WO2002051791A2 - Verfahren zur herstellung von primären und sekundären aminen durch hydrierung von nitrilen und iminen - Google Patents
Verfahren zur herstellung von primären und sekundären aminen durch hydrierung von nitrilen und iminen Download PDFInfo
- Publication number
- WO2002051791A2 WO2002051791A2 PCT/EP2001/015268 EP0115268W WO02051791A2 WO 2002051791 A2 WO2002051791 A2 WO 2002051791A2 EP 0115268 W EP0115268 W EP 0115268W WO 02051791 A2 WO02051791 A2 WO 02051791A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- hydrogenation
- raney
- hydrogen
- shaped
- Prior art date
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- 150000002466 imines Chemical class 0.000 title claims abstract description 23
- 150000002825 nitriles Chemical class 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title abstract description 24
- 150000003141 primary amines Chemical class 0.000 title description 5
- 150000003335 secondary amines Chemical class 0.000 title description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 156
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 71
- 239000001257 hydrogen Substances 0.000 claims abstract description 41
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 41
- 239000007789 gas Substances 0.000 claims abstract description 34
- 150000001412 amines Chemical class 0.000 claims abstract description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 95
- 238000000034 method Methods 0.000 claims description 84
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 63
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 63
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 56
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 37
- 229910052759 nickel Inorganic materials 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 34
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 claims description 31
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 28
- 239000000725 suspension Substances 0.000 claims description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 26
- 229910021529 ammonia Inorganic materials 0.000 claims description 26
- 239000010941 cobalt Substances 0.000 claims description 25
- 239000007868 Raney catalyst Substances 0.000 claims description 24
- 229910017052 cobalt Inorganic materials 0.000 claims description 24
- 238000002360 preparation method Methods 0.000 claims description 23
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 19
- 229910052804 chromium Inorganic materials 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- -1 platinum group metals Chemical class 0.000 claims description 16
- 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 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 10
- FHKPTEOFUHYQFY-UHFFFAOYSA-N 2-aminohexanenitrile Chemical compound CCCCC(N)C#N FHKPTEOFUHYQFY-UHFFFAOYSA-N 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000000304 alkynyl group Chemical group 0.000 claims description 6
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims description 6
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 claims description 6
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 6
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 claims description 4
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 4
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims description 3
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 claims description 3
- 238000010923 batch production Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- FJDUDHYHRVPMJZ-UHFFFAOYSA-N nonan-1-amine Chemical compound CCCCCCCCCN FJDUDHYHRVPMJZ-UHFFFAOYSA-N 0.000 claims description 3
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 claims description 3
- KDDNKZCVYQDGKE-UHFFFAOYSA-N (2-chlorophenyl)methanamine Chemical compound NCC1=CC=CC=C1Cl KDDNKZCVYQDGKE-UHFFFAOYSA-N 0.000 claims description 2
- KANSIUXFEQOHOI-UHFFFAOYSA-N 1,3-bis(3-aminopropoxy)propan-2-ol Chemical compound NCCCOCC(O)COCCCN KANSIUXFEQOHOI-UHFFFAOYSA-N 0.000 claims description 2
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 claims description 2
- FCLPGDSITYLYCH-UHFFFAOYSA-N 2,2,2-trichloroethanamine Chemical compound NCC(Cl)(Cl)Cl FCLPGDSITYLYCH-UHFFFAOYSA-N 0.000 claims description 2
- FRJFKKCYRHRKRP-UHFFFAOYSA-N 2,6-dichloro-n-methylaniline Chemical compound CNC1=C(Cl)C=CC=C1Cl FRJFKKCYRHRKRP-UHFFFAOYSA-N 0.000 claims description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 2
- VKPPFDPXZWFDFA-UHFFFAOYSA-N 2-chloroethanamine Chemical compound NCCCl VKPPFDPXZWFDFA-UHFFFAOYSA-N 0.000 claims description 2
- FAXDZWQIWUSWJH-UHFFFAOYSA-N 3-methoxypropan-1-amine Chemical compound COCCCN FAXDZWQIWUSWJH-UHFFFAOYSA-N 0.000 claims description 2
- FCIGUPDFRXUJSZ-UHFFFAOYSA-N 4-(3-aminopropyl)-4-nitroheptane-1,7-diamine Chemical compound NCCCC(CCCN)(CCCN)[N+]([O-])=O FCIGUPDFRXUJSZ-UHFFFAOYSA-N 0.000 claims description 2
- LFIWXXXFJFOECP-UHFFFAOYSA-N 4-(aminomethyl)benzonitrile Chemical compound NCC1=CC=C(C#N)C=C1 LFIWXXXFJFOECP-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 2
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 2
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 claims description 2
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 claims description 2
- JILXUIANNUALRZ-UHFFFAOYSA-N n',n'-diethylbutane-1,4-diamine Chemical compound CCN(CC)CCCCN JILXUIANNUALRZ-UHFFFAOYSA-N 0.000 claims description 2
- GCOWZPRIMFGIDQ-UHFFFAOYSA-N n',n'-dimethylbutane-1,4-diamine Chemical compound CN(C)CCCCN GCOWZPRIMFGIDQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- FSEKYSAWZRQAPN-UHFFFAOYSA-N pent-1-en-1-amine Chemical compound CCCC=CN FSEKYSAWZRQAPN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims 12
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 7
- 239000011651 chromium Substances 0.000 claims 7
- 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 claims 7
- 229910052750 molybdenum Inorganic materials 0.000 claims 7
- 239000011733 molybdenum Substances 0.000 claims 7
- 229910052702 rhenium Inorganic materials 0.000 claims 7
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims 7
- 229910052715 tantalum Inorganic materials 0.000 claims 7
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims 7
- 239000010936 titanium Substances 0.000 claims 7
- 229910052719 titanium Inorganic materials 0.000 claims 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims 7
- 229910052721 tungsten Inorganic materials 0.000 claims 7
- 239000010937 tungsten Substances 0.000 claims 7
- 229910052720 vanadium Inorganic materials 0.000 claims 7
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims 5
- 229910052787 antimony Inorganic materials 0.000 claims 5
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims 5
- 229910052797 bismuth Inorganic materials 0.000 claims 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims 5
- 229910052732 germanium Inorganic materials 0.000 claims 5
