CN108698975A - 用于制备脂肪胺的大孔催化剂 - Google Patents
用于制备脂肪胺的大孔催化剂 Download PDFInfo
- Publication number
- CN108698975A CN108698975A CN201680081070.1A CN201680081070A CN108698975A CN 108698975 A CN108698975 A CN 108698975A CN 201680081070 A CN201680081070 A CN 201680081070A CN 108698975 A CN108698975 A CN 108698975A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- formula
- reaction
- aminating agent
- woelm alumina
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 150000001412 amines Chemical class 0.000 title claims abstract description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 69
- 238000000034 method Methods 0.000 claims abstract description 44
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 33
- 150000002191 fatty alcohols Chemical class 0.000 claims abstract description 24
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000005751 Copper oxide Substances 0.000 claims abstract description 14
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 25
- 239000001257 hydrogen Substances 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 19
- 125000001931 aliphatic group Chemical group 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 229920006395 saturated elastomer Polymers 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 3
- 150000002910 rare earth metals Chemical class 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 235000019197 fats Nutrition 0.000 claims 1
- 235000021003 saturated fats Nutrition 0.000 claims 1
- 235000021081 unsaturated fats Nutrition 0.000 claims 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 21
- 239000000047 product Substances 0.000 description 17
- 150000003512 tertiary amines Chemical class 0.000 description 11
- 150000001721 carbon Chemical group 0.000 description 10
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- -1 tertiary amine Chemical class 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 239000011324 bead Substances 0.000 description 7
