JP2001070795A - Solid acid catalyst, preparation thereof and method for isomerizing hydrocarbon using the catalyst - Google Patents
Solid acid catalyst, preparation thereof and method for isomerizing hydrocarbon using the catalystInfo
- Publication number
- JP2001070795A JP2001070795A JP24989799A JP24989799A JP2001070795A JP 2001070795 A JP2001070795 A JP 2001070795A JP 24989799 A JP24989799 A JP 24989799A JP 24989799 A JP24989799 A JP 24989799A JP 2001070795 A JP2001070795 A JP 2001070795A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- catalyst
- zirconia
- solid acid
- acid catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 160
- 239000011973 solid acid Substances 0.000 title claims abstract description 53
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 40
- 229930195733 hydrocarbon Natural products 0.000 title claims description 38
- 238000000034 method Methods 0.000 title claims description 34
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 27
- 238000002360 preparation method Methods 0.000 title abstract description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 96
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 82
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 38
- 150000001875 compounds Chemical class 0.000 claims abstract description 34
- 229910021512 zirconium (IV) hydroxide Inorganic materials 0.000 claims abstract description 20
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical group [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims abstract description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims description 47
- 239000000460 chlorine Substances 0.000 claims description 36
- 229910052751 metal Inorganic materials 0.000 claims description 36
- 239000002184 metal Substances 0.000 claims description 36
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 35
- 229910052801 chlorine Inorganic materials 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 239000002994 raw material Substances 0.000 claims description 27
- 238000004519 manufacturing process Methods 0.000 claims description 25
- 238000006317 isomerization reaction Methods 0.000 claims description 24
- 238000001354 calcination Methods 0.000 claims description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 15
- 239000011593 sulfur Substances 0.000 claims description 15
- 229910052717 sulfur Inorganic materials 0.000 claims description 15
- 230000000737 periodic effect Effects 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- 238000006555 catalytic reaction Methods 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 10
- 238000004898 kneading Methods 0.000 claims description 10
- 229910052726 zirconium Inorganic materials 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 6
- 150000001805 chlorine compounds Chemical class 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 25
- 230000000694 effects Effects 0.000 abstract description 17
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052921 ammonium sulfate Inorganic materials 0.000 abstract description 7
- 235000011130 ammonium sulphate Nutrition 0.000 abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 abstract description 5
- 230000004580 weight loss Effects 0.000 abstract description 5
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 abstract description 4
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 abstract description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical group O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 description 56
- 238000006243 chemical reaction Methods 0.000 description 40
- 239000002245 particle Substances 0.000 description 32
- 239000012298 atmosphere Substances 0.000 description 25
- 238000010304 firing Methods 0.000 description 24
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 23
- 230000007423 decrease Effects 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- 238000011282 treatment Methods 0.000 description 14
- 239000008188 pellet Substances 0.000 description 13
- 229910052697 platinum Inorganic materials 0.000 description 10
- 239000013078 crystal Substances 0.000 description 8
- 230000001590 oxidative effect Effects 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- 150000002736 metal compounds Chemical class 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000003377 acid catalyst Substances 0.000 description 4
- -1 alcoholate Chemical compound 0.000 description 4
- 238000005804 alkylation reaction Methods 0.000 description 4
- 150000001491 aromatic compounds Chemical class 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000005917 acylation reaction Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 150000003464 sulfur compounds Chemical class 0.000 description 3
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-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
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- 238000007323 disproportionation reaction Methods 0.000 description 2
- 238000006266 etherification reaction Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000009499 grossing Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
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- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000006396 nitration reaction Methods 0.000 description 2
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- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- RLUFBDIRFJGKLY-UHFFFAOYSA-N (2,3-dichlorophenyl)-phenylmethanone Chemical class ClC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1Cl RLUFBDIRFJGKLY-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
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- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- RKIDDEGICSMIJA-UHFFFAOYSA-N 4-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=C(Cl)C=C1 RKIDDEGICSMIJA-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 238000006237 Beckmann rearrangement reaction Methods 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-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
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- 229910002651 NO3 Inorganic materials 0.000 description 1
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- 238000005260 corrosion Methods 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
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- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical class O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000003921 particle size analysis Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- CENHPXAQKISCGD-UHFFFAOYSA-N trioxathietane 4,4-dioxide Chemical compound O=S1(=O)OOO1 CENHPXAQKISCGD-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は酸触媒反応に高い活
性を有し、取り扱い性に優れた固体酸触媒およびその製
造方法、及びそれを用いた炭化水素の異性化方法に関す
る。The present invention relates to a solid acid catalyst having high activity in acid catalysis and excellent in handleability, a method for producing the same, and a method for isomerizing hydrocarbons using the same.
【０００２】[0002]
【従来の技術】化学工業においては、アルキル化反応、
エステル化反応、異性化反応などの酸触媒反応が知られ
ている。従来、この種の反応には、硫酸、塩化アルミニ
ウム、フッ化水素、リン酸、パラトルエンスルホン酸等
の酸触媒が使用されている。しかし、これらの酸触媒は
金属を腐食させる性質があり、製造装置に高価な耐食材
料の使用あるいは耐食処理を施す必要があった。また通
常、反応後の反応物質との分離が困難な上に廃酸処理が
必要であり、アルカリ洗浄などの煩雑な工程を経なけれ
ばならず、環境面にも大きな問題があった。さらに触媒
を再利用することも非常に困難であった。2. Description of the Related Art In the chemical industry, alkylation reactions,
Acid catalyzed reactions such as an esterification reaction and an isomerization reaction are known. Conventionally, acid catalysts such as sulfuric acid, aluminum chloride, hydrogen fluoride, phosphoric acid, and paratoluenesulfonic acid have been used in this type of reaction. However, these acid catalysts have the property of corroding metals, so that it is necessary to use expensive anticorrosion materials or perform anticorrosion treatment on the production equipment. In addition, usually, it is difficult to separate the reactants from the reactants after the reaction, and furthermore, waste acid treatment is required, and a complicated process such as alkali washing has to be performed. Furthermore, it was very difficult to reuse the catalyst.
【０００３】このような問題に対して、周期律表第IV族
金属水酸化物もしくは水和酸化物を硫酸分含有溶液と接
触させた後、３５０〜８００℃で焼成した硫酸根含有固
体酸触媒が提案された（特公昭５９−６１８１号公
報）。この固体酸触媒は、１００％硫酸（ハメットの酸
度関数Ｈ０は−１１．９３）より強い酸強度を示す。こ
れらの固体酸触媒は、その強い酸強度により様々な酸触
媒反応に対し高い触媒性能を有し、しかも腐食性が低
く、反応物質との分離が容易で廃酸処理も不要であり、
触媒の再利用も可能といった長所を有しており、様々な
工業的反応において、従来の酸触媒の代替が期待されて
いる。[0003] In order to solve such a problem, a sulfate-containing solid acid catalyst which is obtained by bringing a hydroxide or hydrated oxide of a Group IV metal of the periodic table into contact with a sulfuric acid-containing solution and calcining at 350 to 800 ° C. (Japanese Patent Publication No. 59-6181). This solid acid catalyst has an acid strength stronger than that of 100% sulfuric acid (Hammet's acidity function H 0 is −11.93). These solid acid catalysts have high catalytic performance against various acid catalyzed reactions due to their strong acid strength, are low in corrosiveness, are easily separated from reactants, and do not require waste acid treatment.
It has the advantage of being able to reuse catalysts, and is expected to replace conventional acid catalysts in various industrial reactions.
【０００４】硫酸分を含有させたジルコニアゲルを焼成
して得られた触媒に白金を含有させた触媒が炭化水素の
異性化反応に良好な活性を示すことも既に公知である
（米国特許３，０３２，５９９号公報）。It is already known that a catalyst obtained by calcining a zirconia gel containing sulfuric acid and containing platinum in the catalyst shows good activity in isomerization of hydrocarbons (US Pat. 032,599).
【０００５】炭化水素の異性化を主な目的とする白金族
金属と硫酸分を含有する金属酸化物触媒の製造方法とし
て、硫酸分含有化合物による処理と白金族金属を担持す
る工程との間の焼成を省いた製造法、硫酸分含有化合物
による処理と白金族金属の担持の順序を変えた製造法、
硫酸分含有化合物の種類を変えた製造法が特公平５−２
９５０３号公報、特公平５−２９５０４号公報、特公平
５−２９５０５号公報及び特公平５−２９５０６号公報
に開示されている。[0005] As a method for producing a metal oxide catalyst containing a platinum group metal and sulfuric acid for the main purpose of isomerization of hydrocarbons, a method comprising a step of treating with a sulfuric acid-containing compound and a step of supporting the platinum group metal is carried out. A production method that eliminates firing, a production method that changes the order of treatment with a sulfuric acid-containing compound and loading of a platinum group metal,
The production method that changed the type of the sulfuric acid-containing compound is Japanese Patent Publication 5-2.
No. 9503, Japanese Patent Publication No. 5-29504, Japanese Patent Publication No. 5-29505 and Japanese Patent Publication No. 5-29506.
【０００６】また、アルミニウムの水酸化物もしくは酸
化物に硫酸分含有化合物を添加し、それを焼成して得ら
れる固体酸触媒は、１００％硫酸よりも強い酸強度を示
すことが知られている（特開平５−９６１７１号公報、
荒田、Ｔｒｅｎｄｓ ｉｎＰｈｙｓｉｃａｌ Ｃｈｅｍ
ｉｓｔｒｙ２巻、１項（１９９１年））。[0006] It is known that a solid acid catalyst obtained by adding a sulfuric acid-containing compound to an aluminum hydroxide or oxide and calcining the same shows a stronger acid strength than 100% sulfuric acid. (JP-A-5-96171,
Arata, Trends in Physical Chem
issue 2 (1) (1991)).
【０００７】本発明者は、硫酸分を含有する固体酸触媒
の成形物でありながら十分に高い活性を有し、実用上十
分な取り扱い性と必要な機械的強度を有する成形された
固体酸触媒の製造方法として、含水アルミナ、含水ジル
コニア、硫酸分含有化合物を混練し、成形し、正方晶構
造のジルコニアが得られる温度で焼成する方法を既に開
示している。（国際公開 ＷＯ９８／０９７２７）The inventor of the present invention has provided a molded solid acid catalyst which has a sufficiently high activity while being a molded product of a solid acid catalyst containing sulfuric acid, and has practically sufficient handleability and necessary mechanical strength. As a method for producing zirconia, a method has been disclosed in which hydrated alumina, hydrated zirconia, and a compound containing sulfuric acid are kneaded, molded, and fired at a temperature at which zirconia having a tetragonal structure is obtained. (International Publication WO98 / 09727)
【０００８】[0008]
【発明が解決しようとする課題】本発明者による成形さ
れた固体酸触媒の製造方法は、実用上十分な特性を発揮
するが、さらに高い触媒活性、安定した触媒特性を有す
ることが求められている。The method of the present invention for producing a molded solid acid catalyst exhibits practically sufficient characteristics, but is required to have even higher catalytic activity and stable catalytic characteristics. I have.
【０００９】本発明はこのような課題を解決するもの
で、硫酸分を含有する成形物された固体酸触媒としてさ
らに高い活性を有し、安定して高い活性の触媒が得ら
れ、また、触媒反応において、さらに高い反応性が得ら
れる反応方法を提供することにある。[0009] The present invention solves the above-mentioned problems, and a catalyst having a higher activity as a molded solid acid catalyst containing a sulfuric acid component, and a catalyst having a high activity can be obtained stably. An object of the present invention is to provide a reaction method capable of obtaining higher reactivity in the reaction.
【００１０】[0010]
【課題を解決するための手段】本発明者らは、固体酸触
媒の製造方法について鋭意研究を重ねた結果、触媒原料
である含水ジルコニア粉体の水分量が触媒活性に大きな
影響を与えていることを見出し、含水ジルコニア粉体の
灼熱減量に着目して研究を進めて本発明を完成した。Means for Solving the Problems The present inventors have conducted intensive studies on a method for producing a solid acid catalyst, and as a result, the water content of hydrous zirconia powder, which is a catalyst raw material, has a great influence on the catalytic activity. The present inventors have found that the present invention has been completed by focusing on the ignition loss of hydrous zirconia powder.
【００１１】本発明による固体酸触媒の製造方法は、灼
熱減量が５〜１５重量％である含水ジルコニア粉体、含
水アルミナおよび硫酸分含有化合物を混練し、成形し、
得られた成形物を正方晶構造のジルコニアが得られる条
件で焼成するものである。本発明の固体酸触媒の製造方
法においては、正方晶構造のジルコニアが得られる条件
で焼成する際、焼成を１００ｇ／時の触媒生産あたり常
温（２７℃）体積換算で４Ｌ／分以下のガス流通量で行
うこと、また、固体酸触媒に周期律表第VIIIＢ族金属成
分から選ばれる少なくとも１種の金属成分が担持されて
いることが好ましい。さらに、固体酸触媒に塩素分が含
まれていることが好ましい。The method for producing a solid acid catalyst according to the present invention comprises kneading a water-containing zirconia powder having a loss on ignition of 5 to 15% by weight, a water-containing alumina, and a compound containing a sulfuric acid component, and molding.