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- XFKPORAVEUOIRF-UHFFFAOYSA-N 3-(aminomethyl)benzonitrile Chemical compound NCC1=CC=CC(C#N)=C1 XFKPORAVEUOIRF-UHFFFAOYSA-N 0.000 claims 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- BHHGXPLMPWCGHP-UHFFFAOYSA-N Phenethylamine Chemical compound NCCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-N 0.000 claims 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims 1
- 125000003277 amino group Chemical group 0.000 claims 1
- 239000000908 ammonium hydroxide Substances 0.000 claims 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims 1
- 150000002815 nickel Chemical class 0.000 claims 1
- 229910052707 ruthenium Inorganic materials 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 72
- 239000004793 Polystyrene Substances 0.000 description 48
- 229920002223 polystyrene Polymers 0.000 description 48
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
- 239000000843 powder Substances 0.000 description 33
- 229910045601 alloy Inorganic materials 0.000 description 25
- 239000000956 alloy Substances 0.000 description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 239000004372 Polyvinyl alcohol Substances 0.000 description 24
- 229920002451 polyvinyl alcohol Polymers 0.000 description 24
- 239000007864 aqueous solution Substances 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 20
- 229910000838 Al alloy Inorganic materials 0.000 description 19
- 238000002474 experimental method Methods 0.000 description 18
- 239000002904 solvent Substances 0.000 description 17
- 239000011248 coating agent Substances 0.000 description 16
- 238000000576 coating method Methods 0.000 description 16
- 238000007866 imination reaction Methods 0.000 description 16
- 229910052782 aluminium Inorganic materials 0.000 description 15
- 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 13
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 239000000047 product Substances 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- 229910000640 Fe alloy Inorganic materials 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- 239000003426 co-catalyst Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910000990 Ni alloy Inorganic materials 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 125000004093 cyano group Chemical group *C#N 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 125000001841 imino group Chemical group [H]N=* 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- WJYIASZWHGOTOU-UHFFFAOYSA-N Heptylamine Chemical compound CCCCCCCN WJYIASZWHGOTOU-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000004705 aldimines Chemical class 0.000 description 2
- 238000005576 amination reaction Methods 0.000 description 2
- 125000005219 aminonitrile group Chemical group 0.000 description 2
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 125000000879 imine group Chemical group 0.000 description 2
- 150000004658 ketimines Chemical group 0.000 description 2
- 239000012633 leachable Substances 0.000 description 2
- 125000002560 nitrile group Chemical group 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- ANVAOWXLWRTKGA-NTXLUARGSA-N (6'R)-beta,epsilon-carotene Chemical compound CC=1CCCC(C)(C)C=1\C=C\C(\C)=C\C=C\C(\C)=C\C=C\C=C(/C)\C=C\C=C(/C)\C=C\[C@H]1C(C)=CCCC1(C)C ANVAOWXLWRTKGA-NTXLUARGSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- JSHAWLCRADHRGW-UHFFFAOYSA-N 3-(2-aminoethyl)benzonitrile Chemical compound NCCC1=CC=CC(C#N)=C1 JSHAWLCRADHRGW-UHFFFAOYSA-N 0.000 description 1
- WRHUYWPFTWSTDV-UHFFFAOYSA-N 3-(3-aminopropoxy)propan-1-amine;2-phenylethanamine Chemical compound NCCCOCCCN.NCCC1=CC=CC=C1 WRHUYWPFTWSTDV-UHFFFAOYSA-N 0.000 description 1
- WFGYSQDPURFIFL-UHFFFAOYSA-N 3-chloro-n-methylaniline Chemical compound CNC1=CC=CC(Cl)=C1 WFGYSQDPURFIFL-UHFFFAOYSA-N 0.000 description 1
- KBMSFJFLSXLIDJ-UHFFFAOYSA-N 6-aminohexanenitrile Chemical compound NCCCCCC#N KBMSFJFLSXLIDJ-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920012196 Polyoxymethylene Copolymer Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- BLJNPOIVYYWHMA-UHFFFAOYSA-N alumane;cobalt Chemical compound [AlH3].[Co] BLJNPOIVYYWHMA-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 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
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical class [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
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- JIQVGGQJISZHSS-UHFFFAOYSA-N ethene N-octadecanoyloctadecanamide Chemical compound C=C.CCCCCCCCCCCCCCCCCC(=O)NC(=O)CCCCCCCCCCCCCCCCC JIQVGGQJISZHSS-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
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- 235000021384 green leafy vegetables Nutrition 0.000 description 1
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- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical class [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 150000003956 methylamines Chemical group 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- RIWRFSMVIUAEBX-UHFFFAOYSA-N n-methyl-1-phenylmethanamine Chemical compound CNCC1=CC=CC=C1 RIWRFSMVIUAEBX-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 1
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical group [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical group [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 229910052727 yttrium Chemical class 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical class [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc 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
- C07C209/44—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
- B01J25/00—Catalysts of the Raney type
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
Definitions
- the invention is directed to an improved process for the preparation of primary and / or secondary amines from imines and nitriles, comprising the catalytic hydrogenation of nitriles or imines with gases containing hydrogen or hydrogen in the presence of a shaped Raney-type hydrogenation catalyst.
- the invention particularly includes the production of mono- and diamines and the production of amino nitriles. The process allows the use of significantly smaller amounts of catalyst in the production of the amines with the same or higher yields than in the previously known methods.
- Nitriles can be catalytically reduced to amines with hydrogen. As is known, the intermediate stage of an imine is usually passed through in this hydrogenation. For this reason, it can be assumed that the hydrogenation of nitriles always includes the hydrogenation of imines.
- Amines are an extremely important class of substances in organic chemistry. They serve, for example, as starting materials for the production of solvents, surfactants, bactericides, anti-corrosion agents, anti-foaming agents, additives, pharmaceuticals or
- Dyes They are also very important for the production of polyamide and polyurethane plastics.
- Raney catalysts are often preferred because of their good catalytic properties and because they are much easier to produce than supported catalysts.
