CA1064893A - Catalyst composition and method for preparing the same - Google Patents
Catalyst composition and method for preparing the sameInfo
- Publication number
- CA1064893A CA1064893A CA232,563A CA232563A CA1064893A CA 1064893 A CA1064893 A CA 1064893A CA 232563 A CA232563 A CA 232563A CA 1064893 A CA1064893 A CA 1064893A
- Authority
- CA
- Canada
- Prior art keywords
- catalyst
- submerged
- dried
- carbon fiber
- solution
- 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 title claims abstract description 87
- 239000000203 mixture Substances 0.000 title abstract description 66
- 238000000034 method Methods 0.000 title description 19
- 239000004753 textile Substances 0.000 claims abstract description 90
- 229910052751 metal Inorganic materials 0.000 claims abstract description 52
- 239000002184 metal Substances 0.000 claims abstract description 52
- 239000007864 aqueous solution Substances 0.000 claims abstract description 39
- 150000002739 metals Chemical class 0.000 claims abstract description 21
- 239000000835 fiber Substances 0.000 claims abstract description 18
- 229910052709 silver Inorganic materials 0.000 claims abstract description 18
- 229910052737 gold Inorganic materials 0.000 claims abstract description 14
- 230000003197 catalytic effect Effects 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 4
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract 3
- 150000002484 inorganic compounds Chemical class 0.000 claims abstract 2
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract 2
- 229910052697 platinum Inorganic materials 0.000 claims description 21
- 229910052759 nickel Inorganic materials 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052741 iridium Inorganic materials 0.000 claims description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims description 8
- 229910052762 osmium Inorganic materials 0.000 claims description 7
- 229910052703 rhodium Inorganic materials 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000012457 nonaqueous media Substances 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 6
- 229920000049 Carbon (fiber) Polymers 0.000 abstract description 70
- 239000004917 carbon fiber Substances 0.000 abstract description 70
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 61
- 238000006243 chemical reaction Methods 0.000 abstract description 40
- 230000000737 periodic effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 70
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 58
- 238000011282 treatment Methods 0.000 description 38
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 34
- 229910052763 palladium Inorganic materials 0.000 description 34
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 32
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 19
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000004332 silver Substances 0.000 description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 13
- 239000001257 hydrogen Substances 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000010931 gold Substances 0.000 description 11
- 239000011295 pitch Substances 0.000 description 11
- 229920002239 polyacrylonitrile Polymers 0.000 description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 9
- 239000012299 nitrogen atmosphere Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 8
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 7
- -1 gold benzimidazole-thiolate Chemical compound 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000001913 cellulose Substances 0.000 description 6
- 229920002678 cellulose Polymers 0.000 description 6
- 239000011651 chromium Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 239000008246 gaseous mixture Substances 0.000 description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000000197 pyrolysis Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000010948 rhodium Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 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 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 239000004693 Polybenzimidazole Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- VMDTXBZDEOAFQF-UHFFFAOYSA-N formaldehyde;ruthenium Chemical compound [Ru].O=C VMDTXBZDEOAFQF-UHFFFAOYSA-N 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 3
- 229920002480 polybenzimidazole Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 3
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- SMJCGUMERCYCLO-UHFFFAOYSA-L C(CCC)N(C([S-])=S)CCCC.[Pt+2].C(CCC)N(C([S-])=S)CCCC Chemical compound C(CCC)N(C([S-])=S)CCCC.[Pt+2].C(CCC)N(C([S-])=S)CCCC SMJCGUMERCYCLO-UHFFFAOYSA-L 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical group CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XBXHTOUGJGDVMT-UHFFFAOYSA-N [Ag]c1ccccc1 Chemical compound [Ag]c1ccccc1 XBXHTOUGJGDVMT-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- HVURSIGIEONDKB-UHFFFAOYSA-N benzene;chromium Chemical compound [Cr].C1=CC=CC=C1.C1=CC=CC=C1 HVURSIGIEONDKB-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- YMFAWOSEDSLYSZ-UHFFFAOYSA-N carbon monoxide;cobalt Chemical compound [Co].[Co].[Co].[Co].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] YMFAWOSEDSLYSZ-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000007792 gaseous phase Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 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 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000007420 reactivation Effects 0.000 description 2
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- SFCWCYZAJBCVHR-UHFFFAOYSA-N 1,2,3,4,4a,5,6,7,8,8a-decahydronaphthalene naphthalene Chemical compound C1CCCC2CCCCC21.C1=CC=CC2=CC=CC=C21 SFCWCYZAJBCVHR-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 1
- UIQGEWJEWJMQSL-UHFFFAOYSA-N 2,2,4,4-tetramethylpentan-3-one Chemical compound CC(C)(C)C(=O)C(C)(C)C UIQGEWJEWJMQSL-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- OVIBVWLMKUBAFW-UHFFFAOYSA-N C(=CC=CC)[Cr] Chemical compound C(=CC=CC)[Cr] OVIBVWLMKUBAFW-UHFFFAOYSA-N 0.000 description 1
- XXVWSNWRHGLYAN-UHFFFAOYSA-N C(=CC=CC)[Mn] Chemical compound C(=CC=CC)[Mn] XXVWSNWRHGLYAN-UHFFFAOYSA-N 0.000 description 1
- GADDMSWSFHKNIK-UHFFFAOYSA-L C(C1=CC=CC=C1)[Au](Br)Br Chemical compound C(C1=CC=CC=C1)[Au](Br)Br GADDMSWSFHKNIK-UHFFFAOYSA-L 0.000 description 1
- PNANHVNRJUIZHD-UHFFFAOYSA-N C(CCC1=CC=CC=C1)(=O)O.C(C=CC1=CC=CC=C1)(=O)O Chemical compound C(CCC1=CC=CC=C1)(=O)O.C(C=CC1=CC=CC=C1)(=O)O PNANHVNRJUIZHD-UHFFFAOYSA-N 0.000 description 1
- JEUBFEYHHVIGKN-UHFFFAOYSA-N C1(C=CC=C1)C[Ru](=C=O)=C=O Chemical compound C1(C=CC=C1)C[Ru](=C=O)=C=O JEUBFEYHHVIGKN-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- MUQNGPZZQDCDFT-JNQJZLCISA-N Halcinonide Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@]2(F)[C@@H]1[C@@H]1C[C@H]3OC(C)(C)O[C@@]3(C(=O)CCl)[C@@]1(C)C[C@@H]2O MUQNGPZZQDCDFT-JNQJZLCISA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- JNAXZDYLPVPEBJ-UHFFFAOYSA-N N1CCCC2CCCCC12.N1=CC=CC2=CC=CC=C12 Chemical compound N1CCCC2CCCCC12.N1=CC=CC2=CC=CC=C12 JNAXZDYLPVPEBJ-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910021120 PdC12 Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000004283 Sodium sorbate Substances 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- GPWHDDKQSYOYBF-UHFFFAOYSA-N ac1l2u0q Chemical compound Br[Br-]Br GPWHDDKQSYOYBF-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000010420 art technique Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WIRUZQNBHNAMAB-UHFFFAOYSA-N benzene;cyclohexane Chemical compound C1CCCCC1.C1=CC=CC=C1 WIRUZQNBHNAMAB-UHFFFAOYSA-N 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- VMNAEQFHLIPARK-UHFFFAOYSA-N benzoic acid;cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1.OC(=O)C1=CC=CC=C1 VMNAEQFHLIPARK-UHFFFAOYSA-N 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- RBHJBMIOOPYDBQ-UHFFFAOYSA-N carbon dioxide;propan-2-one Chemical compound O=C=O.CC(C)=O RBHJBMIOOPYDBQ-UHFFFAOYSA-N 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- VZFUCHSFHOYXIS-UHFFFAOYSA-N cycloheptane carboxylic acid Natural products OC(=O)C1CCCCCC1 VZFUCHSFHOYXIS-UHFFFAOYSA-N 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 150000001983 dialkylethers Chemical class 0.000 description 1
- SZRLKIKBPASKQH-UHFFFAOYSA-M dibutyldithiocarbamate Chemical compound CCCCN(C([S-])=S)CCCC SZRLKIKBPASKQH-UHFFFAOYSA-M 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229940028332 halog Drugs 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 1
- 239000000171 lavandula angustifolia l. flower oil Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 150000002736 metal compounds Chemical group 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- XIVQMBJJCVVPCF-UHFFFAOYSA-N methylcyclohexane;toluene Chemical compound CC1CCCCC1.CC1=CC=CC=C1 XIVQMBJJCVVPCF-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 125000005609 naphthenate group Chemical group 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000000963 oxybis(methylene) group Chemical group [H]C([H])(*)OC([H])([H])* 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- ZNSWGHZWUUFFKV-UHFFFAOYSA-N piperidine;pyridine Chemical compound C1CCNCC1.C1=CC=NC=C1 ZNSWGHZWUUFFKV-UHFFFAOYSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000010668 rosemary oil Substances 0.000 description 1
- 229940058206 rosemary oil Drugs 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- CRDXBFFVZNNHKE-UHFFFAOYSA-M silver;1,3-benzothiazole-2-thiolate Chemical compound [Ag+].C1=CC=C2SC([S-])=NC2=C1 CRDXBFFVZNNHKE-UHFFFAOYSA-M 0.000 description 1
- MQHGEVXQSFWXCE-UHFFFAOYSA-M silver;cyclohexanecarboxylate Chemical compound [Ag+].[O-]C(=O)C1CCCCC1 MQHGEVXQSFWXCE-UHFFFAOYSA-M 0.000 description 1
- DELBTKKZBXDCEW-UHFFFAOYSA-M silver;n,n-dibutylcarbamodithioate Chemical compound [Ag+].CCCCN(C([S-])=S)CCCC DELBTKKZBXDCEW-UHFFFAOYSA-M 0.000 description 1
- ORYURPRSXLUCSS-UHFFFAOYSA-M silver;octadecanoate Chemical compound [Ag+].CCCCCCCCCCCCCCCCCC([O-])=O ORYURPRSXLUCSS-UHFFFAOYSA-M 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- LROWVYNUWKVTCU-STWYSWDKSA-M sodium sorbate Chemical compound [Na+].C\C=C\C=C\C([O-])=O LROWVYNUWKVTCU-STWYSWDKSA-M 0.000 description 1
- 235000019250 sodium sorbate Nutrition 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- LPEBYPDZMWMCLZ-CVBJKYQLSA-L zinc;(z)-octadec-9-enoate Chemical compound [Zn+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O LPEBYPDZMWMCLZ-CVBJKYQLSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
- C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0219—Coating the coating containing organic compounds
-
- 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
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
-
- 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
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
-
- 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
- C07C29/19—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 in six-membered aromatic rings
-
- 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
- C07C29/19—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 in six-membered aromatic rings
- C07C29/20—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 in six-membered aromatic rings in a non-condensed rings substituted with hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/06—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation
- C07C37/07—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation with simultaneous reduction of C=O group in that ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
- C07C5/11—Partial hydrogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/36—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by hydrogenation of carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/04—One of the condensed rings being a six-membered aromatic ring
- C07C2602/10—One of the condensed rings being a six-membered aromatic ring the other ring being six-membered, e.g. tetraline
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/14—All rings being cycloaliphatic
- C07C2602/26—All rings being cycloaliphatic the ring system containing ten carbon atoms
- C07C2602/28—Hydrogenated naphthalenes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Inorganic Fibers (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A catalyst comprising carbon fiber coated with at least one catalytic metal, such as the metals of group VIII of the Periodic Table or Zn, Cu, Ag, Au, Cr, Mg or Mn. The catalyst is prepared by submerging the carbon fiber, in the form of a filament, yarn or woven or non-woven textile, in a non-aqueous solution containing an organic compound of the metal or metals to be deposited on the fiber, drying and then pyrolyzing the compounds contained thereon. Optionally, the fiber may then be submerged in an aqueous solution containing an inorganic compound of the metal or metals, dried and pyrolyzed. The resultant cata-lyst composition is useful for a variety of chemical reactions, particularly those carried out in the gaseous state.
A catalyst comprising carbon fiber coated with at least one catalytic metal, such as the metals of group VIII of the Periodic Table or Zn, Cu, Ag, Au, Cr, Mg or Mn. The catalyst is prepared by submerging the carbon fiber, in the form of a filament, yarn or woven or non-woven textile, in a non-aqueous solution containing an organic compound of the metal or metals to be deposited on the fiber, drying and then pyrolyzing the compounds contained thereon. Optionally, the fiber may then be submerged in an aqueous solution containing an inorganic compound of the metal or metals, dried and pyrolyzed. The resultant cata-lyst composition is useful for a variety of chemical reactions, particularly those carried out in the gaseous state.
