CN106179400A - Active carbon supported composite metal catalyst and preparation method and application thereof - Google Patents
Active carbon supported composite metal catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN106179400A CN106179400A CN201610528540.6A CN201610528540A CN106179400A CN 106179400 A CN106179400 A CN 106179400A CN 201610528540 A CN201610528540 A CN 201610528540A CN 106179400 A CN106179400 A CN 106179400A
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- China
- Prior art keywords
- catalyst
- formula
- reaction
- activated carbon
- hydrogenation
- Prior art date
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- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 239000003054 catalyst Substances 0.000 title claims abstract description 127
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 42
- 239000002184 metal Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002131 composite material Substances 0.000 title claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 title claims description 17
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 68
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 28
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 21
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 21
- 239000011701 zinc Substances 0.000 claims abstract description 21
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 15
- 239000010941 cobalt Substances 0.000 claims abstract description 15
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 15
- 239000010948 rhodium Substances 0.000 claims abstract description 15
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 13
- 229910052802 copper Inorganic materials 0.000 claims abstract description 13
- 239000010949 copper Substances 0.000 claims abstract description 13
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 9
- -1 amine compounds Chemical class 0.000 claims abstract description 6
- 150000002828 nitro derivatives Chemical class 0.000 claims abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 222
- 238000003756 stirring Methods 0.000 claims description 71
- 239000001257 hydrogen Substances 0.000 claims description 56
- 229910052739 hydrogen Inorganic materials 0.000 claims description 56
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 42
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- 150000001875 compounds Chemical class 0.000 claims description 40
- 239000007788 liquid Substances 0.000 claims description 37
- 238000006722 reduction reaction Methods 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 21
- 239000000376 reactant Substances 0.000 claims description 18
- 230000000694 effects Effects 0.000 claims description 16
- 238000004458 analytical method Methods 0.000 claims description 15
- 239000000706 filtrate Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 13
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 13
- 230000009467 reduction Effects 0.000 claims description 13
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 12
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 12
- 125000001424 substituent group Chemical group 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 11
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 9
- 239000000460 chlorine Substances 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052700 potassium Inorganic materials 0.000 claims description 8
- 239000011591 potassium Substances 0.000 claims description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 230000036632 reaction speed Effects 0.000 claims description 7
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 5
- 235000019253 formic acid Nutrition 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004104 aryloxy group Chemical group 0.000 claims description 4
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 125000004423 acyloxy group Chemical group 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 125000004122 cyclic group Chemical class 0.000 claims description 3
- 150000002431 hydrogen Chemical group 0.000 claims description 3
- 238000012423 maintenance Methods 0.000 claims description 3
- 238000012805 post-processing Methods 0.000 claims description 3
- RWRDJVNMSZYMDV-UHFFFAOYSA-L radium chloride Chemical compound [Cl-].[Cl-].[Ra+2] RWRDJVNMSZYMDV-UHFFFAOYSA-L 0.000 claims description 3
- 229910001630 radium chloride Inorganic materials 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 2
- SVOOVMQUISJERI-UHFFFAOYSA-K rhodium(3+);triacetate Chemical compound [Rh+3].CC([O-])=O.CC([O-])=O.CC([O-])=O SVOOVMQUISJERI-UHFFFAOYSA-K 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical group O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 230000006837 decompression Effects 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 abstract description 23
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- 238000011946 reduction process Methods 0.000 abstract description 2
- 125000003277 amino group Chemical group 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 42
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
- 238000010792 warming Methods 0.000 description 15
- 235000013162 Cocos nucifera Nutrition 0.000 description 14
- 239000008187 granular material Substances 0.000 description 14
- 230000004044 response Effects 0.000 description 14
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 14
- 244000060011 Cocos nucifera Species 0.000 description 13
- 208000012839 conversion disease Diseases 0.000 description 13
- 239000010903 husk Substances 0.000 description 13
- 238000007789 sealing Methods 0.000 description 12
- 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 11
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 11
- 229910052708 sodium Inorganic materials 0.000 description 11
- 239000011734 sodium Substances 0.000 description 11
- 235000011121 sodium hydroxide Nutrition 0.000 description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 8
- 229960003975 potassium Drugs 0.000 description 7
- 239000012453 solvate Substances 0.000 description 7
- 239000011592 zinc chloride Substances 0.000 description 7
- 235000005074 zinc chloride Nutrition 0.000 description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- VBEGHXKAFSLLGE-UHFFFAOYSA-N n-phenylnitramide Chemical class [O-][N+](=O)NC1=CC=CC=C1 VBEGHXKAFSLLGE-UHFFFAOYSA-N 0.000 description 4
- 125000005245 nitryl group Chemical group [N+](=O)([O-])* 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 125000006575 electron-withdrawing group Chemical group 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 235000011118 potassium hydroxide Nutrition 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 2
- XJCVRTZCHMZPBD-UHFFFAOYSA-N 3-nitroaniline Chemical compound NC1=CC=CC([N+]([O-])=O)=C1 XJCVRTZCHMZPBD-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000011026 diafiltration Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229960004979 fampridine Drugs 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- NCBZRJODKRCREW-UHFFFAOYSA-N m-anisidine Chemical compound COC1=CC=CC(N)=C1 NCBZRJODKRCREW-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000000269 nucleophilic effect Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 1
- XGLGESCVNJSAQY-UHFFFAOYSA-N 1-ethoxy-2-nitrobenzene Chemical compound CCOC1=CC=CC=C1[N+]([O-])=O XGLGESCVNJSAQY-UHFFFAOYSA-N 0.000 description 1
- WEZAHYDFZNTGKE-UHFFFAOYSA-N 3-ethoxyaniline Chemical compound CCOC1=CC=CC(N)=C1 WEZAHYDFZNTGKE-UHFFFAOYSA-N 0.000 description 1
- 241000737241 Cocos Species 0.000 description 1
- GJYJYFHBOBUTBY-UHFFFAOYSA-N alpha-camphorene Chemical compound CC(C)=CCCC(=C)C1CCC(CCC=C(C)C)=CC1 GJYJYFHBOBUTBY-UHFFFAOYSA-N 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 239000001508 potassium citrate Substances 0.000 description 1
- 229960002635 potassium citrate Drugs 0.000 description 1
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 1
- 235000011082 potassium citrates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 238000006561 solvent free reaction Methods 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
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Abstract
The invention provides an activated carbon supported composite metal catalyst and a preparation method and application thereof, wherein the catalyst consists of a carrier, an active component and an auxiliary agent, the carrier is activated carbon, the active component is at least one of platinum, palladium and rhodium, and the auxiliary agent is at least one of iron, zinc, cobalt and copper; the catalyst can be applied to the reaction of synthesizing corresponding amine compounds by catalytic hydrogenation of nitro compounds; the catalyst has high catalytic activity and high hydrogenation reaction rate, and the use method of the catalyst favorably promotes the reduction process, and can quickly reduce 100 percent of nitro groups influenced by the power supply groups into amino groups; the catalyst has the advantages of mild condition, good stability and more times of application in the recycling process.
Description
(1) technical field
The present invention relates to a kind of activated carbon supported type composite metal catalyst and preparation method and application, this catalyst can
The nitro-catalytic hydrogenation reduction reaction of electron-donating group is contained on phenyl ring, pyridine ring.