- Raney catalysts that also referred to as activated metal catalysts consist of an alloy of at least one catalytically active metal and at least one metal which can be leached with alkalis. Aluminum is predominantly used for the alkali-soluble alloy component, but other metals such as zinc and silicon can also be used. By adding alkalis to the alloy, the leachable component is released, thereby activating the catalyst.
- document US Pat. No. 5,777,166 describes a process for the hydrogenation of nitriles to amines using doped Raney nickel catalysts treated with alcoholates. It is clear from the examples that the process described is preferably carried out in a batch process with the aid of powder catalysts.
- document DE 223 81 53 describes the hydrogenation of fatty acid nitriles to fatty acid amines by means of cobalt catalysts. In this process, too, the hydrogenation is carried out using Raney powder catalysts.
- Raney powder catalysts have the disadvantage that they can only be used in a batch process and that they have to be separated from the reaction media after the catalytic reaction. For this reason, among others, it is preferred to carry out the production of amines by hydrogenation of nitriles and imines with the aid of molded Raney catalysts and, if possible, in a continuous process. Fixed bed catalysts are necessary for this purpose, in addition to a good one catalytic activity must also have a sufficiently good strength for continuous operation.
- Raney catalysts Metal combinations are also known in Raney catalysts.
- Document US 6087296 describes a process for the hydrogenation of unsaturated organic compounds with the aid of a Raney catalyst, which can contain iron, cobalt and other metals and promoters.
- the patent DE 195 40 191 describes a two-stage process for the preparation of isophoronediamine.
- isophoronenitrile is first converted into isophornonitrilimine in the presence or absence of an imination catalyst with ammonia and the product mixture obtained is hydrogenated to isophoronediamine with the addition of hydrogen.
- Isophoronenitrilimin contains both a hydrogenatable cyano group and a hydrogenatable imino group.
- a shaped Raney catalyst based on cobalt serves as the hydrogenation catalyst.
- the catalyst also contains other metallic cobalt, which acts as a binder to ensure the stability of the shaped body.
- preferably hollow-shaped catalysts with a diameter of 0.05 to 20 mm and a shell thickness of 0.05 to 7 mm are used.
- the catalyst bowls can be impermeable or have a porosity of 80% and higher.
- hollow-body catalysts can be used which consist of one or more layers. If the catalyst bodies have several layers, the catalyst bodies are dried during the production between the individual coating steps. This is preferably carried out in a fluidized bed at temperatures from 60 to 150 ° C. It is also possible to produce a hollow-shaped catalyst with more chic where it has not dried between the individual coating steps.
- the hollow Raney catalysts are used in the activated form. That in the not activated
- Leachable metal present in the catalyst body may have been leached out completely or only partially with alkalis in the activated state.
- extrudates in the process according to the invention, extrudates, granules, fiber tablets or shell-activated can also be used
- Tablets can be preferred for exothermic reactions because of their good heat exchange properties.
- aliphatic and aromatic amines can be produced from the underlying nitriles or imines.
- the amines can be primary and secondary amines.
- the amines can be compounds of the general formula
- R 1 R 2 CH-NHR 3 be, where R 1 , R 2 and R 3 are independently aliphatic and / or aromatic, unbranched and / or branched, substituted and / or unsubstituted, saturated and / or unsaturated radicals or hydrogen. If R 3 is not hydrogen, it is a ketimine or
- the starting compound can be a nitrile, a ketimine
- amines produced according to the invention can be open-chain, alicyclic or aromatic.
- (CH 2 ) n - with n 1 to 30 and R 2 and R 3 are hydrogen.
- Examples are ethylamine, n-propylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine or n-decylamine.
- radicals R 1 , R 2 or R 3 can be substituted radicals. They can be substituted with those radicals which are the basis of the process according to the invention
- Hydrogenation itself could also be hydrogenated or no hydrogenation is accessible.
- the reaction conditions are to be selected such that predominantly the cyano group or the imine group is hydrogenated.
- One or more of these substituents can be contained in the amines prepared according to the invention. It is also possible for the substituent itself to be substituted
- a particularly preferred embodiment of the invention is a process for the preparation of aliphatic ⁇ , ⁇ -diamines of the general formula H 2 N-CH 2 - (CH 2 ) m-CH 2 -NH 2 , in which an integer between 1 and 12, in particular 2, 3, 4, 5 or 6, such as, for example, tetramethylene diamine, pentamethylene diamine,
- Another preferred embodiment of the invention is a process for the preparation of aliphatic ⁇ -amino- ⁇ -nitriles of the general formula NC- (CH 2 ) m -CH 2 -NH 2 , in which m is an integer between 1 and 12, in particular 2 , 3, 4, 5 or 6 means, for example ⁇ -amino-butyronitrile, ⁇ -amino-valerionitrile, ⁇ -amino-capronitrile, ⁇ -amino-heptanoic acid nitrile or ⁇ -amino-octanoic acid nitrile.
- isophoronediamine it is also possible, for example in the production of isophoronediamine, to start from a compound which contains one or more nitrile groups and at the same time one or more imino groups. These compounds can be converted into the corresponding diamines or polyamines using the process according to the invention.
- Another preferred embodiment of the invention is a process for the preparation of methylamines substituted with aromatic radicals.
- mixtures of different amines by the process according to the invention. These mixtures can be obtained, for example, by unselective hydrogenation of starting substances which contain several hydrogenatable cyano or imino groups, or by hydrogenation of mixtures which contain two or more nitriles and / or imines.
- the process according to the invention can be carried out with hydrogen as the hydrogenation gas or with gas mixtures which contain hydrogen, for example a mixture of hydrogen and carbon monoxide and / or carbon dioxide.
- hydrogen for example a mixture of hydrogen and carbon monoxide and / or carbon dioxide.
- the process according to the invention can be carried out batchwise or continuously.
- the reactor can be operated in the bottom or trickle bed process, the trickle bed process being preferred.
- a mixture of at least the nitrile and / or imine and hydrogen is
- solvents can, for example, liquid ammonia, aqueous
- suitable solvents are methanol, ethanol, triethylamine,
- Trimethylamine, tripropylamine, tributylamine, ammonia or hexane Trimethylamine, tripropylamine, tributylamine, ammonia or hexane.
