WO2008099961A1 - アルコール製造用触媒 - Google Patents
アルコール製造用触媒 Download PDFInfo
- Publication number
- WO2008099961A1 WO2008099961A1 PCT/JP2008/052905 JP2008052905W WO2008099961A1 WO 2008099961 A1 WO2008099961 A1 WO 2008099961A1 JP 2008052905 W JP2008052905 W JP 2008052905W WO 2008099961 A1 WO2008099961 A1 WO 2008099961A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- alcohol
- reduction
- producing
- oxide
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 234
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 65
- 239000002184 metal Substances 0.000 claims abstract description 86
- 229910052751 metal Inorganic materials 0.000 claims abstract description 85
- 239000013078 crystal Substances 0.000 claims abstract description 45
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 36
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 36
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 32
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 29
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 29
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 27
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 25
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 23
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 21
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 54
- 239000012018 catalyst precursor Substances 0.000 claims description 43
- 239000001257 hydrogen Substances 0.000 claims description 31
- 229910052739 hydrogen Inorganic materials 0.000 claims description 31
- 229910052763 palladium Inorganic materials 0.000 claims description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 22
- 229910052697 platinum Inorganic materials 0.000 claims description 20
- -1 AK Sc Inorganic materials 0.000 claims description 17
- 239000012298 atmosphere Substances 0.000 claims description 11
- 239000002243 precursor Substances 0.000 claims description 2
- 230000000087 stabilizing effect Effects 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 96
- 238000006722 reduction reaction Methods 0.000 description 75
- 238000006243 chemical reaction Methods 0.000 description 44
- 239000000203 mixture Substances 0.000 description 35
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 33
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 31
- 230000004913 activation Effects 0.000 description 28
- 238000002360 preparation method Methods 0.000 description 28
- 239000007864 aqueous solution Substances 0.000 description 27
- 235000014113 dietary fatty acids Nutrition 0.000 description 26
- 239000000194 fatty acid Substances 0.000 description 26
- 229930195729 fatty acid Natural products 0.000 description 26
- 150000004665 fatty acids Chemical class 0.000 description 26
- 230000006641 stabilisation Effects 0.000 description 23
- 238000011105 stabilization Methods 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 230000003647 oxidation Effects 0.000 description 20
- 238000007254 oxidation reaction Methods 0.000 description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 18
- 239000010941 cobalt Substances 0.000 description 16
- 229910017052 cobalt Inorganic materials 0.000 description 16
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- 230000003197 catalytic effect Effects 0.000 description 15
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 15
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 150000003839 salts Chemical class 0.000 description 14
- 238000002156 mixing Methods 0.000 description 13
- 239000002253 acid Substances 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 238000001354 calcination Methods 0.000 description 10
- 238000010531 catalytic reduction reaction Methods 0.000 description 10
- 238000000975 co-precipitation Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 150000002431 hydrogen Chemical class 0.000 description 9
- 150000004679 hydroxides Chemical class 0.000 description 9
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 8
- 238000010304 firing Methods 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 7
- 229910020641 Co Zr Inorganic materials 0.000 description 7
- 229910020520 Co—Zr Inorganic materials 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000001099 ammonium carbonate Substances 0.000 description 7
- 235000012501 ammonium carbonate Nutrition 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000004580 weight loss Effects 0.000 description 6
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 4
- 239000005909 Kieselgur Substances 0.000 description 4
- 239000005639 Lauric acid Substances 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 239000013585 weight reducing agent Substances 0.000 description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 3
- 239000003426 co-catalyst Substances 0.000 description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 150000004685 tetrahydrates Chemical class 0.000 description 3
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- DJKGDNKYTKCJKD-BPOCMEKLSA-N (1s,4r,5s,6r)-1,2,3,4,7,7-hexachlorobicyclo[2.2.1]hept-2-ene-5,6-dicarboxylic acid Chemical compound ClC1=C(Cl)[C@]2(Cl)[C@H](C(=O)O)[C@H](C(O)=O)[C@@]1(Cl)C2(Cl)Cl DJKGDNKYTKCJKD-BPOCMEKLSA-N 0.000 description 1
- 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 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- YIWGJFPJRAEKMK-UHFFFAOYSA-N 1-(2H-benzotriazol-5-yl)-3-methyl-8-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carbonyl]-1,3,8-triazaspiro[4.5]decane-2,4-dione Chemical compound CN1C(=O)N(c2ccc3n[nH]nc3c2)C2(CCN(CC2)C(=O)c2cnc(NCc3cccc(OC(F)(F)F)c3)nc2)C1=O YIWGJFPJRAEKMK-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910020598 Co Fe Inorganic materials 0.000 description 1
