CN1185995A - 烯化氧类、醇、醛和酮类胺化用的催化剂 - Google Patents
烯化氧类、醇、醛和酮类胺化用的催化剂 Download PDFInfo
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- CN1185995A CN1185995A CN97122818A CN97122818A CN1185995A CN 1185995 A CN1185995 A CN 1185995A CN 97122818 A CN97122818 A CN 97122818A CN 97122818 A CN97122818 A CN 97122818A CN 1185995 A CN1185995 A CN 1185995A
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- China
- Prior art keywords
- catalyzer
- carrier
- amination
- ammonia
- preferred
- Prior art date
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- 238000005576 amination reaction Methods 0.000 title claims description 24
- 125000002947 alkylene group Chemical group 0.000 title claims description 11
- 150000001299 aldehydes Chemical class 0.000 title claims description 10
- 150000002576 ketones Chemical class 0.000 title claims description 10
- 239000003054 catalyst Substances 0.000 title abstract description 33
- 150000001298 alcohols Chemical class 0.000 title description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000001257 hydrogen Substances 0.000 claims abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 19
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 17
- 239000010941 cobalt Substances 0.000 claims abstract description 17
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 17
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 239000010949 copper Substances 0.000 claims abstract description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 5
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 4
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims abstract description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052737 gold Inorganic materials 0.000 claims abstract description 4
- 239000010931 gold Substances 0.000 claims abstract description 4
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 4
- 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 abstract description 4
- 229910052762 osmium Inorganic materials 0.000 claims abstract description 4
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 4
- 239000011574 phosphorus Substances 0.000 claims abstract description 4
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 4
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 4
- 239000010948 rhodium Substances 0.000 claims abstract description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052701 rubidium Inorganic materials 0.000 claims abstract description 4