The obtained molded product is fired under the condition that zirconia having a tetragonal structure is obtained. In the method for producing a solid acid catalyst according to the present invention, when calcination is performed under the condition that zirconia having a tetragonal structure is obtained, the calcination is performed at a gas flow of 4 L / min or less in terms of volume at room temperature (27 ° C.) per 100 g / h of catalyst production. It is preferable that the solid acid catalyst carry at least one metal component selected from the Group VIIIB metal components of the periodic table. Further, it is preferable that the solid acid catalyst contains chlorine.
【００１２】本発明による固体酸触媒は、正方晶構造の
ジルコニア及び／又は含水ジルコニアからなる部分と、
アルミナ及び／又は含水アルミナから成る部分で構成さ
れ成形された担体と、この担体に担持された硫酸分を含
み、触媒中に占めるジルコニアの割合がジルコニウム元
素量として２５〜６０重量％、アルミナの割合がアルミ
ニウム元素量として５〜３０重量％、硫酸分の割合が硫
黄元素重量として１〜６重量％であり、塩素分の割合が
塩素元素重量として０．０２〜１０重量％である酸触媒
反応に用いられる固体酸触媒である。本発明による固体
酸触媒は、触媒中に周期律表第VIIIＢ族から選ばれる１
種以上の金属を０．０１〜１０重量％含むこと、さら
に、炭素数４〜６の飽和炭化水素成分を７０重量％以上
含む炭化水素の異性化反応に用いられることが好まし
い。The solid acid catalyst according to the present invention comprises a portion comprising zirconia having a tetragonal structure and / or hydrous zirconia;
A carrier formed of a portion composed of alumina and / or hydrated alumina, and a sulfuric acid component supported on the carrier, wherein the proportion of zirconia in the catalyst is 25 to 60% by weight of zirconium element and the proportion of alumina Is 5 to 30% by weight as an aluminum element amount, 1 to 6% by weight as a sulfur element weight, and 0.02 to 10% by weight as a chlorine element weight in an acid catalyzed reaction. The solid acid catalyst used. The solid acid catalyst according to the present invention comprises, in the catalyst, 1 selected from Group VIIIB of the periodic table.
It is preferably used for an isomerization reaction of a hydrocarbon containing 0.01 to 10% by weight of at least one kind of metal and 70% by weight or more of a saturated hydrocarbon component having 4 to 6 carbon atoms.
【００１３】本発明による炭化水素の異性化反応方法
は、原料水素と原料炭化水素を固体酸触媒に接触させる
方法において、原料炭化水素が炭素数４〜６の飽和炭化
水素成分を７０重量％以上含み、原料炭化水素と原料水
素中の水分含有量が５ｐｐｍ以下であり、原料炭化水素
と原料水素が塩素重量として０．１〜１００００ｐｐｍ
の塩素化合物を含有する炭化水素の異性化方法である。[0013] The method for isomerizing a hydrocarbon according to the present invention is a method for bringing a raw material hydrogen and a raw material hydrocarbon into contact with a solid acid catalyst, wherein the raw material hydrocarbon contains at least 70% by weight of a saturated hydrocarbon component having 4 to 6 carbon atoms. Water content of the raw material hydrocarbon and the raw material hydrogen is 5 ppm or less, and the raw material hydrocarbon and the raw material hydrogen are 0.1 to 10,000 ppm as chlorine weight.
Is a method for isomerizing a hydrocarbon containing a chlorine compound.
【００１４】[0014]
【発明の作用・効果】本発明は、特定含水量の粉体原料
を用いて、特には焼成時のガス流通をほとんどなくした
状態で焼成することで固体酸触媒を製造するものである
ので、機械的に十分な強度が得られると同時に固体酸触
媒としての高い活性が安定して得られる。特にこの触媒
は炭素数４〜６の飽和炭化水素の異性化に優れた触媒活
性を発揮することができる。According to the present invention, a solid acid catalyst is produced by sintering a powdered raw material having a specific water content, particularly in a state where gas flow during sintering is almost eliminated. At the same time, sufficient mechanical strength can be obtained, and high activity as a solid acid catalyst can be stably obtained. In particular, this catalyst can exhibit excellent catalytic activity for isomerization of a saturated hydrocarbon having 4 to 6 carbon atoms.
【００１５】[0015]
【発明の実施の形態】［含水ジルコニア粉体］固体酸触
媒の製造に用いる含水ジルコニア粉体は、特定の灼熱減
量（水分量）とすることが触媒の性能上好ましい。灼熱
減量は、含水ジルコニアを１４００℃の温度で１時間焼
成した後の重量減少で測定することができる。好ましい
灼熱減量は５〜１５重量％、特には７〜１２重量％であ
る。灼熱減量が少なすぎると、焼成時に含水ジルコニア
粉体が結晶化し、比表面積が低下することにより、得ら
れる固体酸触媒の比表面積も低下し、また触媒活性も低
下する。含水ジルコニア粉体は灼熱減量が多すぎると、
明確な原因は不明だが、恐らく含水ジルコニア粉体の反
応性が増しすぎるため、触媒活性が低下する。なお、一
旦灼熱減量が５重量％以下になった含水ジルコニアに水
等を加えて灼熱減量を５〜１５重量％としたものは好ま
しく用いることはできないのに対し、一旦灼熱減量を５
〜１５重量％とした含水ジルコニアに、水等を加えて灼
熱減量を１５重量％以上としたものは好ましく用いるこ
とができる。BEST MODE FOR CARRYING OUT THE INVENTION [Water-containing zirconia powder] The water-containing zirconia powder used for producing a solid acid catalyst preferably has a specific ignition loss (moisture content) in terms of the performance of the catalyst. The loss on ignition can be measured by the weight loss after sintering hydrous zirconia at a temperature of 1400 ° C. for 1 hour. The preferred loss on ignition is 5 to 15% by weight, in particular 7 to 12% by weight. If the ignition loss is too small, the hydrous zirconia powder will crystallize during firing, and the specific surface area will decrease. As a result, the specific surface area of the obtained solid acid catalyst will decrease, and the catalytic activity will also decrease. If the hydrated zirconia powder has too much loss on ignition,
The exact cause is unknown, but the reactivity of the hydrous zirconia powder is likely to increase too much, reducing the catalytic activity. It is not possible to preferably use water-containing zirconia having a loss on ignition of 5% by weight or less by adding water or the like to reduce the loss on ignition by 5 to 15% by weight.
It is preferable to use water-containing zirconia having a weight loss of about 15% by weight or more by adding water or the like to water-containing zirconia having a weight of about 15% by weight.
【００１６】含水ジルコニア粉体は、Ｘ線、電子線の回
折により明確な結晶構造を持たない無定形とすること
で、触媒の圧壊強度が向上し、またジルコニアが安定し
やすい。The hydrous zirconia powder is made amorphous having no clear crystal structure by diffraction of X-rays and electron beams, whereby the crushing strength of the catalyst is improved and zirconia is easily stabilized.
【００１７】含水ジルコニア粉体は、凝集粒子の平均粒
径が０．２〜１０μｍ、特には０．２〜５μｍ、さらに
は０．５〜２μｍを用いることが、触媒の活性および機
械的強度向上のために好ましい。凝集粒子の平均粒径
は、水中に分散した粒子群にレーザー光を照射し、その
散乱光から求めるなどの方法により測定することができ
る。The hydrated zirconia powder having an average particle diameter of agglomerated particles of 0.2 to 10 μm, particularly 0.2 to 5 μm, and more preferably 0.5 to 2 μm can improve the activity and mechanical strength of the catalyst. Preferred for The average particle size of the aggregated particles can be measured by irradiating a group of particles dispersed in water with a laser beam and determining from the scattered light.
【００１８】含水ジルコニア粉体は、どのように製造し
ても構わないが、一般にはジルコニウム塩や有機金属化
合物、例えばオキシ塩化物、アルコラート、塩化物、硫
酸塩、硝酸塩、オキシ硫酸塩などを中和もしくは加水分
解し、洗浄、乾燥することにより得ることができる。含
水ジルコニア粉体の主成分は、ジルコニウム水酸化物と
ジルコニウム水和酸化物の混合物、ジルコニウム水酸化
物、または、ジルコニウム水和酸化物である。The hydrous zirconia powder may be produced in any manner, but generally contains a zirconium salt or an organic metal compound such as oxychloride, alcoholate, chloride, sulfate, nitrate or oxysulfate. It can be obtained by summing or hydrolyzing, washing and drying. The main component of the hydrous zirconia powder is a mixture of zirconium hydroxide and zirconium hydrated oxide, zirconium hydroxide, or zirconium hydrated oxide.
【００１９】さらに、含水ジルコニア粉体は、複合金属
水酸化物および／または複合金属水和酸化物として用い
ることもできる。含水ジルコニア粉体に含まれるジルコ
ニウムの水酸化物および／または水和酸化物には、他の
金属の水酸化物および／または水和酸化物および／また
は塩を加えても構わない。他の金属としては、チタン、
ハフニウム、バナジウム、クロム、マンガン、鉄、ケイ
素、錫、アルミニウム、ガリウムなどが好適に用いられ
る。これら他の金属の化合物は複合金属化合物でも構わ
ない。しかし、ジルコニア粉体としては、実質的に金属
成分としてジルコニウムのみを有するもの、具体的に
は、ジルコニア粉体中の全金属重量のうち、ジルコニア
をその金属重量として７０重量％以上、特には９０重量
％以上のものが好ましく用いられる。Furthermore, the hydrous zirconia powder can be used as a composite metal hydroxide and / or a composite metal hydrated oxide. To the hydroxide and / or hydrated oxide of zirconium contained in the hydrous zirconia powder, a hydroxide and / or hydrated oxide and / or salt of another metal may be added. Other metals include titanium,
Hafnium, vanadium, chromium, manganese, iron, silicon, tin, aluminum, gallium and the like are preferably used. These other metal compounds may be complex metal compounds. However, as the zirconia powder, one having substantially only zirconium as a metal component, specifically, zirconia is 70% by weight or more, especially 90% by weight, of the total metal weight in the zirconia powder. Those having a weight percent or more are preferably used.
【００２０】［含水アルミナ粉体］固体酸触媒の製造に
用いる含水アルミナ粉体としては、いろいろな製法によ
り得られたものを用いることができるが、特に、擬ベー
マイトなどのベーマイト構造を有するアルミニウム水和
酸化物を用いることが触媒活性を向上できるので好まし
い。アルミナ粉体としてα−アルミナやγ−アルミナを
用いると、相対的に、触媒成形体の機械的強度が低下
し、また、触媒活性が低下する。[Hydrous Alumina Powder] As the hydrated alumina powder used for the production of the solid acid catalyst, those obtained by various production methods can be used. In particular, aluminum water having a boehmite structure such as pseudo-boehmite can be used. It is preferable to use a hydrated oxide because the catalytic activity can be improved. When α-alumina or γ-alumina is used as the alumina powder, the mechanical strength of the molded catalyst decreases relatively, and the catalytic activity decreases.
【００２１】含水アルミナ粉体の灼熱減量（水分率）は
２０〜４０重量％であることが好ましい。この灼熱減量
は、含水アルミナを１４００℃の温度で１時間焼成した
後の重量減少で測定することができる。特に好ましい灼
熱減量は２５〜３５重量％である。含水アルミナ粉体
は、繊維状の粒子形状を有することが、触媒成形体の機
械的強度の向上、特に、成形ペレットの水安定性を向上
するために好ましい。繊維状の粒子形状として、具体的
には、アスペクト比が１０より、特には２０より大きい
ことが好ましい。通常、アスペクト比の上限は、２００
程度である。ここでアスペクト比は、粒子の短軸と長軸
の長さの比（［長軸の長さ］／［短軸の長さ］）を意味
し、例えば、アルミナ粉体を透過型電子顕微鏡などによ
って観察し、粒子の短軸と長軸の長さの比を測定し、そ
れらの平均から求めることができる。粒子が球状の場
合、アスペクト比は最小の１となる。代表的には、この
ような粒子形状は、長軸の長さ０．１μｍ以上の１次粒
子や、１次粒子が一定方向に配向した２次粒子として得
られる。また、平均した値であるアスペクト比が１０よ
り、特には２０より大きくなる範囲において、繊維状以
外の形状の、例えば板状の粒子が含まれていてもよい。The loss on ignition (moisture percentage) of the hydrated alumina powder is preferably 20 to 40% by weight. This burning loss can be measured by weight loss after sintering hydrated alumina at a temperature of 1400 ° C. for 1 hour. A particularly preferred loss on ignition is from 25 to 35% by weight. It is preferable that the hydrated alumina powder has a fibrous particle shape in order to improve the mechanical strength of the molded catalyst, particularly to improve the water stability of the molded pellet. Specifically, the fibrous particle shape preferably has an aspect ratio of more than 10, particularly preferably more than 20. Usually, the upper limit of the aspect ratio is 200
It is about. Here, the aspect ratio means the ratio of the length of the minor axis to the major axis of the particles ([length of major axis] / [length of minor axis]). And the ratio of the length of the short axis to the length of the long axis of the particle is measured, and the ratio can be determined from the average thereof. If the particles are spherical, the aspect ratio will be a minimum of 1. Typically, such a particle shape is obtained as a primary particle having a major axis length of 0.1 μm or more or a secondary particle in which the primary particle is oriented in a certain direction. Further, in a range where the average value of the aspect ratio is larger than 10, particularly larger than 20, for example, plate-like particles other than fibrous shapes may be contained.
