCCC(Br)=O FVENDMFTYXWGLT-UHFFFAOYSA-N 0.000 description 1
- PUIBKAHUQOOLSW-UHFFFAOYSA-N octanedioyl dichloride Chemical compound ClC(=O)CCCCCCC(Cl)=O PUIBKAHUQOOLSW-UHFFFAOYSA-N 0.000 description 1
- STRJPIQDBSJULU-UHFFFAOYSA-N octanedioyl diiodide Chemical compound IC(=O)CCCCCCC(I)=O STRJPIQDBSJULU-UHFFFAOYSA-N 0.000 description 1
- REEZZSHJLXOIHL-UHFFFAOYSA-N octanoyl chloride Chemical compound CCCCCCCC(Cl)=O REEZZSHJLXOIHL-UHFFFAOYSA-N 0.000 description 1
- PFIQBDPTFTXQFA-UHFFFAOYSA-N octanoyl iodide Chemical compound CCCCCCCC(I)=O PFIQBDPTFTXQFA-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical group 0.000 description 1
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 1
- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- FDOHPUYPQQKECS-UHFFFAOYSA-N pentanoyl bromide Chemical compound CCCCC(Br)=O FDOHPUYPQQKECS-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- JOGJKIHLHQDIOG-UHFFFAOYSA-N phenyl acetate hydrobromide Chemical compound CC(=O)OC1=CC=CC=C1.Br JOGJKIHLHQDIOG-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- RIBFXMJCUYXJDZ-UHFFFAOYSA-N propanoyl bromide Chemical compound CCC(Br)=O RIBFXMJCUYXJDZ-UHFFFAOYSA-N 0.000 description 1
- RZWZRACFZGVKFM-UHFFFAOYSA-N propanoyl chloride Chemical compound CCC(Cl)=O RZWZRACFZGVKFM-UHFFFAOYSA-N 0.000 description 1
- GLCSNYFRXVGJJF-UHFFFAOYSA-N propanoyl iodide Chemical compound CCC(I)=O GLCSNYFRXVGJJF-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- SULCFFJNLVZXGH-UHFFFAOYSA-N rhodium(3+);trinitrate;dihydrate Chemical compound O.O.[Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SULCFFJNLVZXGH-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- PYLHQFUYUMDOMF-UHFFFAOYSA-N tetradecanoyl bromide Chemical compound CCCCCCCCCCCCCC(Br)=O PYLHQFUYUMDOMF-UHFFFAOYSA-N 0.000 description 1
- GAYAGKAJQBQLJS-UHFFFAOYSA-N tetradecanoyl iodide Chemical compound CCCCCCCCCCCCCC(I)=O GAYAGKAJQBQLJS-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- TYLYVJBCMQFRCB-UHFFFAOYSA-K trichlororhodium;trihydrate Chemical compound O.O.O.[Cl-].[Cl-].[Cl-].[Rh+3] TYLYVJBCMQFRCB-UHFFFAOYSA-K 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は有機酸ハロゲン化物の脱カルボニル化
方法に関するものである。更に詳細には、新規な
脱カルボニル化触媒を用いる有機酸ハロゲン化物
の脱カルボニル化方法に関するものである。
有機酸ハロゲン化物を触媒を用いて部分又は完
全脱カルボニル化し、塩素置換された芳香族化合
物、塩素置換された脂肪族化合物等を製造する方
法は公知である。たとえば、芳香族酸ハロゲン化
物の部分又は完全脱カルボニル化反応において、
白金、パラジウム又はニツケルの金属又は化合物
を触媒として用いることは、英国特許第957957号
明細書に開示されている。しかし、上述のような
脱カルボニル化触媒を用いる場合そこに示された
条件で転化率が約50〜75%と低く、工業的に十分
満足されたものではない。また、脂肪族酸ハロゲ
ン化物の部分又は完全脱カルボニル化反応におい
て、パラジウム、ロジウムの金属又は化合物を触
媒として用いることは、J.Amer.Chem.Soc.,ジ
ヤーナル・オブ・アメリカン・ケミカル・ソサエ
テイー,90,94(1968)に開示されている。しか
しこの場合には、比較的反応は、進行し易い反応
であるにもかかわらずそこに示された条件で転化
率は、約70〜90%であり、必ずしも充分なもので
はない。
本発明者らは、高活性な脱カルボニル化触媒の
探索につき種々の研究の結果特定の金属又は金属
化合物の併用触媒が高活性な触媒作用を有するこ
とを見出し、本発明を完成するに至つた。
すなわち、本発明は有機酸ハロゲン化物の脱カ
ルボニル化反応に於いて、(a)パラジウム及びロジ
ウムから選ばれた金属又はこれらの金属の化合物
の少なくとも1種及び担体とは異なる鉄、コバル
ト、ニツケル、マグネシウム、亜鉛、銅、クロ
ム、ビスマス、モリブデン、白金および金の化合
物からなる群より選ばれた少くとも1種を担体に
担持せしめてなる触媒を使用することを特徴とす
