JPH0720553B2 - Method for producing platinum-supported catalyst - Google Patents
Method for producing platinum-supported catalystInfo
- Publication number
- JPH0720553B2 JPH0720553B2 JP61265255A JP26525586A JPH0720553B2 JP H0720553 B2 JPH0720553 B2 JP H0720553B2 JP 61265255 A JP61265255 A JP 61265255A JP 26525586 A JP26525586 A JP 26525586A JP H0720553 B2 JPH0720553 B2 JP H0720553B2
- Authority
- JP
- Japan
- Prior art keywords
- platinum
- carrier
- solvent
- reaction
- treatment
- 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 - Lifetime
Links
- 239000003054 catalyst Substances 0.000 title claims description 35
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 103
- 229910052697 platinum Inorganic materials 0.000 claims description 52
- 239000002904 solvent Substances 0.000 claims description 31
- 238000004108 freeze drying Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 description 36
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 31
- 239000010457 zeolite Substances 0.000 description 28
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 24
- 229910021536 Zeolite Inorganic materials 0.000 description 24
- 238000011282 treatment Methods 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 16
- -1 boria Chemical compound 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 11
- 239000003921 oil Substances 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 238000005899 aromatization reaction Methods 0.000 description 8
- 239000000969 carrier Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 8
- 150000002430 hydrocarbons Chemical class 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 229910000323 aluminium silicate Inorganic materials 0.000 description 7
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000003125 aqueous solvent Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052680 mordenite Inorganic materials 0.000 description 4
- 150000003058 platinum compounds Chemical class 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- KHCPSOMSJYAQSY-UHFFFAOYSA-L azane;dichloroplatinum Chemical compound N.N.N.N.Cl[Pt]Cl KHCPSOMSJYAQSY-UHFFFAOYSA-L 0.000 description 3
- NOWPEMKUZKNSGG-UHFFFAOYSA-N azane;platinum(2+) Chemical compound N.N.N.N.[Pt+2] NOWPEMKUZKNSGG-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000006317 isomerization reaction Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- QEGNUYASOUJEHD-UHFFFAOYSA-N 1,1-dimethylcyclohexane Chemical compound CC1(C)CCCCC1 QEGNUYASOUJEHD-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- HNRMPXKDFBEGFZ-UHFFFAOYSA-N 2,2-dimethylbutane Chemical compound CCC(C)(C)C HNRMPXKDFBEGFZ-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical compound CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Natural products CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 description 2
- SGVYKUFIHHTIFL-UHFFFAOYSA-N 2-methylnonane Chemical compound CCCCCCCC(C)C SGVYKUFIHHTIFL-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-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
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- FCUFAHVIZMPWGD-UHFFFAOYSA-N [O-][N+](=O)[Pt](N)(N)[N+]([O-])=O Chemical compound [O-][N+](=O)[Pt](N)(N)[N+]([O-])=O FCUFAHVIZMPWGD-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- ZUBZATZOEPUUQF-UHFFFAOYSA-N isononane Chemical compound CCCCCCC(C)C ZUBZATZOEPUUQF-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- ATQUFXWBVZUTKO-UHFFFAOYSA-N 1-methylcyclopentene Chemical compound CC1=CCCC1 ATQUFXWBVZUTKO-UHFFFAOYSA-N 0.000 description 1
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- 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
- ZRNSSRODJSSVEJ-UHFFFAOYSA-N 2-methylpentacosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC(C)C ZRNSSRODJSSVEJ-UHFFFAOYSA-N 0.000 description 1
- PKXHXOTZMFCXSH-UHFFFAOYSA-N 3,3-dimethylbut-1-ene Chemical compound CC(C)(C)C=C PKXHXOTZMFCXSH-UHFFFAOYSA-N 0.000 description 1
- VBWYZPGRKYRKNV-UHFFFAOYSA-N 3-propanoyl-1,3-benzoxazol-2-one Chemical compound C1=CC=C2OC(=O)N(C(=O)CC)C2=C1 VBWYZPGRKYRKNV-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- JIUFYGIESXPUPL-UHFFFAOYSA-N 5-methylhex-1-ene Chemical compound CC(C)CCC=C JIUFYGIESXPUPL-UHFFFAOYSA-N 0.000 description 1
- DFVOXRAAHOJJBN-UHFFFAOYSA-N 6-methylhept-1-ene Chemical compound CC(C)CCCC=C DFVOXRAAHOJJBN-UHFFFAOYSA-N 0.000 description 1
- YKHFZRXJMPLNTJ-UHFFFAOYSA-N 7-methyloct-1-ene Chemical compound CC(C)CCCCC=C YKHFZRXJMPLNTJ-UHFFFAOYSA-N 0.000 description 1
- DMFDIYIYBVPKNT-UHFFFAOYSA-N 8-methylnon-1-ene Chemical compound CC(C)CCCCCC=C DMFDIYIYBVPKNT-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 208000005156 Dehydration Diseases 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
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- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- FOSZYDNAURUMOT-UHFFFAOYSA-J azane;platinum(4+);tetrachloride Chemical compound N.N.N.N.[Cl-].[Cl-].[Cl-].[Cl-].[Pt+4] FOSZYDNAURUMOT-UHFFFAOYSA-J 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- 229910001423 beryllium ion Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229910052676 chabazite Inorganic materials 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 229910001603 clinoptilolite Inorganic materials 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- LMGZGXSXHCMSAA-UHFFFAOYSA-N cyclodecane Chemical compound C1CCCCCCCCC1 LMGZGXSXHCMSAA-UHFFFAOYSA-N 0.000 description 1
- UCIYGNATMHQYCT-OWOJBTEDSA-N cyclodecene Chemical compound C1CCCC\C=C\CCC1 UCIYGNATMHQYCT-OWOJBTEDSA-N 0.000 description 1
- ZXIJMRYMVAMXQP-UHFFFAOYSA-N cycloheptene Chemical compound C1CCC=CCC1 ZXIJMRYMVAMXQP-UHFFFAOYSA-N 0.000 description 1
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 1
- 239000004914 cyclooctane Substances 0.000 description 1
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 1
- 239000004913 cyclooctene Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 229910052675 erionite Inorganic materials 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012013 faujasite Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 235000021539 instant coffee Nutrition 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- CZMAIROVPAYCMU-UHFFFAOYSA-N lanthanum(3+) Chemical compound [La+3] CZMAIROVPAYCMU-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 150000001457 metallic cations Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N monofluoromethane Natural products FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000004376 petroleum reforming Methods 0.000 description 1
- PKELYQZIUROQSI-UHFFFAOYSA-N phosphane;platinum Chemical compound P.[Pt] PKELYQZIUROQSI-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- KGRJUMGAEQQVFK-UHFFFAOYSA-L platinum(2+);dibromide Chemical compound Br[Pt]Br KGRJUMGAEQQVFK-UHFFFAOYSA-L 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 102200118166 rs16951438 Human genes 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 1
- AIWZOHBYSFSQGV-LNKPDPKZSA-M sodium;(z)-4-oxopent-2-en-2-olate Chemical compound [Na+].C\C([O-])=C\C(C)=O AIWZOHBYSFSQGV-LNKPDPKZSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910001427 strontium ion Inorganic materials 0.000 description 1
- 239000003826 tablet Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 1
Classifications
-
- 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
Description
【発明の詳細な説明】 [産業上の利用分野] この発明は、白金担持触媒の製造法に関し、詳しくは、
炭化水素の異性化反応、芳香族化反応、石油の改質反
応、オレフィンの水素化反応、水素化分解反応などの様
々な反応の触媒として、とりわけ芳香族化反応の触媒と
して好適に使用することができる担持白金触媒の製造法
に関する。TECHNICAL FIELD The present invention relates to a method for producing a platinum-supported catalyst, and more specifically,
Suitable for use as a catalyst for various reactions such as hydrocarbon isomerization reaction, aromatization reaction, petroleum reforming reaction, olefin hydrogenation reaction, and hydrocracking reaction, especially as an aromatization reaction catalyst. The present invention relates to a method for producing a supported platinum catalyst capable of producing.