Description
~6~1~5a3 1 This in~ention relates to a novel method for the pre-paration of highly improved catalyst compositions which effectively catalyze reaction between an extensive combination of reactants in either the liquid or gaseous phases. More particularly, this inven-~ tion relates to a novel catalyst composition and a method for pre-; paring the same, which comprises carbon fiber as a carrier and transition metals uniformly deposited on the carrier by means of a metal coating process wher~in non-aqueous solutions of appro-priate organic derivatives of said metals are coated onto said carrier, followed by the pyrolysis thereof.
This invention also relates to a modified procedure and the products obtained thereby which comprise a multiple coating ~ of various catalytic compositions. This procedure involves the - successive pyrolysis of the composition which has been initially ~ -;
coated on the carbon fiber carrier by the non-aqueous process, and then submerged in an aqueous solution of inorganic salts of the same or other kinds of metals.
The application and use of carbon fiber as a carrier has ` been known in the art because of i~s excellent resistance against ~ heat and its chemical stability. However, the use thereof has involved difficulties in connection with the separation of the products from the catalyst used as well as troublesome problems ; both in the recovery and re-activation of the inactivated catalyst.
These problems prompted the present inventors to find an improved catalyst composition and method for preparing the same which would solve most of the difficulties which have hitherto been e~perienced with such carriers and which would fully meet the necessary re-quirements of the catalyst art. An essentially disadvantageous nature of carbon fiber in this connection lies in the fact that carbon fiber initially has ver~ little affinity toward an aqueous ::
: :, ., -~, . . . .
~06~ 3 1 system. This property, inherent to carbon fibers, immediately conflicts with obtaining a uniform coating of metals as providad by conventional aqueous procedures. This factor has definitely limited the application of carbon fibers as a catalyst carrier in spite of its excellent thermal and chemical stabilities.
Hence, the key feature of this invention directly relates to the solution of the above-mentioned difficulty by a novel and improved combination of techniques. Hence, the catalytic composi-tion of the invention is prepared by submerging the carbon fiber in a non-aqueous solution of suitable organic derivatives of the metals whi¢h are to actually act as the catalyst, drying the fiber and subsequently pyrolyzing it. By this procedure, a ca~alyst ;, composition composed of carbon fiber firmly and uniformly coated with the given metal is unfailingly obtained. Furth~rmore, the metal-coated fiber thus obtained is further treated analogously with an aqueous solution of inorganic salts of the same or another metal, dried and subsequently pyrolyzed to form a combined compo-sition which i9 firmly coated with a thick metal layer.
.. . .
Accordingly, one of the object of the present invention is to provide a catalyst composition comprising carbon fiber having a coating of an appropriate metal which acts as a catalyst firmly bonded thereon~
Another object of the invention is to provide a method for preparing said catalyst composition.
A further object of the invention is to provide a catalyst - composition comprising a multiple coating of various catalytic metals on carbon fiber and a process for preparing the same.
A still further object of the invention is to provide a novel catalyst composition and a method for preparing the same 3~ which overcomes the disadvantages and drawbacks of the prior art~
`:
These and other objects and advantages oE the present invention will become apparent to those skilled in the art from a consideration of the following specification and claims.
Carbon fibers to be employed in the present invention may be obtained from polyacrylonitrile, cellulose, various pitches, etc., and all such carbon fibers are equally applicable. An en-tirely wide rang~ of dimensional forms of carbon fibers, including filaments, yarn, woven or non-woven textiles, etc., can be employed in the present invention.
-' 10 The catalytic metals to be deposited upon said carbon fibers are selected from the metals of Group VIII of the Periodic Table, such as platinum, palladium, ruthenium, rhodium, osmium, iridium, iron, cobalt and nickel and other metals ~;uch as zincr copper, silver, gold, chromium, magnesium and manganese. Mixtures of such metals may be employed. Since the invention relates to a catalyst composition, the primary requirement of such a metal is that it be capable of acting as a catalyst in c~nnection with any desired chemical reaction.
The organic derivativ s of the metals to be employed in the present invention should fulfil the requirement that the thermal decomposition thereof proceeds such that only the organic component is cleaved therefrom to leave the elemental metal on ~ ;
the surface of the carbon fiber. Exemplary compounds which can be used in the present invention include tetrakis (triphenyl-. ~
phosphine) palladium, phenyl silver, benzyldibromogold, platinum naphthenate, palladium naphthenate, ruthenium naphthenate, rhodium naphthenate, iridium naphthenate, iron naphthenate, silver naphthe- -nate, gold naphthenate, platinum rosinate, palladium rosinate, ruthenium rosinate, rhodium rosinate, iridium rosinate, iron 3~ -rosinate, silver rosinate, gold rosinate, palladium abietate, :;:
., ~.
.~ .
1~4i 3~3 1 silver abietate, zinc stearate, silver stearate, zinc oleate, cyclopentane ~arboxylic acid silver salt, cyclohexane carboxylic acid silver salt, platinum dibutyldithiocarbamate, palladium dibutyldithiocarbamate, copper clibutyldithiocarbamate, silver dibutyldithiocarbamate, bis-cyclohexanone oxime-palladium dichloride, bis-furfuraldoxime-palladium dichloride, bis-benz-aldoxime-palladium dichloride, bis-methylethylketone, oxime-palladium dichloride, bis-acetoxime-palladium dichloride, bis-acetaldoxime~palladium dichloride, pentacarbonylruthenium, dode-; 10 cacarbonyl-triruthenium, dihydro-ruthenium-tetracarbonyl, octa-carbonyl-dirhodium, dodecacarbonyl-triosmium, dodecacarbonyl- -~
tetrairidium, nonacarbonyl-diiron, dodecacarbonyl~tetracobalt, - tetracarbonyl-nickel, hexacarbonyl-chromium, actylpentacarbonyl-manganese, methylpentacarbonyl manganese, ~-cyclopentadienyl-trimethyl-platinum, ~-cyclopentadienyl-trimethyl-platinum, ~-allyl-~-cyclopentadienyl-palladium, di-~-cyclopentadienyl-tetracarbonyl--diruthenium, ~-cyclopentadienyl-dicarbonyl-ruthenium, ~-cyclo-pentadienyl-dicarbonyl-rhodium, di-~-cyclopentadienyl-tetra-carbonyl-diosmium, di-~-cyclopentadienyl-osmium, ferrocene, 20 ~-cyclopentadienyl-dicarbonyl-cobalt, di-~-cyclopentadienylcobalt tribromide, di-~-cyclopentadienyl-nickel, ~-cyclopentadienyl-~-allyl-nickel, dibenzene-chromium, di-~-cyclopentadienyl-manganese, platinum tert-butyl mercaptide, palladium tert-butyl mercaptide, copper tert-butyl mercaptide, silver tert-butyl mercaptide, gold tert-butyl mercaptide, palladium benzimidazole-thiolate, silver ?
benzoimidazole-thiolate, gold benzimidazole-thiolate, palladium benzothiazole-thiolate, silver benzothiazole-thiolate, and gold benzothiazole-thiolate.
Liquid organic compounds which may be used as solvents 30 ~or these organic derivatives include organic solvents such as benzene, toluene, xylene, halog~nated benzenes, tetralin, nitro-benzene, etc.; alcoholic solvents such as isopropanol, tertiary-. ;. . ~ ::: .
1o6;~l393 1 butanol, propylene glycol, benzyl alcohol, c~clohexanol, etc.;
ether-type solvents such as dialkyl ether, tetrahydrofuran, dioxane, polyethylene glycol, etc:.; terpenoid compounds such as terpineol, lavender oil, rosemary oil, etc.; ketone-type solvents such as methyl ethyl ketone, methyl isobutyl ketone, etc.; esters such as alkyl formates, alkyl acetates, etc.; aliphatic hydro-carbons and their halogenated compounds such as chloroform, carbon tetrachloride, ethylene dichloride, trichloroethylene, cyclohexane, pentane, hexane, etc., and various miscellaneous solvents including dimethylformamide, dimethylacetoamide, dimethyl sulfoxide, cyclo-hexanone ! etc. Mixtures o~ these solvents may be employed as appropriate.
The method by which the catalytic metals are applied on the carbon fiber is described in the following. The carbon fiber .; .
- as a carrier in the form of a filament, yarn or woven or non-woven textile is submerged in a non-aqueous solution of the above-mentioned organometallic derivatives, then dried and pyroly2ed.
This treatment is repeatedly carried out when required.
Further treatment of the above-obtained composition with inorganic metal salts is carried out as follows. The compo-sition is submerged in an aqueous solution of the inorganic salts, then dried and subse~uently pyrolyzed. In some cases, the treat-ment is accomplished under relatively mild conditions.
Inorganic salts employed in this invention include palladium chloride, ammonium palladium chloride, chloroplatinic acid, ruthenium chloride, iridium chlorider rhodium chloride, silver nitrate, chloroauric acid, nickel sulfate, cobalt nitrate and chromium nitrate. As to the concentration of the aqueous solution of inorganic salt, no strict restriction thereon is ;
necessary. HoweverJ a concentration of about 3~ to 15% by weight ~ 5 ~
,.. ,,. , . - - ~
... :~: ~ ., .
, . ~ ;
::: :: ^ : .
. ~: - , generally gives satisfactory results. A too highly concentrated solution thereoE tends to cause a poor uniformity of coating, and too great of a dilu~ion may make it necessary to conduct the treatment several times because of a deficient amount of metal ;- deposited upon the carbon fiber.
The chemical species of the catalytic layer formed in connection with the invention depends upon the nature of the metal used. For example, hardly oxidizable metals such as silver, platinum, gold, palladium and the like form an elemental metallic 0 layer, whereas readily oxidizable metals such as manganese, nickel, chromium and the like form an oxide layer upon pyrolysis of their `;~ organic or inorganic derivatives. Hence, in the present applica-A- tion, the term "metal" should be understood as including both metals and metal oxides.
The use of a compound of a metal provides a layer of a single kind of metal on the carbon fiber, whereas the use of a . .
- mixture containing a plurality of different metal compounds forms a multiplicity of metallic layers or alloys, depending upon the conditions of pyrolysis and the nature of the metals employed.
Also, the thickness of the metallic layer is easily controlled by a modification of the treatment conditions.
Xn accordance with the invention, the employment of - soluble organometallic derivatives has been found to afford the ; ready and facile preparation of stock solutions, which provides :
many advantages over previously known coating procedures.
The use of carbon fibers as carriers in the form of a textile involves the significant advantage that, since a great , . . variety of shapes of carrier is thus available, the catalyst composition can be easily separated from the resulting products and unconverted material, as compared with the procedures known in the prior art where activated carbon particles are used as the ... ..
:.-- ~ '. ;; : .
: . .
:.', `. ' ' ' " ' :
~L0~i~893 1 carrier. This i5 especially txue when filaments, yarn or woven or non-woven textiles are used as the carrier, the catalytic ; composition itself serving as the filtering agent. Moreover, re-activation of the spent catalyst can be carried out very readily. In fact, in some cases, re~activation can be performed merely by washing the composition with appropriate solvents in order to remove any products or by-products adsorbed on the surface of the catalyst.
Because of the excellent thermal and chemical stability of carbon fiber, the removal of adsorbed contaminants can be easily carried out either by heat treatment at elevated temperatures or by a chemical treatment such as oxidation, reduction or the use ; of a strong mineral acid or organic solvent. This is an obvious advantageous characteristic of the present invention.
Another advantage of the invention is that reactions at elevated temperatures can be performed with the use of conventional autoclaves.
The following examples are given merely as illustrative . . . .
of the present invention and are not to be considered as limiting.
Unless otherwise noted, the percentages recited therein are by weight.
The reactions exemplified, particularly those carried out in the gaseous phase at ordinary pressure with the catalyst compositions of the invention, were performed with the use of - the following apparatus in the manner described herein. The composition prepared in the form of a textile material was formed into round plates having a diameter of 3 to 5 cm, and then the plates were laminated and bound with a stainless steel ring to form a packed solid. The resulting solid material was perpendi-cularly supported in the middle part of a Pyrex glass tube having an inner diameter of 4 cm. The reaction t~e thus obtained was _ 7 _ . .: ::
:, . ~,, . ; , , :
.. :.,. . . :
:.. - -. . ~ ~
. . . . .
10~i4~ 3 1 used for the desired reactions. The reaction temperature was controlled with the use of an appropriate electric furnace.
The mixture of gases was circulated at a rate of flow of 0.02 - 0.08 m/min.
Liquid phase reactions were carried out using a conven-tional reaction flask equipped with a refluxing condenser, and the catalyst composition was placed at the center of the bottom thereof.
