CN108014821A - A kind of catalyst for synthesizing polyether amine and its preparation method and application - Google Patents
A kind of catalyst for synthesizing polyether amine and its preparation method and application Download PDFInfo
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- CN108014821A CN108014821A CN201711251017.4A CN201711251017A CN108014821A CN 108014821 A CN108014821 A CN 108014821A CN 201711251017 A CN201711251017 A CN 201711251017A CN 108014821 A CN108014821 A CN 108014821A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 148
- 229920000570 polyether Polymers 0.000 title claims abstract description 62
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 47
- 150000001412 amines Chemical class 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910018162 SeO2 Inorganic materials 0.000 claims abstract description 19
- 238000006703 hydration reaction Methods 0.000 claims abstract description 7
- 150000002822 niobium compounds Chemical class 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 239000001257 hydrogen Substances 0.000 claims description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims description 27
- 229920005862 polyol Polymers 0.000 claims description 27
- 150000003077 polyols Chemical class 0.000 claims description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- NTVYFDOMBHOLGP-UHFFFAOYSA-N gold nitric acid Chemical compound [Au].O[N+]([O-])=O NTVYFDOMBHOLGP-UHFFFAOYSA-N 0.000 claims description 9
- MCAHWIHFGHIESP-UHFFFAOYSA-N selenous acid Chemical compound O[Se](O)=O MCAHWIHFGHIESP-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 claims description 6
- WPCMRGJTLPITMF-UHFFFAOYSA-I niobium(5+);pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Nb+5] WPCMRGJTLPITMF-UHFFFAOYSA-I 0.000 claims description 6
- DDYSHSNGZNCTKB-UHFFFAOYSA-N gold(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Au+3].[Au+3] DDYSHSNGZNCTKB-UHFFFAOYSA-N 0.000 claims description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- MJPUVFCFWDNTML-UHFFFAOYSA-N carbonic acid;niobium Chemical compound [Nb].OC(O)=O MJPUVFCFWDNTML-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- TYOIKSXJQXGLFR-UHFFFAOYSA-N niobium nitric acid Chemical compound [Nb].[N+](=O)(O)[O-] TYOIKSXJQXGLFR-UHFFFAOYSA-N 0.000 claims description 4
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- 150000002815 nickel Chemical class 0.000 claims description 3
- 239000010955 niobium Substances 0.000 claims description 3
- 229910052711 selenium Inorganic materials 0.000 claims description 3
- 239000011669 selenium Substances 0.000 claims description 3
- 229940091258 selenium supplement Drugs 0.000 claims description 3
- 150000005846 sugar alcohols Polymers 0.000 claims description 3
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- MBTAJVUPEWSQLE-UHFFFAOYSA-N chloro hypochlorite;selenium Chemical compound [Se].ClOCl MBTAJVUPEWSQLE-UHFFFAOYSA-N 0.000 claims description 2
- RNGFNLJMTFPHBS-UHFFFAOYSA-L dipotassium;selenite Chemical compound [K+].[K+].[O-][Se]([O-])=O RNGFNLJMTFPHBS-UHFFFAOYSA-L 0.000 claims description 2
- BVTBRVFYZUCAKH-UHFFFAOYSA-L disodium selenite Chemical compound [Na+].[Na+].[O-][Se]([O-])=O BVTBRVFYZUCAKH-UHFFFAOYSA-L 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical class Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 claims description 2
- 230000036571 hydration Effects 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims description 2
- 229960001471 sodium selenite Drugs 0.000 claims description 2
- 235000015921 sodium selenite Nutrition 0.000 claims description 2
- 239000011781 sodium selenite Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- 150000003839 salts Chemical class 0.000 claims 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 238000007598 dipping method Methods 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- 229910052799 carbon Inorganic materials 0.000 abstract description 6
- 238000005245 sintering Methods 0.000 abstract description 6
- 229910052737 gold Inorganic materials 0.000 abstract description 5
- 238000003746 solid phase reaction Methods 0.000 abstract description 3
- 238000010671 solid-state reaction Methods 0.000 abstract description 2
- 239000010931 gold Substances 0.000 description 17
- 238000005576 amination reaction Methods 0.000 description 13
- 229910052802 copper Inorganic materials 0.000 description 13
- 239000010949 copper Substances 0.000 description 13
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 description 10
- 230000002779 inactivation Effects 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910052593 corundum Inorganic materials 0.000 description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 description 8
- 208000012839 conversion disease Diseases 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000004176 ammonification Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 238000006356 dehydrogenation reaction Methods 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 150000002466 imines Chemical class 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000004570 mortar (masonry) Substances 0.000 description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- 238000007873 sieving Methods 0.000 description 5
- 239000009261 D 400 Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- -1 polyoxy Polymers 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 229910052727 yttrium Inorganic materials 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- WEZFSPBRWBWQSI-UHFFFAOYSA-N niobium sulfuric acid Chemical compound [Nb].S(O)(O)(=O)=O WEZFSPBRWBWQSI-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 238000006268 reductive amination reaction Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 3
