CN111195523B - A kind of catalyst for producing amine by hydrogenation of cyanide compound, preparation method and application thereof - Google Patents
A kind of catalyst for producing amine by hydrogenation of cyanide compound, preparation method and application thereof Download PDFInfo
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- CN111195523B CN111195523B CN201811367106.XA CN201811367106A CN111195523B CN 111195523 B CN111195523 B CN 111195523B CN 201811367106 A CN201811367106 A CN 201811367106A CN 111195523 B CN111195523 B CN 111195523B
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- catalyst
- substituted
- auxiliary agent
- carrier
- active metal
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- 239000003054 catalyst Substances 0.000 title claims abstract description 105
- 150000001412 amines Chemical class 0.000 title claims abstract description 43
- -1 cyanide compound Chemical class 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000005984 hydrogenation reaction Methods 0.000 title abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 35
- 239000002184 metal Substances 0.000 claims abstract description 30
- 229910052802 copper Inorganic materials 0.000 claims abstract description 9
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 239000011148 porous material Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 43
- 239000012752 auxiliary agent Substances 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 150000003839 salts Chemical class 0.000 claims description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 17
- 229910052593 corundum Inorganic materials 0.000 claims description 17
- 150000002825 nitriles Chemical group 0.000 claims description 17
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 17
- 229910052681 coesite Inorganic materials 0.000 claims description 16
- 229910052906 cristobalite Inorganic materials 0.000 claims description 16
- 239000000377 silicon dioxide Substances 0.000 claims description 16
- 229910052682 stishovite Inorganic materials 0.000 claims description 16
- 229910052905 tridymite Inorganic materials 0.000 claims description 16
- 239000010949 copper Substances 0.000 claims description 15
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 15
- 229910052736 halogen Inorganic materials 0.000 claims description 13
- 150000002367 halogens Chemical group 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 238000005470 impregnation Methods 0.000 claims description 13
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 10
- 230000004913 activation Effects 0.000 claims description 9
- 125000003277 amino group Chemical group 0.000 claims description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 9
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- 229910052788 barium Inorganic materials 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 230000003213 activating effect Effects 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 229940078494 nickel acetate Drugs 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- 125000002560 nitrile group Chemical group 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- HRLYFPKUYKFYJE-UHFFFAOYSA-N tetraoxorhenate(2-) Chemical compound [O-][Re]([O-])(=O)=O HRLYFPKUYKFYJE-UHFFFAOYSA-N 0.000 claims description 4
- UPPLJLAHMKABPR-UHFFFAOYSA-H 2-hydroxypropane-1,2,3-tricarboxylate;nickel(2+) Chemical compound [Ni+2].[Ni+2].[Ni+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O UPPLJLAHMKABPR-UHFFFAOYSA-H 0.000 claims description 3
- QSHYGLAZPRJAEZ-UHFFFAOYSA-N 4-(chloromethyl)-2-(2-methylphenyl)-1,3-thiazole Chemical compound CC1=CC=CC=C1C1=NC(CCl)=CS1 QSHYGLAZPRJAEZ-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- 229910021586 Nickel(II) chloride 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
- XZQYTGKSBZGQMO-UHFFFAOYSA-I Rhenium(V) chloride Inorganic materials Cl[Re](Cl)(Cl)(Cl)Cl XZQYTGKSBZGQMO-UHFFFAOYSA-I 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 125000005619 boric acid group Chemical group 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 3
- 229940116318 copper carbonate Drugs 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- UXMRNSHDSCDMLG-UHFFFAOYSA-J tetrachlororhenium Chemical compound Cl[Re](Cl)(Cl)Cl UXMRNSHDSCDMLG-UHFFFAOYSA-J 0.000 claims description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical class N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000002243 precursor Substances 0.000 description 14
- 238000001035 drying Methods 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 238000001994 activation Methods 0.000 description 9
- 238000005303 weighing Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- SUSQOBVLVYHIEX-UHFFFAOYSA-N phenylacetonitrile Chemical compound N#CCC1=CC=CC=C1 SUSQOBVLVYHIEX-UHFFFAOYSA-N 0.000 description 6
- 229910052804 chromium Inorganic materials 0.000 description 5
- 229910052702 rhenium Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 4
- WSGYTJNNHPZFKR-UHFFFAOYSA-N 3-hydroxypropanenitrile Chemical compound OCCC#N WSGYTJNNHPZFKR-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 3
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000012716 precipitator Substances 0.000 description 3
- 150000003141 primary amines Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000012430 stability testing Methods 0.000 description 2
- 239000005749 Copper compound Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910020350 Na2WO4 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910019891 RuCl3 Inorganic materials 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 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
- 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
- B01J23/8896—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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8986—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with manganese, technetium or rhenium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
- C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application discloses a catalyst for producing amine by hydrogenation of cyanogen compounds, which comprises an active component and a carrier; the active component comprises an active metal element; the active metal elements include M and Re; m is at least one selected from Ni, Co and Cu; the carrier is selected from at least one of inorganic porous materials. The catalyst has simple preparation method, practical significance, can continuously hydrogenate nitrile compounds to prepare amine, and has the advantages of high activity, high selectivity and good stability.