- the presence of one or more solvents can, on the one hand, result in the operating parameters such as pressure and temperature being in more moderate ranges than in the case of a solvent-free procedure.
- the selectivity of the hydrogenation reaction can be increased by the clever choice of solvents. This is particularly important if, in addition to the nitrile groups or imine groups, there are other hydrogenation-accessible ones oo IV ) IV) P 1 P 1
- aliphatic, cycloaliphatic or aromatic radicals Preferred examples are tetramethyl, tetraethyl, tetra-n-propyl and tetra-n-butylammonium hydroxide. Suitable concentrations of are 0.01 to 100 mmol, preferably 0.2 to 20 mmol, of a tetraalkylammonium hydroxide per mole of the isophoronenitrile.
- ammonia can help reduce the rate of the reaction in the reaction.
- the compound to be hydrogenated and the reaction parameters it may be preferred for ammonia to be present during the hydrogenation.
- the ammonia present can help reduce the rate of the reaction in the reaction.
- ammonia is 0 to 80% by weight based on the entire mixture subjected to the hydrogenation. If no positive effect is achieved by adding ammonia or if the by-product formation is only slight, the addition of ammonia can preferably be dispensed with. For example, the addition of ammonia is not necessary in many cases when using cobalt catalysts.
- co-catalysts in the preparation of amines according to the invention by hydrogenating nitriles and imines with hollow-body Raney catalysts.
- Suitable co-catalysts are, for example, salts of cobalt, nickel, lanthanum, cerium or yttrium, preferably salts of cobalt and nickel.
- a preferred amount of co-catalyst is 0.01 to 0.5 mol, in particular 0.05 to 0.2 mol, of co-catalyst per mole of cobalt catalyst.
- the co-catalyst or catalysts can be added to the Raney catalyst or the reaction mixture in the form of anhydrous or water-containing salts, in powder form, as a solution or as a suspension.
- Nitriles or imines are used as starting materials for the production of amines according to the invention.
- the invention also encompasses the production of amines from imines by catalytic hydrogenation, in which the imine is formed in situ in the hydrogenation reaction or in which the imine is formed only immediately before the hydrogenation to the amine.
- imines can only be prepared in situ in the hydrogenation reactor in the presence of ammonia or primary amines from aldehydes and ketones, which can be converted into the desired amine under the given hydrogenation conditions.
- the imination can also take place immediately before the hydrogenation, so that a more or less complex mixture containing at least one imine is subjected to the hydrogenation.
- This " procedure according to the invention is particularly preferred in the production of isophoronediamine, in which isophoronenitrile isophoronenitrileimine is first produced immediately before the hydrogenation or in situ and is then hydrogenated by amination.
- a corresponding procedure is also possible for the preparation of other amines.
- the invention relates to the production of isophoronediamine. It is possible to carry out the production of isophoronediamine in one or more stages. If the process is carried out in one step, isophoronenitrile becomes hollow in the presence of ammonia, hydrogen
- Raney catalyst and optionally other additives are hydrogenated by amination.
- isophoronenitrilimine is first formed in situ, which is then hydrogenated.
- the reaction temperature can be between 10 and 150 ° C, preferably between 60 and 130 ° C and in particular between 80 and 120 ° C.
- the imination reaction is preferably carried out at pressures in the range from 2 to 30 MPa.
- a solvent from the series consisting of an alcohol having 1 to 4 carbon atoms, preferably a monohydric primary alcohol and in particular methanol, or a to use water-soluble ethers such as tetrahydrofuran or dioxane.
- a mixture containing isophoronenitrile, liquid ammonia and methanol is preferably fed to the imination reactor.
- the mixture advantageously contains 10 to 40% by weight, preferably 10 to 30% by weight of isophoronenitrile and 10 to 40% by weight, preferably 20 to 40% by weight of ammonia.
- Imination catalyst the catalyst in the form of a suspension catalyst or a fixed bed catalyst Application.
- the use of a fixed bed catalyst is advantageous since this eliminates the need for complex steps to separate the reaction mixture from the catalyst.
- this is used in the form of conventional catalyst moldings such as extruded bars, pellets and tablets as a bed in a fixed bed reactor.
- the imination catalyst can be arranged in a separate reactor. However, it is also possible to arrange the imination catalyst in a reactor which contains both a bed of the imination catalyst and a bed of the catalyst used for the aminating hydrogenation.
- the bed of the imination catalyst is above (trickle bed reactor) or below (bubble reactor) the bed of the hydrogenation catalyst. It has proven to be advantageous to use a single reactor which has a bed of the hydrogenation catalyst and a bed of
- Ammonia and alcohol, especially methanol, are added to the reactor head.
- hydrogen advantageously expediently flows into the reactor from above for the aminating hydrogenation.
- Isophoronediamine is the catalytic hydrogenation using a hollow Raney catalyst.
- Raney catalysts with nickel, copper, iron, palladium or platinum can in principle also be used for the hydrogenation, of the hollow Raney catalysts described are those based on cobalt and co>rv> P 1 P 1 o c ⁇ o c ⁇ o C ⁇
- the aminating hydrogenation can be carried out with an excess of hydrogen of 4.5 to 30 molar equivalents. If the process according to the invention is carried out in a continuous process, the hydrogen can be supplied in cocurrent or in countercurrent.
- the aminating hydrogenation can usually be carried out at a temperature in the range from 20 to 150 ° C., preferably 90 to 130 ° C. and at a pressure in the range from 0. 3 to 10 MPa, preferably at 5 to 8 MPa and in particular below 8 MPa. Due to the moderate operating pressures mentioned, which are possible when using the preferred mixtures of isophoronenitrile, ammonia, hydrogen and solvents under the specified temperature conditions, the investment volume is reduced and thus the economy compared to processes which require a high operating pressure is increased.
- a solvent for example methanol
- the indicated pressure is understood to mean the total pressure, which is composed of the partial pressures of ammonia, hydrogen, Ci to C 4 alcohol and the other constituents of the reaction mixture.