Carbon fiber woven textile made from polyacrylonitrile (250 m2/g) was submerged in a 5% chloroform solution of palladium naphthenate and dried. It was then thermally treated for one hour at 220C.
A similar treatment was repeated three times and, as a - result, there was obtained a catalytic composition coated with ~.7%
- of palladium.
EXAMPLE ?
. f~Jy~r~l7y . 3~ Carbon fiber non-woven textile made from~alcohol (PVA) ; 20 (80 m2/g) was immersed in a 10~ toluene solution of palladium tert-butylmercaptide, dried and then heat-treated for one hour at 250C.
Treatment in this manner two times gave a catalytic -composition with 7~ of palladium. ;
.
Carbon fiber woven textile made- from PVA (120 m2/g) was -submerged in a 5% dimethylformamide solution of bis-acetaldoxime - palladium dichloride, dried and subsequently pyrolyzed over a period of 2 hours at 200C.
Treatment in this manner three times yielded a composi-tion bearing 6~ of palladium.
~064~3 Carbon fiber woven t~xtile made from polyacrylonitrile (160 m2/g) was submerged in a 3% chloroform solution of platinum naphthenate and drLed. It was then thermally treated for one hour at 270C.
A similar treatment was repeated three times and, as a result, there was obtained a catalyst having 6~ of platin~n.
. .
Carbon fiber non-woven textile made from PVA (110 m2/g) was submerged in a 3~ ethereal solution of ~-cyclopentadienyl-trimethylplatinum and dried. The resulting material was then thermally treated for one hour at 150C.
A similar treatment was repeated three times, and there was obtained a catalyst having 7~ of platinum.
EXAMPLE 6 ~ :
Carbon fiber woven textile made from polyacrylonitrile (120 m2/g) was submerged in a 5~ ethereal solution of phenyl silver maintained at -50C in dry ice-acetone, and was then kept at 50C in a nitrogen atmosphere for one hour.
This treatment was repeated three times to give a catalyst containing 10~ silver.
EXAMPLE 7 ;
Carbon fiber woven textile made from PVA (170 m2/g) was submerged in a 5~ chloroform solution of silver naphthenate and dried, and then was thermally treated for one hour at 250C.
A similar treatment was repeated three times, and there was obtained a catalyst having 7% of silverO
Carbon fiber woven textile made from PVA (120 m2/g) was ' ' _ g _ .... . . :. ~.
-.
10~ 3 1 submerged in a 10% chloroform solution of silver naphthenate a~d dried, and then it was thermally treated for 2 hours at 250C.
A similar treatment was repeated three times and, as a result, there was ~btained a catalyst having 8~ of silver.
Carbon fiber woven textile made from polyacrylonitrile (80 m /g) was submerged in a 3~ ethereal solution of dodecacarbonyl~
triruthenium and dried, and then was thermally treated for one 1 hour at 160C.
O
A similar treatment was repeated three times, and the material was further treated for 3 hours at 300C with the result ~hat a catalyst having 5% of ruthenium oxide was obtained. ;
- EXAMPLE lO
~ Carbon fiber non-woven textile made from polyacrylo-; nitrile (80 m2/g) was submerged in a 3% tetrahydrofuran solution . of cyclopentadienyl-methyl-dicarbonyl-ruthenium. Ethanol was~ `-:, ., added to the above solution which was kept at 50C for one hour, and then the composition was washed, dried and further treated with a 10% hydrogen peroxide solution to give a composition coated - ;~
with 7% of ruthenium oxide.
Carbon fiber woven from pitch (120 m2/g) was submerged in a 5~ ethereal solution of di-~-cyclopentadienyl-osmium and dried. It was then thermally treated ~or one hour at 200 C.
A similar treatment was repeated three times, and there was obtained a catalyst having 6~ of osmium.
- --Carbon fiber woven textile made from polybenzimidazole ~80 m2/g) was submerged in a 5~ ethereal solution of di-~-cyclo ;`` ~ .' ...:: ::
1~6~1~93 pentadienyl-manganese, dried and then thermally treated for one hour at 200C.
A similar treatment was repeated three times and there was obtained a cat~lyst having 7~ of man~anese dioxide.
Carbon fiber woven textile made from cellulose (80 m2/g) was submerged in a 10% ethereal solution of methyl-pentacarbonyl-manganese, dried and then thermally treated for 2 hours at 200C.
A similar treatment was repeated three tlmes and, as a result, there was obtained a catalyst having 11~ of manganese dioxide.
-:
; Carbon fiber woven textile made from pitch (80 m2/g) was submerged in a 5% tetrahydrofuran solution of ~-cyclopenta-dienyl-~-allyl-nickel, dried and then thermally treated in a hydrogen atmosphere at 100C for one hour.
This treatment was repeated two times, and there was obtained a catalyst having 5% of nickel. -EXAMPLE 15 .
Carbon fiber woven textile from pitch (80 m2/g) was submerged in a 6% ethereal solution of tetracarbonyl-nickel and dried. It was then thermally treated in a nitrogen atmosphere at 130C for one hour. ~ -: This treatment was repeated three times, and there was obtained a catalyst having 5~ of nic]cel.
Carbon fiber woven textile made from PVA (120 m2/g) was submerged in a 6% tetrahydrofuran solution of di~-cyclopentadienyl- `-cobalt-tribromide, dried and then thermally treated in a nitrogen atmosphere at 100C for one hour.
:, ", ~
: . .
, .. , :. .
: . - . . .
,: , 106~1!393 1 A similar treatment was repeated three times, and there was obtained a catalyst having 5% of cobalt.
Carbon fiber woven textile made from polyacrylonitrile (200 m~/g) was suhmerged in a 10% ethereal solution of dodeca-carbonyl-tetracobalt and dried. It was then thermally treated in a nitrogen atmosphere at 150C for one hour.
A similar treatment was repeated three times and, as a xesult, there was obtained a catalyst containing 7~ of cobalt.
.
Carbon fiber woven textile from pitch (200 m2/g~ was submerged in a 5% benzene solution of di(benzene)-chromium, dried :~
and then tbermally treated in a nitrogen atmosphere at 300C for one hour. There was obtained a catalyst having 1.5% of chromium.
Carbon fiber non-woven textile made from PVA (80 m2/g) was submerged in a 10% trichlene solution of iridium naphthenate ~ -20 and dried. It was then thermally treated for one hour at 300C. ;~
This treatment was repeated two times, and there wasobtained a catalyst containing 7% of iridium.
Carbon fiber non-woven textile made from PVA ~110 m2~g) ; was submerged in an 8% diisopropyl-ethereal solution of octa- -carbonyl-dirhodium and dried. The resultant was then thermally treated for one hour at 80C.
;~ A similar treatment was repeated three times, and there was obtained a catalyst having 7% o~ rhodium.
. ~.
~ - 12 -: ' :
~1 06~ 3 1 EX~MPLE 21 _ .
Carbon fiber non-woven textile made from cellulose (80 m2/g) was submerged in a 5~ tetrahydrofuran solution of acetyl-pentacarbonyl-manganese, ciried, and then thermally treated for one hour at 100C.
~ similar treatment was repeated three times, and there was obtained a catalyst having 6% of manganese dioxide.
The obtained composition was further submerged in a 5~
chloroform solution of palladium naphthenate, dried and then heated at 250C for 30 minutes to give a composition coated with 1.5% of palladium.
~- EXAMPLE 22 Carbon fiber woven textile made from polybenzimidazole ~80 m2~g) was submerged in a 5~ ethereal solution of nonacarbonyl-diiron, dried and then thermally treated for one hour at 200~.
The above-treated textile was further submerged in a 5%
i tetrahydrofuran solution of dodecacarbonyl-triruthenium, dried and then thermally treated for one hour at 200C.
As a resultj there was obtained a catalyst having 7 - of metal.
~EXAMPLE 23 ; Carbon fiber woven textile made from polyacrylonitrile (80 m /g) was submerged in an ethereal solution containing 1.5%
of dodecacarbonyl-triruthenium and 1.5~ of octacarbonyl-dirhodium, dried and then thermally treated for one hour at 160C.
After a similar treatment was repeated three times, the above textile was thermally treated in air at 400C. As a result, there was obtained a catalyst having 4% of metal.
' - 13 - ~
11~6~ 3 Carbon fiber woven textile made from polyacrylonitrile (250 m2/g) was submerged in a chloroform solution containing 5~
of palladium naphthenate and 1% of ruthenium naphthenate, dried and then thermally treated for 2 hours at 400C.
A similar treatment was repeated three times, and there was obtained a catalyst having 4.0~ of metal.
. .
~ EXAMPLE 25 ..
A carbon fiber woven textile made from polybenzimidazole (80 m2/g) was submerged in an ethereal solution containing 5% of di-~-cyclopentadienyl-manganese and 5% of nonacarbonyl-diiron, and then dried and pyrolyzed at 350C for one hour.
This treatment was repeated three times, followed by ~aking in air at 400C for 3 hours, to produce a textile coated with 8% by weight of metal. The resulting composition was sub-sequently submerged in a chloroform solution containing 0.2~ of palladium naphthenate and 0.2~ of platinum naphthenate, dried and then pyrolyzed at 300C for 2 hours to give a catalyst having ~ ;
0.1% of platinum and palladium. ~
EXAMPLE 26 ~ -... :. - :
A carbon fiber woven textile made from pitch ~80 m2/g) ;-~
was submerged in a 5% pentane solution of methyl-pentacarbonyl-manganese and dried. It was then heated in a hydrogen àtmosphere '~
at 100C for one hour.
The treated textile was then submerged in a 5% aqueous - solution of ruthenium chloride and pyrolyzed at 400C for 3 hours to give a catalyst having 5% of metal.
EX~MPLE 27 --- Carhon fiber woven textile made from cellulose (170 m2/g) was submerged in a 5% chloroform solution of palladium naphthenate, ' ' ,:
. .
, ~(~6~393 1 dried and then thermally treated at 220C ~or one hour. There was obtained a composition having 2% of palladium.
The composition obtained in the above procedure was submerged in a formaldehyde-aqueous solution containing 30% of PdC12 maintained at -10C. To the mixture was added 30~ potassium hydroxide aqueous solution, and it was kept at 60C for 30 minutes.
The composition was washed, dried and subsequently treated at 100C for one hour to give a catalyst having 5% of palladium.
A carbon fiber woven textile made from polyacrylonitrile ~- (200 m2/g) was submerged in a 5% chloroform solution of palladi~
naphthenate, dried and thermally treated at 200C for 30 minutes to give a composition containing 3.5~ of palladium.
The treated textile subsequently was submerged in an aqueous solution consisting of 2% of ammonium palladium chloride and small amounts of formic acid. The solution was heated up to 60C and a 30% aqueous solution of potassium hydroxide was added thereto. After 30 minutes, the textile was dried, and, as a result, there was obtained a catalyst having 5.5% of palladium.
A carbon fiber non-woven textile made from polyacrylo-nitrile (120 m2/g) was submerged in a 5% chloroform solution of palladium naphthenate, dried and then thermally treated at 230C
for 2 hours.
The obtained composition was submerged in an aqueous solution containing 20% sodium sorbate, a small amount of sodium hydroxide and palladium chloride dissolved in dilute hydrochloric acid. The whole mixture was heated up to 60C, dried and finally treated with hydrogen at 80C for 2 hours to give a catalyst having 6% palladium.
:- .: : : : , - :
Carbon fiber non-woven textile made from PVA (170 m2/g) was submer~ed in a 5% toluene solution of platinum dibutyldithio-carbamate, dried and then thermally treated for 2 hours at 250C.
The above-treated textile was further submerged in an ; .
aqueous solution of chloroplatinic acid and was alkalized by - adding NaCO3 thereto. After the addition of hydrazine, the mixture was heated to 60C and allowed to stand for one hour and dried. A catalyst having 5% platinum was obtained.
A carbon fiber woven textile made from PVA (80 m2/g) was submerged in a 5% tetrahydrofuran solution of ~~allyl-~~cyclo-pentadienyl platinum, dried and then thermally treated at 130C
for one hour. The treated textile was then submerged in a S0 aqueous solution of hexachloroplatinic acid, and 40% formalin was added to the solution. To the resulting mixture maintained at 0C, a 30% aqueous solution of sodium hydroxide was added, and the mixture was allowed to stand for 12 hours. Washing the produced composition with water and then drying at 50C gave a ~ ~
catalyst having 4~ of platinum. ~;
Carbon fiber non~woven textile made from PVA (80 m2/g) was subme~ged in a 3% toluene solution of platinum tert-butyl mercaptide, dried and then thermally treated for one hour at 200C~ The composition thus obtained was further treated similarly as described in the latter part of Example 31, and there was obtained a catalyst containing 5~ of platinum.
