JP2017526688A - コバルト完全接触触媒を使用して第一級アミンを製造する方法 - Google Patents
コバルト完全接触触媒を使用して第一級アミンを製造する方法 Download PDFInfo
- Publication number
- JP2017526688A JP2017526688A JP2017511894A JP2017511894A JP2017526688A JP 2017526688 A JP2017526688 A JP 2017526688A JP 2017511894 A JP2017511894 A JP 2017511894A JP 2017511894 A JP2017511894 A JP 2017511894A JP 2017526688 A JP2017526688 A JP 2017526688A
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- Japan
- Prior art keywords
- catalyst
- compound
- cobalt
- hydrogenation
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 144
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 72
- 239000010941 cobalt Substances 0.000 title claims abstract description 72
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims description 81
- 230000008569 process Effects 0.000 title claims description 48
- 150000003141 primary amines Chemical class 0.000 title claims description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 83
- 150000002825 nitriles Chemical class 0.000 claims abstract description 54
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 21
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 20
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 18
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 13
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 11
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 11
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 83
- 238000005984 hydrogenation reaction Methods 0.000 claims description 74
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 44
- 239000001257 hydrogen Substances 0.000 claims description 44
- 229910052739 hydrogen Inorganic materials 0.000 claims description 44
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 38
- MTPJEFOSTIKRSS-UHFFFAOYSA-N 3-(dimethylamino)propanenitrile Chemical compound CN(C)CCC#N MTPJEFOSTIKRSS-UHFFFAOYSA-N 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 230000009467 reduction Effects 0.000 claims description 24
- 239000007858 starting material Substances 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 22
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 21
- 229910021529 ammonia Inorganic materials 0.000 claims description 21
- 229910052744 lithium Inorganic materials 0.000 claims description 21
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 239000006227 byproduct Substances 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 13
- 239000011149 active material Substances 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 239000011572 manganese Substances 0.000 claims description 10
- 125000001931 aliphatic group Chemical group 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 239000013543 active substance Substances 0.000 claims description 6
- 125000002723 alicyclic group Chemical group 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 4
- KBMSFJFLSXLIDJ-UHFFFAOYSA-N 6-aminohexanenitrile Chemical compound NCCCCCC#N KBMSFJFLSXLIDJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- SWVGZFQJXVPIKM-UHFFFAOYSA-N n,n-bis(methylamino)propan-1-amine Chemical compound CCCN(NC)NC SWVGZFQJXVPIKM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000010948 rhodium Substances 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 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 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 claims description 2
