JP6538692B2 - 4,4′−メチレンジアニリンの水素化方法 - Google Patents
4,4′−メチレンジアニリンの水素化方法 Download PDFInfo
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- JP6538692B2 JP6538692B2 JP2016538672A JP2016538672A JP6538692B2 JP 6538692 B2 JP6538692 B2 JP 6538692B2 JP 2016538672 A JP2016538672 A JP 2016538672A JP 2016538672 A JP2016538672 A JP 2016538672A JP 6538692 B2 JP6538692 B2 JP 6538692B2
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- 238000000034 method Methods 0.000 title claims description 93
- 230000008569 process Effects 0.000 title claims description 58
- 238000005984 hydrogenation reaction Methods 0.000 title claims description 31
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 title claims description 26
- 239000003054 catalyst Substances 0.000 claims description 74
- 239000000463 material Substances 0.000 claims description 46
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 41
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 38
- 239000011148 porous material Substances 0.000 claims description 37
- 229910052707 ruthenium Inorganic materials 0.000 claims description 36
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 32
- 239000001257 hydrogen Substances 0.000 claims description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 22
- 239000000725 suspension Substances 0.000 claims description 21
- 238000009826 distribution Methods 0.000 claims description 17
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 19
- 239000000203 mixture Substances 0.000 description 19
- 229920000642 polymer Polymers 0.000 description 19
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- 150000001875 compounds Chemical class 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 14
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical class C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 10
- 230000008021 deposition Effects 0.000 description 10
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- 238000004817 gas chromatography Methods 0.000 description 9
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 7
- 229910052753 mercury Inorganic materials 0.000 description 7
- 150000001491 aromatic compounds Chemical class 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000002638 heterogeneous catalyst Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 150000002894 organic compounds Chemical class 0.000 description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 238000010079 rubber tapping Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 239000012876 carrier material Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 150000003303 ruthenium Chemical class 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- UTNMPUFESIRPQP-UHFFFAOYSA-N 2-[(4-aminophenyl)methyl]aniline Chemical compound C1=CC(N)=CC=C1CC1=CC=CC=C1N UTNMPUFESIRPQP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229920002396 Polyurea Polymers 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- -1 heteroaromatic amines Chemical class 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000010626 work up procedure Methods 0.000 description 2
- IYWJIYWFPADQAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;ruthenium Chemical compound [Ru].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O IYWJIYWFPADQAN-LNTINUHCSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 description 1
- NWYDEWXSKCTWMJ-UHFFFAOYSA-N 2-methylcyclohexane-1,1-diamine Chemical compound CC1CCCCC1(N)N NWYDEWXSKCTWMJ-UHFFFAOYSA-N 0.000 description 1
- BHMDNHIWCXQHCM-UHFFFAOYSA-N 4-(cyclohexylmethyl)cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCCCC1 BHMDNHIWCXQHCM-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 102100025837 JNK1/MAPK8-associated membrane protein Human genes 0.000 description 1
- 101710176060 JNK1/MAPK8-associated membrane protein Proteins 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical group O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910001963 alkali metal nitrate Inorganic materials 0.000 description 1
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 1
- 229910001964 alkaline earth metal nitrate Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001934 cyclohexanes Chemical class 0.000 description 1
- OYOFUEDXAMRQBB-UHFFFAOYSA-N cyclohexylmethanediamine Chemical compound NC(N)C1CCCCC1 OYOFUEDXAMRQBB-UHFFFAOYSA-N 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- PNPIRSNMYIHTPS-UHFFFAOYSA-N nitroso nitrate Chemical compound [O-][N+](=O)ON=O PNPIRSNMYIHTPS-UHFFFAOYSA-N 0.000 description 1
- YLPJWCDYYXQCIP-UHFFFAOYSA-N nitroso nitrate;ruthenium Chemical compound [Ru].[O-][N+](=O)ON=O YLPJWCDYYXQCIP-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/70—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by reduction of unsaturated amines
- C07C209/72—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by reduction of unsaturated amines by reduction of six-membered aromatic rings
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- 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
- 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
- B01J35/31—Density
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
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Description
実施例
使用された本発明による触媒の製造
1. ZrO2上の1%Ruの固定床触媒の製造
ZrO2ストランド(Φ3mm、NorPro社のSZ 31108、表面積:73m2/g、細孔容積:0.30ml/g、細孔容積分布:マクロ孔6%、メソ孔94%)238gに、浸漬ドラム中で、VE水35mlで希釈したニトロシル硝酸Ru(III)溶液(希硝酸中の15.95質量%のニトロシル硝酸Ru(III)(Heraeus社))19.81gを吹き付ける。その後、この押出物を空気循環乾燥庫中で120℃で16時間乾燥し、引き続きマッフル炉中で180℃で2時間焼成する。この触媒を、次いで200℃で2時間(H2 4l/h;N2 40l/h)最初に還元し、室温で空気10体積%とN2 90体積%との混合物で1時間不動態化する。こうして製造された活性材料は、Ru1質量%及び酸化ジルコニウム99質量%を含む。
硝酸ニトロシルRu(III)溶液(希硝酸中の硝酸ニトロシルRu(III)15.95質量%(Heraeus社))30.51gをメスシリンダに装入し、VE水で37.5mlの全体積まで満たす。その後、酸化ジルコニウム粉末(D9-89、BASF、BET表面積:78m2/g、細孔容積:0.84ml/g、細孔容積分布:マクロ孔68%、メソ孔32%)50gをセラミック製シャーレに装入し、この溶液を添加しかつ均質に混合する。引き続き、この粉末を、循環空気乾燥庫中で120℃で16時間乾燥し、200℃で2時間空気中で焼成する。次いで、この粉末を回転管炉中で、初めは20分間N2 40l/hでパージし、次いで90分間還元する(水素3l/h及び窒素53l/h)。室温に冷却後に水素を止め、窒素約60l/hでパージする。不動態化のために、まず窒素60lh/及び空気1l/hを添加し、次いで空気量を10l/hにまでゆっくりと高める(窒素0l/h)。この場合、触媒が35℃より高く温まらないように留意しなければならない。こうして製造された活性材料は、Ru 10質量%及びZrO2 90質量%を含む。こうして製造された触媒は次の特性を示す:タップ密度は1.13kg/L、細孔容量(Hgポロシメトリー)は0.32ml/g、BET表面積は75m2/g、細孔分布は次のようである:メソ孔(2〜50nm)0%、マクロ孔(>50nm)100%。