.
--------__ Carbon fiber woven textile made from pitch (120 m2/g) was submerged in an 8~ ethereal solution of platinum tert-butyl-mercaptide, dried and then thermally treated for one hour at 200C
,:
.; ............. ~ . . ............................ ..
.-:: -: . . . .
-: .
iO~4893 to give a composition having l~ of platin~n. Furthexmore, the above textile was submerged in a 50~ aqueous solution of chloro-platinic acid, and 40~ of formalin was added to the solution.
To the resulting mixture maintained at 0C, a 30%
aqueous solution of sodium hydroxide was added, and the mixture was allowed to stand for 12 hours. Washing the treated composition with water and drying at 50C gave a catalyst having 4% of platinum.
Carbon fiber woven textile from PV~ (120 m2/g) was sub-merged in a 2~ chloroform solution of gold naphthenate, dried and then thermally treated for one hour at 240C to give a catalyst composition having l~ of gold.
The above-treated textile was submerged in an aqueous solution containing ammonium palladium chloride and formic acid, and then a 20% aqueous solution of potassium hydroxide was added to the solution. The resulting mixture was maintained at 60C
for one hour, dried at 50C and, as a result, there was obtained a catalyst having 4% of palladium. -Caxbon fiber non-woven textile from PVA (80 m2/g) was submerged in a 2% chloroform solution of gold naphthenate and dried. It was then thermally treated for one hour at 230C. By this treatment, the textile obtained contained 1% of gold.
The ~bove-treated textile was submerged in an aqueous solution containing 30% of chloroplatinic acid and 30% of formalin.
To the resulting mixture maintained at 0C a 50% sodium hydroxide solution was added and the mixture was allowed to stand for 12 hours. Washing the treated textile with water accompanied by drying at 50C gave a catalyst having 7% of platinum.
~)648~3 ~ EXAMPLE 36_ -~ Carbon fiber woven textile from PVA ~120 m2/g) was sub-merged in a 10~ chloroform solution of gold naphthenate, dried and then thermally treated for 2 hours at 240C. By this treat-ment, the textile was coated with 1% of gold.
The textile was further submerged in an aqueous solution consisting of 2~ of ammonium palladium chloride and formic acid.
To the mixture maintained at 60Cj a 30~ aqueous solution of ;~ potassium hydroxide was added and, after 30 minutes, it was washed with water and dried at 50C. The catalyst obtained contained 66 of palladium.
' A carbon fiber woven textile made from PVA (130 m2/g) was submerged in a 5% chloroform solution of silver naphthenate and dried. It was then thermally treated for one hour at 200C. ~ ~-The above-treated textile was submerged in an aqueous -solution containing 30% of silver nitrate and 10% of sodi~
hydroxide, and a 30% aqueous solution of hydrogen peroxide was further added slowly thereto. The mixture was kept at 30C for one hour, dried at 50C and a catalyst having 10% of silver was obtained.
Carbon fiber woven textile from pitch ~80 m2/g) was - submerged in a 5% ethereal solution of di-~-cyclopentadienyl~-tetracarbonyl-diosmium and dried. It was then thermally treated in a nitrogen atmosphere at 100C for 2 hours. By means of this treatment, the above textile was coated with 2% of osmium. ~-.
The textile was then submerged in an aqueous solution ; 30 containing 2% of ammonium palladium chloride and formic acld. A
' .
.,. - . ~:
8~3 1 30% aqueous solution of potassium hydroxide was added thereto and the solution was heated up to 60C. After 30 minutes, washing with water and drying at 50C gave a catalyst containing 5~ palladium.
Carbon fiber woven textile made from PVA (120 m2/g) was submerged in a 10% e-thereal solution of di-~-cyclopentadienyl-nickel, dried and then thermally treated in a nitrogen atmosphere at 150C for 2 hours. By this treatment, the textile was coated with 2% of nickel.
The textile was furthermore submerged in an aqueous solution containing 30% of nickel sulfate, 10% of sodi~n hypo-phosphite and lO~i of sodium acetate, allowed to stand for 30 minutes at 98-99C, and then dried. The treated textile was ; finally subjected to a hydrogen atmosphere at 250C for 2 hours and, as a result, a catalyst having 5% of nickel was obtained.
EX~4PLE 4D
A carbon fiber woven textile made from pitch (80 m2/g) was submerged in a 6~i tetrahydrofuran solution of ~-cyclopenta-- 20 dienyl-~-allyl nickel and dried. It was then thermally treated `
under nitrogen at 130C for 2 hours. By this treatment, the textile was coated with 2~i of nickel.
Ater a lO~i aqueous solution of sodium hypophosphite was added to the 30~ aqueous solution of nickel sulfate, the treated textile was submerged therein, and it was maintained at `-98-99C for 30 minutes. After washing with water and drying, the treated textile was finally treated in a hydro~en atmosphere at 250C for 2 hours, and a catalyst having 6% of nickel was obtained.
~ 30 : ':
~ - 19 - ., ; . - . . ~ ,. ,,:
1~6413~3 A carbon fiber woven textile made from PVA (120 m2/y) was submerged in a 7~ tetrahydrofuran solution of ~-cyclopenta-dienyl-dicarbonyl-cobalt and dried. It was then thermally treated under nitrogen at 130C for 2 hours. By this treatment, the textile was coated with 1% of cobalt.
The above-treated was further submerged in a 30% aqueous solution of cobalt nitrate, and a 4~ aqueous solution of sodium hydrogen carbonate was added thereto. The solution was maintained at 80C for 2 hours.
After washing with water and drying, the textile was finally treated in a hydrogen atmosphere at ~70C for 2-3 hours, and a catalyst having 4% of cobalt was obtained.
A carbon fiber woven textile made from polyacrylonitrile - (80 m2/g) was submerged in a 10% ethereal solution of dodeca-carbonyl-tetracobalt and dried. It was then thermally treated in l a nitrogen atmosphere at 160C for one hour. Subsequently, the '! 20 above-treated textile was submerged in a 30% a~ueous solution of cobalt nitrate. A 4% aqueous solution of sodium hydrogen carbonate was added thereto, and the solution was heated at 80C for 2 hours.
; Aftex washing and drying, the treated textile was final]y treated in a hydrogen atmosphere at 270C for 2-3 hours, and a catalyst having 6% of cobalt was obtained.
.
Carbon fiber woven textile made from pitch (160 m2/g) was submerged in an 8% tetrahydrofuran solution of di-~-cyclo- ;
pentadienyl-chromium and dried. It was then thermally treated in a nitrogen atmosphere at 180C for 2 hours. By this treatment, the above textile was coated with 2% of chromium.
.~.. , - ~ .
-, .
L8~3 The treated textile was furthermore submerged in an aqueous solution containing a 1 normal concentration of chromium nitrate and a 1 normal concentratlon of ammonium nitrate, R 1 normal concentration of aqueous ammonium was added thereto, and the solution was stirred at 80-90C. After washing and drying, the treated textile was subjected to a hydrogen atmosphere at 250C for 3 hours, and a catalyst having 5% of chromium was obtained.
~,' .
. 1 0 Carbon fiber woven textile made from polyacrylonitrile (200 m /g) was submerged in a 10% chloroform solution of ruthenium rosinate, dried and then thermally treated for one hour at 150C.
Subsequently, the above-treated textile was submerged in a 10%
aqueous solution of ruthenium chloride and was thermally treated at 400C. As a result, a catalyst having 3% of ruthenium oxide was obtained.
-Carbon fiber non-woven textile from cellulose (80 m2/g) was submerged in a 5~ tatrahydrofuran solution of palladium rosinate and dried. It was then thermally treated for one hour at 300C.
The above-treated textile was further submerged in a 5%
aqueous soiution of ruthenium chloride, dried and thermally treated at 400 C for 30 minutes. A catalyst having 1.5% of metal was obtained.
A carbon fiber woven textile from pitch (120 m2/y) was submerged in a 5~ cyclohexanone solution of dodecacarbonyl-tri-ruthenium and dried. It was then thermally treated for one hourat 150C.
.
;~. : , . . : .
. . .
1~6~893 a The abova-treated tex-tile was further submerged in a 5% aqueous solution of rhodium chloride and thermally treated at 300C for one hour. A catalyst containing 2% of metal was obtained.
:, Carbon fiber non-woven textile made from cellulose (80 m /g~ was submerged in a 0.5~ chloroform solution of palladium naphthenate and dried. It was then thermally treated for 30 minutes at 250C. By this treatment, the above non~woven textile ; was coated with 0.1% of palladium.
The textile was further submerged in an aqueous solution containing 10% of ruthenium chloride and 20~ of silver nitrate, dried and thermally treated at 500C for one hour. The latter treatment was repeated three times, and a catalyst haviny 5% of , ruthenium and silver was obtained.
.`' ' ~ . .
` EXAMPLE 48 .
A mixture of circulating gases composed of CO (15%),
This invention also relates to a modified procedure and the products obtained thereby which comprise a multiple coating ~ of various catalytic compositions. This procedure involves the - successive pyrolysis of the composition which has been initially ~ -;
coated on the carbon fiber carrier by the non-aqueous process, and then submerged in an aqueous solution of inorganic salts of the same or other kinds of metals.
The application and use of carbon fiber as a carrier has ` been known in the art because of i~s excellent resistance against ~ heat and its chemical stability. However, the use thereof has involved difficulties in connection with the separation of the products from the catalyst used as well as troublesome problems ; both in the recovery and re-activation of the inactivated catalyst.
These problems prompted the present inventors to find an improved catalyst composition and method for preparing the same which would solve most of the difficulties which have hitherto been e~perienced with such carriers and which would fully meet the necessary re-quirements of the catalyst art. An essentially disadvantageous nature of carbon fiber in this connection lies in the fact that carbon fiber initially has ver~ little affinity toward an aqueous ::
: :, ., -~, . . . .
~06~ 3 1 system. This property, inherent to carbon fibers, immediately conflicts with obtaining a uniform coating of metals as providad by conventional aqueous procedures. This factor has definitely limited the application of carbon fibers as a catalyst carrier in spite of its excellent thermal and chemical stabilities.
Hence, the key feature of this invention directly relates to the solution of the above-mentioned difficulty by a novel and improved combination of techniques. Hence, the catalytic composi-tion of the invention is prepared by submerging the carbon fiber in a non-aqueous solution of suitable organic derivatives of the metals whi¢h are to actually act as the catalyst, drying the fiber and subsequently pyrolyzing it. By this procedure, a ca~alyst ;, composition composed of carbon fiber firmly and uniformly coated with the given metal is unfailingly obtained. Furth~rmore, the metal-coated fiber thus obtained is further treated analogously with an aqueous solution of inorganic salts of the same or another metal, dried and subsequently pyrolyzed to form a combined compo-sition which i9 firmly coated with a thick metal layer.
.. . .
Accordingly, one of the object of the present invention is to provide a catalyst composition comprising carbon fiber having a coating of an appropriate metal which acts as a catalyst firmly bonded thereon~
Another object of the invention is to provide a method for preparing said catalyst composition.
A further object of the invention is to provide a catalyst - composition comprising a multiple coating of various catalytic metals on carbon fiber and a process for preparing the same.
A still further object of the invention is to provide a novel catalyst composition and a method for preparing the same 3~ which overcomes the disadvantages and drawbacks of the prior art~
`:
These and other objects and advantages oE the present invention will become apparent to those skilled in the art from a consideration of the following specification and claims.
Carbon fibers to be employed in the present invention may be obtained from polyacrylonitrile, cellulose, various pitches, etc., and all such carbon fibers are equally applicable. An en-tirely wide rang~ of dimensional forms of carbon fibers, including filaments, yarn, woven or non-woven textiles, etc., can be employed in the present invention.
-' 10 The catalytic metals to be deposited upon said carbon fibers are selected from the metals of Group VIII of the Periodic Table, such as platinum, palladium, ruthenium, rhodium, osmium, iridium, iron, cobalt and nickel and other metals ~;uch as zincr copper, silver, gold, chromium, magnesium and manganese. Mixtures of such metals may be employed. Since the invention relates to a catalyst composition, the primary requirement of such a metal is that it be capable of acting as a catalyst in c~nnection with any desired chemical reaction.
