CN1211347C - 胺化方法 - Google Patents
胺化方法 Download PDFInfo
- Publication number
- CN1211347C CN1211347C CNB988110245A CN98811024A CN1211347C CN 1211347 C CN1211347 C CN 1211347C CN B988110245 A CNB988110245 A CN B988110245A CN 98811024 A CN98811024 A CN 98811024A CN 1211347 C CN1211347 C CN 1211347C
- Authority
- CN
- China
- Prior art keywords
- amination
- metal
- temperature
- weight
- ruthenium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000005576 amination reaction Methods 0.000 title claims abstract description 23
- 229920000768 polyamine Polymers 0.000 claims abstract description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 33
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- 229910052707 ruthenium Inorganic materials 0.000 claims description 10
- 238000005984 hydrogenation reaction Methods 0.000 claims description 9
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 8
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- 229910052702 rhenium Inorganic materials 0.000 claims description 7
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 150000003141 primary amines Chemical class 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 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 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052770 Uranium Inorganic materials 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229910052793 cadmium Inorganic materials 0.000 claims description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052792 caesium Inorganic materials 0.000 claims description 4
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 229910052762 osmium Inorganic materials 0.000 claims description 4
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 239000010948 rhodium Substances 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052701 rubidium Inorganic materials 0.000 claims description 4
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 230000009466 transformation Effects 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims description 2
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 claims 2
- 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 1
- 238000006243 chemical reaction Methods 0.000 abstract description 19
- 239000006227 byproduct Substances 0.000 abstract description 5
- 239000000047 product Substances 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000004383 yellowing Methods 0.000 abstract 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 231100000756 time-weighted average Toxicity 0.000 abstract 1