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 38
- 238000007792 addition Methods 0.000 description 32
- 239000012018 catalyst precursor Substances 0.000 description 19
- 239000007789 gas Substances 0.000 description 17
- 239000007788 liquid Substances 0.000 description 16
- 239000012876 carrier material Substances 0.000 description 14
- 239000002904 solvent Substances 0.000 description 14
- -1 alkali metal bicarbonate Chemical class 0.000 description 13
- 238000001556 precipitation Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 238000000465 moulding Methods 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000005470 impregnation Methods 0.000 description 10
- 230000001788 irregular Effects 0.000 description 9
- JJDFVIDVSCYKDS-UHFFFAOYSA-N 1,3,3-trimethyl-5-oxocyclohexane-1-carbonitrile Chemical compound CC1(C)CC(=O)CC(C)(C#N)C1 JJDFVIDVSCYKDS-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 238000012856 packing Methods 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000001339 alkali metal compounds Chemical class 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 150000003335 secondary amines Chemical class 0.000 description 6
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 5
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 238000000137 annealing Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000007868 Raney catalyst Substances 0.000 description 3
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- 125000004429 atom Chemical group 0.000 description 3
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- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 150000002642 lithium compounds Chemical class 0.000 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000002823 nitrates Chemical class 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
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- 238000010298 pulverizing process Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
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- 229910002651 NO3 Inorganic materials 0.000 description 2
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
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- 229910052786 argon Inorganic materials 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
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- 239000008117 stearic acid Substances 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- NUMQCACRALPSHD-UHFFFAOYSA-N tert-butyl ethyl ether Chemical compound CCOC(C)(C)C NUMQCACRALPSHD-UHFFFAOYSA-N 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- JVPSOVALWVNDAM-UHFFFAOYSA-N 2,5-diaminopentanenitrile Chemical compound NCCCC(N)C#N JVPSOVALWVNDAM-UHFFFAOYSA-N 0.000 description 1
- FHKPTEOFUHYQFY-UHFFFAOYSA-N 2-aminohexanenitrile Chemical group CCCCC(N)C#N FHKPTEOFUHYQFY-UHFFFAOYSA-N 0.000 description 1
- RXFCIXRFAJRBSG-UHFFFAOYSA-N 3,2,3-tetramine Chemical compound NCCCNCCNCCCN RXFCIXRFAJRBSG-UHFFFAOYSA-N 0.000 description 1