The organic derivativ s of the metals to be employed in the present invention should fulfil the requirement that the thermal decomposition thereof proceeds such that only the organic component is cleaved therefrom to leave the elemental metal on ~ ;
the surface of the carbon fiber. Exemplary compounds which can be used in the present invention include tetrakis (triphenyl-. ~
phosphine) palladium, phenyl silver, benzyldibromogold, platinum naphthenate, palladium naphthenate, ruthenium naphthenate, rhodium naphthenate, iridium naphthenate, iron naphthenate, silver naphthe- -nate, gold naphthenate, platinum rosinate, palladium rosinate, ruthenium rosinate, rhodium rosinate, iridium rosinate, iron 3~ -rosinate, silver rosinate, gold rosinate, palladium abietate, :;:
., ~.
.~ .
1~4i 3~3 1 silver abietate, zinc stearate, silver stearate, zinc oleate, cyclopentane ~arboxylic acid silver salt, cyclohexane carboxylic acid silver salt, platinum dibutyldithiocarbamate, palladium dibutyldithiocarbamate, copper clibutyldithiocarbamate, silver dibutyldithiocarbamate, bis-cyclohexanone oxime-palladium dichloride, bis-furfuraldoxime-palladium dichloride, bis-benz-aldoxime-palladium dichloride, bis-methylethylketone, oxime-palladium dichloride, bis-acetoxime-palladium dichloride, bis-acetaldoxime~palladium dichloride, pentacarbonylruthenium, dode-; 10 cacarbonyl-triruthenium, dihydro-ruthenium-tetracarbonyl, octa-carbonyl-dirhodium, dodecacarbonyl-triosmium, dodecacarbonyl- -~
tetrairidium, nonacarbonyl-diiron, dodecacarbonyl~tetracobalt, - tetracarbonyl-nickel, hexacarbonyl-chromium, actylpentacarbonyl-manganese, methylpentacarbonyl manganese, ~-cyclopentadienyl-trimethyl-platinum, ~-cyclopentadienyl-trimethyl-platinum, ~-allyl-~-cyclopentadienyl-palladium, di-~-cyclopentadienyl-tetracarbonyl--diruthenium, ~-cyclopentadienyl-dicarbonyl-ruthenium, ~-cyclo-pentadienyl-dicarbonyl-rhodium, di-~-cyclopentadienyl-tetra-carbonyl-diosmium, di-~-cyclopentadienyl-osmium, ferrocene, 20 ~-cyclopentadienyl-dicarbonyl-cobalt, di-~-cyclopentadienylcobalt tribromide, di-~-cyclopentadienyl-nickel, ~-cyclopentadienyl-~-allyl-nickel, dibenzene-chromium, di-~-cyclopentadienyl-manganese, platinum tert-butyl mercaptide, palladium tert-butyl mercaptide, copper tert-butyl mercaptide, silver tert-butyl mercaptide, gold tert-butyl mercaptide, palladium benzimidazole-thiolate, silver ?
benzoimidazole-thiolate, gold benzimidazole-thiolate, palladium benzothiazole-thiolate, silver benzothiazole-thiolate, and gold benzothiazole-thiolate.
Liquid organic compounds which may be used as solvents 30 ~or these organic derivatives include organic solvents such as benzene, toluene, xylene, halog~nated benzenes, tetralin, nitro-benzene, etc.; alcoholic solvents such as isopropanol, tertiary-. ;. . ~ ::: .
1o6;~l393 1 butanol, propylene glycol, benzyl alcohol, c~clohexanol, etc.;
ether-type solvents such as dialkyl ether, tetrahydrofuran, dioxane, polyethylene glycol, etc:.; terpenoid compounds such as terpineol, lavender oil, rosemary oil, etc.; ketone-type solvents such as methyl ethyl ketone, methyl isobutyl ketone, etc.; esters such as alkyl formates, alkyl acetates, etc.; aliphatic hydro-carbons and their halogenated compounds such as chloroform, carbon tetrachloride, ethylene dichloride, trichloroethylene, cyclohexane, pentane, hexane, etc., and various miscellaneous solvents including dimethylformamide, dimethylacetoamide, dimethyl sulfoxide, cyclo-hexanone ! etc. Mixtures o~ these solvents may be employed as appropriate.
The method by which the catalytic metals are applied on the carbon fiber is described in the following. The carbon fiber .; .
- as a carrier in the form of a filament, yarn or woven or non-woven textile is submerged in a non-aqueous solution of the above-mentioned organometallic derivatives, then dried and pyroly2ed.
This treatment is repeatedly carried out when required.
Further treatment of the above-obtained composition with inorganic metal salts is carried out as follows. The compo-sition is submerged in an aqueous solution of the inorganic salts, then dried and subse~uently pyrolyzed. In some cases, the treat-ment is accomplished under relatively mild conditions.
Inorganic salts employed in this invention include palladium chloride, ammonium palladium chloride, chloroplatinic acid, ruthenium chloride, iridium chlorider rhodium chloride, silver nitrate, chloroauric acid, nickel sulfate, cobalt nitrate and chromium nitrate. As to the concentration of the aqueous solution of inorganic salt, no strict restriction thereon is ;
necessary. HoweverJ a concentration of about 3~ to 15% by weight ~ 5 ~
,.. ,,. , . - - ~
... :~: ~ ., .
, . ~ ;
::: :: ^ : .
. ~: - , generally gives satisfactory results. A too highly concentrated solution thereoE tends to cause a poor uniformity of coating, and too great of a dilu~ion may make it necessary to conduct the treatment several times because of a deficient amount of metal ;- deposited upon the carbon fiber.
The chemical species of the catalytic layer formed in connection with the invention depends upon the nature of the metal used. For example, hardly oxidizable metals such as silver, platinum, gold, palladium and the like form an elemental metallic 0 layer, whereas readily oxidizable metals such as manganese, nickel, chromium and the like form an oxide layer upon pyrolysis of their `;~ organic or inorganic derivatives. Hence, in the present applica-A- tion, the term "metal" should be understood as including both metals and metal oxides.
The use of a compound of a metal provides a layer of a single kind of metal on the carbon fiber, whereas the use of a . .
- mixture containing a plurality of different metal compounds forms a multiplicity of metallic layers or alloys, depending upon the conditions of pyrolysis and the nature of the metals employed.
Also, the thickness of the metallic layer is easily controlled by a modification of the treatment conditions.
Xn accordance with the invention, the employment of - soluble organometallic derivatives has been found to afford the ; ready and facile preparation of stock solutions, which provides :
many advantages over previously known coating procedures.
The use of carbon fibers as carriers in the form of a textile involves the significant advantage that, since a great , . . variety of shapes of carrier is thus available, the catalyst composition can be easily separated from the resulting products and unconverted material, as compared with the procedures known in the prior art where activated carbon particles are used as the ... ..
:.-- ~ '. ;; : .
: . .
:.', `. ' ' ' " ' :
~L0~i~893 1 carrier. This i5 especially txue when filaments, yarn or woven or non-woven textiles are used as the carrier, the catalytic ; composition itself serving as the filtering agent. Moreover, re-activation of the spent catalyst can be carried out very readily. In fact, in some cases, re~activation can be performed merely by washing the composition with appropriate solvents in order to remove any products or by-products adsorbed on the surface of the catalyst.
Because of the excellent thermal and chemical stability of carbon fiber, the removal of adsorbed contaminants can be easily carried out either by heat treatment at elevated temperatures or by a chemical treatment such as oxidation, reduction or the use ; of a strong mineral acid or organic solvent. This is an obvious advantageous characteristic of the present invention.
Another advantage of the invention is that reactions at elevated temperatures can be performed with the use of conventional autoclaves.
The following examples are given merely as illustrative . . . .
of the present invention and are not to be considered as limiting.
Unless otherwise noted, the percentages recited therein are by weight.
The reactions exemplified, particularly those carried out in the gaseous phase at ordinary pressure with the catalyst compositions of the invention, were performed with the use of - the following apparatus in the manner described herein. The composition prepared in the form of a textile material was formed into round plates having a diameter of 3 to 5 cm, and then the plates were laminated and bound with a stainless steel ring to form a packed solid. The resulting solid material was perpendi-cularly supported in the middle part of a Pyrex glass tube having an inner diameter of 4 cm. The reaction t~e thus obtained was _ 7 _ . .: ::
:, . ~,, . ; , , :
.. :.,. . . :
:.. - -. . ~ ~
. . . . .
10~i4~ 3 1 used for the desired reactions. The reaction temperature was controlled with the use of an appropriate electric furnace.
The mixture of gases was circulated at a rate of flow of 0.02 - 0.08 m/min.
Liquid phase reactions were carried out using a conven-tional reaction flask equipped with a refluxing condenser, and the catalyst composition was placed at the center of the bottom thereof.
Carbon fiber woven textile made from polyacrylonitrile (250 m2/g) was submerged in a 5% chloroform solution of palladium naphthenate and dried. It was then thermally treated for one hour at 220C.
A similar treatment was repeated three times and, as a - result, there was obtained a catalytic composition coated with ~.7%
- of palladium.
EXAMPLE ?
. f~Jy~r~l7y . 3~ Carbon fiber non-woven textile made from~alcohol (PVA) ; 20 (80 m2/g) was immersed in a 10~ toluene solution of palladium tert-butylmercaptide, dried and then heat-treated for one hour at 250C.
Treatment in this manner two times gave a catalytic -composition with 7~ of palladium. ;
.
Carbon fiber woven textile made- from PVA (120 m2/g) was -submerged in a 5% dimethylformamide solution of bis-acetaldoxime - palladium dichloride, dried and subsequently pyrolyzed over a period of 2 hours at 200C.
Treatment in this manner three times yielded a composi-tion bearing 6~ of palladium.
~064~3 Carbon fiber woven t~xtile made from polyacrylonitrile (160 m2/g) was submerged in a 3% chloroform solution of platinum naphthenate and drLed. It was then thermally treated for one hour at 270C.
A similar treatment was repeated three times and, as a result, there was obtained a catalyst having 6~ of platin~n.
. .
Carbon fiber non-woven textile made from PVA (110 m2/g) was submerged in a 3~ ethereal solution of ~-cyclopentadienyl-trimethylplatinum and dried. The resulting material was then thermally treated for one hour at 150C.
A similar treatment was repeated three times, and there was obtained a catalyst having 7~ of platinum.
EXAMPLE 6 ~ :
Carbon fiber woven textile made from polyacrylonitrile (120 m2/g) was submerged in a 5~ ethereal solution of phenyl silver maintained at -50C in dry ice-acetone, and was then kept at 50C in a nitrogen atmosphere for one hour.
This treatment was repeated three times to give a catalyst containing 10~ silver.
EXAMPLE 7 ;
Carbon fiber woven textile made from PVA (170 m2/g) was submerged in a 5~ chloroform solution of silver naphthenate and dried, and then was thermally treated for one hour at 250C.
A similar treatment was repeated three times, and there was obtained a catalyst having 7% of silverO
Carbon fiber woven textile made from PVA (120 m2/g) was ' ' _ g _ .... . . :. ~.
-.
10~ 3 1 submerged in a 10% chloroform solution of silver naphthenate a~d dried, and then it was thermally treated for 2 hours at 250C.
A similar treatment was repeated three times and, as a result, there was ~btained a catalyst having 8~ of silver.
Carbon fiber woven textile made from polyacrylonitrile (80 m /g) was submerged in a 3~ ethereal solution of dodecacarbonyl~
triruthenium and dried, and then was thermally treated for one 1 hour at 160C.
O
A similar treatment was repeated three times, and the material was further treated for 3 hours at 300C with the result ~hat a catalyst having 5% of ruthenium oxide was obtained. ;
- EXAMPLE lO
~ Carbon fiber non-woven textile made from polyacrylo-; nitrile (80 m2/g) was submerged in a 3% tetrahydrofuran solution . of cyclopentadienyl-methyl-dicarbonyl-ruthenium. Ethanol was~ `-:, ., added to the above solution which was kept at 50C for one hour, and then the composition was washed, dried and further treated with a 10% hydrogen peroxide solution to give a composition coated - ;~
with 7% of ruthenium oxide.
Carbon fiber woven from pitch (120 m2/g) was submerged in a 5~ ethereal solution of di-~-cyclopentadienyl-osmium and dried. It was then thermally treated ~or one hour at 200 C.
A similar treatment was repeated three times, and there was obtained a catalyst having 6~ of osmium.
- --Carbon fiber woven textile made from polybenzimidazole ~80 m2/g) was submerged in a 5~ ethereal solution of di-~-cyclo ;`` ~ .' ...:: ::
1~6~1~93 pentadienyl-manganese, dried and then thermally treated for one hour at 200C.
A similar treatment was repeated three times and there was obtained a cat~lyst having 7~ of man~anese dioxide.
Carbon fiber woven textile made from cellulose (80 m2/g) was submerged in a 10% ethereal solution of methyl-pentacarbonyl-manganese, dried and then thermally treated for 2 hours at 200C.