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 18
- -1 heterocycle amine Chemical class 0.000 description 15
- 229910052799 carbon Inorganic materials 0.000 description 10
- 150000001721 carbon Chemical group 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 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 4
- DPRMFUAMSRXGDE-UHFFFAOYSA-N ac1o530g Chemical compound NCCN.NCCN DPRMFUAMSRXGDE-UHFFFAOYSA-N 0.000 description 4
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 4
- CBFCDTFDPHXCNY-UHFFFAOYSA-N icosane Chemical compound CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 150000003335 secondary amines Chemical class 0.000 description 4
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 3
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- YCOZIPAWZNQLMR-UHFFFAOYSA-N pentadecane Chemical compound CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 description 1
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical group CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 1
- PQXKWPLDPFFDJP-UHFFFAOYSA-N 2,3-dimethyloxirane Chemical group CC1OC1C PQXKWPLDPFFDJP-UHFFFAOYSA-N 0.000 description 1
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 description 1
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 1
- TZYRSLHNPKPEFV-UHFFFAOYSA-N 2-ethyl-1-butanol Chemical compound CCC(CC)CO TZYRSLHNPKPEFV-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- BLFRQYKZFKYQLO-UHFFFAOYSA-N 4-aminobutan-1-ol Chemical compound NCCCCO BLFRQYKZFKYQLO-UHFFFAOYSA-N 0.000 description 1
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 1
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Catalysts (AREA)
Abstract
本发明涉及一种生产多元胺的胺化方法。该方法的目的是增加对直链胺化产物的选择性并防止形成变色副产物或以后可造成变色的副产物。按照该方法,该目的这样实现:在该方法的第一部分,胺化在某个比例时间加权平均温度下进行,达到根据多元胺总量计算50-98%重量的转化率,所述温度高于在剩余部分的比例时间加权平均温度至少15℃。
Description
本发明涉及一种用于生产多元胺的胺化方法。该方法在特定温度条件下进行,从而增加对直链多元胺的选择性并降低颜色。
胺化方法的理想目标是增加直链胺化产物的量并减少形成环状胺化产物。参见例如美国专利2365721和3766184,以及EP-A-146508、EP-A-254335、EP-A-729785和EP-A-737669。
胺化方法的另一理想目标是降低副产物的量,否则会本身造成多元胺变色,或在以后阶段,造成多元胺在用作中间体或用于组合物时变色。已经提出许多降低颜色的方法。例如,美国专利3723529提出用活性炭进行处理,美国专利4347381则提出用漂白剂进行处理。EP-A-262562公开了一种在含氢气氛下,通过将带色的多元胺在升高的温度和压力下与催化有效量的氢化催化剂进行接触而降低颜色的方法。尽管所有这些方法都能降低颜色,但其后处理昂贵且不能防止出现变色。
本发明的目的是增加对直链胺化产物的选择性,同时防止形成变色副产物或以后例如在用酸中和所述胺化产物时可能成为变色源的副产物。此外,解决上述任务的方法不应复杂,也不应造成其它问题。