- 238000005576 amination reaction Methods 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 150000003335 secondary amines Chemical class 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 4
- 150000002081 enamines Chemical class 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 150000003141 primary amines Chemical class 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 3
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 3
- 235000003642 hunger Nutrition 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000376 reactant 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910001679 gibbsite Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- DCNHQNGFLVPROM-QXMHVHEDSA-N (z)-n,n-dimethyloctadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN(C)C DCNHQNGFLVPROM-QXMHVHEDSA-N 0.000 description 1
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 1
- 150000000215 1-octanols Chemical class 0.000 description 1
- 150000000218 1-tetradecanols Chemical class 0.000 description 1
- LTHNHFOGQMKPOV-UHFFFAOYSA-N 2-ethylhexan-1-amine Chemical compound CCCCC(CC)CN LTHNHFOGQMKPOV-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical class CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- YJLYANLCNIKXMG-UHFFFAOYSA-N N-Methyldioctylamine Chemical compound CCCCCCCCN(C)CCCCCCCC YJLYANLCNIKXMG-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 229910001680 bayerite Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- NAPSCFZYZVSQHF-UHFFFAOYSA-N dimantine Chemical compound CCCCCCCCCCCCCCCCCCN(C)C NAPSCFZYZVSQHF-UHFFFAOYSA-N 0.000 description 1
- 229950010007 dimantine Drugs 0.000 description 1
- LAWOZCWGWDVVSG-UHFFFAOYSA-N dioctylamine Chemical compound CCCCCCCCNCCCCCCCC LAWOZCWGWDVVSG-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- YXUPZGKORWTXID-UHFFFAOYSA-N domiphen Chemical compound CCCCCCCCCCCC[N+](C)(C)CCOC1=CC=CC=C1 YXUPZGKORWTXID-UHFFFAOYSA-N 0.000 description 1