[従来の技術およびその問題点] 一般にアルミナ、シリカ、シリカーアルミナ、ゼオライ
ト等の担体に白金を担持した触媒は、炭化水素の異性化
反応、脱水素反応、芳香族化反応等の種々の反応に使用
されている。[Prior Art and its Problems] Generally, a catalyst in which platinum is supported on a carrier such as alumina, silica, silica-alumina, or zeolite is used for various reactions such as hydrocarbon isomerization reaction, dehydrogenation reaction, aromatization reaction, and the like. Is used for.
従来、このような白金担持触媒の調整法においては、担
体に白金化合物を担持した後、常圧下に、0〜200℃で
乾燥する。Conventionally, in such a method for preparing a platinum-supported catalyst, a platinum compound is supported on a carrier and then dried at 0 to 200 ° C. under normal pressure.
しかしながら、この方法によると、担持に用いた水等の
溶媒が担体の表面から蒸発により除去されるので、溶媒
に溶解している白金成分が溶媒とともに内部に移動し、
その結果、白金が担体の内部に偏析し、その分布が不均
一になり、不媒性能が低下したり、高価な白金が有効に
作用しないという問題点があった。However, according to this method, since the solvent such as water used for loading is removed from the surface of the carrier by evaporation, the platinum component dissolved in the solvent moves inside together with the solvent,
As a result, there are problems that platinum is segregated inside the carrier, its distribution becomes non-uniform, immobility performance is lowered, and expensive platinum does not act effectively.
[発明の目的] この発明の目的は、前記問題点を解消し、白金が担体の
内部に偏析することがなく、白金の分布が均一であり、
したがって白金が有効に作用し、かつ不媒性能が著しく
向上した白金担持触媒を得ることのできる、白金担持触
媒の製造法を提供することである。[Object of the Invention] An object of the present invention is to solve the above problems, to prevent platinum from segregating inside the carrier, and to provide a uniform distribution of platinum.
Therefore, it is an object of the present invention to provide a method for producing a platinum-supported catalyst, which makes it possible to obtain a platinum-supported catalyst in which platinum effectively acts and which has significantly improved immobility performance.
[前記目的を達成するための手段] この発明者らは、前記事情に基づき、触媒調製時の乾燥
工程に着目し種々の改良を重ねた結果、担持に用いた溶
媒を凍結後減圧下に溶媒を除去する方法、いわゆる凍結
乾燥法を適用することにより前記目的を容易に達成でき
ることを見い出してこの発明を完成するに至った。[Means for Achieving the Object] Based on the above circumstances, the inventors of the present invention focused on the drying step at the time of catalyst preparation and made various improvements. As a result, the solvent used for loading was freeze-dried under reduced pressure. The present invention has been completed by finding that the above object can be easily achieved by applying a so-called freeze-drying method.
すなわち、この発明は、溶媒を用いて白金含有成分を担
体に担持した後、前記溶媒を凍結乾燥法によって除去す
ることを特徴とする白金担持触媒の製造法に関するもの
である。That is, the present invention relates to a method for producing a platinum-supported catalyst, which comprises supporting a platinum-containing component on a carrier using a solvent and then removing the solvent by freeze-drying.
前記担体としては、特に制限はなく、通常担持触媒用の
担体として用いる金属酸化物担体、複合金属酸化物担
体、炭素担体、金属窒化物担体、金属ホウ化物担体、金
属炭化物担体、金属リン酸塩担体、有機ポリマー担体、
イオン交換樹脂等の様々な担体を使用することができ
る。The carrier is not particularly limited and is usually used as a carrier for a supported catalyst, such as a metal oxide carrier, a composite metal oxide carrier, a carbon carrier, a metal nitride carrier, a metal boride carrier, a metal carbide carrier, and a metal phosphate. Carrier, organic polymer carrier,
Various carriers such as ion exchange resins can be used.
なかでも多孔質もしくは高表面積の酸化物系担体、高表
面積の炭素担体が好適に用いられる。Among them, a porous or high surface area oxide-based support and a high surface area carbon support are preferably used.