- aminating hydrogenation in other temperature or pressure ranges, for example between 150 and 250 ° C. or at pressures up to 50 MPa, for example if no organic solvent is present in the reaction mixture.
- Range from 1 h -1 to 4 h -1, and more preferably at about 2 h "" 1 to 3 h -1 .
- a trickle bed reactor contains a lower bed of hydrogenation catalyst and an upper bed of imination catalyst in the production of isophoronediamine, the respective bed height of the corresponding catalyst activity
- the imination can expediently be carried out in the presence of hydrogen.
- the reaction mixture leaving the hydrogenation reactor of isophorondia is worked up in a manner known per se.
- This work-up usually comprises distilling off the ammonia, then distilling off the solvents, if solvents are present, and fractional distillation of the crude product.
- the hollow body-shaped Raney catalyst used according to the invention has a significantly lower bulk density than previously used Raney catalysts. As a result, much less catalyst material is required than in the previously known processes.
- the catalyst used in the process according to the invention has very good strength. This results in very good hydrogenation activity that lasts for a long time.
- the catalytic activity of the catalyst of Examples 1-8 during the hydrogenation of butyronitrile to butylamine was compared.
- 20 ml of catalyst from 11 to 41 grams of the corresponding catalyst
- the temperature of the reaction became 75 ° C
- the concentration of the butyronitrile in the methanol became 20% by weight
- the pressure of the reaction became 40 bar.
- the throughput of hydrogen was 60 l / h and the LHSV became 0.6 h -1 .
- the product mixture was analyzed by GC.
- a catalyst was produced according to DE 197 21 897 AI with a 50% by weight cobalt / 50% by weight aluminum alloy.
- a twin-screw extruder (Werner &Pfleider; extruder ZSK 30), a mixture prepared at room temperature, consisting of 15% by weight of a polyoxymethylene copolymer and 85% by weight of the cobalt / aluminum alloy at a temperature of 190 ° C with a mass flow of 10 kg / h extruded.
- the Polyoxymethlencopolymere contained 2.7% by weight of butanediol formal as Comono older (Ultra ® N2320) and had a MVR (190 ° C, 2.16 kg) of 6.7 -8.5 on.
- the green bodies were first heated to 120 ° C. in an oven within 10 minutes. The decomposition then took place within 90 minutes with a continuous increase in temperature from 120 to 280 ° C. After this time, the decomposition was largely complete. The temperature was then increased to 800 ° C. in the course of 125 minutes. At this temperature, the greens were calcined for a further 140 minutes.
- a coating solution was prepared by suspending 1730 grams of 50% Co and 50% Al alloy powder in 1557 ml of an aqueous solution containing about 2% by weight polyvinyl alcohol. This suspension was then sprayed onto 1,000 ml of polystyrene balls approximately 2 mm in diameter while suspended in an upward air stream. 1 liter of this sphere was further coated with an alloy solution.
- the solution for the second layer consisted of 1203 grams of 50% Co and 50% Al alloy powder in 1557 ml of an aqueous solution containing about 2% by weight polyvinyl alcohol.
- This suspension was then made up to 1,000 ml of the previously mentioned, with Co / Al pre-coated polystyrene balls sprayed while they were suspended in an upward air stream (nitrogen and other gases can also be used).
- the balls were heated to 500 ° C. in order to burn out the polystyrene.
- the Co / Al hollow spheres were then heated to 800 ° C.
- the hollow spheres were then suspended in a 20 wt .-% sodium hydroxide solution activated about 1.5 hrs. At 80 ° C •.
- the activated hollow spheres obtained had a diameter of approximately 3.3 mm and a shell thickness of approximately 700 ⁇ m. 20 ml (14.61 grams) of this catalyst were tested according to Application Example 1 and the results of this experiment are shown in Table 2.
- a catalyst was made according to Example 2, where the amount of metal was changed so that 20 ml of the catalyst weighed 11.86 grams instead of 14.61 grams. 20 ml (11.86 gram) of this catalyst were tested according to Application Example 1 and the results of this experiment are shown in Table 3.
- a free-flowing, pelletizable catalyst mixture was prepared according to the instructions in EP 0 648 534 AI for a catalyst from 1000 grams of 50% Co and 50% Al alloy powder, 150 grams of pure cobalt powder and 50 grams of ethylene-bis-stearoylamide. Tablets with a diameter of 3 mm and a thickness of 3 mm were compressed from this mixture. The molded articles were calcined at 700 ° C for 2 hours. After the calcination, the tablets were activated for 2 hours at 80 ° C. in 20% sodium hydroxide solution. 20 ml (40.8 grams) of this catalyst were tested according to Application Example 1 and the results of this experiment are shown in Table 4.
- the Ni / Al / Cr / Fe hollow spheres were then heated to 800 ° C to sinter the alloy particles and nickel powder together.
- the hollow spheres were then activated in a 20% strength by weight sodium hydroxide solution at 80 ° C. for about 1.5 hours.
- the activated hollow spheres obtained had a diameter of approximately 3.3 mm and a shell thickness of approximately 700 ⁇ m.
- 20 ml (15.54 grams) of this catalyst were tested according to Application Example 1 and the results of this experiment are shown in Table 5.
- Polystyrene balls with the aforementioned solutions were heated to 500 ° C to burn out the polystyrene.
- the Ni / Al hollow spheres were then heated to 800 ° C to sinter the alloy particles and nickel powder together.
- the hollow spheres were then activated in a 20% strength by weight sodium hydroxide solution at 80 ° C. for about 1.5 hours.
- the activated hollow spheres obtained had a diameter of approximately 3.3 mm and a shell thickness of approximately 700 ⁇ m.
- 20 ml (16.69 grams) of this catalyst were tested in accordance with Application Example 1 and the results of this experiment are shown in Table 6.
- the activated hollow spheres obtained had a diameter of approximately 3.3 mm and a shell thickness of approximately 700 ⁇ m.
- This catalyst was doped with a sodium molybdate solution and the final Mo content of the catalyst became 0.3%. 20 ml (18.74 grams) of this catalyst were tested in accordance with Application Example 1 and the results of this experiment are shown in Table 8.
