JP6236344B2 - 芳香族炭化水素用の水素化触媒、及び環状飽和炭化水素の製造方法 - Google Patents
芳香族炭化水素用の水素化触媒、及び環状飽和炭化水素の製造方法 Download PDFInfo
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- JP6236344B2 JP6236344B2 JP2014072648A JP2014072648A JP6236344B2 JP 6236344 B2 JP6236344 B2 JP 6236344B2 JP 2014072648 A JP2014072648 A JP 2014072648A JP 2014072648 A JP2014072648 A JP 2014072648A JP 6236344 B2 JP6236344 B2 JP 6236344B2
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- Prior art keywords
- hydrogenation catalyst
- active
- nickel
- tin
- metal element
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- 238000005984 hydrogenation reaction Methods 0.000 title claims description 221
- 239000003054 catalyst Substances 0.000 title claims description 203
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 125000004122 cyclic group Chemical group 0.000 title claims description 12
- 229930195734 saturated hydrocarbon Natural products 0.000 title claims description 12
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title description 33
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 93
- 229910052751 metal Inorganic materials 0.000 claims description 72
- 239000002184 metal Substances 0.000 claims description 69
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 61
- 239000000654 additive Substances 0.000 claims description 46
- 230000000996 additive effect Effects 0.000 claims description 46
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 44
- 238000002441 X-ray diffraction Methods 0.000 claims description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 25
- 239000001257 hydrogen Substances 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- 239000000377 silicon dioxide Substances 0.000 claims description 22
- 238000001228 spectrum Methods 0.000 claims description 16
- 239000004480 active ingredient Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 239000013078 crystal Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 126
- 229910052759 nickel Inorganic materials 0.000 description 63
- 229910052718 tin Inorganic materials 0.000 description 53
- 238000006243 chemical reaction Methods 0.000 description 30
- 239000000047 product Substances 0.000 description 29
- 150000003839 salts Chemical class 0.000 description 24
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 22
- 239000007864 aqueous solution Substances 0.000 description 16
- 239000012266 salt solution Substances 0.000 description 14
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 13
- 229910045601 alloy Inorganic materials 0.000 description 13
- 239000000956 alloy Substances 0.000 description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 12
- 238000009826 distribution Methods 0.000 description 12
- 238000000731 high angular annular dark-field scanning transmission electron microscopy Methods 0.000 description 12
- 239000002243 precursor Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 11