- 229910020639 Co-Al Inorganic materials 0.000 description 1
- 229910002519 Co-Fe Inorganic materials 0.000 description 1
- 229910020675 Co—Al Inorganic materials 0.000 description 1
- 229910020514 Co—Y Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- REROKLPNVNAPBD-UHFFFAOYSA-N azane;tetrahydrate Chemical compound N.O.O.O.O REROKLPNVNAPBD-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- ZPNZVFLUFBRUJR-UHFFFAOYSA-N benzoic acid;16-methylheptadecanoic acid Chemical compound OC(=O)C1=CC=CC=C1.CC(C)CCCCCCCCCCCCCCC(O)=O ZPNZVFLUFBRUJR-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 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
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- VZFUCHSFHOYXIS-UHFFFAOYSA-N cycloheptane carboxylic acid Natural products OC(=O)C1CCCCCC1 VZFUCHSFHOYXIS-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- JWHOQZUREKYPBY-UHFFFAOYSA-N rubonic acid Natural products CC1(C)CCC2(CCC3(C)C(=CCC4C5(C)CCC(=O)C(C)(C)C5CC(=O)C34C)C2C1)C(=O)O JWHOQZUREKYPBY-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- B01J23/74—Iron group metals
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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
- B01J23/83—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 rare earths or actinides
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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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- 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
- B01J23/84—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
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
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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
- B01J23/89—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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- B01J23/70—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
- B01J23/8933—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/894—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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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
- B01J23/89—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
- B01J23/8933—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8993—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 also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
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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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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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
- B01J37/12—Oxidising
- B01J37/14—Oxidising with gases containing free oxygen
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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
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
Definitions
- the present invention relates to a catalyst for hydrogenating a carboxylic acid to produce an alcohol, a method for producing the catalyst, and a method for producing an alcohol for hydrogenating the carboxylic acid.
- a method for producing an alcohol a method of catalytic hydrogenation of a carboxylic acid ester is generally known and widely used industrially.
- attempts to obtain alcohol by catalytic hydrogenation of free carboxylic acid with a catalyst have been tried for a long time.
- JP-A 6 1-5 0 3 6 uses a Co catalyst containing a metal selected from Al, Zr, Mo, Y and the like and a metal selected from Cu, Pt, Pd and the like.
- a method for producing alcohol was disclosed.
- JP-A 4 8-6 2 7 0 8 discloses a method for producing an alcohol using a Co catalyst in which Fe, Zn, P and the like are combined.
- the present invention (1) is a catalyst for producing an alcohol by hydrogenating a carboxylic acid, comprising Co metal as an essential component and Zr, Y, La, Ce, Si as the first promoter component. , Al,
- This book describes a catalyst precursor containing ⁇ and one or more elements selected from Zr, Y, La, Ce, Si, AK Sc, V and Mo in a hydrogen atmosphere.
- a method for producing a catalyst for alcohol production according to the present invention (1) which comprises a reduction treatment under a temperature condition of 0 ° C., wherein the Cubic phase is 20% or more of the Co metal crystal phase.
- the present invention provides a method for producing an alcohol, wherein carboxylic acid is used as a raw material, and hydrogenation is carried out using the catalyst of the present invention (1).
- the present invention provides a use for producing an alcohol by hydrogenating the carboxylic acid of the catalyst of the present invention (1).
- JP-A 6 1-5 0 3 6 does not have a cubic phase because the processing temperature is low.
- JP-A 4 8-6 2 70 8 uses a cocatalyst different from that of the present invention, or even when the same cocatalyst is used, it has a cubic phase because the treatment temperature is low. do not do.
- the present invention provides a catalyst for use in the production of alcohol by hydrogenating carboxylic acid, which has a high catalytic activity and is industrially satisfactory, and a method for producing the alcohol.
- the present inventors have improved catalytic activity when it has Co metal and a specific promoter component, and Co metal as the main component of the catalyst has a cubic phase as a crystal phase at a specific ratio.