具体例としては、たとえば、γ−アルミナ、η−アルミ
ナなどのアルミナ担体、シリカゲル、マグネシア、チタ
ニア、ジルコニア、酸化ニオブ、トリア、ボリア、クロ
ミア、酸化亜鉛;シリカアルミナ、アルミナボリア、シ
リカマグネシア、クロミアアルミナ、モリブデナアルミ
ナ、酸化タングステン−アルミナ、シリカチタニア等の
非結晶性複合酸化物;A型ゼオライト、X型ゼオライト、
L型ゼオライト、オメガ型ゼオライト、ウルトラステイ
ブルY型ゼオライト、ZSM−5型ゼオライト、ZSM−11型
ゼオライトなどのZSM型ゼオライト、様々な脱アルミゼ
オライト、ハイシリカゼオライト、モルデナイト、脱ア
ルミモルデナイト、高シリカモルデナイト等の合成ゼオ
ライトもしくは合成結晶性アルミノシリケート;ガロシ
リケート、アルミノガロシリケート、鉄シリケート、鉄
アルミノシリケート等の結晶性シリケートおよび金属置
換型アルミノシリケート類;シリカライト;クリノプチ
ロライト、チャバサイト、エリオナイト、ホージャサイ
ト等の天然ゼオライトもしくは天然結晶性アルミノシリ
ケート;ケイソウ土、活性白土、粘土、雲母類、結晶性
リン酸アルミニウム(アルポ)、非結晶性リン酸アルミ
ニウム、結晶性リン酸ジルコニウム、非結晶性リン酸ジ
ルコニウム等の結晶性または非結晶酸リン酸塩;ペロブ
スカイト等のペロブスカイト型複合酸化物、シーライト
等のシーライト型複合金属酸化物等;活性炭、木炭等の
アモルファス炭素担体、炭素センイ、炭素クロス等の炭
素もしくは炭素質担体、ポリスチレン、ナイロン、ナフ
ィオン等のポリマー担体等を挙げることができる。これ
らの中でも、γ−アルミナ、η−アルミナ、シリカアル
ミナ、シリカ、シリカライト、X型ゼオライト、Y型ゼ
オライト、ウルトラステイブルY型ゼオライト、L型ゼ
オライト、モルデナイト、ZSM−5型ゼオライト、脱ア
ルミゼオライト、脱アルミモルデナイト、スチーム処理
ゼオライト、高シリカゼオライト、アルミノガロシリケ
ート等の合成ゼオライト類もしくは合成結晶性アルミノ
シリケート類等が好適に使用でき、合成ゼオライト類が
特に好適に用いられる。Specific examples include alumina carriers such as γ-alumina and η-alumina, silica gel, magnesia, titania, zirconia, niobium oxide, thoria, boria, chromia, zinc oxide; silica alumina, alumina boria, silica magnesia, chromia alumina. , Non-crystalline composite oxides such as molybdena alumina, tungsten oxide-alumina, and silica-titania; A-type zeolite, X-type zeolite,
ZSM type zeolites such as L type zeolite, Omega type zeolite, Ultrastable Y type zeolite, ZSM-5 type zeolite, ZSM-11 type zeolite, various dealuminated zeolite, high silica zeolite, mordenite, dealuminated mordenite, high silica mordenite Synthetic zeolite or synthetic crystalline aluminosilicate, etc .; crystalline silicates such as gallosilicate, aluminogallosilicate, iron silicate, iron aluminosilicate, and metal-substituted aluminosilicates; silicalite; clinoptilolite, chabazite, erionite , Natural zeolites such as faujasite or natural crystalline aluminosilicates; diatomaceous earth, activated clay, clay, mica, crystalline aluminum phosphate (alpo), non-crystalline aluminum phosphate, crystalline phosphoric acid Crystalline or amorphous acid phosphates such as ruconium and amorphous zirconium phosphate; perovskite type complex oxides such as perovskite; celite type complex metal oxides such as celite; amorphous carbon carriers such as activated carbon and charcoal Examples thereof include carbon or carbonaceous carriers such as carbon fiber and carbon cloth, and polymer carriers such as polystyrene, nylon and Nafion. Among these, γ-alumina, η-alumina, silica alumina, silica, silicalite, X-type zeolite, Y-type zeolite, ultrastable Y-type zeolite, L-type zeolite, mordenite, ZSM-5 type zeolite, dealuminated zeolite, Synthetic zeolites such as dealuminated mordenite, steam-treated zeolite, high-silica zeolite, and aluminogallosilicate or synthetic crystalline aluminosilicates can be preferably used, and synthetic zeolites are particularly preferably used.
これらの担体なかには、たとえば、ゼオライト類、シリ
ケート類、結晶性アルミノシリケート類等のように、陽
イオン交換能を有するものがあるが、そのようなものに
ついてはその陽イオン成分が、水素イオン、アンモニウ
ムイオン、2〜4級アンモニウムイオン、その他のオキ
ソニウムイオン等の非金属性陽イオン、ナトリウムイオ
ン、カリウムイオン、リチウムイオン、セシウムイオ
ン、ベリリウムイオン、マグネシウムイオン、カルシウ
ムイオン、ストロンチウムイオン、バリウムイオン等の
アルカリ金属やアルカリ土類金属イオン、ランタンイオ
ン、セリウムイオンなどの希土類元素イオン、鉄イオ
ン、コバルトイオン、マンガンイオン、ニッケルイオ
ン、銅イオン、銀イオン、パラジウムイオン、ロジウム
イオン、イリジウムイオン、オスミウムイオン、ルテニ
ウムイオン、クロムイオン等の様々の遷移金属イオンも
しくはそれらの錯イオン、亜鉛イオン、カドミウムイオ
ン、タリウムイオン、スズイオン等の典型金属イオンも
しくはそれらの錯イオン等の様々の金属イオン等の中か
ら選ばれる1種または2種以上の陽イオンであってもよ
い。Among these carriers, there are those having a cation exchange ability, such as zeolites, silicates, and crystalline aluminosilicates, and the cation components of such carriers are hydrogen ion and ammonium. Ions, secondary to quaternary ammonium ions, other non-metallic cations such as oxonium ions, sodium ions, potassium ions, lithium ions, cesium ions, beryllium ions, magnesium ions, calcium ions, strontium ions, barium ions, etc. Rare earth element ions such as alkali metal and alkaline earth metal ions, lanthanum ion, cerium ion, iron ion, cobalt ion, manganese ion, nickel ion, copper ion, silver ion, palladium ion, rhodium ion, iridium ion , Various osmium ions, ruthenium ions, various transition metal ions such as chromium ions or complex ions thereof, zinc ions, cadmium ions, thallium ions, tin metal ions such as typical metal ions or various metal ions such as complex ions thereof, etc. It may be one or more cations selected from the above.
さらに前記担体は、必要に応じて、フッ素またはフッ化
物処理、塩素または塩素化合物処理、シリル化処理、テ
トラアルコキシシラン処理等のケイ素化合物処理、酸処
理、アルカリ処理、脱水処理、水熱処理、スチーム処
理、ホスフィン修飾、X線処理、イオンビーム処理、γ
−線処理、部分還元処理、酸素処理、熱処理、摩砕処理
などの化学的もしくは物理的処理を施して、その表面の
化学的性質や細孔径、細孔分布等を調節して用いてもよ
い。Further, the carrier, if necessary, fluorine or fluoride treatment, chlorine or chlorine compound treatment, silylation treatment, silicon compound treatment such as tetraalkoxysilane treatment, acid treatment, alkali treatment, dehydration treatment, hydrothermal treatment, steam treatment , Phosphine modification, X-ray treatment, ion beam treatment, γ
-Chemical or physical treatment such as linear treatment, partial reduction treatment, oxygen treatment, heat treatment, and grinding treatment may be performed to adjust the surface chemical properties, pore diameter, pore distribution, etc. .
