JP6499753B2 - 押出Cu−Al−Mn水素化触媒 - Google Patents
押出Cu−Al−Mn水素化触媒 Download PDFInfo
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- JP6499753B2 JP6499753B2 JP2017513213A JP2017513213A JP6499753B2 JP 6499753 B2 JP6499753 B2 JP 6499753B2 JP 2017513213 A JP2017513213 A JP 2017513213A JP 2017513213 A JP2017513213 A JP 2017513213A JP 6499753 B2 JP6499753 B2 JP 6499753B2
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- 239000003054 catalyst Substances 0.000 title claims description 158
- 238000005984 hydrogenation reaction Methods 0.000 title claims description 34
- 229910018131 Al-Mn Inorganic materials 0.000 title description 4
- 229910018461 Al—Mn Inorganic materials 0.000 title description 4
- 239000000203 mixture Substances 0.000 claims description 82
- 239000002244 precipitate Substances 0.000 claims description 64
- 239000011148 porous material Substances 0.000 claims description 46
- 239000010949 copper Substances 0.000 claims description 43
- 239000007864 aqueous solution Substances 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 34
- 239000011230 binding agent Substances 0.000 claims description 31
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- 229910052782 aluminium Inorganic materials 0.000 claims description 28
- 229910052751 metal Inorganic materials 0.000 claims description 28
- 239000002184 metal Substances 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 27
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 22
- -1 rare earths Substances 0.000 claims description 22
- 239000011572 manganese Substances 0.000 claims description 17
- 229910001593 boehmite Inorganic materials 0.000 claims description 16
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 16
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 15
- 229910052802 copper Inorganic materials 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 13
- 229910052753 mercury Inorganic materials 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 11
- 239000000314 lubricant Substances 0.000 claims description 11
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 238000009826 distribution Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 238000001125 extrusion Methods 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000005749 Copper compound Substances 0.000 claims description 6
- 150000001880 copper compounds Chemical class 0.000 claims description 6
- 150000002697 manganese compounds Chemical class 0.000 claims description 6