(2) technical background
It is the important basic organic synthesis of a class that nitro is reduced into amino process, is widely used in pigment, dyestuff, doctor
In the catalyst preparation such as medicine, pesticide and rubber chemicals, resin, sensitive material.Traditional synthetic route generally uses chemistry
Reducing process, this method uses akali sulphide, iron powder etc. to generate amino with nitro generation redox reaction in acid medium.This technique
Easy and simple to handle, course of reaction steadily fluctuates little, and reactant converts thoroughly.But reduzate mixes in sulfide waste residue or iron cement
In, separate difficulty, energy consumption height.The a large amount of waste residues Han Organic substance simultaneously produced are the most disposable, seriously polluted.Liquid phase catalytic hydrogenation is also
Former method because of its have that the three wastes are few, superior product quality and low power consumption and other advantages and receive much concern, be an eco-friendly green work
Skill.At present, the reduction process of nitro the most commonly used catalytic hydrogenation method.
When nitro is directly connected with phenyl ring, the π track of nitro constitutes delocalized orbitals, due to nitrogen and oxygen with the π track of phenyl ring
The electronegativity that atom is stronger, the delocalization deflection nitryl group of electronics.Accordingly, with respect to other reproducibility groups, nitro is one
Be easier to the group being reduced, generally reaction temperature be 100 DEG C, below Hydrogen Vapor Pressure 2.0MPa reduction reaction can occur.Separately
Outward, nitro is the conjugation hybrid of two equal limit structures, and the result of electron delocalization makes negative charge be distributed evenly over two
On oxygen atom.Therefore, nitro reduction belongs to nucleophilic displacement of fluorine mechanism.When being connected with electron-withdrawing group on phenyl ring, the electronics on phenyl ring to
Electron-withdrawing group offsets, and the atom N of nitro presents higher power shortage state, and nitro is the most easily reduced.In contrast, when on phenyl ring
When being connected with power supplying groups, nitro just becomes to be difficult to be reduced.Such as, common Nitrobenzol, chloronitrobenzene, m-nitrobenzene sulfonic acid
Nitro reduction rate in the compounds such as sodium is fast, and conversion ratio all can reach 100%.And meta-dinitro-benzent [application chemical industry,
2011,40 (1): 51], during ethoxynitrobenzene [Chemical Manufacture and technology, 2007,14 (3): 29] hydrogenating reduction, due to
Nitro is electron withdraw group, and therefore first nitro reduction rate is very fast, but after this nitro is reduced into amino, by electron-withdrawing group
Group becomes electron-donating group, and second nitro reduction rate is remarkably decreased, and conversion ratio is the most relatively difficult to reach 100%.Connect on phenyl ring
Some electron-donating groups are the most, electron-donating the strongest, and nitro reduction is more difficult to.
In published document, the most common about nitro reducing catalyst and catalytic performance thereof, but for phenyl ring
The upper nitro-catalytic hydrogenation reduction reaction containing electron-donating group, yet there are no systematic study report, and prior art can't be real
Now quickly, high conversion, high stability its catalytic hydrogenating reduction being synthesized corresponding amino-compound, this has become puzzlement and has urged
Change one of common technology difficult problem of field of hydrogenation.
(3) summary of the invention
It is an object of the invention to provide a kind of activated carbon supported type composite metal catalyst and preparation method and application,
This catalyst can be applicable in the reaction that catalytic hydrogenation of nitro compound synthesizes corresponding aminated compounds, especially at phenyl ring, pyridine
High conversion, high catalytic activity, high stability is shown containing in the nitro-catalytic hydrogenation reduction reaction of electron-donating group on ring
Feature.
For achieving the above object, the present invention adopts the following technical scheme that
A kind of activated carbon supported type composite metal catalyst, described catalyst is made up of carrier, active component, auxiliary agent,
Described carrier is activated carbon, and described active component is at least one in platinum, palladium, rhodium, described auxiliary agent be ferrum, zinc, cobalt,
At least one in copper；Quality based on carrier, in described active component, the load capacity of each metal is: palladium 0wt%～
10.0wt%, platinum 0wt%～10.0wt%, rhodium 0wt%～5.0wt%, and the load capacity of palladium, platinum, rhodium is not 0；Described help
In agent, ferrum, zinc, cobalt, the load capacity of copper are 0wt%～5.0wt%, and the load capacity of ferrum, zinc, cobalt, copper is not 0.
Further, in described catalyst, described active component and load capacity thereof are selected from one of following combination:
Palladium 0.5wt%～8.0wt%, platinum 0.5wt%～8.0wt%；
Palladium 0.5wt%～8.0wt%, rhodium 0.1wt%～3.0wt%；
Platinum 0.5wt%～8.0wt%, rhodium 0.1wt%～3.0wt%；
Described auxiliary agent is any two kinds in ferrum, zinc, cobalt, copper, and the load capacity of these any two kinds of metal promoters is
0.1wt%～4.0wt%.
In the present invention, the ash of described carrier active carbon is 0.01wt%～5.0wt%, specific surface area be 500～
2000m2/ g, micropore specific area proportion is not less than 50%, and activated carbon granule granularity is D10: 1～5 μm, D50: 10～15 μ
M, D90: 20～35 μm；The material of described activated carbon can be coconut husk or wooden.
Present invention also offers the preparation method of a kind of described activated carbon supported type composite metal catalyst, described preparation
Method is:
Adding in ethylene glycol A by soluble-salt and the citrate of activity component metal, stirring, to being completely dissolved, obtains body
It is A；Activated carbon is mixed with ethylene glycol B, stirs 0.5～5h (preferably 1～4h) in 35～150 DEG C (preferably 50～120 DEG C),
To system B；In system B drip system A, after dripping off in 35～150 DEG C (preferably 50～120 DEG C) stir 1～10h (preferably 2～
8h)；It is subsequently added into the soluble-salt of promoter metal, continues at 35～150 DEG C (preferably 50～120 DEG C) stirring 1～10h (preferably 2
～8h)；Then regulation pH to 7～14 (preferably 8～12), adds reducing agent and carries out reduction reaction, afterwards through filtering, washing, i.e.
Obtain described activated carbon supported type composite metal catalyst.
Obtained activated carbon supported type composite metal catalyst can pass through ethylene glycol diafiltration, makes ethylene glycol in catalyst
Content is more than 50wt%, or direct being stored in ethylene glycol by prepared catalyst sealing preserves.
In preparation method of the present invention, the soluble-salt of described activity component metal can be Palladous chloride., Palladous nitrate., chlorine palladium
In acid, palladium, platinous chloride, platinum tetrachloride, chloroplatinic acid, platinum nitrate, platinic sodium chloride, radium chloride, rhodium nitrate, rhodium acetate extremely
Few one.
Generally, the consumption of described ethylene glycol A be under room temperature by the soluble-salt of activity component metal and citrate just
Dissolve.
Described citrate is sodium citrate and/or potassium citrate, and the quality consumption of described citrate is activity group
0.5～5 times of metal simple-substance quality in the soluble-salt that parting belongs to.
The volumetric usage of described ethylene glycol B is calculated as 2～10mL/g with the quality of activated carbon, preferably 3～8mL/g.