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000001994 activation Methods 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011437 continuous method Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229910006415 θ-Al2O3 Inorganic materials 0.000 description 2
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 1
- GODZNYBQGNSJJN-UHFFFAOYSA-N 1-aminoethane-1,2-diol Chemical compound NC(O)CO GODZNYBQGNSJJN-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910018054 Ni-Cu Inorganic materials 0.000 description 1
- 229910018481 Ni—Cu Inorganic materials 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate group Chemical group [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- SFNALCNOMXIBKG-UHFFFAOYSA-N ethylene glycol monododecyl ether Chemical compound CCCCCCCCCCCCOCCO SFNALCNOMXIBKG-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 150000002924 oxiranes Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 229940065287 selenium compound Drugs 0.000 description 1
- 150000003343 selenium compounds Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0573—Selenium; Compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- 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
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
- C08G65/325—Polymers modified by chemical after-treatment with inorganic compounds containing nitrogen
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of catalyst for synthesizing polyether amine, it includes NbAlO4NiO, the Au of carrier and load on the carrier2O3And SeO2Wherein, based on overall catalyst weight, the content of active component NiO is 1 15wt%, Au to active component in catalyst2O3Content be 0.01 2wt%, SeO2Content be 0.01 1wt%, NbAlO4Carrier containing the solid-state reaction between niobium compound and aluminium oxide by preparing.Preparation method invention additionally discloses above-mentioned catalyst and the application in synthesizing polyether amine, especially low molecular polyether amine.The catalyst of the present invention, can show high activity, high selectivity, high stability, excellent anti-hydration, anti-carbon and anti-sintering property in.
Description
Technical field
The present invention relates to polyetheramine preparation field, and in particular to a kind of improved catalyst for synthesizing polyether amine and its
Preparation method, and carry out in polyether polyol facing the application in hydrogen aminating reaction synthesizing polyether amine.
Background technology
It is molecule master that polyetheramine, which is also known as amine terminated polyether (Amino-Terminated Polyether, abbreviation ATPE),
Chain is polyether skeleton, and end is by amino-terminated polyoxyalkylene compounds.These amine terminated polyethers are mostly with polyethers (poly- second two
Alcohol, polyethenoxy ether etc.) it is reaction raw materials, by different chemical treatment methods, the end position hydroxyl of polyether polyol is changed into
Corresponding amido or amino (end position group is typically the primary amine groups containing active hydrogen, secondary amine or more amidos).Due to polyethers
The reactivity of skeleton end position Amino End Group or amido, this can be acted on a variety of reactive groups, such as epoxide group and different
Cyanate group etc.；Further, since in polyether chain ehter bond presence, and cause its be soluble in gas chromatography, this is widened significantly
Application range of the polyetheramine in industrial circle.Therefore, polyetheramine is widely used in epoxy resin and is consolidated with its superior performance
The fields such as agent, polyurethane (polyureas) industry and cleaning dispersant for gasoline.
The synthetic method of polyetheramine mainly has reductive amination method, leaving group method and polyethers nitrile reduction method.Wherein, amine is reduced
Change method also referred to as faces hydrogen amination method, and the process route is the most advanced, while the product quality produced is stablized the most, and more meets
The requirement of environmental protection, therefore become the industrialized main production process of domestic and international polyetheramine.
And the key of the production technology is that the selection and preparation of catalyst.Suitable for the catalyst bag of reductive amination
Containing metal such as Ni, Co and Cu as active component, sometimes referred to as hydrogenation/dehydrogenation catalyst, because they are two kinds of
It is active in reaction.Other elements in the periodic table of elements are also incorporated into the catalyst often, so that the catalyst
With optimal active or selective.
US4014933 discloses a kind of aluminium oxide or silicon dioxide carried Co-Ni-Cu catalyst and for polypropylene glycol amine
The method of change.Catalyst includes 10%Co, 10%Ni, 4%Cu and 0.4% phosphoric acid, remaining is Al2O3.The catalyst is suitable for dividing
The aminating reaction of polyether polyol of the son amount more than 1400.
US4152353 and US4153581 disclose a kind of alumina load Ni, Cu and in Fe and Zn auxiliary agents one
The catalyst of kind or two kinds of metals, the catalyst include 30%Ni (or 30%Co), 63%Cu and 7%Fe and/or Zn, remaining
For Al2O3.There is active low, poor selectivity problem in the catalyst.
US4209424 discloses a kind of alumina load transition metal amination catalysis and uses it for polyether polyol
Amination, the catalyst include at least one or both of Ni, Co and Cu, wherein, tenor accounts for 30-70%, remaining is
Al2O3。
US4973761 discloses a kind of alumina load Ni, Co and Cu amination catalysis and uses it for PolyTHF
The amination of ether glycol.The catalyst is suitable for molecular weight between the amination of the polyether polyol of 640-4000, and there are catalyst work
The problem of property is low, selectivity of product is poor.