A similar treatment was repeated three tlmes and, as a result, there was obtained a catalyst having 11~ of manganese dioxide.
-:
; Carbon fiber woven textile made from pitch (80 m2/g) was submerged in a 5% tetrahydrofuran solution of ~-cyclopenta-dienyl-~-allyl-nickel, dried and then thermally treated in a hydrogen atmosphere at 100C for one hour.
This treatment was repeated two times, and there was obtained a catalyst having 5% of nickel. -EXAMPLE 15 .
Carbon fiber woven textile from pitch (80 m2/g) was submerged in a 6% ethereal solution of tetracarbonyl-nickel and dried. It was then thermally treated in a nitrogen atmosphere at 130C for one hour. ~ -: This treatment was repeated three times, and there was obtained a catalyst having 5~ of nic]cel.
Carbon fiber woven textile made from PVA (120 m2/g) was submerged in a 6% tetrahydrofuran solution of di~-cyclopentadienyl- `-cobalt-tribromide, dried and then thermally treated in a nitrogen atmosphere at 100C for one hour.
:, ", ~
: . .
, .. , :. .
: . - . . .
,: , 106~1!393 1 A similar treatment was repeated three times, and there was obtained a catalyst having 5% of cobalt.
Carbon fiber woven textile made from polyacrylonitrile (200 m~/g) was suhmerged in a 10% ethereal solution of dodeca-carbonyl-tetracobalt and dried. It was then thermally treated in a nitrogen atmosphere at 150C for one hour.
A similar treatment was repeated three times and, as a xesult, there was obtained a catalyst containing 7~ of cobalt.
.
Carbon fiber woven textile from pitch (200 m2/g~ was submerged in a 5% benzene solution of di(benzene)-chromium, dried :~
and then tbermally treated in a nitrogen atmosphere at 300C for one hour. There was obtained a catalyst having 1.5% of chromium.
Carbon fiber non-woven textile made from PVA (80 m2/g) was submerged in a 10% trichlene solution of iridium naphthenate ~ -20 and dried. It was then thermally treated for one hour at 300C. ;~
This treatment was repeated two times, and there wasobtained a catalyst containing 7% of iridium.
Carbon fiber non-woven textile made from PVA ~110 m2~g) ; was submerged in an 8% diisopropyl-ethereal solution of octa- -carbonyl-dirhodium and dried. The resultant was then thermally treated for one hour at 80C.
;~ A similar treatment was repeated three times, and there was obtained a catalyst having 7% o~ rhodium.
. ~.
~ - 12 -: ' :
~1 06~ 3 1 EX~MPLE 21 _ .
Carbon fiber non-woven textile made from cellulose (80 m2/g) was submerged in a 5~ tetrahydrofuran solution of acetyl-pentacarbonyl-manganese, ciried, and then thermally treated for one hour at 100C.
~ similar treatment was repeated three times, and there was obtained a catalyst having 6% of manganese dioxide.
The obtained composition was further submerged in a 5~
chloroform solution of palladium naphthenate, dried and then heated at 250C for 30 minutes to give a composition coated with 1.5% of palladium.
~- EXAMPLE 22 Carbon fiber woven textile made from polybenzimidazole ~80 m2~g) was submerged in a 5~ ethereal solution of nonacarbonyl-diiron, dried and then thermally treated for one hour at 200~.
The above-treated textile was further submerged in a 5%
i tetrahydrofuran solution of dodecacarbonyl-triruthenium, dried and then thermally treated for one hour at 200C.
As a resultj there was obtained a catalyst having 7 - of metal.
~EXAMPLE 23 ; Carbon fiber woven textile made from polyacrylonitrile (80 m /g) was submerged in an ethereal solution containing 1.5%
of dodecacarbonyl-triruthenium and 1.5~ of octacarbonyl-dirhodium, dried and then thermally treated for one hour at 160C.
After a similar treatment was repeated three times, the above textile was thermally treated in air at 400C. As a result, there was obtained a catalyst having 4% of metal.
' - 13 - ~
11~6~ 3 Carbon fiber woven textile made from polyacrylonitrile (250 m2/g) was submerged in a chloroform solution containing 5~
of palladium naphthenate and 1% of ruthenium naphthenate, dried and then thermally treated for 2 hours at 400C.
A similar treatment was repeated three times, and there was obtained a catalyst having 4.0~ of metal.
. .
~ EXAMPLE 25 ..
A carbon fiber woven textile made from polybenzimidazole (80 m2/g) was submerged in an ethereal solution containing 5% of di-~-cyclopentadienyl-manganese and 5% of nonacarbonyl-diiron, and then dried and pyrolyzed at 350C for one hour.
This treatment was repeated three times, followed by ~aking in air at 400C for 3 hours, to produce a textile coated with 8% by weight of metal. The resulting composition was sub-sequently submerged in a chloroform solution containing 0.2~ of palladium naphthenate and 0.2~ of platinum naphthenate, dried and then pyrolyzed at 300C for 2 hours to give a catalyst having ~ ;
0.1% of platinum and palladium. ~
EXAMPLE 26 ~ -... :. - :
A carbon fiber woven textile made from pitch ~80 m2/g) ;-~
was submerged in a 5% pentane solution of methyl-pentacarbonyl-manganese and dried. It was then heated in a hydrogen àtmosphere '~
at 100C for one hour.
The treated textile was then submerged in a 5% aqueous - solution of ruthenium chloride and pyrolyzed at 400C for 3 hours to give a catalyst having 5% of metal.
EX~MPLE 27 --- Carhon fiber woven textile made from cellulose (170 m2/g) was submerged in a 5% chloroform solution of palladium naphthenate, ' ' ,:
. .
, ~(~6~393 1 dried and then thermally treated at 220C ~or one hour. There was obtained a composition having 2% of palladium.
The composition obtained in the above procedure was submerged in a formaldehyde-aqueous solution containing 30% of PdC12 maintained at -10C. To the mixture was added 30~ potassium hydroxide aqueous solution, and it was kept at 60C for 30 minutes.
The composition was washed, dried and subsequently treated at 100C for one hour to give a catalyst having 5% of palladium.
A carbon fiber woven textile made from polyacrylonitrile ~- (200 m2/g) was submerged in a 5% chloroform solution of palladi~
naphthenate, dried and thermally treated at 200C for 30 minutes to give a composition containing 3.5~ of palladium.
The treated textile subsequently was submerged in an aqueous solution consisting of 2% of ammonium palladium chloride and small amounts of formic acid. The solution was heated up to 60C and a 30% aqueous solution of potassium hydroxide was added thereto. After 30 minutes, the textile was dried, and, as a result, there was obtained a catalyst having 5.5% of palladium.
A carbon fiber non-woven textile made from polyacrylo-nitrile (120 m2/g) was submerged in a 5% chloroform solution of palladium naphthenate, dried and then thermally treated at 230C
for 2 hours.
The obtained composition was submerged in an aqueous solution containing 20% sodium sorbate, a small amount of sodium hydroxide and palladium chloride dissolved in dilute hydrochloric acid. The whole mixture was heated up to 60C, dried and finally treated with hydrogen at 80C for 2 hours to give a catalyst having 6% palladium.
:- .: : : : , - :
Carbon fiber non-woven textile made from PVA (170 m2/g) was submer~ed in a 5% toluene solution of platinum dibutyldithio-carbamate, dried and then thermally treated for 2 hours at 250C.
The above-treated textile was further submerged in an ; .
aqueous solution of chloroplatinic acid and was alkalized by - adding NaCO3 thereto. After the addition of hydrazine, the mixture was heated to 60C and allowed to stand for one hour and dried. A catalyst having 5% platinum was obtained.
A carbon fiber woven textile made from PVA (80 m2/g) was submerged in a 5% tetrahydrofuran solution of ~~allyl-~~cyclo-pentadienyl platinum, dried and then thermally treated at 130C
for one hour. The treated textile was then submerged in a S0 aqueous solution of hexachloroplatinic acid, and 40% formalin was added to the solution. To the resulting mixture maintained at 0C, a 30% aqueous solution of sodium hydroxide was added, and the mixture was allowed to stand for 12 hours. Washing the produced composition with water and then drying at 50C gave a ~ ~
catalyst having 4~ of platinum. ~;
Carbon fiber non~woven textile made from PVA (80 m2/g) was subme~ged in a 3% toluene solution of platinum tert-butyl mercaptide, dried and then thermally treated for one hour at 200C~ The composition thus obtained was further treated similarly as described in the latter part of Example 31, and there was obtained a catalyst containing 5~ of platinum.
.
--------__ Carbon fiber woven textile made from pitch (120 m2/g) was submerged in an 8~ ethereal solution of platinum tert-butyl-mercaptide, dried and then thermally treated for one hour at 200C
,:
.; ............. ~ . . ............................ ..
.-:: -: . . . .
-: .
iO~4893 to give a composition having l~ of platin~n. Furthexmore, the above textile was submerged in a 50~ aqueous solution of chloro-platinic acid, and 40~ of formalin was added to the solution.
To the resulting mixture maintained at 0C, a 30%
aqueous solution of sodium hydroxide was added, and the mixture was allowed to stand for 12 hours. Washing the treated composition with water and drying at 50C gave a catalyst having 4% of platinum.
Carbon fiber woven textile from PV~ (120 m2/g) was sub-merged in a 2~ chloroform solution of gold naphthenate, dried and then thermally treated for one hour at 240C to give a catalyst composition having l~ of gold.
The above-treated textile was submerged in an aqueous solution containing ammonium palladium chloride and formic acid, and then a 20% aqueous solution of potassium hydroxide was added to the solution. The resulting mixture was maintained at 60C
for one hour, dried at 50C and, as a result, there was obtained a catalyst having 4% of palladium. -Caxbon fiber non-woven textile from PVA (80 m2/g) was submerged in a 2% chloroform solution of gold naphthenate and dried. It was then thermally treated for one hour at 230C. By this treatment, the textile obtained contained 1% of gold.
The ~bove-treated textile was submerged in an aqueous solution containing 30% of chloroplatinic acid and 30% of formalin.
To the resulting mixture maintained at 0C a 50% sodium hydroxide solution was added and the mixture was allowed to stand for 12 hours. Washing the treated textile with water accompanied by drying at 50C gave a catalyst having 7% of platinum.
~)648~3 ~ EXAMPLE 36_ -~ Carbon fiber woven textile from PVA ~120 m2/g) was sub-merged in a 10~ chloroform solution of gold naphthenate, dried and then thermally treated for 2 hours at 240C. By this treat-ment, the textile was coated with 1% of gold.
The textile was further submerged in an aqueous solution consisting of 2~ of ammonium palladium chloride and formic acid.
To the mixture maintained at 60Cj a 30~ aqueous solution of ;~ potassium hydroxide was added and, after 30 minutes, it was washed with water and dried at 50C. The catalyst obtained contained 66 of palladium.
' A carbon fiber woven textile made from PVA (130 m2/g) was submerged in a 5% chloroform solution of silver naphthenate and dried. It was then thermally treated for one hour at 200C. ~ ~-The above-treated textile was submerged in an aqueous -solution containing 30% of silver nitrate and 10% of sodi~
hydroxide, and a 30% aqueous solution of hydrogen peroxide was further added slowly thereto. The mixture was kept at 30C for one hour, dried at 50C and a catalyst having 10% of silver was obtained.
Carbon fiber woven textile from pitch ~80 m2/g) was - submerged in a 5% ethereal solution of di-~-cyclopentadienyl~-tetracarbonyl-diosmium and dried. It was then thermally treated in a nitrogen atmosphere at 100C for 2 hours. By means of this treatment, the above textile was coated with 2% of osmium. ~-.
The textile was then submerged in an aqueous solution ; 30 containing 2% of ammonium palladium chloride and formic acld. A
' .
.,. - . ~:
8~3 1 30% aqueous solution of potassium hydroxide was added thereto and the solution was heated up to 60C. After 30 minutes, washing with water and drying at 50C gave a catalyst containing 5~ palladium.
Carbon fiber woven textile made from PVA (120 m2/g) was submerged in a 10% e-thereal solution of di-~-cyclopentadienyl-nickel, dried and then thermally treated in a nitrogen atmosphere at 150C for 2 hours. By this treatment, the textile was coated with 2% of nickel.
The textile was furthermore submerged in an aqueous solution containing 30% of nickel sulfate, 10% of sodi~n hypo-phosphite and lO~i of sodium acetate, allowed to stand for 30 minutes at 98-99C, and then dried. The treated textile was ; finally subjected to a hydrogen atmosphere at 250C for 2 hours and, as a result, a catalyst having 5% of nickel was obtained.