The soluble-salt of described promoter metal is at least one in ferrum, zinc, cobalt, hydrochlorate that copper is corresponding, nitrate.
The regulation of described pH value recommends the ethylene glycol solution of alkaline matter, described alkaline matter be sodium hydroxide,
Sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate or potassium bicarbonate.
The method of described reduction reaction is wet reducing, and described reducing agent is selected from formaldehyde, formic acid, hypophosphites, hydration
Hydrazine or hydrogen；The condition of reduction reaction is: temperature 35～100 DEG C, the time 1～10h；When reducing agent is formaldehyde, formic acid, hypophosphorous acid
When salt or hydrazine hydrate, the consumption of reducing agent is the soluble-salt of activity component metal and the soluble-salt of promoter metal is reduced to
Needed for metal simple-substance 1～10 times of the amount of theoretical material, when reducing agent is hydrogen, hydrogen is passed through below serosity liquid level, hydrogen
Flow is 10～100mL/min, and the pressure of hydrogen is normal pressure.
It should be noted that in preparation method of the present invention, the soluble-salt of activity component metal, promoter metal
Soluble-salt, the inventory of activated carbon can carry out theoretical conversion according to the load capacity of component each in above-mentioned catalyst, and as real
The inventory on border.Because of according to known in this area and experimental verification, after pH adjusted and reduction, activity component metal solvable
Property salt, promoter metal soluble-salt in metal simple-substance be substantially all carried on activated carbon with theoretical amount.
In preparation method of the present invention, described ethylene glycol A, ethylene glycol B do not have special implication, refer both to generally anticipate
Ethylene glycol in justice, is labeled as " A ", " B " is only intended to distinguish in different operating step the ethylene glycol used.
Activated carbon supported type composite metal catalyst of the present invention can be applicable to catalytic hydrogenation of nitro compound synthesis
In the reaction of corresponding aminated compounds, it is particularly applicable on phenyl ring, pyridine ring the nitro-catalytic hydrogenation containing electron-donating group
Reduction reaction.
Concrete, the application process of catalyst of the present invention is:
Compound shown in catalyst of the present invention, formula (II) and/or solvent are put in high-pressure hydrogenation reactor, confined reaction
Still, with opening stirring after hydrogen exchange air, temperature be 20～150 DEG C, Hydrogen Vapor Pressure be 0.1～8.5MPa (preferably 0.2～
Under conditions of 6.5MPa) (in still, material is in melted or solution state), instill compound shown in reactant formula (I), drip off follow-up
Continuous reaction to Hydrogen Vapor Pressure in 15min constant time, stopped reaction, sample analysis, the separated post processing of hydrogenation liquid obtains product formula
(II) compound shown in；
In above-mentioned application process, compound shown in the formula (II) of input high-pressure hydrogenation reactor is replaced with formula (IV) institute
Showing compound, compound shown in the reactant formula (I) of instillation replaces with compound shown in formula (III), then obtain product formula (IV)
Shown compound；
In formula (I) or (II), Rn represents the one or more substituent groups on phenyl ring, and wherein R represents substituent group, n=1,2,
3,4 or 5, described substituent group each stands alone as amino, the substituted amino of C1～C5 alkyl, hydroxyl, aryloxy group, C1～C3 alcoxyl
Base, acyloxy or acylamino-；
In formula (III) or (IV), R ' m represents the one or more substituent groups on pyridine ring, and wherein R ' represents substituent group, m
=1,2,3 or 4, described substituent group each stands alone as amino, the substituted amino of C1～C5 alkyl, hydroxyl, aryloxy group, C1～C3
Alkoxyl, acyloxy or acylamino-.
In application process of the present invention, described reaction can carry out under condition of no solvent, carry out in a solvent or
Person is carried out in the compound shown in the formula (II) corresponding with product or formula (IV) and solvent are with the mixture of arbitrary proportion.Institute
State compound shown in formula (I) or (III) to drip with molten condition, or drip after the dissolving of hydrogenation reaction solvent for use.
Fit in the case of the fusing point of reactant and product is all less than 150 DEG C (i.e. less than the higher limit of range of reaction temperature)
For solvent-free reaction.Under condition of no solvent, can be corresponding with product by putting in high-pressure hydrogenation reactor in advance
Compound shown in formula (II) or formula (IV), with dispersed catalyst and the reactant that instills afterwards.Generally, described in advance at height
The volumetric usage of the compound shown in the formula corresponding with product (II) put in pressure hydrogenation reaction kettle or formula (IV) is with reaction
The quality of thing [compound shown in compound shown in formula (I) or formula (III)] is calculated as 0.5～15mL/g, preferably 1～10mL/g.
When reaction carry out in a solvent time, described reaction be suitable for solvent be methanol, ethanol, water, normal propyl alcohol, isopropanol,
The mixed solvent of one or more arbitrary proportions in n-butyl alcohol, isobutanol, sec-butyl alcohol, the tert-butyl alcohol；Generally, described solvent
Volumetric usage be calculated as 0.5～15mL/g with the quality of reactant [compound shown in compound shown in formula (I) or formula (III)],
Preferably 1～10mL/g.
When reaction is the compound shown in the formula (II) corresponding with product or formula (IV) and solvent mixing with arbitrary proportion
When carrying out in compound, the volumetric usage of described mixture is with reactant [compound shown in compound shown in formula (I) or formula (III)]
Quality be calculated as 0.5～15mL/g, preferably 1～10mL/g.
Reactant [compound shown in compound shown in formula (I) or formula (III)] described in recommendation and catalysis of the present invention
The mass ratio that feeds intake of agent is 100:0.1～4.0, preferably 100:0.2～2.0.
The method of described hydrogenation liquid separation post processing is: hydrogenation liquid filters to isolate catalyst, and filtrate is after rectification under vacuum
Obtain product；In last handling process, the catalyst cake that hydrogenation liquid is filtrated to get may return to reactor to carry out catalyst and applies mechanically；
The application process of catalyst of the present invention can also use continuous reaction process, it may be assumed that formula (II) or formula (IV) institute
The compound shown and/or solvent and catalyst follow in the sealing and circulating system between catalyst filtration device and hydrogenation reactor
Ring.Molten state or the reactant [compound shown in compound shown in formula (I) or formula (III)] being dissolved in solvent instill with continuous
Mode add in reactor, reaction carry out in the way of complete mixing flow, the hydrogenation liquid of outflow reactor is through catalyst filtration device
After separation, filtrate i.e. obtains product through rectification under vacuum.The hydrogenation liquid of outflow reactor and the molten state of instillation or be dissolved in solvent
Reactant on volume, keep equal, with material balance in maintenance system.In this cyclic process, depending on hydrogenation reaction speed and
Conversion ratio, quantitative fresh makeup catalyst and the catalyst taken out in using, to keep the catalytic reaction of system inner catalyst to live
Property.