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052709 silver Inorganic materials 0.000 claims abstract description 4
- 239000004332 silver Substances 0.000 claims abstract description 4
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 4
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052716 thallium Inorganic materials 0.000 claims abstract description 4
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052718 tin Inorganic materials 0.000 claims abstract description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 4
- 239000010937 tungsten Substances 0.000 claims abstract description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 45
- 229910021529 ammonia Inorganic materials 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 7
- 238000005984 hydrogenation reaction Methods 0.000 claims description 7
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- 150000003141 primary amines Chemical class 0.000 claims description 6
- 238000006424 Flood reaction Methods 0.000 claims description 5
- 150000003335 secondary amines Chemical class 0.000 claims description 5
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052702 rhenium Inorganic materials 0.000 claims description 3
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 2
- DLISVFCFLGSHAB-UHFFFAOYSA-N antimony arsenic Chemical compound [As].[Sb] DLISVFCFLGSHAB-UHFFFAOYSA-N 0.000 claims 1
- ZIXVIWRPMFITIT-UHFFFAOYSA-N cadmium lead Chemical compound [Cd].[Pb] ZIXVIWRPMFITIT-UHFFFAOYSA-N 0.000 claims 1
- VNTLIPZTSJSULJ-UHFFFAOYSA-N chromium molybdenum Chemical compound [Cr].[Mo] VNTLIPZTSJSULJ-UHFFFAOYSA-N 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 150000002367 halogens Chemical class 0.000 claims 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 229960001866 silicon dioxide Drugs 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 238000007598 dipping method Methods 0.000 abstract description 11
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052804 chromium Inorganic materials 0.000 abstract description 4
- 239000011651 chromium Substances 0.000 abstract description 4
- 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 abstract description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052787 antimony Inorganic materials 0.000 abstract description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052785 arsenic Inorganic materials 0.000 abstract description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052793 cadmium Inorganic materials 0.000 abstract description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 abstract description 3
