CN102500374A - Copper-based nano catalyst for preparing high-carbon alcohol from synthetic gas as well as preparation method and application thereof - Google Patents
Copper-based nano catalyst for preparing high-carbon alcohol from synthetic gas as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN102500374A CN102500374A CN2011103948676A CN201110394867A CN102500374A CN 102500374 A CN102500374 A CN 102500374A CN 2011103948676 A CN2011103948676 A CN 2011103948676A CN 201110394867 A CN201110394867 A CN 201110394867A CN 102500374 A CN102500374 A CN 102500374A
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- China
- Prior art keywords
- copper
- catalyst
- tropsch
- fischer
- constituent element
- Prior art date
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- 239000010949 copper Substances 0.000 title claims abstract description 116
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 68
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 60
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 49
- 229910052799 carbon Inorganic materials 0.000 title abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 75
- 150000001298 alcohols Chemical class 0.000 claims abstract description 54
- 230000009467 reduction Effects 0.000 claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 48
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 43
- 230000008569 process Effects 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 134
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 66
- 238000006722 reduction reaction Methods 0.000 claims description 61
- 229910052751 metal Inorganic materials 0.000 claims description 56
- 239000002184 metal Substances 0.000 claims description 56
- 238000005406 washing Methods 0.000 claims description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 51
- 239000000470 constituent Substances 0.000 claims description 49
- 239000000243 solution Substances 0.000 claims description 46
- 239000007789 gas Substances 0.000 claims description 41
- 239000007787 solid Substances 0.000 claims description 37
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 34
- 239000002904 solvent Substances 0.000 claims description 34
- 239000003638 chemical reducing agent Substances 0.000 claims description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims description 27
- 238000005119 centrifugation Methods 0.000 claims description 26
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 26
- 239000002105 nanoparticle Substances 0.000 claims description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 14
- 238000004140 cleaning Methods 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 14
- 239000012046 mixed solvent Substances 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 14
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 12
- 238000007885 magnetic separation Methods 0.000 claims description 12
- 239000012266 salt solution Substances 0.000 claims description 12
- 239000003381 stabilizer Substances 0.000 claims description 12
- 238000006073 displacement reaction Methods 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- 150000001879 copper Chemical class 0.000 claims description 9
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 8
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 8
- 150000002815 nickel Chemical class 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 7
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 7
- 150000001868 cobalt Chemical class 0.000 claims description 7
- 235000011187 glycerol Nutrition 0.000 claims description 7
- 229910052707 ruthenium Inorganic materials 0.000 claims description 7
- 238000009938 salting Methods 0.000 claims description 7
- 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 6
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- 229910000085 borane Inorganic materials 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 6
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 6
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 150000003303 ruthenium Chemical class 0.000 claims description 6
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 6
- -1 1 for use Chemical compound 0.000 claims description 5
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 4
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 150000001299 aldehydes Chemical class 0.000 claims description 4
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- NUHXWPRATKOXDB-UHFFFAOYSA-L diazanium;cobalt(2+);disulfate Chemical compound [NH4+].[NH4+].[Co+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O NUHXWPRATKOXDB-UHFFFAOYSA-L 0.000 claims description 4
- 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 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 150000005846 sugar alcohols Polymers 0.000 claims description 4
- 239000011975 tartaric acid Substances 0.000 claims description 4
- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- 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 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 3
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 3
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 claims description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- 229930003268 Vitamin C Natural products 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- DAPUDVOJPZKTSI-UHFFFAOYSA-L ammonium nickel sulfate Chemical compound [NH4+].[NH4+].[Ni+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DAPUDVOJPZKTSI-UHFFFAOYSA-L 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 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
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 claims description 3