- 238000001935 peptisation Methods 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 150000001728 carbonyl compounds Chemical class 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 150000003623 transition metal compounds Chemical class 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 238000007561 laser diffraction method Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 28
- 150000002736 metal compounds Chemical class 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 238000004519 manufacturing process Methods 0.000 description 19
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 18
- QUQFTIVBFKLPCL-UHFFFAOYSA-L copper;2-amino-3-[(2-amino-2-carboxylatoethyl)disulfanyl]propanoate Chemical compound [Cu+2].[O-]C(=O)C(N)CSSCC(N)C([O-])=O QUQFTIVBFKLPCL-UHFFFAOYSA-L 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 15
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 12
- 150000002148 esters Chemical class 0.000 description 12
- 238000005259 measurement Methods 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 235000014113 dietary fatty acids Nutrition 0.000 description 10
- 239000000194 fatty acid Substances 0.000 description 10
- 229930195729 fatty acid Natural products 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 239000011701 zinc Substances 0.000 description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- ZZBAGJPKGRJIJH-UHFFFAOYSA-N 7h-purine-2-carbaldehyde Chemical compound O=CC1=NC=C2NC=NC2=N1 ZZBAGJPKGRJIJH-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- 150000004665 fatty acids Chemical class 0.000 description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- UQDUPQYQJKYHQI-UHFFFAOYSA-N methyl laurate Chemical compound CCCCCCCCCCCC(=O)OC UQDUPQYQJKYHQI-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 150000001299 aldehydes Chemical class 0.000 description 5
- 150000001735 carboxylic acids Chemical class 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 description 5
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 150000002576 ketones Chemical class 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 150000007524 organic acids Chemical class 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 230000006641 stabilisation Effects 0.000 description 5
- 238000011105 stabilization Methods 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 4
- 239000005751 Copper oxide Substances 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 4
- 150000008041 alkali metal carbonates Chemical class 0.000 description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 4