- 150000002739 metals Chemical class 0.000 abstract description 3
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 3
- 239000011733 molybdenum Substances 0.000 abstract description 3
- 229910052700 potassium Inorganic materials 0.000 abstract description 3
- 239000011591 potassium Substances 0.000 abstract description 3
- 229910052708 sodium Inorganic materials 0.000 abstract description 3
- 239000011734 sodium Substances 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 150000004820 halides Chemical class 0.000 abstract description 2
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- XERMIIYGOQTIKJ-UHFFFAOYSA-N [Zn].[Re] Chemical compound [Zn].[Re] XERMIIYGOQTIKJ-UHFFFAOYSA-N 0.000 abstract 1
- 238000001354 calcination Methods 0.000 abstract 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- -1 ruthenium halide Chemical class 0.000 description 39
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 20
- 239000000243 solution Substances 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 229910000765 intermetallic Inorganic materials 0.000 description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 2
- 125000004343 1-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 2
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 2
- NGIISMJJMXRCCT-UHFFFAOYSA-N [Ru].[N+](=O)(O)[O-] Chemical compound [Ru].[N+](=O)(O)[O-] NGIISMJJMXRCCT-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 125000005767 propoxymethyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])[#8]C([H])([H])* 0.000 description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 125000006734 (C2-C20) alkoxyalkyl group Chemical group 0.000 description 1
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 description 1
- MNCMBBIFTVWHIP-UHFFFAOYSA-N 1-anthracen-9-yl-2,2,2-trifluoroethanone Chemical group C1=CC=C2C(C(=O)C(F)(F)F)=C(C=CC=C3)C3=CC2=C1 MNCMBBIFTVWHIP-UHFFFAOYSA-N 0.000 description 1