已经惊人地发现,上述目的可通过在特定温度条件下生产多元胺的胺化方法而实现。更具体地说,在该方法的第一部分,在某个比例时间加权平均温度下,胺化进行至转化度50-98%重量,优选55-95%重量,根据多元胺的总产率计算,所述温度高于剩余部分比例时间加权平均温度至少15℃,优选25-100℃,最优选35-70℃。在本文中,术语“时间加权平均温度”是一种按比例考虑反应时间时的平均温度。
通过本发明方法,提高了直链胺化产物如乙二胺、二亚乙基三胺、三亚乙基四胺和氨乙基乙醇胺的量,同时降低了环状化合物的量。同时,基本上可以减少变色。该方法可在一种配有温度控制装置以实现上述条件的反应器中进行,或可在各自具有温度控制的至少两个单独的反应器中进行。通常,催化剂在整个或多个反应区都不变,但也可在一个或多个反应区中具有不同的脱氢/氢化催化剂,如选择性不同的催化剂。在反应第一部分时的平均温度可以是160-300℃,优选170-230℃;在剩余部分时,该温度为100-190℃,优选110-180℃。
本发明的胺化反应包括用氨或伯胺或仲胺将醇、酚、二醇、链烷醇胺和烯化氧胺化。胺化的化合物应该优选双官能的。氨基上的所有氢原子都可被参与反应的烯化氧、羟基或羰基化合物的烷基所取代,因此反应产物是伯胺、仲胺和叔胺的混合物。如果将化合物如乙二醇和乙醇胺进行胺化,不仅可得到直链二-和多元胺,而且可得到支链二-和多元胺和六元杂环胺如哌嗪、吗啉及其衍生物。
在生产乙二胺时,最理想的产物是主要包含伯和仲氨基的那些。包含叔氨基和杂环的胺化产物一般商业价值较小。本发明方法可惊人地提高对形成伯胺、仲胺和非环状胺化合物的选择性。
用于胺化的烯化氧是亚烷基中具有2-22个碳原子的那些。具体例子是环氧乙烷、1,2-环氧丙烷、1,2-环氧丁烷和2,3-环氧丁烷。可在本发明方法中胺化的脂族醇包括具有1-30个碳原子的饱和脂族一元醇和多元醇。饱和一元醇的例子为甲醇、乙醇、丙醇、异丙醇、正丁醇、仲丁醇、叔丁醇、异丁醇、正戊醇、异戊醇、新戊醇、正己醇、异己醇、2-乙基己醇、环己醇、正庚醇、正辛醇、2-辛醇、异辛醇和叔辛醇以及壬醇、癸醇、十一烷醇、十二烷醇、十三烷醇、十四烷醇、十六烷醇和十八烷醇和二十烷醇的各种异构体。具有2-30个碳原子的脂族二元醇的例子包括乙二醇、二甘醇、三甘醇、四甘醇、和高级聚乙二醇(polyethylene glycols)、1,2-和1,3-丙二醇、双丙甘醇、三丙甘醇和高级聚丙二醇(polypropylene glycols)、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、2,3-丁二醇、二亚丁基二醇、三亚丁基二醇或高级多亚丁基二醇,以及戊二醇、己二醇、辛二醇、壬二醇、癸二醇、十一烷二醇、十二烷二醇和十三烷二醇、十四烷二醇、十五烷二醇、十六烷二醇、十八烷二醇、二十烷二醇的异构体。具有3-30个碳原子的三元醇或高级多元醇的例子包括甘油、赤藓醇、季戊四醇、山梨醇、甘露醇、三羟甲基乙烷、三羟甲基丙烷、庚三醇和癸三醇。
适用于胺化的酚类化合物包括苯酚、邻甲酚、间甲酚、对甲酚、邻苯二酚、间苯二酚、对苯二酚以及二甲苯酚的异构体。合适的脂族氨基醇是具有2-30个碳原子的那些,如单乙醇胺、二乙醇胺、氨乙基乙醇胺、丙醇胺、丁醇胺、戊醇胺、己醇胺、庚醇胺、辛醇胺、癸醇胺、十二烷醇胺、十四烷醇胺、十六烷醇胺、十八烷醇胺和二十烷醇胺。此外,可以采用包含羟基的任何前述化合物的混合物,例如乙二醇与单乙醇胺的混合物或通过烯化氧与氨的反应而得到的链烷醇胺的混合物。
胺化剂可以是氨、伯胺或仲胺。这些胺一般具有1-20个碳原子的烷基、5-8个碳原子的环烷基或6-40个碳原子的芳基或芳烷基或其混合形式。合适的胺的例子为甲胺、乙胺、正丁胺、异丁胺、乙二胺、苄胺、二甲胺和二乙胺。胺化剂可单独或结合使用。
用于本发明方法的脱氢/氢化催化剂可以是任何常规胺化催化剂。通常,该催化剂包含至少一种金属作为催化活性部分,所述金属选自镍、铬、钴、铜、钌、铁、钙、镁、锶、锂、钠、钾、钡、铯、钨、银、锌、铀、钛、铑、钯、铂、铱、锇、金、钼、铼、镉、铅、铷、硼和锰、及其混合形式。催化剂的金属部分应该包含至少70%重量,优选80%重量以上的镍、铬、钴、铜、钯、钌或铁或其混合物,主要起脱氢/氢化催化作用。通过存在少量其它金属可促进所述催化效果,例如可提高对所需产物的选择性,这些其它金属选自钙、镁、锶、锂、钠、钾、钡、铯、钨、铁、钌、锌、铀、钛、铑、钯、铂、铱、锇、银、金、钼、铼、镉、铅、铷、硼和锰。这些助催化剂通常占催化金属总量的0.1-30%重量,优选1-20%重量。催化金属通常由多孔金属氧化物载体承载,但也可采用其它类型的载体如碳。合适的载体材料的例子为各种形式的氧化铝、二氧化硅、硅藻土、氧化铝-二氧化硅、氧化铝-二氧化钛、氧化铝-氧化镁和氧化铝-氧化锆。载体通常占整个催化剂的50-97%重量。在一个优选实施方案中,催化剂是一种在含氧化铝的多孔金属氧化物载体上的金属催化剂,其中包含金属形式的镍且被钌、铼、钯或铂或其混合物所促进。催化剂的量并不严格,但在间歇式方法中,通常为起始反应物总量的0.1-25%重量,优选1-15%重量。上述脱氢/氢化催化剂可例如参见EP-A-146508、EP-A-729785、EP-A-737669、美国专利2365721和美国专利4123462。
胺化剂与欲胺化的化合物间的反应最好在氢气的存在下进行,这样可抑制或减少催化剂的中毒,而且可以保证所需脂族胺产物达到高产率。一般来说,所需的氢气量较少,相当于每摩尔欲胺化的化合物约0.1至约2摩尔的比率。可以使用较高量的氢气,但一般不会有任何显著的有益效果。氨之类的胺化剂应该在该混合物中过量,例如该比率为2-30摩尔胺化剂/摩尔欲胺化的化合物,但优选5至约15摩尔/摩尔欲胺化的化合物。