なお、これらの担体は1種単独で使用しても、2種以上
を組み合せて使用してもよい。These carriers may be used alone or in combination of two or more.
また、前記担体は、天然品、合成品、市販品、新たに調
製されたもの等いずれのものも用いることができ、押出
し成形品、プレス成形品、ビーズ状、ペレット状、錠剤
状、果粒状、円筒状、柱状、粒状、細片状、板状、膜
状、薄膜状、粉末状、微粉末状、超微粒子状、長繊維
状、短繊維状、中空繊維状、中空円筒状、中空ビーズ
状、中空柱状、クロス状、管状、網状、モノリス体等の
様々な形状、粒径のもの、種々の成形品等として用いる
ことができ、形状や粒径を整えるため、あるいは成形の
ために、種々のバインダーが使用されているものであっ
てもよい。As the carrier, any of natural products, synthetic products, commercially available products, freshly prepared products and the like can be used, and extrusion molded products, press molded products, beads, pellets, tablets, fruit granules can be used. , Cylindrical, columnar, granular, strip, plate, film, thin film, powder, fine powder, ultrafine particle, long fiber, short fiber, hollow fiber, hollow cylinder, hollow bead Shape, hollow columnar shape, cross shape, tubular shape, net shape, various shapes such as monoliths, particle size, various molded articles, etc., to adjust the shape and particle size, or for molding, Various binders may be used.
この発明の方法に用いる前記白金含有成分としては、溶
媒に溶解、もしくは均一なコロイド状に分散可能なもの
であれば特に制限はなく、金属白金、白金コロイド;白
金酸、白金酸塩、白金塩、白金錯体などの白金化合物を
用いることができるが、なかでも溶媒に溶解し易い白金
化合物が好ましく、特に水系溶媒に溶解し易い白金化合
物を好適に用いることができる。The platinum-containing component used in the method of the present invention is not particularly limited as long as it can be dissolved in a solvent or dispersed in a uniform colloidal state, metal platinum, platinum colloid; platinum acid, platinum acid salt, platinum salt. Although a platinum compound such as a platinum complex can be used, a platinum compound that is easily dissolved in a solvent is preferable, and a platinum compound that is easily dissolved in an aqueous solvent is particularly preferably used.
具体的には、たとえば、塩化白金酸、臭化白金酸、ヨウ
化白金酸、フッ化白金酸等のハロゲン化白金酸;塩化白
金酸ナトリウム等のハロゲン化白金酸塩、テトラアンミ
ン白金(II)塩化物、テトラアンミン白金(II)臭化
物、テトラアンミン白金(II)水酸化物、ジニトロジア
ミノ白金、塩化白金、臭化白金、フッ化白金ヨウ化白
金、白金ニトリル錯体、白金ニトロシル錯体、白金カル
ボニル錯体、白金アンミン錯体、白金ホスフィン錯体、
白金アセチルアセトナト錯体、などを挙げることができ
る。これらの中では、塩化白金酸、テトラアンミン白金
(II)塩化物、テトラアンミン白金(II)水酸化物、ジ
ニトロジアミノ白金等を好適に用いることができ、塩化
白金酸、テトラアンミン白金(II)塩化物等を特に好適
に用いることができる。Specifically, for example, chloroplatinic acid, bromoplatinic acid, iodoplatinic acid, fluoroplatinic acid, and other halogenoplatinic acid; sodium chloroplatinate, etc., haloplatinic acid salts, tetraammineplatinum (II) chloride, etc. Substance, tetraammine platinum (II) bromide, tetraammine platinum (II) hydroxide, dinitrodiamino platinum, platinum chloride, platinum bromide, platinum fluoride platinum iodide, platinum nitrile complex, platinum nitrosyl complex, platinum carbonyl complex, platinum ammine Complex, platinum phosphine complex,
Platinum acetylacetonato complex, etc. can be mentioned. Among these, chloroplatinic acid, tetraammineplatinum (II) chloride, tetraammineplatinum (II) hydroxide, dinitrodiaminoplatinum, etc. can be preferably used, and chloroplatinic acid, tetraammineplatinum (II) chloride, etc. Can be used particularly preferably.
なお、これらの白金含有成分は、1種単独で用いても、
2種以上を組み合せて用いてもよい。In addition, even if these platinum-containing components are used alone,
You may use it in combination of 2 or more type.
この発明の方法においては、前記白金含有成分を溶媒に
溶解した溶液または、均一高分散白金コロイド溶液を前
記担体に担持する。In the method of the present invention, a solution obtained by dissolving the platinum-containing component in a solvent or a uniform highly dispersed platinum colloidal solution is supported on the carrier.
使用する溶媒は、用いる白金含有成分を溶解するもの、
あるいは、均一コロイド溶液として安定に保ちうるもの
であれば、特に制限はなく、水系溶媒、非水系溶媒、あ
るいはこれらの混合系溶媒のいずれのものも使用可能で
ある。The solvent used is one that dissolves the platinum-containing component used,
Alternatively, there is no particular limitation as long as it can be stably maintained as a uniform colloidal solution, and any of an aqueous solvent, a non-aqueous solvent, or a mixed solvent thereof can be used.
具体的には、たとえば純水、イオン交換水、水道水、工
業用水などの水;メタノール、エタノール、イソプロパ
ノール、ヘキサノール、オクタノール等のアルコール;
ペンタン、石油エーテル、ヘキサン、シクロヘキサン、
ベンゼン、トルエン、キシレンなどの炭化水素溶媒;ア
セトン、エチルメチルケトン、シクロヘキサノン、アセ
トフェノン等のケトン類;塩化メチル、塩化メチレン、
クロロホルム、四塩化炭素、ジクロロエタン、テトラク
ロロエタン、塩化プロピル、クロロベンゼン、ジクロロ
ベンゼン、フッ化メチル等のハロゲン化炭化水素系溶
媒;酢酸メチル、酢酸エチル、酢酸プロピル等のエステ
ル類;ジエチルエーテル、ジプロピルエーテル、テトラ
ヒドロフラン、ジオキサンなどのエーテル類;アセトニ
トリル、プロピオニトリル等のニトリル類;酢酸、フロ
ピオン酸等の有機酸類;ジメチルアミン、トリメチルア
ミン、トリエチルアミン、プロピルアミン、アニリン等
のアミン類;ジメチルホルムアミド、ジエチルホルムア
ミド、ジメチルアセトアミド等のアミド類等を挙げるこ
とができる。Specifically, for example, water such as pure water, ion-exchanged water, tap water, and industrial water; alcohol such as methanol, ethanol, isopropanol, hexanol, octanol;
Pentane, petroleum ether, hexane, cyclohexane,
Hydrocarbon solvents such as benzene, toluene, xylene; ketones such as acetone, ethyl methyl ketone, cyclohexanone, acetophenone; methyl chloride, methylene chloride,
Chloroform, carbon tetrachloride, dichloroethane, tetrachloroethane, propyl chloride, chlorobenzene, dichlorobenzene, halogenated hydrocarbon solvents such as methyl fluoride; esters such as methyl acetate, ethyl acetate, propyl acetate; diethyl ether, dipropyl ether , Ethers such as tetrahydrofuran, dioxane; nitriles such as acetonitrile and propionitrile; organic acids such as acetic acid and flopionic acid; amines such as dimethylamine, trimethylamine, triethylamine, propylamine, aniline; dimethylformamide, diethylformamide, Examples thereof include amides such as dimethylacetamide.