- 125000004066 1-hydroxyethyl group Chemical group [H]OC([H])([*])C([H])([H])[H] 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 125000003890 2-phenylbutyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006201 3-phenylpropyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004860 4-ethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002853 C1-C4 hydroxyalkyl group Chemical group 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical class OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000005263 alkylenediamine group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000002078 anthracen-1-yl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C([*])=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 125000000748 anthracen-2-yl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C([H])=C([*])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 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
- 230000002508 compound effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
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- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
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- 150000002736 metal compounds Chemical class 0.000 description 1
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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
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
- C07C209/16—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble 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
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
Abstract
一种催化剂含有(wt%按照催化剂的总重量计)在多孔金属氧化物载体上的钴、镍或其混合物>6—50;钌0.001—25;铜0—10;助剂,选自铁,铑,钯,铂0—5;铱,锇,银,金,铬,钼,钨,铼,锌,镉,铅,锰,锡,锂,钠,钾,铷,铯,磷,砷,锑,铋,碲,铊及其混合物。通过下述步骤制备上述催化剂:(a)用金属,助剂或其化合物浸渍载体;(b)干燥和焙烧浸渍的载体,和(c)在氢气流中还原已经焙烧的载体;不用卤化物浸渍载体。
Description
本发明涉及含有钌、镍和/或钴的催化剂,它可用于烯化氧类、醇、醛和酮类的胺化作用。本发明还涉及制备该催化剂的方法,在胺化反应中使用该催化剂以及制备胺化产品的方法。
EP-A2-0 146 508公开了含有钌、镍和/或钴的脱氢/加氢用催化剂。所用的催化剂含有约0.25-1.0wt%的钌,约7.5wt%或10wt%镍,或10wt%钴,或4wt%镍和4wt%钴,上述的含量是按照催化剂的总重量计的且在一种氧化铝载体上。该催化剂还可含有加到镍上的铜和铬,加到镍和钴上的铁。将钌以卤化钌溶液形式加入到催化剂中,在高压釜中使用该催化剂进行氨和单乙醇胺的胺化作用。
EP-A1-0 254 335公开了一种加氢和/脱氢催化剂的制备方法,该催化剂含有约10wt%镍,约0.5wt%的钌,上述的含量是按照催化剂的总重量计的且涂到一种氧化铝载体上。通过用硝酸镍或硝酸钴溶液浸渍载体,然后用含水盐酸浸渍,接着用亚硝酰基硝酸钌溶液浸渍。而不使用卤化钌浸渍载体。在高压釜中使用该催化剂用于氨和单乙醇胺的反应。
公知的催化剂由于浸渍含有了氯化物,在催化剂制备和使用催化剂反应期间,如果在载体上存在氯化物,例如从催化剂中释放出氢氯酸,将会产生腐蚀问题。因此,催化剂的稳定性是不充分的,特别是在EP-A-0 254 335中描述的催化剂。如在EP-A-0 254 335中描述的用含水氢氯酸浸渍载体,因为由于酸附着到氧化物载体上,导致催化剂的机械性能很差。其结果,催化剂的机械性能下降,使催化剂的操作寿命缩短,人们认为这是由于催化剂分解造成的。在单乙醇胺和氨的反应中,所获得的对于1,2-乙二胺的选择性对于连续过程是不足够的。
本发明的目的是提供胺化催化剂,该催化剂克服了已有的催化剂的缺陷,特别不会引起腐蚀,同时具有优良的稳定性以及在用氨和单乙醇胺的胺化作用中对于1,2-乙二胺具有高选择性。
我们已经找到提供含有下列成分的催化剂可实现上述的目的,以催化剂的总重量计: 含有的组分 wt%
钴、镍或其混合物 >6-50
钌 0.001-25
铜 0-10
助剂,选自铁,铑,钯,铂 0-5
铱,锇,银,金,铬
钼,钨,铼,锌,镉
铅,锰,锡,锂,钠
钾,铷,铯,磷,砷
锑,铋,碲,铊或其混合物