EX~4PLE 4D
A carbon fiber woven textile made from pitch (80 m2/g) was submerged in a 6~i tetrahydrofuran solution of ~-cyclopenta-- 20 dienyl-~-allyl nickel and dried. It was then thermally treated `
under nitrogen at 130C for 2 hours. By this treatment, the textile was coated with 2~i of nickel.
Ater a lO~i aqueous solution of sodium hypophosphite was added to the 30~ aqueous solution of nickel sulfate, the treated textile was submerged therein, and it was maintained at `-98-99C for 30 minutes. After washing with water and drying, the treated textile was finally treated in a hydro~en atmosphere at 250C for 2 hours, and a catalyst having 6% of nickel was obtained.
~ 30 : ':
~ - 19 - ., ; . - . . ~ ,. ,,:
1~6413~3 A carbon fiber woven textile made from PVA (120 m2/y) was submerged in a 7~ tetrahydrofuran solution of ~-cyclopenta-dienyl-dicarbonyl-cobalt and dried. It was then thermally treated under nitrogen at 130C for 2 hours. By this treatment, the textile was coated with 1% of cobalt.
The above-treated was further submerged in a 30% aqueous solution of cobalt nitrate, and a 4~ aqueous solution of sodium hydrogen carbonate was added thereto. The solution was maintained at 80C for 2 hours.
After washing with water and drying, the textile was finally treated in a hydrogen atmosphere at ~70C for 2-3 hours, and a catalyst having 4% of cobalt was obtained.
A carbon fiber woven textile made from polyacrylonitrile - (80 m2/g) was submerged in a 10% ethereal solution of dodeca-carbonyl-tetracobalt and dried. It was then thermally treated in l a nitrogen atmosphere at 160C for one hour. Subsequently, the '! 20 above-treated textile was submerged in a 30% a~ueous solution of cobalt nitrate. A 4% aqueous solution of sodium hydrogen carbonate was added thereto, and the solution was heated at 80C for 2 hours.
; Aftex washing and drying, the treated textile was final]y treated in a hydrogen atmosphere at 270C for 2-3 hours, and a catalyst having 6% of cobalt was obtained.
.
Carbon fiber woven textile made from pitch (160 m2/g) was submerged in an 8% tetrahydrofuran solution of di-~-cyclo- ;
pentadienyl-chromium and dried. It was then thermally treated in a nitrogen atmosphere at 180C for 2 hours. By this treatment, the above textile was coated with 2% of chromium.
.~.. , - ~ .
-, .
L8~3 The treated textile was furthermore submerged in an aqueous solution containing a 1 normal concentration of chromium nitrate and a 1 normal concentratlon of ammonium nitrate, R 1 normal concentration of aqueous ammonium was added thereto, and the solution was stirred at 80-90C. After washing and drying, the treated textile was subjected to a hydrogen atmosphere at 250C for 3 hours, and a catalyst having 5% of chromium was obtained.
~,' .
. 1 0 Carbon fiber woven textile made from polyacrylonitrile (200 m /g) was submerged in a 10% chloroform solution of ruthenium rosinate, dried and then thermally treated for one hour at 150C.
Subsequently, the above-treated textile was submerged in a 10%
aqueous solution of ruthenium chloride and was thermally treated at 400C. As a result, a catalyst having 3% of ruthenium oxide was obtained.
-Carbon fiber non-woven textile from cellulose (80 m2/g) was submerged in a 5~ tatrahydrofuran solution of palladium rosinate and dried. It was then thermally treated for one hour at 300C.
The above-treated textile was further submerged in a 5%
aqueous soiution of ruthenium chloride, dried and thermally treated at 400 C for 30 minutes. A catalyst having 1.5% of metal was obtained.
A carbon fiber woven textile from pitch (120 m2/y) was submerged in a 5~ cyclohexanone solution of dodecacarbonyl-tri-ruthenium and dried. It was then thermally treated for one hourat 150C.
.
;~. : , . . : .
. . .
1~6~893 a The abova-treated tex-tile was further submerged in a 5% aqueous solution of rhodium chloride and thermally treated at 300C for one hour. A catalyst containing 2% of metal was obtained.
:, Carbon fiber non-woven textile made from cellulose (80 m /g~ was submerged in a 0.5~ chloroform solution of palladium naphthenate and dried. It was then thermally treated for 30 minutes at 250C. By this treatment, the above non~woven textile ; was coated with 0.1% of palladium.
The textile was further submerged in an aqueous solution containing 10% of ruthenium chloride and 20~ of silver nitrate, dried and thermally treated at 500C for one hour. The latter treatment was repeated three times, and a catalyst haviny 5% of , ruthenium and silver was obtained.
.`' ' ~ . .
` EXAMPLE 48 .
A mixture of circulating gases composed of CO (15%),
2 (17~) and N2 (68~) was treated with the catalyst obtained in Example 21 at 100C with a flow rate of 0.08 m3/min. and under 1 atmosphere. Analysis of the resulting mixture disclosed a ., 98.8% conversion of CO into CO2.
The catalyst obtained in Example 21 was used with a ` circulating gaseous mixture composed of CO (8~), SO2 (10%~, 2 I (20~) and N2 (62~) at 40C and 1 atmosphere with a flow rate of - 0.06 m3/min.
`¦ The convarsion rate of CO and SO2 were as follows.
, 30 ~i - ~ , . . . . .
.:~: , . . .
., ~ , 1~ ~ 4~ ~
1 at 40C CO : 93.3%
SO2: 96.7~
at 100C CO : 98.9%
SO2: 99.4%
EXAMPLE SO
The catalyst obtained in Example 2 was treated in a hydrogen stream at 80C for 2 hours, and then it was used in a circulating methanolic solution of quinone at room tempera~ure, the flow rate thereof being 30 l/min. After 3 hours, hydroquinone was obtained a~ a conversion rate of Z2%~ Then, the temperature ~ was raised to 60C to prevent the deposition of hydroquinone.
After further reaction was conducted for an additional 6 hours, hydroquinone was obtained with a final conversion rate of 97.4~.
.~' . .
; EXAMPLE 51 ., . . -- . .
The catalyst obtained in Example 14 was put in a 500;cc.
flask equipped with a H2 inlet tube and a refluxing condenser.
Gaseous hydrogen was introduced to an ethanolic solution of benzo-nitrile in the flask at 35C for 6 hours to give both benzylamine (64~) and diben2ylamine (12%). ~;
A dioxane solution of glycolic acid was reduced at 47 ~` ; -atm. at 145C for 30 minutes in an autoclave with the use of the catalyst obtained in Example 10~ From this reaction, ethylene glycol was obtained with a conversion rate of 44~. Under similar conditions, a conversion rate of 66% was obtained undex a pressure ` of 78 atm. ;
A dioxane solution of adipic acid was treated at 60 atm.
.' .
.. . .. . .
: l.t;3 ~48~3 1 at 176C for one hour by a procedure analogous to that described in Example 52. From this reaction, hexamethylene glycol wa~
obtained with a 60% conversion rate.
An ethanolic solution of benzaldehyda was reduced at 25C at 1 atm. with the use of the catalyst obtained in Example 1.
After reduction with hydrogen for half an hour~ benzyl alcohol was obtained in an 87% conversion rate~ A further reduction for 6 hours gave toluene in an 88% yielcl.
.
; In a mixture composed of 10% ethylene and 90% nitrogen, the ratalyst obtained in Example 37 was maintained at 250C for one hour. Then, the catalyst was used for the preparation of ethylene oxide under the following conditions:
reaction pressure13.5 kg/cm2 reaction temperature 265C
: flow rate 0.05 m3/min.
- ~0 reaction time 200 hours .
Composition of circulated gases:
ethylene 6.3%
O
C2 8%
The conversion rate to ethylene oxide was 88.4%;
C2H4O/hr/Ag(g) = 31.6, which is higher by 4.3% than the 27.3%
mean value previously accepted for the alumina-silver catalyst. ; `~
j EX~MPLE 56 A mixture composèd of:
: . :
.~ :
~ . . - . , 1 propylene 10%
2 13.5%
~2 8.5 N2 68%
was similarly treated as in Example 55 at 375C. Propylene oxide was obtained therefrom with a maximum yield of 91.3% C3H6O/hr/Ag(g)=
33.4.
A circulating gas mixture containing methanol (20%~, oxygen (10%) and nitrogen (70%) was treated using the catalyst --- obtained in Example 37 at 340C and 7~5 kg/cm2 for 160 hours, the flow rate of the mixed gas being 0.08 m3/min. From this run, formaldehyde HCHO(g)/hr/Ag(g~=26.3, was obtained with a selectivity of 99.5~ and a conversion rate of 58.4%.
These values are slightly higher in comparison with the case where Ag-A12O3 catalyst was used with a selectivity of 99.5%
and a conversion rate of 51.6%.
A gaseous mixture composed of N2 (70%)' 2 (10%) and ethyl alcohol (20%) was treated in a similar manner under similar reaction conditions as in Example 57 to give acetaldehyde in a 21.6% conversion rate with a selectivity of 84.7%.
The air oxidation of benzene was conducted with the use of the catalyst obtained in Example 43 in a circular reaction system.
gas composition: C~H6: 10%
air: 90%
reaction temperature 370C -~`
. 10~;4B93 reaction pressure 1 kg/cm2 flow rat~ 0.06 m3/min.
, From this system, maleic anhydride was obtained with a 47% conversion rate after 12 hours, and in an 84% conversion rate after 60 hours.
. =_ . . :
The catalyst obtained in Example 38 was used for the reaction of a gaseous mixture composed of NO (24~), 2 (20%) and N2 (56~) having a flow rate of 0.06 m3/min~ at a reaction pressure of 3.5 kg/cm2. The conversion rate ~rom NO to NO2 was as follows:
after 6 hours: 64% at 40C
7~ at 60C
96.6% at 66C
91% at 80C
88% at 100C
86% at 120C ~ ~
63% at 160C ~ -., . :~ , In the case where a catalyst containing silica and alumina as the carrier was used in a similar reaction, a maximum conversion rate of 96% is attained at 270-300C. Hence, the use of the composition of the invention attains a higher conversion rate at lower temperatures as compared with the prior art techniques.
' ~ . . . ~
The catalyst obtained in Example 31 is put in a 500 cc.
1ask equipped with a hydrogen inlet tube and a refluxing condenser.
To an acetic acid solution of phenol in the flask, gaseous hydrogen was introduced at 40C. After 4 hours of reaction, cyclohexanol (72~) and cyclohexane (16%) were obtained.
, ~ ~, .. . . ... . ... ....
An acetic acid solution of benzoic acid was reduced at 20C for 3 hours by a procedure analogous to that described in Example 61 to produce cyclohexane carboxylic acid in an 88~ yield.
The catalyst obtained in Example 30 was used for the reduction of certain aromatic organic compounds with the use of tetrahydrofuran as a solvent at 5 atm. in an autoclave. The results were as follows:
1. biphenyl phenylcyclohexanein 82~ yield (60C, 1 hr) 2. hydroquinone 1,4-cyclohexane-diolin 66% yield (50C, 1 hr)
The catalyst obtained in Example 21 was used with a ` circulating gaseous mixture composed of CO (8~), SO2 (10%~, 2 I (20~) and N2 (62~) at 40C and 1 atmosphere with a flow rate of - 0.06 m3/min.
`¦ The convarsion rate of CO and SO2 were as follows.
, 30 ~i - ~ , . . . . .
.:~: , . . .
., ~ , 1~ ~ 4~ ~
1 at 40C CO : 93.3%
SO2: 96.7~
at 100C CO : 98.9%
SO2: 99.4%
EXAMPLE SO
The catalyst obtained in Example 2 was treated in a hydrogen stream at 80C for 2 hours, and then it was used in a circulating methanolic solution of quinone at room tempera~ure, the flow rate thereof being 30 l/min. After 3 hours, hydroquinone was obtained a~ a conversion rate of Z2%~ Then, the temperature ~ was raised to 60C to prevent the deposition of hydroquinone.
After further reaction was conducted for an additional 6 hours, hydroquinone was obtained with a final conversion rate of 97.4~.
.~' . .
; EXAMPLE 51 ., . . -- . .
The catalyst obtained in Example 14 was put in a 500;cc.
flask equipped with a H2 inlet tube and a refluxing condenser.
Gaseous hydrogen was introduced to an ethanolic solution of benzo-nitrile in the flask at 35C for 6 hours to give both benzylamine (64~) and diben2ylamine (12%). ~;
A dioxane solution of glycolic acid was reduced at 47 ~` ; -atm. at 145C for 30 minutes in an autoclave with the use of the catalyst obtained in Example 10~ From this reaction, ethylene glycol was obtained with a conversion rate of 44~. Under similar conditions, a conversion rate of 66% was obtained undex a pressure ` of 78 atm. ;
A dioxane solution of adipic acid was treated at 60 atm.