【００２２】含水アルミナ粉体は、凝集粒子の平均粒径
０．５〜５０μｍ、特には０．５〜２０μｍ、さらには
２〜１５μｍの形状を用いることが好ましい。通常、こ
の凝集粒子は、繊維状の粒子が凝集したものである。The hydrated alumina powder preferably has an average particle diameter of aggregated particles of 0.5 to 50 μm, particularly 0.5 to 20 μm, and more preferably 2 to 15 μm. Usually, the agglomerated particles are formed by aggregating fibrous particles.
【００２３】［硫黄分含有化合物］硫黄分含有化合物
は、硫酸分を含有する化合物、または、その後の焼成な
どの処理により硫酸分に変換されうる硫黄分を含んだ化
合物である。硫黄分含有化合物としては、硫酸、硫酸ア
ンモニウム、亜硫酸、亜硫酸アンモニウム、塩化チオニ
ル、ジメチル硫酸などが挙げられるが、硫酸分を含んだ
硫酸分含有化合物が好ましく用いられ、硫酸アンモニウ
ム、ジメチル硫酸が製造装置の腐食性も低く好ましい。
特には硫酸アンモニウムが最も好ましく用いられる。[Sulfur-containing compound] The sulfur-containing compound is a compound containing a sulfuric acid or a compound containing a sulfur that can be converted into a sulfuric acid by a subsequent treatment such as calcination. Examples of the sulfur-containing compound include sulfuric acid, ammonium sulfate, sulfurous acid, ammonium sulfite, thionyl chloride, dimethyl sulfate, and the like. Sulfuric acid-containing compounds containing sulfuric acid are preferably used, and ammonium sulfate and dimethyl sulfuric acid cause corrosion of the production equipment. It is also preferred because of its low property.
Particularly, ammonium sulfate is most preferably used.
【００２４】硫黄分含有化合物はそのままでも、または
水溶液のような溶液として用いても構わない。硫黄分含
有化合物は、固体の状態でも、液状でも、溶液の濃度に
関しても特に限定はなく、混練に必要な溶液量などを考
えて調製することができる。硫酸分含有化合物の添加量
は、最終的に得られる固体酸触媒中に占める理論硫酸分
（ＳＯ４）量が硫黄元素重量として２．５〜１０重量
％、特には３〜８重量％となるようにすることが好まし
い。The sulfur-containing compound may be used as it is or as a solution such as an aqueous solution. The sulfur-containing compound may be prepared in consideration of the amount of the solution necessary for kneading, and there is no particular limitation on the concentration of the solution, whether in a solid state or a liquid state. The amount of the sulfuric acid-containing compound added is such that the theoretical sulfuric acid content (SO 4 ) in the finally obtained solid acid catalyst is 2.5 to 10% by weight, particularly 3 to 8% by weight as elemental sulfur. It is preferable to do so.
【００２５】［混練］混練の方法には特に限定は無く、
一般に触媒調製に用いられる混練機を用いることができ
る。通常は原料を投入し、水を加えて攪拌羽根で混合す
るような方法が好適に用いられるが、原料および添加物
の投入順序など特に限定はない。混練の際には通常水を
加えるが、加える液体としては、エタノール、イソプロ
パノール、アセトン、メチルエチルケトン、メチルイソ
ブチルケトンなどの有機溶媒でも良い。混練時の温度や
混練時間は、原料となる含水ジルコニア粉体と含水アル
ミナ粉体、硫黄分含有化合物により異なるが、好ましい
細孔構造が得られる条件であれば、特に制限はない。同
様に本発明の触媒性状が維持される範囲内であれば、硝
酸などの酸やアンモニアなどの塩基、有機化合物、バイ
ンダー、セラミックス繊維、界面活性剤、ゼオライトな
どを加えて混練しても構わない。[Kneading] The method of kneading is not particularly limited.
A kneader generally used for catalyst preparation can be used. Usually, a method in which the raw materials are charged, water is added, and the mixture is mixed with a stirring blade is suitably used, but there is no particular limitation on the sequence of charging the raw materials and the additives. Water is usually added during kneading, but the liquid to be added may be an organic solvent such as ethanol, isopropanol, acetone, methyl ethyl ketone, and methyl isobutyl ketone. Kneading temperature and kneading time vary depending on the hydrated zirconia powder, the hydrated alumina powder and the sulfur-containing compound as raw materials, but are not particularly limited as long as a preferable pore structure can be obtained. Similarly, as long as the catalytic properties of the present invention are maintained, an acid such as nitric acid or a base such as ammonia, an organic compound, a binder, a ceramic fiber, a surfactant, a zeolite, or the like may be added and kneaded. .
【００２６】［成形］混練後の成形方法には特に限定は
無く、一般に触媒調製に用いられている成形方法を用い
ることができる。特に、ペレット状、ハニカム状等の任
意の形状に効率よく成形できるので、スクリュー式押出
機などを用いた押出成形が好ましく用いられる。成形物
のサイズは特に制限はないが、通常、その断面の長さが
０．５〜２０ｍｍの大きさに成形される。例えば円柱状
のペレットであれば、通常直径０．５〜１０ｍｍ、長さ
０．５〜１５ｍｍ程度のものを容易に得ることができ
る。[Molding] The shaping method after kneading is not particularly limited, and a shaping method generally used for catalyst preparation can be used. In particular, extrusion molding using a screw type extruder or the like is preferably used because it can be efficiently molded into an arbitrary shape such as a pellet shape or a honeycomb shape. Although the size of the molded product is not particularly limited, it is usually molded to have a cross-sectional length of 0.5 to 20 mm. For example, if it is a columnar pellet, a pellet having a diameter of about 0.5 to 10 mm and a length of about 0.5 to 15 mm can be easily obtained.
【００２７】［成形後の焼成］成形後の焼成は、空気ま
たは窒素などのガス雰囲気中において行われるが、特に
は空気中で行うことが好ましい。焼成は、正方晶構造の
酸化ジルコニウムが得られる条件で行うことが好まし
い。この構造はＸ線回折により確認でき、具体的には、
CuＫα線による、２θ＝２８．２°と２θ＝３０．２°
のＸ線回折ピーク面積比（以下Ｓ28.2／Ｓ30.2比と略記
する。Ｓ28.2は２θ＝２８．２°における単斜晶ジルコ
ニアのピークの面積、Ｓ30.2は２θ＝３０．２°におけ
る正方晶ジルコニアのピークの面積）が、１．０以下、
好ましくは、０．５以下、さらに好ましくは０．１以下
である。単斜晶構造がほとんど存在していない方が、高
い触媒活性が得られる。[Firing After Molding] Firing after molding is carried out in a gas atmosphere such as air or nitrogen, but is particularly preferably carried out in air. The calcination is preferably performed under a condition that can obtain tetragonal zirconium oxide. This structure can be confirmed by X-ray diffraction. Specifically,
2θ = 28.2 ° and 2θ = 30.2 ° by CuKα ray
(Hereinafter abbreviated as S28.2 / S30.2 ratio. S28.2 is the peak area of monoclinic zirconia at 2θ = 28.2 °, and S30.2 is 2θ = 30.2). ° the area of the peak of tetragonal zirconia) is 1.0 or less,
Preferably it is 0.5 or less, more preferably 0.1 or less. High catalytic activity is obtained when almost no monoclinic structure is present.
【００２８】本焼成中には、水分や過剰の硫酸分等が発
生する。特に炭素数４〜６の飽和炭化水素を７０重量％
以上、好ましくは９０重量％以上含む炭化水素の異性化
反応用触媒としては、過剰の硫酸分をなるべく滞留させ
る条件で焼成することが好ましい。このためには、焼成
装置内のガスの流通量をできるだけ減らすことが好まし
い。例えば、焼成後の触媒生産量＝１００ｇ／時の場合
（バッチ式焼成においては［触媒生産量＝得られる触媒
量／焼成時間］とする）、ガス、特には空気の流通量を
常温（２７℃）体積換算で４Ｌ／分以下、さらには１Ｌ
／分以下、特には０．５Ｌ／分以下とすることが好まし
い。この好ましいガス流通量の上限は触媒生産量に比例
する。焼成温度は焼成時間、ガス流通量など他の焼成条
件によっても異なるが、一般に４５０〜８００℃、特に
５００〜８００℃、さらには６００〜８００℃が好まし
い。焼成時間は焼成温度、ガス流通量など他の焼成条件
によっても異なるが、一般に０．０５〜２０時間、特に
０．１〜１０時間、さらには０．２〜５時間が好まし
い。焼成温度が高すぎるかあるいは焼成時間が長すぎる
と、酸化ジルコニウムの結晶構造における単斜晶の割合
が増え、Ｓ28.2／Ｓ30.2比が１を越えてしまう場合があ
り、触媒活性が低下するため好ましくない。また、焼成
温度が低すぎるかあるいは焼成時間が短すぎると酸化ジ
ルコニウムが結晶化せず、触媒活性が低下するため好ま
しくない。焼成時の雰囲気は酸化雰囲気または不活性雰
囲気であればよく、通常は、空気雰囲気である。During the main baking, moisture, excess sulfuric acid and the like are generated. In particular, 70% by weight of a saturated hydrocarbon having 4 to 6 carbon atoms
As described above, the catalyst for the isomerization reaction of hydrocarbon containing preferably 90% by weight or more is preferably calcined under the condition that excess sulfuric acid is retained as much as possible. For this purpose, it is preferable to reduce the amount of gas flow in the firing device as much as possible. For example, when the catalyst production amount after calcination is 100 g / hour (in the case of batch-type calcination, [catalyst production amount = amount of catalyst to be obtained / calcination time]), the flow rate of gas, particularly air, is changed to normal temperature (27 ° C.). ) 4L / min or less in volume conversion, and 1L
/ Min, particularly preferably 0.5 L / min or less. The upper limit of this preferable gas flow rate is proportional to the catalyst production rate. The firing temperature varies depending on other firing conditions such as the firing time and the gas flow rate, but is generally 450 to 800 ° C, preferably 500 to 800 ° C, and more preferably 600 to 800 ° C. The firing time varies depending on other firing conditions such as the firing temperature and the gas flow rate, but is generally 0.05 to 20 hours, preferably 0.1 to 10 hours, and more preferably 0.2 to 5 hours. If the calcination temperature is too high or the calcination time is too long, the proportion of monoclinic crystals in the crystal structure of zirconium oxide increases, and the S28.2 / S30.2 ratio may exceed 1, resulting in reduced catalytic activity. Is not preferred. On the other hand, if the firing temperature is too low or the firing time is too short, zirconium oxide does not crystallize and the catalytic activity decreases, which is not preferable. The atmosphere during the firing may be an oxidizing atmosphere or an inert atmosphere, and is usually an air atmosphere.
【００２９】［周期律表第VIIIＢ族金属成分及びその担
持］本発明の固体酸触媒は、必要に応じて、例えば、異
性化などの転化反応に用いられる場合には、周期律表第
VIIIＢ族金属成分を含むことが好ましい。本発明の触媒
に用いられる周期律表第VIIIＢ族金属成分から選ばれる
金属成分としては、白金、パラジウム、ルテニウム、ニ
ッケルなどが好ましく、特には白金が好適に用いられ
る。これらは金属そのものよりも化合物の形態になって
いるものを担持成分として用いる方が好ましい。これら
の金属化合物は、無水物としても、水和物としても用い
ることができる。さらにこれらの金属化合物は１種で
も、２種以上を混合したものでも良い。また周期律表第
VIIIＢ族金属成分には、他の族の金属成分が含まれてい
ても構わない。これら金属化合物の添加量は、固体酸触
媒中に占める周期律表第VIIIＢ族金属成分の合計量が金
属重量として０．０１〜１０重量％、特には０．１〜５
重量％となるように添加することが好ましい。[Group VIIIB metal component and its support] The solid acid catalyst of the present invention may be used, if necessary, in a conversion reaction such as isomerization.