- 239000013081 microcrystal Substances 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 239000006227 byproduct Substances 0.000 description 8
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 7
- 229910000765 intermetallic Inorganic materials 0.000 description 7
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 7
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 7
- 239000006104 solid solution Substances 0.000 description 7
- 238000005211 surface analysis Methods 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 238000000975 co-precipitation Methods 0.000 description 6
- 238000013507 mapping Methods 0.000 description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 6
- 229910052763 palladium Inorganic materials 0.000 description 6
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 6
- 239000011135 tin Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 238000010504 bond cleavage reaction Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 150000004678 hydrides Chemical class 0.000 description 5
- 230000003472 neutralizing effect Effects 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910052733 gallium Inorganic materials 0.000 description 4
- 229910052732 germanium Inorganic materials 0.000 description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000017858 demethylation Effects 0.000 description 3
- 238000010520 demethylation reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000000386 microscopy Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- -1 tin Chemical compound 0.000 description 3
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000009423 ventilation Methods 0.000 description 3
- ZMXIYERNXPIYFR-UHFFFAOYSA-N 1-ethylnaphthalene Chemical compound C1=CC=C2C(CC)=CC=CC2=C1 ZMXIYERNXPIYFR-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RJTJVVYSTUQWNI-UHFFFAOYSA-N beta-ethyl naphthalene Natural products C1=CC=CC2=CC(CC)=CC=C21 RJTJVVYSTUQWNI-UHFFFAOYSA-N 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910000373 gallium sulfate Inorganic materials 0.000 description 1
- SBDRYJMIQMDXRH-UHFFFAOYSA-N gallium;sulfuric acid Chemical compound [Ga].OS(O)(=O)=O SBDRYJMIQMDXRH-UHFFFAOYSA-N 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- B01J23/56—Platinum group metals
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/624—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with germanium
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/825—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with gallium, indium or thallium
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/835—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
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- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0205—Impregnation in several steps
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/44—Hydrogenation of the aromatic hydrocarbons
- C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
- C10G45/48—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