.' .
.. . .. . .
: l.t;3 ~48~3 1 at 176C for one hour by a procedure analogous to that described in Example 52. From this reaction, hexamethylene glycol wa~
obtained with a 60% conversion rate.
An ethanolic solution of benzaldehyda was reduced at 25C at 1 atm. with the use of the catalyst obtained in Example 1.
After reduction with hydrogen for half an hour~ benzyl alcohol was obtained in an 87% conversion rate~ A further reduction for 6 hours gave toluene in an 88% yielcl.
.
; In a mixture composed of 10% ethylene and 90% nitrogen, the ratalyst obtained in Example 37 was maintained at 250C for one hour. Then, the catalyst was used for the preparation of ethylene oxide under the following conditions:
reaction pressure13.5 kg/cm2 reaction temperature 265C
: flow rate 0.05 m3/min.
- ~0 reaction time 200 hours .
Composition of circulated gases:
ethylene 6.3%
O
C2 8%
The conversion rate to ethylene oxide was 88.4%;
C2H4O/hr/Ag(g) = 31.6, which is higher by 4.3% than the 27.3%
mean value previously accepted for the alumina-silver catalyst. ; `~
j EX~MPLE 56 A mixture composèd of:
: . :
.~ :
~ . . - . , 1 propylene 10%
2 13.5%
~2 8.5 N2 68%
was similarly treated as in Example 55 at 375C. Propylene oxide was obtained therefrom with a maximum yield of 91.3% C3H6O/hr/Ag(g)=
33.4.
A circulating gas mixture containing methanol (20%~, oxygen (10%) and nitrogen (70%) was treated using the catalyst --- obtained in Example 37 at 340C and 7~5 kg/cm2 for 160 hours, the flow rate of the mixed gas being 0.08 m3/min. From this run, formaldehyde HCHO(g)/hr/Ag(g~=26.3, was obtained with a selectivity of 99.5~ and a conversion rate of 58.4%.
These values are slightly higher in comparison with the case where Ag-A12O3 catalyst was used with a selectivity of 99.5%
and a conversion rate of 51.6%.
A gaseous mixture composed of N2 (70%)' 2 (10%) and ethyl alcohol (20%) was treated in a similar manner under similar reaction conditions as in Example 57 to give acetaldehyde in a 21.6% conversion rate with a selectivity of 84.7%.
The air oxidation of benzene was conducted with the use of the catalyst obtained in Example 43 in a circular reaction system.
gas composition: C~H6: 10%
air: 90%
reaction temperature 370C -~`
. 10~;4B93 reaction pressure 1 kg/cm2 flow rat~ 0.06 m3/min.
, From this system, maleic anhydride was obtained with a 47% conversion rate after 12 hours, and in an 84% conversion rate after 60 hours.
. =_ . . :
The catalyst obtained in Example 38 was used for the reaction of a gaseous mixture composed of NO (24~), 2 (20%) and N2 (56~) having a flow rate of 0.06 m3/min~ at a reaction pressure of 3.5 kg/cm2. The conversion rate ~rom NO to NO2 was as follows:
after 6 hours: 64% at 40C
7~ at 60C
96.6% at 66C
91% at 80C
88% at 100C
86% at 120C ~ ~
63% at 160C ~ -., . :~ , In the case where a catalyst containing silica and alumina as the carrier was used in a similar reaction, a maximum conversion rate of 96% is attained at 270-300C. Hence, the use of the composition of the invention attains a higher conversion rate at lower temperatures as compared with the prior art techniques.
' ~ . . . ~
The catalyst obtained in Example 31 is put in a 500 cc.
1ask equipped with a hydrogen inlet tube and a refluxing condenser.
To an acetic acid solution of phenol in the flask, gaseous hydrogen was introduced at 40C. After 4 hours of reaction, cyclohexanol (72~) and cyclohexane (16%) were obtained.
, ~ ~, .. . . ... . ... ....
An acetic acid solution of benzoic acid was reduced at 20C for 3 hours by a procedure analogous to that described in Example 61 to produce cyclohexane carboxylic acid in an 88~ yield.
The catalyst obtained in Example 30 was used for the reduction of certain aromatic organic compounds with the use of tetrahydrofuran as a solvent at 5 atm. in an autoclave. The results were as follows:
1. biphenyl phenylcyclohexanein 82~ yield (60C, 1 hr) 2. hydroquinone 1,4-cyclohexane-diolin 66% yield (50C, 1 hr)
3. ~-naphthol 1,2,3,4-tetrahydro-2-in 62% yield (50C~ 1 hr) - naphthol The catalyst obtained in Example 38 was made up into a solid having a thickness of 1 cm. The obtained solid was used in connection with the treatment of a gaseous mixture comprising C0, H2S, N0 and S02 at 40C for over 20 hours. The rate of flow was maintained at 0.05 m3/~in. The decrease in pressure owing to transit through the catalytic textile was 0.2%.
The decrease of volume percentage of the components was as follows~
; C0 : from11.6 to 0.3 ;
H2S: from7.3 to 0.9 N0 : from6.8 to 0.2 . . .
S02: from3.8 to 1.6 30Using the catalyst in Example 32, gaseous hydrogen was introduced at 25C at 1 atm., the solvent being acetic acid. The :, -, - - : .. : . . .
1 conversion rates using the following compounds in this procedure were as follows:
, After 2 hours:
1. from toluene hexahydrotoluene (67~) ; 2. from benzoic acid hexahydrobenzoic acid (76~) 3. from naphthalene decalin (88%)
The decrease of volume percentage of the components was as follows~
; C0 : from11.6 to 0.3 ;
H2S: from7.3 to 0.9 N0 : from6.8 to 0.2 . . .
S02: from3.8 to 1.6 30Using the catalyst in Example 32, gaseous hydrogen was introduced at 25C at 1 atm., the solvent being acetic acid. The :, -, - - : .. : . . .
1 conversion rates using the following compounds in this procedure were as follows:
, After 2 hours:
1. from toluene hexahydrotoluene (67~) ; 2. from benzoic acid hexahydrobenzoic acid (76~) 3. from naphthalene decalin (88%)
4. from pyridine piperidine ~97~) : .
5. from benzene cyclohexane ~65%~
tO 6. from quinoline decahydroquinoline (59%) 7. from cinnamic acid hydrocinnamic acid (44~
, Hence, it can readily be seen from the above description that the present invention provides a catalyst composition utiliz-ing carbon fiber as a carrier wherein an organometallic compound, including ~-bonded organometallic compounds, of a catalytic metal is coated on the fiber, the thus-treated fiber is dried, and then it is heated at a temperature sufficient to pyrolyze the compound contained thereon. Plural coatings of the same or different metals may be employed, if desired.
The invention being thus described, it will be obvious that the same may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention, and all such modifications are intended to be included within the scope of the following claims.
. . ~
.
~, ~
.. .~ . - .
tO 6. from quinoline decahydroquinoline (59%) 7. from cinnamic acid hydrocinnamic acid (44~
, Hence, it can readily be seen from the above description that the present invention provides a catalyst composition utiliz-ing carbon fiber as a carrier wherein an organometallic compound, including ~-bonded organometallic compounds, of a catalytic metal is coated on the fiber, the thus-treated fiber is dried, and then it is heated at a temperature sufficient to pyrolyze the compound contained thereon. Plural coatings of the same or different metals may be employed, if desired.
The invention being thus described, it will be obvious that the same may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention, and all such modifications are intended to be included within the scope of the following claims.
. . ~
.
~, ~
.. .~ . - .
Claims (2)
1. A catalyst comprising carbon fibre in a form chosen from the group consisting of a filament, yarn and woven or non-woven textile coated with at least one catalytic metal selected from the group consisting of Pt, Ru, Rh, Os, Ir, Fe, Co, Ni, Zn, Cu, Ag, Au, Cr, Mg, and Mn and alloys thereof.
2. A process for preparing a catalyst comprising carbon fibre in a form chosen from the group consisting of a filament, yarn and woven or non-woven textile as a carrier and at least one catalytically active metal layer, the metal being selected from the group consisting of Pt, Ru, Rh, Os, Ir, Fe, Co, Ni, Zn, Cu, Ag, Au, Cr, Mg, and Mn and alloys thereof, uniformly deposited on the carbon fibre which comprises submerging the fibre in one or more non-aqueous solutions containing one or a plurality of organic compounds of the metal or metals to be deposited on said fibre, drying the thus-treated fibre, heating the dried carbon fibre at a temperature sufficient to pyrolyze the com-pounds contained thereon, further submerging the obtained metal coated carbon fibre in at least one aqueous solution containing one or more inorganic compounds of said metal or metals, drying the thus-treated fibre, and heating the dried carbon fibre at a temperature sufficient to pyrolyze the compounds contained thereon.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7489377A JPS5018878B1 (en) | 1974-08-03 | 1974-08-03 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1064893A true CA1064893A (en) | 1979-10-23 |
Family
ID=13968982
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA232,563A Expired CA1064893A (en) | 1974-08-03 | 1975-07-30 | Catalyst composition and method for preparing the same |
Country Status (6)
Country | Link |
---|---|
JP (1) | JPS5018878B1 (en) |
AU (1) | AU496822B2 (en) |
BR (1) | BR7504940A (en) |
CA (1) | CA1064893A (en) |
DE (1) | DE2532254C3 (en) |
FR (1) | FR2280430A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4863893A (en) * | 1986-08-06 | 1989-09-05 | Engelhard Corporation | Low temperature light off ammonia oxidation |
US5108730A (en) * | 1986-08-06 | 1992-04-28 | Engelhard Corporation | Low temperatue light off ammonia oxidation |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58146446A (en) * | 1982-02-25 | 1983-09-01 | Asahi Chem Ind Co Ltd | Fixed bed catalyst |
DE3781629T2 (en) * | 1986-08-06 | 1993-02-18 | Engelhard Corp | PLATINUM-COATED PLATINUM AND RHODIUM CATALYST FIBERS, THEIR PRODUCTION AND USE FOR THE OXYDATION OF AMMONIA. |
DE3931420A1 (en) * | 1989-09-21 | 1991-04-04 | Bayer Ag | CATALYSTS BASED ON METAL-Doped CARBON FIBERS, THEIR PRODUCTION AND THEIR USE |
FR2825296B1 (en) * | 2001-05-30 | 2003-09-12 | Toulouse Inst Nat Polytech | PROCESS FOR PRODUCING SUPPORTED METAL NANOPARTICLES IN A FLUIDIZED BED |
EP1726565A4 (en) * | 2003-12-05 | 2010-03-31 | Mitsubishi Heavy Ind Ltd | Carbon material and flue gas treatment apparatus |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3053775A (en) * | 1959-11-12 | 1962-09-11 | Carbon Wool Corp | Method for carbonizing fibers |
CH550121A (en) * | 1971-06-10 | 1974-06-14 | Lonza Ag | Carbon fibre and active carbon fibre prodn - from organic materials in melt or soln. form by a combined centrifugal or blow spinning and carbonisation process |
GB1436245A (en) * | 1972-09-08 | 1976-05-19 | Kanebo Ltd | Catalysts for the oxidation of carbon monoxide and their pro duction |
-
1974
- 1974-08-03 JP JP7489377A patent/JPS5018878B1/ja active Pending
-
1975
- 1975-07-11 AU AU82978/75A patent/AU496822B2/en not_active Expired
- 1975-07-18 DE DE2532254A patent/DE2532254C3/en not_active Expired
- 1975-07-30 CA CA232,563A patent/CA1064893A/en not_active Expired
- 1975-07-31 FR FR7524016A patent/FR2280430A1/en active Granted
- 1975-08-01 BR BR7504940*A patent/BR7504940A/en unknown
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4863893A (en) * | 1986-08-06 | 1989-09-05 | Engelhard Corporation | Low temperature light off ammonia oxidation |
US5108730A (en) * | 1986-08-06 | 1992-04-28 | Engelhard Corporation | Low temperatue light off ammonia oxidation |
Also Published As
Publication number | Publication date |
---|---|
DE2532254A1 (en) | 1976-02-12 |
AU8297875A (en) | 1977-01-13 |
AU496822B2 (en) | 1978-11-02 |
DE2532254B2 (en) | 1980-04-24 |
DE2532254C3 (en) | 1980-12-11 |
FR2280430B1 (en) | 1979-07-13 |
JPS5018878B1 (en) | 1975-07-02 |
BR7504940A (en) | 1976-07-27 |
FR2280430A1 (en) | 1976-02-27 |
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