る有機酸ハロゲン化物の脱カルボニル化方法であ
る。
以下に本発明方法を更に詳細に説明する。
本発明方法の実施に当り触媒の構成成分である
(a)成分としては、パラジウム及び/又はロジウム
の金属及び/又は金属化合物が用いられる。金属
化合物としては、塩化物、臭化物、ヨウ化物、酸
化物、硝酸塩、硫酸塩、塩化金属酸又はその塩等
があげられる。
特に塩化物、塩化金属酸又はその塩が好まし
い。触媒の一方の構成成分である(b)の金属化合物
としては、担体とは異なるベリリウム、マグネシ
ウム、ホウ素、アルミニウム、セリウム、ネオジ
ウム、チタン、ジルコニウム、ハフニウム、パナ
ジウム、ニオブ、タンタル、クロム、モリブデ
ン、タングステン、マンガン、レニウム、鉄、コ
バルト、ニツケル、ルテニウム、インジウム、白
金、金、銅、亜鉛、カドミウム、水銀、ゲルマニ
ウム、スズ、アンチモン、ビスマス、セレン、テ
ルル等の金属のハロゲン化物、酸化物、硫酸塩、
硝酸塩、金属酸又はその塩、塩化金属酸又はその
塩等があげられる。
特に好ましくは鉄、白金、銅、ビスマス、コバ
ルト、ニツケル、クロム、金のハロゲン化物、硫
酸塩、硝酸塩、塩化金属酸又はその塩が用いられ
る。
しかして、パラジウム又はロジウムの金属又は
金属化合物単独では脱カルボニル化活性が比較的
低いのであるが、これに単味では脱カルボニル化
活性が殆んどない(b)成分を併用することによつ
て、パラジウム及び/又はロジウムの金属又は化
合物に比べて脱カルボニル化活性が著しく増大す
るという効果が生ずるのである。
(a)成分と(b)成分の併用割合は、重量比で一般に
1:0.05〜20、好ましくは1:0.1〜10の範囲で
用いられる。(b)成分の併用割合が0.05未満になる
と併用効果が僅かしかなく、一方20以上になつて
も併用効果が僅かしかなくなるので好ましくな
い。
(a)成分のパラジウム及び/又はロジウムの金属
又はその金属化合物の担持率は、担体の重量当り
0.1重量%以上、特に0.2〜5重量%の範囲が好ま
しく用いられる。(a)成分の担持率が0.1重量%よ
り少量になると活性が低く生産性が低下するし、
また担持量が増えてもそれに比較した効果が得ら
れないので一般に10重量%以下量担持させて使用
される。
本発明方法の(a)及び(b)の触媒成分は担体に担持
させた状態で用いることが必要であり、担体とし
ては表面積1m2/g以上、好ましくは10m2/g以
上のものであればどのような担体でも利用できる
が、一般にはシリカ、アルミナ、活性炭、ケイソ
ウ土、チタニア、ジルコニア、クロミア、酸化亜
鉛、シリカアルミナ、シリカチタニア、シリカジ
ルコニア、アルミナチタニア、アルミナジルコニ
ア、シリカクロミア、アルミナクロミア、チタニ
アクロミア等の球状物、ペレツト、顆粒状物又は
粉末が用いられる。
好ましくは担体としては、アルミナ、シリカ、
シリカアルミナ、アルミナチタニア、アルミナジ
ルコニア、アルミナクロミア、シリカチタニア、
シリカジルコニア、シリカクロミア等が用いられ
る。
触媒調製法としては公知の方法が採用される
が、一般に担体に(a)のパラジウム及び/又はロジ
ウム化合物を含む溶液をしみ込ませた後、乾燥必
要に応じ還元し、その後(b)の金属化合物を含む溶
液を再度しみ込ませ乾燥、焼成する方法又は(a)成
分と(b)成分を溶媒にとかし、担体にしみ込ませ乾
燥、必要に応じ(a)成分をパラジウム、ロジウムに
還元し、焼成する方法等が用いられる。
本発明方法の実施に当たり原料有機酸ハロゲン
化物としては、ベンゾイルクロライド、ベンゾイ
ルブロミド、ベンゾイルヨーダイド、フタル酸ク
ロリド、フタル酸ブロミド、フタル酸ヨーダイ
ド、イソフタル酸クロリド、イソフタル酸ブロミ
ド、イソフタル酸ヨーダイド、テレフタル酸クロ
リド、テレフタル酸ブロミド、テレフタル酸ヨー
ダイド、トリメリツト酸クロリド、トリメリツト
酸ブロミド、トリメリツト酸ヨーダイド、ヘミメ
リツト酸クロリド、ヘミメリツト酸ブロミド、ヘ
ミメリツト酸ヨーダイド、トリメシン酸クロリ
ド、トリメシン酸ブロミド、トリメシン酸ヨーダ
イド、プレニト酸クロリド、プレニト酸ブロミ
ド、プレニト酸ヨーダイド、ピロメリト酸クロリ
ド、ピロメリト酸ブロミド、ピロメリト酸ヨーダ
イド等の芳香族酸ハロゲン化物及びハロゲン、ア
ルキル基、ニトロ基等の置換基を有する上記芳香
族酸ハロゲン化物、アセチルクロリド、アセチル
ブロミド、アセチルヨーダイド、プロピオン酸ク
ロリド、プロピオン酸ブロミド、プロピオン酸ヨ
ーダイド、酪酸クロリド、酪酸ブロミド、酪酸ヨ
ーダイド、吉草酸クロリド、吉草酸ブロミド、吉
草酸ヨーダイド、カプロン酸クロリド、カプロン
酸ブロミド、カプロン酸ヨーダイド、カプリル酸
クロリド、カプリル酸ブロミド、カプリル酸ヨー
ダイド、ペラルゴン酸クロリド、ペラルゴン酸ブ
ロミド、ペラルゴン酸ヨーダイド、カプリン酸ク
ロリド、カプリン酸ブロミド、ラウリン酸クロリ
ド、ラウリン酸ブロミド、ラウリン酸ヨーダイ
ド、ミリスチル酸クロリド、ミリスチル酸ブロミ
ド、ミリスチル酸ヨーダイド、アジピン酸クロリ
ド、アジピン酸ブロミド、アジピン酸ヨーダイ
ド、ピメリン酸クロリド、ピメリン酸ブロミド、
ピメリン酸ヨーダイド、スベリン酸クロリド、ス
ベリン酸ブロミド、スベリン酸ヨーダイド、セバ
シン酸クロリド、セバシン酸ブロミド、セバシン
酸ヨーダイド等の脂肪族酸ハロゲン化物及びハロ
ゲン化アルキル基等の置換基を有する脂肪族酸ハ
ロゲン化物、フエニル酢酸クロリド、フエニル酢
酸ブロミド、フエニル酢酸ヨーダイド、フエニル
プロピオン酸クロリド、フエニルプロピオン酸ブ
ロミド、フエニルプロピオン酸ヨーダイド等のフ
エニル基を有する脂肪族酸ハロゲン化物等をあげ
ることができる。特に本発明方法は、芳香族酸ハ
ロゲン化物の部分又は完全脱カルボニル化反応に
有効である。
本発明方法の実施に当り脱カルボニル化反応は
液相又は気相のいずれでも実施することができ、
また脱カルボニル化反応温度は約50〜450℃で行
なうことができるが、この温度は原料である有機
酸ハロゲン化物の反応性から決定されるものであ
る。一般にあまり高温で行なうと副生物の生成が
著しく増大する傾向があり、一方あまり低温にな
ると転化率が低下するようになるので、液相反応
では50〜300℃、気相反応では原料有機酸ハロゲ
ン化物が十分蒸発する温度から450℃までの温度
範囲で実施される。
圧力は特に制限されるものではなく、減圧下常
圧下、加圧下のいれでも実施することができる。
反応終了後、触媒にタール状の残渣が存在する
が、反応後の触媒を空気中で加熱、必要に応じ還
元することにより残渣の大部分は除去される。該
加熱後の触媒は新たに調製された触媒とほとんど
同様の作用を有するので、触媒の空気中での加熱