なお、これらの溶媒は、1種単独で用いても、2種以上
を組み合せて用いてもよい。In addition, these solvent may be used individually by 1 type, or may be used in combination of 2 or more type.
さらに、これらの溶媒もしくはこれらの溶媒と白金含有
成分とからなる溶液系には、必要に応じて、酸、塩酸、
塩、酸化剤、還元剤、pH調整剤、緩衝剤、溶解促進剤、
錯化剤、白金凝集防止剤等の添加剤を添加して用いるこ
ともできる。Furthermore, if necessary, an acid, hydrochloric acid, or a hydrochloric acid may be added to these solvents or a solution system consisting of these solvents and a platinum-containing component.
Salt, oxidizing agent, reducing agent, pH adjusting agent, buffer agent, dissolution accelerator,
An additive such as a complexing agent or a platinum agglomeration inhibitor may be added and used.
そのような添加剤としては、たとえば、塩酸、硝酸、ア
ンモニア、炭酸ナトリウム、酢酸ナトリウム、水酸化ナ
トリウム、水酸化テトラメチルアンモニウム、ヒドロキ
シルアミン、モルホリン、塩化アンモニウム、硝酸アン
モニウム、テトラメチルアンモニウムクロリド、ギ酸、
シュウ酸、ヒドラジン、EDTA、エチレンジアミン、アセ
チルアセトン、ナトリウムアセチルアセトナート、クラ
ウンエーテル、ロッシェル塩、トリフェニルホスフィ
ン、等の様々のものを挙げることができる。なお、これ
らの添加剤は1種単独で用いても、2種以上を組み合せ
て用いてもよい。Examples of such additives include hydrochloric acid, nitric acid, ammonia, sodium carbonate, sodium acetate, sodium hydroxide, tetramethylammonium hydroxide, hydroxylamine, morpholine, ammonium chloride, ammonium nitrate, tetramethylammonium chloride, formic acid,
Various substances such as oxalic acid, hydrazine, EDTA, ethylenediamine, acetylacetone, sodium acetylacetonate, crown ether, Rochelle salt, triphenylphosphine and the like can be mentioned. These additives may be used alone or in combination of two or more.
この発明の方法においては、使用する担体の種類または
担持方法にしたがって、前記白金含有成分と前記溶媒、
あるいは必要ならばこれらと前記添加剤とを適切に選択
し、それらを組み合せて白金含有溶液を調製し、該白金
含有溶液を担体に接触せしめ、白金成分を担体に担持す
る。In the method of the present invention, the platinum-containing component and the solvent, according to the type of carrier used or the supporting method,
Alternatively, if necessary, these and the above additives are appropriately selected, they are combined to prepare a platinum-containing solution, the platinum-containing solution is brought into contact with a carrier, and the platinum component is supported on the carrier.
使用する白金含有成分溶液の濃度としては特に制限がな
いが、目的とする白金の担持量と用いる担体の量および
使用する溶液の量とのバランスを考慮して設定すればよ
い。The concentration of the platinum-containing component solution to be used is not particularly limited, but may be set in consideration of the balance between the target amount of platinum supported, the amount of carrier used and the amount of solution used.
この溶液の使用量としては、用いる担体の全体に十分に
接触するのに充分な量、あるいは、用いる担体のみかけ
の飽和含水率程度もしくは、それより少し多い程度の量
に設定することが望ましい。The amount of this solution to be used is preferably set to an amount sufficient to contact the entire carrier to be used, or to an apparent saturated water content of the carrier to be used, or an amount slightly higher than that.
ここで、溶液の使用量が、上記の適量に対して、大過剰
であると、凍結乾燥処理に、長時間を要したり、凍結乾
燥処理前に、予備乾燥を必要とする場合があったりし
て、不利になることがある。Here, if the amount of the solution used is a large excess with respect to the above-mentioned appropriate amount, the freeze-drying process may take a long time, or pre-drying may be required before the freeze-drying process. Then, it may be disadvantageous.
白金の担持量は、使用目的や反応により異なるが、白金
金属として、通常、0.1〜5.0重量%好ましくは0.3〜1.5
重量%とすればよい。The amount of platinum supported varies depending on the purpose of use and reaction, but as platinum metal, it is usually 0.1 to 5.0% by weight, preferably 0.3 to 1.5.
It may be weight%.
担持方法としては、特に制限はなく、通常の湿式担持方
法、たとえば、含浸法、浸漬法、湿式吸着法、イオン交
換法等、溶媒蒸発法、およびこれらを組み合せた方法等
を採用することができる。この担持に際しての操作方式
としては、静置法、撹拌法、溶液流通法、溶媒リフラッ
クス法等およびこれらを組み合せた方式を用いることが
できる。The supporting method is not particularly limited, and a usual wet supporting method, for example, an impregnation method, an immersion method, a wet adsorption method, an ion exchange method, a solvent evaporation method, a method combining these, or the like can be adopted. . As an operation method for supporting the particles, a static method, a stirring method, a solution flow method, a solvent reflux method, or a combination of these methods can be used.
このような担持方法および操作方式を適当に組み合せる
ことによって、用いた白金含有成分もしくは、溶液に調
製する際、または担体に接触もしくは担持する際に生成
した白金成分を担体に担持して、実質的に未乾燥状態の
白金担持担体を得る。By appropriately combining such loading methods and operating methods, the platinum-containing component used, or the platinum component produced when preparing a solution or contacting or loading the carrier, is supported on the carrier, and An undried state platinum-supporting carrier is obtained.