Description
Technical Field
The application relates to a catalyst for preparing amine by hydrogenating a nitrile compound, in particular to a catalyst for preparing amine by hydrogenating a nitrile compound under an ammonia-contacting condition, belonging to the field of catalysis.
Background
The amine is a derivative in which a hydrogen atom in an ammonia molecule is substituted with a hydrocarbon group. Amines can be classified into primary amines, secondary amines, and tertiary amines according to the number of substituted hydrogen atoms in the amine molecule. Amines are widely present in the biological world and have very important physiological activities and biological activities, such as proteins, nucleic acids, many hormones, antibiotics, alkaloids and the like are complex derivatives of amines, and most of the drugs used clinically are amines or derivatives of amines, so that the study of the properties and synthetic methods of amines is the basis for the research of these complex natural products and the better maintenance of human health. Amines are widely used as solvents, pesticides and pharmaceuticals, and the earliest dye industry developed was based on aniline.
Amines are widely distributed in nature, most of which are produced by decarboxylation of amino acids. The industrial preparation of amines is mostly carried out by reacting ammonia with alcohol or alkyl halide, the product is a mixture of amines of different levels, and the pure product is obtained after fractionation. The corresponding amines can also be obtained by catalytic reduction of aldehydes, ketones in the presence of ammonia. It is also common in industry to prepare amines by catalytic reduction of nitro compounds, nitriles, amides or nitrogen-containing heterocyclic compounds. The reductive preparation of amines from nitriles is a very important and common process.
CN103965057 discloses a method for preparing primary amine from nitrile, which relates to a copper compound catalyst, nitrile and potassium borohydride are subjected to reduction reaction in a solvent, and after the reaction is completed, a primary amine product is obtained through post-treatment. CN101855197 discloses a raney metal catalyst which can produce diamines by continuous hydrogenation of dinitrile compounds. However, the stability of the catalyst is not ideal, and the performance of the regenerated catalyst is lower than that of a fresh catalyst. CN1075806C discloses a group IV B element doped raney catalyst made from a Ni/Al doped element metallurgical precursor alloy. The method not only has complex catalyst preparation process, but also needs to use a solvent. In conclusion, the catalyst in the invention disclosed at present has a complex preparation process, and the activity and selectivity of the catalyst are still to be further improved.
The invention aims to provide a catalyst which is simple in preparation method and practical, can be used for continuously hydrogenating nitrile compounds to prepare amine, and has the advantages of high activity, high selectivity and good stability.
Disclosure of Invention
According to one aspect of the application, the catalyst for producing the amine by hydrogenating the cyanogen compound is provided, the preparation method of the catalyst is simple and has practical significance, the nitrile compound can be continuously hydrogenated to prepare the amine, and the catalyst has the advantages of high activity, high selectivity and good stability.
The catalyst for producing amine by hydrogenation of cyanogen compounds is characterized in that,
the catalyst comprises an active component and a carrier;
the active component comprises an active metal element; the active metal elements include M and Re; m is at least one selected from Ni, Co and Cu;
the carrier is selected from at least one of inorganic porous materials.
Optionally, the weight percentage of M in the catalyst is 5.0-50.0%; the weight percentage of Re in the catalyst is 0.1-15.0%.
Optionally, the weight percentage of the active metal element M in the catalyst is 10.0-25.0%.
The weight percentage of Re in the catalyst is 1.0-5.0%.
Optionally, the catalyst further comprises an auxiliary agent;
the auxiliary agent comprises an auxiliary agent element, and the auxiliary agent element comprises at least one of Fe, Cr, W, Ru, B, Mg, Ba, Mn, La and Mo;
the auxiliary agent comprises an oxide of the auxiliary agent element;
the weight percentage of the auxiliary agent in the catalyst is 0.2-10.0%.
Optionally, the weight percentage of the auxiliary agent in the catalyst is 1.0-5.0%;
wherein, the weight percentage of the auxiliary agent is calculated by the weight percentage of the auxiliary agent element.
Optionally, the auxiliary element is at least one selected from Ru, B, Mn, Ba.
Optionally, the upper limit of the weight percent content of M in the catalyst is selected from 6.0%, 7.0%, 8.0%, 9.0%, 10.0%, 15.0%, 20.0%, 25.0%, 30.0%, 35.0%, 40.0%, 45.0%, or 50%; the lower limit is selected from 5.0%, 6.0%, 7.0%, 8.0%, 9.0%, 10.0%, 15.0%, 20.0%, 25.0%, 30.0%, 35.0%, 40.0%, 45.0%, 50%.
Alternatively, the upper limit of the weight percent content of Re in the catalyst is selected from 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 8%, 10%, 12%, or 15%; the lower limit is selected from 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 8%, 10% or 12%.