- W specific ratio
- the catalyst of the present invention has high catalytic activity and is industrially satisfactory.
- alcohol can be produced in high yield from carboxylic acid as a raw material. It is extremely advantageous industrially.
- the fatty acid may contain an ester group.
- a preferred embodiment (la) of the present invention (1) is a catalyst for producing an alcohol by hydrogenating a carboxylic acid, comprising Co metal as an essential component and Zr, Y, La, Ce as a first promoter component. , Si, Al, Sc, and V.
- the catalyst for alcohol production contains one or more elements selected from Si, V, and the Cu phase is 20% or more of the Co metal crystal phase.
- a catalyst precursor containing Co and one or more elements selected from Zr, Y, La, Ce, Si, Al, Sc and V is used in a hydrogen atmosphere under a hydrogen atmosphere.
- a preferred embodiment (2) of the present invention (1) is a catalyst for producing an alcohol by hydrogenating a carboxylic acid, comprising Co metal as an essential component and Zr, Y, La, Ce as a first promoter component.
- a catalyst for alcohol production having a phase of 20% or more.
- a preferred embodiment of the present invention includes Co, one or more elements selected from Zr, Y, La, Ce, Si, Al, Sc, and V, and one or more elements selected from Pt and Pd.
- a preferred embodiment (3) of the present invention (1) is a catalyst for producing an alcohol by hydrogenating a carboxylic acid, comprising Co metal and Mo as essential components, and Zr, Y, La as first promoter components. , Ce, Si, Al, Sc and V containing one or more elements selected from the group consisting of one or more elements selected from Pt and Pd as the second promoter component, and a Co metal crystal phase Among them, the catalyst for alcohol production has a Cubic phase of 20% or more.
- a preferred embodiment of the present invention includes Co, Mo, one or more elements selected from Zr, Y, La, Ce, Si, Al, Sc, and V, and one or more elements selected from Pt and Pd.
- the catalyst precursor according to the above aspect (3) comprising a step of reducing the catalyst precursor containing at a temperature of 300 to 800 ° C. in a hydrogen atmosphere.
- the alcohol production catalyst of the present invention comprises Co metal as an essential component, and the first promoter component is selected from Zr, Y, La, Ce, Si, Al, Sc, V, and Mo. And the Cubic phase of the Co metal crystal phase is 20% or more.
- the Co metal is known to have two crystal phases, the Cub ic phase and the Hexagona scale, but the present inventors have found that the presence of the Cub ic phase greatly contributes to the catalytic activity.
- the crystal phase of Co metal in the catalyst of the present invention is determined by measuring under the following conditions with an X-ray crystal diffraction (hereinafter abbreviated as XRD) apparatus. From the XRD peak pattern, the cubic phase and the hexagona are identified, and the crystal phase composition is determined from the detected peak intensity.
- XRD X-ray crystal diffraction
- the catalyst of the present invention has a Cubic phase ratio in the Co metal crystal phase calculated by the following formula (1).
- Co in the catalyst of the present invention preferably has a reduction rate of 40% or more, more preferably 70% or more, and even more preferably 80% or more.
- the Co reduction rate is a value obtained by calculation by the method shown in the examples.
- the first promoter component in the catalyst of the present invention contains one or more elements selected from Zr, Y, La, Ce, Si, Al, Sc, V, Mo, Zr, Y, La, Ce, Mo is preferred. These elements may be in any chemical state such as metals, oxides, hydroxides.
- the ratio of Co to the first promoter component is preferably 0.1 mole or more, more preferably 1 mole or more with respect to 100 moles of Co, from the viewpoint of catalytic activity. Moreover, 100 mol or less is preferable and 25 mol or less is more preferable.
- the catalyst of the present invention can further contain a second promoter component selected from Pd and Pt. By containing these components, the reduction can be promoted and the reduction temperature can be lowered. Thereby, a high specific surface area can be obtained and the activity can be further improved.
- the ratio of Co to the second promoter component is preferably 0.001 mol or more, more preferably 0.001 mol or more with respect to Co 100 mol, from the viewpoint of catalytic activity. Preferably, 0.1 mol or more is more preferable. There is no particular upper limit, but it is preferably 10 mol or less.