US5003107 discloses a kind of alumina load Ni, Cu, Cr, Mo amination catalysis and uses it for the Asia of polyoxy four
The amination of methyl glycol.The catalyst includes 70-75%Ni, 20-25%Cu, 0.5-5%Cr and 1-5%Mo, remaining is Al2O3。
Use serialization tubular reactor, in the PolyTHF polyethers ammonifying process that molecular weight is 1000 and 2000, raw material conversion
Rate reaches 91-96%, selectivity of product 92-97%.The catalyst is not directed to the amination of polyether polyol of the molecular weight less than 500.
CN102780571 discloses a kind of Al2O3The preparation method of loaded catalyst.Based on catalyst total amount, Ni contents
For 16-22%, Co content be 17-21%, Cu content be 9-11%, Sn content be 0.5-2%, yttrium, lanthanum, cerium and/or hafnium content
For 0.5-2%, remaining is Al2O3。
CN106669731A discloses a kind of Al2O3The preparation method of loaded catalyst.Based on catalyst total amount, activity
Component Ni contents be 5wt%-30wt%, Cu content be 5-25%, Pd content be 0.3-2.0%, auxiliary agent V, Cr, Mn, Fe, Co,
Zn, Mo, W, Sn, Pb, Bi, La, Ce, Nd and/or Sm content are 0-5%, remaining is Al2O3。
Above-mentioned loaded catalyst common problem：Catalyst in use its activity with usage time
Increase and reduce, is i.e. catalyst inactivation.Cause the factor of catalyst inactivation very much, influence, the reaction of raw material impurity can be attributed to
Inactivation caused by the change of catalytic component and structure, such as poisoning, carbon distribution, blocking, sintering in the influence of condition and reaction process
With the various factors such as heat inactivation.The deactivation cause of synthesizing polyether amine loaded catalyst can be attributed to following three aspects：
(1) according to reaction mechanism, the synthesis of polyetheramine generally comprises dehydrogenation, ammonification, dehydration, hydrogenation, and amination is anti-
There is the generation of a large amount of water during answering.Patent US4766245 point out Raney's nickel/Al catalysts deactivation rate and reaction in produce
The amount of water is directly proportional, and compared with the polyethers of high molecular weight, the polyethers of low molecular weight produces more water during the reaction, catalysis
Agent inactivates faster.And in high temperature, high pressure and under having the reaction condition of water, with γ-Al2O3Water again can occur for the catalyst of carrier
Phenomenon is closed, so as to cause the microstructure of catalyst to change, causes declining for catalyst strength or even collapsing for skeleton structure
Fall into, blockage of the micro orifice, pore volume reduces, and specific surface area of catalyst significantly declines, so that catalyst produces irreversible inactivation.Cause
This, γ-Al2O3Rehydrated problem be to cause first factor of catalyst inactivation.
(2) according to reaction mechanism, the aminating reaction in the presence of hydrogenation catalyst and hydrogen is a dehydrogenation/be hydrogenated with
Journey, i.e. alcohol dehydrogenation generation aldehydes or ketones first, then react generation imines, imines is reduced under the action of hydrogenation catalyst with ammonia
Into primary amine, primary amine generates corresponding secondary amine and tertiary amine with carbonyls by Schiff base intermediate.Acted in hydrogenation catalyst
Under, oligomerisation easily occurs for the imines of generation and polymerisation forms the second factor that carbon distribution is the inactivation for causing catalyst.
(3) the 3rd factor of catalyst inactivation is sintering.Active ingredient copper is low-melting-point metal, is melted when temperature reaches it
Point 30% when, easily sinter so that particle diameter increase, surface area reduction, cause catalyst inactivation.
For Catalysts Deactivation Problems, domestic and international researcher has carried out the study on the modification of catalyst.
US5352835 discloses a kind of preparation method of the alumina supported catalyst of mechanically stable phase, by catalyst
Total amount meter, Ni contents are that 15-30%, Cu content are that 3-20%, Mo content are 0.5-1%, and carrier is θ-Al2O3.The carrier by
γ-Al2O3Obtained by high-temperature roasting, there is preferable stability.But there are problems with for catalyst preparation process：(1) carry
The pore-size distribution of body requires harshness, and it is big to prepare the carrier difficulty met the requirements.(2) prepared, impregnated using molte-salt synthesis
Exist to saltout in journey and cause carrier duct blockage problem.(3) content of metal is high, and metal dispersion is uneven, and it is difficult to there is preparation
And the problem of metal loss.