Optionally, the upper limit of the weight percent of promoter in the catalyst is selected from 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 8%, or 10%; the lower limit is selected from 0.2%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% or 8%.
Optionally, the specific surface area of the carrier is 50-600 m2The pore volume is 0.2-1.5 ml/g.
Optionally, the specific surface area of the carrier is 200-500 m2The pore volume is 0.4-1.0 ml/g.
Optionally, the support is selected from porous Al2O3Porous SiO2Porous Al2O3-SiO2At least one of (1).
Specifically, the catalyst provided by the invention comprises an active component, an auxiliary agent and a carrier: the active component is M-Re bimetal, wherein M is one or more than two of transition metals Ni, Co or Cu, and is preferably metal Ni.
The auxiliary agent is one or more of nonmetal, metal or metal oxide of one or more of Fe, Cr, W, Ru, B, Mg, Ba, Mn, La and Mo, and preferably one or more of the auxiliary agents Ru, B, Mn or Ba.
The carrier is porous material Al2O3、SiO2Or Al2O3-SiO2One or more than two of them.
The weight of the active component M accounts for 5.0-50.0% of the weight of the catalyst, preferably 10.0-25.0%; the weight of Re accounts for 0.1-15.0% of the weight of the catalyst, preferably 1.0-5.0%; the weight of the auxiliary agent accounts for 0.2-10.0% of the weight of the catalyst, preferably 1.0-5.0%; the specific surface area of the porous carrier is 50-600 m2A concentration of 200 to 500m is preferred2(ii)/g; the porous carrier has a pore volume of 0.2 to 1.5ml/g, preferably 0.4 to 1.0 ml/g.
Optionally, the cyanogen compound has a structural formula shown as formula I and formula II;
R-CN is of formula I;
formula II;
wherein R is selected from C1～C20Alkyl, halogen substituted C1～C20Hydrocarbyl, hydroxy-substituted C1～C20Alkyl, amino substituted C1～C20Alkyl, carboxyl substituted C1～C20A hydrocarbon group, a nitrile group-substituted C1～C20A hydrocarbon group of (a);
r' is selected from C1～C20Alkyl, halogen, hydroxyl, amino, carboxyl, nitrile group, halogen substituted C1～C20Hydrocarbyl, hydroxy-substituted C1～C20Alkyl, amino substituted C1～C20Alkyl, carboxyl substituted C1～C20A hydrocarbon group, a nitrile group-substituted C1～C20A hydrocarbon group of (1).
Alternatively, R is selected from C1～C10Alkyl, halogen substituted C1～C10Hydrocarbyl, hydroxy-substituted C1～C10Alkyl, amino substituted C1～C10Alkyl, carboxyl substituted C1～C10A hydrocarbon group, a nitrile group-substituted C1～C10A hydrocarbon group of (1).
Alternatively, R' is selected from C1～C10Alkyl, halogen, hydroxyl, amino, carboxyl, nitrile group, halogen substituted C1～C10Hydrocarbyl, hydroxy-substituted C1～C10Alkyl, amino substituted C1～C10Alkyl, carboxyl substituted C1～C10A hydrocarbon group, a nitrile group-substituted C1～C10A hydrocarbon group of (1).
Alternatively, R is selected from C1～C6Alkyl, halogen substituted C1～C6Hydrocarbyl, hydroxy-substituted C1～C6Alkyl, amino substituted C1～C6Alkyl, carboxyl substituted C1～C6A hydrocarbon group, a nitrile group-substituted C1～C6A hydrocarbon group of (1).
Alternatively, R' is selected from C1～C6Alkyl, halogen, hydroxyl, amino, carboxyl, nitrile group, halogen substituted C1～C6Hydrocarbyl, hydroxy-substituted C1～C6Alkyl, amino substituted C1～C6Alkyl, carboxyl substituted C1～C6A hydrocarbon group, a nitrile group-substituted C1～C6A hydrocarbon group of (1).
Optionally, the cyanogen compound is selected from at least one of 3-hydroxypropionitrile, adiponitrile, and phenylacetonitrile.
According to another aspect of the present application, a preparation method of the catalyst is provided, which is simple and feasible and is suitable for industrial production.
The preparation method of the catalyst is characterized by comprising at least one of an impregnation method and a precipitation method.
Optionally, the method comprises: soaking a carrier in a solution containing an active metal element source, and roasting to obtain the catalyst; or
Adding a solution containing an active metal element source and a precipitating agent into a suspension containing a carrier, and precipitating to obtain the catalyst.
Optionally, the solution contains a source of an auxiliary element.
Optionally, the roasting conditions are: the temperature is 300-700 ℃, and the time is 0.5-10.0 h.
Optionally, the source of active metal element is selected from at least one of soluble salts of active metal elements;
the auxiliary element source is selected from at least one of soluble salts of auxiliary elements.
Optionally, the soluble salt of the active metal element Ni comprises at least one of nickel nitrate, nickel acetate, nickel chloride, nickel sulfate, and nickel citrate.