It preferably contains a Group VIIIB metal component. Platinum, palladium, ruthenium, nickel and the like are preferable as the metal component selected from Group VIIIB metal components of the periodic table used in the catalyst of the present invention, and platinum is particularly preferably used. It is preferable to use those in the form of a compound as the supporting component rather than the metal itself. These metal compounds can be used both as anhydrides and hydrates. Further, these metal compounds may be used alone or as a mixture of two or more. Also the periodic table No.
The group VIIIB metal component may contain a metal component of another group. The addition amount of these metal compounds is such that the total amount of the Group VIIIB metal component of the periodic table occupying in the solid acid catalyst is 0.01 to 10% by weight, particularly 0.1 to 5% by weight, as metal weight.
It is preferable to add so that it may become a weight%.
【００３０】これらの金属成分を担持する方法には特に
制限はないが、スプレー、浸漬などによる含浸法や、イ
オン交換法等が好適に用いられる。The method for supporting these metal components is not particularly limited, but an impregnation method such as spraying or immersion, or an ion exchange method is preferably used.
【００３１】［周期律表第VIIIＢ族金属成分担持後の処
理］上記の担持された触媒は、乾燥、焼成、還元などに
よって安定化される。乾燥、焼成は空気または窒素など
のガス雰囲気中において行われるが、特には空気中で行
うことが好ましい。焼成は、正方晶構造の酸化ジルコニ
ウムが保たれる条件で行われることが好ましい。還元は
水素を含む気流中で行うことが好ましい。[Treatment after Supporting Group VIIIB Metal Component of Periodic Table] The supported catalyst is stabilized by drying, calcining, reducing and the like. Drying and calcination are performed in a gas atmosphere such as air or nitrogen, and particularly preferably performed in air. The firing is preferably performed under the condition that the tetragonal zirconium oxide is maintained. The reduction is preferably performed in a stream containing hydrogen.
【００３２】焼成温度は焼成時間など他の焼成条件によ
っても異なるが、一般に３００〜８００℃、特に５００
〜７００℃が好ましい。焼成時間は他の温度など他の焼
成条件によっても異なるが、一般に０．０５〜２０時
間、特に０．１〜１０時間、さらには０．２〜５時間が
好ましい。The firing temperature varies depending on other firing conditions such as the firing time, but is generally 300 to 800 ° C., particularly 500 ° C.
~ 700 ° C is preferred. The firing time varies depending on other firing conditions such as other temperatures, but is generally 0.05 to 20 hours, preferably 0.1 to 10 hours, and more preferably 0.2 to 5 hours.
【００３３】［塩素含有化合物との接触］本発明の固体
酸触媒は、その触媒活性を増強させるために、必要に応
じて塩素分を含有することが好ましい。塩素分を含有さ
せるためには、成形後の焼成の後、周期律表第VIIIＢ族
金属成分担持の際、または、その後の処理の後に担体ま
たは固体酸触媒を塩素含有化合物と接触させることが好
ましい。塩素含有化合物に特に限定はなく、塩素、無機
塩素含有化合物、有機塩素含有化合物が好適に用いられ
る。特には塩素、塩酸、塩化アルミニウム、塩化ジルコ
ニウム、塩化アンモニウム、四塩化炭素、クロロホル
ム、塩化メチレン、ジクロロエタン、トリクロロエタ
ン、及びそれらの混合物等が好ましい。塩素含有化合物
との接触の後は、触媒中に塩素分を安定に含有させるた
めに、必要に応じて焼成、分解、酸化、還元等の後処理
を施すことが好ましい。塩素含有化合物との接触の後、
固体酸触媒に占める塩素含有量は、０．０２〜１０重量
％、好ましくは０．１〜５重量％、特には０．２〜３重
量％である。[Contact with Chlorine-Containing Compound] The solid acid catalyst of the present invention preferably contains a chlorine component, if necessary, in order to enhance its catalytic activity. In order to contain a chlorine content, it is preferable that the support or the solid acid catalyst is brought into contact with the chlorine-containing compound after firing after molding, when supporting the metal component of Group VIIIB of the Periodic Table, or after the subsequent treatment. . The chlorine-containing compound is not particularly limited, and chlorine, an inorganic chlorine-containing compound, and an organic chlorine-containing compound are preferably used. Particularly preferred are chlorine, hydrochloric acid, aluminum chloride, zirconium chloride, ammonium chloride, carbon tetrachloride, chloroform, methylene chloride, dichloroethane, trichloroethane, and mixtures thereof. After the contact with the chlorine-containing compound, post-treatments such as calcination, decomposition, oxidation, and reduction are preferably performed as necessary in order to stably contain chlorine in the catalyst. After contact with the chlorine-containing compound,
The chlorine content in the solid acid catalyst is 0.02 to 10% by weight, preferably 0.1 to 5% by weight, particularly 0.2 to 3% by weight.
【００３４】［固体酸触媒］本発明の固体酸触媒は、正
方晶構造のジルコニアおよび／または含水ジルコニアか
らなる部分と、アルミナおよび／または含水アルミナか
らなる部分で構成され成形された担体と、この担体に担
持された硫酸分を含む。本発明の固体酸触媒のジルコニ
ア部分は正方晶構造であることが好ましい。触媒中のジ
ルコニア部分の結晶構造は、Ｓ28.2／Ｓ30.2比が、１．
０以下、より好ましくは０．５以下、さらに好ましくは
０．１以下である。単斜晶構造がほとんど存在していな
い方が、高い触媒活性が得られる。固体酸触媒は１００
％硫酸より高い酸強度、酸強度Ho（ハメットの酸度関
数）が−１１．９３より強い酸性を示す固体超強酸であ
ることが好ましい。[Solid Acid Catalyst] The solid acid catalyst according to the present invention comprises a carrier composed of a portion composed of tetragonal zirconia and / or hydrous zirconia, and a portion composed of alumina and / or hydrous alumina. Contains sulfuric acid supported on a carrier. The zirconia portion of the solid acid catalyst of the present invention preferably has a tetragonal structure. The crystal structure of the zirconia portion in the catalyst has an S28.2 / S30.2 ratio of 1.
It is 0 or less, more preferably 0.5 or less, and further preferably 0.1 or less. High catalytic activity is obtained when almost no monoclinic structure is present. 100 solid acid catalysts
% Sulfuric acid, and a solid superacid having an acid strength Ho (Hammet acidity function) higher than -11.93.
【００３５】触媒中に占めるジルコニアの割合はジルコ
ニウム元素重量として２５〜６０重量％であり、好まし
くは３０〜５５重量％である。ジルコニアの割合が少な
すぎると触媒の活性が低下する。ジルコニアの割合が多
すぎると、触媒の機械的強度が低下し、また比表面積の
低下や細孔容積の減少、硫酸分の含有量の減少により触
媒活性が低下する。触媒中に占めるアルミナの割合はア
ルミニウム元素重量として５〜３０重量％であり、好ま
しくは１０〜２５重量％である。アルミナの割合が少な
すぎると触媒の機械的強度が低下し、また比表面積の低
下や細孔容積の減少、硫酸分の含有量の減少により触媒
活性が低下する。アルミナの割合が多すぎると、触媒の
活性が低下する。また、触媒中に占めるジルコニア部分
とアルミナ部分の合計重量は、触媒活性、成形物の強度
の点などから７０重量％以上、より好ましくは８０重量
％以上になるようにすることが好ましい。触媒中に占め
る硫酸分（ＳＯ４）の割合は硫黄元素重量として１〜６
重量％であり、好ましくは２〜５重量％である。硫酸分
が多すぎても少なすぎても触媒活性は低下する。The proportion of zirconia in the catalyst is from 25 to 60% by weight, preferably from 30 to 55% by weight, as zirconium element weight. If the proportion of zirconia is too small, the activity of the catalyst decreases. If the proportion of zirconia is too large, the mechanical strength of the catalyst decreases, and the catalytic activity decreases due to a decrease in specific surface area, a decrease in pore volume, and a decrease in the content of sulfuric acid. The proportion of alumina in the catalyst is 5 to 30% by weight, preferably 10 to 25% by weight, as elemental aluminum. If the proportion of alumina is too small, the mechanical strength of the catalyst decreases, and the catalytic activity decreases due to a decrease in specific surface area, a decrease in pore volume, and a decrease in the content of sulfuric acid. If the proportion of alumina is too large, the activity of the catalyst is reduced. The total weight of the zirconia portion and the alumina portion in the catalyst is preferably 70% by weight or more, more preferably 80% by weight or more, from the viewpoints of catalytic activity, strength of the molded product, and the like. The ratio of sulfuric acid (SO 4 ) in the catalyst is 1 to 6 in terms of elemental sulfur.
%, Preferably 2 to 5% by weight. If the sulfuric acid content is too high or too low, the catalytic activity decreases.
【００３６】本発明の固体酸触媒は塩素分を含有する。
触媒中に占める塩素分の割合は、０．０２〜１０重量
％、好ましくは０．１〜５重量％、特には０．２〜３重
量％である。塩素分の含有量が少なすぎると、酸触媒性
能向上効果が低く好ましくない。塩素分の含有量が多す
ぎると、触媒の比表面積や細孔容積の低下を引き起こす
ため好ましくない。The solid acid catalyst of the present invention contains chlorine.
The proportion of chlorine in the catalyst is from 0.02 to 10% by weight, preferably from 0.1 to 5% by weight, particularly from 0.2 to 3% by weight. If the chlorine content is too small, the effect of improving the acid catalyst performance is low, which is not preferable. If the chlorine content is too high, the specific surface area and the pore volume of the catalyst are undesirably reduced.
【００３７】本発明の固体酸触媒は、その触媒性能向上
のため必要に応じて周期律表第VIIIＢ族金属成分から選
ばれる１種以上の金属を含有する。第VIIIＢ族金属とし
ては、白金、パラジウム、ルテニウム、ロジウム、イリ
ジウム、ニッケル、鉄、コバルト、オスミウムが挙げら
れるが、好ましくは白金、パラジウム、ルテニウム、特
には白金が好適に用いられる。触媒中に占める周期律表
第VIIIＢ族金属成分の割合は、金属元素重量として０．
０１〜１０重量％、好ましくは０．０５〜５重量％、特
には０．１〜２重量％である。周期律表第VIIIＢ族金属
成分の含有量が少なすぎると、触媒性能向上効果が低く
好ましくない。周期律表第VIIIＢ族金属成分の含有量が
多すぎると、触媒の比表面積や細孔容積の低下を引き起
こすため好ましくない。The solid acid catalyst of the present invention contains at least one metal selected from Group VIIIB metal components of the periodic table, if necessary, for improving the catalytic performance. Examples of the Group VIIIB metal include platinum, palladium, ruthenium, rhodium, iridium, nickel, iron, cobalt, and osmium. Platinum, palladium, ruthenium, and particularly platinum are preferably used. The ratio of the Group VIIIB metal component of the periodic table in the catalyst is 0.1% by weight of the metal element.
It is from 0.01 to 10% by weight, preferably from 0.05 to 5% by weight, especially from 0.1 to 2% by weight. If the content of the Group VIIIB metal component in the periodic table is too small, the effect of improving the catalyst performance is unpreferably low. If the content of the Group VIIIB metal component in the periodic table is too large, the specific surface area and pore volume of the catalyst are undesirably reduced.
【００３８】本発明の固体酸触媒の比表面積は１００〜
３００ｍ２／ｇ、好ましくは１５０〜３００ｍ２／ｇ、
特には１５０〜２００ｍ２／ｇである。比表面積は通常
知られているＢＥＴ法によって測定できる。比表面積が
低すぎると、焼成しすぎあるいはジルコニアの正方晶構
造が保持できないことなどにより触媒活性は低下する。
比表面積が高すぎると、焼成が不十分であること、焼成
時の硫酸分の滞留が不十分であることなどにより触媒活
性が低下する。The specific surface area of the solid acid catalyst of the present invention is from 100 to
300m 2 / g, preferably 150~300m 2 / g,
In particular, it is 150 to 200 m 2 / g. The specific surface area can be measured by a generally known BET method. If the specific surface area is too low, the catalytic activity is lowered due to excessive firing or the inability to maintain the tetragonal structure of zirconia.
If the specific surface area is too high, the catalytic activity will be reduced due to insufficient calcination and insufficient retention of sulfuric acid during calcination.