US20140179952 discloses a kind of CoO-Y2O3The preparation method of-PdO catalyst and its loaded catalyst, is pressed
Catalyst total amount meter, the content of CoO is 57-90%, Y in the catalyst2O3Content be that the content of 9-17%, PdO is 0.9-
25.7%.Patent points out that cobalt and yttrium are high to the compatibility of the compatibility comparison water of amine compounds and hydrogen in catalyst, therefore this is urged
Agent has preferable stability.But there are problems with for catalyst：(1) coprecipitation preparation process is used, there are technique to answer
It is miscellaneous, poor reproducibility problem.(2) cobalt containing high-content, rare metal yttrium and precious metal palladium in catalyst, and support type is urged
In agent the content of active component also be up to 50% (by weight), there are catalyst it is of high cost the problem of.(3) catalyst
For batch technology, continuous processing application example is not directed to.
The catalyst of the above-mentioned prior art is born in anti-hydration, anti-carbon and anti-sintering property and preparation process, metal
The one or more aspects such as carrying capacity, catalyst cost need to further improve.Meanwhile prior art catalyst is for low molecular weight
The catalyst stability that the aminating reaction of the polyether polyol of polyether polyol, especially average molecular weight less than 500 is shown
It is not ideal enough.
The content of the invention
It is an object of the present invention to provide a kind of improved catalyst for synthesizing polyether amine, by active oxidation
Aluminium is modified processing, with overcome it is existing face the shortcomings that hydrogen amination catalyst anti-hydration is poor, while catalyst activity it is high,
Selectivity is good.
The catalyst for synthesizing polyether amine of the present invention includes NbAlO4Carrier and load are on the carrier
NiO、Au2O3And SeO2Active component.
Preferably, based on overall catalyst weight, the content of active component NiO is 1-15wt%, Au in catalyst2O3Content
For 0.01-2wt%, SeO2Content be 0.01-1wt%.
It is highly preferred that in terms of overall catalyst weight, the content of active component NiO is 5-10wt%, Au2O3Content 0.5-
1.5wt%, SeO2Content be 0.1-0.5wt%.
Another aspect of the present invention is to provide the preparation method of above-mentioned catalyst, includes the following steps：
(1) NbAlO is prepared4Carrier：By being prepared containing the solid-state reaction between niobium compound and aluminium oxide, niobium chemical combination will be contained
Thing is uniformly mixed with aluminium oxide, and dry, roasting, shaping obtain carrier, are optionally ground, sieve before the drying；
(2) catalyst is prepared：Formed according to the content of catalyst, the carrier impregnation that step (1) is obtained is containing solvable
Property nickel salt, gold salt and selenium-containing compound aqueous solution in, it is dry after balance to be adsorbed, roast and obtain catalyst, be preferably etc.
Volume impregnation.
In the step (1) nitric acid niobium, sulfuric acid niobium, niobium hydroxide, niobium oxalate and carbonic acid niobium can be selected from containing niobium compound
In one or more, preferably niobium hydroxide and/or niobium oxalate.
In the step (1) in screening process, the mesh number of solid powder is preferably controlled in the range of 100-200 mesh.
Calcination temperature can be 700-1500 DEG C, preferably 900-1100 DEG C in the step (1)；Roasting time is 10-
40h, preferably 20-30h.
Nickel salt can be excellent selected from the one or more in sulfate, nitrate and acylate described in the step (2)
Select nitrate；Gold salt can be selected from the one or more in nitric acid gold, chlorauride and four hydration gold chlorides, preferably nitric acid gold；Contain
Selenium compound can be selected from the one or more in selenous acid, sodium selenite, potassium selenite, dichloro oxygen selenium, preferably selenous acid.
In the step (2) calcination temperature be 100-600 DEG C, preferably 300-500 DEG C, roasting time 1-24h, preferably 8-
16h。
Another aspect of the object of the invention is to provide above-mentioned catalyst and carries out facing the conjunction of hydrogen aminating reaction in polyether polyol
Into the application in polyetheramine.The catalyst of the present invention is especially suitable for anti-as the reduction amination of the polyalcohol of skeleton unit using polyethers
Should, the polyether polyol preferably comprises ethylene oxide (EO) and/or propylene oxide (PO) skeleton, and average molecular weight is 100-
5000, preferred molecular weight 200-600.The polyether polyol contains two or more hydroxyl.
Certainly, it will be appreciated by those skilled in the art that before polyetheramine is catalyzed and synthesized, it is also necessary to which the catalyst is reduced
Activation process, such as reduction activation is carried out under pure hydrogeneous atmosphere at 220 DEG C or so, for example, in hydrogen atmosphere in 150~
Reductase 12~24h, preferably 8~16h at 500 DEG C, preferably 200~400 DEG C.