Compared with prior art, beneficial effects of the present invention is embodied in:
(1) catalyst activity of the present invention is high, and hydrogenation reaction speed is fast, the nitro that can quickly will be affected by power supplying groups
Group 100% is reduced into amino；
(2) catalyst using method of the present invention, during catalytic hydrogenation reaction, can remain higher
The ratio of catalyst and nitroso reaction thing, can reduce ammonification by the nitryl group affected by power supplying groups 100% being difficult to reduce
Base；
(3) catalyst of the present invention and catalyst using method thereof, combine the catalytic performance that catalyst is good, urge
Change the efficient utilization of catalyst in hydrogenation technique design, considerably improve hydrogenation reaction speed, substantially reduce the response time,
Achieve the hydrogenating reduction of nitryl group in high conversion rate.
(4) catalyst of the present invention recycles process condition gentleness, good stability, and catalyst amount is low, applies mechanically often,
Life-span is long.
In sum, owing to nitro reduction is nucleophilic displacement of fluorine mechanism, the electron-donating group that phenyl ring, pyridine ring contain weakens
The short of electricity of atom N, causes nitro reduction difficulty to strengthen, presents non-zero order reaction phenomenon, and catalytic hydrogenation reaction speed is slack-off,
Conversion ratio is difficult to reach 100%.Existing catalyst system still can not meet industrialization production requirements.And catalyst of the present invention is urged
Changing activity high, hydrogenation reaction speed is fast, and its using method has advantageously facilitated the process of reduction, can will be affected by power supplying groups
Nitryl group quick 100% be reduced into amino.
(4) detailed description of the invention
Further illustrate technical scheme with specific embodiment below, but protection scope of the present invention is not limited to
This.
Embodiment 1
Described carrier active carbon physical parameter: ash is 3.0wt%, specific surface area is 1500m2/ g, micropore specific area
Proportion is not less than 75%, and activated carbon granule granularity is D10: 2.5 μm, D50: 12 μm, D90:30μm；The material of described activated carbon
For coconut husk.
Weigh content be Palladous chloride. that 0.5g palladium is corresponding, content be the platinous chloride and 2.5g citric acid that 0.3g platinum is corresponding
Sodium, adds ethylene glycol and stirs to being completely dissolved；10g activated carbon and 50ml ethylene glycol are mixed and made into serosity, after being warming up to 50 DEG C
Stirring 2 hours, then instill the ethylene glycol solution of active component, constant temperature stirs 5 hours；Adding content is the chlorine that 0.1g ferrum is corresponding
Changing ferrum is the zinc chloride that 0.2g zinc is corresponding with content, continues constant temperature and stirs 5 hours；The ethylene glycol solution of dropping sodium hydroxide, adjusts
Joint pH value of solution is to 8；Adding 1ml hydrazine hydrate (80wt%) at 50 DEG C to reduce, the time is 3 hours.Eventually pass filter, use water
Washing i.e. obtains described catalyst after being neutrality to filtrate.Gained catalyst sealing is stored in ethylene glycol liquid.
Embodiment 2
Described carrier active carbon physical parameter: ash is 4.0wt%, specific surface area is 1200m2/ g, micropore specific area
Proportion is not less than 70%, and activated carbon granule granularity is D10: 4.5 μm, D50: 15 μm, D90:32μm；The material of described activated carbon
For coconut husk.
Weigh content be Palladous chloride. that 0.5g palladium is corresponding, content be the platinous chloride and 3.5g citric acid that 0.3g platinum is corresponding
Sodium, adds ethylene glycol and stirs to being completely dissolved；10g activated carbon and 40ml ethylene glycol are mixed and made into serosity, after being warming up to 80 DEG C
Stirring 2 hours, then instill the ethylene glycol solution of active component, constant temperature stirs 3 hours；Adding content is the chlorine that 0.1g ferrum is corresponding
Changing ferrum is the zinc chloride that 0.2g zinc is corresponding with content, continues constant temperature and stirs 5 hours；The ethylene glycol solution of dropping sodium hydroxide, adjusts
Joint pH value of solution is to 10；Being cooled to 70 DEG C, add 1.5ml hydrazine hydrate (80wt%) and reduce, the time is 3 hours.Eventually pass
Filter, to be washed with water to filtrate be i.e. to obtain described catalyst after neutrality.Gained catalyst sealing is stored in ethylene glycol liquid.
Embodiment 3
Described carrier active carbon physical parameter: ash is 3.0wt%, specific surface area is 1500m2/ g, micropore specific area
Proportion is not less than 75%, and activated carbon granule granularity is D10: 2.5 μm, D50: 12 μm, D90:30μm；The material of described activated carbon
For coconut husk.
Weigh content be Palladous chloride. that 0.6g palladium is corresponding, content be the platinous chloride and 2.5g citric acid that 0.2g platinum is corresponding
Sodium, adds ethylene glycol and stirs to being completely dissolved；10g activated carbon and 50ml ethylene glycol are mixed and made into serosity, after being warming up to 50 DEG C
Stirring 2 hours, then instill the ethylene glycol solution of active component, constant temperature stirs 5 hours；Adding content is the chlorine that 0.2g ferrum is corresponding
Changing ferrum is the zinc chloride that 0.3g zinc is corresponding with content, continues constant temperature and stirs 5 hours；The ethylene glycol solution of dropping sodium hydroxide, adjusts
Joint pH value of solution is to 8；Adding 2ml hydrazine hydrate (80wt%) at 50 DEG C to reduce, the time is 5 hours.Eventually pass filter, use water
Washing i.e. obtains described catalyst after being neutrality to filtrate.Gained catalyst sealing is stored in ethylene glycol liquid.
Embodiment 4
Described carrier active carbon physical parameter: ash is 1.0wt%, specific surface area is 1600m2/ g, micropore specific area
Proportion is not less than 78%, and activated carbon granule granularity is D10: 2.0 μm, D50: 10 μm, D90:25μm；The material of described activated carbon
For wooden.
Weigh content be Palladous chloride. that 0.5g palladium is corresponding, content be the platinous chloride and 2.5g citric acid that 0.3g platinum is corresponding
Potassium, adds ethylene glycol and stirs to being completely dissolved；10g activated carbon and 50ml ethylene glycol are mixed and made into serosity, after being warming up to 50 DEG C
Stirring 2 hours, then instill the ethylene glycol solution of active component, constant temperature stirs 5 hours；Adding content is that 0.05g cobalt is corresponding
Cobalt nitrate and the copper chloride that content is that 0.1g copper is corresponding, continue constant temperature and stir 5 hours；The ethylene glycol solution of dropping sodium hydroxide,
Regulation pH value of solution is to 8；Adding 2ml formic acid at 50 DEG C to reduce, the time is 3 hours.Eventually pass filter, be washed with water to filter
Liquid is i.e. to obtain described catalyst after neutrality.In gained catalyst cake, quality of glycol content 80%.
Embodiment 5
Described carrier active carbon physical parameter: ash is 3.0wt%, specific surface area is 1500m2/ g, micropore specific area
Proportion is not less than 75%, and activated carbon granule granularity is D10: 2.5 μm, D50: 12 μm, D90:30μm；The material of described activated carbon
For coconut husk.