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Description
0.01≦M2/(M1+M2)≦0.6 (1)
図1(b)は、従来の芳香族炭化水素用の水素化触媒の表面を示す模式図である。従来の水素化触媒10は、例えば、ニッケル、パラジウム及び白金より選ばれる1種の活性金属元素8と、活性金属元素8が担持された担体3と、を備える。従来の水素化触媒10は、活性金属元素8からなる複数の活性部位7を備える。
本発明者らは、構造敏感型反応である炭素−炭素結合切断反応の進行を抑制するためには、水素化触媒の活性成分から構成される1つの活性部位において、活性金属元素を高度に分散させることが重要であると考え、本発明に係る水素化触媒に想い到った。
0.01≦M2/(M1+M2)≦0.6 (1)
本実施形態に係る環状飽和炭化水素の製造方法は、上述の水素化触媒及び水素の存在下で、芳香族炭化水素を水素化する工程を備える。
本実施形態に係る水素化触媒が、活性成分と、活性成分が担持される担体を備える場合、水素化触媒は以下の共沈法、又は逐次含浸法によって製造される。
担体としてシリカを用いた。硫酸ニッケル水溶液及び硫酸スズ水溶液を混合して、混合塩溶液を調製した。混合塩溶液におけるニッケル及びスズのモル比を、3:1に調整した。シリカを混合塩溶液に加えた。シリカを含む混合塩溶液に、中和剤として、炭酸ナトリウム水溶液を加え、混合塩溶液のpHを9に調整して、硫酸ニッケル、硫酸スズ及び担体を含む共沈物を得た。共沈物を乾燥した後、大気雰囲気下、450℃で焼成した。得られた活性成分の前駆体を水素雰囲気下、400℃で熱処理することによって、水素化触媒A−1を得た。水素化触媒A−1におけるニッケルの担持量は、水素化触媒A−1の全質量に対して、9.37質量%であった。水素化触媒A−1におけるスズの担持量は、水素化触媒A−1の全質量に対して、5.78質量%であった。また、水素化触媒A−1の活性成分の全モル量(M1+M2)に対するスズのモル量M2の割合(M2/(M1+M2))は0.23であった。
シリカに担持される活性金属元素(ニッケル)及び添加元素(スズ)のモル比が3:2となるように、混合塩溶液を調製したこと以外は、実施例1と同様にして、水素化触媒A−2を得た。水素化触媒A−2におけるニッケルの担持量は水素化触媒A−2の全質量に対して、9.32質量%であった。水素化触媒A−2におけるスズの担持量は、水素化触媒A−2の全質量に対して、11.58質量%であった。また、水素化触媒A−2のM2/(M1+M2)は0.38であった。
シリカに担持されるニッケル及びスズのモル比が3:4となるように、混合塩溶液を調製したこと以外は、実施例1と同様にして、水素化触媒A−3を得た。水素化触媒A−3におけるニッケルの担持量は、水素化触媒A−3の全質量に対して、9.61質量%であった。水素化触媒A−3におけるスズの担持量は、水素化触媒A−3の全質量に対して、24.60質量%であった。また、水素化触媒A−3のM2/(M1+M2)は0.56であった。
シリカに担持されるニッケル及びスズのモル比が6:1となるように、混合塩溶液を調製したこと以外は、実施例1と同様にして、水素化触媒A−4を得た。水素化触媒A−4におけるニッケルの担持量は、水素化触媒A−4の全質量に対して、9.54質量%であった。水素化触媒A−4におけるスズの担持量は、水素化触媒A−4の全質量に対して、3.00質量%であった。また、水素化触媒A−4のM2/(M1+M2)は0.13であった。
混合塩溶液におけるニッケル塩及びスズ塩の各濃度を実施例1の場合によりも低い値に調整し、ニッケル及びスズの担持量を調整したこと以外は、実施例1と同様にして、水素化触媒A−5を得た。水素化触媒A−5におけるニッケルの担持量は、水素化触媒A−5の全質量に対して、5.57質量%であった。水素化触媒A−5におけるスズの担持量は、水素化触媒A−5の全質量に対して、3.51質量%であった。また、水素化触媒A−5のM2/(M1+M2)は0.24であった。
担体としてシリカを用いた。まず、シリカに対して所定量のニッケルを含む硝酸ニッケル水溶液を調製した。その硝酸ニッケル水溶液をシリカに含浸させた。得られたニッケル含浸物を乾燥した後、大気雰囲気下、450℃で焼成した。得られた焼成物を水素雰囲気下、400℃で熱処理することによって、ニッケル担持物を得た。次いで、シリカに担持されるニッケル及びスズのモル比が3:1となるように調製した塩化スズ溶液を、ニッケル担持物に含浸させた。得られたスズ含浸物を乾燥した後、大気雰囲気下、450℃で焼成した。得られた活性成分の前駆体を水素雰囲気下、400℃で熱処理することによって、水素化触媒A−6を得た。
シリカに担持されるニッケル及びスズのモル比が3:2となるように、硝酸ニッケル水溶液及び塩化スズ溶液の量を調整した以外は、実施例6と同様にして、水素化触媒A−7を得た。水素化触媒A−7におけるニッケルの担持量は、水素化触媒A−7の全質量に対して、8.11質量%であった。水素化触媒A−7におけるスズの担持量は、水素化触媒A−7の全質量に対して、11.09質量%であった。また、水素化触媒A−7のM2/(M1+M2)は0.40であった。
水素化触媒B−1として、市販されているNEケムキャット製のN−5256を用いた。水素化触媒B−1は共沈法により作製されたものである。水素化触媒B−1におけるニッケルの担持量は、水素化触媒B−1の全質量に対して、57質量%であった。水素化触媒B−1におけるスズの担持量は、水素化触媒B−1の全質量に対して、0質量%であった。
担体としてシリカを用いた。シリカに対して所定量のニッケルを含む硝酸ニッケル水溶液を調製した。その硝酸ニッケル水溶液をシリカに含浸させた。得られたニッケル含浸物を乾燥した後、大気雰囲気下、450℃で焼成した。得られた活性成分の前駆体を、水素雰囲気下、400℃で熱処理することによって、水素化触媒B−2を得た。水素化触媒B−2におけるニッケルの担持量は、水素化触媒B−2の全質量に対して、9.74質量%であった。水素化触媒B−2におけるスズの担持量は、水素化触媒B−2の全質量に対して、0質量%であった。
担体としてシリカを用いた。シリカに対して所定量のニッケルを含む硫酸ニッケル水溶液を調製し、シリカを硫酸ニッケル水溶液に加えた。シリカを含む硫酸ニッケル水溶液に、中和剤として、炭酸ナトリウム水溶液を加え、混合塩溶液のpHを9に調整して、硫酸ニッケル及び担体を含む沈殿物を得た。沈殿物を乾燥した後、大気雰囲気下、450℃で焼成した。得られた活性成分の前駆体を、水素雰囲気下、400℃で熱処理することによって、水素化触媒B−3を得た。水素化触媒B−3におけるニッケルの担持量は、水素化触媒B−3の全質量に対して、10質量%であった。水素化触媒B−3におけるスズの担持量は、水素化触媒B−3の全質量に対して、0質量%であった。