Present invention also offers the method for synthesizing polyether amine, this method includes, and under above-mentioned catalyst action, utilizes polyethers
Polyalcohol carries out facing hydrogen aminating reaction synthesizing polyether amine.In a preferred embodiment, using continuity method fixed-bed process, lead to
Enter the ammonia of 5~30 times of polyether polyol mole, the hydrogen that 0.1~10 times of polyether polyol mole, is 180 in reaction temperature
~240 DEG C, reaction pressure carries out facing hydrogen aminating reaction under the conditions of being 10.0~18.0MPa.
In the application, " optionally " represents to carry out or without follow-up operation.
The beneficial effects of the present invention are：The catalyst of the present invention is applicable not only to the amine of the polyether polyol of macromolecule
Change reaction, there is high activity, selectivity particularly with the aminating reaction of low molecular weight (molecular weight is less than 500) polyether polyol
And stability.Using catalyst Aethoxy Sklerol aminating reaction of the present invention, particularly it is less than 500 for being catalyzed average molecular weight
The amination of polyether polyol, aminated product yield can reach more than 99.0%, and feed stock conversion can reach more than 99%.
In the present invention, have surprisingly found that, Nb is introduced into activated alumina by solid phase reaction2O5, alumina toward rehydration
Stability be significantly improved.The NbAlO of generation4Tend to be attached to the big of the easy fast rehydration in oxidation aluminium surface
On amount of activated site so that exposed to the Al of carrier surface3+(namely anion vacancy) is reduced, and in high temperature, high pressure and is had
In the environment of water generation, water absorption subtracts significantly in oxidation aluminium surface anion vacancy position, the probability that aluminium oxide reacts with water
It is few.Therefore, Nb2O5Introducing can effectively suppress the rehydrated generation of aluminium oxide.
Meanwhile SeO2Introducing, add the dispersion degree of Ni and Au, active surface area and anti-agglutinatting property in catalyst
Can, so as to improve the activity and selectivity of catalyst.
According to aminating reaction mechanism, the dehydrogenation generation of alcohol has the aldehyde of reactivity, and aldehyde forms imines with amine, and hydrogen is shifted by alcohol
Amine is formed to imines.The introducing of Au is conducive to the transfer of hydrogen in active component, suppresses the oligomerisation of imines and the generation of polymerisation,
Enhance the anti-carbon performance of catalyst.
Catalyst metal loadings amount of the invention is low, anti-hydration, anti-carbon and anti-sintering property are good, preparation process letter
Single, good economy performance, has good application prospect.
Embodiment
With reference to embodiment, the present invention is further described, but the invention is not restricted to listed embodiment,
The equivalent improvement and deformation of the technical solution that the present patent application the appended claims define should be also included in.
Gas chromatograph：Shimadzu GC-2014 (FID) detector, SE-30 capillary columns (φ 0.30mm × 30m), injection port
270 DEG C, 270 DEG C of detector；Heating schedule：70 DEG C, constant temperature 1min, 240 DEG C then are risen to the speed of 40 DEG C/min, is kept
5min。
Hydroxy value measuring method：Referring to GB/T 12008.3-2009.
Total amine value measurement：Product is titrated using the hydrochloric acid solution of 0.5mol/L, passes through the hydrochloric acid matter of consumption
Amount can calculate total amine value of product.
Feed stock conversion：Total total hydroxyl value × 100% of amine value/raw material of product.
Product yield：Quality × 100% of the quality of polyethers amine product/raw material polyether polyol.
Reductive amination process device is fixed bed reactors in embodiment.
Polyether polyol (PPG-230, D-400, D-2000, D-5000, T-403, T-2000)：Ten thousand magnificent chemical groups shares
Co., Ltd.
Embodiment 1
(1) carrier NbAlO is prepared by niobium hydroxide4
99.1g niobium hydroxides and 28.5g aluminium oxide are added in mortar and are uniformly mixed, 100- is obtained by grinding, sieving
The mixture of 200 mesh, then, then the mixture is transferred in crucible, the dry 24h at 110 DEG C, then the sky at 1050 DEG C
20h (heating rates are roasted in gas：3℃/min；Heating rate refers to rise to temperature most from room temperature with the rate of constant speed really per minute
Finishing temperature).Yield：(x-ray diffraction analysis shows are the NbAlO that purity is higher than 98% to 100g white powders4).By tabletting into
Type obtains the column like catalyst carrier of 3*3mm.