Weigh content be Palladous chloride. that 0.5g palladium is corresponding, content be the radium chloride and 2.5g citric acid that 0.3g rhodium is corresponding
Sodium, adds ethylene glycol and stirs to being completely dissolved；10g activated carbon and 50ml ethylene glycol are mixed and made into serosity, after being warming up to 80 DEG C
Stirring 2 hours, then instill the ethylene glycol solution of active component, constant temperature stirs 5 hours；Adding content is the chlorine that 0.2g ferrum is corresponding
Changing ferrum is the cobalt nitrate that 0.1g cobalt is corresponding with content, continues constant temperature and stirs 5 hours；The ethylene glycol solution of dropping sodium bicarbonate, adjusts
Joint pH value of solution is to 8；Being cooled to 50 DEG C, add 3.5ml formaldehyde (40wt%) and reduce, the time is 3 hours.Eventually pass filter,
Being washed with water to filtrate is i.e. to obtain described catalyst after neutrality.Gained catalyst sealing is stored in ethylene glycol liquid.
Embodiment 6
Described carrier active carbon physical parameter: ash is 5.0wt%, specific surface area is 1000m2/ g, micropore specific area
Proportion is not less than 60%, and activated carbon granule granularity is D10: 2.5 μm, D50: 12 μm, D90:30μm；The material of described activated carbon
For coconut husk.
Weigh content be platinum chloride that 0.5g platinum is corresponding, content be the rhodium nitrate and 4.0g citric acid that 0.3g rhodium is corresponding
Sodium, adds ethylene glycol and stirs to being completely dissolved；10g activated carbon and 80ml ethylene glycol are mixed and made into serosity, after being warming up to 100 DEG C
Stirring 1 hour, then instill the ethylene glycol solution of active component, constant temperature stirs 4 hours；Adding content is the chlorine that 0.3g ferrum is corresponding
Changing ferrum is the zinc chloride that 0.3g zinc is corresponding with content, continues constant temperature and stirs 5 hours；The ethylene glycol solution of dropping potassium hydroxide, adjusts
Joint pH value of solution is to 9；Being cooled to 50 DEG C, add 2.5ml hydrazine hydrate (80wt%) and reduce, the time is 4 hours.Eventually pass
Filter, to be washed with water to filtrate be i.e. to obtain described catalyst after neutrality.Gained catalyst sealing is stored in ethylene glycol liquid.
Embodiment 7
Described carrier active carbon physical parameter: ash is 3.0wt%, specific surface area is 1500m2/ g, micropore specific area
Proportion is not less than 75%, and activated carbon granule granularity is D10: 2.5 μm, D50: 12 μm, D90:30μm；The material of described activated carbon
For coconut husk.
Weigh content be Palladous chloride. that 0.7g palladium is corresponding, content be the rhodium nitrate and 3.0g citric acid that 0.1g rhodium is corresponding
Potassium, adds ethylene glycol and stirs to being completely dissolved；10g activated carbon and 50ml ethylene glycol are mixed and made into serosity, after being warming up to 80 DEG C
Stirring 2 hours, then instill the ethylene glycol solution of active component, constant temperature stirs 5 hours；Adding content is the chlorine that 0.4g zinc is corresponding
Change zinc, continue constant temperature and stir 5 hours；The ethylene glycol solution of dropping sodium hydroxide, regulation pH value of solution is to 8；It is cooled to 50 DEG C, adds
1.5ml hydrazine hydrate (80wt%) reduces, and the time is 3 hours.Eventually pass filter, be washed with water to after filtrate is neutrality and get final product
Described catalyst.Gained catalyst sealing is stored in ethylene glycol liquid.
Embodiment 8
Described carrier active carbon physical parameter: ash is 4.0wt%, specific surface area is 1800m2/ g, micropore specific area
Proportion is not less than 80%, and activated carbon granule granularity is D10: 4.5 μm, D50: 15 μm, D90:35μm；The material of described activated carbon
For coconut husk.
Weigh content be Palladous chloride. that 0.5g palladium is corresponding, content be the platinous chloride and 2.5g citric acid that 0.3g platinum is corresponding
Sodium/potassium, adds ethylene glycol and stirs to being completely dissolved；10g activated carbon and 50ml ethylene glycol are mixed and made into serosity, are warming up to 50 DEG C
Rear stirring 2 hours, then instills the ethylene glycol solution of active component, and constant temperature stirs 5 hours；Adding content is that 0.3g ferrum is corresponding
Iron chloride and the zinc chloride that content is that 0.3g zinc is corresponding, continue constant temperature and stir 5 hours；The ethylene glycol solution of dropping potassium hydroxide,
Regulation pH value of solution is to 8；Adding 4g ammonium hypophosphite at 50 DEG C to reduce, the time is 3 hours.Eventually pass filter, wash with water
Described catalyst is i.e. obtained after being neutrality to filtrate.Gained catalyst sealing is stored in ethylene glycol liquid.
Embodiment 9
Described carrier active carbon physical parameter: ash is 3.0wt%, specific surface area is 1500m2/ g, micropore specific area
Proportion is not less than 75%, and activated carbon granule granularity is D10: 2.5 μm, D50: 12 μm, D90:30μm；The material of described activated carbon
For coconut husk.
Weigh content be Palladous nitrate. that 0.5g palladium is corresponding, content be the platinum tetrachloride and 2.5g citric acid that 0.3g platinum is corresponding
Sodium/potassium, adds ethylene glycol and stirs to being completely dissolved；10g activated carbon and 50ml ethylene glycol are mixed and made into serosity, are warming up to 50 DEG C
Rear stirring 2 hours, then instills the ethylene glycol solution of active component, and constant temperature stirs 5 hours；Adding content is that 0.3g copper is corresponding
Copper nitrate and the zinc chloride that content is that 0.3g zinc is corresponding, continue constant temperature and stir 5 hours；The ethylene glycol solution of dropping sodium hydroxide,
Regulation pH value of solution is to 8；Being warming up to 80 DEG C, add 1ml hydrazine hydrate (80wt%) and reduce, the time is 3 hours.Eventually pass
Filter, to be washed with water to filtrate be i.e. to obtain described catalyst after neutrality.Gained catalyst sealing is stored in ethylene glycol liquid.
Embodiment 10
Described carrier active carbon physical parameter: ash is 3.0wt%, specific surface area is 1500m2/ g, micropore specific area
Proportion is not less than 75%, and activated carbon granule granularity is D10: 2.5 μm, D50: 12 μm, D90:30μm；The material of described activated carbon
For coconut husk.
Weigh content be Palladous chloride. that 0.5g palladium is corresponding, content be the platinous chloride and 2.5g citric acid that 0.3g platinum is corresponding
Sodium/potassium, adds ethylene glycol and stirs to being completely dissolved；10g activated carbon and 50ml ethylene glycol are mixed and made into serosity, are warming up to 50 DEG C
Rear stirring 1 hour, then instills the ethylene glycol solution of active component, and constant temperature stirs 3 hours；Adding content is that 0.2g ferrum is corresponding
Ferric nitrate and the zinc nitrate that content is that 0.4g zinc is corresponding, continue constant temperature and stir 6 hours；The ethylene glycol solution of dropping sodium hydroxide,
Regulation pH value of solution is to 10；Adding 1.5ml hydrazine hydrate (80wt%) at 50 DEG C to reduce, the time is 3 hours.Eventually pass
Filter, to be washed with water to filtrate be i.e. to obtain described catalyst after neutrality.Gained catalyst sealing is stored in ethylene glycol liquid.