- HPDFFVBPXCTEDN-UHFFFAOYSA-N copper manganese Chemical compound [Mn].[Cu] HPDFFVBPXCTEDN-UHFFFAOYSA-N 0.000 description 4
- 229910000431 copper oxide Inorganic materials 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 150000002191 fatty alcohols Chemical class 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 229910052596 spinel Inorganic materials 0.000 description 4
- 239000011029 spinel Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 238000002459 porosimetry Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- PLLBRTOLHQQAQQ-UHFFFAOYSA-N 8-methylnonan-1-ol Chemical compound CC(C)CCCCCCCO PLLBRTOLHQQAQQ-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229910018565 CuAl Inorganic materials 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001339 alkali metal compounds Chemical class 0.000 description 2
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 2
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical compound [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000005576 amination reaction Methods 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229940116318 copper carbonate Drugs 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(i) oxide Chemical compound [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000011656 manganese carbonate Substances 0.000 description 2
- 235000006748 manganese carbonate Nutrition 0.000 description 2
- 229940093474 manganese carbonate Drugs 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 235000011181 potassium carbonates Nutrition 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000002909 rare earth metal compounds Chemical class 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 238000007126 N-alkylation reaction Methods 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical group O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- FNXOLMOVPQLUKW-UHFFFAOYSA-N [O-2].[Al+3].[Cr](=O)([O-])[O-].[Cu+2] Chemical compound [O-2].[Al+3].[Cr](=O)([O-])[O-].[Cu+2] FNXOLMOVPQLUKW-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- PRKQVKDSMLBJBJ-UHFFFAOYSA-N ammonium carbonate Chemical class N.N.OC(O)=O PRKQVKDSMLBJBJ-UHFFFAOYSA-N 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 235000011162 ammonium carbonates Nutrition 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 150000001785 cerium compounds Chemical class 0.000 description 1
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 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