- 229960000629 domiphen Drugs 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical class CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000006194 liquid suspension Substances 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- YWWNNLPSZSEZNZ-UHFFFAOYSA-N n,n-dimethyldecan-1-amine Chemical compound CCCCCCCCCCN(C)C YWWNNLPSZSEZNZ-UHFFFAOYSA-N 0.000 description 1
- SFBHPFQSSDCYSL-UHFFFAOYSA-N n,n-dimethyltetradecan-1-amine Chemical compound CCCCCCCCCCCCCCN(C)C SFBHPFQSSDCYSL-UHFFFAOYSA-N 0.000 description 1
- ZWRUINPWMLAQRD-UHFFFAOYSA-N n-Nonyl alcohol Natural products CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 1
- MWKFXSUHUHTGQN-UHFFFAOYSA-N n-decyl alcohol Natural products CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 1
- ATBNMWWDBWBAHM-UHFFFAOYSA-N n-decyl-n-methyldecan-1-amine Chemical compound CCCCCCCCCCN(C)CCCCCCCCCC ATBNMWWDBWBAHM-UHFFFAOYSA-N 0.000 description 1
- IKVDMBQGHZVMRN-UHFFFAOYSA-N n-methyldecan-1-amine Chemical compound CCCCCCCCCCNC IKVDMBQGHZVMRN-UHFFFAOYSA-N 0.000 description 1
- OMEMQVZNTDHENJ-UHFFFAOYSA-N n-methyldodecan-1-amine Chemical compound CCCCCCCCCCCCNC OMEMQVZNTDHENJ-UHFFFAOYSA-N 0.000 description 1
- SEGJNMCIMOLEDM-UHFFFAOYSA-N n-methyloctan-1-amine Chemical compound CCCCCCCCNC SEGJNMCIMOLEDM-UHFFFAOYSA-N 0.000 description 1
- QWERMLCFPMTLTG-UHFFFAOYSA-N n-methyltetradecan-1-amine Chemical class CCCCCCCCCCCCCCNC QWERMLCFPMTLTG-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical class CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J23/72—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/651—50-500 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
一种用于制备脂肪胺的方法,该方法包括在催化剂的存在下使脂肪醇与胺化剂反应。该催化剂包含在由多孔氧化铝制成的载体上的氧化铜,其中该多孔氧化铝具有从10ml/100g至95ml/100g的对应于直径大于
Description
技术领域
本发明涉及一种用于制备脂肪胺的方法。该方法包括使脂肪醇与胺化剂在包含在由多孔氧化铝制成的载体上的氧化铜的催化剂的存在下反应。
背景技术
脂肪胺具有相当大的工业重要性并且发现脂肪胺在现代技术、农业和医药的几乎每个领域都有应用。脂肪胺例如叔胺,可用作消毒剂的中间体、家用液体洗涤剂的泡沫促进剂、用于护发剂的活性剂、用于衣服的软化剂、用于温和染色的试剂等。