上述细分是在多孔的金属氧化物载体上,通过下述步骤制备:
(a)用金属,助剂或其化合物浸渍载体;
(b)干燥和焙烧浸渍的载体,和
(c)在氢气流中还原已经焙烧的载体;
不用卤化物浸渍载体。
优选使用的催化剂载体是一种多孔的金属氧化物,该氧化物选自氧化铝,铝硅酸盐,二氧化钛,二氧化锆,氧化镁及其混合物。优选使用氧化铝载体,特别优选氧化铝组成的载体。
施加到催化剂载体上的钴,镍及其混合物>6-50wt%,优选>6-40wt%,特别优选>6-20wt%。除有其它方面的规定,一般按照催化剂的总重量计。施加到载体上的钴,优选>3-25wt%,较优选>3-20wt%,特别优选>3-10wt%,最优选5-10wt%。施加到载体上的镍,优选>3-25wt%,较优选>3-20wt%,最优选3-10wt%,特别优选5-10wt%。
催化剂而且还含有在载体上的钌为0.001-25wt%,常为0.01-25wt%,优选0.1-10wt%,较优选0.5-5wt%,特别优选0.5-2wt%。
铜可施加到载体上。铜的含量为0-10wt%,优选0.1-10wt%,特别优选0.5-5wt%。
可在载体上的助催化剂为0-5wt%,它们选自铁,铑,钯,铂,铱,锇,银,金,铬,钼,钨,铼,锌,镉,铅,锰,锡,锂,钠,钾,铷,铯,磷,砷,锑,铋,碲,铊及其混合物
特别优选,催化剂含有5-10wt%的钴,5-10wt%的镍,0.5-5wt%的钌和0.5-5wt%的铜。在催化剂中,特别优选镍的含量为7-9wt%,钴的含量为7-9wt%,铜的含量为1.3-1.9wt%,钌的含量为0.5-1.5wt%。
通过加入含有上述助催化剂,催化剂的载体的添加剂控制催化剂的选择性。助催化剂含量优选0.001-5wt%,特别优选0.01-3wt%。
通过下述步骤制备催化剂:
(a)用金属,助剂或其化合物浸渍载体;
(b)干燥和焙烧浸渍的载体,和
(c)在氢气流中还原已经焙烧的载体;
下面将讨论金属和助催化剂,它们一起统称为金属。
通过任意的所需的适宜的方法在步骤(a)中用金属或金属化合物浸渍载体,例如载体可用金属化合物溶液浸渍,载体浸渍也可通过将其喷洒在溶液上或者将载体与溶液混合在一起,或者通过在载体上沉积金属或金属化合物。
含有金属的载体的浸渍优选使用没有卤化物的金属盐溶液的形成,例如可使用硝酸盐,甲酸盐,草酸盐或者氨合物。优选甲酸盐和硝酸盐,特别优选硝酸盐。
不用卤化物浸渍载体,特别是不用金属卤化物或金属卤化物溶液或者如含水氢氯酸溶液的另一类含卤化物溶液浸渍载体。
上述描述的问题是要避免的,从而给出一种优良的催化剂。
用金属或金属盐溶液浸渍催化剂可以任意希望的方法进行,例如催化剂载体可用含有各种金属的盐溶液浸渍,载体还可连续的用多种含有所使用的一种或多种金属的盐类溶液浸渍。所有的或单个浸渍层可被施加(浸渍)几次。也可改变浸渍的次序。在多次浸渍的情况下,特别是几次喷洒溶液或用溶液浸渍载体几次时,溶液中的金属盐的浓度可以保持得很低。还可形成各种溶液或单个溶液的浓度,以作为单个应用的或浸渍的产物在载体上含有所希望量的金属。在用金属或金属化合物的载体浸渍之后,已浸渍载体优选在80-150℃,特别优选在80-120℃下干燥。然后已浸渍的载体在150-500℃,优选300-500℃焙烧。接着已浸渍和焙烧的载体在氢气流中在150-500℃,优选在200-400℃还原。为了这种目的,优选载体在焙烧之后第一次被冷却,作为一种纯净的氢气流或者作为一种稀释的氢气流用作氢气流可用于如氮气的惰性气体中。
也可以称作活化的还原可以直接在后续使用的反应器中进行。如果在一个独立的反应器中进行催化剂的还原,在催化剂从反应器除去之前,催化剂表面被钝化了,优选与含有游离氧的气体混合物一起钝化,其钝化的温度为10-60℃,特别优选20-40℃。在安装在反应器内供合成用的钝化的催化剂可在氢气流中活化,优选在氮气/氢气流中,温度在150-200℃,优选在170-190℃活化。它们还可使用而不用再进一步活化。
可以任意适宜的形状例如压出物状,片状或粉状的压制形使用新催化剂。可用金属或金属化合物浸渍成形的载体,或者浸渍的载体可以是所需的形状。当载体和金属或金属化合物掺合在一起或沉积在一起时,该生成的材料可以压制成基本规则的形状。特别在连续的方法中,可以压制物的形状使用催化剂。
在大量的反应中使用新催化剂,按照本发明,优选催化剂使用在加氢反应中,脱氢反应中或者加氢/脱氢反应中。特别是催化剂用于用氨或伯胺,仲胺胺化烯化氧类,醇,醛或酮类。特别优选催化剂用于胺化醇类,尤其是在用氨和单乙醇胺反应得到乙二胺中。新催化剂在整个较长的时间内表现出机械性能稳定并且不会降低活度。在与具有与高含量的镍和钴的已知催化剂相同的活度相结合,它们还表现出在用氨的胺化作用中,在伯胺化产品的形成中具有较高的选择性。大致说来,它们的寿命延长了,并且不会释放出任意的腐蚀化合物。
本发明还涉及通过在游离氢和在上述催化剂存在下使烯化氧类,醇,醛或酮类与氨或伯胺,或仲胺反应制备胺化产品的方法。
通过下述反应进行胺化作用,所述的反应是氨成伯氨基或仲氨基与羟基,醛或酮基,或烯化氧基反应,经受还原胺化作用并由氨基取代羟基。氨基类和胺化的基类可以以不同的分子或以相同的分子存在。如果彼此待反应的基团以相同的分子存在,环状化合物可以生成。在其中存在有氨基和待胺化的基的化合物可以作为一种胺化化合物、或作为一种待胺化的化合物作用。
例如,特别在单乙醇胺(MEA)和氨的胺化作用中,可以获得乙二胺(EDA),氨乙基乙醇胺(AEEA),二亚乙基三胺(DETA)和哌嗪。
可以使用含有二个或二个以上的羟基,醛基,酮基或烯化氧基的化合物。也可以混合基团存在。特别是可以使用二醇或多元醇,特别是1,2-亚乙基二醇。其它适宜的化合物是那些含有多个伯氨基或仲氨基的化合物,例如亚烷基二胺,特别是1,2-乙二胺。例如1,2-亚乙基二醇或乙醇胺可以与或在氨,乙醇胺,1,2-乙二胺,二亚乙基三胺存在下被胺化。