ここで、上記の担持操作によって得られた生成物系中に
白金担持担体とともに、溶媒もしくは白金含有溶液が過
剰に残存する場合には、これをそのまま、後述の凍結乾
燥処理することも可能であるが、溶媒が多量に残留する
と、凍結乾燥に長時間を要したり、得られる白金担持触
媒中の白金の分布が不均一となることがあるので、通
常、この残存する溶媒または溶液の過剰な分を分離除去
するか、あるいは溶媒の過剰な分を蒸発させることによ
って担持をみかけ上完成せしめるなどの処理を施して、
白金担持担体を実質的に未乾燥状態の白金担持担体とし
て回収することが望ましい。Here, in the case where the solvent or the platinum-containing solution remains in excess in the product system obtained by the above-mentioned supporting operation together with the platinum-supporting carrier, this may be directly subjected to the freeze-drying treatment described later. However, if a large amount of the solvent remains, it may take a long time for freeze-drying or the distribution of platinum in the obtained platinum-supported catalyst may become non-uniform, so that an excessive amount of this residual solvent or solution is usually used. By separating and removing the components, or by evaporating the excess amount of the solvent, the treatment is carried out such as apparently completing the loading,
It is desirable to recover the platinum-supporting carrier as a substantially undried platinum-supporting carrier.
この溶媒または溶液の過剰分の分離方法としては、ろ
過、遠心分離、デカンテーション等の通常の固液分離方
法を用いることができる。また、溶媒の過剰分の分離、
除去法としては、上記の分離方法のほかに、自然蒸発
法、加熱蒸発法、送風蒸発法、気体流通バブル蒸発法等
の方法がある。As a method for separating the excess of the solvent or solution, a usual solid-liquid separation method such as filtration, centrifugation, decantation or the like can be used. Also, separation of excess solvent,
As the removal method, in addition to the above separation method, there are methods such as a natural evaporation method, a heating evaporation method, a blast evaporation method, and a gas flow bubble evaporation method.
この発明の方法においては、このようにして、実質的に
未乾燥状態の白金担持体を得る。In the method of the present invention, a platinum carrier substantially in an undried state is thus obtained.
ここで、実質的に未乾燥状態とは、その乾燥度の上限が
少なくとも担体の細孔内が、好ましくは担体微粒子間が
白金成分含有溶液で実質的に満たされている程度の乾燥
状態にあるものをいう。Here, the substantially undried state is a dry state in which the upper limit of the degree of dryness is at least in the pores of the carrier, preferably between the carrier fine particles is substantially filled with the platinum component-containing solution. Say something.
一方、その乾燥度の下限には、制限はないが、少なくと
もたとえば、前記のデカンテーションなどによって溶液
もしくは溶媒を分離除去した程度の乾燥状態のものを、
好適な乾燥状態の下限と言うことができる。On the other hand, the lower limit of the degree of dryness is not limited, but at least, for example, one in a dry state in which the solution or the solvent is separated and removed by decantation or the like,
It can be said to be the lower limit of a suitable dry state.
前記乾燥度が、前記上限を超えると凍結乾燥を行って
も、得られた白金担持触媒中の白金の分布が不均一とな
ったり、担体の細孔内部に白金が偏析したりする場合が
ある。Even if freeze-drying when the dryness exceeds the upper limit, the distribution of platinum in the obtained platinum-supported catalyst may become non-uniform, or platinum may segregate inside the pores of the carrier. .
この発明の方法において重要な点の1つとは、前記のよ
うにして得られた実質的に未乾燥状態にある白金担持担
体もしくは白金成分溶液または溶媒と白金担持担体とが
共存する系を、凍結乾燥することによって残存する溶媒
を実質的に除去し、白金の均一な分布状態での担持を完
成させ、かつ実質的に乾燥する点である。One of the important points in the method of the present invention is to freeze the substantially undried platinum-supporting carrier or platinum-component solution or the system in which the solvent and the platinum-supporting carrier coexist as described above. This is the point that the remaining solvent is substantially removed by drying, the supporting of platinum in a uniform distribution state is completed, and the platinum is substantially dried.
ここで凍結乾燥とは、低温にして溶媒の一部または全部
を凍結せしめ、その状態で減圧乾燥する方法である。Here, freeze-drying is a method in which a part or all of the solvent is frozen at a low temperature and then dried under reduced pressure.
この凍結乾燥を行うに際しての温度は、用いる溶媒の種
類などによって異なるが、水または水系溶媒を用いる場
合には、通常、−30℃以下とすれば、十分である。ま
た、前記減圧乾燥する際の圧力は、温度や用いる溶媒な
どの種類によって異なるが、通常、10Torr以下とすれば
十分である。乾燥に要する時間は、系中に含まれる溶媒
の量および他の諸々の条件によって異なるので一様に規
定できないが、通常、3〜10時間程度とすればよい。The temperature for performing this freeze-drying varies depending on the type of solvent used and the like, but when water or an aqueous solvent is used, it is usually sufficient to set it to −30 ° C. or lower. Further, the pressure at the time of drying under reduced pressure varies depending on the temperature and the kind of the solvent used, but is usually 10 Torr or less. The time required for drying cannot be uniformly defined because it depends on the amount of solvent contained in the system and various other conditions, but it is usually about 3 to 10 hours.
なおこの凍結乾燥の方式としては、他の固体、たとえ
ば、いわゆるインスタントコーヒー製造の際に使用され
る乾燥法等の公知の方式によって行うことができる。The freeze-drying method may be a known method such as a drying method used in the production of other solids such as so-called instant coffee.
このようにして凍結乾燥することによって、目的とする
白金担持触媒を得ることができる。By freeze-drying in this manner, the target platinum-supported catalyst can be obtained.
得られた白金担持触媒は、そのままあるいは、必要なら
ば、さらに通常のオーブン等による加熱乾燥処理を施し
て、また、必要に応じて、不活性ガスによる熱処理、水
素等の還元ガスによる還元処理、空気等による酸化処理
等、あるいはこれらを組み合せた処理などの公知の適切
な前処理もしくは活性化処理を施して、触媒として反応
に用いることができる。The obtained platinum-supported catalyst is, as it is, or, if necessary, further subjected to heat drying treatment in an ordinary oven or the like, and if necessary, heat treatment with an inert gas, reduction treatment with a reducing gas such as hydrogen, A known suitable pretreatment or activation treatment such as an oxidation treatment with air or the like, or a treatment in which these are combined can be applied to the reaction as a catalyst.