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- WMWXXXSCZVGQAR-UHFFFAOYSA-N dialuminum;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3] WMWXXXSCZVGQAR-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- FCBBRODPXVPZAH-UHFFFAOYSA-N nonan-5-ol Chemical compound CCCCC(O)CCCC FCBBRODPXVPZAH-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 239000012254 powdered material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 description 1
- 229910000026 rubidium carbonate Inorganic materials 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 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
- 239000002002 slurry Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
Classifications
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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
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- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Description
本発明は、押出形態の触媒成形体の全重量を基準として、20〜43重量%の範囲、好ましくは25〜42重量%の範囲の量のCu、20〜40重量%の範囲、好ましくは25〜34重量%の範囲のAlおよび1〜10重量%の範囲の、好ましくは2〜8重量%の範囲の、特に好ましくは3〜6重量%の範囲の量のMnを含有し、
上記触媒成形体が、DIN66133に従う水銀圧入法により測定される、250〜700mm3/gの範囲の、好ましくは400〜650mm3/gの範囲の、特に好ましくは450〜600mm3/gの範囲の細孔容積を有する、
押出形態の触媒成形体に関する。
(a)(i)銅−、アルミニウム−、マンガン−および任意選択的に遷移金属化合物の少なくとも1種の水溶液および(ii)少なくとも1種の炭酸塩含有水溶液を合わせることにより沈澱物を形成させること、沈澱物を分離し、任意選択的に、分離した沈澱物を洗浄すること、ならびに分離した沈澱物を乾燥して、乾燥された沈澱物を得ること、
(b)ステップ(a)で得られた乾燥された沈澱物を、ベーマイトおよび擬ベーマイトからなる群から選択されるアルミニウム含有バインダーと混合すること、
(c)ステップ(b)で得られた混合物の押出により押出物を得ること、および
(d)ステップ(c)で得られた押出物を300℃〜750℃の範囲、好ましくは600℃〜750℃の範囲の温度、特に約750℃で焼成して、押出された成形体を得ること、
を含む、押出された形態にあるCu−、Al−およびMn含有触媒成形体(Cu−Al−Mn触媒成形体)の製造方法に関する。
本発明の押出された触媒成形体は、押出形態の触媒成形体の全重量を基準として、20〜43重量%の範囲、好ましくは25〜42重量%の範囲、さらに好ましくは30〜35重量%の範囲の量の銅を含有する。ここで、銅は基本的に、酸化銅(CuO)、銅−アルミニウムスピネル(例えばCuAl2O4)、銅−マンガンスピネル(例えばCuMn2O4またはCu1.5Mn1.5O4)、元素の銅(Cu)および/またはそれらの混合物の形態で存在する。
本願に記載される物理的パラメーターは、特段の記載がない限り、以下のように測定する:
伝導率は、DIN 38404第8部に従って測定する。
以下の非限定的な例に基づいて、本発明をより詳細に説明する。これらの例は、 本発明の具体的な実施形態を記載するが、それらは本発明の具体的な説明のためだけに用いられ、いかなる方法でも本発明を限定するものとして解釈されるべきではない。当業者に理解されるように、多数の変形を、添付の特許請求の範囲により特定されるような本発明の保護範囲から逸脱することなく、実施することが可能である。
非焼成材料の製造を、炭酸ナトリウムで金属硝酸塩を沈澱させてそれらの炭酸塩とし、引き続き沈殿物をろ過し、洗浄し、噴霧乾燥することによって行う。
焼成材料を、非焼成材料(参照例1に記載されるように製造した)を空気循環炉において730℃で3時間焼成することにより、製造する。1000℃での残留強熱減量(Restgluehverlust)(LOI)は約5%である。
触媒1の製造のために、17gのPural SCF 55を34gの2.5%酢酸で解膠し、続いて320gの非焼成材料(参照例1に記載されるように製造した)および165gの脱イオン水と、ダブル−Z−ニーダー中で混合する。該混合物に、10gのステアタイト油(Steatitoel)を潤滑剤として混加する。引き続き、混合物を、3.2mmの直径および3〜10mmの範囲の長さを有するストランドに押し出す。押出物を120℃で16時間乾燥し、続いて750℃で3時間焼成する。