在本发明的一个实施例中,使用新方法用采由通式(II)的伯醇或仲醇和通式(III)的伯胺或仲胺制备通式(I)的胺;其中,通式(I)为:
R1R2N-CHR3R4 (I)
式中R1,R2,R3和R4独立地是每个氢,C1-C200-烷基,C3-C12-环烷基,取代氨的、取代C1-C20-烷基氨的、取代二-C1-C20-烷基氨的和/或取代羟基的C-1C20-烷基,C2-C30-烷氧基烷基,R5(OCHR6CH2)n,芳基,C7-C20-芳烷基,或CC烷基芳基,或者R1和R2一起形成(CH2)1-X(CH2)m,式中:R5是氢或C1-C4-烷基;
R6是氢或甲基;
X是氧或NR6;
n是2-30的整数;
l是2-4的整数;
m是1-4的整数;
其中,通式(II)为:
R3R4CHOH或R3R4CO (II)
式中R3和R4具有上述的含意;
其中,通式(III)为
R1R2NH (III)
式中R1和R2具有上述的含意;
R1,R2,R3和R4特别是R1和R2可是C1-C200-烷基,优选C1-C8-烷基,例如甲基,乙基,正-丙基,异丙基,正-丁基,异丁基,仲-丁基,叔-丁基,异戊基,仲-戊基,新戊基,1,2-二甲基丙基,正-己基,异己基,仲-己基,正-庚基,异庚基,正-辛基,异辛基,2-乙基己基,正-暌基,2-正-丙基-正-庚基,正-三暌基,2-正-丁基-正-壬基,或3-正-丁基-正-壬基,特别优选异丙基,2-乙基己基,正-暌基,2-正-丙基-正-庚基,正-三暌基,2-正-丁基-正-壬基,或3-正-丁基-正-壬基,或C40-C200-烷基,例如聚丁基,聚异丁基,聚丙基,聚异丙基,或聚乙基,特别优选聚丁基或聚异丁基。
R1和R2一起可以是-(CH2)1-X-(CH2)m,式中X是氧或NR6其含意在以下规定,l是2-4的整数例如2,3或4,优选2或3,特别优选2,m是1-4的整数例如1,2,3或4,优选2,3或4,特别优选2或3。
R1,R2,R3和R4每个可是C3-C12-环烷基,优选C3-C8-环烷基,例如环丙基,环丁基,环戊基,环己基,环庚基,环辛基,特别优选环戊基,环己基或环辛基。
它们可是芳基,例如苯基,1-萘基,2-萘基,1-蒽基,2-蒽基,或9-蒽基,优选苯基,1-萘基或2-萘基,特别优选苯基。
它们可是C7-C20-烷芳基,优选C7-C12-烷苯基,例如2-甲基苯基,3-甲基苯基,4-甲基苯基,2,4-二甲基苯基,2,5-二甲基苯基,2,6-二甲基苯基,3,4-二甲基苯基,3,5-二甲基苯基,2,3,4-三甲基苯基,2,3,5-三甲基苯基,2,3,6-三甲基苯基,2,4,6-三甲基苯基,2-乙基苯基,3-乙基苯基,4-乙基苯基,2-正-丙基苯基,3-正-丙基苯基或4-正-丙基苯基。
它们可是C7-C20-芳烷基,优选C7-C12-苯烷基例如苄基,1-苯基乙基,2-苯基乙基,1-苯基丙基,2-苯基丙基,3-苯基丙基,1-苯基丁基,2-苯基丁基,3-苯基丁基或4-苯基丁基,特别优选苄基,1-苯基乙基或2-苯基乙基。
特别的,R1可是C1-C20-烷基,优选C1-C8-烷基,例如甲基,乙基,正-丙基,异丙基,正-丁基,异丁基,仲-丁基,叔-丁基,正-戊基,异戊基,仲-戊基,新戊基,1,2-二甲基苯基,正-己基,异己基,仲-己基,正-庚基,异庚基,正-辛基,异辛基,特别优选C1-C4-烷基,例如甲基,乙基,正-丙基,异丙基,正-丁基,异丁基,仲-丁基或叔-丁基。
特别的,R3和R4可是C1-C20-羟基烷基,优选C1-C8-羟基烷基,特别优选C1-C4-羟基烷基,例如羟基甲基,1-羟基乙基,2-羟基乙基,1-羟基-正-丙基,2-羟基-正-丙基,3-羟基-正-丙基,或1-羟基甲基乙基,或取代氨的,和/或取代烷基氨的,和/或取代二烷基氨的,和/或取代羟基的C1-C20-烷基,优选C1-C8-烷基,特别优选C1-C4-烷基,例如N-(羟乙基)氨乙基或N-(氨乙基)氨乙基。
它们可是C2-C30-烷氧基烷基,优选C2-C20-烷氧基烷基,特别优选C2-C8-烷氧基烷基,例如甲氧基甲基,乙氧基甲基,正-丙氧基甲基,异丙氧基甲基,正-丁氧基甲基,异丁氧基甲基,仲-丁氧基甲基,叔-丁氧基甲基,1-甲氧基甲基或2-甲氧基甲基,特别优选C2-C4-烷氧基烷基,例如甲氧基甲基,乙氧基甲基,正-丙氧基甲基,异丙氧基甲基,正-丁氧基甲基,异丁氧基甲基,仲-丁氧基甲基,叔-丁氧基甲基,1-甲氧基甲基或2-甲氧基甲基。
它们可是R5-(COHR6CH2)n,式中R5是C1-C4-烷基,例如甲基,乙基,正-丙基,异丙基,正-丁基,异丁基,仲-丁基或叔-丁基,优选甲基,乙基,特别优选甲基,R6是氢或甲基。
n是2-10的整数,优选2-8,例如2,3,4,5,6,7或8,特别优选2,3,4,5或6。
所有的R1-R6基团可是氢。
新方法可以间歇进行,优选连续的进行。优选连续方法在管式反应器中通过细流床或液相法进行。特别在醇的胺化中,采用温度为120-250℃,优选150-190℃,采用压力为150-300巴,优选180-220巴。一般采用温度为80-250℃,采用压力为100-400巴。
在用氨反应中,使用氨作为试剂或作为溶剂,可用1-20优选6-20摩尔氨/摩尔烯化氧,醇,醛或酮。催化剂空速优选为0.05-2.0,特别优选0.1-1.0Kg烯化氧,醇,醛或酮/升催化剂/小时。反应可在水存在下进行,按照总的水的反应混合物可加入高达15wt%。
根据本发明在该方法中新催化剂的用途容许,特别是在单乙醇胺同氨的反应中,1,2-乙二胺的高收率是由于新催化剂的高选择性。