- QNZRVYCYEMYQMD-UHFFFAOYSA-N copper;pentane-2,4-dione Chemical compound [Cu].CC(=O)CC(C)=O QNZRVYCYEMYQMD-UHFFFAOYSA-N 0.000 claims description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 3
- KFIKNZBXPKXFTA-UHFFFAOYSA-N dipotassium;dioxido(dioxo)ruthenium Chemical compound [K+].[K+].[O-][Ru]([O-])(=O)=O KFIKNZBXPKXFTA-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 150000004675 formic acid derivatives Chemical class 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 229940095064 tartrate Drugs 0.000 claims description 3
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 claims description 3
- 235000019154 vitamin C Nutrition 0.000 claims description 3
- 239000011718 vitamin C Substances 0.000 claims description 3
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 2
- MNQZXJOMYWMBOU-VKHMYHEASA-N D-glyceraldehyde Chemical compound OC[C@@H](O)C=O MNQZXJOMYWMBOU-VKHMYHEASA-N 0.000 claims description 2
- 239000005715 Fructose Substances 0.000 claims description 2
- 229930091371 Fructose Natural products 0.000 claims description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 239000012448 Lithium borohydride Substances 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- SRBFZHDQGSBBOR-LECHCGJUSA-N alpha-D-xylose Chemical compound O[C@@H]1CO[C@H](O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-LECHCGJUSA-N 0.000 claims description 2
- 239000003093 cationic surfactant Substances 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 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 2
- 229960003280 cupric chloride Drugs 0.000 claims description 2
- CEYULKASIQJZGP-UHFFFAOYSA-L disodium;2-(carboxymethyl)-2-hydroxybutanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O CEYULKASIQJZGP-UHFFFAOYSA-L 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 2
- 229960003511 macrogol Drugs 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 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 2
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 claims description 2
- 229940113115 polyethylene glycol 200 Drugs 0.000 claims description 2
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 229960003487 xylose Drugs 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 229940075513 stannous chloride,anhydrous Drugs 0.000 claims 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims 1
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 description 22
- 238000003756 stirring Methods 0.000 description 22
- 238000001816 cooling Methods 0.000 description 17
- 229910021645 metal ion Inorganic materials 0.000 description 16
- 239000005457 ice water Substances 0.000 description 12
- 238000010790 dilution Methods 0.000 description 10
- 239000012895 dilution Substances 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 9
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 8
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003245 coal Substances 0.000 description 6
- PXRKCOCTEMYUEG-UHFFFAOYSA-N 5-aminoisoindole-1,3-dione Chemical compound NC1=CC=C2C(=O)NC(=O)C2=C1 PXRKCOCTEMYUEG-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- IYWJIYWFPADQAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;ruthenium Chemical compound [Ru].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O IYWJIYWFPADQAN-LNTINUHCSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 229910017816 Cu—Co Inorganic materials 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 229910010082 LiAlH Inorganic materials 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Natural products CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- XLSMFKSTNGKWQX-UHFFFAOYSA-N hydroxyacetone Chemical compound CC(=O)CO XLSMFKSTNGKWQX-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 2
- 235000019254 sodium formate Nutrition 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- 229910017752 Cu-Zn Inorganic materials 0.000 description 1
- 229910017943 Cu—Zn Inorganic materials 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 241000549556 Nanos Species 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 235000010210 aluminium Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- ZKXWKVVCCTZOLD-FDGPNNRMSA-N copper;(z)-4-hydroxypent-3-en-2-one Chemical compound [Cu].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O ZKXWKVVCCTZOLD-FDGPNNRMSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZOCHARZZJNPSEU-UHFFFAOYSA-N diboron Chemical compound B#B ZOCHARZZJNPSEU-UHFFFAOYSA-N 0.000 description 1
- 239000013070 direct material Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a copper-based nano catalyst for preparing high-carbon alcohol from synthetic gas as well as a preparation method and application thereof. The catalyst is a copper-based polymetallic nano catalyst, which is composed of copper and at least one Fischer-Tropsch component. The preparation method is selected from one of replacement reaction method, step-by-step reduction method and simultaneous reduction method. The catalyst disclosed by the invention is small in particle size, large in specific surface and high in utilization rate; the preparing process is simple and convenient for operation; and when the catalyst is used for the synthesis of high-carbon alcohol from synthetic gas, by controlling the component and ratio of the catalyst, the selectivity of the alcohols higher than ethanol in the obtained alcohols is up to 95wt% and the selectivity of high-carbon alcohols higher than hexanol reaches more than 80wt%.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method and application that is used for by the synthesis gas preparation higher alcohols, particularly relate to a kind of copper-based nano-catalyst and method for making and application that is used for the synthesis gas preparation higher alcohols.