胺化工艺优选在较高压力下进行。所施加的压力取决于反应物的摩尔比、反应温度、氢气的量以及操作类型。一般来说,压力应该足够高以保持大多数反应物为液相。该压力一般为8-40Mpa,优选为15-30Mpa。
本发明通过以下实施例进一步说明。
实施例1
在脱氢/氢化催化剂和氢气的存在下,在第一反应步骤中,将单乙醇胺与氨以1∶4的重量比连续反应,进行胺化工艺。按照欧洲专利254335,该催化剂承载在活性氧化铝载体上,包含10%重量镍和0.75%重量钌。第一反应步骤的反应温度为200℃,55%重量的单乙醇胺转化成胺化产物。在随后的反应步骤中,反应温度降至170℃,且在与第一步骤相同的脱氢/氢化催化剂的存在下,以间歇方式继续进行该反应以使单乙醇胺的转化率达到75%。这意味着,第一反应步骤的转化率达到约73%重量。
作为对比试验,分两步进行如上相同的反应至75%的单乙醇胺转化率,只是第二步骤的温度也是200℃。分析反应产物的乙二胺(EDA)、哌嗪(PIP)、二亚乙基四胺(DETA)、氨乙基乙醇胺(AEEA)的量以及哌嗪化合物的总量。
从反应混合物中去除氨和氢气,然后以1∶1的重量比用水稀释。加入氢氯酸至pH值3.5,然后按照Hazen方法来测定变色情况。
得到以下结果。
表1
方法 | 量,%重量 | 颜色Hazen | ||||
EDA | PIP | DETA | AEEA | 总PIP | ||
本发明 | 46.7 | 17.2 | 15.5 | 10.3 | 20.4 | 150 |
对比 | 52.6 | 19.9 | 11.6 | 7.8 | 23.1 | 320 |
从这些结果显然看出,与对比例相比,在本发明的工艺中,环状哌嗪化合物的形成减少了约12%重量。此外,可显著降低颜色。
实施例2
按照实施例1的相同方式进行胺化反应。但用于第二步骤的催化剂包含15%重量的金属镍或15%重量的金属镍,在一些实例中用0.75%重量的钌、钯、铼或铂来促进。另外进行对比试验,同样将第二步骤的温度保持在200℃。
反应之后,按照实施例1的相同方式测定所得胺化混合物的含量和变色情况。
得到以下结果。
表2
试验 | 辅助催化剂 | 量,%重量 | 颜色Hazen | ||||
EDA | PIP | DETA | AEEA | 总PIP | |||
12345 | -RuRePtPd | 51.552.352.746.844.2 | 16.516.720.217.719.3 | 14.714.512.615.216.0 | 8.27.86.98.78.4 | 19.319.523.421.223.1 | 52587613232 |
ABCDE | -RuRePtPd | 49.753.451.150.849.0 | 23.217.723.019.920.8 | 11.113.010.212.512.5 | 5.57.36.57.17.1 | 28.821.127.723.624.9 | 6812012835060 |
从这些结果显然看出,与对比例(试验A-E)相比,如果按照本发明(试验1-5)进行操作,可同时降低哌嗪混合物的总量和颜色。
Claims (10)
1.一种在催化有效量的脱氢/氢化催化剂的存在下生产多元胺的胺化方法,其特征在于,在该方法的第一部分,所述胺化在某个比例时间加权平均温度下进行,达到根据多元胺总量计算50-98%重量的转化率,所述温度高于在剩余部分反应时间内的比例时间加权平均温度至少15℃。
2.根据权利要求1的方法,其特征在于,第一部分时的温度比剩余部分时的温度高25-100℃。
3.根据权利要求1的方法,其特征在于,第一部分时的温度为160-300℃,且剩余部分时的温度为100-190℃。
4.根据权利要求1的方法,其特征在于,所述多元胺通过用氨或伯胺或仲胺将醇、酚、二醇、链烷醇胺和烯化氧胺化而得到。
5.根据权利要求4的方法,其特征在于,所述方法是一种用氨胺化单乙醇胺的胺化方法。
6.根据权利要求1-5任一项的方法,其特征在于,所述脱氢/氢化催化剂包含至少一种金属作为催化活性部分,所述金属选自镍、铬、钴、铜、钌、钙、镁、锶、锂、钠、钾、钡、铯、钨、铁、锌、铀、钛、铑、钯、铂、铱、锇、银、金、钼、铼、镉、铅、铷、硼和锰,或其混合物。
7.根据权利要求6的方法,其特征在于,所述催化剂的金属部分包含至少70%重量的选自镍、铬、钴、铜、钯、钌或铁或其混合物的金属。
8.根据权利要求7的方法,其特征在于,所述催化剂用占金属总量的1-20%的选自钙、镁、锶、锂、钠、钾、钡、铯、钨、铁、钌、锌、铀、钛、铑、钯、铂、铱、锇、银、金、钼、铼、镉、铅、铷、硼、和锰的金属来促进。
9.根据权利要求6的方法,其特征在于,所述金属承载在多孔金属氧化物载体上。
10.根据权利要求6的方法,其特征在于,所述催化剂含有承载在含氧化铝的多孔金属氧化物上的用钌、铼、钯或铂或其混合物促进的金属镍。
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SE97041164 | 1997-11-11 | ||
SE9704116-4 | 1997-11-11 | ||
SE9704116A SE513250C2 (sv) | 1997-11-11 | 1997-11-11 | Amineringsförfarande för framställning av polyaminer |
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PL (1) | PL192835B1 (zh) |