【００３９】本発明の固体酸触媒の細孔構造は、細孔直
径０．００２〜０．０５μｍの範囲については窒素吸着
法、細孔直径０．０５〜１０μｍの範囲は水銀圧入法に
より測定できる。細孔直径０．００２〜１０μｍの細孔
容積は０．２ｍｌ／ｇ以上、好ましくは０．３ｍｌ／ｇ
以上、特には０．３５ｍｌ／ｇ〜１．０ｍｌ／ｇであ
る。細孔直径０．００２〜０．０５μｍの細孔容積は
０．２ｍｌ／ｇ以上であることが好ましい。細孔直径
０．００２〜０．０５μｍの平均細孔直径は２０〜２０
０オングストローム、特には３０〜１５０オングストロ
ーム、さらには４０〜１００オングストロームであるこ
とが好ましい。細孔直径０．０５〜１０μｍの細孔分布
において、直径０．０５〜１μｍの範囲、特に０．０５
〜０．５μｍの範囲にピークを有し、それ以外にはピー
クが無いことが好ましい。ピークを有する細孔分布と
は、累積細孔容量を細孔直径について微分した値を、細
孔直径に対してプロットした、いわゆる細孔分布曲線が
明瞭な極大値を有することを意味する。また、直径０．
０５〜１μｍの細孔容積が０．０５〜０．５ｍｌ／ｇ、
特には０．０５〜０．３ｍｌ／ｇであり、直径１〜１０
μｍの細孔容積が０．０５ｍｌ／ｇ未満、特には０．０
２ｍｌ／ｇ未満であることが触媒の機械的強度を高める
ために好ましい。The pore structure of the solid acid catalyst of the present invention can be measured by a nitrogen adsorption method for a pore diameter of 0.002 to 0.05 μm, and by a mercury intrusion method for a pore diameter of 0.05 to 10 μm. . The pore volume with a pore diameter of 0.002 to 10 μm is 0.2 ml / g or more, preferably 0.3 ml / g.
As mentioned above, it is especially 0.35 ml / g to 1.0 ml / g. The pore volume with a pore diameter of 0.002 to 0.05 μm is preferably 0.2 ml / g or more. The average pore diameter of the pore diameter of 0.002 to 0.05 μm is 20 to 20.
The thickness is preferably 0 Å, particularly 30 to 150 Å, and more preferably 40 to 100 Å. In a pore distribution having a pore diameter of 0.05 to 10 μm, a diameter of 0.05 to 1 μm, particularly 0.05
It is preferable to have a peak in the range of ０．５0.5 μm and no other peak. The pore distribution having a peak means that a value obtained by differentiating the accumulated pore volume with respect to the pore diameter is plotted against the pore diameter, that is, a so-called pore distribution curve has a clear maximum value. In addition, a diameter of 0.
0.05-1 μm pore volume of 0.05-0.5 ml / g,
In particular, the concentration is 0.05 to 0.3 ml / g, and the diameter is 1 to 10 ml.
μm pore volume of less than 0.05 ml / g,
It is preferably less than 2 ml / g in order to increase the mechanical strength of the catalyst.
【００４０】本発明の触媒は、粉体でなく、成形された
形状であり、０．５〜２０ｍｍの大きさのものを容易に
得ることができ、通常、平均粒径として０．２〜５０ｍ
ｍ、特には、０．５〜２０ｍｍが好ましく用いられる。
触媒の機械的強度は、直径１．５ｍｍの円柱ペレットの
側面圧壊強度として２ｋｇ以上、より好ましくは３ｋｇ
以上、さらに好ましくは４〜８ｋｇが得られる。本発明
による成形された固体酸触媒は、水中に放置した状態で
もその形状が維持される。水中でその形状が維持されな
いペレットは、触媒製造時の担持工程や触媒反応時にお
いて、ペレットが粉化や割れを起こすことにより、歩留
まりの低下やプロセスのトラブルにつながり、実用上好
ましくない。The catalyst of the present invention is not a powder but has a molded shape and can easily be obtained in a size of 0.5 to 20 mm, and usually has an average particle size of 0.2 to 50 m.
m, particularly preferably 0.5 to 20 mm.
The mechanical strength of the catalyst is 2 kg or more, more preferably 3 kg, as the side crushing strength of a cylindrical pellet having a diameter of 1.5 mm.
As described above, more preferably, 4 to 8 kg is obtained. The shape of the solid acid catalyst formed according to the present invention is maintained even when left in water. Pellet whose shape is not maintained in water is not preferable in practical use because the pellet may be powdered or cracked during a supporting step or a catalytic reaction in the production of a catalyst, leading to a decrease in yield and a process trouble.
【００４１】［酸触媒反応］本発明による固体酸触媒が
適用される酸触媒反応としては、従来、塩化アルミニウ
ム系触媒に代表されるルイス酸触媒または硫酸に代表さ
れるブレンステッド酸触媒を用いていた酸触媒反応を挙
げることができる。特には、異性化、不均化、ニトロ
化、分解、アルキル化、エステル化、アシル化、エーテ
ル化、転位、重合などの様々な反応に好ましく用いられ
る。主な反応対象は、炭化水素類、すなわち、炭化水
素、および、その炭化水素に置換基を付与したような炭
化水素誘導体、特には炭化水素または含酸素炭化水素化
合物である。特には、炭化水素類の転化反応に好ましく
用いられる。[Acid-Catalyzed Reaction] As the acid-catalyzed reaction to which the solid acid catalyst according to the present invention is applied, a Lewis acid catalyst represented by an aluminum chloride-based catalyst or a Bronsted acid catalyst represented by sulfuric acid is conventionally used. Acid catalyzed reactions. In particular, it is preferably used for various reactions such as isomerization, disproportionation, nitration, decomposition, alkylation, esterification, acylation, etherification, rearrangement, and polymerization. The main reaction target is hydrocarbons, that is, hydrocarbons and hydrocarbon derivatives obtained by adding substituents to the hydrocarbons, particularly hydrocarbons or oxygen-containing hydrocarbon compounds. In particular, it is preferably used for a conversion reaction of hydrocarbons.
【００４２】具体的な反応としては、ライトナフサの異
性化反応、ワックスの異性化反応、オレフィンの異性化
反応、キシレンの異性化反応、トルエンの不均化反応、
芳香族化合物のニトロ化反応、フロン類の分解反応、ク
メンハイドロパーオキサイドの分解反応、ブテンとブタ
ンのアルキル化反応、芳香族化合物のアルキル化反応、
メタクリル酸などのエステル化反応、無水フタル酸のエ
ステル化反応、芳香族化合物のアシル化反応、イソブテ
ンとメタノールのエーテル化反応、ベックマン転位反
応、テトラヒドロフランの開環重合反応、オレフィンの
重合反応、メタンの酸化的カップリング反応などに用い
ることができる。Specific reactions include isomerization of light naphtha, isomerization of wax, isomerization of olefin, isomerization of xylene, disproportionation of toluene,
Nitration reaction of aromatic compounds, decomposition reaction of fluorocarbons, decomposition reaction of cumene hydroperoxide, alkylation reaction of butene and butane, alkylation reaction of aromatic compound,
Esterification reaction of methacrylic acid, etc., esterification reaction of phthalic anhydride, acylation reaction of aromatic compound, etherification reaction of isobutene and methanol, Beckmann rearrangement reaction, ring-opening polymerization reaction of tetrahydrofuran, polymerization reaction of olefin, methane It can be used for oxidative coupling reactions and the like.
【００４３】［酸化雰囲気中での処理］本発明の触媒
は、使用前、または、使用後に酸化雰囲気中で熱処理す
ることで触媒活性が向上する。通常、空気などの酸素の
存在した雰囲気で３００〜５００℃の熱処理を行う。雰
囲気の酸素の含有量は０．１〜５０容量％、特には１〜
３０容量％が好ましく、窒素と酸素の混合物、窒素と空
気の混合物、空気などが好適に用いられる。特に、処理
温度３５０〜４８０℃、処理時間０．１〜１００時間が
好ましい。処理圧力は、減圧、常圧、加圧下で処理が可
能であるが、常圧での処理が簡便であり、好ましい。こ
の酸化雰囲気中での処理により、触媒は乾燥され、ま
た、吸着物質や使用により付着した堆積物が酸化され除
去されることにより活性化されると考えられるので、用
いる空気は水分などの不純物が低減された空気を用いる
ことが、特に触媒使用前には好ましい。具体的には、２
０℃における相対湿度を５％以下に除湿した雰囲気が好
ましく用いられる。処理温度が高すぎると触媒の性状が
変化し、また処理温度が低すぎると触媒が十分に乾燥さ
れず、何れの場合も活性が低下する。触媒製造時の焼成
などの熱処理の後、１日以上、特には、１０日以上の期
間、大気中におかれていた触媒、または、酸触媒反応に
使用された触媒に対してこの処理は有効である。また、
非酸化雰囲気（酸素を含まない気流）中で処理を行って
も触媒の活性は低下する。[Treatment in Oxidizing Atmosphere] The catalyst of the present invention is improved in catalytic activity by heat treatment in an oxidizing atmosphere before or after use. Usually, heat treatment at 300 to 500 ° C. is performed in an atmosphere in which oxygen such as air is present. The oxygen content of the atmosphere is 0.1 to 50% by volume, especially 1 to 50% by volume.
30% by volume is preferable, and a mixture of nitrogen and oxygen, a mixture of nitrogen and air, and air are suitably used. In particular, a processing temperature of 350 to 480 ° C. and a processing time of 0.1 to 100 hours are preferable. The processing can be performed under reduced pressure, normal pressure, and increased pressure, but processing under normal pressure is simple and preferable. It is considered that the catalyst is dried by the treatment in the oxidizing atmosphere, and is activated by oxidizing and removing adsorbed substances and deposits adhered by use, so that the air used contains impurities such as moisture. It is preferred to use reduced air, especially before using the catalyst. Specifically, 2
An atmosphere in which the relative humidity at 0 ° C. is reduced to 5% or less is preferably used. If the treatment temperature is too high, the properties of the catalyst will change. If the treatment temperature is too low, the catalyst will not be sufficiently dried, and in any case, the activity will decrease. This treatment is effective for catalysts that have been exposed to the atmosphere for one day or more, especially for 10 days or more after heat treatment such as calcination during catalyst production, or for catalysts used for acid-catalyzed reactions. It is. Also,
Even if the treatment is performed in a non-oxidizing atmosphere (a stream containing no oxygen), the activity of the catalyst is reduced.
【００４４】酸化雰囲気中での処理の後、触媒は水分な
どの吸着をさける必要がある。このため、この処理は、
反応を行う反応装置や反応器に触媒を導入した後に行
い、大気を実質的に導入することなく、目的の酸触媒反
応を開始することが好ましい。目的の酸触媒反応が水素
雰囲気などの還元雰囲気で行われる場合には、反応開始
前に、窒素ガスまたはアルゴンガスなどの希ガスのよう
な不活性雰囲気に置換してからその反応を開始すること
が好ましい。なお、１日程度の期間、大気に暴露しても
活性は大きく低下はしないので、小規模な反応装置など
では、反応容器外でこの酸化雰囲気中の処理を行ない、
その後、反応容器に触媒を導入してもよい。After treatment in an oxidizing atmosphere, the catalyst must avoid adsorption of moisture and the like. Therefore, this process
It is preferable to carry out the reaction after introducing the catalyst into a reaction device or a reactor for carrying out the reaction, and to start a target acid-catalyzed reaction without substantially introducing air. If the target acid-catalyzed reaction is carried out in a reducing atmosphere such as a hydrogen atmosphere, replace it with an inert atmosphere such as a rare gas such as nitrogen gas or argon gas before starting the reaction, and then start the reaction. Is preferred. In addition, since the activity does not decrease significantly even when exposed to the atmosphere for about one day, in a small-scale reactor or the like, the treatment in the oxidizing atmosphere is performed outside the reaction vessel.
Thereafter, a catalyst may be introduced into the reaction vessel.
【００４５】また、反応装置や反応器中で反応に使用さ
れ、活性が低下した触媒に適用することもできる。特
に、触媒上にコークと呼ばれるような炭素質が析出して
いる場合には、酸素濃度を０．１〜２０容量％、特には
０．２〜５容量％として、急激に炭素質の酸化が行われ
ないようにすることが好ましい。Further, the present invention can be applied to a catalyst which has been used in a reaction in a reaction apparatus or a reactor and has reduced activity. In particular, when carbonaceous material such as coke is precipitated on the catalyst, the oxygen concentration is set to 0.1 to 20% by volume, particularly 0.2 to 5% by volume, and the oxidation of carbonaceous material is rapidly performed. It is preferable not to do this.
【００４６】［異性化反応用炭化水素］本発明の異性化
反応の原料となる炭化水素は、特に限定されないが、沸
点範囲−２０℃〜１５０℃程度の石油留分中にある炭化
水素が好ましく用いられる。さらには炭素数４〜６の飽
和炭化水素が全体の７０重量％以上、特には９０重量％
以上を占めるような炭化水素に好ましく用いられる。好
ましい反応は、直鎖パラフィンが分岐パラフィンに異性
化され、オレフィンや芳香族化合物が水素化されて鎖状
あるいは環状のパラフィンになり、さらに異性化される
反応である。炭化水素化合物の異性化の反応条件として
は、好ましい反応温度の範囲が２０〜３００℃、特には
１００〜２５０℃であり、好ましい反応圧力の範囲が１
〜５０ｋｇｆ／ｃｍ２、好ましいＬＨＳＶの範囲が０．
２〜１０／ｈｒ、好ましい水素／原料比の範囲は、原料
炭化水素に含まれる不飽和分（オレフィン分、芳香族
分）を飽和させるために必要な水素量以上、特には０．
０１〜１０ｍｏｌ／ｍｏｌである。[Hydrocarbon for Isomerization Reaction] The hydrocarbon used as a raw material for the isomerization reaction of the present invention is not particularly limited, but hydrocarbons in a petroleum fraction having a boiling range of about -20 ° C to 150 ° C are preferable. Used. Further, the saturated hydrocarbon having 4 to 6 carbon atoms accounts for 70% by weight or more, particularly 90% by weight of the whole.