(2) 7%NiO-1%Au2O3- 0.2%SeO2/NbAlO4The preparation of catalyst
According to the content of catalyst form, using equi-volume impregnating by above-mentioned carrier immerse nickel nitrate containing 29.7g,
In the aqueous solution of 1.68g nitric acid gold and 0.25g selenous acid, dried after balance to be adsorbed, then 11h roasted in 450 DEG C of air,
Obtain catalyst precarsor 7%NiO-1%Au2O3- 0.2%SeO2/NbAlO4。
(3) evaluation of catalyst
Faced with polyether polyol PPG-230 (two degrees of functionality, molecular weight 230) exemplified by hydrogen ammonification prepares polyetheramine, used
Continuity method fixed-bed process is evaluated.Catalyst at 280 DEG C (under normal pressure) before use, reduce 10h in the hydrogen gas stream.Reactor
Interior temperature Temperature fall boosts to 14.0MPa, after system is stablized, by molar ratio NH to 210 DEG C3The liquid of/PPG-230=15
Flow through pump to be driven into reactor, be passed through the hydrogen of 5 times of PPG-230 moles, it is filtered, vacuumize after reacting a period of time
Distill to obtain polyethers amine product.Through chemical analysis, reaction conversion ratio 100.0%, primary amine selectivity 99.5%.Catalyst is continuous
1000h sampling analyses are run, it is as a result unchanged.
Embodiment 2
(1) carrier NbAlO is prepared by carbonic acid niobium4
136.0g carbonic acid niobium and 28.5g aluminium oxide are added in mortar and are uniformly mixed, 100- is obtained by grinding, sieving
The mixture of 200 mesh, then, then the mixture is transferred in crucible, the dry 24h at 120 DEG C, then the sky at 900 DEG C
24h (heating rates are roasted in gas：5℃/min.Heating rate refers to rise to temperature most from room temperature with the rate of constant speed really per minute
Finishing temperature).Yield：(x-ray diffraction analysis shows are the NbAlO that purity is higher than 98% to 100g white powders4).By tabletting into
Type obtains the column like catalyst carrier of 3*3mm.
(2) 10%NiO-0.7%Au2O3- 0.3%SeO2/NbAlO4The preparation of catalyst
According to the content of catalyst form, using equi-volume impregnating by above-mentioned carrier immerse nickel nitrate containing 43.7g,
In the aqueous solution of 1.21g nitric acid gold and 0.39g selenous acid, dried after balance to be adsorbed, then 14h roasted in 300 DEG C of air,
Obtain catalyst precarsor 10%NiO-0.7%Au2O3- 0.3%SeO2/NbAlO4。
(3) evaluation of catalyst
Faced with polyether polyol D-400 (two degrees of functionality, molecular weight 430) exemplified by hydrogen ammonification prepares polyetheramine, using even
Continuous method fixed-bed process is evaluated.Catalyst at 200 DEG C (under normal pressure) before use, reduce 15h in the hydrogen gas stream.In reactor
Temperature is warming up to 220 DEG C naturally, 17.0MPa is boosted to, after system is stablized, by molar ratio NH3The liquid of/D-400=15 flows through
Pump is driven into reactor, is passed through the hydrogen of 1 times of D-400 moles, filtered, vacuumize and distill after reacting a period of time
Polyethers amine product.Through chemical analysis, reaction conversion ratio 100.0%, primary amine selectivity 98.0%.Catalyst is continuously run
800h sampling analyses, it is as a result unchanged.
Embodiment 3
(1) carrier NbAlO is prepared by nitric acid niobium4
226.5g nitric acid niobium and 28.5g aluminium oxide are added in mortar and are uniformly mixed, 100- is obtained by grinding, sieving
The mixture of 200 mesh, then, then the mixture is transferred in crucible, the dry 20h at 120 DEG C, then the sky at 1100 DEG C
22h (heating rates are roasted in gas：4℃/min.Heating rate refers to rise to temperature most from room temperature with the rate of constant speed really per minute
Finishing temperature.) yield：(x-ray diffraction analysis shows are the NbAlO that purity is higher than 97% to 100g white powders4).By extrusion into
Type obtains the strip carrier of 3*3mm.
(2) 5%NiO-0.8%Au2O3- 0.5%SeO2/NbAlO4The preparation of catalyst
According to the content of catalyst form, using equi-volume impregnating by above-mentioned carrier immerse nickel nitrate containing 20.8g,
In the aqueous solution of 1.32g nitric acid gold and 0.62g selenous acid, dried after balance to be adsorbed, then 12h roasted in 400 DEG C of air,
Obtain catalyst precarsor 5%NiO-0.8%Au2O3- 0.5%SeO2/NbAlO4。
(3) evaluation of catalyst
Faced with polyether polyol D-2000 (two degrees of functionality, molecular weight 2000) exemplified by hydrogen ammonification prepares polyetheramine, used
Continuity method fixed-bed process is evaluated.Catalyst at 400 DEG C (under normal pressure) before use, reduce 8h in the hydrogen gas stream.Reactor
Interior temperature Temperature fall boosts to 14.0MPa, after system is stablized, by molar ratio NH to 215 DEG C3The liquid flow of/D-2000=18
It is driven into through pump in reactor, is passed through the hydrogen of 2 times of D-2000 moles, it is filtered, vacuumize distillation after reacting a period of time
Obtain polyethers amine product.Through chemical analysis, reaction conversion ratio 98.8%, primary amine selectivity 99.5%.Catalyst is continuously run
900h sampling analyses, it is as a result unchanged.