による再生を考えると触媒使用量はきわめて少く
なる。
以上詳述した本発明方法によれば従来知られて
いる触媒に比べ触媒活性が高く、触媒当りの有機
酸ハロゲン化物反応量が多くなるという工業的利
点がある。
以下に本発明方法を実施例により更に詳細に説
明するが、本発明方法はこれにより制限されるも
のではない。
実施例1、比較例1
塩化パラジウム1.67gを濃塩酸4mlと水10mlの
塩酸水溶液にとかし、さらに水を100ml加えて希
釈したのち、粒径3〜4mmφ、比表面積150m2/
gの活性アルミナ100gとよく混合し、ときどき
かきまぜながら乾固させた。その後、水素気流中
250℃において6時間還元を行なつた。これを触
媒A(比較用)と称す。
この触媒Aを10gとり、塩化第二鉄の5重量%
水溶液10gとよく混合し、ときどきかきまぜなが
ら乾固させ、その後空気中で400℃において4時
間乾燥を行なつた。これを触媒Bと称す。
触媒Aはパラジウムを1重量%担持するアルミ
ナ触媒、触媒Bはパラジウム1重量%、塩化第2
鉄5重量%を担持するアルミナ触媒であつた。
上記塩化第二鉄のかわりに電気陰性度の依存性
を見るために塩化ナトリウム、塩化カルシウム、
塩化マグネシウム、塩化亜鉛、塩化銅、塩化クロ
ムまたは塩化ビスマスを用いて同様にして触媒を
調製した。それらをそれぞれ触媒C.D.E.F.G.H.I
と称す。(触媒C.Dは比較用)
上記塩化第二鉄の5重量%水溶液のかわりに塩
化モリブデンの5重量%エタノール水溶液を用い
て、同様にして触媒を調製した。これを触媒Jと
称す。
これらの触媒について第1表にとりまとめた。
The present invention relates to a method for decarbonylating organic acid halides. More specifically, the present invention relates to a method for decarbonylating organic acid halides using a novel decarbonylation catalyst. A method for partially or completely decarbonylating an organic acid halide using a catalyst to produce chlorine-substituted aromatic compounds, chlorine-substituted aliphatic compounds, etc. is known. For example, in partial or complete decarbonylation reactions of aromatic acid halides,
The use of platinum, palladium or nickel metals or compounds as catalysts is disclosed in GB 957,957. However, when using the decarbonylation catalyst as described above, the conversion rate is as low as about 50 to 75% under the conditions shown therein, which is not fully satisfactory industrially. In addition, the use of palladium or rhodium metals or compounds as catalysts in partial or complete decarbonylation reactions of aliphatic acid halides has been published by J.Amer.Chem.Soc., Journal of the American Chemical Society, 90 , 94 (1968). However, in this case, although the reaction progresses relatively easily, the conversion rate is about 70 to 90% under the conditions shown therein, which is not necessarily sufficient. As a result of various studies in search of highly active decarbonylation catalysts, the present inventors discovered that a catalyst containing a specific metal or a combination of metal compounds has a highly active catalytic action, which led to the completion of the present invention. . That is, in the decarbonylation reaction of an organic acid halide, the present invention comprises (a) at least one metal selected from palladium and rhodium or a compound of these metals and a carrier different from iron, cobalt, nickel, A method for removing organic acid halides characterized by using a catalyst comprising at least one compound selected from the group consisting of magnesium, zinc, copper, chromium, bismuth, molybdenum, platinum and gold supported on a carrier. This is a carbonylation method. The method of the present invention will be explained in more detail below. It is a constituent component of the catalyst in carrying out the method of the present invention.