It is preferably used for hydrocarbons occupying the above. A preferred reaction is a reaction in which linear paraffin is isomerized into branched paraffin, and olefins and aromatic compounds are hydrogenated to form a chain or cyclic paraffin, and further isomerized. As the reaction conditions for the isomerization of the hydrocarbon compound, a preferable reaction temperature range is 20 to 300 ° C, particularly 100 to 250 ° C, and a preferable reaction pressure range is 1 to 3.
５０50 kgf / cm 2 , and the preferable range of LHSV is 0.
The preferable range of the hydrogen / raw material ratio is 2 to 10 / hr, which is equal to or more than the amount of hydrogen necessary to saturate the unsaturated components (olefin content and aromatic content) contained in the raw material hydrocarbon, and particularly preferably 0.1 to 0.1 / hr.
01 to 10 mol / mol.
【００４７】本発明の異性化反応の原料となる炭化水素
中の硫黄化合物の含有量は、硫黄重量として５００ｐｐ
ｍ以下、特には１００ｐｐｍ以下、さらには１ｐｐｍ以
下であることが好ましい。本発明の異性化反応の原料と
なる炭化水素中の水分量としては、１００ｐｐｍ以下、
さらに好ましくは５ｐｐｍ以下、特には１ｐｐｍ以下で
あることが好ましい。The content of the sulfur compound in the hydrocarbon used as a raw material for the isomerization reaction of the present invention is 500 pp as sulfur weight.
m, particularly preferably 100 ppm or less, more preferably 1 ppm or less. The amount of water in the hydrocarbon as a raw material for the isomerization reaction of the present invention is 100 ppm or less,
It is more preferably at most 5 ppm, particularly preferably at most 1 ppm.
【００４８】本発明中の炭化水素の異性化反応では、触
媒活性を継続的に保つために、必要に応じて原料炭化水
素中に塩素含有化合物を導入し、反応系内に供給する。
塩素含有化合物としては、塩素、無機塩素含有化合物、
有機塩素含有化合物が挙げられるが、特には有機塩素含
有化合物が好適に用いられる。有機塩素含有化合物とし
ては特には限定はないが、例えばクロロホルム、四塩化
炭素、塩化メチレン、次クロロエタン、トリクロロエタ
ンや、それらの混合物などが好適に用いられる。塩素含
有化合物の導入量は、原料炭化水素中に占める塩素量と
して０．１ｐｐｍ〜１００００ｐｐｍ、好ましくは１〜
１０００ｐｐｍである。In the hydrocarbon isomerization reaction of the present invention, a chlorine-containing compound is introduced into the raw material hydrocarbon as necessary and supplied into the reaction system in order to maintain the catalytic activity continuously.
As chlorine-containing compounds, chlorine, inorganic chlorine-containing compounds,
Although an organic chlorine-containing compound is mentioned, an organic chlorine-containing compound is particularly preferably used. Although the organic chlorine-containing compound is not particularly limited, for example, chloroform, carbon tetrachloride, methylene chloride, hypochloroethane, trichloroethane, and a mixture thereof are preferably used. The amount of the chlorine-containing compound introduced is 0.1 ppm to 10000 ppm, preferably 1 to 1 ppm, as the chlorine amount in the raw hydrocarbon.
1000 ppm.
【００４９】[0049]
【実施例】以下、実施例により詳細に説明する。まず、
評価方法を説明する。The present invention will be described below in detail with reference to examples. First,
The evaluation method will be described.
【００５０】[含水ジルコニア粉及び含水アルミナ粉の
灼熱減量（水分量）測定方法]試料粉５０ｇをるつぼに
入れ、１４００℃で１時間以上、空気雰囲気で保持した
後、重量減少率を測定し、灼熱減量とした。[Method of Measuring Ignition Loss (Water Content) of Hydrated Zirconia Powder and Hydrated Alumina Powder] A sample powder (50 g) was placed in a crucible, kept at 1400 ° C. for 1 hour or more in an air atmosphere, and the weight loss rate was measured. Burning loss was assumed.
【００５１】[凝集粒子の平均粒径測定方法]日機装
（株）ＭＩＣＲＯＴＲＡＣ粒度分析計を用い、湿式測定
法で測定した。これは、粉体を水中に分散させ、流れる
凝集粒子群にレーザー光を照射し、その前方散乱光によ
り粒度分析を行うものである。[Method of Measuring Average Particle Size of Aggregated Particles] The average particle size was measured by a wet method using a MICROTRAC particle size analyzer manufactured by Nikkiso Co., Ltd. In this method, a powder is dispersed in water, a group of agglomerated particles flowing is irradiated with a laser beam, and a particle size analysis is performed by the forward scattered light.
【００５２】[アスペクト比の測定方法]日立製作所製Ｈ
−９０００ＵＨＲ透過型電子顕微鏡を用いて粉体を観察
し、画像フィールド中に存在する粒子から無差別に１０
個を抽出し、その粒子の長軸と短軸の長さの比を測定し
てそれらの平均を求めるものである。[Method of measuring aspect ratio] H manufactured by Hitachi, Ltd.
-Observe the powder using a 9000 UHR transmission electron microscope and indiscriminately remove 10 particles from the particles present in the image field.
Individual particles are extracted, the ratio of the major axis to the minor axis of the particles is measured, and the average thereof is determined.
【００５３】[Ｘ線回折による結晶種比の算出方法]Ｘ線
回折チャートからジルコニアの正方晶と単斜晶のピーク
分離を行い、２θ＝２８．２゜における単斜晶ジルコニ
アのピークの面積と、２θ＝３０．２゜における正方晶
ジルコニアのピークの面積との比（Ｓ２８．２／Ｓ３
０．２比）を算出した。なお、Ｓ２８．２／Ｓ３０．２
比が０．０２以下では、単斜晶ピークが不明瞭となり検
出不能であった。 広角Ｘ線測定装置；理学電機（株）製 ＲＡＤ−１Ｃ
横型ゴニオメーター Ｘ線管球；封入管型Ｃｕ管球（出力３０ｋＶ−２０ｍ
Ａ、波長１．５４０６Å） 測定領域（２θ）；３〜９０゜ ステップ幅；０．０２゜ スキャンスピード；４゜／ｍｉｎ スリット幅；ダイバージェントスリット（ＤＳ）＝１゜ スキャッタリングスリット（ＳＳ）＝１゜ レシービングスリット（ＲＳ）＝０．３ｍｍ スムージング条件；Savitzky, Golayの１５点の重み付
き平滑化法 ピーク分離使用領域（２θ）；２６．５〜３２．５゜ 分離対象ピーク数；４本（単斜晶２本、正方晶１本、非
晶質１本） 結晶種比算出使用ピーク； 単斜晶；２θ＝２８．２゜（ｄ＝３．１６３、ｈｋｌ＝
１１１） 正方晶；２θ＝３０．２゜（ｄ＝２．９６０、ｈｋｌ＝
１１１）[Calculation method of crystal seed ratio by X-ray diffraction] From the X-ray diffraction chart, the peaks of tetragonal and monoclinic zirconia were separated, and the area of the peak of monoclinic zirconia at 2θ = 28.2 ° was determined. , Ratio to the area of the tetragonal zirconia peak at 2θ = 30.2 ° (S28.2 / S3
0.2 ratio). Note that S28.2 / S30.2
When the ratio was 0.02 or less, the monoclinic peak was unclear and undetectable. Wide-angle X-ray measuring device; RAD-1C manufactured by Rigaku Corporation
Horizontal goniometer X-ray tube; sealed tube type Cu tube (output 30kV-20m
A, wavelength 1.5406 °) Measurement area (2θ); 3 to 90 ° Step width; 0.02 ° Scan speed; 4 ° / min Slit width; divergent slit (DS) = 1 ° Scattering slit (SS) = 1 ゜ Receiving slit (RS) = 0.3 mm Smoothing condition; Savitzky, Golay weighted smoothing method of 15 points Peak separation use area (2θ); 26.5-32.5 ゜ Number of peaks to be separated; 4 ( (2 monoclinics, 1 tetragonal, 1 amorphous) Peak used for crystal seed ratio calculation; monoclinic; 2θ = 28.2 ゜ (d = 3.163, hkl =
111) tetragonal; 2θ = 30.2 ° (d = 2.960, hkl =
111)
【００５４】[細孔構造の測定方法]比表面積及び細孔直
径０．００２〜０．０５μｍの範囲の細孔構造について
は、Ｍｉｃｒｏｍｅｒｉｔｉｃｓ社製ＡＳＡＰ２４００
型測定器を用い、窒素吸着法にて測定した。細孔直径
０．０５〜１０μｍの範囲については、Ｍｉｃｒｏｍｅ
ｒｉｔｉｃｓ社製ＡｕｔｏＰｏｒｅ９２００型測定器を
用い、水銀圧入法にて測定した。[Measurement Method of Pore Structure] With respect to the specific surface area and the pore structure having a pore diameter in the range of 0.002 to 0.05 μm, ASAP2400 manufactured by Micromeritics, Inc.
It was measured by a nitrogen adsorption method using a mold measuring device. For a pore diameter range of 0.05 to 10 μm, Microme
It was measured by a mercury intrusion method using an AutoPore 9200 type measuring instrument manufactured by RITICS Corporation.
【００５５】[平均圧壊強度の測定方法]富山産業（株）
製ＴＨ−２０３ＣＰ錠剤破壊強度測定器を用い、円柱状
に押出成形し、乾燥、焼成したサンプルを用いて側面圧
壊強度を測定した。測定プローブは先端が直径４．５ｍ
ｍの円形状のものを使用した。測定サンプルを、円柱サ
ンプルの側面中央に当てて測定する操作を２０回繰り返
し、その平均値を算出した。[Method of measuring average crushing strength] Toyama Sangyo Co., Ltd.
The side crushing strength was measured using a sample extruded in a cylindrical shape, dried and calcined using a TH-203CP tablet breaking strength measuring instrument manufactured by Toshiba Corporation. The tip of the measuring probe is 4.5m in diameter
m was used. The operation of applying the measurement sample to the center of the side surface of the cylindrical sample and measuring was repeated 20 times, and the average value was calculated.
【００５６】[触媒Ａ]市販の乾燥水酸化ジルコニウムを
乾燥して灼熱減量９重量％の含水ジルコニア粉体を得
た。この粉体は平均粒径１．２μｍであった。また、市
販の擬ベーマイト粉のうち、アスペクト比５８の繊維状
の粒子形状を有する、灼熱減量２７重量％、平均粒径１
０μｍの粉体を選び含水アルミナ粉体として用いた。こ
の含水ジルコニア粉体１８６０ｇと含水アルミナ粉体１
１２０ｇを加え、さらに硫酸アンモニウム５７５ｇを加
え、攪拌羽根のついた混練機で水を加えながら４５分間
混練を行った。得られた混練物を直径１．６ｍｍの円形
開口を有する押出機より押し出して円柱状のペレットを
成形し、１１０℃で乾燥して乾燥ペレットを得た。続い
てこの乾燥ペレットの一部を空気の流通量を０．４ｌ／
分としてバッチ式焼成装置を用い、７２５℃で１時間
（室温から７２５℃まで１時間で昇温）焼成し、触媒Ａ
１８７ｇを得た。[Catalyst A] Commercially available dried zirconium hydroxide was dried to obtain a hydrous zirconia powder having a loss on ignition of 9% by weight. This powder had an average particle size of 1.2 μm. In addition, among commercially available pseudo-boehmite powders, having a fibrous particle shape with an aspect ratio of 58, a loss on ignition of 27% by weight, and an average particle size of 1
A powder of 0 μm was selected and used as a hydrated alumina powder. 1860 g of this hydrous zirconia powder and hydrous alumina powder 1
120 g, further 575 g of ammonium sulfate were added, and kneading was carried out for 45 minutes while adding water with a kneader equipped with stirring blades. The obtained kneaded material was extruded from an extruder having a circular opening having a diameter of 1.6 mm to form a cylindrical pellet, and dried at 110 ° C. to obtain a dried pellet. Subsequently, a part of the dried pellets was subjected to an air flow rate of 0.4 l /
The catalyst A was fired at 725 ° C. for 1 hour (the temperature was raised from room temperature to 725 ° C. in 1 hour) using a batch-type firing apparatus.