通过新方法得到产品是适宜的,特别是如在US3,275,554,DE-A-21 25 039或DE-A-36 11 230中描述的作为制备燃料添加剂的中间体。根据本发明得到的化合物可用于制备表面活性剂,药物,收成保护剂,以及硫化加速剂。下述实例描述本发明。
实例1
将135g直径为4mm的Al2O3压出物(D10-10,BASF AG,Ludwigshafen生产)竖放在88ml含水浸渍溶液中,上述溶液含有8.88gNiO,8.88gCoO和3.55gCuO,在室温下重复充分的搅拌2小时,在120℃干燥催化剂前体16小时,在400℃焙烧4小时。重复这种工艺。然后将140g这些压出物加入浸渍鼓中并将含有1.57g钌的73.5ml的含水硝酸钌溶液喷洒在其上,整个过程10分钟。以硝酸盐的形式使用镍,钴和铜。
然后在120℃干燥催化剂前体16小时,在400℃焙烧4小时,冷却后,将压出物置于还原设备中,用每小时20升N2冲洗2小时,用速率为20升H2/小时的氢气流以加热速率2℃/分钟将其加热到300℃,在该温度保持20小时,在氮气流中冷却后,用空气/氮气混合物钝化催化剂,最高温度升高20℃是容许的。制备的催化剂含有在氧化铝上有1wt%的钌,7.9wt%的镍,7.9wt%的钴,3.2wt%的铜,单乙醇胺的胺化结果列于表1。在操作时间303小时后催化剂仍然完好无损。
比较例V1
用在EP-AI-254 335中,实例1规定的方法制备催化剂,得到的催化剂含有在氧化铝上有10wt%的镍和0.5wt%的钌(D10-10,来自BASF AG,Ludwigshafen)。单乙醇胺的胺化结果列于表1。在操作时间48小时后催化剂完全粉碎。
比较例V2
用在EP-AI-0 254 335中,实例13规定的方法制备催化剂,得到的催化剂含有在氧化铝上有10wt%的钴和0.5wt%的钌((D10-10,来自BASF AG,Ludwigshafen)。单乙醇胺的胺化结果列于表1。在操作时间48小时后催化剂完全粉碎。
胺化
在实例1,比较例V1和比较例V2的催化剂存在下,进行单乙醇胺的胺化如下:在一容量100ml,长55cm,内径1.5cm的管式反应器内装有50g钝化的催化剂,后者在180℃,用20%体积的氢气/80%体积的氮气然后再用100%体积的氢气第一次活化,在反应温度达到175-195℃后,取决于催化剂的活度,反应器装载有10-30g/h单乙醇胺,20-70g/h氨和3-10升(S.T.P)/h氢。关于组分1,2-乙二胺(EDA),氨乙基乙醇胺(AEEA),二亚乙基三胺(DETA)和哌嗪的转化率和选择性通过气体色谱分析出料确定。催化剂的空速根据单乙醇胺。其结果汇总在下面的表1中。
实例2
使用实例1描述的催化剂。
胺化
在催化剂存在下进行单乙醇胺的胺化如下:在容量1升的管式反应器中在二层之间装有500ml的钝化催化剂,每层含有250mlV2A不锈钢环,操作开始而不用进一步预处理。在反应温度达到155-200℃后,决定于催化剂的活度,反应器装载有130-200g/hMEA,MEA∶NH3=1∶8和用10-50升(S.T.P)/h氢。如上所述进行反应器出料的分析,结果汇总于下面的表1。
表1
MEA=单乙醇胺 AEEA=氨乙基乙醇胺EDA=1,2-乙二胺 DETA=二亚乙基三胺
催化剂来源 | 载体 | 压力(巴) | 温度(℃) | MEA空速(kg/l·h) | NH3/MEA(mol/mol) | 转化率(%) | EDA(%) | AEEA(%) | 哌嗪(%) | DETA(%) |
比较例V1 | Al2O3 | 200 | 175 | 0.45 | 8 | 33.3 | 55.6 | 20.7 | 4.90 | 12.6 |
比较例V2 | Al2O3 | 200200 | 170185 | 0.450.45 | 88 | 32.246.4 | 62.561.8 | 17.915.0 | 2.65.0 | 5.77.4 |
实例1 | Al2O3 | 200 | 170185 | 0.450.45 | 88 | 32.246.4 | 62.561.8 | 17.915.0 | 2.65.0 | 5.77.4 |
实例2 | Al2O3 | 180 | 165 | 0.45 | 8 | 44.4 | 66.5 | 10.6 | 6.3 | 12.1 |
表1结果显示关于1,2-乙二胺,在使用新催化剂时其选择性与使用现有的催化剂比较较高。而新催化剂的稳定性高于对比催化剂的稳定性。
Claims (10)
1.一种催化剂含有(wt%按照催化剂的总重量计)在多孔金属氧化物载体上的
钴、镍或其混合物 >6-50
钌 0.001-25
铜 0-10
助剂,选自铁,铑,钯,铂 0-5
铱,锇,银,金,铬
钼,钨,铼,锌,镉
铅,锰,锡,锂,钠
钾,铷,铯,磷,砷
锑,铋,碲,铊或其混合物
通过下述步骤制备上述催化剂:
(a)用金属,助剂或其化合物浸渍载体;
(b)干燥和焙烧浸渍的载体,和
(c)在氢气流中还原已经焙烧的载体;
不用卤化物浸渍载体。
2.按照权利要求1的催化剂,含有大于3-25wt%的钴,大于3-25wt%的镍。
3.按照权利要求1或2的催化剂,其中多孔的金属氧化物选自氧化铝,二氧化硅,铝硅酸盐,二氧化钛,二氧化锆,氧化镁及其混合物。
4.按照权利要求1-3的任一个催化剂,其中基本没有卤素。
5.一种制备权利要求1-3的任一个催化剂的方法:
(a)用金属,助剂或其化合物浸渍载体;
(b)干燥和焙烧浸渍的载体,和
(c)在氢气流中还原已经焙烧的载体。
6.按照权利要求1-4的任一个催化剂的用途,用于加氢反应,脱氢反应或加氢/脱氢反应。
7.权利要求6的用途,其中加氢/脱氢反应是烯化氧,醇,醛或酮和氨或伯胺或仲胺的胺化。