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SA (1) | SA99191259B1 (zh) |
SE (1) | SE513250C2 (zh) |
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DE10359811A1 (de) * | 2003-12-19 | 2005-07-21 | Basf Ag | Verfahren zur Erhöhung der Raum-Zeit-Ausbeute (RZA) in einem Verfahren zur Herstellung eines symmetrischen sekundären Amins |
JP4972315B2 (ja) * | 2005-12-28 | 2012-07-11 | 花王株式会社 | 含窒素化合物の製造方法 |
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US20100240894A1 (en) * | 2007-08-29 | 2010-09-23 | Basf Se | Method for producing amines from glycerin |
EP2231583B1 (en) * | 2008-01-03 | 2015-08-05 | Akzo Nobel N.V. | Process to prepare ethylene amines |
EP2352585B1 (en) * | 2008-10-06 | 2020-06-17 | Union Carbide Corporation | Low metal loaded, alumina supported, catalyst compositions and amination process |
BRPI0914054A2 (pt) * | 2008-10-06 | 2015-11-03 | Union Carbide Chem Plastic | método para produzir etilenoaminas |
CN102171178B (zh) | 2008-10-06 | 2015-07-29 | 联合碳化化学品及塑料技术公司 | 乙二胺和其它乙撑胺的连续氨基转移 |
ES2433422T3 (es) | 2008-10-06 | 2013-12-11 | Union Carbide Chemicals & Plastics Technology Llc | Métodos para preparar triaminas N-aminofuncionales cíclicas |
EP2340113B1 (en) * | 2008-10-06 | 2020-06-03 | Union Carbide Corporation | Low metal (nickel and rhenium) catalyst compositions including acidic mixed metal oxide as support |
DE102011004465A1 (de) * | 2010-09-10 | 2012-03-15 | Evonik Degussa Gmbh | Verfahren zur direkten Aminierung sekundärer Alkohole mit Ammoniak zu primären Aminen |
CN102091641B (zh) * | 2010-12-03 | 2012-12-19 | 烟台万华聚氨酯股份有限公司 | 一种负载型银钴或银镍还原氨化催化剂及其制备方法和用途 |
DE102011003595B4 (de) * | 2011-02-03 | 2014-04-17 | Evonik Degussa Gmbh | Herstellung von in ihrer Hauptkette linearen primären Diaminen für Polyamidsynthesen |
CN102614895B (zh) * | 2012-03-04 | 2013-11-13 | 浙江大学 | 一正丙胺歧化反应合成二正丙胺的方法和所用催化剂 |
KR101439431B1 (ko) * | 2012-09-27 | 2014-09-11 | 롯데케미칼 주식회사 | 환원성 아민화 반응용 코발트-이트륨계 담지 촉매 및 이를 사용한 폴리에테르아민 화합물의 제조 방법 |
EP3077444B1 (en) | 2013-12-02 | 2018-04-25 | Dow Global Technologies LLC | Preparation of high molecular weight, branched, acyclic polyalkyleneamines and mixtures thereof |
TWI534131B (zh) | 2014-11-27 | 2016-05-21 | 財團法人工業技術研究院 | 氫化4,4’-二胺基二苯甲烷的觸媒與方法 |
JP2020530455A (ja) | 2017-08-11 | 2020-10-22 | ヌーリオン ケミカルズ インターナショナル ベスローテン フェノーツハップNouryon Chemicals International B.V. | 環式アルキレン尿素をそれらの対応するアルキレンアミンに変換するマルチステップ方法 |
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