As component (a), a metal and/or a metal compound of palladium and/or rhodium is used. Examples of the metal compound include chlorides, bromides, iodides, oxides, nitrates, sulfates, chlorinated metal acids, or salts thereof. Particularly preferred are chlorides, chlorinated metal acids, or salts thereof. The metal compound (b) that is one of the components of the catalyst includes beryllium, magnesium, boron, aluminum, cerium, neodymium, titanium, zirconium, hafnium, panadium, niobium, tantalum, chromium, molybdenum, and tungsten, which are different from the carrier. , manganese, rhenium, iron, cobalt, nickel, ruthenium, indium, platinum, gold, copper, zinc, cadmium, mercury, germanium, tin, antimony, bismuth, selenium, tellurium, and other metal halides, oxides, and sulfates. ,
Examples include nitrates, metal acids or salts thereof, chlorinated metal acids or salts thereof, and the like. Particularly preferred are iron, platinum, copper, bismuth, cobalt, nickel, chromium, gold halides, sulfates, nitrates, chlorinated metal acids, or salts thereof. Therefore, the decarbonylation activity of palladium or rhodium metal or metal compound alone is relatively low, but by combining it with component (b), which alone has almost no decarbonylation activity, The effect is that the decarbonylation activity is significantly increased compared to metals or compounds of palladium and/or rhodium. The weight ratio of component (a) and component (b) is generally 1:0.05 to 20, preferably 1:0.1 to 10. If the ratio of component (b) used in combination is less than 0.05, the combination effect will be slight, and even if it is 20 or more, the combination effect will be slight, which is not preferable. (a) The supporting ratio of component palladium and/or rhodium metal or its metal compound is per weight of the carrier.
It is preferably used in an amount of 0.1% by weight or more, particularly in the range of 0.2 to 5% by weight. If the loading rate of component (a) is less than 0.1% by weight, the activity will be low and productivity will decrease;
Furthermore, even if the amount supported is increased, no comparable effect can be obtained, so the amount supported is generally 10% by weight or less. The catalyst components (a) and (b) of the method of the present invention must be used in a state supported on a carrier, and the carrier may have a surface area of 1 m 2 /g or more, preferably 10 m 2 /g or more. Any carrier can be used, but commonly silica, alumina, activated carbon, diatomaceous earth, titania, zirconia, chromia, zinc oxide, silica alumina, silica titania, silica zirconia, alumina titania, alumina zirconia, silica chromia, alumina chromia Spheres, pellets, granules, or powders such as , titania chromia, etc. are used. Preferably, the carrier is alumina, silica,
Silica alumina, alumina titania, alumina zirconia, alumina chromia, silica titania,
Silica zirconia, silica chromia, etc. are used. A known method is used to prepare the catalyst, but generally the carrier is impregnated with a solution containing the palladium and/or rhodium compound (a), dried and reduced if necessary, and then the metal compound (b) is impregnated with a solution containing the palladium and/or rhodium compound. Components (a) and (b) are dissolved in a solvent, impregnated into a carrier, dried, and if necessary, component (a) is reduced to palladium or rhodium and fired. methods etc. are used. In carrying out the method of the present invention, the raw material organic acid halides include benzoyl chloride, benzoyl bromide, benzoyl iodide, phthalic acid chloride, phthalic acid bromide, phthalic acid iodide, isophthalic acid chloride, isophthalic acid bromide, isophthalic acid iodide, and terephthalic acid. Chloride, terephthalic acid bromide, terephthalic acid iodide, trimellitic acid chloride, trimellitic acid bromide, trimellitic acid iodide, hemimellitic acid chloride, hemimellitic acid bromide, hemimellitic acid iodide, trimesic acid chloride, trimesic acid bromide, trimesic acid iodide, prenitic acid chloride, Aromatic acid halides such as prenitic acid bromide, prenic acid iodide, pyromellitic acid chloride, pyromellitic acid bromide, pyromellitic acid iodide, and the above aromatic acid halides having substituents such as halogen, alkyl group, and nitro group, acetyl chloride, Acetyl bromide, acetyl iodide, propionic acid chloride, propionic acid bromide, propionic acid iodide, butyric acid chloride, butyric acid bromide, butyric acid iodide, valeric acid chloride, valeric acid bromide, valeric acid chloride, caproic acid chloride, caproic acid bromide, caproic acid Iodide, caprylic acid chloride, caprylic acid bromide, caprylic acid iodide, pelargonic acid chloride, pelargonic acid bromide, pelargonic acid iodide, capric acid chloride, capric acid chloride, lauric acid chloride, lauric acid bromide, lauric acid iodide, myristylic acid chloride, myristic acid bromide, myristic acid iodide, adipic acid chloride, adipic acid bromide, adipic acid iodide, pimelic acid chloride, pimelic acid bromide,