- the catalyst of the present invention can eat a support. Examples of the carrier include diatomaceous earth, alumina, silica, silica-alumina, magnesia, zirconia, titania, seria, activated carbon, and composite oxides thereof. By using a carrier, Co and cocatalyst components can be highly dispersed, and the activity can be improved.
- the amount of the support in the whole catalyst is preferably 80% by weight or less, and more preferably 50% by weight or less.
- the catalyst of the present invention can contain components for molding such as a binder component and a lubricant.
- the production method of the catalyst of the present invention is not particularly limited, but is generally prepared by the steps of preparation of catalyst precursor, drying / calcination, reduction, Co, Zr, Y, La, Ce, Having a step of reducing a catalyst precursor containing one or more elements selected from Si, Al, Sc, V, and Mo under a hydrogen atmosphere at a temperature condition of 300 to 800 ° C. Is preferred, and further reduction treatment More preferably, after the step of treating, there is a step of forming an oxide film on the surface of the reduced catalyst and stabilizing it.
- a coprecipitation method, a physical mixing method, and an impregnation supporting method are preferably used as a method for preparing the catalyst precursor.
- the coprecipitation method comprises a mixed aqueous solution of each metal salt comprising Co, and one or more first promoter components selected from Zr, Y, La, Ce, Si, Al, Sc, V, and Mo, This is a method of mixing with a precipitant.
- a coprecipitation method in which a precipitant is added to a mixed aqueous solution of each metal salt obtained by further adding one or more second promoter components selected from Pd and Pt may be used.
- Any metal salt may be used as long as it is water-soluble, but in general, sulfate, nitrate, ammonium complex, acetate or chloride can be used.
- alkaline aqueous solutions such as ammonia, urea, ammonium carbonate, sodium hydrogen carbonate, sodium carbonate, sodium hydroxide, potassium hydroxide, etc. are used.
- the physical mixing method is selected from Co, and one or more first promoter components selected from Zr, Y, La, Ce, Si, Al, SV, and Mo, or in addition to them, Pd and Pt This is a method in which compounds such as oxides, hydroxides, carbonates, phosphates, and nitrates of each of the one or more second promoter components are sufficiently physically mixed.
- the impregnation support method is a method of precipitating or impregnating and supporting a metal compound as a promoter component on a Co compound.
- a precipitate obtained by mixing the above precipitant with an aqueous metal salt solution that can be a promoter component other than Co examples include a method of washing, drying, and firing the material, or a method of impregnating and supporting a metal salt that can be a promoter component other than Co on a Co oxide from the state of an aqueous solution.
- the catalyst of the present invention can be supported on a known carrier.
- the carrier include carriers such as diatomaceous earth, alumina, silica, silica-alumina, magnesia, zirconium, titania, ceria, activated carbon, and composite oxides thereof.
- a coprecipitation method in which a metal salt and a precipitant are mixed in a slurry in which the carrier is suspended, or a method in which a metal that can be a catalyst component is impregnated simultaneously or sequentially on the carrier.
- the coprecipitation method or the impregnation support method is preferred.
- the catalyst precursor prepared by the method as described above is preferably dried at 30 to 120 ° C. for 1 to 24 hours, and then usually at 300 to 80,000 for 2 to 10 hours. It is preferable to fire. By this firing operation, Co becomes an oxide. Next, the catalyst precursor is reduced. The catalyst is activated by this reduction treatment.
- a gaseous reducing agent As a reducing agent, hydrogen, carbon monoxide, formaldehyde, etc. can be used.
- a gaseous reducing agent When a gaseous reducing agent is used, it may be used alone, or may be used by mixing with an inert gas such as nitrogen or with water vapor. Of these, it is desirable to use hydrogen as the reducing agent.
- a gas phase system in which hydrogen gas is brought into contact with a dry catalyst precursor may be used, or a liquid phase system in which hydrogen is allowed to flow by immersing the catalyst precursor in a liquid. It may be used.
- Such liquids include hydrocarbons such as liquid paraffin, fats Aromatic alcohols or aliphatic esters, or carboxylic acids as hydrogenation raw materials can be used.
- hydrogen When hydrogen is used as a reducing agent for reduction activation in a gas phase system, it is preferably carried out at a temperature of 300 ° C or higher, more preferably 400 ° C or higher, more preferably 420 ° C or higher, particularly under hydrogen flow. Preferably, it is 450 ° C or higher.