187 g were obtained.
【００５７】成形された触媒Ａは、平均直径１．５ｍ
ｍ、平均長さ５ｍｍの円柱状であり、平均圧壊強度は
３．８ｋｇであった。触媒ＡのＳ28.2／Ｓ30.2比は０．
０５であり、単斜晶構造はほとんど存在していない。触
媒Ａ中に占めるジルコニアの割合はジルコニウム元素重
量として４６．６％、アルミナの割合はアルミニウム元
素重量として１５．５％、硫酸分の割合は硫黄元素重量
として２．５％、塩素分の割合は０．０１重量％以下で
あった。触媒Ａの比表面積は１６９ｍ２／ｇ、細孔直径
０．００２〜１０μｍの細孔容積は０．４７ｍｌ／ｇで
あった。触媒Ａの細孔直径０．０５〜１０μｍの細孔容
積は０．１５ｍｌ／ｇであり、０．１８μｍにのみ明確
なピークが認められた。触媒Ａの細孔直径０．００２〜
０．０５μｍの細孔容積は０．３２ｍｌ／ｇであり、平
均細孔直径は５７Åであった。The formed catalyst A had an average diameter of 1.5 m.
m, a columnar shape with an average length of 5 mm, and an average crushing strength of 3.8 kg. The S28.2 / S30.2 ratio of catalyst A is 0.
05, indicating almost no monoclinic structure. The proportion of zirconia in catalyst A is 46.6% in terms of zirconium element weight, the proportion of alumina is 15.5% in terms of aluminum element weight, the proportion of sulfuric acid is 2.5% in terms of sulfur element, and the proportion of chlorine is It was 0.01% by weight or less. The specific surface area of the catalyst A was 169 m 2 / g, and the pore volume with a pore diameter of 0.002 to 10 μm was 0.47 ml / g. The pore volume of catalyst A having a pore diameter of 0.05 to 10 μm was 0.15 ml / g, and a clear peak was observed only at 0.18 μm. 0.002 pore diameter of catalyst A
The pore volume at 0.05 μm was 0.32 ml / g and the average pore diameter was 57 °.
【００５８】[触媒Ｂ]１２５ｇの触媒Ａに、触媒中の白
金量が０．５重量％になるように塩化白金酸の水溶液を
スプレー担持した。これを乾燥後、５００℃で１時間
（室温から５００℃まで１時間で昇温）焼成して触媒Ｂ
約１２５ｇを得た。触媒Ｂの形状、平均圧壊強度、結晶
構造、ジルコニアの割合、アルミナの割合、硫酸分の割
合、塩素分の割合、比表面積、細孔直径０．００２〜１
０μｍの細孔容積、細孔直径０．０５〜１０μｍの細孔
構造、細孔直径０．００２〜０．０５μｍの細孔容積は
触媒Ａと同等であった。触媒Ｂ中に占める白金の割合は
０．５重量％、触媒Ｂの細孔直径０．００２〜０．０５
μｍの範囲の平均細孔直径は６２Åであった。[Catalyst B] An aqueous solution of chloroplatinic acid was spray-loaded onto 125 g of Catalyst A so that the amount of platinum in the catalyst was 0.5% by weight. After drying, the mixture was calcined at 500 ° C. for 1 hour (the temperature was raised from room temperature to 500 ° C. in 1 hour) to obtain catalyst B
About 125 g were obtained. Catalyst B shape, average crushing strength, crystal structure, zirconia ratio, alumina ratio, sulfuric acid ratio, chlorine ratio, specific surface area, pore diameter 0.002 to 1
The pore volume of 0 μm, the pore structure with a pore diameter of 0.05 to 10 μm, and the pore volume with a pore diameter of 0.002 to 0.05 μm were equivalent to those of the catalyst A. The proportion of platinum in catalyst B was 0.5% by weight, and the pore diameter of catalyst B was 0.002 to 0.05.
The average pore diameter in the μm range was 62 °.
【００５９】[触媒Ｃ]市販の乾燥水酸化ジルコニウムを
乾燥して灼熱減量（水分量）９重量％の含水ジルコニア
粉体を得た。この粉体は平均粒径１．２μｍであった。
また、市販の擬ベーマイト粉のうち、アスペクト比５８
の繊維状の粒子形状を有する、水分量２７％、平均粒径
１０μｍの粉体を選び含水アルミナ粉体として用いた。
この含水ジルコニア粉体１８６０ｇと含水アルミナ粉体
１１２０ｇを加え、さらに硫酸アンモニウム５７５ｇを
加え、攪拌羽根のついた混練機で水を加えながら４５分
間混練を行った。得られた混練物を直径１．６ｍｍの円
形開口を有する押出機より押し出して円柱状のペレット
を成形し、１１０℃で乾燥して乾燥ペレットを得た。続
いてこの乾燥ペレットの一部を、空気の流通量を０．４
Ｌ／分としてバッチ式焼成装置を用い、６７５℃で２時
間（室温から６７５℃まで１時間で昇温）焼成し、触媒
Ｃ１９０ｇを得た。[Catalyst C] Commercially available dried zirconium hydroxide was dried to obtain a hydrous zirconia powder having a loss on ignition (water content) of 9% by weight. This powder had an average particle size of 1.2 μm.
Further, of the commercially available pseudo-boehmite powder, the aspect ratio is 58%.
A powder having a water content of 27% and an average particle size of 10 μm having a fibrous particle shape of was used as a hydrated alumina powder.
1860 g of the hydrated zirconia powder and 1120 g of the hydrated alumina powder were added, and 575 g of ammonium sulfate was further added. The mixture was kneaded for 45 minutes while adding water using a kneader equipped with stirring blades. The obtained kneaded material was extruded from an extruder having a circular opening having a diameter of 1.6 mm to form a cylindrical pellet, and dried at 110 ° C. to obtain a dried pellet. Subsequently, a part of the dried pellets was reduced to a flow rate of air of 0.4.
The mixture was fired at 675 ° C. for 2 hours (from room temperature to 675 ° C. in 1 hour) using a batch firing apparatus at L / min to obtain 190 g of a catalyst C.
【００６０】成形された触媒Ｃは、平均直径１．５ｍ
ｍ、平均長さ５ｍｍの円柱状であり、平均圧壊強度は
３．６ｋｇであった。触媒ＡのＳ28.2／Ｓ30.2比は０．
０５であり、単斜晶構造はほとんど存在していない。触
媒Ｃ中に占めるジルコニアの割合はジルコニウム元素重
量として４６．１重量％、アルミナの割合はアルミニウ
ム元素重量として１５．４重量％、硫酸分の割合は硫黄
元素重量として２．８重量％、塩素分の割合は０．０１
重量％以下であった。触媒Ｃの比表面積は１７０ｍ ２／
ｇ、細孔直径０．００２〜１０μｍの細孔容積は０．４
７ｍｌ／ｇであった。触媒Ｃの細孔直径０．０５〜１０
μｍの細孔容積は０．１５ｍｌ／ｇであり、０．１８μ
ｍにのみ明確なピークが認められた。触媒Ｃの細孔直径
０．００２〜０．０５μｍの細孔容積は０．３２ｍｌ／
ｇであり、平均細孔直径は５６Åであった。The formed catalyst C had an average diameter of 1.5 m.
m, cylindrical shape with an average length of 5 mm, the average crushing strength
It was 3.6 kg. The S28.2 / S30.2 ratio of catalyst A is 0.
05, indicating almost no monoclinic structure. Touch
The proportion of zirconia in the medium C is the weight of zirconium element.
46.1% by weight, the proportion of alumina was aluminum
15.4% by weight of elemental sulfur and sulfuric acid as sulfur
2.8% by weight as elemental weight, chlorine content is 0.01%
% By weight or less. The specific surface area of catalyst C is 170 m 2/
g, pore volume of 0.002 to 10 μm is 0.4
It was 7 ml / g. Catalyst C pore diameter 0.05 to 10
The pore volume of μm is 0.15 ml / g and 0.18 μm
A clear peak was observed only in m. Pore diameter of catalyst C
The pore volume of 0.002 to 0.05 μm is 0.32 ml /
g and the average pore diameter was 56 °.
【００６１】[触媒Ｄ]１２５ｇの触媒Ｃに、触媒中の白
金量が０．５％になるように塩化白金酸の水溶液をスプ
レー担持した。これを乾燥後、６８０℃で０．２時間
（室温から６８０℃まで０．５時間で昇温）焼成して触
媒Ｄ約１２５ｇを得た。触媒Ｄの形状、平均圧壊強度、
結晶構造、ジルコニアの割合、アルミナの割合、硫酸分
の割合、塩素分の割合、比表面積、細孔直径０．００２
〜１０μｍの細孔容積、細孔直径０．０５〜１０μｍの
細孔構造、細孔直径０．００２〜０．０５μｍの細孔容
積は触媒Ｃと同等であった。触媒Ｄ中に占める白金の割
合は０．５重量％、触媒Ｄの細孔直径０．００２〜０．
０５μｍの範囲の平均細孔直径は６３Åであった。[Catalyst D] An aqueous solution of chloroplatinic acid was spray-loaded onto 125 g of Catalyst C so that the amount of platinum in the catalyst was 0.5%. After drying, the mixture was calcined at 680 ° C. for 0.2 hours (from room temperature to 680 ° C. in 0.5 hours) to obtain about 125 g of Catalyst D. Catalyst D shape, average crush strength,
Crystal structure, ratio of zirconia, ratio of alumina, ratio of sulfuric acid, ratio of chlorine, specific surface area, pore diameter 0.002
The pore volume of 〜１０10 μm, the pore structure of pore diameter of 0.05 to 10 μm, and the pore volume of pore diameter of 0.002 to 0.05 μm were equivalent to those of the catalyst C. The proportion of platinum in catalyst D was 0.5% by weight, and the pore diameter of catalyst D was 0.002 to 0.5%.
The average pore diameter in the range of 05 μm was 63 °.
【００６２】[アシル化反応]攪拌効率を上げるため触媒
（触媒Ａ、Ｃ）を乳鉢で粉砕し、３２メッシュ以下に篩
い分けた触媒２０．０ｇをオートクレーブ内に入れ、空
気雰囲気に変えて４００℃、１時間の前処理を行った。
その後、大気を導入することなく、オートクレーブ内を
窒素雰囲気とし、クロロベンゼン２２５ｇ、p-クロロベ
ンゾイルクロリド３５ｇを加え、１３５℃で攪拌しなが
ら反応を行った。３時間反応後の反応液をガスクロマト
グラフにより分析した。[Acylation reaction] In order to increase the stirring efficiency, the catalysts (catalysts A and C) were pulverized in a mortar, 20.0 g of the catalyst sieved to 32 mesh or less was placed in an autoclave, and the atmosphere was changed to an air atmosphere at 400 ° C. Pre-treatment for 1 hour was performed.
Thereafter, 225 g of chlorobenzene and 35 g of p-chlorobenzoyl chloride were added to the autoclave under a nitrogen atmosphere without introducing air, and the reaction was carried out with stirring at 135 ° C. After the reaction for 3 hours, the reaction solution was analyzed by gas chromatography.
【００６３】アシル化体であるジクロロベンゾフェノン
の収率は、触媒Ａを用いた場合２８％、触媒Ｃを用いた
場合も２８％であった。The yield of the acylated dichlorobenzophenone was 28% when the catalyst A was used and 28% when the catalyst C was used.
【００６４】[異性化反応]１６〜２４メッシュに整粒し
た触媒（触媒Ｂ、Ｄ）４ｃｃを、長さ５０ｃｍ、内径１
ｃｍの固定床流通式反応器中に充填し、前処理の後、ラ
イトナフサの異性化反応を行った。前処理は、温度：４
００℃、圧力：常圧、雰囲気：空気で１時間行った。そ
の後、大気を導入することなく、反応器内を窒素雰囲気
とし、さらに水素雰囲気としてから、異性化反応を開始
した。[Isomerization Reaction] 4 cc of a catalyst (catalysts B and D) sized to 16 to 24 mesh was charged with a length of 50 cm and an inner diameter of 1 cm.
The mixture was packed in a fixed-bed flow-type reactor having a diameter of 1 cm, and after the pretreatment, an isomerization reaction of light naphtha was performed. Pretreatment temperature: 4
The process was performed at 00 ° C., pressure: normal pressure, and atmosphere: air for one hour. Thereafter, the isomerization reaction was started after the inside of the reactor was set to a nitrogen atmosphere and further to a hydrogen atmosphere without introducing air.