触媒2の製造のために、125gのPural SCF 55を250gの2.5%酢酸で解膠し、続いて720gの非焼成材料(参考例1に記載されるように製造した)および370gの脱イオン水とダブル−Z−ニーダー中で混合する。混合物に20gのステアタイト油を潤滑剤として混加する。引き続き、混合物を、3.2mmの直径および3〜10mmの範囲の長さを有するストランドに押し出す。押出物を120℃で16時間乾燥し、続いて750℃で3時間焼成する。
触媒3の製造のために、600gのPural SCF 55を1200gの2.5%酢酸で解膠し、続いて1950gの非焼成材料(参照例1に記載されるように製造した)および1000gの脱イオン水と、ダブル−Z−ニーダー中で混合する。該混合物に、80gのステアタイト油を潤滑剤として混加する。引き続き、混合物を、3.2mmの直径および3〜10mmの範囲の長さを有するストランドに押し出す。押出物を120℃で16時間乾燥し、続いて750℃で3時間焼成する。
触媒4の製造のために、173gのPural SCF 55を346gの2.5%酢酸で解膠し、続いて320gの非焼成材料(参照例1に記載されるように製造した)および165gの脱イオン水と、ダブル−Z−ニーダー中で混合する。該混合物に、15gのステアタイト油を潤滑剤として混加する。引き続き、混合物を、3.2mmの直径および3〜10mmの範囲の長さを有するストランドに押し出す。押出物を120℃で16時間乾燥し、続いて750℃で3時間焼成する。
触媒5の製造のために、262gのPural SCF 55を520gの2.5%酢酸で解膠し、続いて320gの非焼成材料(参照例1に記載されるように製造した)および165gの脱イオン水と、ダブル−Z−ニーダー中で混合する。該混合物に、17.5gのステアタイト油を潤滑剤として混加する。引き続き、混合物を、3.2mmの直径および3〜10mmの範囲の長さを有するストランドに押し出す。押出物を120℃で16時間乾燥し、続いて750℃で3時間焼成する。
触媒成形体6の製造を、溝付きの押出物用のダイを押出のために使用する(直径約3.2mm)以外は、触媒成形体3(例3に記載されるように)と同様に行う。同じく、乾燥および焼成を例3に記載したのと同様に行う。完成した押出物は、約0.7mmの深さおよび約1.2mmの幅を有する長さ方向の3つの溝を有する。
触媒7の製造のために、600gのPural SCF 55を1950gの非焼成材料(参照例1に記載されるように製造した)とダブル−Z−ニーダー中で混合する。その後、まず1200gの2.5%酢酸を、直後に1000gの脱イオン水を添加し、得られた混合物を60分間混練する。混練後、混合物に80gのステアタイト油を潤滑剤として混加し、続いて混合物の押出を行う(直径3.2mm)。押出物を120℃で16時間乾燥し、続いて750℃で3時間焼成する。
参照触媒Aの製造のために、100gの焼成材料(参照例2に記載されるように製造した)および3gのグラファイトを混合し、約3mmの直径および約3mmの高さを有する成形体にタブレット化する。
参照触媒Bの製造のために、150gのVolclay SPVを450gの非焼成材料(参照例1に記載されるように製造した)および50gの脱イオン水と混合する。続いて、混合物の押出を行う(直径3.2mm)。押出物を120℃で16時間乾燥し、続いて750℃で3時間焼成する。
参照触媒Cの製造のために、375gのLudox AS40を450gの非焼成材料(参照例1に記載されるように製造した)、10gのZusoplast C−92 (プレス助剤および潤滑助剤)および250gの脱イオン水と混合する。続いて、混合物の押出を行う(直径3.2mm)。押出物を120℃で16時間乾燥し、続いて750℃で3時間焼成する。
細孔容積は、DIN66133に従う水銀圧入法により測定される。表1は、本発明の触媒および参照触媒の細孔容積を示す:
触媒の化学的分析のために、これらを最初に二硫酸カリウム融解(Kaliumdisulfat−Schmelzaufschluss)で溶液にして、引き続きICP(誘導結合プラズマ)法により化学組成を決定する。表2に、種々の触媒の化学組成を示す。値は、強熱減量なしで示す。強熱減量はDIN ISO 803/806に従って測定した。
粒径の測定は、DIN ISO 13320に従ってレーザー回折法により、Malvern製Mastersizer 2000を用いて製造業者の指示に従って行い、ここで、サンプルを助剤の添加なしで脱イオン水中での測定の前に均一化し、5分間超音波で処理する。上記のD値は、サンプル体積を基準とする。
触媒のCu−金属表面積は、N2O分解(N2Oパルス吸着)の原理によって測定される:
2Cu+N2O→Cu2O+N2
そのために、サンプルを還元炉TRACE GC ULTRA(Brechbuehler社)において、240℃で16時間、水素で還元する(フォーミングガスHe中5%H2)。続いて、サンプルをThermo Electron社のTPDRO 1100シリーズ装置に移し、Heでフラッシュし、N2Oパルス吸着を開始する。Cu−金属表面積が、熱伝導率検出器によって測定されるHe中のN2の生成量から得られる。
嵩密度はDIN ISO 903に従って測定される。表4に、種々の触媒の嵩密度を示す。
側方圧砕強度は、DIN EN 1094−5に従って測定される。側方圧砕強度は、100回の測定の算術平均から得られる。押出物に関する側方圧砕強度の表示は、測定される押出物の長さを基準として行われ(N/押出物の長さmm)、ここで、押出物の長さは、押出形態にある約100個の触媒成形体の測定された長さの算術平均である。タブレットに関して、一定の寸法に基づいて、側方圧砕強度の具体的な値を示すことができる。