在多种已知的用于制备脂肪胺的方法中,一种方法是脂肪醇(如长链脂肪醇)与各种起始胺(如氨、伯胺和仲胺)的一步胺化。例如,该方法可以是脂肪醇与二甲胺的反应,以产生相应的烷基二甲胺。这种反应是通过起始脂肪醇的脱氢成相应的醛,同时产生两个氢来引发的,如以下反应方案所示:
RCH2OH→RCHO+2H (1)起始脂肪醇的脱氢作用
RCHO+Me2NH→RCH(OH)NMe2 (2)将Me2NH非催化加成到醛
RCH(OH)NMe2+2H→RCH2NMe2+H2O (3)加成物氢解成叔胺
RCH(OH)NMe2→R’CH=CHNMe2+H2O (4)加成物脱水以形成烯胺
R’CH=CHNMe2+2H→RCH2NMe2 (5)烯胺氢化成叔胺
向生成的醛上加成Me2NH以非催化的方式进行从而形成相应的醛-胺加成物,随后将该加成物氢解成最终的叔胺RCH2NMe2,同时释放出水或通过加成物脱水以形成烯胺,然后将该烯胺氢化成最终的RNMe2。脂肪醇与伯胺(如MeNH2)的胺化通过相同的反应机理进行,从而首先形成相应的仲胺RNHMe,其再次与起始脂肪醇反应以形成二烷基叔胺R2NMe。与氨的氨基化通过类似的逐步机理进行,从而经由形成中间体RNH2和R2NH,以形成三烷基胺R3N。上面所示的反应方案表明,对于氢解步骤(3)和氢化步骤(5)不需要提供大量氢,因为所要求的氢是通过起始脂肪醇的脱氢作用产生的。然而,该方法优选在额外的氢气的存在下进行。
对于通过使用一步胺化法备脂肪胺的方法,已经研究了各种催化剂,值得注意的是含铜催化剂。已知非负载的元素铜的催化剂可用于一步胺化法。然而,一个问题是这种催化剂具有有限的寿命,并且可以在数天或数周的时间内观察到催化活性的逐渐降低。为了减轻这种缺点,可以将催化剂金属(如铜)沉积在具有高表面积的载体表面,并且因此与非负载的对应物相比具有更高的活性。
在美国专利号4,654,440中披露了一种含有铜作为催化金属的催化剂,该催化剂由γ-氧化铝负载,可用于通过使用醇和氨作为起始材料制备单烷基胺的方法。特别地,已知γ-氧化铝主要含有直径为至(埃)的孔(参见:Catalytic AluminasI.Surface Chemistry of Eta and Gamma Alumina;D.S.Maciver、etc.;Journal ofCatalysis 2、485-497;1963[催化氧化铝I.η和γ氧化铝的表面化学;D.S.Maciver等人,催化杂志2,485-497;1963]。此外,在美国专利号5,916,838中披露了一种含有钌、镍和/或钴的催化剂,该催化剂在BASF D10-10氧化铝载体上,可用于胺化反应。披露了BASF D10-10氧化铝具有在从至的介孔范围内的孔直径分布的最大值(参见:美国专利公开号2007/0191212)。
对于通过使用一步胺化法制备脂肪胺,所希望的是获得脂肪醇的高转化率,同时保持最低水平的副反应。例如,在通过将脂肪醇与二甲胺反应制备烷基二甲胺时,一个显著的副反应是Me2NH歧化成MeNH2和Me3N,这将降低目标叔胺的产量。提供具有长效活性并且可以产生反应的高效率和良好选择性的催化剂仍然是一个挑战。
发明内容
在本发明的一个方面中,提供了一种使式(I)的脂肪醇与具有式(II)的胺化剂反应用于获得式(III)、(IV)或(V)的脂肪胺的方法
R1CH2OH
(I),
其中,R1是具有从3至21个碳原子的直链或支链的、饱和或不饱和的脂肪族基团(aliphatic group),
其中,R2和R3相同或不同,是氢或具有从1至24个碳原子的直链或支链的、饱和或不饱和的脂肪族基团
其中,该反应在包含在由多孔氧化铝制成的载体上的氧化铜的催化剂的存在下进行;其中,该多孔氧化铝具有从10ml/100g至95ml/100g的对应于直径大于的孔的体积。
优选地,该多孔氧化铝具有从20ml/100g至95ml/100g的对应于直径大于的孔的体积。
更优选地,该多孔氧化铝具有从30ml/100g至95ml/100g的对应于直径大于的孔的体积。
该多孔氧化铝优选地具有从10m2/g至280m2/g的比表面积。
更优选地,该多孔氧化铝具有从50m2/g至280m2/g的比表面积。
该催化剂可以进一步包含至少一种选自Fe、Co、Zn、Ni、Cr、Mn、Mg、Ba和稀土金属的元素的化合物。
该催化剂可以包含从5wt%至50wt%的氧化铜,重量百分比基于该催化剂的总重量。
值得注意地,该胺化剂具有式(VI)
其中,R4和R5相同或不同,是具有从1至24个碳原子的直链或支链的、饱和或不饱和的脂肪族基团,该脂肪胺具有式(VII):