- the catalytic activity of the catalyst of Examples 9 and 10 during the hydrogenation of benzonitrile to benzylamine was compared.
- 20 ml of catalyst (from 15 to 41 grams of the corresponding catalyst) were introduced into a tubular reactor and tested in a trickle phase.
- the temperature of the reaction became 75 ° C
- the concentration of the benzonitrile in the methanol became 20% by weight
- the pressure of the reaction became 40 bar.
- a free-flowing, pelletizable catalyst mixture was according to the instructions in EP 0 648 534 AI for a catalyst made of 1000 grams of 50% Co and 50% Al
- This suspension was then poured onto 1,000 ml of the aforementioned polystyrene balls precoated with Co / Al sprayed on while suspended in an upward stream of air (nitrogen and other gases can also be used).
- the balls were heated to 500 ° C. in order to burn out the polystyrene.
- the Co / Al hollow spheres were then heated to 800 ° C.
- the hollow spheres were then activated in a 20% strength by weight sodium hydroxide solution at 80 ° C. for about 1.5 hours.
- the activated hollow spheres obtained had a diameter of approximately 3.3 mm and a shell thickness of approximately 700 ⁇ m. 20 ml (15.76 grams) of this catalyst were tested in accordance with Application Example 2 and the results of this experiment are shown in Table 10.
- the catalyst activity of the catalyst of Examples 11 to 17 during the hydrogenation of adiponitrile (ADN) to hexamethylenediamine (HMD) and aminocapronitrile (ACN) were compared.
- ADN adiponitrile
- HMD hexamethylenediamine
- ACN aminocapronitrile
- This suspension was then sprayed onto 1,000 ml of the aforementioned Ni / Al precoated polystyrene balls while suspended in an upward air stream (nitrogen and other gases can also be used).
- the balls were heated to 500 ° C. in order to burn out the polystyrene.
- the Ni / Al hollow spheres were then heated to 800 ° C to sinter the alloy particles and nickel powder together.
- the hollow spheres were then activated in a 20% strength by weight sodium hydroxide solution at 80 ° C. for about 1.5 hours.
- the activated hollow spheres obtained had one
- Diameter by approx. 3.3 mm and a jacket thickness by approx. 700 ⁇ m. 40 ml (35.17 grams) of this catalyst were tested according to Application Example 3 and the results of this experiment are shown in Table 12.
- a catalyst was produced according to Example 2, where the amount of metal was changed so that 20 ml of the
- a free-flowing, pelletizable catalyst mixture was prepared according to the instructions in EP 0 648 534 AI for a catalyst from 1000 grams of 50% Co and 50% Al alloy powder, 150 grams of pure cobalt powder and 50 grams of ethylene-bis-stearoylamide. Tablets with a diameter of 3 mm and a thickness of 3 mm were compressed from this mixture. The molded articles were calcined at 700 ° C for 2 hours. After the calcination, the tablets were activated for 2 hours at 80 ° C. in 20% sodium hydroxide solution. 40 ml (82.38 grams) of this catalyst were tested according to Application Example 3 and the results of this experiment are shown in Table 14.
- a coating solution was prepared by suspending 1730 grams of 47.4% Co, 50% Al, 1.3% Cr and 1.3% Ni alloy powder in 1557 ml of an aqueous solution containing about 2% by weight polyvinyl alcohol. This Suspension was then sprayed onto 1,000 ml polystyrene balls approximately 2 mm in diameter while suspended in an upward air stream. 1 liter of this sphere was further coated with an alloy solution.
- the solution for the second layer consisted of 1203 grams of 47.4% Co, 50% Al, 1.3% Cr and 1.3% Ni alloy powder in 1557 ml of an aqueous solution containing about 2% by weight polyvinyl alcohol.
- This suspension was then sprayed onto 1,000 ml of the aforementioned polystyrene balls precoated with Co / Al / Cr / Ni while suspended in an upward air stream (nitrogen and other gases can also be used).
- the balls were heated to 500 ° C. in order to burn out the polystyrene.
- the Co / Al / Cr / Ni hollow spheres were then heated to 800 ° C.
- the hollow spheres were then activated in a 20% strength by weight sodium hydroxide solution at 80 ° C. for about 1.5 hours.
- the activated hollow spheres obtained had a diameter of approximately 3.3 mm and a shell thickness of approximately 700 ⁇ m. 40 ml (33.32 grams) of this catalyst were tested according to Application Example 3 and the results of this experiment are shown in Table 15.
- the Ni / Al / Cr / Fe hollow spheres were then heated to 800 ° C to sinter the alloy particles and nickel powder together.
- the hollow spheres were then activated in a 20% strength by weight sodium hydroxide solution at 80 ° C. for about 1.5 hours.
- the activated hollow spheres obtained had a diameter of approximately 3.3 mm and a shell thickness of approximately 700 ⁇ m.
- 40 ml (30.63 grams) of this catalyst were tested according to Application Example 3 and the results of this experiment are shown in Table 16.
- a coating solution was prepared by suspending 1730 grams of 47.4% Co, 50% Al, 1.3% Cr and 1.3% Ni alloy powder in 1557 ml of an aqueous solution containing about 2% by weight polyvinyl alcohol.
- the catalytic activity of the catalyst of Example 18 during the hydrogenation of adiponitrile (ADN) to hexamethylenediamine (HMD) and aminocapronitrile (ACN) was compared.
- 40 ml of catalyst (30.63 grams of the corresponding catalyst) were introduced into a tubular reactor and tested in a trickle phase.
- the temperature of the reaction was from 110 to 154 ° C
- the concentration of the ADN in the methanol became 20% by weight
- the concentration of the NaOH became 1.9 grams per liter of the ADN + methanol solution
- the pressure of the reaction became 65 bar.
- the throughput of hydrogen was from 65 to 129 1 / h and the LHSV was from 0.13 to 1.03 h "1.
- the product mixture was analyzed by GC.
- This suspension was then sprayed onto 1,000 ml of the aforementioned polystyrene balls precoated with Ni / Al / Cr / Fe while suspended in an upward air stream (nitrogen and other gases can also be used).
- the balls were heated to 500 ° C. in order to burn out the polystyrene.