触媒の活性は 脂肪酸メチルエステル(FAME)の水素化に関して試験される。そのために、電気的に加熱した25mlの反応容積を有する固定床反応器を使用する。試験には、ラウリン酸メチルエステル(C12−メチルエステル)を使用する。エステル転化率および脂肪アルコールに関する選択性の、または副生成物の形成の評価のために、生成した反応生成物をガスクロマトグラフィーを用いて分析する。転化率は、使用したエステルの物質量および生成物中に残ったエステルの物質量から算出される。
GC:FIDを備えたAgilent 7890A
カラム:PhenomenexのZB−1,60mx0.25mm
ソフトウェア:EZ Chrom Elite Version 3.3.2 SP1
反応温度:160℃、180℃、240℃
圧力:280bar
GHSV(H2):20000h−1
LHSV(エステル):1.4h−1
なお、本願は、特許請求の範囲に記載の発明に関するものであるが、他の態様として以下も包含し得る。
1.押出形態の触媒成形体であって、押出形態の触媒成形体の全重量を基準として、20〜43重量%の範囲、好ましくは25〜42重量%の範囲の量のCu、20〜40重量%の範囲、好ましくは25〜34重量%の範囲のAlおよび1〜10重量%の範囲の、好ましくは2〜8重量%の範囲の、特に好ましくは3〜6重量%の範囲の量のMnを含有し、
DIN66133に従う水銀圧入法により測定される、250〜700mm 3 /gの範囲の、好ましくは400〜650mm 3 /gの範囲の、特に好ましくは450〜600mm 3 /gの範囲の細孔容積を有する、押出形態の触媒成形体。
2.モノモーダルな細孔半径分布を有し、細孔容積の50%以上、好ましくは70%以上、特に好ましくは80%以上が7〜40nmの範囲の細孔半径を有する孔によって形成され、上記細孔半径分布および細孔容積がDIN66133に従って水銀圧入法によって測定される、上記1に記載の触媒成形体。
3.DIN ISO903によって測定される、300〜800g/Lの範囲、好ましくは400〜700g/Lの範囲、特に好ましくは450〜650g/Lの範囲の嵩密度を有する、上記1または2に記載の触媒成形体。
4.アルカリ金属、アルカリ土類金属、希土類、Fe、Ni、Cr、Co、ZnおよびZrからなる群から選択される少なくとも1種のさらなる金属を含有する、上記1、2または3に記載の触媒成形体。
5.成形体が押出物の長さを基準として、5〜40N/mmの範囲、好ましくは10〜30N/mmの範囲の側方圧砕強度を有し、上記側方圧砕強度がDIN EN 1094−5に従って測定される、上記1〜4のいずれか1つに記載の触媒成形体。
6.成形体が1〜6mmの範囲、好ましくは1.5〜3.5mmの範囲の直径を有する、上記1〜5のいずれか1つに記載の触媒成形体。
7.成形体が0.3mm〜0.9mmの範囲の、好ましくは約0.7mmの深さおよび1.0〜1.5mmの範囲の、好ましくは約1.2mmの幅を有する溝を長さ方向に有する、上記1〜6のいずれか1つに記載の触媒成形体。
8.還元形態において、触媒成形体に含有されるCu量を基準として、N 2 Oパルス化学吸着を用いて測定される20m 2 /g Cu 〜60m 2 /g Cu の範囲、好ましくは25m 2 /g Cu 〜50m 2 /g Cu の範囲、特に好ましくは30m 2 /g Cu 〜45m 2 /g Cu の範囲のCu−金属表面積を有する、上記1〜7のいずれか1つに記載の触媒成形体。
9.以下のステップ:
(a)(i)銅化合物、アルミニウム化合物、マンガン化合物および任意選択的に遷移金属化合物の少なくとも1種の水溶液および(ii)少なくとも1種の炭酸塩含有水溶液を合わせることにより沈澱物を形成させること、沈澱物を分離し、任意選択的に、分離した沈澱物を洗浄すること、ならびに分離した沈澱物を乾燥して、乾燥された沈澱物を得ること、
(b)ステップ(a)で得られる乾燥された沈澱物を、ベーマイトおよび擬ベーマイトからなる群から選択されるアルミニウム含有バインダーと混合すること、
(c)ステップ(b)で得られる混合物の押出により押出物を得ること、および
(d)ステップ(c)で得られる押出物を300℃〜750℃の範囲、好ましくは600℃〜750℃の範囲の温度、特に約750℃で焼成して、押出された触媒成形体を得ること、
を含む、押出された触媒成形体を製造する方法。
10.ステップ(b)が以下:
(b1)ステップ(a)で得られる乾燥された沈殿物を、250℃〜900℃の範囲の温度、好ましくは300℃〜750℃の範囲の温度、特に好ましくは600℃〜750℃の範囲で焼成して、焼成された沈殿物を得ること、
(b2)ステップ(a)で得られる乾燥された沈澱物を、ステップ(b1)で得られる焼成された沈殿物と、2:98〜98:2の範囲、好ましくは10:90〜90:10の範囲、より好ましくは15:85〜85:15の範囲、特に好ましくは20:80〜50:50の範囲の乾燥された沈殿物と焼成された沈殿物との重量比で混合して、混合物を得ること、および
(b3)ステップ(b2)で得られる混合物を、ベーマイトおよび擬ベーマイトからなる群から選択されるアルミニウム含有バインダーと混合すること、
を含む、上記9に記載の方法。
11.アルミニウム含有バインダーが、酸の、好ましくは有機酸の添加により解膠され、ここで、当該解膠が、好ましくは、ステップ(b)の前またはステップ(b)の間に実施される、上記9または10に記載の方法。
12.有機酸が酢酸およびクエン酸から選択される、上記11に記載の方法。
13.ステップ(b)またはステップ(b3)から得られる混合物に、押出の前に、押出される物質の全重量を基準として0.1〜5重量%の範囲の量の滑剤が添加される、上記9〜12のいずれか1つに記載の方法。