Aliphatic acid halides such as pimelic acid iodide, suberic acid chloride, suberic acid bromide, suberic acid iodide, sebacic acid chloride, sebacic acid bromide, sebacic acid iodide, and aliphatic acid halides having substituents such as halogenated alkyl groups , phenyl acetate chloride, phenyl acetate bromide, phenyl acetate iodide, phenylpropionic acid chloride, phenylpropionic acid bromide, phenylpropionic acid iodide, and other aliphatic acid halides having a phenyl group. In particular, the method of the present invention is effective for partial or complete decarbonylation reactions of aromatic acid halides. In carrying out the method of the present invention, the decarbonylation reaction can be carried out in either liquid phase or gas phase,
Further, the decarbonylation reaction temperature can be carried out at about 50 to 450°C, but this temperature is determined depending on the reactivity of the organic acid halide used as the raw material. In general, if the temperature is too high, the formation of by-products tends to increase significantly, while if the temperature is too low, the conversion rate will decrease. The temperature range is from the temperature at which the compound evaporates sufficiently to 450°C. The pressure is not particularly limited, and the reaction can be carried out either under reduced pressure, normal pressure, or increased pressure. After the completion of the reaction, tar-like residue is present on the catalyst, but most of the residue is removed by heating the reacted catalyst in air and reducing it if necessary. Since the heated catalyst has almost the same effect as a freshly prepared catalyst, the amount of catalyst used becomes extremely small when regeneration by heating the catalyst in air is considered. The method of the present invention described in detail above has industrial advantages in that the catalytic activity is higher than that of conventionally known catalysts, and the amount of organic acid halide reaction per catalyst is increased. The method of the present invention will be explained in more detail with reference to examples below, but the method of the present invention is not limited thereto. Example 1, Comparative Example 1 1.67 g of palladium chloride was dissolved in a hydrochloric acid aqueous solution of 4 ml of concentrated hydrochloric acid and 10 ml of water, and after diluting by adding 100 ml of water, a particle size of 3-4 mmφ and a specific surface area of 150 m 2 /
The mixture was thoroughly mixed with 100 g of activated alumina, and dried with occasional stirring. Then, in a hydrogen stream
Reduction was carried out at 250°C for 6 hours. This is called catalyst A (for comparison). Take 10g of this catalyst A and 5% by weight of ferric chloride.
The mixture was thoroughly mixed with 10 g of an aqueous solution, dried with occasional stirring, and then dried in air at 400° C. for 4 hours. This is called catalyst B. Catalyst A is an alumina catalyst supporting 1% by weight of palladium, Catalyst B is an alumina catalyst supporting 1% by weight of palladium and dichloride.
It was an alumina catalyst supporting 5% by weight of iron. In order to see the electronegativity dependence, instead of the above ferric chloride, sodium chloride, calcium chloride,
Catalysts were similarly prepared using magnesium chloride, zinc chloride, copper chloride, chromium chloride or bismuth chloride. catalyze them respectively CDEFGHI
It is called. (Catalyst CD is for comparison) A catalyst was prepared in the same manner using a 5% by weight ethanol aqueous solution of molybdenum chloride instead of the 5% by weight aqueous solution of ferric chloride. This is called catalyst J. Table 1 summarizes these catalysts.
【表】【table】
【表】
次に内径17mmφのパイレツクスガラス管に前記
触媒を6ml充填し、360℃に加熱した後、イソフ
タル酸クロリドを30体積%含む窒素ガスを3l/
Hrの速度で流通接触せしめ脱カルボニル化反応
を2時間行つた。反応管出口で得られた一酸化炭
素以外の有機化合物からなる生成物の組成を分析
したところ、第2表のようであつた。[Table] Next, fill a Pyrex glass tube with an inner diameter of 17 mmφ with 6 ml of the catalyst, heat it to 360°C, and then add 3 liters of nitrogen gas containing 30% by volume of isophthalic acid chloride.
The decarbonylation reaction was carried out for 2 hours by flowing contact at a rate of Hr. When the composition of the product consisting of organic compounds other than carbon monoxide obtained at the outlet of the reaction tube was analyzed, it was as shown in Table 2.
【表】
反応後の触媒をとり出し、空気中6時間400℃
に加熱し、金属酸化物触媒に再生した。
再生後上記反応を再度行つたが、触媒性能は第
2表の結果ほとんど同一であつた。
実施例2、比較例2
撹拌機付きの100mlの丸底フラスコ中にカプリ
ル酸ブロミド50gと各触媒4gを添加し、200℃
の温度に加熱し5時間脱カルボニル化反応させ
た。触媒は前記実施例1に示したものを乳ばちで
粉砕して用いた。反応後得られた有機酸からなる
生成物の組成を分析したところ第3表のようであ
つた。[Table] After the reaction, the catalyst was taken out and placed in air at 400℃ for 6 hours.
was heated to regenerate it into a metal oxide catalyst. After regeneration, the above reaction was carried out again, and the catalyst performance was almost the same as shown in Table 2. Example 2, Comparative Example 2 50 g of caprylic acid bromide and 4 g of each catalyst were added to a 100 ml round bottom flask equipped with a stirrer, and heated at 200°C.
The decarbonylation reaction was carried out for 5 hours by heating to a temperature of . The catalyst shown in Example 1 was used by crushing it with a mortar. The composition of the organic acid product obtained after the reaction was analyzed and was as shown in Table 3.