水素化触媒A−1〜A−7及び水素化触媒B−3其々のXRDスペクトルを、以下の条件で測定した。
装置:RINT 2500(株式会社リガク製)。
X線源:CuKα(モノクロメータ使用)
管電圧:50kV
管電流:200mA
発散スリット:1/2°
散乱スリット:1/2°
受光スリット:0.15mm
回折角2θ:5〜90°
水素化触媒A−1及びA−2について、下記の走査透過型電子顕微鏡による分析を行った。各水素化触の表面の3箇所を分析した。水素化触媒A−1の分析結果を図4〜6に示す。水素化触媒A−2の分析結果を図7〜9に示す。
以下の方法で、トルエンの水素化を行った。
トルエンの転化率(%)={1−(m1/m0)}×100
m1は、生成油中のトルエンのモル量であり、GC−FIDによる分析に基づく値である。m0は、反応器へ供給したトルエンのモル量である。
Claims (4)
- 活性金属元素と、添加元素と、を含む活性成分を備え、
前記活性金属元素がニッケルであり、かつ前記添加元素がスズであり、
前記活性金属元素の単体mの結晶構造に由来する回折X線の回折角が、dmであるとき、
前記活性成分のX線回折スペクトルが、前記回折角dmとは異なる回折角daにおいて極大値を有する、
トルエン用の水素化触媒。 - 前記活性成分に含まれる前記活性金属元素のモル数をM1、前記活性成分に含まれる前記添加元素のモル数をM2としたとき、M1及びM2が下記式(1)を満たす、請求項1に記載の水素化触媒。
0.01≦M2/(M1+M2)≦0.6 (1) - 前記活性成分が担持されたシリカをさらに備える、請求項1又は2に記載の水素化触媒。
- 請求項1〜3のいずれか一項に記載の水素化触媒及び水素の存在下で、トルエンを水素化する工程を備える、環状飽和炭化水素の製造方法。
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US14/669,149 US20150274612A1 (en) | 2014-03-31 | 2015-03-26 | Hydrogenation catalyst for aromatic hydrocarbon, and method for producing cyclic saturated hydrocarbon |
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US3399132A (en) * | 1966-07-28 | 1968-08-27 | Chevron Res | Hydrocaracking of hydrocarbons with a catalyst composite comprising nickel and tin associated with a porous acidic inorganic oxide carrier |
US3480531A (en) * | 1968-07-12 | 1969-11-25 | Chevron Res | Hydrogenation of hydrocarbons with mixed tin and nickel catalyst |
US3535228A (en) * | 1968-09-18 | 1970-10-20 | Chevron Res | Hydrotreating catalyst and process |
US3632500A (en) * | 1969-07-18 | 1972-01-04 | Chevron Res | Hydrocracking catalyst comprising a layered clay-type aluminosilicate component a group viii component and iron and process using said catalyst |
US3632502A (en) * | 1969-08-06 | 1972-01-04 | Chevron Res | Hydrocracking catalyst comprising a layered clay-type crystalline aluminosilicate component a group viii component and a rare earth component and process using said catalyst |
US3790501A (en) * | 1971-05-06 | 1974-02-05 | Phillips Petroleum Co | Oxidative dehydrogenation catalyst |
US4251394A (en) * | 1978-08-25 | 1981-02-17 | Exxon Research & Engineering Co. | Coprecipitated copper-nickel-silica catalysts, preparation and use thereof |
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US9233899B2 (en) * | 2011-12-22 | 2016-01-12 | Celanese International Corporation | Hydrogenation catalysts having an amorphous support |
US9024086B2 (en) * | 2012-01-06 | 2015-05-05 | Celanese International Corporation | Hydrogenation catalysts with acidic sites |
US9126194B2 (en) * | 2012-02-29 | 2015-09-08 | Celanese International Corporation | Catalyst having support containing tin and process for manufacturing ethanol |
US8927786B2 (en) * | 2012-03-13 | 2015-01-06 | Celanese International Corporation | Ethanol manufacturing process over catalyst having improved radial crush strength |
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