其中,R1是具有从3至21个碳原子的直链或支链的、饱和或不饱和的脂肪族基团,R4和R5如式(VI)中所定义。
优选地,将脂肪醇和胺化剂与氢气流一起混合在并且将该混合物连续引入到反应区中,其中该脂肪醇/该胺化剂/该氢气的摩尔比是在从1:1:5至1:2:20的范围内。
更优选地,该脂肪醇/该胺化剂/该氢气的摩尔比是在从1:1:5至1:1.2:15的范围内。
该反应可以在从150℃至350℃的温度下进行。
优选地,该反应在从200℃至250℃的温度下进行。
该反应可以在从0巴至5巴的压力下进行。
优选地,该反应在从0巴至0.5巴的压力下进行。
在本发明的一个方面,提供了一种组合物,该组合物包含:
式(I)的脂肪醇
R1CH2OH
(I),
其中,R1是具有从3至21个碳原子的直链或支链的、饱和或不饱和的脂肪族基团;
式(II)的胺化剂
其中,R2和R3相同或不同,是氢或具有从1至24个碳原子的直链或支链的、饱和或不饱和的脂肪族基团;以及
包含在由多孔氧化铝制成的载体上的氧化铜的催化剂;其中,该多孔氧化铝具有从10ml/100g至95ml/100g的对应于直径大于的孔的体积。
具体实施方式
贯穿本说明,包括权利要求书,术语“包含一个/一种(comprising one)”或者“包含一个/一种(comprising a)”应理解为是与术语“包含至少一个/一种”同义,除非另外指明,“在…之间”和“从...至...”应理解为包括极限值。
如在此使用的,“重量百分比”、“wt%”、“按重量计的百分比”、“按重量计%”、以及其变体指的是当将那种物质的重量除以组合物的总重量并且乘以100时的物质浓度。
在本发明的上下文中,术语“大孔隙率”是指直径大于的孔;术语“介孔”是指直径大于并且小于的孔。
本发明涉及通过将脂肪醇与胺化剂反应制备脂肪胺的方法。本发明的脂肪醇具有式(I):
R1CH2OH
(I)
其中,R1是具有从3至21个碳原子、优选地从3至17个碳原子、更优选地从7至17个碳原子的直链或支链的、饱和或不饱和的脂肪族基团。
本方法的胺化剂可以选自下组,该组由以下各项组成:氨、伯胺、仲胺及其混合物。应当理解的是胺化剂可以是单一种类的胺化合物或多于一种胺化合物的混合物。本发明的胺化剂由式(II)表示:
其中,R2和R3相同或不同,是氢或具有从1至24个碳原子、优选地从1至18个碳原子、更优选地从1至4个碳原子的直链或支链的、饱和或不饱和的脂肪族基团。
在此形成的脂肪胺类由式(III)、(IV)或(V)表示:
其中,R1、R2和R3是如以上所定义的。
可以在此使用的脂肪醇类的实例包括1-辛醇、1-癸醇、1-十二烷醇、1-十四烷醇、1-十六烷醇、1-十八烷醇、2-乙基-1-己醇、油醇、1-壬醇及其混合物。
可以在此使用的伯胺包括单甲胺、单乙胺、十二烷胺、十六胺、2-乙基己胺及其混合物。可以在此使用的仲胺包括二甲胺、二乙胺、十二烷胺、二辛胺及其混合物。
可以在此制备的脂肪胺包括辛基二甲胺、辛基单甲胺、二辛基甲胺、辛基胺、癸基二甲胺、癸基单甲胺、二癸基甲胺、癸胺、十二烷基二甲胺、十二烷基单甲胺、双十二烷基甲胺、双十二烷基胺、十二烷胺、2-乙基己基二甲胺、油烯基二甲胺、十四烷基二甲胺、十四烷基单甲胺、双十四烷基甲胺、十四烷胺、十六烷基二甲胺以及十八烷基二甲胺。
在本发明的一个优选的实施例中,胺化剂是具有式(VI)的仲胺:
其中,R4和R5相同或不同,是具有从1至24个碳原子、优选地从1至18个碳原子、更优选地从1至4个碳原子的直链或支链的、饱和或不饱和的脂肪族基团。相应地,形成的脂肪胺具有式(VII):
其中,R1是如式(I)中所定义,R4和R5是如式(VI)中所定义的。
根据本发明,脂肪醇和胺化剂的反应在包含在由多孔氧化铝制成的载体上的氧化铜的催化剂的存在下进行;其中,该多孔氧化铝具有从10ml/100g至95ml/100g的对应于直径大于的孔的体积。
优选地,该多孔氧化铝具有从20ml/100g至95ml/100g的对应于直径大于的孔的体积。
更优选地,该多孔氧化铝具有从30ml/100g至95ml/100g的对应于直径大于的孔的体积。
本发明的多孔氧化铝值得注意地具有在大孔隙率范围内的孔径分布。具有直径大于的孔的体积表示由所有具有大于的孔径的孔产生的总体积。该体积可以通用本领域技术人员熟知的汞渗透技术测量。该测量可以根据制造商的说明通过使用市售的水银孔隙度仪方便地进行。
大孔隙率有利地在通过下述技术成形颗粒的过程中形成,或者例如像,添加生孔剂形成。