Background technology
Higher alcohols refer generally to contain the above monohydric alcohol of 6 carbon atoms, and it is the raw material of synthetic surfactant, washing agent, plasticizer and other fine chemical product, have advantages such as unit output value height, added value are big.The preparation higher alcohols have two kinds of routes basically, and first natural oil route is a raw material with the animal and plant grease, through hydrogenation preparing, but the restriction that lacked by oil sources, the large-scale production difficulty.Another is a chemical synthesis route, has scale property, is divided into two kinds of ziegler process and oxo synthesis by and large.Ziegler process is raw material with ethene, and triethyl aluminum is a catalyst, prepares even carbon number alcohol, and this process flow is long, needs to consume a large amount of triethyl aluminums, technical sophistication, and cost is high.The direct material of oxo synthesis is an alpha-olefin, adopts cobalt-based or rhodium base catalyst, and preparation is Duoed the higher alcohols of a carbon atom than alpha-olefin.Required alpha-olefin can make through methods such as ethylene oligomerization, alkane oxidation, wax cracking/oxidations, but the oxo synthesis side reaction is many, and branched-chain alcoho content is high in the product, and biological degradability is poor.
Ziegler process still is that oxo synthesis is all big to the oil product interdependency.Current petroleum resources are in short supply day by day, and the efficient utilization that develops other fossil energy such as coal, natural gas etc. helps alleviating the dependence to petroleum resources.China is a big coal country, and coal occupies leading position in resource provisioning, and development more has important meaning to the utilization of coal.Wherein, from coal through synthesis gas (CO+H
2) produce alcohol, especially higher alcohols, be one of approach that efficiently utilizes coal resources.Because the synthesis gas source is wide, it is short directly to prepare the higher alcohols route from synthesis gas, and products obtained therefrom higher alcohols added value is high, so this route is the method that has the synthesizing bigh carbon alcohol of economic worth, also is one of alternative method of current higher alcohols preparation.
Existing at present directly from the catalyst report of synthesis gas preparation mixed alcohol, these catalyst can be classified as following four big types generally:
(1) (A-Cu-Zn/Al A-Zn-Cr), is obtained by adding alkali metal or alkaline earth metal compound modification in the methanol synthesis catalyst modified methanol synthetic catalyst; Represent patent to have: EP 0034338A2 and US Patent 4513100.By Italian Snam company and the exploitation of German Lugi company, main alcohol product is methyl alcohol and isobutanol to this type catalyst the earliest;
On behalf of patent, (2) modification fischer-tropsch synthetic catalyst (Cu-Co) have: US Patent 4122110 and 4291126, GB Patent2118061 and 2158730; This type catalyst is proposed by France Petroleum Institute (IFP) the earliest, is primarily aimed at Cu-Co series; Main alcohol product is methyl alcohol and C
2～C
6The straight chain n-alkanol;
(3) noble metal catalyst, catalyst based with Rh is the typical case, represents patent to have: US Patent 4014913 and 4096164; This type of catalyst ethanol selectivity is high, but because of its expensive, and total pure selectivity is not high enough, so report less in recent years;
(4) catalyst with base of molybdenum is divided into MoS
2US Patent 4882360) and Mo catalyst basedly (represent patent:
2C is catalyst based; MoS
2Catalyst basedly propose by U.S. Dow company the earliest; Catalyst with base of molybdenum obtains researcher's attention because of its anti-preferably sulphur property; But this catalyst promoter is easy to run off, and activity and selectivity are unstable, and the life-span falls short of, and CO in the product
2Content is high.
In the mixed alcohol of above catalyst gained, higher alcohols content is very little, even does not have.
At present, less relatively for the catalyst research that directly prepares higher alcohols by synthesis gas both at home and abroad.U.S. Pat Patent4504600 has reported a kind of iron-based FT catalyst of thallium auxiliary agent, contains C in its product hydrocarbon
6-C
12Higher alcohols, but only account for the 5wt%～10wt% of total hydrocarbon.European patent EP 1017657B1 has reported and has been used for mixed alcohol synthetic CuCoMn and CuCoMg catalyst that this catalyst adopts the coprecipitation preparation, contains C in the gained alcohol
5-C
11Higher alcohols, but content is all below 40wt%.It is active component with Co that Chinese patent CN 101310856B has reported a kind of, is higher alcohols synthetic catalyst of carrier and preparation method thereof with the active carbon, and this catalyst is used for the directly synthetic C of CO hydrogenation one-step method
2-C
18Straight chain higher alcohol.So far, utilize copper-based nano-catalyst to pass through the direct highly selective synthesizing bigh carbon alcohol of synthesis gas and still do not have bibliographical information.