【表】
実施例3、比較例3
撹拌機付きの100mlの丸底フラスコ中にフエニ
ル酢酸クロリド50gと参考例1の触媒B50gを添
加し、250℃に加熱し、4時間脱カルボニル化反
応を実施した後、生成物の組成をしらべたところ
第4表のようであつた。
実施例1の触媒B及びGについても同様の実験
を行なつた。その結果を第4表に示す。[Table] Example 3, Comparative Example 3 50 g of phenyl acetate chloride and 50 g of catalyst B from Reference Example 1 were added to a 100 ml round bottom flask equipped with a stirrer, heated to 250°C, and decarbonylated for 4 hours. After that, the composition of the product was as shown in Table 4. Similar experiments were conducted for catalysts B and G of Example 1. The results are shown in Table 4.
【表】
実施例4、比較例4
塩化ロジウム・三水和物5.16gを濃塩酸6mlと
水16mlの塩酸水溶液にとかし、さらに水を130ml
加えて希釈したのち、粒径3〜4mmφ、比表面積
210m2/gのシリカアルミナ担体とよく混合し、
ときどきかきまぜながら乾固させた。その後水素
気流中で300℃において、4時間還元を行つた。
これを触媒K(比較用)と称す。
触媒Kを10gとり、塩化白金酸の1.2重量%水
溶液10mlとよく混合し、ときどきかきまぜながら
乾固させ、その後空気中で300℃において4時間
乾燥を行つた。これを触媒Lと称す。
塩化白金酸の1.2重量%水溶液にかえ、塩化金
酸の1重量%水溶液10gを用いて、同様に触媒を
調製した。これを触媒Mと称す。[Table] Example 4, Comparative Example 4 Dissolve 5.16 g of rhodium chloride trihydrate in a hydrochloric acid aqueous solution of 6 ml of concentrated hydrochloric acid and 16 ml of water, and then add 130 ml of water.
After adding and diluting, the particle size is 3 to 4 mmφ and the specific surface area is
Mix well with 210 m 2 /g of silica alumina support,
The mixture was allowed to dry while stirring occasionally. Thereafter, reduction was carried out at 300° C. for 4 hours in a hydrogen stream.
This is called catalyst K (for comparison). 10 g of catalyst K was taken and thoroughly mixed with 10 ml of a 1.2% by weight aqueous solution of chloroplatinic acid, dried with occasional stirring, and then dried in air at 300° C. for 4 hours. This is called catalyst L. A catalyst was similarly prepared using 10 g of a 1% by weight aqueous solution of chloroauric acid instead of the 1.2% by weight aqueous solution of chloroplatinic acid. This is called catalyst M.
【表】
次に、実施例1と同一の反応管に前記のごとく
調製した触媒6mlを充填し、360℃に加熱した後
5−クロルイソフタル酸クロリドを30体積%含む
窒素ガスを3l/Hの速度で流通接触せしめ、脱カ
ルボニル化反応を2時間行つた。反応管出口で得
られた一酸化炭素以外の有機化合物からなる生成
物の組成を分析したところ、第6表のようであつ
た。[Table] Next, 6 ml of the catalyst prepared as described above was filled in the same reaction tube as in Example 1, heated to 360°C, and nitrogen gas containing 30% by volume of 5-chloroisophthalic acid chloride was added at a rate of 3 liters/h. The decarbonylation reaction was carried out for 2 hours by flowing contact at high speed. When the composition of the product consisting of organic compounds other than carbon monoxide obtained at the outlet of the reaction tube was analyzed, it was as shown in Table 6.
【表】
実施例 5
触媒A10gを硫酸第一鉄の5重量%溶液10gと
各々よく混合し、ときどきかきまぜながら乾固さ
せ、その後空気中で400℃において4時間乾燥を
行つた。この触媒Nと称する。
上記、硫酸第一鉄に代えて硝酸第二鉄を用いた
以外は同様にして触媒を調製した。この触媒を触
媒Oと称する。
触媒NまたはOを用いて実施例4と同様の反応
を行つた。結果を第7表に示す。[Table] Example 5 10 g of catalyst A was thoroughly mixed with 10 g of a 5% by weight solution of ferrous sulfate, dried with occasional stirring, and then dried in air at 400° C. for 4 hours. This catalyst is called catalyst N. A catalyst was prepared in the same manner as above except that ferric nitrate was used instead of ferrous sulfate. This catalyst is called catalyst O. A reaction similar to Example 4 was carried out using catalyst N or O. The results are shown in Table 7.
【表】
実施例6、比較例5
触媒A10gと塩化第二鉄の0.03,0.5,2,10重
量%水溶液10gとそれぞれよく混合し、ときどき
かきまぜながら乾固させ、その後空気中で400℃
において、4時間乾燥を行つた。これらをそれぞ
れ触媒P,Q,R,Sと称す。これらの触媒は塩
化第二鉄をそれぞれ0.03,0.5,2,10重量%担
持するパラジウム1塩化第二鉄1アルミナ触媒で
ある。
次に触媒P,Q,RまたはSを用いて実施例1
と同一の操作にて脱カルボニル化反応を重施し
た。結果を第8表に示す。[Table] Example 6, Comparative Example 5 10 g of catalyst A and 10 g of 0.03, 0.5, 2, and 10% by weight aqueous solution of ferric chloride were mixed well, and dried with occasional stirring, and then heated at 400°C in air.
Drying was carried out for 4 hours. These are called catalysts P, Q, R, and S, respectively. These catalysts are palladium, ferric chloride, and alumina catalysts carrying 0.03, 0.5, 2, and 10% by weight of ferric chloride, respectively. Next, using catalyst P, Q, R or S, Example 1
The decarbonylation reaction was carried out in the same manner as above. The results are shown in Table 8.