- RHRVANRKEISTIR-UHFFFAOYSA-N 3-[2-(2-cyanoethylamino)ethylamino]propanenitrile Chemical compound N#CCCNCCNCCC#N RHRVANRKEISTIR-UHFFFAOYSA-N 0.000 description 1
- UDBBPOHVRDIERQ-UHFFFAOYSA-N 3-[2-(3-aminopropylamino)ethylamino]propanenitrile Chemical compound NCCCNCCNCCC#N UDBBPOHVRDIERQ-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000008362 aminopropionitriles Chemical class 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000037237 body shape Effects 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 150000001983 dialkylethers Chemical class 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- BSRDNMMLQYNQQD-UHFFFAOYSA-N iminodiacetonitrile Chemical compound N#CCNCC#N BSRDNMMLQYNQQD-UHFFFAOYSA-N 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- LAQPNDIUHRHNCV-UHFFFAOYSA-N isophthalonitrile Chemical compound N#CC1=CC=CC(C#N)=C1 LAQPNDIUHRHNCV-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- XKPJKVVZOOEMPK-UHFFFAOYSA-M lithium;formate Chemical compound [Li+].[O-]C=O XKPJKVVZOOEMPK-UHFFFAOYSA-M 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- SCHTXWZFMCQMBH-UHFFFAOYSA-N pentane-1,3,5-triamine Chemical compound NCCC(N)CCN SCHTXWZFMCQMBH-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- RHSBIGNQEIPSCT-UHFFFAOYSA-N stearonitrile Chemical compound CCCCCCCCCCCCCCCCCC#N RHSBIGNQEIPSCT-UHFFFAOYSA-N 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
- C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
- B01J23/70—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
- B01J23/78—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 alkali- or alkaline earth metals
-
- 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
- B01J35/19—Catalysts containing parts with different compositions
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/75—Cobalt
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
Description
i)高い割合の触媒活性物質(活性成分)を有すること、
ii)比較的小さな表面積を有すること、及び/又は
iii)不活性担体材料の割合を全く有さないこと、又はそれを比較的低い割合でしか有さないこと、
を特徴としている。
i)コバルト(Co)
ii)任意で、鉄(Fe)、ニッケル(Ni)、ルテニウム(Ru)、ロジウム(Rh)、パラジウム(Pd)、オスミウム(Os)、イリジウム(Ir)、又は白金(Pt)から選択される少なくとも1種のさらなる元素、及び/又は
iii)任意で、クロム(Cr)、マンガン(Mn)、モリブデン(Mo)、チタン(Ti)、亜鉛(Zn)、スズ(Sn)、アルカリ金属、アルカリ土類金属、希土類金属、又はリン(P)から選択される少なくとも1種の助触媒
である。
i)最大50m2/g、好ましくは最大40m2/g、特に好ましくは最大30m2/gの表面積を有すること、及び/又は
ii)担体材料の割合が最大10質量%(触媒の合計質量を基準とする)、好ましく最大5質量%、好適には最大1質量%であり、殊にコバルト完全接触触媒が担体材料を含有しないこと
が好ましい。
を有する体積単位あたりの外部表面積(mms 2/mm3)である。
1.成形体の内部細孔を特定(例えば、室温及び1barの合計圧で吸水率[触媒1gあたりのml]を測定することで特定)する。
2.液体に浸漬する際の成形体の押しのけ体積を特定(例えば、ヘリウムピクノメーターを用いたガス押しのけ体積により特定)する。
3.両体積の合計を出す。
・計量供給した溶液のリチウム濃度は高過ぎてはならない。というのも、そうでなければリチウムが反応器において堆積する/詰まるからである。
・送り込みは、LiOHが反応混合物と良好に混ざるように、流速が大きい反応器の箇所で行われるべきである。LiOHは、水及びたいていの有機溶媒において溶解性が低い。
i)水素化に使用されるニトリルが水を0.01〜10質量%含有すること、及び/又は
ii)副生成物として形成される第二級アミンの割合が0.5GC面積%より大きくなり次第、化合物(I)を装置(V1)に添加すること、及び/又は
iii)装置(V1)へと化合物(I)を添加することで、装置(V1)中のニトリルグラム原子を基準として0.01〜500ppmのアルカリ金属、アルカリ土類金属、及び/又は希土類金属を水素化混合物に添加すること、好適には、触媒負荷が、触媒1L及び1時間あたり0.01〜10kgの出発物質である場合に、装置(V1)中で副生成物として形成される第二級アミンの割合が0.5GC面積%より大きくなり次第、装置(V1)へと化合物(I)を添加することで、水素化混合物に、装置(V1)中のニトリルグラム原子を基準として0.01〜500ppmのアルカリ金属、アルカリ土類金属、及び/又は希土類金属を添加すること。
水酸化リチウム水溶液を繰り返し供給しながらコバルト完全接触触媒の存在下でジメチルアミノプロピオニトリル(DMAPN)を水素化してジメチルアミノプロピルアミンにする。