14.上記バインダーが、300〜700mm 3 /gの範囲の、好ましくは400〜600mm 3 /gの範囲の、特に好ましくは450〜550mm 3 /gの範囲の細孔容積を有し、上記細孔容積がDIN 66133に従う水銀圧入法により測定される、上記9〜13のいずれか1つに記載の方法。
15.上記バインダーが、DIN ISO 13320に従うレーザー回折法によって測定される、10〜40μmの範囲の、好ましくは15〜35μmの範囲の、特に好ましくは20〜30μmの範囲の粒径D 50 を有する、上記9〜14のいずれか1つに記載の方法。
16.以下のステップ:
(e)ステップ(d)で得られる押出された触媒成形体を還元して、還元された触媒成形体を得ること、
を含む、上記9〜15のいずれか1つに記載の方法。
17.上記9〜16のいずれか1つに記載の方法により得ることができる触媒成形体。
18.上記1〜8または17のいずれか1つに記載の触媒成形体のカルボニル化合物の水素化のための使用。
Claims (18)
- 押出形態の触媒成形体であって、押出形態の触媒成形体の全重量を基準として、20〜43重量%の範囲の量のCu、20〜40重量%の範囲のAlおよび1〜10重量%の範囲の量のMnを含有し、
DIN66133に従う水銀圧入法により測定される、250〜700mm3/gの範囲の細孔容積を有する、押出形態の触媒成形体。 - モノモーダルな細孔半径分布を有し、細孔容積の50%以上が7〜40nmの範囲の細孔半径を有する孔によって形成され、上記細孔半径分布および細孔容積がDIN66133に従って水銀圧入法によって測定される、請求項1に記載の触媒成形体。
- DIN ISO903によって測定される、300〜800g/Lの範囲の嵩密度を有する、請求項1または2に記載の触媒成形体。
- アルカリ金属、アルカリ土類金属、希土類、Fe、Ni、Cr、Co、ZnおよびZrからなる群から選択される少なくとも1種のさらなる金属を含有する、請求項1、2または3に記載の触媒成形体。
- 成形体が押出物の長さを基準として、5〜40N/mmの範囲の側方圧砕強度を有し、上記側方圧砕強度がDIN EN 1094−5に従って測定される、請求項1〜4のいずれか1つに記載の触媒成形体。
- 成形体が1〜6mmの範囲の直径を有する、請求項1〜5のいずれか1つに記載の触媒成形体。
- 成形体が0.3mm〜0.9mmの範囲の深さおよび1.0〜1.5mmの範囲の幅を有する溝を長さ方向に有する、請求項1〜6のいずれか1つに記載の触媒成形体。
- 還元形態において、触媒成形体に含有されるCu量を基準として、N2Oパルス化学吸着を用いて測定される20m2/gCu〜60m2/gCuの範囲のCu−金属表面積を有する、請求項1〜7のいずれか1つに記載の触媒成形体。
- 以下のステップ:
(a)(i)銅化合物、アルミニウム化合物、マンガン化合物および任意選択的に遷移金属化合物の少なくとも1種の水溶液および(ii)少なくとも1種の炭酸塩含有水溶液を合わせることにより沈澱物を形成させること、沈澱物を分離し、任意選択的に、分離した沈澱物を洗浄すること、ならびに分離した沈澱物を乾燥して、乾燥された沈澱物を得ること、
(b)ステップ(a)で得られる乾燥された沈澱物を、ベーマイトおよび擬ベーマイトからなる群から選択されるアルミニウム含有バインダーと混合すること、
(c)ステップ(b)で得られる混合物の押出により押出物を得ること、および
(d)ステップ(c)で得られる押出物を300℃〜750℃の範囲の温度で焼成して、押出された触媒成形体を得ること、
を含む、DIN66133に従う水銀圧入法により測定される250〜700mm3/gの範囲の細孔容積を有する、押出された触媒成形体を製造する方法。 - ステップ(b)が以下:
(b1)ステップ(a)で得られる乾燥された沈殿物を、250℃〜900℃の範囲の温度で焼成して、焼成された沈殿物を得ること、
(b2)ステップ(a)で得られる乾燥された沈澱物を、ステップ(b1)で得られる焼成された沈殿物と、2:98〜98:2の範囲の乾燥された沈殿物と焼成された沈殿物との重量比で混合して、混合物を得ること、および
(b3)ステップ(b2)で得られる混合物を、ベーマイトおよび擬ベーマイトからなる群から選択されるアルミニウム含有バインダーと混合すること、
を含む、請求項9に記載の方法。 - アルミニウム含有バインダーが、酸の添加により解膠される、請求項9または10に記載の方法。
- 上記解膠が、ステップ(b)の前またはステップ(b)の間に実施される、請求項11に記載の方法。
- 酸が酢酸およびクエン酸から選択される、請求項11または12に記載の方法。
- ステップ(b)またはステップ(b3)から得られる混合物に、押出の前に、押出される物質の全重量を基準として0.1〜5重量%の範囲の量の滑剤が添加される、請求項9〜13のいずれか1つに記載の方法。
- 上記バインダーが、300〜700mm3/gの範囲の細孔容積を有し、上記細孔容積がDIN 66133に従う水銀圧入法により測定される、請求項9〜14のいずれか1つに記載の方法。
- 上記バインダーが、DIN ISO 13320に従うレーザー回折法によって測定される、10〜40μmの範囲の粒径D50を有する、請求項9〜15のいずれか1つに記載の方法。
- 以下のステップ:
(e)ステップ(d)で得られる押出された触媒成形体を還元して、還元された触媒成形体を得ること、
を含む、請求項9〜16のいずれか1つに記載の方法。 - 請求項1〜8のいずれか1つに記載の触媒成形体のカルボニル化合物の水素化のための使用。
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