Embodiment 4
(1) carrier NbAlO is prepared by niobium oxalate4
301.3g niobium oxalates and 28.5g aluminium oxide are added in mortar and are uniformly mixed, 100- is obtained by grinding, sieving
The mixture of 200 mesh, then, then the mixture is transferred in crucible, the dry 16h at 130 DEG C, then the sky at 1050 DEG C
28h (heating rates are roasted in gas：5℃/min.Heating rate refers to rise to temperature most from room temperature with the rate of constant speed really per minute
Finishing temperature).Yield：(x-ray diffraction analysis shows are the NbAlO that purity is higher than 99% to 100g white powders4).By tabletting into
Type obtains the column like catalyst carrier of 3*3mm.
(2) 6%NiO-1.4%Au2O3- 0.4%SeO2/NbAlO4The preparation of catalyst
According to the content of catalyst form, using equi-volume impregnating by above-mentioned carrier immerse nickel nitrate containing 25.3g,
In the aqueous solution of 2.35g nitric acid gold and 0.50g selenous acid, dried after balance to be adsorbed, then 9h roasted in 500 DEG C of air,
Obtain catalyst precarsor 6%NiO-1.4%Au2O3- 0.4%SeO2/NbAlO4。
(3) evaluation of catalyst
Faced with polyether polyol T-403 (three-functionality-degree, molecular weight 440) exemplified by hydrogen ammonification prepares polyetheramine, using even
Continuous method fixed-bed process is evaluated.Catalyst at 400 DEG C (under normal pressure) before use, reduce 8h in the hydrogen gas stream.In reactor
Temperature Temperature fall boosts to 11.0MPa, after system is stablized, by molar ratio NH to 240 DEG C3The liquid of/T-403=10 flows through
Pump is driven into reactor, is passed through the hydrogen of 3 times of T-403 moles, filtered, vacuumize and distill after reacting a period of time
Polyethers amine product.Through chemical analysis, reaction conversion ratio 100.0%, primary amine selectivity 99.8%.Catalyst is continuously run
1200h sampling analyses, it is as a result unchanged.
Embodiment 5
(1) carrier NbAlO is prepared by sulfuric acid niobium4
186.4g sulfuric acid niobium and 28.5g aluminium oxide are added in mortar and are uniformly mixed, 100- is obtained by grinding, sieving
The mixture of 200 mesh, then, then the mixture is transferred in crucible, the dry 20h at 110 DEG C, then the sky at 950 DEG C
30h (heating rates are roasted in gas：3℃/min.Heating rate refers to rise to temperature most from room temperature with the rate of constant speed really per minute
Finishing temperature).Yield：(x-ray diffraction analysis shows are the NbAlO that purity is higher than 97% to 100g white powders4).By tabletting into
Type obtains the column like catalyst carrier of 3*3mm.
(2) 9%NiO-0.6%Au2O3- 0.1%SeO2/NbAlO4The preparation of catalyst
According to the content of catalyst form, using equi-volume impregnating by above-mentioned carrier immerse nickel nitrate containing 38.8g,
In the aqueous solution of 1.03g nitric acid gold and 0.13g selenous acid, dried after balance to be adsorbed, then 8h roasted in 550 DEG C of air,
Obtain catalyst precarsor 9%NiO-0.6%Au2O3- 0.1%SeO2/NbAlO4。
(3) evaluation of catalyst
Faced with polyether polyol D-5000 (two degrees of functionality, molecular weight 5000) exemplified by hydrogen ammonification prepares polyetheramine, used
Continuity method fixed-bed process is evaluated.Catalyst at 350 DEG C (under normal pressure) before use, reduce 16h in the hydrogen gas stream.Reactor
Interior temperature Temperature fall boosts to 13.0MPa, after system is stablized, by molar ratio NH to 180 DEG C3The liquid flow of/D-5000=15
It is driven into through pump in reactor, is passed through the hydrogen of 6 times of D-5000 moles, it is filtered, vacuumize distillation after reacting a period of time
Obtain polyethers amine product.Through chemical analysis, reaction conversion ratio 97.0%, primary amine selectivity 98.5%.Catalyst is continuously run
1050h sampling analyses, it is as a result unchanged.
Comparative example 1
Difference lies in catalyst is the preparation according to catalyst in patent US5352835A embodiments XIX with embodiment 1
Method is prepared for 19.9%Ni-7.6%Cu/ θ-Al2O3Catalyst.After the catalyst continuously runs 500h, activity is obvious to be reduced,
Reaction conversion ratio is 82%, primary amine selectivity 97.0%.Spectroscopic methodology is derived by X-ray, utilizes boehmite peak value to θ-oxidation
The rehydrated degree of the integrated intensity estimation alumina composition of aluminium peak value is 30%.And by continuously being run in embodiment 1
Catalyst after 1000h carries out x-ray diffraction analysis, the results showed that catalyst carrier is still the NbAlO that purity is higher than 98%4。
From the foregoing, it will be observed that catalyst of the present invention has excellent anti-hydration, and the stability of catalyst of the present invention is obvious
Better than prior art alumina supported catalyst.