Optionally, the soluble salt of the active metal element Co includes at least one of cobalt chloride, cobalt nitrate, cobalt carbonate, and cobalt sulfate.
Optionally, the soluble salt of the active metal element Cu includes at least one of copper nitrate, copper chloride, copper carbonate, copper sulfate.
Alternatively, the soluble salt of the active metal element Re includes at least one of ammonium rhenate, perrhenic acid, and rhenium chloride.
Optionally, the auxiliary element is a metal, and the soluble salt of the auxiliary element comprises at least one of nitrate of the auxiliary element and chloride of the auxiliary element;
the assistant element is B, and the assistant element source is boric acid.
The preparation method of the catalyst of the invention can adopt one or the combination of an impregnation method and a precipitation method to load the active component and the auxiliary agent on the carrier.
Optionally, the impregnation method comprises the steps of:
and (3) soaking the carrier in an aqueous solution containing an active component precursor and an auxiliary agent precursor, naturally airing, and roasting I to obtain the catalyst.
Optionally, the roasting I temperature is 300-700 ℃, the heating rate is 0.5-20.0 ℃/min, and the roasting I time is 0.5-10.0 h.
Optionally, the precipitation method comprises the steps of:
adding an active component precursor and an auxiliary agent precursor into a suspension containing a carrier, adding a precipitator, and aging, washing, filtering, drying and roasting II to obtain the catalyst.
Optionally, the temperature of the roasting II is 300-700 ℃, the heating rate is 0.5-20.0 ℃/min, and the time of the roasting II is 0.5-10.0 h.
Optionally, the active component precursor comprises soluble salts of Ni, Co, Cu and Re.
Optionally, the promoter precursor comprises a soluble precursor of B.
Specifically, the active component M-Re (M is one or more than two of transition metals Ni, Co or Cu) bimetal.
The soluble salt of Ni may be nickel nitrate, nickel acetate, nickel chloride, nickel sulfate or nickel citrate, preferably nickel nitrate or nickel acetate.
The soluble salt of Co used may be cobalt chloride, cobalt nitrate, cobalt carbonate or cobalt sulphate, with cobalt nitrate being preferred.
The soluble salt of Cu used may be copper nitrate, copper chloride, copper carbonate or copper sulfate, preferably copper nitrate, copper sulfate.
The soluble salt of Re used is ammonium rhenate, perrhenic acid or rhenium chloride, preferably ammonium rhenate; the soluble salt of the metal auxiliary agent is nitrate or chloride.
The nonmetal auxiliary agent B is boric acid.
Alternatively, the catalyst is prepared by supporting a catalyst precursor on a support material by an impregnation process.
In the impregnation method embodiment, the active ingredient and the auxiliary agent may be supported on the carrier by co-impregnation or stepwise impregnation.
Alternatively, the step of the impregnation method may be: preparing an aqueous solution containing an active component M-Re (M is one or more than two of transition metals of Ni, Co and Cu) and an auxiliary agent, wherein the weight of the active component M accounts for 5.0-50.0% of the weight of the catalyst, the weight of the active component Re accounts for 0.1-15.0% of the weight of the catalyst, and the weight of the auxiliary agent accounts for 0.2-10.0% of the weight of the catalyst, impregnating the carrier with the aqueous solution containing the active component and the auxiliary agent, and naturally airing and roasting the impregnated carrier.
Alternatively, the impregnation method may be one-time impregnation or multi-stage impregnation.
Optionally, the roasting temperature is usually 300-700 ℃, the heating rate is usually 0.5-20.0 ℃/min, and the roasting time is usually 0.5-10.0 h.
The catalyst precursor may also be supported on a carrier by precipitation.
The steps for preparing the catalyst by the precipitation method can be as follows: the carrier material is suspended in water, soluble precursors of active components M-Re (M is one or more of transition metals Ni, Co and Cu) and auxiliary agents, such as metal salts, are added, and then a precipitant is added to precipitate the precursors on the suspended carrier. Wherein the weight of the active component M accounts for 5.0-50.0% of the weight of the catalyst, the weight of the active component Re accounts for 0.1-15.0% of the weight of the catalyst, and the weight of the auxiliary agent accounts for 0.2-10.0% of the weight of the catalyst. And (4) aging, washing, filtering, drying and roasting the precipitated sample.
Alternatively, the precipitant used is preferably an inorganic base, preferably sodium hydroxide, sodium carbonate, potassium hydroxide or potassium carbonate.
Optionally, the precipitating agent is an inorganic base.
Optionally, the precipitant is selected from at least one of sodium hydroxide, sodium carbonate, potassium hydroxide, and potassium carbonate.
Alternatively, the precipitant used may also be an ammonium salt, which may be ammonium carbonate, ammonium hydroxide or ammonium halide.
Alternatively, the precipitant used is an ammonium salt.
Optionally, the precipitant is selected from at least one of ammonium carbonate, ammonium hydroxide, ammonium halide. Optionally, the precipitation temperature may be 20 to 90 ℃, preferably 40 to 70 ℃.