以上のようにして得られた白金担持触媒および適切な前
処理を施して得られた活性化白金担持触媒においては、
白金もしくは白金成分の担体の内部への偏析が少なく、
その分布が著しく均一であり、したがって、白金の耐凝
集性、分散性が向上しているので、たとえば、炭化水素
の異性化反応、環化反応、芳香族化反応などに触媒とし
て用いたときに、従来の乾燥方法で調製された触媒と比
較して、その活性が著しく向上しており、かつ、寿命が
改善されているなどの優れた効果を得ることができる。In the platinum-supported catalyst obtained as described above and the activated platinum-supported catalyst obtained by performing a suitable pretreatment,
There is little segregation of platinum or platinum component inside the carrier,
Its distribution is extremely uniform, and therefore platinum's cohesive resistance and dispersibility are improved. Therefore, when it is used as a catalyst for hydrocarbon isomerization reaction, cyclization reaction, aromatization reaction, etc. As compared with the catalyst prepared by the conventional drying method, it is possible to obtain an excellent effect that the activity is remarkably improved and the life is improved.
この発明方法によって得られる白金担持触媒を、反応に
使用するに際しては、その反応の種類、目的などにした
がって使用する担体や触媒の種類を選択し、触媒の前処
理、活性化処理、反応条件、反応方式などを適切に選定
して行なえばよい。When the platinum-supported catalyst obtained by the method of the present invention is used in the reaction, the type of the reaction, the type of the carrier or the catalyst to be used is selected according to the purpose, and the pretreatment of the catalyst, activation treatment, reaction conditions, The reaction method and the like may be appropriately selected.
以下に、C6〜C10の非芳香族炭化水素油の芳香族化反応
への応用例について説明する。Hereinafter, application examples of the C 6 to C 10 non-aromatic hydrocarbon oil to the aromatization reaction will be described.
この芳香族化反応の原料として用いるC6〜C10の非芳香
族炭化水素油としては、たとえば、n−ヘキサン、イソ
ヘキサン、ネオヘキサン、n−ヘプタン、イソヘプタ
ン、n−オクタン、イソオクタン、n−ノナン、イソノ
ナン、n−デカン、イソデカン、メチルシクロペンタ
ン、シクロヘキサン、メチルシクロヘキサン、ジメチル
シクロヘキサン、エチルシクロヘキサン、シクロオクタ
ン、シクロデカン、ヘキセン、イソヘキセン、ネオヘキ
セン、ヘプテン、イソヘプテン、オクテン、イソオクテ
ン、ノネン、イソノネン、デセン、イソデセン、シクロ
ヘキセン、メチルシクロペンテン、シクロヘプテン、シ
クロオクテン、シクロデセン等およびこれらの混合物を
挙げることができる。また、これらの炭化水素中には、
ベンゼン、トルエン、キシレン、エチルベンゼンなどの
芳香族炭化水素あるいは、C5留分以下の炭化水素、C11
以上の炭化水素を含有するものであってもよい。Examples of the C 6 to C 10 non-aromatic hydrocarbon oil used as a raw material for this aromatization reaction include n-hexane, isohexane, neohexane, n-heptane, isoheptane, n-octane, isooctane and n-nonane. , Isononane, n-decane, isodecane, methylcyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, cyclooctane, cyclodecane, hexene, isohexene, neohexene, heptene, isoheptene, octene, isooctene, nonene, isononene, decene, isodecene. , Cyclohexene, methylcyclopentene, cycloheptene, cyclooctene, cyclodecene and the like, and mixtures thereof. In addition, in these hydrocarbons,
Aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, or hydrocarbons with a C 5 fraction or less, C 11
It may contain the above hydrocarbons.
この反応に使用する触媒としては、この発明の方法で製
造された様々の白金担持触媒を使用することができる
が、たとえば、白金担持γ−アルミナ、白金担持η−ア
ルミナ、白金担持シリカアルミナ、白金担持Y型ゼオラ
イト、白金担持L型ゼオライト、白金担持ZSM−5型ゼ
オライト白金担持モルデナイトなどの白金担持ゼオライ
ト類もしくは白金担持結晶性アルミノシリケート等を好
適に使用することができる。As the catalyst used in this reaction, various platinum-supported catalysts produced by the method of the present invention can be used. For example, platinum-supported γ-alumina, platinum-supported η-alumina, platinum-supported silica alumina, platinum. Platinum-supported zeolites such as supported Y-type zeolite, platinum-supported L-type zeolite, platinum-supported ZSM-5 type zeolite platinum-supported mordenite or platinum-supported crystalline aluminosilicate can be preferably used.
これらの触媒は、反応に際して、通常、200〜610℃、好
ましくは300〜560℃の範囲で、水素ガスまたは水素ガス
含有の不活性ガス等により活性化して用いるのが好適で
ある。活性化に要する時間は、その温度等の条件によっ
て異なるが、通常0.5〜10時間程度で十分である。During the reaction, these catalysts are preferably used in the range of usually 200 to 610 ° C., preferably 300 to 560 ° C. after activation with hydrogen gas or an inert gas containing hydrogen gas. The time required for activation varies depending on the conditions such as the temperature, but normally 0.5 to 10 hours is sufficient.
反応温度は、通常、350〜600℃、好ましくは、400〜550
℃に設定し、反応圧力は、通常、0〜30kg/cm2G、好ま
しくは0〜15Kg/cm2Gに設定すればよい。The reaction temperature is usually 350 to 600 ° C., preferably 400 to 550.
The reaction pressure is usually 0 to 30 kg / cm 2 G, preferably 0 to 15 kg / cm 2 G.
また、反応は、通常、水素ガス共存下で行い、その際、
使用する水素ガスと原料油の割合を、H2/原料油(モル
比)として、通常、1〜20程度に設定する。The reaction is usually carried out in the presence of hydrogen gas,
The ratio of the hydrogen gas to be used as the feedstock oil is usually set to about 1 to 20 as H 2 / feedstock oil (molar ratio).
反応方式としては、連続流通式、回分式などのいずれの
方式でも可能であるが、連続流通式が好適である。The reaction system may be either a continuous flow system or a batch system, but the continuous flow system is preferred.
反応を連続流通式で行う場合には、重量空間速度(WHS
V)を、通常0.1〜10hr-1の範囲に設定すればよい。When the reaction is carried out in a continuous flow system, the weight hourly space velocity (WHS
V) is usually set in the range of 0.1 to 10 hr -1 .
また、反応型式としては、とくに制限はなく、固定床
式、移動床式、流通床式ライザー方式などの公知のいず
れの型式も可能であるが、固定床式等が好適に採用でき
る。The reaction type is not particularly limited, and any known type such as a fixed bed type, a moving bed type, and a flow bed type riser system can be used, but a fixed bed type or the like can be preferably adopted.
反応装置の形式についても特に制限はなく、管型反応器
などの常用の反応装置を用いて行うことができる。The type of reactor is not particularly limited, and a conventional reactor such as a tubular reactor can be used.