根据本发明的一个特征,多孔氧化铝展现出从15ml/100g至120ml/100g的总的孔体积,具有对应于直径大于的从15ml/100g至120ml/100g的孔的孔体积。根据本发明的另一个特征,多孔氧化铝展现出从20ml/100g至150ml/100g的总的孔体积,具有对应于直径大于的从20ml/100g至150ml/100g的孔的孔体积。这种孔的体积测量可以通过使用与上述类似的方法进行。
有利地,本发明的多孔氧化铝具有从10m2/g至280m2/g、优选地从20m2/g至280m2/g、更优选地从50m2/g至280m2/g的比表面积。
在本发明的上下文中,比表面积值得注意的是根据ASTM标准D3663-78通过氮吸附测定的BET比表面积,该标准基于在期刊“The Journal of the American Society”[“美国化学会杂志”],60,309(1938)中描述的布鲁诺-埃梅特-特勒(Brunauer-Emmett-Teller)法。
优选地,本发明的催化剂包含从5wt%至50wt%的氧化铜,重量百分比基于该催化剂的总重量;更优选地,该催化剂包含从10wt%至50wt%的氧化铜,重量百分比基于该催化剂的总重量;甚至更优选地,该催化剂包含从10wt%至30wt%的氧化铜,重量百分比基于该催化剂的总重量。
在一些方面,本发明的催化剂进一步包含至少一种选自Fe、Co、Zn、Ni、Cr、Mn、Mg、Ba和稀土金属(例如Y、Nd、Pr、Sm、Gd、Ce、La、Er、Dy和Ho)的元素的化合物。所述化合物值得注意的是上述元素的氧化物。优选地,该元素是Mg。这种化合物值得注意地可以起到促进剂的作用,从而进一步增强催化剂的催化活性。促进剂可以是单一化合物或多于一种元素的化合物的混合物。基于该催化剂的总重量,可以包含从0.1wt%至20wt%、优选地从0.5wt%至10wt%、更优选地从0.5wt%至5wt%的这种促进剂。
不希望受理论束缚,据信催化剂的比孔隙率在催化作用中表现出高的循环时间。在多孔氧化铝的孔的表面处存在氧化铜以及任选的促进剂,使得有可能比使用非负载的块状形式的催化剂的多孔氧化铝具有更好的催化效果。
通常,本发明的多孔氧化铝是通过三水铝石、拜三水铝石、诺三水铝石或它们的各种混合物的脱水获得的。例如,可以参见柯克-奥思默化工百科全书(Kirk-Othmerencyclopedia),第2卷,第291-297页。
在本发明中使用的多孔氧化铝可以通过将精细分离形式的水合氧化铝与温度在400℃与1000℃之间的热气流接触,然后将该水合物和气体接触持续范围从几分之一秒到10秒的时间,并且最后将部分脱水的氧化铝和热气体分离来制备。特别地,可以提及美国专利号2,915,365中描述的方法。
也可以在水性介质中、任选地在酸的存在下,在高于100℃并且优选地在150℃与250℃之间的温度下,对上述获得的氧化铝的团聚体进行高压处理优选地在1与20小时之间的时间,然后干燥它们并且煅烧它们。
调节煅烧温度,以获得在上述指示值范围内的比表面积和孔体积。
由于它们的主要制造工艺,在本方法中使用的多孔氧化铝最常含有钠,该钠的含量通常以相对于氧化铝的重量的Na2O的重量表示。
催化剂可以以各种形式使用,例如粉末、球粒、破碎材料、挤出物或粒料,任选地成形有可能使用黏合剂进行。
它可以首先是由油滴成形(或凝结成滴)产生的氧化铝球。这种类型的球可以例如,通过根据专利EP-A-0,015,801或EP-A-0,097,539传授的方法制备。孔隙率的控制尤其可以根据专利EP-A-0,097,539中描述的方法,通过凝结成氧化铝的水溶液悬浮液或分散体或碱性铝盐溶液的液滴来进行,以由有机相、水相和表面活性剂或乳化剂组成的乳液的形式提供。所述有机相尤其可以是烃。
它也可以是破碎的氧化铝材料。这些破碎的材料可以是任何类型的氧化铝基材料的破碎结果,例如像通过所有类型的方法(油滴、盘式造粒机或滚筒)获得的球或挤出物。这些破碎材料的孔隙率的控制通过选择被破碎以生产它们的氧化铝基材料来实现。
它也可以是氧化铝挤出物。后者可以通过捏合然后挤出氧化铝基材料获得,所述材料有可能由三水铝矿的快速脱水或由氧化铝凝胶的沉淀产生。这些挤出物的孔隙率的控制可以通过所使用氧化铝的选择以及通过该氧化铝的制备条件或通过挤出前该氧化铝的捏合条件实现。因此,可以将该氧化铝在捏合过程中与成孔剂混合。举例来说,这些挤出物可以通过在美国专利号3,856,708中描述的方法来制备。
根据本发明,包含负载在多孔氧化铝上的一种或多种催化金属的催化剂通常可以通过用盐或上述元素的化合物溶液浸渍多孔氧化铝载体,并且然后在大于或等于400℃的温度下干燥和煅烧,以任选地和有利地将所述化合物或盐类转化成氧化的化合物、优选地转化成氧化物获得。