【表】
実施例 7
硝酸ニツケル・六水和物24.8gを150mlの水に
とかし、粒径40mmφ、比表面積300m2/gの活性
アルミナ95gとよく混合し、ときどきかきまぜな
がら、蒸発乾固させた。その後空気中500℃6時
間焼成を行つた。
焼成後、このうちから50gをとり、塩化パラジ
ウム0.83gを含む塩酸溶液50g中に浸漬し、よく
撹拌混合しながら、蒸発乾固させる。その後水素
気流中400℃6時間還元を行つた。これを触媒T
と称す。
触媒Tを用いて、実施例1と同様の反応を行つ
た。結果を第9表に示す。[Table] Example 7 24.8 g of nickel nitrate hexahydrate was dissolved in 150 ml of water, mixed well with 95 g of activated alumina with a particle size of 40 mmφ and a specific surface area of 300 m 2 /g, and evaporated to dryness while stirring occasionally. . Thereafter, it was fired in air at 500°C for 6 hours. After firing, 50 g of this was taken, immersed in 50 g of a hydrochloric acid solution containing 0.83 g of palladium chloride, and evaporated to dryness while thoroughly stirring and mixing. Thereafter, reduction was carried out at 400°C for 6 hours in a hydrogen stream. This is catalyst T
It is called. A reaction similar to that in Example 1 was carried out using Catalyst T. The results are shown in Table 9.
【表】
比較例 6
塩化第二鉄5gを水100mlにとかした後、粒径
3〜4mmφ、比表面積150m2/gの活性アルミナ
100gとよく混合し、ときどきかきまぜながら乾
固させ、その後空気中で400℃において、4時間
乾燥を行つた。これを触媒Uと称す。
上記塩化第二鉄のかわりに、塩化マグネシウ
ム、塩化亜鉛、塩化銅、塩化クロム、塩化ビスマ
スを用いて、同様にして触媒を調製した。これら
をそれぞれ触媒V,W,X,Y,Zと称す。[Table] Comparative Example 6 After dissolving 5 g of ferric chloride in 100 ml of water, activated alumina with a particle size of 3 to 4 mmφ and a specific surface area of 150 m 2 /g was prepared.
The mixture was thoroughly mixed with 100 g and dried with occasional stirring, and then dried in air at 400° C. for 4 hours. This is called catalyst U. Catalysts were prepared in the same manner using magnesium chloride, zinc chloride, copper chloride, chromium chloride, and bismuth chloride instead of the ferric chloride. These are called catalysts V, W, X, Y, and Z, respectively.
【表】【table】
【表】
実施例1と同一の方法により、脱カルボニル化
を行つた。結果を第11表に示す。[Table] Decarbonylation was carried out by the same method as in Example 1. The results are shown in Table 11.
【表】
実施例 8
硝酸ロジウム二水和物3.37gを水100mlにとか
したのち、粒径4mmφ比表面積100m2/gのアル
ミナチタニア100gとよく混合し、ときどきかき
まぜながら乾固させた。その後空気気流中で200
℃にいて4時間乾燥を行つた。
乾燥後の触媒を10gとり、塩化第二銅の4重量
%水溶液20gとよく混合し、ときどきかきまぜな
がら乾固させ、その後空気中400℃において、6
時間焼成を行つた。これを触媒と称す。
触媒は硝酸ロジウムとして3重量%、塩化第
二銅8重量%を担持するアルミナチタニア触媒で
あつた。
これとは別に塩化パラジウム2.17gを濃塩酸4
mlと水10mlの塩酸水溶液にとかしさらに水を100
ml加えて希釈したのち、粒径4mmφ比表面積100
m2/gのアルミナジルコニア100gとよく混合し、
ときどきかきまぜながら乾固させた。その後空気
気流中で200℃において、4時間乾燥を行つた。
乾燥後の触媒を10gとり臭化コバルトの3重量
%水溶液20gとよく混合し、ときどきかきまぜな
がら乾固させ、その後空気中500℃において、6
時間焼成を行つた。これを触媒と称す。
触媒は酸化パラジウム1.5重量%、塩化コバ
ルト6重量%を担持するアルミナジルコニア触媒
であつた。触媒の調製方法において焼成温度を
200℃にかえた以外はまつたく同様にして触媒を
調製した。得られた触媒を触媒と称す。触媒
は塩化パラジウム2.2重量%、塩化コバルト6重
量%を担持するアルミナ、ジルコニア触媒であつ
た。次に、内径17mmφのパイレツクスガラス管に
前記のごとく調製した触媒6mlを充填し、360℃
に加熱した后、パラクロルベンゾイルクロリドを
20体積%含む窒素ガスを3/Hの速度で流通接
触せしめ、脱カルボニル化反応を2時間行つた。
反応管出口で得られた一酸化炭素以外の有機化合
物からなる生成物の組成を分析したところ第12表
のようであつた。[Table] Example 8 After dissolving 3.37 g of rhodium nitrate dihydrate in 100 ml of water, it was thoroughly mixed with 100 g of alumina titania having a particle diameter of 4 mmφ and a specific surface area of 100 m 2 /g, and was dried with occasional stirring. then 200 in air stream
Drying was carried out at ℃ for 4 hours. Take 10g of the dried catalyst, mix well with 20g of a 4% by weight aqueous solution of cupric chloride, dry with occasional stirring, and then heat in air at 400°C for 6
Time firing was performed. This is called a catalyst. The catalyst was an alumina titania catalyst supporting 3% by weight of rhodium nitrate and 8% by weight of cupric chloride. Separately, add 2.17 g of palladium chloride to 4 ml of concentrated hydrochloric acid.