Optionally, the roasting temperature is usually 300-700 ℃, the heating rate is usually 0.5-20.0 ℃/min, and the roasting time is usually 0.5-10.0 h.
According to another aspect of the present application, there is provided a method for producing an amine by hydrogenating a nitrile compound, characterized by reacting a raw material containing ammonia and the nitrile compound in the presence of a catalyst in a hydrogen atmosphere to produce the amine; the catalyst is selected from the group consisting of the catalyst, the catalyst prepared according to the method.
Optionally, the reaction conditions are: the reaction temperature is 50-200 ℃, the reaction pressure is 5.0-20.0 MPa, and the volume space velocity of hydrogen gas is 50.0-2000.0 h-1The molar ratio of ammonia to nitrile compound is 1.0: 20.0-80.0: 1.0.
Optionally, the catalyst is subjected to an activation treatment; the conditions of the activation treatment are as follows: reducing and activating under hydrogen-containing atmosphere; the pressure is 0.1-1.0 MPa, and the volume space velocity of hydrogen gas is 500-5000 h-1The temperature is 200-700 ℃, and the reduction time is 0.5-10.0 h.
Optionally, the conditions of the activation treatment are: reducing and activating under hydrogen-containing atmosphere; the pressure is 0.1-0.5 MPa, and the volume space velocity of hydrogen gas is 1000-3000 h-1The temperature is 350-550 ℃, and the reduction time is 1.5-6.0 h.
Alternatively, the catalyst prepared by the impregnation method or the precipitation method is usually activated in a reducing atmosphere before use.
Alternatively, the reducing atmosphere may be hydrogen or a mixed gas of hydrogen and other inert gases, preferably hydrogen.
Alternatively, the activation process may be carried out in a tube furnace or a fixed bed reactor.
Optionally, the pressure of the activation process is 0.1-1.0 MPa, and the volume space velocity of hydrogen gas is 500-5000 h-1The temperature is 200-700 ℃, and the reduction time is 0.5-10.0 h. Optionally, the pressure in the activation process is 0.1-0.5 MPa, and the volume space velocity of hydrogen gas is 1000-3000 h-1The temperature is 350-550 ℃, and the time is 1.5-6.0 h.
The catalyst is applied to the reaction of producing amine by hydrogenating nitrile compounds, and the mixture of the nitrile compounds and ammonia is pumped into a preheater, mixed with hydrogen, preheated to 100 ℃ and then enters a fixed bed reactor without adding any solvent for dissolution and dilution. The reaction conditions are as follows: the filling amount of the catalyst can be 0.5-10.0 ml, preferably 2.0-5.0 ml; the reaction temperature can be 50-200 ℃, and preferably 70-150 ℃; the reaction pressure is 5.0-20.0 MPa, preferably 6.0-10.0 MPa; the volume space velocity of the nitrile liquid is 0.1-10.0 h-1Preferably 0.2 to 1.0 hour-1(ii) a The volume space velocity of the hydrogen gas is 50.0-2000.0 h-1Preferably 200.0 to 800.0 hours-1(ii) a The molar ratio of ammonia to nitrile is 1.0:20.0 to 80.0:1.0, preferably 1.0:1.0 to 20.0: 1.0.
Compared with the prior art, the catalyst provided by the invention can obviously improve the conversion rate of nitrile compounds, the yield of the target product amine, the service life of the catalyst, the reaction process simplification and the process economy and environmental protection.
In the present application, an "element" is present in the form of a simple substance or a compound;
for example, "reactive metal elements include M, Re; m comprises at least one of Ni, Co and Cu, and represents that the active metal element can be an active metal simple substance or an active metal compound; the active metal compound can be an active metal oxide or an active metal salt;
for example, "the additive comprises at least one of Fe, Cr, W, Ru, B, Mg, Ba, Mn, La and Mo elements", and means that the additive is a simple substance or a compound of Fe, Cr, W, Ru, B, Mg, Ba, Mn, La and Mo; the compound can be oxide and salt;
“C1～C20alkyl, halogen substituted C1～C20Hydrocarbyl, hydroxy-substituted C1～C20Alkyl, amino substituted C1～C20Alkyl, carboxyl substituted C1～C20A hydrocarbon group, a nitrile group-substituted C1～C20The term "hydrocarbyl" includes alkane, alkene, alkyne.
The beneficial effects that this application can produce include:
1) the catalyst for producing amine by hydrogenating the nitrile compound provided by the application improves the conversion rate of the nitrile compound;
2) the catalyst for producing amine by hydrogenating nitrile compounds, which is provided by the application, can improve the yield of the target product amine;
3) the catalyst for producing amine by hydrogenating nitrile compounds provided by the application reduces the selectivity of by-product amines;
4) the catalyst for producing amine by hydrogenating nitrile compounds, which is provided by the application, reduces the cost of the catalyst;
5) the catalyst for producing amine by hydrogenating nitrile compounds, which is provided by the application, has the advantage that the service life of the catalyst is prolonged;
6) the catalyst for producing amine by hydrogenating nitrile compounds, which is provided by the application, is easy to operate.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
Al2O3Purchased from Shandong aluminum industries; SiO 22Purchased from Qingdao ocean chemical; al (Al)2O3-SiO2Purchased from Shandong aluminum industries, Inc.