このような方法で、前記原料油から、ベンゼン、トルエ
ン、キシレン、エチルベンゼンなどの芳香族化合物を高
濃度で含有する生成物油を得ることができる。By such a method, a product oil containing a high concentration of an aromatic compound such as benzene, toluene, xylene, and ethylbenzene can be obtained from the raw material oil.
得られた生成油は、そのまま、あるいは通常行なわれる
後処理を施して、高オクタン価ガソリンもしくはその成
分として好適に用いることができ、また、該生成油か
ら、蒸留等の公知の分離操作を施して、ベンゼン、トル
エン、キシレン、エチルベンゼン等の芳香族化合物もし
くはそれら主成分とする留分として回収することができ
る。The obtained product oil can be suitably used as a high octane gasoline or a component thereof after being subjected to a usual post-treatment as it is, or subjected to a known separation operation such as distillation from the product oil. , Aromatic compounds such as benzene, toluene, xylene, and ethylbenzene or fractions containing them as the main component can be recovered.
[発明の効果] この発明によると、白金が担体の内部に偏在することな
く均一に分布し、白金の耐凝集性、分散性が向上し、炭
化水素油の芳香族化反応などの反応に用いた場合、著し
く向上した活性を示すと共に長寿命であるなどの優れた
触媒特性を備えた白金担持触媒を製造する方法を提供す
ることができる。EFFECTS OF THE INVENTION According to the present invention, platinum is uniformly distributed in the carrier without being unevenly distributed, and the coagulation resistance and dispersibility of platinum are improved, which is useful for reactions such as aromatization reaction of hydrocarbon oil. If so, it is possible to provide a method for producing a platinum-supported catalyst having excellent catalytic properties such as a significantly improved activity and a long life.
[実施例] (実施例1) 合成L型ゼオライトに対して白金金属として0.5重量%
の塩化テトラアンミン白金 [Pt(NH3)4Cl2]をゼオライトの飽和含水率に相当す
る量の脱イオン水に溶解し白金をゼオライトに含浸せし
めた。担持後、凍結乾燥装置に入れ、−40℃以下まで冷
却した後、減圧(0.1Torr以下)下に乾燥し、白金担持
触媒Aを得た。この白金担持触媒Aを用いて、n−ヘキ
サンからベンゼンを合成する反応を行った。[Example] (Example 1) 0.5 wt% as platinum metal based on synthetic L-type zeolite
Tetraammineplatinum chloride [Pt (NH 3 ) 4 Cl 2 ] was dissolved in deionized water in an amount corresponding to the saturated water content of the zeolite to impregnate the zeolite with platinum. After loading, the catalyst was placed in a freeze-drying apparatus, cooled to −40 ° C. or lower, and then dried under reduced pressure (0.1 Torr or lower) to obtain a platinum-supported catalyst A. Using this platinum-supported catalyst A, a reaction for synthesizing benzene from n-hexane was performed.
すなわち16〜32メッシュの触媒0.5gを採取し、石英反応
管に充填した後、水素を流通させ520℃に昇温後、3時
間水素還元を行った。次に水素対n−ヘキサン5:1(モ
ル比)の原料を重量空間速度(WHSV)2.0hr-1、圧力1kg
/cm2G、温度500℃の条件で上記反応管に通して反応させ
た。That is, 0.5 g of a 16-32 mesh catalyst was sampled and filled in a quartz reaction tube, hydrogen was circulated, the temperature was raised to 520 ° C., and hydrogen reduction was performed for 3 hours. Next, using hydrogen: n-hexane 5: 1 (molar ratio) as a raw material, weight hourly space velocity (WHSV) 2.0 hr -1 , pressure 1 kg.
The reaction was carried out by passing through the reaction tube under the conditions of / cm 2 G and temperature of 500 ° C.
結果を第1図に示す。The results are shown in Fig. 1.
第1図から、ベンゼン収率が60%以上を維持する時間は
210時間であった。From Figure 1, the time to maintain the benzene yield above 60% is
It was 210 hours.
(比較例1) 実施例1と同様の方法でL型ゼオライトに白金を含浸
後、熱風乾燥器で、80℃、6時間乾燥し触媒Bを得た。
この触媒Bを用いて、実施例1と同じ様な条件でn−ヘ
キサンからベンゼンを合成する反応を行った。結果を第
1図に示す。第1図よりベンゼン収率が60重量%以上維
持する時間は90時間であった。(Comparative Example 1) L-type zeolite was impregnated with platinum in the same manner as in Example 1 and dried at 80 ° C for 6 hours in a hot air drier to obtain a catalyst B.
Using this catalyst B, a reaction for synthesizing benzene from n-hexane was performed under the same conditions as in Example 1. The results are shown in Fig. 1. From Fig. 1, the time for maintaining the benzene yield of 60% by weight or more was 90 hours.
第1図はこの発明の方法により得られた白金担持触媒を
使用して芳香族化反応を行なった結果を示すグラフであ
る。FIG. 1 is a graph showing the results of an aromatization reaction using the platinum-supported catalyst obtained by the method of the present invention.
フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 FI 技術表示箇所 C07C 15/04 C10G 35/085 6958−4H 35/095 6958−4H // C07B 61/00 300 Continuation of the front page (51) Int.Cl. 6 Identification number Office reference number FI technical display location C07C 15/04 C10G 35/085 6958-4H 35/095 6958-4H // C07B 61/00 300
Claims (1)
た後、前記溶媒を凍結乾燥法によって除去することを特
徴とする白金担持触媒の製造方法。1. A method for producing a platinum-supported catalyst, which comprises supporting a platinum-containing component on a carrier using a solvent and then removing the solvent by freeze-drying.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP61265255A JPH0720553B2 (en) | 1986-11-07 | 1986-11-07 | Method for producing platinum-supported catalyst |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP61265255A JPH0720553B2 (en) | 1986-11-07 | 1986-11-07 | Method for producing platinum-supported catalyst |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS63119853A JPS63119853A (en) | 1988-05-24 |
JPH0720553B2 true JPH0720553B2 (en) | 1995-03-08 |
Family
ID=17414687
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP61265255A Expired - Lifetime JPH0720553B2 (en) | 1986-11-07 | 1986-11-07 | Method for producing platinum-supported catalyst |
Country Status (1)
Country | Link |
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JP (1) | JPH0720553B2 (en) |
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---|---|---|---|---|
JPS59196740A (en) * | 1983-04-21 | 1984-11-08 | Kiyataraa Kogyo Kk | Formation of porous alumina coating film on inorganic carrier |
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- 1986-11-07 JP JP61265255A patent/JPH0720553B2/en not_active Expired - Lifetime
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