触媒(150mg)の定義された量を、ジオキサン中の4,4′−メチレンジアニリン(MDA)の9質量%の溶液7mlと共に、10mlの容量を有するオートクレーブに注ぎ込んだ。引き続き、この反応混合物を、140barの水素圧で、攪拌しながら相応する反応温度に加熱し、180分にわたり一定に維持する。その後、この溶液を室温に冷却し、オートクレーブを大気圧に放圧する。反応混合物の分析を、GCクロマトグラフィーにより行い、この方法は下記されている。この結果を表1に示す。触媒の製造を、本発明による触媒の製造と同様に、相応する金属塩/担体の使用下で実施した。
触媒(ZrO2上の10%Ru、150mg)の定義された量を、ジオキサン中の4,4′−メチレンジアニリン(MDA)の9質量%の溶液7mlと共に、10mlの容量を有するオートクレーブに注ぎ込んだ。引き続き、この反応混合物を、140barの水素圧で、攪拌しながら120℃に加熱し、180分にわたり一定に維持する。その後、この溶液を室温に冷却し、オートクレーブを大気圧に放圧する。反応混合物の分析を、GCクロマトグラフィーにより行い、この方法は下記されている。この結果を表2に示す。触媒の製造を、本発明による触媒の製造と同様に、相応する担体の使用下で実施した。
本発明による触媒(ZrO2上の10質量%Ru)の定義された量を、ジオキサン中の4,4′−メチレンジアニリン(MDA)の9質量%の溶液7mlと共に、10mlの容量を有するオートクレーブに注ぎ込んだ。引き続き、この反応混合物を、140barの水素圧で、攪拌しながら相応する反応温度に加熱し、定義された期間にわたり一定に維持する。その後、この溶液を室温に冷却し、オートクレーブを大気圧に放圧する。反応混合物の分析を、GCクロマトグラフィーにより行い、この方法は下記されている。この結果を、表3及び4に示す:
不動態化された本発明によるルテニウム担持触媒(ZrO2上の1質量%のRu)120mLを、外部ジャケットにより加熱する管型反応器(高さ1.4m、内径12mm)に充填した。反応器にまず水素を汪溢させた後に、引き続きこの反応器に4,4′−メチレンジアニリン(MDA)10質量%の溶液を供給した。温度を変化させかつ140℃の圧力で水素化し、触媒空間速度は0.04kg MDA/kg Kat・hであり、かつこの反応器を循環で運転し、つまり搬出物の一部を反応器に返送した。この反応搬出物を、ガスクロマトグラフィーにより分析し、かつ異性体分布を決定した。この方法を下記に示す。この結果を、表5に示し、これは、本発明による触媒の使用によって80℃で、トランス,トランス−異性体の19%の特に低い割合が達成されることを示す。
他の本発明による反応を実施した。この結果を表6に示す。
カラム:30m RTX5 Amin;0.25mm;0.5μm
温度プログラム:80℃−0min−20℃/min−200℃−0min−4℃/min−260℃−5min ⇒ 26min 全体期間
保持時間[min]: トランス,トランス 18.39
シス,トランス 18.58
シス,シス 18.75
MDA(出発物質) 25.00
Claims (15)
- 触媒の存在で水素による4,4′−メチレンジアニリンの水素化方法において、前記触媒は、酸化ジルコニウム担体材料上のルテニウムを含み、
前記酸化ジルコニウム担体材料は、単斜晶相、正方晶相又はこれらの変態の混合相の形で存在する、ことを特徴とする、4,4′−メチレンジアニリンの水素化方法。 - 前記方法を、懸濁液中で又は固定床中で実施することを特徴とする、請求項1に記載の方法。
- 前記方法を、連続式で又は不連続式で実施することを特徴とする、請求項1又は2に記載の方法。
- 前記方法を、固定床中で、50〜190℃の温度で実施することを特徴とする、請求項2又は3に記載の方法。
- 前記方法を、懸濁液中で、50〜190℃の温度で実施することを特徴とする、請求項2又は3に記載の方法。
- 前記方法を、60〜300barの圧力で実施することを特徴とする、請求項1から5までのいずれか1項に記載の方法。
- 前記触媒は、ルテニウムを、全体の触媒を基準として0.05〜20質量%の量で含むことを特徴とする、請求項1から6までのいずれか1項に記載の方法。
- 前記酸化ジルコニウム担体材料は、30〜300m2/gのBET表面積、0.1〜1cm3/gの細孔容積、及び500〜2000kg/m3のタップ密度を示すことを特徴とする、請求項1から7までのいずれか1項に記載の方法。
- 前記触媒は、30〜300m2/gのBET表面積、0.1〜1cm3/gの細孔容積、及び500〜2000kg/m3のタップ密度を示すことを特徴とする、請求項1から8までのいずれか1項に記載の方法。
- 固定床中で使用される触媒の前記酸化ジルコニウム担体材料は、存在する細孔の50%より多くが、2nm〜50nmの直径のメソ孔により形成され、かつ残り100%までが、>50nmの直径のマクロ孔により形成される細孔サイズ分布を示すことを特徴とする、請求項1から9までのいずれか1項に記載の方法。
- 固定床中で使用される触媒は、存在する細孔の50%より多くが、2nm〜50nmの直径のメソ孔により形成され、かつ残り100%までが、>50nmの直径のマクロ孔により形成される細孔サイズ分布を示すことを特徴とする、請求項1から10までのいずれか1項に記載の方法。
- 懸濁液中で使用される触媒の酸化ジルコニウム担体材料は、存在する細孔の40%より多くが、>50nmの直径のマクロ孔により形成され、かつ残り100%までが、2nm〜50nmの直径のメソ孔により形成される細孔サイズ分布を示すことを特徴とする、請求項1から9までのいずれか1項に記載の方法。
- 懸濁液中で使用される触媒は、存在する細孔の40%より多くが、>50nmの直径のマクロ孔により形成され、かつ残り100%までが、2nm〜50nmの直径のメソ孔により形成される細孔サイズ分布を示すことを特徴とする、請求項1から9までのいずれか1項に記載の方法。
- 反応時間は10〜400minであることを特徴とする、請求項1から13までのいずれか1項に記載の方法。
- 前記水素化を有機溶媒中で行うことを特徴とする、請求項1から14までのいずれか1項に記載の方法。
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