- the hydrogen used may be 100% or diluted with an inert gas. In order to prevent heat generation due to rapid reduction, a diluted one is preferable, a hydrogen concentration of 0.5 to 50 volZvol% is more preferable, and a 1 to 1 OvolZvol% is more preferable.
- Such high-temperature reduction can increase the degree of reduction and increase the content of the Cubic phase.
- the temperature is preferably 800 ° C or lower, more preferably 600 ° C or lower.
- the reduction should be processed until no hydrogen absorption is observed.
- the reduction-activated catalyst When the reduction-activated catalyst is left in the air as it is, it may react strongly with oxygen in the air and generate heat. Therefore, it is preferable to stabilize by forming an oxide film on the surface of the reduction activated catalyst.
- This oxidation stabilization treatment is performed at 0 to 200 ° C., preferably 20 to 100 ° C., more preferably 20 to 50 ° C. in the presence of an inert gas such as nitrogen containing 0.1 to 5% by volume of oxygen. Therefore, it is preferable in terms of handling to form an oxide film on the surface of the catalyst and stabilize it over 1 to 24 hours.
- the method for producing an alcohol of the present invention is a method in which carboxylic acid is used as a raw material and hydrogenation is performed using the catalyst of the present invention.
- the carboxylic acid used in the present invention may be either a monocarboxylic acid or a polycarboxylic acid.
- monocarboxylic acid aliphatic carboxylic acid, aromatic carboxylic acid, araliphatic carboxylic acid, and alicyclic carboxylic acid are used, and as aliphatic carboxylic acid, aliphatic dicarboxylic acid and aromatic dicarboxylic acid are used. Is done.
- strong rubonic acid examples include acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, strong bronic acid, strong prillic acid, strong purine acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, isostearic acid Benzoic acid, oxalic acid, tartaric acid, maleic acid, succinic acid, daltaric acid, adipic acid, azelaic acid, cyclohexanecarboxylic acid and the like. These carboxylic acids may be free carboxylic acids or acid anhydrides.
- the alcohol production method of the present invention can be carried out in either a suspension bed reaction system or a fixed bed reaction system.
- a suspension bed reaction method a powdered catalyst is used, and the following reaction conditions are selected.
- the reaction temperature is preferably 150 to 300 ° C.
- the reaction pressure is preferably 1 to 3 O MPa, more preferably 5 to 3 O MPa.
- the amount of the catalyst used is preferably 0.5 to 20% by weight, more preferably 1 to 10% by weight, based on the starting carboxylic acid.
- the amount of catalyst can be arbitrarily selected within a range where a practical reaction rate can be obtained, depending on the reaction temperature or reaction pressure.
- a catalyst formed for the purpose is used. wo 2 ⁇ 8 / ⁇ 96 ⁇
- the anti-J3 ⁇ 4 ⁇ ⁇ is preferably from 1 b 0 to 30, more preferably from 180 to 25 ° C.
- the reaction pressure is preferably 1 to 3 OMPa, more preferably 5 to 3 OMPa.
- the liquid hourly space velocity (LHSV) is arbitrarily determined according to the reaction conditions. However, when productivity or reactivity is taken into consideration, a range of 0.2 to 5 [1 / hr] is desirable.
- a solvent for the reaction it is desirable to carry out the reaction without a solvent in consideration of productivity.
- an alcohol, an ether such as dioxane, a hydrocarbon or the like that does not adversely influence the reaction is selected.
- Co in the catalyst has a reduction rate of preferably 40% or more, more preferably 70% or more, and 80% or more from the viewpoint of catalytic activity. More preferably.
- the reduction rate of Co was calculated as an actually measured weight reduction amount when the theoretical weight reduction amount of Co oxide (Co 3 0 4 ) in the catalyst to Co metal was defined as 100.
- the first promoter component in the catalyst contains one or more elements selected from Zr, Y, La, Ce, Si, Al, Sc, and V, and Zr, Y, La Ce is preferred. These elements may be in any chemical state such as metals, oxides, hydroxides.
- the ratio of Co to the first promoter component is preferably 0.1 mole or more, more preferably 1 mole or more with respect to 100 moles of Co, from the viewpoint of catalytic activity. Moreover, 100 mol or less is preferable and 25 mol or less is more preferable.