8.一种制备胺化产品的方法,其特征在于通过在游离氢和权利要求1-3的任一个催化剂存在下使烯化氧,醇,醛或酮与氨或伯胺或仲胺反应制取上述胺化产品。
9.按照权利要求8的方法,其中1,2-亚乙基二醇或乙醇胺同或在氨,乙醇胺,1,2-乙二胺或二亚乙基三胺存在下被胺化。
10.按照权利要求8的方法是连续进行的。
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US20220177410A1 (en) | 2019-03-06 | 2022-06-09 | Basf Se | Method for the production of ethyleneamines |
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US4014933A (en) * | 1969-10-23 | 1977-03-29 | Basf Aktiengesellschaft | Production of amines from alcohols |
US4152353A (en) * | 1977-08-29 | 1979-05-01 | The Dow Chemical Company | Method of producing amines from alcohols, aldehydes, ketones and mixtures thereof |
US4171287A (en) * | 1977-09-23 | 1979-10-16 | Engelhard Minerals & Chemicals Corporation | Catalyst compositions and the method of manufacturing them |
SE457608B (sv) * | 1986-07-11 | 1989-01-16 | Berol Kemi Ab | Foerfarande foer framstaellning av en ruteniumdopad nickel- och/eller koboltkatalysator paa en poroes metalloxidbaerare samt anvaendning av katalysatorn i en hydrerings- och/eller dehydreringsreaktion |
SE461095B (sv) * | 1983-09-09 | 1990-01-08 | Berol Kemi Ab | Amineringsfoerfarande med anvaendning av en ruteniumdopad nickel och/eller kovoltkatalysator |
US4727052A (en) * | 1986-06-27 | 1988-02-23 | Engelhard Corporation | Catalyst compositions and methods of making the same |
GB8819663D0 (en) * | 1988-08-18 | 1988-09-21 | Bp Chem Int Ltd | Chemical process |
US5003107A (en) * | 1989-12-18 | 1991-03-26 | Texaco Chemical Company | Catalytic method for the reductive amination of poly(oxytetramethyle) glycols |
US5352835A (en) * | 1993-02-08 | 1994-10-04 | Texaco Chemical Company | Supported catalysts for amination |
DE4339138A1 (de) * | 1993-11-16 | 1995-05-18 | Basf Ag | Trägerkatalysatoren |
-
1996
- 1996-10-31 DE DE19645047A patent/DE19645047A1/de not_active Withdrawn
-
1997
- 1997-10-21 US US08/955,121 patent/US5958825A/en not_active Expired - Fee Related
- 1997-10-28 EP EP97118717A patent/EP0839575A3/de not_active Withdrawn
- 1997-10-29 JP JP9296886A patent/JPH10174875A/ja not_active Withdrawn
- 1997-10-31 CN CN97122818A patent/CN1185995A/zh active Pending
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Also Published As
Publication number | Publication date |
---|---|
US5958825A (en) | 1999-09-28 |
JPH10174875A (ja) | 1998-06-30 |
EP0839575A3 (de) | 1998-08-12 |
DE19645047A1 (de) | 1998-05-07 |
EP0839575A2 (de) | 1998-05-06 |
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