The mesh number refers to the number of meshes in a length of 1 inch, for example, 20-40 mesh has a particle size of 0.425-0.850 mm;
the percentage of the catalyst composition is the weight percentage of each component in the catalyst.
The conversion, selectivity, in the examples of the present application were calculated as follows:
wherein C0 is the molar concentration of nitrile compounds before reaction, and C is the molar concentration of amine products in a reaction system after reaction; n is the molar weight of the amine product after the reaction, and Ntotal is the molar weight of all reaction products after the reaction.
Example 1
The catalyst is 10% Ni-2% Re/Al2O3. Weighing 8.8 g of 20-40 mesh Al2O3Oven-drying at 120 deg.C for 4 hr before use, and preparing 20ml solution containing 4.955 g Ni (NO)3)2·6H2O, 0.288 g NH4ReO4With which the above-mentioned Al is impregnated2O3And naturally airing the carrier, drying at 100 ℃ for 2 hours, roasting at 400 ℃ for 3 hours, and raising the temperature at the rate of 5 ℃/min.
Example 2
The catalyst is 15 percent of Ni-1 percent of Re-1.5 percent of B/SiO2. Weighing 8.25 g of 20-40 mesh SiO2Dried at 120 ℃ for 4 hours before use to prepare 20ml of Ni (NO) containing 7.432 g3)2·6H2O, 0.144 g NH4ReO40.859 g H3BO3By impregnating the above SiO with the aqueous solution2And naturally airing the carrier, drying at 100 ℃ for 4 hours, roasting at 400 ℃ for 5 hours, and raising the temperature at the rate of 5 ℃/min.
Example 3
The catalyst is 8 percent of Ni-8 percent of Co-2 percent of Re-1 percent of Mn/Al2O3. Weighing8.9 g of 20-40 mesh Al2O3Dried at 120 ℃ for 4 hours before use to prepare 20ml of Ni (NO) containing 3.964 g3)2·6H2O, 3.951 g Co (NO)3)2·6H2O, 0.288 g NH4ReO40.651 g of Mn (NO)3)2With which the above-mentioned Al is impregnated2O3And naturally airing the carrier, drying at 100 ℃ for 4 hours, roasting at 400 ℃ for 1 hour, and raising the temperature at a speed of 10 ℃/min.
Example 4
The catalyst is 20 percent of Ni-2.5 percent of Re-1 percent of Ru-1 percent of B/SiO2. Weighing 7.55 g of 20-40 mesh SiO2Dried at 120 ℃ for 4 hours before use to prepare 20ml of Ni (NO) containing 9.909 g3)2·6H2O, 0.360 g NH4ReO40.205 g RuCl3·3H2O, 0.573 g H3BO3By impregnating the above SiO with the aqueous solution2And naturally airing the carrier, drying at 120 ℃ for 4 hours, roasting at 500 ℃ for 10 hours, and raising the temperature at a rate of 10 ℃/min.
Example 5
The catalyst is 10 percent of Co-10 percent of Cu-1.5 percent of Re-1.5 percent of Cr/SiO2-Al2O3. Weighing 7.7 g of 20-40 mesh SiO2-Al2O3Dried at 120 ℃ for 4 hours before use to prepare 20ml of solution containing 4.939 g of Co (NO)3)2·6H2O, 2.951 g Cu (NO)3)20.216 g NH4ReO40.687 g Cr (NO)3)3By impregnating the above SiO with the aqueous solution2-Al2O3And naturally airing the carrier, drying at 120 ℃ for 4 hours, roasting at 500 ℃ for 8 hours, and raising the temperature at the rate of 15 ℃/min.
Example 6
The catalyst is 10 percent of Ni-10 percent of Cu-3 percent of Re/SiO2-Al2O3. Weighing 7.7 g of 100 mesh SiO2-Al2O3Drying at 120 deg.C for 4 hr before use to remove SiO2-Al2O3Dispersed in 50ml of water to form a suspension, and stirred at a constant temperature of 50 ℃ with moderate speed.The formulation contained 4.955 g of Ni (NO)3)2·6H2O, 2.951 g Cu (NO)3)20.432 g NH4ReO4The precursor liquid of (4). The precipitant is 4mol/L KOH solution. And (3) simultaneously dripping the precursor liquid and the precipitator into the suspension at the speed of 10 ml/min, keeping the pH value at 9 until the precipitation is complete, washing the precipitate to be neutral by using deionized water, filtering, airing, drying at 120 ℃ for 4 hours, roasting at 500 ℃ for 8 hours, and increasing the temperature at the rate of 2 ℃/min.