- the second promoter component contains one or more elements selected from Pt and Pd, and Pd is preferable. These elements may be in any chemical state such as metals, oxides, hydroxides. By containing the second promoter component, the reduction can be promoted and the reduction temperature can be lowered. Thereby, a high specific surface area can be obtained, and the activity can be further improved.
- the proportion of Co and the second promoter component is preferably 0.001 mol or more of the second promoter component with respect to 100 mol of Co from the viewpoint of catalytic activity.
- 0, 0 1 mol or more is more preferable, and 0.05 mol or more is more preferable.
- the production method of the catalyst of the present invention is not particularly limited.
- the catalyst is prepared by steps of preparation of a catalyst precursor, drying / calcination, reduction, and Co, Zr, Y, La, A catalyst precursor containing one or more elements selected from Ce, Si, AK Sc, and V, and one or more elements selected from Pt and Pd, in a hydrogen atmosphere at 300 to 80 ° C. It is preferable to have a reduction process under the temperature condition, and more preferably, after the reduction process, an oxide film is formed on the surface of the reduced catalyst and stabilized.
- the coprecipitation method comprises Co, and one or more first promoter components selected from Zr, Y, La, Ce, Si, Al, Sc, and V, Pt, and Pd.
- the physical mixing method comprises Co, and one or more first promoter components selected from Zr, Y, La, Ce, Si, Al, Sc, and V, Pt, and Pd.
- This is a method in which compounds such as oxides, hydroxides, carbonates, phosphates, nitrates, etc. of each of the one or more selected second promoter components are sufficiently physically mixed.
- the Co metal and Mo and a specific promoter component are included, and the Co metal as the main component of the catalyst has a cubic phase as a crystal phase in a specific ratio, the catalyst activity and Durability is improved. wo 2008/099961
- the catalyst contains Co metal and Mo as essential components, and contains at least one element selected from Zr, Y, La, Ce, Si, Al, Sc, and V as the first promoter component.
- the second promoter component contains one or more elements selected from Pt and Pd, and the Cubic phase is 20% or more of the Co metal crystal phase.
- the Co metal is known to have two crystal phases, a Cubic phase and a Hexagonal phase, but the present inventors have confirmed that the presence of the CuMc phase greatly contributes to the catalytic activity. I found it.
- the crystal phase of Co metal in the catalyst of the present invention is determined by measuring under the following conditions with an X-ray crystal diffraction (hereinafter abbreviated as XRD) apparatus.
- Co in the catalyst has a reduction rate of preferably 40% or more, more preferably 70% or more, and 80% or more from the viewpoint of catalytic activity. More preferably.
- the reduction rate of Co was calculated as an actually measured weight reduction amount when the theoretical weight reduction amount of Co oxide (Co 3 0 4 ) in the catalyst to Co metal was defined as 100.
- Mo in the catalyst may be in any chemical state such as a metal, oxide, or hydroxide.
- the proportion of Co and Mo is preferably 0.05 mol or more and more preferably 0.5 mol or more with respect to 100 mol of Co. Further, it is preferably 100 mol or less, more preferably 25 mol or less.
- the first promoter component in the catalyst is Zr, Y, La, Ce, Si,
- the ratio of 1 to the promoter component is The catalyst component is preferably 0.1 mol or more, more preferably 1 mol or more. Moreover, 100 mol or less is preferable and 25 mol or less is more preferable.
- the second promoter component in the catalyst contains one or more elements selected from Pt and Pd, and Pd is preferable. These elements may be in any chemical state such as metals, oxides, hydroxides.
- the ratio of Co to the second promoter component is preferably 0.001 mol or more of the second promoter component with respect to 100 mol of Co from the viewpoint of catalytic activity. , More preferably 0.1 mol or more, and even more preferably 0.05 mol or more. There is no particular upper limit, but it is preferably 10 moles or less.
- the catalyst may contain a support.
- the carrier include diatomaceous earth, alumina, silica, silica-alumina, magnesia, zirconia, titania, ceria, activated carbon, or a composite oxide thereof.
- the amount of the carrier in the whole catalyst is preferably 80% by weight or less, and more preferably 50% by weight or less.