- the Ni / Al / Cr / Fe hollow spheres were then heated to 800 ° C to sinter the alloy particles and nickel powder together.
- the hollow spheres were then activated in a 20% strength by weight sodium hydroxide solution at 80 ° C. for about 1.5 hours.
- the activated hollow spheres obtained had a diameter of approximately 3.3 mm and a shell thickness of approximately 700 ⁇ m. 40 ml (30.63 grams) of this catalyst were tested in accordance with Application Example 4 and the results of this experiment are shown in Table 18.
- Examples 19 and 20 during the hydrogenation of adiponitrile (ADN) to hexamethylenediamine (HMD) and aminocapronitrile (ACN) were compared.
- ADN adiponitrile
- HMD hexamethylenediamine
- ACN aminocapronitrile
- a coating solution was prepared by suspending 1730 grams of 50% Co and 50% Al alloy powder in 1557 ml of an aqueous solution containing about 2% by weight polyvinyl alcohol. This suspension was then sprayed onto 1,000 ml of polystyrene balls approximately 2 mm in diameter while suspended in an upward air stream. 1 liter of this sphere was further coated with an alloy solution.
- the solution for the second layer consisted of 1203 grams of 50% Co and 50% Al alloy powder in 1557 ml of an aqueous solution containing about 2% by weight polyvinyl alcohol. This suspension was then sprayed onto 1,000 ml of the aforementioned polystyrene balls precoated with Co / Al, while these were directed in an upward direction
- Air flow nitrogen and other gases can also be used
- the balls were heated to 500 ° C. in order to burn out the polystyrene.
- the Co / Al hollow spheres were then heated to 800 ° C.
- the hollow spheres were then activated in a 20% strength by weight sodium hydroxide solution at 80 ° C. for about 1.5 hours.
- the activated hollow spheres obtained had a diameter of approximately 3.3 mm and a shell thickness of approximately 700 ⁇ m. 11.50 grams of this catalyst were tested according to Application Example 5 and the catalyst shows an activity of 0.3425 ml H 2 uptake per minute with an ADN selectivity of 77%.
- Example 20 Example 20
- the catalytic activity of the catalyst of Example 21 during the hydrogenation of adiponitrile (ADN) to hexamethylenediamine (HMD) and aminocapronitrile (ACN) were compared.
- ADN adiponitrile
- HMD hexamethylenediamine
- ACN aminocapronitrile
- a coating solution was prepared by suspending 1730 grams of 50% Co and 50% Al alloy powder in 1557 ml of an aqueous solution containing about 2% by weight polyvinyl alcohol. This suspension was then sprayed onto 1,000 ml of polystyrene balls approximately 2 mm in diameter while suspended in an upward air stream. 1 liter of this sphere was further coated with an alloy solution.
- the solution for the second layer consisted of 1203 grams of 50% Co and 50% Al alloy powder in 1557 ml of an aqueous solution containing about 2% by weight polyvinyl alcohol. This suspension was then sprayed onto 1,000 ml of the aforementioned polystyrene balls precoated with Co / Al while suspended in an upward air stream (nitrogen and other gases can also be used). After coating the
- Polystyrene balls with the aforementioned solutions were heated to 500 ° C to burn out the polystyrene.
- the Co / Al hollow spheres were then heated to 800 ° C.
- the hollow spheres were then activated in a 20% strength by weight sodium hydroxide solution at 80 ° C. for about 1.5 hours.
- the activated hollow spheres obtained had a diameter of approximately 3.3 mm and a shell thickness of approximately 700 ⁇ m. 11.50 grams of this catalyst were tested according to Application Example 5 and the catalyst shows an activity of 0.375 ml H 2 uptake per minute with an ADN selectivity of 92 s.
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Abstract
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Priority Applications (2)
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EP01988070A EP1343749A2 (de) | 2000-12-23 | 2001-12-21 | Verfahren zur herstellung von primären und sekundären aminen durch hydrierung von nitrilen und iminen |
JP2002552890A JP2004516308A (ja) | 2000-12-23 | 2001-12-21 | ニトリルおよびイミンの水素化により第一級および第二級アミンを製造する方法 |
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DE10065031A DE10065031A1 (de) | 2000-12-23 | 2000-12-23 | Verfahren zur Herstellung von primären und sekundären Aminen durch Hydrierung von Nitrilen und Imine |
DE10065031.7 | 2000-12-23 | ||
EP0112566 | 2001-10-31 | ||
EPPCT/EP01/12566 | 2001-10-31 |
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WO2002051791A2 true WO2002051791A2 (de) | 2002-07-04 |
WO2002051791A3 WO2002051791A3 (de) | 2002-10-10 |
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PCT/EP2001/015268 WO2002051791A2 (de) | 2000-12-23 | 2001-12-21 | Verfahren zur herstellung von primären und sekundären aminen durch hydrierung von nitrilen und iminen |
Country Status (4)
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US (1) | US6649799B2 (de) |
JP (1) | JP2004516308A (de) |
CN (1) | CN1483016A (de) |
WO (1) | WO2002051791A2 (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3075721A1 (de) | 2015-03-30 | 2016-10-05 | Evonik Degussa GmbH | Verfahren zur Herstellung von 3-Aminomethyl-3,5,5-trimethylcyclohexylamin |