Embodiment 11
Described carrier active carbon physical parameter: ash is 3.0wt%, specific surface area is 1500m2/ g, micropore specific area
Proportion is not less than 75%, and activated carbon granule granularity is D10: 2.5 μm, D50: 12 μm, D90:30μm；The material of described activated carbon
For coconut husk.
Weigh content be Palladous chloride. that 0.5g palladium is corresponding, content be the platinous chloride and 2.5g citric acid that 0.3g platinum is corresponding
Sodium/potassium, adds ethylene glycol and stirs to being completely dissolved；10g activated carbon and 50ml ethylene glycol are mixed and made into serosity, are warming up to 50 DEG C
Rear stirring 2 hours, then instills the ethylene glycol solution of active component, and constant temperature stirs 5 hours；Adding content is that 0.3g cobalt is corresponding
Cobalt nitrate, continues constant temperature and stirs 5 hours；The ethylene glycol solution of dropping sodium hydroxide, regulation pH value of solution is to 8；Add at 50 DEG C
2.5ml hydrazine hydrate (80wt%) reduces, and the time is 3 hours.Eventually pass filter, be washed with water to after filtrate is neutrality and get final product
Described catalyst.Gained catalyst sealing is stored in ethylene glycol liquid.
Embodiment 12
Described carrier active carbon physical parameter: ash is 3.0wt%, specific surface area is 1500m2/ g, micropore specific area
Proportion is not less than 75%, and activated carbon granule granularity is D10: 2.5 μm, D50: 12 μm, D90:30μm；The material of described activated carbon
For coconut husk.
Weigh content be Palladous chloride. that 0.5g palladium is corresponding, content be the platinous chloride and 2.5g citric acid that 0.3g platinum is corresponding
Sodium/potassium, adds ethylene glycol and stirs to being completely dissolved；10g activated carbon and 50ml ethylene glycol are mixed and made into serosity, are warming up to 50 DEG C
Rear stirring 2 hours, then instills the ethylene glycol solution of active component, and constant temperature stirs 5 hours；Adding content is that 0.1g ferrum is corresponding
Iron chloride, content be the cobalt nitrate that 0.1g cobalt is corresponding be the zinc chloride that 0.2g zinc is corresponding with content, continue constant temperature stir 5 hours；
The ethylene glycol solution of dropping sodium hydroxide, regulation pH value of solution is to 8；It is warming up to 90 DEG C, is passed through 50ml/min hydrogen and reduces, time
Between be 8 hours.Eventually pass filter, be washed with water to after filtrate is neutrality, then spent glycol diafiltration, obtain described catalyst.Institute
Obtain in catalyst cake, quality of glycol content 70%.
Comparative example 1
Described carrier active carbon physical parameter: ash is 3.5wt%, specific surface area is 1350m2/ g, micropore specific area
Proportion 55%, activated carbon granule granularity is D10: 9.5 μm, D50: 25 μm, D90:50μm；The material of described activated carbon is coconut palm
Shell.
Prepared by conventional palladium on carbon hydrogenation catalyst: by coconut husk preparing active carbon in 120 DEG C of vacuum dehydration 3h；Pipette 10mL
Concentration be the chlorine palladium acid solution (wherein concentration of hydrochloric acid 0.1mol/L) of 0.05g/mL in 50mL deionized water, with hydrochloric acid regulation make
Its pH value is 0.8；Then being dipped in palladium liquid by the 10g activated carbon through vacuum dehydration, 80 DEG C are sufficiently stirred for impregnating 5h, use
Sodium hydroxide regulation pH value is to 8～10；After half an hour, drip 2.5mL hydrazine hydrate, 35 DEG C of reductase 12 h.It is down to room temperature afterwards, instead
Answering system to filter, filter cake is washed with deionized to neutrality, 105 DEG C of drying and dehydrating 3h, obtains simple substance supported palladium catalyst.
Embodiment 13
0.5g embodiment 1 catalyst and 100ml methanol solvate are put in high-pressure hydrogenation reactor, closed reactor, use
Open stirring after hydrogen exchange air, control temperature be 90 DEG C, under conditions of Hydrogen Vapor Pressure is 1.5MPa, by 50 grams of m-nitros
Instill reactor after amine is melted and carry out hydrogenation reaction.After dropping, when in 15 minutes, Hydrogen Vapor Pressure is constant, stopped reaction,
Filtering and separate hydrogenation liquid and catalyst cake, analysis result is: reaction conversion ratio 100%, m-diaminobenzene. selectivity 100%, instead
It is 30 minutes between Ying Shi.
Embodiment 14
0.5g embodiment 2 catalyst and 100ml alcohol solvent are put in high-pressure hydrogenation reactor, closed reactor, use
Open stirring after hydrogen exchange air, control temperature be 100 DEG C, under conditions of Hydrogen Vapor Pressure is 1.5MPa, by nitro between 50 grams
Instill reactor after aniline is melted and carry out hydrogenation reaction.After dropping, when in 15 minutes, Hydrogen Vapor Pressure is constant, stop anti-
Should, filtering and separate hydrogenation liquid and catalyst cake, analysis result is: reaction conversion ratio 100%, m-diaminobenzene. selectivity 100%,
Response time is 25 minutes.
Embodiment 15
0.5g embodiment 5 catalyst, 50ml methanol and 70ml alcohol solvent are put in high-pressure hydrogenation reactor, airtight instead
Answer still, with opening stirring after hydrogen exchange air, control temperature be 100 DEG C, under conditions of Hydrogen Vapor Pressure is 1.0MPa, by 50 grams
Instill reactor after meta nitro aniline is melted and carry out hydrogenation reaction.After dropping, when in 15 minutes, Hydrogen Vapor Pressure is constant, stop
Only reaction, filters and separates hydrogenation liquid and catalyst cake, and analysis result is: reaction conversion ratio 100%, m-diaminobenzene. selectivity
100%, the response time is 28 minutes.
Embodiment 16
0.5g embodiment 7 catalyst, 150ml normal propyl alcohol solvent are put in high-pressure hydrogenation reactor, closed reactor, use
Open stirring after hydrogen exchange air, control temperature be 100 DEG C, under conditions of Hydrogen Vapor Pressure is 1.0MPa, by nitro between 50 grams
Instill reactor after aniline is melted and carry out hydrogenation reaction.After dropping, when in 15 minutes, Hydrogen Vapor Pressure is constant, stop anti-
Should, filtering and separate hydrogenation liquid and catalyst cake, analysis result is: reaction conversion ratio 100%, m-diaminobenzene. selectivity 100%,
Response time is 32 minutes.
Embodiment 17
0.5g embodiment 10 catalyst, 150ml normal propyl alcohol and 100ml n-butanol solvent are put into high-pressure hydrogenation reactor
In, closed reactor, with opening stirring after hydrogen exchange air, control temperature be 110 DEG C, Hydrogen Vapor Pressure be the condition of 0.8MPa
Under, instill reactor after being melted by 50 grams of meta nitro anilines and carry out hydrogenation reaction.After dropping, treat Hydrogen Vapor Pressure in 15 minutes
Time constant, stopped reaction, filter and separate hydrogenation liquid and catalyst cake, analysis result is: reaction conversion ratio 100%, isophthalic two
Amine selectivity 100%, the response time is 35 minutes.