Comparative example 2
Method according to embodiment 1 is prepared for 7%NiO-1%Au2O3- 0.2%ZrO2/NbAlO4Catalyst, uses at the same time
Same process condition evaluates the catalyst in embodiment 1, it turns out that, after catalyst continuously runs 300h, activity is bright
It is aobvious to reduce, reaction conversion ratio 75%, primary amine selectivity 95.5%.Metal dispersity is carried out using Pulse Chemisorption method
Measure, the results showed that, the dispersion degree of W metal and Au are greatly lowered.And by embodiment 1 continuously operation 1000h after
Catalyst carries out Pulse Chemisorption method analysis, the results showed that the dispersion degree of Ni and Au and fresh catalyst basic one in catalyst
Cause.
From the foregoing, it will be observed that catalyst SeO of the present invention2Introducing, with reference to specific carrier, add Ni and Au in catalyst
Dispersion degree, active surface area and anti-sintering property, so as to improve the activity and selectivity of catalyst.
Obviously, the above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and is not pair
The restriction of embodiments of the present invention.For those of ordinary skill in the field, may be used also on the basis of the above description
To make other variations or changes in different ways.Here all embodiments can not be exhaustive.It is every to belong to this hair
The obvious changes or variations that bright technical solution is extended out is within the scope that the present invention covers.
Claims (9)
1. a kind of catalyst for synthesizing polyether amine, it includes NbAlO4Carrier and load NiO on the carrier,
Au2O3And SeO2Active component.
2. catalyst according to claim 1, wherein, based on overall catalyst weight, the content of active component NiO in catalyst
For 1-15wt%, Au2O3Content be 0.01-2wt%, SeO2Content be 0.01-1wt%；
Preferably, in terms of overall catalyst weight, the content of active component NiO is 5-10wt%, Au2O3Content 0.5-1.5wt%,
SeO2Content be 0.1-0.5wt%.
3. the preparation method of the catalyst described in claim 1 or 2, includes the following steps：
(1) NbAlO is prepared4Carrier：Niobium compound will be contained to be uniformly mixed with aluminium oxide, dry, roasting, shaping obtain carrier, optionally
It is ground, sieves before the drying；
(2) catalyst is prepared：Formed according to the content of catalyst, the carrier impregnation that step (1) obtains is being contained into soluble nickel
In the aqueous solution of salt, gold salt and selenium-containing compound, dry after balance to be adsorbed, roasting obtains catalyst, is preferably isometric
Dipping.
4. preparation method according to claim 3, wherein, in the step (1) nitric acid niobium, sulfuric acid are selected from containing niobium compound
One or more in niobium, niobium hydroxide, niobium oxalate and carbonic acid niobium, preferably niobium hydroxide and/or niobium oxalate；
One or more of the nickel salt in sulfate, nitrate and acylate, preferably nitric acid described in the step (2)
Salt；
One or more of the gold salt in nitric acid gold, chlorauride and four hydration gold chlorides, preferably nitric acid gold；
One or more of the selenium-containing compound in selenous acid, sodium selenite, potassium selenite, dichloro oxygen selenium, preferably selenous acid.
5. the preparation method according to claim 3 or 4, wherein, in the step (1) in screening process, solid powder
Mesh number is controlled in the range of 100-200 mesh.
6. the preparation method according to claim 3 or 4, wherein, calcination temperature is 700-1500 DEG C in the step (1),
It is preferred that 900-1100 DEG C；Roasting time is 10-40h, preferably 20-30h；
In the step (2) calcination temperature be 100-600 DEG C, preferably 300-500 DEG C, roasting time 1-24h, preferably 8-16h.
7. the catalyst described in claim 1 or 2 carries out facing the application in hydrogen aminating reaction synthesizing polyether amine in polyether polyol,
The polyether polyol preferably comprises ethylene oxide (EO) and/or propylene oxide (PO) skeleton, and average molecular weight is 100-
5000, preferred molecular weight 200-600.
8. a kind of method of synthesizing polyether amine, this method include：Under the catalyst action described in claim 1 or 2, using poly-
Ethoxylated polyhydric alcohol carries out facing hydrogen aminating reaction synthesizing polyether amine.
9. according to the method described in claim 8, wherein, using continuity method fixed-bed process, it is passed through polyether polyol mole 5
~30 times of ammonia, the hydrogen that 0.1~10 times of polyether polyol mole, is 180~240 DEG C in reaction temperature, reaction pressure is
Carry out facing hydrogen aminating reaction under the conditions of 10.0~18.0MPa.
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