Example 7
The catalyst is 15 percent of Cu-2 percent of Re/SiO2. Weighing 8.3 g of 100 mesh SiO2Drying at 120 deg.C for 4 hr before use to remove SiO2Dispersing in water to form a suspension, and stirring at a constant temperature of 50 deg.C with medium speed. The formulation contained 4.427 g of Cu (NO)3)20.288 g NH4ReO4The precursor liquid of (4). The precipitant is 4mol/L (NH)4)2·CO3And (3) solution. And (3) slowly dripping the precursor liquid and a precipitator into the suspension liquid at the same time, keeping the pH value at 7-9 until the precipitation is complete, washing the precipitate to be neutral by using deionized water, filtering, airing, drying for 4 hours at 120 ℃, roasting for 5 hours at 600 ℃, and raising the temperature at the rate of 2 ℃/min.
Example 8
The catalyst is 15 percent of Co-15 percent of Cu-5 percent of Re-2.5 percent of La/Al2O3. Weighing 6.25 g of 20-40 mesh Al2O3Dried at 120 ℃ for 4 hours before use to prepare 20ml of a mixture containing 7.408 g of Co (NO)3)2·6H2O, 4.427 g Cu (NO)3)20.720 g NH4ReO40.779 g La (NO)3)3·6H2An aqueous solution of O, and impregnating the Al with the aqueous solution2O3And naturally airing the carrier, drying at 120 ℃ for 4 hours, roasting at 600 ℃ for 10 hours, and raising the temperature at the rate of 20 ℃/min.
Example 9
The catalyst is 25 percent of Ni-2.5 percent of Re-2 percent of W/SiO2. Weighing 7.05 g of 20-40 mesh SiO2Dried at 120 ℃ for 4 hours before use to prepare 20ml of Ni (NO) containing 12.387 g3)2·6H2O, 0.360 g NH4ReO40.359 g Na2WO4·2H2An aqueous solution of O, impregnating the above SiO with the aqueous solution2And naturally airing the carrier, drying at 120 ℃ for 4 hours, roasting at 600 ℃ for 3 hours, and raising the temperature at a rate of 10 ℃/min.
Example 10 catalyst Activity test
The catalysts prepared in examples 1 to 9 were subjected to reaction evaluation using a fixed bed reactor. Before reaction, activating in hydrogen atmosphere at 500 deg.C, normal pressure and hydrogen gas volume space velocity of 1500h-1The activation time is 5 h. After the activation treatment, the temperature was lowered to the reaction temperature. The reaction temperature is 100 ℃, the reaction pressure is 8.0MPa, and the volume space velocity of nitrile liquid is 0.5h-1The volume space velocity of hydrogen gas is 1000h-1The molar ratio of ammonia to nitrile was 5.0: 1.0. Sampling and analyzing by adopting an Agilent 7890 gas chromatograph, wherein the chromatographic column is a DB-35 capillary chromatographic column, and the detector is a hydrogen flame detector. Quantitative analysis was performed using N, N-Dimethylformamide (DMFA) as an internal standard. The results are summarized in Table 1. Table 1 shows that when the catalysts prepared in examples 1 to 7 are used for preparing 3-aminopropanol by catalytic hydrogenation of 3-hydroxypropionitrile, the conversion rate of 3-hydroxypropionitrile is over 90 percent and can even reach one hundred percent; the selectivity of the 3-aminopropanol is more than 92 percent. The catalyst prepared in example 8 is used for preparing hexanediol by catalytic hydrogenation of adiponitrile, and the conversion rate of adiponitrile is 97.5%; the selectivity to hexanediol was 95.6%. The catalyst prepared in the embodiment 8 is used for preparing phenethyl alcohol by catalytic hydrogenation of phenylacetonitrile, and the conversion rate of the phenylacetonitrile is 96.0%; the selectivity of the phenethyl alcohol is 97.4 percent.
Table 1: evaluation results of catalysts for producing amines by hydrogenation of nitrile compounds.
Example 10 catalyst stability testing
The catalysts prepared in examples 1-9 were tested for stability. For the catalyst prepared in example 1, 10% Ni-2% Re/Al2O3Go on toThe stability test at 500 hours, the activation and operation of the catalyst were carried out under the same conditions as those of the activity test in example 9, and the experimental data are shown in Table 2. As can be seen from Table 2, after 500 hours of testing, the activity and selectivity of the catalyst were not substantially changed, the conversion of 3-hydroxypropionitrile was above 94%, and the selectivity of 3-aminopropanol was above 94%. The stability of the catalysts prepared in examples 2-8 was similar to that of example 1.
Table 2 catalyst stability testing
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (23)
1. A method for producing amine by hydrogenating nitrile compounds is characterized in that raw materials containing ammonia and nitrile compounds react to prepare amine in the presence of a catalyst in a hydrogen atmosphere;
the catalyst comprises an active component and a carrier;
the active component comprises an active metal element; the active metal elements include M and Re; m is selected from one of Ni, Co and Cu;
the carrier is selected from at least one of inorganic porous materials;
the catalyst also comprises an auxiliary agent;
the auxiliary agent comprises an auxiliary agent element, and the auxiliary agent element comprises at least one of W, B, Mn and La;
the mol ratio of ammonia to nitrile compound is 1.0: 1.0-20.0: 1.0;
no solvent is included in the feed.