Dissolve 10ml of water in a hydrochloric acid aqueous solution and add 100ml of water.
After adding ml and diluting, the particle size is 4mmφ and the specific surface area is 100.
Mix well with 100g of alumina zirconia of m 2 /g,
The mixture was allowed to dry while stirring occasionally. Thereafter, it was dried for 4 hours at 200° C. in an air stream. Take 10g of the dried catalyst, mix well with 20g of a 3% by weight aqueous solution of cobalt bromide, dry with occasional stirring, and then heat in air at 500°C for 6
Time firing was performed. This is called a catalyst. The catalyst was an alumina zirconia catalyst supporting 1.5% by weight of palladium oxide and 6% by weight of cobalt chloride. Calcination temperature in catalyst preparation method
A catalyst was prepared in the same manner as Matsutaku except that the temperature was changed to 200°C. The obtained catalyst is called a catalyst. The catalyst was an alumina, zirconia catalyst supporting 2.2% by weight of palladium chloride and 6% by weight of cobalt chloride. Next, 6 ml of the catalyst prepared as above was filled into a Pyrex glass tube with an inner diameter of 17 mmφ, and the temperature was increased to 360°C.
After heating parachlorobenzoyl chloride to
Nitrogen gas containing 20% by volume was brought into contact by flowing at a rate of 3/H, and the decarbonylation reaction was carried out for 2 hours.
When the composition of the product consisting of organic compounds other than carbon monoxide obtained at the outlet of the reaction tube was analyzed, it was as shown in Table 12.
Claims (1)
おいて、(a)パラジウム及びロジウムから選ばれた
金属又はこれら金属の化合物のうちの少なくとも
1種及び(b)鉄、コバルト、ニツケル、マグネシウ
ム、亜鉛、銅、クロム、ビスマス、モリブデン、
白金、金のハロゲン化物、硫酸塩、硝酸塩、塩化
金属酸又はその塩の少なくとも1種を垣体に担持
せしめてなる触媒を用いることを特徴とする有機
酸ハロゲン化物の脱カルボニル化方法。 2 (a)成分と(b)成分の併用割合が重量比で1:
0.05〜20である特許請求の範囲第1項記載の有機
酸ハロゲン化物の脱カルボニル化方法。 3 触媒成分(a)の担持率が担体当たり0.1重量%
以上である特許請求の範囲第1または2項記載の
有機酸ハロゲン化物の脱カルボニル化方法。 4 (a)成分がパラジウム、ロジウム、パラジウム
又はロジウムの塩化物、臭化物、ヨウ化物、酸化
物、硝酸塩、硫酸塩、塩化金属酸又はその塩であ
る特許請求の範囲第1,2または3項記載の有機
酸ハロゲン化物の脱カルボニル化方法。[Scope of Claims] 1. In the decarbonylation reaction of an organic acid halide, (a) at least one metal selected from palladium and rhodium or a compound of these metals, and (b) iron, cobalt, nickel, Magnesium, zinc, copper, chromium, bismuth, molybdenum,
A method for decarbonylating organic acid halides, which comprises using a catalyst comprising at least one of platinum, gold halides, sulfates, nitrates, chlorinated metal acids, or salts thereof supported on a matrix. 2 The combined ratio of component (a) and component (b) is 1:
0.05-20. The method for decarbonylating an organic acid halide according to claim 1. 3 Supporting rate of catalyst component (a) is 0.1% by weight per carrier
The method for decarbonylating an organic acid halide according to claim 1 or 2, which is the above. 4. Claims 1, 2, or 3, wherein component (a) is palladium, rhodium, palladium, or a chloride, bromide, iodide, oxide, nitrate, sulfate, chloride metal acid, or a salt thereof. A method for decarbonylating organic acid halides.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP14007881A JPS5841828A (en) | 1981-09-04 | 1981-09-04 | Decarbonylating method of organic acid halide |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP14007881A JPS5841828A (en) | 1981-09-04 | 1981-09-04 | Decarbonylating method of organic acid halide |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5841828A JPS5841828A (en) | 1983-03-11 |
JPH0154332B2 true JPH0154332B2 (en) | 1989-11-17 |
Family
ID=15260444
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP14007881A Granted JPS5841828A (en) | 1981-09-04 | 1981-09-04 | Decarbonylating method of organic acid halide |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5841828A (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5375054B2 (en) * | 2007-11-30 | 2013-12-25 | 三菱化学株式会社 | Method for producing furan compound |
JP5315679B2 (en) * | 2007-11-30 | 2013-10-16 | 三菱化学株式会社 | Method for producing furan compound |
WO2009069714A1 (en) * | 2007-11-30 | 2009-06-04 | Mitsubishi Chemical Corporation | Process for production of furan compound |
JP6242733B2 (en) * | 2013-04-23 | 2017-12-06 | 花王株式会社 | Olefin production method |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5089341A (en) * | 1973-12-17 | 1975-07-17 |
-
1981
- 1981-09-04 JP JP14007881A patent/JPS5841828A/en active Granted
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5089341A (en) * | 1973-12-17 | 1975-07-17 |
Also Published As
Publication number | Publication date |
---|---|
JPS5841828A (en) | 1983-03-11 |
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