触媒として、コバルト90.4質量%、マンガン5.1質量%、ナトリウム0.3質量%、及びリン3.1質量%という組成のコバルト完全接触触媒(ストランド直径2mm、欧州特許出願公開第636409号明細書(EP−A636409)の実施例1により製造したもの)を使用する。この触媒40.2gを水素化反応器に充填し、12時間以内に1時間あたり25NLの水素を供給しながら280℃まで加熱し、1時間あたり25NLの水素を送りながらこの温度で12時間維持し、水素のもと冷却する。
先に記載した触媒を固定床触媒として用いて、高さ1メートル、直径0.6cmの特殊鋼製管型反応器(内部管 1.4571)においてダウンフロー方式で水素化を実施する。水素化の反応排出物を冷却し、放圧し、部分的に放出し、部分的に反応器に返送する。
最初に一回LiOH水溶液で触媒を含浸させながら、コバルト接触触媒の存在下でDMAPNを水素化してDMAPAにする。
コバルト完全接触触媒の存在下で、並びにアンモニアの存在下若しくはアンモニアの不在下でDMAPNを水素化してDMAPAにする(水酸化リチウムの添加なし)。
Claims (15)
- 第一級アミンを製造する方法において、少なくとも1種のニトリルを装置(V1)にてコバルト完全接触触媒の存在下で水素化して、少なくとも1種の第一級アミンを獲得し、ここで少なくとも1種の化合物(I)が、繰り返し又は連続的に装置(V1)に添加され、化合物(I)が、アルカリ金属、アルカリ土類金属、又は希土類金属から選択される少なくとも1種の成分を含有することを特徴とする前記方法。
- 請求項1に記載の方法において、化合物(I)を酸化物、水酸化物、及び/若しくは塩の形態で使用すること、及び/又は化合物(I)を水溶液として使用することを特徴とする前記方法。
- 請求項2に記載の方法において、リチウム、カリウム、セシウム、マグネシウム、カルシウム、ランタン、及び/又はセリウムの酸化物、水酸化物、又は塩の水溶液、好ましくは水酸化リチウムの水溶液を使用することを特徴とする前記方法。
- 請求項1から3までのいずれか一項に記載の方法において、
i)水素化に使用されるニトリルが水を0.01〜10質量%含有すること、及び/又は
ii)副生成物として形成される第二級アミンの割合が0.5GC面積%より大きくなり次第、化合物(I)を装置(V1)に添加すること、及び/又は
iii)装置(V1)へと化合物(I)を添加することで、装置(V1)中のニトリルグラム原子を基準として0.01〜500ppmのアルカリ金属、アルカリ土類金属、及び/又は希土類金属を水素化混合物に添加すること、好適には、触媒負荷が、触媒1L及び1時間あたり0.01〜10kgの出発物質である場合に、装置(V1)中で副生成物として形成される第二級アミンの割合が0.5GC面積%より大きくなり次第、装置(V1)へと化合物(I)を添加することで、水素化混合物に、装置(V1)中のニトリルグラム原子を基準として0.01〜500ppmのアルカリ金属、アルカリ土類金属、及び/又は希土類金属を添加すること
を特徴とする前記方法。 - 請求項1から4までのいずれか一項に記載の方法において、水素化がアンモニアの不在下で実施されることを特徴とする前記方法。
- 請求項1から5までのいずれか一項に記載の方法において、装置(V1)が反応器であり、好適にはその空塔速度が、反応器の断面積1m2及び1秒あたり5〜50kgの流量であることを特徴とする前記方法。
- 請求項1から6までのいずれか一項に記載の方法において、水素化が1〜300barの圧力で実施されることを特徴とする前記方法。
- 請求項1から7までのいずれか一項に記載の方法において、コバルト完全接触触媒が、装置(V1)で固定床触媒として使用されることを特徴とする前記方法。
- 請求項1から8までのいずれか一項に記載の方法において、ニトリルが、脂肪族モノニトリル、脂肪族ジニトリル、若しくは脂肪族トリニトリル、脂環式モノニトリル若しくは脂環式ジニトリル、α−アミノニトリル、β−アミノニトリル、若しくはω−アミノニトリル、又はアルコキシニトリルであることを特徴とする前記方法。
- 請求項1から9までのいずれか一項に記載の方法において、
i)N,N−ジメチルアミノプロピルアミン(DMAPA)を製造するためにN,N−ジメチルアミノプロピオニトリル(DMAPN)を使用すること、又は
ii)イソホロンジアミンを製造するためにイソホロンニトリルイミンを使用すること、又は
iii)ヘキサメチレンジアミン(HMD)を製造するために、又は6−アミノカプロニトリル(6−ACN)及びHMDを製造するためにアジポジニトリル(ADN)を使用すること
を特徴とする前記方法。 - 請求項1から10までのいずれか一項に記載の方法において、コバルト完全接触触媒が、少なくとも70質量%、好適には少なくとも80質量%、特に好ましくは少なくとも90質量%、極めて特に好ましくは少なくとも95質量%、触媒活性物質から成ることを特徴とする前記方法。
- 請求項1から11までのいずれか一項に記載の方法において、コバルト完全接触触媒が、触媒活性物質として成分i)、及び任意で成分ii)、及び/又は成分iii)を含み、ここでこれらの成分が
i)コバルト(Co)、
ii)任意で、鉄(Fe)、ニッケル(Ni)、ルテニウム(Ru)、ロジウム(Rh)、パラジウム(Pd)、オスミウム(Os)、イリジウム(Ir)、又は白金(Pt)から選択される少なくとも1種のさらなる元素、及び/又は
iii)任意で、クロム(Cr)、マンガン(Mn)、モリブデン(Mo)、チタン(Ti)、亜鉛(Zn)、スズ(Sn)、アルカリ金属、アルカリ土類金属、希土類金属、又はリン(P)から選択される少なくとも1種の助触媒
であることを特徴とする前記方法。 - 請求項1から12までのいずれか一項に記載の方法において、コバルト完全接触触媒の触媒活性物質が、コバルト55〜98質量%、リン0.2〜15質量%、マンガン0.2〜15質量%、及びアルカリ金属0.2〜15質量%から成り(水素で還元する前のCoO、H3PO4、MnO2、又はアルカリ金属酸化物として計算)、好適には、触媒物質を第一工程にて550〜750℃の最終温度で、第二工程にて800〜1000℃の最終温度で焼成することによりコバルト完全接触触媒を製造することを特徴とする前記方法。
- 請求項1から13までのいずれか一項に記載の方法において、コバルト完全接触触媒が、
i)最大50m2/g、好ましくは最大40m2/g、特に好ましくは最大30m2/gの表面積を有すること、及び/又は
ii)担体材料の割合が、最大10質量%(触媒の合計質量を基準とする)、好ましく最大5質量%、特に好ましくは最大1質量%であり、殊にコバルト完全接触触媒が担体材料を含有しないこと
を特徴とする前記方法。 - 請求項1から14までのいずれか一項に記載の方法において、流(S1)が装置(V1)から排出され、ここで流(S1)が第一級アミンを含有し、かつ流(S1)が少なくとも部分的に装置(V1)に返送され、
好適にはまず化合物(I)が流(S1)の返送部分流に供給され、流(S1)の構成要素として装置(V1)に送り込まれ、
特に好ましくは化合物(I)が水溶液として流(S1)の返送部分流に添加されることを特徴とする前記方法。
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