2. The method of claim 1, wherein M is 5.0 to 50.0% by weight of the catalyst; the weight percentage of Re in the catalyst is 0.1-15.0%.
3. The method according to claim 1, wherein the weight percentage of the active metal element M in the catalyst is 10.0-25.0%;
the weight percentage of Re in the catalyst is 1.0-5.0%.
4. The method of claim 1,
the auxiliary agent comprises an oxide of the auxiliary agent element;
the weight percentage content of the auxiliary agent in the catalyst is 0.2-10.0%;
wherein, the weight percentage of the auxiliary agent is calculated by the weight percentage of the auxiliary agent element.
5. The method of claim 4, wherein the promoter is present in the catalyst in an amount of 1.0% to 5.0% by weight.
6. The method according to claim 4, wherein the auxiliary element is at least one selected from B, Mn, Ba.
7. The method according to claim 1, wherein the specific surface area of the carrier is 50 to 600m2The pore volume is 0.2-1.5 ml/g.
8. The method according to claim 1, wherein the specific surface area of the carrier is 200 to 500m2The pore volume is 0.4-1.0 ml/g.
9. The method of claim 1, wherein the support is selected from porous Al2O3Porous SiO2Porous Al2O3-SiO2At least one of (1).
10. The method according to claim 1, wherein the nitrile compound has a structural formula shown as formula I or formula II;
wherein R is selected from C1 ~ C20Alkyl, halogen substituted C1 ~ C20Hydrocarbyl, hydroxy-substituted C1 ~ C20Alkyl, amino substituted C1 ~ C20Alkyl, carboxyl substituted C1 ~ C20A hydrocarbon group, a nitrile group-substituted C1 ~ C20A hydrocarbon group of (a);
r' is selected from C1 ~ C20Alkyl, halogen, hydroxyl, amino, carboxyl, nitrile group, halogen substituted C1 ~ C20Hydrocarbyl, hydroxy-substituted C1 ~ C20Alkyl, amino substituted C1 ~ C20Alkyl, carboxyl substituted C1 ~ C20A hydrocarbon group, a nitrile group-substituted C1 ~ C20A hydrocarbon group of (1).
11. The method of any of claims 1 to 10, wherein the catalyst is prepared by a method comprising at least one of impregnation and precipitation.
12. The method of claim 11, wherein the catalyst is prepared by a method comprising: soaking a carrier in a solution containing an active metal element source, and roasting to obtain the catalyst; or
Adding a solution containing an active metal element source and a precipitating agent into a suspension containing a carrier, and precipitating to obtain the catalyst.
13. The method of claim 12, wherein the solution contains a source of an auxiliary element.
14. The method of claim 12, wherein the firing conditions are: the temperature is 300-700 ℃, and the time is 0.5-10.0 h.
15. The method of claim 12, wherein the source of the reactive metal element is selected from at least one of soluble salts of the reactive metal element;
the auxiliary element source is selected from at least one of soluble salts of auxiliary elements.
16. The method of claim 15, wherein the soluble salt of the active metal element Ni comprises at least one of nickel nitrate, nickel acetate, nickel chloride, nickel sulfate, and nickel citrate.
17. The method of claim 15, wherein the soluble salt of the active metal element Co comprises at least one of cobalt chloride, cobalt nitrate, cobalt carbonate, and cobalt sulfate.
18. The method of claim 15, wherein the soluble salt of the active metal element Cu comprises at least one of copper nitrate, copper chloride, copper carbonate, and copper sulfate.
19. The method of claim 15, wherein the soluble salt of the active metal element Re comprises at least one of ammonium rhenate, perrhenic acid, and rhenium chloride.
20. The method of claim 15, wherein the auxiliary element is a metal, and the soluble salt thereof comprises at least one of a nitrate of the auxiliary element and a chloride of the auxiliary element;
the assistant element is B, and the assistant element source is boric acid.
21. The process according to claim 1, characterized in that the reaction conditions for the preparation of the amine are: the reaction temperature is 50-200 ℃, the reaction pressure is 5.0-20.0 MPa, and the volume space velocity of hydrogen is 50.0-2000.0 h-1。
22. The method of claim 1, wherein the catalyst is subjected to an activation treatment; the conditions of the activation treatment are as follows: reducing and activating under hydrogen-containing atmosphere; the pressure is 0.1-1.0 MPa, and the volume space velocity of hydrogen gas is 500-5000 h-1The temperature is 200-700 ℃, and the reduction time is 0.5-10.0 h.
23. The method according to claim 22, wherein the conditions of the activation treatment are: reducing and activating under hydrogen-containing atmosphere; the pressure is 0.1-0.5 MPa, and the volume space velocity of hydrogen gas is 1000-3000 h-1The temperature is 350-550 ℃, and the reduction time is 1.5-6.0 h.
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