- the method for producing the catalyst is not particularly limited, but it is prepared by the steps of precursor preparation, drying / calcination, reduction, for example, Co, Mo, Zr, Y, La,
- a catalyst precursor containing one or more elements selected from Ce, Si, Al, Sc, and V and one or more elements selected from Pt and Pd is heated under a high-temperature condition (preferably 30). 0 ⁇ 8 0
- the catalyst having the target cubic phase can be obtained by reduction treatment at 0 ° C).
- the It is more preferable to have a step of forming an oxide film on the surface of the reduced catalyst.
- the impregnation supporting method is made of Co, and one or more first promoter components selected from Zr, Y, La, Ce, Si, Al, Sc, and V, Pt, and Pd.
- an aqueous solution of an Mo compound is added and impregnated on a compound containing one or more selected second promoter components.
- the precipitate obtained by mixing the mixed aqueous solution of the metal salts of Co and the promoter component and the precipitant is washed with water, dried, or further baked and molded, etc.
- any metal salt of Co and the promoter component used may be used as long as they are water-soluble, but in general, sulfate, nitrate, ammonium complex, acetate or chloride is used.
- the precipitating agent an aqueous solution of ammonia such as ammonia, urea, ammonium carbonate, sodium hydrogen carbonate, sodium carbonate, sodium hydroxide or lithium hydroxide is used.
- the Mo compound includes paramolybdic acid, maleophosphoric acid, pyromolybdic acid, molybdenum-containing heteropoly acid, molybdophosphoric acid, etc .; sodium molybdate dihydrate (Na 2 Mo0 4 ⁇ 2 H 2 0), 7 Molybdate 6 Ammonium ⁇ Tetrahydrate [( ⁇ 4 ) 6 ⁇ 7 0 24 ⁇ 4 ⁇ 2 0] and other salts, Molybdenum trioxide ( ⁇ 0 3 ) and other oxides And halides such as molybdenum chloride (MoOCl 4 , Mo0 2 Cl 2 ).
- the coprecipitation method includes Co, Mo, and Zr, Y, La, Ce, Si, Al,
- the physical mixing method comprises Co, and one or more first promoter components selected from Zr, Y, La, Ce, Si, Al, Sc, and V, Pt, and Pd. After thoroughly mixing the compounds such as oxide, hydroxide, carbonate, phosphate, nitrate, chloride, etc. of one or more selected second co-catalyst components and drying, or after further firing Or a method of sufficiently physically mixing the Mo acids or salts thereof, oxides, hydroxides, etc. together with the carrier during molding.
- the catalyst can be supported on a known carrier.
- the carrier include carriers such as diatomaceous earth, alumina, silica, silica-alumina, magnesium, zirconia, titania, ceria, activated carbon, and composite oxides thereof.
- a coprecipitation method in which a metal salt and a precipitant are mixed in a slurry in which the carrier is suspended, or a metal that can be a catalyst component on the carrier simultaneously or The method of impregnating sequentially is mentioned.
- the impregnation support method or the coprecipitation method is preferable among the preparation methods of the catalyst precursor.
- the method of supporting the catalyst component on the support or mixing both is not particularly limited.
- it is performed by the following method.
- a precipitate obtained by a coprecipitation method in which a precipitant is added to an aqueous metal salt solution that can be a catalyst component other than the carrier component is washed with water, dried, or calcined, or on the carrier component other than the carrier component Impregnation of metal salt that can be a catalyst component from the state of aqueous solution Holding w 2 ⁇ ! ⁇ 99 ⁇ ⁇
- the method of firing, or the carrier component and the metal component oxides, hydroxides, carbonates, etc. composing the catalyst component are uniformly mixed and then fired Prepared by methods.
- FIG. 1-11 is a peak pattern showing the results of XRD analysis of the catalyst obtained in Example 1-11.
- Figure 2-1 is a peak pattern showing the XRD analysis results of the catalyst obtained in Example 2-1.
- Figure 3-1 is a peak pattern showing the XRD analysis results of the catalyst obtained in Example 3-1.
- the present invention describes the practice of the present invention in the following examples. The examples are illustrative of the invention and are not intended to limit the invention.