Embodiment 18
1.0g embodiment 12 catalyst, 200ml m-diaminobenzene. (about 230g) are put in high-pressure hydrogenation reactor, airtight instead
Answer still, after hydrogen exchange air, be warming up to melted open stirring, control temperature be 100 DEG C, Hydrogen Vapor Pressure be the bar of 2.0MPa
Under part, instill reactor after being melted by 50 grams of meta nitro anilines and carry out hydrogenation reaction.After dropping, hydrogen pressure in treating 15 minutes
When power is constant, stopped reaction, filter and separate hydrogenation liquid and catalyst cake, analysis result is: reaction conversion ratio 100%, isophthalic
Diamidogen selectivity 100%, the response time is 32 minutes.
Embodiment 19
1.0g embodiment 8 catalyst, 200ml m-diaminobenzene. (about 230g) and 50ml methanol solvate are put into high-pressure hydrogenation anti-
In answering still, closed reactor, with opening stirring after hydrogen exchange air, control temperature be 100 DEG C, Hydrogen Vapor Pressure be 2.0MPa's
Under the conditions of, instill reactor after being melted by 50 grams of meta nitro anilines and carry out hydrogenation reaction.After dropping, treat hydrogen in 15 minutes
When pressure is constant, stopped reaction, filter and separate hydrogenation liquid and catalyst cake, analysis result is: reaction conversion ratio 100%,
Phenylenediamine selectivity 100%, the response time is 32 minutes.
Embodiment 20
1.0g embodiment 1 catalyst, 200ml methanol solvate are put in high-pressure hydrogenation reactor, closed reactor, use hydrogen
Open stirring after gas displaced air, control temperature be 100 DEG C, under conditions of Hydrogen Vapor Pressure is 2.0MPa, by 50 grams of m-nitros
Instill reactor after ether is melted and carry out hydrogenation reaction.After dropping, when in 15 minutes, Hydrogen Vapor Pressure is constant, stop anti-
Should, filtering and separate hydrogenation liquid and catalyst cake, analysis result is: reaction conversion ratio 100%, m-phenetidine selectivity
100%, the response time is 30 minutes.
Embodiment 21
1.0g embodiment 1 catalyst, 100ml m-Anisidine are put in high-pressure hydrogenation reactor, closed reactor,
With opening stirring after hydrogen exchange air, control temperature be 100 DEG C, under conditions of Hydrogen Vapor Pressure is 2.0MPa, by nitre between 50 grams
Instill reactor after base methyl phenyl ethers anisole is melted and carry out hydrogenation reaction.After dropping, when in 15 minutes, Hydrogen Vapor Pressure is constant, stop
Reaction, filters and separates hydrogenation liquid and catalyst cake, and analysis result is: reaction conversion ratio 100%, m-Anisidine selectivity
100%, the response time is 32 minutes.
Embodiment 22
1.0g embodiment 1 catalyst, 100ml methanol solvate are put in high-pressure hydrogenation reactor, closed reactor, use hydrogen
Open stirring after gas displaced air, control temperature be 100 DEG C, under conditions of Hydrogen Vapor Pressure is 2.0MPa, by 50 gram 2,6-diamino
The methanol solution of base-3,5-di nitryl pyridine instills reactor and carries out hydrogenation reaction.After dropping, hydrogen pressure in treating 15 minutes
When power is constant, stopped reaction, filter and separate hydrogenation liquid and catalyst cake, analysis result is: reaction conversion ratio 100%, 2,3,
5,6-4-aminopyridine selectivitys 100%, the response time is 32 minutes.
Embodiment 23
1.0g embodiment 1 catalyst, 100ml methanol solvate are put in high-pressure hydrogenation reactor, closed reactor, use hydrogen
Open stirring after gas displaced air, control temperature be 100 DEG C, under conditions of Hydrogen Vapor Pressure is 2.0MPa, by 50 gram 2,6-diamino
The methanol solution of base-3,5-di nitryl pyridine instills reactor and carries out hydrogenation reaction.After dropping, hydrogen pressure in treating 15 minutes
When power is constant, stopped reaction, filter and separate hydrogenation liquid and catalyst cake, analysis result is: reaction conversion ratio 100%, 2,3,
5,6-4-aminopyridine selectivitys 100%, the response time is 32 minutes.
Embodiment 24
1.0g embodiment 1 catalyst, 100ml methanol solvate are put in high-pressure hydrogenation reactor, closed reactor, use hydrogen
Open stirring after gas displaced air, control temperature be 100 DEG C, under conditions of Hydrogen Vapor Pressure is 2.0MPa, with high-pressure pump will between nitre
The methanol solution of base aniline pumps into complete mixing flow reactor and carries out hydrogenation reaction.The outlet of reactor is associated with a catalyst filtration dress
Put, catalyst filtration device has material taking mouth and the charge door of catalyst.The hydrogenation liquid of outflow reactor through filtration after, filtrate
Enter rectifier unit rectification under vacuum and i.e. obtain product m-diaminobenzene..The hydrogenation liquid of outflow reactor is dissolved in methanol with pump into
M-nitro amine aqueous solution keeps equal on volume, with material balance in maintenance system.Reactor and catalyst filtration device it
Between high-pressure pump is set, make catalyst and reactant liquor circulate in this system.In this cyclic process, depending on hydrogenation reaction speed and turn
Rate, quantitative fresh makeup catalyst and the catalyst taken out in using, to keep the catalytic reaction activity of system inner catalyst.
Analysis result is: the when of reaction 5 hours, and catalyst is not added, meta nitro aniline charging 800g, reaction conversion ratio 100%,
Phenylenediamine selectivity 100%.
The reaction result of table 1 embodiment 24
Comparative example 2
Embodiment 25～34 is to use comparative example 1 catalyst under the corresponding reaction condition of embodiment 13～22, carries out
Nitro-catalytic hydrogenation reaction application result, as shown in table 2.
Table 2 comparative example 1 catalyst application result under the corresponding reaction condition of embodiment 13～22
| Embodiment | Reaction condition | Conversion ratio % | Selectivity % | Response time min |
| Embodiment 25 | Embodiment 13 | 100 | 98.29 | 190 |
| Embodiment 26 | Embodiment 14 | 100 | 98.36 | 199 |
| Embodiment 27 | Embodiment 15 | 98.36 | 97.26 | 95 |
| Embodiment 28 | Embodiment 16 | 97.25 | 97.25 | 120 |
| Embodiment 29 | Embodiment 17 | 98.25 | 97.14 | 110 |
| Embodiment 30 | Embodiment 18 | 97.69 | 96.58 | 135 |
| Embodiment 31 | Embodiment 19 | 98.62 | 95.85 | 126 |
| Embodiment 32 | Embodiment 20 | 90.21 | 94.47 | 280 |
| Embodiment 33 | Embodiment 21 | 94.52 | 93.15 | 320 |
| Embodiment 34 | Embodiment 22 | 90.25 | 95.24 | 350 |
Comparative example 3
0.5g comparative example 1 catalyst, 50 grams of meta nitro anilines and 100ml methanol solvate are put into high-pressure hydrogenation reactor
In, closed reactor, with opening stirring after hydrogen exchange air, control temperature be 90 DEG C, Hydrogen Vapor Pressure be the condition of 1.5MPa
Under carry out hydrogenation reaction.When question response no longer inhales hydrogen, continue constant temperature and pressure and stir 1 hour, stopped reaction, filters and separates hydrogenation liquid
And catalyst cake, analysis result is: reaction conversion ratio 98.7%, m-diaminobenzene. selectivity 99.5%, and the response time is 130 points
Clock.