Families Citing this family (25)
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DE10010825A1 (de) * | 2000-03-08 | 2001-09-13 | Basf Ag | Verfahren zur Abtrennung eines Azepin-Derivats aus einer Mischung enthaltend ein Amin und ein Azepin-Derivat |
DE10101646A1 (de) * | 2001-01-16 | 2002-07-18 | Degussa | Verfahren zur Herstellung von gesättigten organischen Verbindungen |
US6762324B2 (en) * | 2002-05-01 | 2004-07-13 | Air Products And Chemicals, Inc. | Metal modified Pd/Ni catalysts |
EP1809596A1 (de) * | 2004-11-10 | 2007-07-25 | Degussa GmbH | Festbetthydrierung von fettsäurenitrilen zu fettaminen |
DE102005003315A1 (de) * | 2005-01-24 | 2006-08-03 | Basf Ag | Verfahren zur Herstellung eines Xylylendiamins |
DE102005008929A1 (de) * | 2005-02-24 | 2006-08-31 | Basf Ag | Verfahren zur Herstellung eines Xylylendiamins |
DE102007011483A1 (de) * | 2007-03-07 | 2008-09-18 | Evonik Degussa Gmbh | Verfahren zur Herstellung von 3-Aminomethyl-3,5,5-trimethylcyclohexylamin |
CN101678337B (zh) * | 2007-05-29 | 2012-12-19 | 赢创德固赛有限责任公司 | 活化的碱金属催化剂 |
CN101678336B (zh) | 2007-05-29 | 2012-12-19 | 赢创德固赛有限责任公司 | 活化的碱金属催化剂 |
JP5562235B2 (ja) * | 2007-05-29 | 2014-07-30 | エボニック デグサ ゲーエムベーハー | 活性化卑金属触媒 |
EP2203249A1 (de) * | 2007-10-15 | 2010-07-07 | Evonik Degussa GmbH | Schnell filtrierende pulverförmige katalysatormischungen |
WO2010089266A2 (de) * | 2009-02-09 | 2010-08-12 | Basf Se | Verfahren zur verbesserung der katalytischen aktivität von monolithischen katalysatoren |
CN102267915B (zh) * | 2011-06-16 | 2013-11-20 | 浙江大学 | 芳香腈的还原方法 |
CN102924291B (zh) | 2011-08-08 | 2014-08-06 | 万华化学集团股份有限公司 | 3-氨甲基-3,5,5-三甲基环己胺的制备方法 |
CN102924286B (zh) * | 2012-10-31 | 2014-06-11 | 万华化学集团股份有限公司 | 一种n1-(2-氨乙基)-1,2-乙二胺的制备方法 |
EP2930166B1 (de) | 2012-12-07 | 2018-06-20 | Wanhua Chemical Group Co., Ltd. | Verfahren zur herstellung von 3-aminomethyl-3,5,5-trimethylcyclohexylamin |
US9878314B2 (en) * | 2013-11-26 | 2018-01-30 | Infra XTL Technology Ltd. | Catalyst for direct production of isoparaffins-rich synthetic oil and a method for preparing the catalyst |
EP3050870A1 (de) | 2015-01-30 | 2016-08-03 | Evonik Degussa GmbH | Verfahren zur Herstellung von 3-Aminomethyl-3,5,5-trimethylcyclohexylamin |
CN106582709B (zh) * | 2016-11-23 | 2020-05-19 | 西安凯立新材料股份有限公司 | 一种用于芳香腈氢化合成芳香伯胺的催化剂及其制备方法 |
EP3406589B1 (de) | 2017-05-23 | 2020-04-08 | Evonik Operations GmbH | Verfahren zur herstellung von aminoverbindungen aus nitrilverbindungen |
JP7514465B2 (ja) | 2020-03-24 | 2024-07-11 | 日本ゼオン株式会社 | アミン化合物の製造方法 |
CN111377820B (zh) * | 2020-04-23 | 2022-11-29 | 中国天辰工程有限公司 | 一种2-甲基戊二胺的制备方法 |
CN111875501A (zh) * | 2020-09-02 | 2020-11-03 | 山东驰越化工有限公司 | 癸二胺生产加氢连续工艺 |
JP7284879B1 (ja) * | 2021-07-02 | 2023-05-31 | 日揮触媒化成株式会社 | スポンジコバルト触媒組成物 |
CN117899920A (zh) * | 2024-02-04 | 2024-04-19 | 河南能源集团研究总院有限公司 | 一种1,4-丁二腈加氢催化剂及其制备方法 |
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WO1995017959A1 (fr) * | 1993-12-28 | 1995-07-06 | Rhone-Poulenc Chimie | Catalyseur d'hydrogenation de nitriles en amines, son procede de preparation et procede d'hydrogenation en faisant application |
DE19721897A1 (de) * | 1997-05-26 | 1998-12-03 | Degussa | Geformter Metall-Festbettkatalysator, Verfahren zu seiner Herstellung und seine Verwendung |
EP1068900A1 (de) * | 1999-07-16 | 2001-01-17 | Degussa-Hüls Aktiengesellschaft | Metallkatalysatoren umfassend hohle Formen |
-
2001
- 2001-12-21 JP JP2002552890A patent/JP2004516308A/ja active Pending
- 2001-12-21 WO PCT/EP2001/015268 patent/WO2002051791A2/de not_active Application Discontinuation
- 2001-12-21 US US10/024,488 patent/US6649799B2/en not_active Expired - Fee Related
- 2001-12-21 CN CNA018212549A patent/CN1483016A/zh active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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WO1995017959A1 (fr) * | 1993-12-28 | 1995-07-06 | Rhone-Poulenc Chimie | Catalyseur d'hydrogenation de nitriles en amines, son procede de preparation et procede d'hydrogenation en faisant application |
DE19721897A1 (de) * | 1997-05-26 | 1998-12-03 | Degussa | Geformter Metall-Festbettkatalysator, Verfahren zu seiner Herstellung und seine Verwendung |
EP1068900A1 (de) * | 1999-07-16 | 2001-01-17 | Degussa-Hüls Aktiengesellschaft | Metallkatalysatoren umfassend hohle Formen |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3075721A1 (de) | 2015-03-30 | 2016-10-05 | Evonik Degussa GmbH | Verfahren zur Herstellung von 3-Aminomethyl-3,5,5-trimethylcyclohexylamin |
CN106008231A (zh) * | 2015-03-30 | 2016-10-12 | 赢创德固赛有限公司 | 制备3-氨基甲基-3,5,5-三甲基环己基胺的方法 |
US9937483B2 (en) | 2015-03-30 | 2018-04-10 | Evonik Degussa Gmbh | Process for preparing 3-aminomethyl-3,5,5-trimethylcyclohexylamine |
Also Published As
Publication number | Publication date |
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CN1483016A (zh) | 2004-03-17 |
US6649799B2 (en) | 2003-11-18 |
WO2002051791A3 (de) | 2002-10-10 |
JP2004516308A (ja) | 2004-06-03 |
US20020173676A1 (en) | 2002-11-21 |
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