- the Co reduction ratios described in Examples and Comparative Examples were calculated by the following method. Gu Co reduction rate calculation method>
- the Co reduction rate is the cobalt reduction obtained from the composition analysis by considering the reduction of the weight before and after the activation and stabilization as the catalyst activation method, with the weight loss before and after the activation and stabilization, and the reduction from cobalt oxide to the metal cobalt. It calculated
- the Co element had a composition consisting only of Co metal or cobalt oxide (CoO).
- ⁇ GC analysis method Take 1 drop of the reaction product in a 10 ml sample bottle, put trimethylsilyl (TMS) agent (TMSI-HZ GL Sciences Inc.) in it, and treat for about 5 minutes (40 ° C warming). Dilute with 1.5 ml of hexane and filter with membrane filter 0. ⁇ ⁇ for GC analysis.
- TMS trimethylsilyl
- Catalyst activation Catalyst reduction / oxidation stabilization was carried out in the same manner as (2) in Example 1-11, except that the catalyst reduction temperature was 400 ° C.
- Table 1 shows the Co reduction rate of the obtained catalyst and the ratio of the Cubic phase in the Co metal crystal phase.
- Example 1-1 (3) Production of alcohol Using WO OSQ, the same method as (3) in Example 1-1 was prepared. Table 11 shows the composition of the produced alcohol and residual fatty acid after completion of the reaction. Comparative Example 1 1 1
- Example 1-11 (3) Production of alcohol An alcohol was produced in the same manner as in Example 1-11 (3) using the obtained catalyst cake (3.75 g as a dry oxide). Table 11 shows the composition of the produced alcohol and residual fatty acid after completion of the reaction.
- Co-Al oxide was obtained in the same manner as in (1).
- Catalyst activation Catalyst reduction / oxidation stabilization was carried out in the same manner as in Example 1-1 (2) except that the catalyst reduction temperature was 350 ° C.
- Table 11 shows the Co reduction rate of the obtained catalyst and the ratio of the Cubic phase in the Co metal crystal phase. This is a catalyst described in the prior art JP-A 48-62708.
- a palladium nitrate aqueous solution prepared so as to be 0.1 parts by weight as Pd was added to the obtained Co—Zr oxide, and thoroughly mixed to impregnate Pd. Furthermore, it was dried at 110 ° C. to obtain a palladium-supported Co—Zr oxide.
- composition of the product was determined by the following gas chromatography (GC) analysis. Furthermore, alcohol was repeatedly produced in the same manner using a spent catalyst. Table 3-1 shows the product alcohol and residual fatty acid composition of the products after the first and third reaction. In addition, the durability of the catalyst was evaluated by the following method. The results are also shown in Table 3-1.
- GC gas chromatography
- Table 1 shows the Co reduction rate of the obtained catalyst and the ratio of the Cubic phase in the Co metal crystal phase.
- catalyst precursor A mixture of cobalt nitrate, yttrium nitrate (n-hydrate), palladium nitrate with an atomic ratio of cobalt to yttrium to palladium of 100: 5: 0.08 and an aqueous solution of ammonium carbonate at room temperature. Stir and mix. The resulting precipitate was thoroughly washed with water and dried at 110 ° C. After drying, calcination was performed at 600 ° C. for 4 hours to obtain a Co—Y—Pd oxide. The obtained firing catalyst had an atomic ratio of CoZYZPd-lOOZ 2 / 0.08.
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US12/526,518 US8329961B2 (en) | 2007-02-16 | 2008-02-14 | Catalyst for producing alcohol |
CN2008800049913A CN101610838B (zh) | 2007-02-16 | 2008-02-14 | 醇制造用催化剂 |
ES08711694T ES2887932T3 (es) | 2007-02-16 | 2008-02-14 | Método para la producción de alcohol |
EP08711694.3A EP2116300B1 (en) | 2007-02-16 | 2008-02-14 | A method for alcohol production |
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Publication number | Publication date |
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WO2008099961A9 (ja) | 2011-06-09 |
MY149064A (en) | 2013-07-15 |
US8329961B2 (en) | 2012-12-11 |
CN101610838B (zh) | 2012-05-23 |
EP2116300B1 (en) | 2021-08-25 |
ES2887932T3 (es) | 2021-12-29 |
EP2116300A1 (en) | 2009-11-11 |
US20100029996A1 (en) | 2010-02-04 |
EP2116300A4 (en) | 2013-11-13 |
CN101610838A (zh) | 2009-12-23 |
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