Embodiment 35
Experimental result applied mechanically by the catalyst of embodiment 14.As shown in table 3.
Experimental result applied mechanically by the catalyst of table 3 embodiment 14
Claims (10)
1. an activated carbon supported type composite metal catalyst, it is characterised in that described catalyst by carrier, active component,
Auxiliary agent forms, and described carrier is activated carbon, and described active component is at least one in platinum, palladium, rhodium, and described auxiliary agent is
At least one in ferrum, zinc, cobalt, copper；Quality based on carrier, in described active component, the load capacity of each metal is: palladium 0wt%
～10.0wt%, platinum 0wt%～10.0wt%, rhodium 0wt%～5.0wt%, and the load capacity of palladium, platinum, rhodium is not 0；Described
In auxiliary agent, ferrum, zinc, cobalt, the load capacity of copper are 0wt%～5.0wt%, and the load capacity of ferrum, zinc, cobalt, copper is not 0.
Activated carbon supported type composite metal catalyst the most as claimed in claim 1, it is characterised in that in described catalyst,
Described active component and load capacity thereof are selected from one of following combination:
Palladium 0.5wt%～8.0wt%, platinum 0.5wt%～8.0wt%；
Palladium 0.5wt%～8.0wt%, rhodium 0.1wt%～3.0wt%；
Platinum 0.5wt%～8.0wt%, rhodium 0.1wt%～3.0wt%；
Described auxiliary agent is any two kinds in ferrum, zinc, cobalt, copper, and the load capacity of these any two kinds of metal promoters is
0.1wt%～4.0wt%.
3. the preparation method of an activated carbon supported type composite metal catalyst as claimed in claim 1, it is characterised in that institute
The preparation method stated is:
Adding in ethylene glycol A by soluble-salt and the citrate of activity component metal, stirring, to being completely dissolved, obtains system A；
Activated carbon is mixed with ethylene glycol B, stirs 0.5～5h in 35～150 DEG C, obtain system B；In system B, drip system A, drip
1～10h is stirred in 35～150 DEG C after complete；Be subsequently added into the soluble-salt of promoter metal, continue at 35～150 DEG C stirring 1～
10h；Then regulation pH to 7～14, adds reducing agent and carries out reduction reaction, afterwards through filtering, washing, i.e. obtain described activity
Carbon loaded type composite metal catalyst.
4. preparation method as claimed in claim 3, it is characterised in that the soluble-salt of described activity component metal is chlorination
Palladium, Palladous nitrate., the acid of chlorine palladium, palladium, platinous chloride, platinum tetrachloride, chloroplatinic acid, platinum nitrate, platinic sodium chloride, radium chloride, nitric acid
At least one in rhodium, rhodium acetate.
5. preparation method as claimed in claim 3, it is characterised in that described citrate is sodium citrate and/or Fructus Citri Limoniae
Acid potassium, in the soluble-salt that quality consumption is activity component metal of described citrate 0.5～5 times of metal simple-substance quality.
6. preparation method as claimed in claim 3, it is characterised in that the soluble-salt of described promoter metal be ferrum, zinc, cobalt,
At least one in hydrochlorate that copper is corresponding, nitrate.
7. preparation method as claimed in claim 3, it is characterised in that the method for described reduction reaction is wet reducing, described
Reducing agent selected from formaldehyde, formic acid, hypophosphites, hydrazine hydrate or hydrogen；The condition of reduction reaction is: temperature 35～100 DEG C, time
Between 1～10h, when reducing agent is formaldehyde, formic acid, hypophosphites or hydrazine hydrate, the consumption of reducing agent is activity component metal
The soluble-salt of soluble-salt and promoter metal is reduced to needed for metal simple-substance 1～10 times of the amount of theoretical material, works as reduction
When agent is hydrogen, hydrogen is passed through below serosity liquid level, and hydrogen flowing quantity is 10～100ml/min, and the pressure of hydrogen is normal pressure.
Activated carbon supported type composite metal catalyst the most as claimed in claim 1 is corresponding in catalytic hydrogenation of nitro compound synthesis
Application in the reaction of aminated compounds.
Apply the most as claimed in claim 8, it is characterised in that the method for described application is:
Compound shown in catalyst described in claim 1, formula (II) and/or solvent are put in high-pressure hydrogenation reactor, close
Close reactor, with opening stirring after hydrogen exchange air, temperature be 20～150 DEG C, Hydrogen Vapor Pressure be 0.1～8.5MPa bar
Under part, instill compound shown in reactant formula (I), continue after dripping off reaction to Hydrogen Vapor Pressure in 15min constant time, stop anti-
Should, sample analysis, the separated post processing of hydrogenation liquid obtains compound shown in product formula (II)；
In described application process, compound shown in the formula (II) of input high-pressure hydrogenation reactor is replaced with formula (IV) shownization
Compound, compound shown in the reactant formula (I) of instillation replaces with compound shown in formula (III), then obtain shown in product formula (IV)
Compound；
Shown in compound shown in described reactant formula (I) or formula (III), compound with the mass ratio that feeds intake of described catalyst is
100:0.1～4.0；Described solvent is methanol, ethanol, water, normal propyl alcohol, isopropanol, n-butyl alcohol, isobutanol, sec-butyl alcohol, tertiary fourth
The mixed solvent of one or more arbitrary proportions in alcohol；
In formula (I) or (II), Rn represents the one or more substituent groups on phenyl ring, and wherein R represents substituent group, n=1,2,3,4 or
5, described substituent group each stands alone as amino, the substituted amino of C1～C5 alkyl, hydroxyl, aryloxy group, C1～C3 alkoxyl, acyl
Epoxide or acylamino-；
In formula (III) or (IV), R ' m represents the one or more substituent groups on pyridine ring, and wherein R ' represents substituent group, m=1,
2,3 or 4, described substituent group each stands alone as amino, the substituted amino of C1～C5 alkyl, hydroxyl, aryloxy group, C1～C3 alcoxyl
Base, acyloxy or acylamino-.
Apply the most as claimed in claim 9, it is characterised in that the method for described application uses continuous reaction process, it may be assumed that formula
Or close between catalyst filtration device and hydrogenation reactor of the compound shown in formula (IV) and/or solvent and catalyst (II)
Closed loop system circulates；Molten state reactant or the reactant being dissolved in solvent add reactor in the way of instillation continuously
In, reaction is carried out in the way of complete mixing flow, and the hydrogenation liquid of outflow reactor is after catalyst filtration device separates, and filtrate is through decompression
Rectification i.e. obtains product；The molten state reactant of the hydrogenation liquid of outflow reactor and instillation or the reactant that is dissolved in solvent are at body
Long-pending upper holding is equal, with material balance in maintenance system；In this cyclic process, depending on hydrogenation reaction speed and conversion ratio, quantitatively
Fresh makeup catalyst and the catalyst taken out in using, to keep the catalytic reaction activity of system inner catalyst.
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