【００６５】反応原料となるライトナフサ（反応原料
１）は、脱硫ライトナフサをモレキュラーシーブ３Ａに
よって脱水して得た。反応原料１はブタンを４．９重量
％、ペンタンを５６．３重量％、ヘキサンを３２．６重
量％、シクロペンタンを２．３重量％、メチルシクロペ
ンタン及びシクロヘキサンを２．８重量％、ベンゼンを
１．１重量％含み、オレフィンを０．１重量％含んでい
た。また、水分の濃度は０．１重量ｐｐｍ以下であり、
硫黄化合物の濃度は硫黄換算１重量ppm以下、窒素化合
物の濃度は窒素換算０．１重量ｐｐｍ以下、水以外の酸
素化合物の濃度は酸素換算で０．１重量ｐｐｍ以下、塩
素化合物の濃度は塩素換算で０．１重量ｐｐｍ以下であ
った。また、反応原料１中に水を添加し、水分濃度４０
ｐｐｍとした反応原料を反応原料２とした。Light naphtha (reaction raw material 1) as a reaction raw material was obtained by dewatering desulfurized light naphtha with a molecular sieve 3A. Reaction material 1 was 4.9% by weight of butane, 56.3% by weight of pentane, 32.6% by weight of hexane, 2.3% by weight of cyclopentane, 2.8% by weight of methylcyclopentane and cyclohexane, benzene And 1.1% by weight of olefin. The concentration of water is 0.1 ppm by weight or less,
The concentration of sulfur compounds is 1 wtppm or less in terms of sulfur, the concentration of nitrogen compounds is 0.1 wtppm or less in terms of nitrogen, the concentration of oxygen compounds other than water is 0.1 wtppm or less in terms of oxygen, and the concentration of chlorine compounds is chlorine. It was 0.1 ppm by weight or less in conversion. Further, water is added to the reaction raw material 1 so that the water concentration becomes 40%.
The reaction raw material in ppm was used as reaction raw material 2.
【００６６】また、反応に持ちいた水素ガスは純度９
９．９９容量％で、水分は０．５重量ｐｐｍ以下であ
り、他の不純物として、硫黄化合物の濃度は硫黄換算で
１重量ｐｐｍ以下、窒素化合物の濃度は０．１重量ｐｐ
ｍ以下、水以外の酸素化合物の濃度は酸素換算で０．１
重量ｐｐｍ以下、塩素化合物の濃度は塩素換算で０．１
重量ｐｐｍ以下であった。The hydrogen gas brought to the reaction has a purity of 9%.
At 9.99% by volume, the water content was 0.5 ppm by weight or less, and as other impurities, the concentration of sulfur compound was 1% by weight or less in terms of sulfur, and the concentration of nitrogen compound was 0.1% by weight.
m or less, the concentration of oxygen compounds other than water is 0.1
Weight ppm or less, the concentration of chlorine compound is 0.1
It was less than ppm by weight.
【００６７】ライトナフサの異性化反応は、反応圧力
（ゲージ圧）：３０ｋｇ／ｃｍ２、ＬＨＳＶ＝２／ｈ
ｒ、水素／油比（Ｈ２／Ｏｉｌ）：２（ｍｏｌ／ｍｏ
ｌ）で行った。通油開始２５０時間後の反応管出口組成
をガスクロマトグラフィーにより分析した。分析結果で
ある反応管出口組成を表１に示す。表中ｉ−Ｃ５／ΣＣ
５は炭素数５の鎖状炭化水素留分中に占めるイソペンタ
ンの割合（重量％）、２，２’−ＤＭＢ／ΣＣ６は炭素
数６の鎖状炭化水素留分中に占める２，２’−ジメチル
ブタンの割合（重量％）である。反応原料１、２のｉ−
Ｃ５／ΣＣ５は４０．０重量％、２，２’−ＤＭＢ／Σ
Ｃ６は１．２重量％であった。The light naphtha isomerization reaction is performed under the following conditions: reaction pressure (gauge pressure): 30 kg / cm 2 , LHSV = 2 / h
r, hydrogen / oil ratio (H 2 / Oil): 2 (mol / mo)
1). The composition of the outlet of the reaction tube 250 hours after the start of oil passage was analyzed by gas chromatography. Table 1 shows the composition of the outlet of the reaction tube as the analysis result. I-C5 / ΣC in the table
5 is the proportion (% by weight) of isopentane in the chain hydrocarbon fraction having 5 carbon atoms, and 2,2′-DMB / ΔC6 is 2,2′- in the chain hydrocarbon fraction having 6 carbon atoms. It is the ratio (% by weight) of dimethylbutane. I- of reaction raw materials 1 and 2
C5 / {C5 is 40.0% by weight, 2,2′-DMB / Σ
C6 was 1.2% by weight.
【００６８】[0068]
【表１】 [Table 1]
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ１０Ｇ 35/085 Ｃ１０Ｇ 35/085 // Ｃ０７Ｂ 61/00 ３００ Ｃ０７Ｂ 61/00 ３００ Ｆターム(参考） 4G069 AA03 AA08 BA01A BA01B BA05A BA05B BA45A BD08A BD08B BD12A BD12B CB41 EC22X EC22Y FB30 4H006 AA02 AC27 BA09 BA10 BA17 BA30 BA36 BA37 BA68 BA81 BC32 4H029 CA00 DA00 4H039 CA19 CJ10 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C10G 35/085 C10G 35/085 // C07B 61/00 300 C07B 61/00 300 F-term (Reference) 4G069 AA03 AA08 BA01A BA01B BA05A BA05B BA45A BD08A BD08B BD12A BD12B CB41 EC22X EC22Y FB30 4H006 AA02 AC27 BA09 BA10 BA17 BA30 BA36 BA37 BA68 BA81 BC32 4H029 CA00 DA00 4H039 CA19 CJ10
Claims (10)
および硫黄分含有化合物を混練し、成形し、得られた成
形物を正方晶構造のジルコニアが得られる条件で焼成す
る固体酸触媒の製造方法において、含水ジルコニア粉体
の灼熱減量が５〜１５重量％である固体酸触媒の製造方
法。1. A method for producing a solid acid catalyst, comprising kneading hydrated zirconia powder, hydrated alumina powder, and a sulfur-containing compound, molding the mixture, and calcining the resulting molded product under the condition that zirconia having a tetragonal structure is obtained. The method for producing a solid acid catalyst according to any one of claims 1 to 3, wherein the zirconia powder has a loss on ignition of 5 to 15% by weight.
温（２７℃）体積換算で４Ｌ／分以下のガス流通量で行
う請求項１記載の固体酸触媒の製造方法。2. The method for producing a solid acid catalyst according to claim 1, wherein the calcination is performed at a gas flow rate of 4 L / min or less in terms of volume at normal temperature (27 ° C.) per 100 g / h of catalyst production.
分から選ばれる少なくとも１種の金属成分が担持されて
いる請求項１または２記載の固体酸触媒の製造方法。3. The method for producing a solid acid catalyst according to claim 1, wherein at least one metal component selected from Group VIIIB metal components of the periodic table is supported on the solid acid catalyst.
項１ないし３記載の固体酸触媒の製造方法。4. The method for producing a solid acid catalyst according to claim 1, wherein the solid acid catalyst contains chlorine.
ジルコニアからなる部分と、アルミナ及び／または含水
アルミナからなる部分で構成され成形された担体と、こ
の担体に担持された硫酸分を含み、触媒中に占めるジル
コニアの割合がジルコニウム元素重量として２５〜６０
重量％、アルミナの割合がアルミニウム元素重量として
５〜３０重量％、硫酸分の割合が硫黄元素重量として１
〜６重量％、塩素分の割合が塩素元素重量として０．０
２〜１０重量％である酸触媒反応に用いられる固体酸触
媒。5. A catalyst comprising a part formed of zirconia and / or hydrous zirconia having a tetragonal structure, a part formed of alumina and / or hydrous alumina, and a sulfuric acid supported on the support, comprising a catalyst. The ratio of zirconia in the zirconia is 25 to 60 as the weight of zirconium element.
% By weight, the ratio of alumina is 5 to 30% by weight in terms of aluminum element weight, and the proportion of sulfuric acid is 1 in terms of sulfur element weight.
-6% by weight, and the chlorine content is 0.0
A solid acid catalyst used in an acid catalyzed reaction of 2 to 10% by weight.
コニウム元素重量として３０〜５５重量％、アルミナの
割合がアルミニウム元素重量として１０〜２５重量％、
硫酸分の割合が硫黄元素重量として２〜５重量％であ
り、比表面積が１００〜３００ｍ２／ｇである請求項５
記載の固体酸触媒。6. A catalyst wherein the proportion of zirconia in the catalyst is 30 to 55% by weight as zirconium element weight, the proportion of alumina is 10 to 25% by weight as aluminum element weight,
The proportion of sulfuric acid is 2 to 5% by weight as elemental sulfur and the specific surface area is 100 to 300 m 2 / g.
The solid acid catalyst as described above.
ら選ばれる１種以上の金属を０．０１〜１０重量％含む
請求項５または６記載の固体酸触媒。7. The solid acid catalyst according to claim 5, wherein the catalyst contains 0.01 to 10% by weight of one or more metals selected from Group VIIIB metal components of the periodic table.
素成分を７０重量％以上含む炭化水素の異性化反応であ
る請求項５ないし７記載の固体酸触媒。8. The solid acid catalyst according to claim 5, wherein the acid-catalyzed reaction is an isomerization reaction of a hydrocarbon containing 70% by weight or more of a saturated hydrocarbon component having 4 to 6 carbon atoms.
し８記載の固体酸触媒に接触させる炭化水素の異性化方
法において、原料炭化水素が、炭素数４〜６の飽和炭化
水素成分を７０重量％以上含み、原料炭化水素と原料水
素中の水分含有量が５ｐｐｍ以下であり、原料炭化水素
と原料水素が塩素元素重量として０．１ｐｐｍ〜１００
００ｐｐｍの塩素化合物を含有する炭化水素の異性化方
法。9. The method for isomerizing hydrocarbons, wherein the raw material hydrogen and the raw material hydrocarbon are brought into contact with the solid acid catalyst according to any one of claims 5 to 8, wherein the raw material hydrocarbon comprises a saturated hydrocarbon component having 4 to 6 carbon atoms. % By weight, and the content of water in the raw hydrocarbon and the raw hydrogen is 5 ppm or less.
A method for isomerizing a hydrocarbon containing 00 ppm of a chlorine compound.
１以上１０以下である請求項９記載の炭化水素の異性化
方法。10. A hydrogen / feed hydrocarbon molar ratio of 0.0
The hydrocarbon isomerization method according to claim 9, wherein the number is 1 or more and 10 or less.
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|---|---|---|---|
| JP24989799A JP2001070795A (en) | 1999-09-03 | 1999-09-03 | Solid acid catalyst, preparation thereof and method for isomerizing hydrocarbon using the catalyst |
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|---|---|---|---|
| JP24989799A JP2001070795A (en) | 1999-09-03 | 1999-09-03 | Solid acid catalyst, preparation thereof and method for isomerizing hydrocarbon using the catalyst |
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|---|---|
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ID=17199850
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|---|---|---|---|
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| Country | Link |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002088114A (en) * | 2000-09-13 | 2002-03-27 | Japan Polychem Corp | Catalyst components for olefin polymerization, catalyst for olefin polymerization and method of producing polyolefin using the same |
| JP2009525179A (en) * | 2006-02-03 | 2009-07-09 | サン−ゴバン セラミックス アンド プラスティクス，インコーポレイティド | Articles containing tetragonal zirconia and methods for making the same |
| JP2011083701A (en) * | 2009-10-15 | 2011-04-28 | Jx Nippon Oil & Energy Corp | Hydrogenation catalyst exhibiting excellent anti-poison property to impurity in hydrogen source and method for producing the catalyst |
| JP2013169480A (en) * | 2012-02-17 | 2013-09-02 | Osaka Gas Co Ltd | Methane oxidation catalyst and method of manufacturing the same |
| CN109021648A (en) * | 2018-07-18 | 2018-12-18 | 赵阳 | A kind of preparation method of the dedicated super-hydrophobic antisepsis erosion chlorinated paraffin of coating |
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1999
- 1999-09-03 JP JP24989799A patent/JP2001070795A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002088114A (en) * | 2000-09-13 | 2002-03-27 | Japan Polychem Corp | Catalyst components for olefin polymerization, catalyst for olefin polymerization and method of producing polyolefin using the same |
| JP2009525179A (en) * | 2006-02-03 | 2009-07-09 | サン−ゴバン セラミックス アンド プラスティクス，インコーポレイティド | Articles containing tetragonal zirconia and methods for making the same |
| JP2011083701A (en) * | 2009-10-15 | 2011-04-28 | Jx Nippon Oil & Energy Corp | Hydrogenation catalyst exhibiting excellent anti-poison property to impurity in hydrogen source and method for producing the catalyst |
| JP2013169480A (en) * | 2012-02-17 | 2013-09-02 | Osaka Gas Co Ltd | Methane oxidation catalyst and method of manufacturing the same |
| CN109021648A (en) * | 2018-07-18 | 2018-12-18 | 赵阳 | A kind of preparation method of the dedicated super-hydrophobic antisepsis erosion chlorinated paraffin of coating |
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