为了进行本发明的方法,根据所希望的摩尔比将反应物脂肪醇和反应物胺化剂混合。优选地将该反应物混合物与氢气流一起混合在。可以将该混合物预热至200℃-400℃。然后可以将该混合物连续引入到反应区中。该脂肪醇与该胺化剂的摩尔比可以在从1:1至1:2的范围内、优选地在从1:1至1:1.5的范围内、更优选地在从1:1至1:1.2的范围内。该脂肪醇与氢的摩尔比可以在从1:5至1:20的范围内、优选地在从1:10至1:18的范围内、更优选地在从1:10至1:15的范围内。或者,可以将惰性气体如氮气加入到该反应物混合物中并将其引入反应区中。
优选地,本发明的方法是气相反应。在这种情况下,将反应混合物以气相形式,以从0.05kg至5.0kg醇/kg催化剂/小时、优选地从0.1kg至2.0kg醇/kg催化剂/小时、更优选地从0.5kg至1kg醇/kg催化剂/小时的液时空速度(液态醇体积/催化剂体积/小时)引入反应区中。
该反应优选在装载有根据本发明的催化剂的固定床上进行。应该理解的是该反应也可以在搅拌釜中进行,该搅拌釜可以被加热并且设置有用于反应物混合物循环的装置。在这种情况下,可以在反应开始之前将反应物和催化剂装载到容器中。因而,在本发明的还另一方面,提供了一种组合物,值得注意的是一种反应系统,该组合物包含:
式(I)的脂肪醇
R1CH2OH
(I),
其中,R1是具有从3至21个碳原子的直链或支链的、饱和或不饱和的脂肪族基团;
式(II)的胺化剂
其中,R2和R3相同或不同,是氢或具有从1至24个碳原子的直链或支链的、饱和或不饱和的脂肪族基团;以及
包含在由多孔氧化铝制成的载体上的氧化铜的催化剂;其中,该多孔氧化铝具有从10ml/100g至95ml/100g的对应于直径大于的孔的体积。
反应温度可以在从150℃至350℃的范围内、优选在从200℃至300℃的范围内、更优选在从200℃至250℃的范围内。反应区的压力可以在0巴至5巴的范围内、优选在0巴至2巴的范围内、更优选在从0巴至1巴的范围内、甚至更优选在从0巴至0.5巴的范围内。
可以通过关闭进入反应器的输入流来停止反应。在反应完成后,反应区中的反应产物可以通过使用本领域技术人员熟知的方法进行进一步的步骤,如蒸馏、冷凝和再循环,以回收所希望的产物。在一个实施例中,在含有所希望的烷基二甲胺产物的反应区中的流出液穿过冷凝器从而将反应产物冷却至30℃至150℃。将氢、未反应的二甲胺、水以及少量单甲胺和三甲胺副产物从塔顶除去。然后将冷凝的液体产物送到蒸馏阶段,其中将所希望的烷基二甲胺产物与较重的产物,如二烷基甲胺分离。
应当理解,本发明的方法可以采用单个固定床反应器或多个固定床反应器。例如,在后一种情况下,该方法可以采用两个固定床反应器,其中将第一固定床反应器中的反应产物与胺化剂的新鲜流一起引入到第二固定床反应器中。第二固定床反应器中的条件可以与上述第一固定床反应器中的条件基本相同。优选地,第二固定床反应器中的反应温度比第一固定床反应器中的反应温度低5℃-30℃。
实例
在多孔氧化铝载体上包含氧化铜(或氧化铜和氧化镁)的各种催化剂通过用铜和/或镁的可溶盐的水溶液浸渍多孔氧化铝珠粒来制备。所使用的多孔氧化铝珠粒已经在美国专利号6,262,259中描述。对应于直径大于的孔的体积以及多孔氧化铝的比表面积示于下表1中。为了制备含有铜的催化剂,用具有适当浓度的Cu(NO3)2/2.5H2O水溶液浸渍多孔氧化铝珠粒。然后将这些珠粒在烘箱中在120℃下干燥4小时并且在500℃下煅烧2小时,升温速率为1℃/min。为了制备含有铜和镁的催化剂,首先使用上述铜溶液浸渍多孔氧化铝珠粒。然后用具有适当浓度的Mg(NO3)2/6H2O水溶液浸渍这些珠粒。然后将这些珠粒在烘箱中在120℃下干燥4小时并且在500℃下煅烧2小时,升温速率为1℃/min。
所使用的这些催化剂的组分以及多孔氧化铝示于下表1中(比表面积=SS;总的孔体积=TPV;具有直径大于的具有直径大于的CuO和MgO的重量百分比是基于该催化剂的总重量)。
表1
为了研究上述催化剂的催化行为,将催化剂分别装载到管式固定床反应器(直径为2英寸并且长度为1米)中。然后,将十二烷醇和二甲胺的混合物与氢气流一起在215℃下通过汽化器加热。醇/二甲胺/氢气的摩尔比是1:1.2:14.7。然后将处于气相的预热混合物以0.5kg醇/kg催化剂/小时的进料速率引入到装载有催化剂的固定床反应器中。将固定床反应器中的反应温度设定在215℃并且将压力设定在0.2巴。通过热交换器将来自固定床反应器出口的产物流冷却至环境温度并且收集产物流样品进行分析。对收集的样品进行气相色谱分析。根据下式测定醇的转化率(DC)以及所希望叔胺的选择性:
醇的转化率(DC)=(输入的醇的总摩尔数-产物混合物中未反应的醇的总摩尔数)/输入的醇的总摩尔数
叔胺的选择性=产物混合物中叔胺的总摩尔数/(输入的醇的总摩尔数-产物混合物中未反应的醇的总摩尔数)
结果示于下表2中:
表2
编号 | 醇的转化率(%) | 叔胺的选择性(%) |
1 | 98 | 96 |
2 | 97 | 96 |
3 | 87 | 90 |
4 | 82 | 93 |
5 | 80 | 91 |
6 | 79 | 89 |
结果表明,与具有低于10ml/100g的值的载体的多孔氧化铝相比,根据本发明的负载在多孔氧化铝(具有高于10ml/100g的值)上的催化剂显示出明显更高的醇转化率和明显更高的叔胺选择性。
Claims (15)
1.一种使式(I)的脂肪醇与具有式(II)的胺化剂反应用于获得式(III)、(IV)或(V)的脂肪胺的方法
R1CH2OH
(I),
其中,R1是具有从3至21个碳原子的直链或支链的、饱和或不饱和的脂肪族基团,
其中,R2和R3相同或不同,是氢或具有从1至24个碳原子的直链或支链的、饱和或不饱和的脂肪族基团
其中,该反应在包含在由多孔氧化铝制成的载体上的氧化铜的催化剂的存在下进行;其中,该多孔氧化铝具有从10ml/100g至95ml/100g的对应于直径大于的孔的体积。
2.根据权利要求1所述的方法,其中,该多孔氧化铝具有从20ml/100g至95ml/100g的对应于直径大于的孔的体积。
3.根据权利要求1或2所述的方法,其中,该多孔氧化铝具有从30ml/100g至95ml/100g的对应于直径大于的孔的体积。
4.根据权利要求1至3中任一项所述的方法,其中,该多孔氧化铝具有从10m2/g至280m2/g的比表面积。
5.根据权利要求1至4中任一项所述的方法,其中,该多孔氧化铝具有从50m2/g至280m2/g的比表面积。
6.根据权利要求1至5中任一项所述的方法,其中,该催化剂进一步包含至少一种选自Fe、Co、Zn、Ni、Cr、Mn、Mg、Ba和稀土金属的元素的化合物。
7.根据权利要求1至6中任一项所述的方法,其中,该催化剂包含从5wt%至50wt%的氧化铜,重量百分比基于该催化剂的总重量。
8.根据权利要求1至7中任一项所述的方法,其中,该胺化剂具有式(VI)
其中,R4和R5相同或不同,是具有从1至24个碳原子的直链或支链的、饱和或不饱和的脂肪族基团,该脂肪胺具有式(VII):
其中,R1是具有从3至21个碳原子的直链或支链的、饱和或不饱和的脂肪族基团,R4和R5是如式(VI)中所定义的。
9.根据权利要求1至8中任一项所述的方法,其中,将该脂肪醇和该胺化剂与氢气流一起混合并且将该混合物连续引入到反应区中,其中该脂肪醇/该胺化剂/该氢气的摩尔比是在从1:1:5至1:2:20的范围内。
10.根据权利要求9所述的方法,其中,该脂肪醇/该胺化剂/该氢气的摩尔比是在从1:1:5至1:1.2:15的范围内。
11.根据权利要求1至10中任一项所述的方法,其中,该反应在从150℃至350℃的温度下进行。
12.根据权利要求1至11中任一项所述的方法,其中,该反应在从200℃至250℃的温度下进行。
13.根据权利要求1至12中任一项所述的方法,其中,该反应在从0巴至5巴的压力下进行。
14.根据权利要求1至13中任一项所述的方法,其中,该反应在从0巴至0.5巴的压力下进行。
15.一种组合物,该组合物包含:
式(I)的脂肪醇
R1CH2OH
(I),
其中,R1是具有从3至21个碳原子的直链或支链的、饱和或不饱和的脂肪族基团;
式(II)的胺化剂
其中,R2和R3相同或不同,是氢或具有从1至24个碳原子的直链或支链的、饱和或不饱和的脂肪族基团;以及包含在由多孔氧化铝制成的载体上的氧化铜的催化剂;其中,该多孔氧化铝具有从10ml/100g至95ml/100g的对应于直径大于的孔的体积。
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US20190031596A1 (en) | 2019-01-31 |
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US11084776B2 (en) | 2021-08-10 |
CN108698975B (zh) | 2021-10-08 |
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