Summary of the invention
The technical problem that the present invention will solve provides a kind of copper-based nano-catalyst and method for making and application that is used for the synthesis gas preparation higher alcohols.
For solving the problems of the technologies described above; The copper-based nano-catalyst that is used for the synthesis gas preparation higher alcohols of the present invention; It is a kind of copper Quito metal (Cu-M) nanocatalyst; Be made up of copper and at least a Fischer-Tropsch constituent element, wherein, said Fischer-Tropsch constituent element is selected from least a in ruthenium (Ru), iron (Fe), cobalt (Co) and the nickel (Ni).
In the said copper-based nano-catalyst, the mol ratio of copper and Fischer-Tropsch constituent element is 0.01～100, is preferably 0.1～10.
The particle diameter of said copper-based nano-catalyst is 0.5～300nm, is preferably 2～100nm.
In addition, the invention also discloses a kind of preparation method who is used for the copper-based nano-catalyst of synthesis gas preparation higher alcohols, be selected from any one method in displacement reaction method, step-by-step reduction method, the while reducing process.
Said displacement reaction method prepares the high metal nanoparticle of metal active through reduction earlier, adds the lower metal salt solution of other metal active again, and both displacement reaction take place and obtain many metal nanos catalyst; Specifically can operate by following IA or IB:
IA, be used to prepare CuRu bimetal nano catalyst, step comprises:
Mantoquita is dissolved in forms solution in the solvent,, obtain copper nano particles with the reducing agent reduction; In gained copper nano particles dispersion liquid, add Fischer-Tropsch constituent element Ru salting liquid, carry out displacement reaction, centrifugation after reaction is accomplished with the Cu nano particle; Solid matter is with water, low mass molecule alcohol or washing with acetone; After removing cleaning solvent, drying promptly gets CuRu bimetal nano catalyst.
IB, be used to prepare the catalyst except that CuRu bimetal nano catalyst, step comprises:
To contain at least a Fischer-Tropsch constituent element salt among Fe, Co and the Ni and be dissolved in and form solution in the solvent,, obtain Fischer-Tropsch constituent element nano particle with the reducing agent reduction; In gained Fischer-Tropsch constituent element nanoparticulate dispersion, add copper salt solution; Carry out displacement reaction with Fischer-Tropsch constituent element nano particle; Back centrifugation or magnetic separation are accomplished in reaction, and solid matter is with water, low mass molecule alcohol or washing with acetone, remove cleaning solvent after; Drying promptly gets copper Quito metal nano catalyst.
Said step-by-step reduction method is that each metal component in the catalyst is reduced successively, specifically can operate by following IIA, IIB, IIC or IID:
IIA, the reduction Cu of elder generation restore the Fischer-Tropsch constituent element, and step comprises:
Mantoquita is dissolved in forms solution in the solvent,, obtain copper nano particles with the reducing agent reduction; In gained copper nano particles dispersion liquid, add reducing agent, splash into Fischer-Tropsch constituent element salting liquid then and carry out reduction reaction; Back centrifugation or magnetic separation are accomplished in reduction, and solid matter is with water, low mass molecule alcohol or washing with acetone, remove cleaning solvent after, drying promptly gets copper Quito metal nano catalyst.
IIB, the reduction Cu of elder generation restore the Fischer-Tropsch constituent element, and step comprises:
Mantoquita is dissolved in forms solution in the solvent,, obtain copper nano particles with the reducing agent reduction; In gained copper nano particles dispersion liquid, add Fischer-Tropsch constituent element salting liquid, splash into reducing agent then and carry out reduction reaction; Back centrifugation or magnetic separation are accomplished in reduction, and solid matter is with water, low mass molecule alcohol or washing with acetone, remove cleaning solvent after, drying promptly gets copper Quito metal nano catalyst.
IIC, elder generation's reduction Fischer-Tropsch constituent element restore Cu, and step comprises:
Fischer-Tropsch constituent element salt is dissolved in forms solution in the solvent,, obtain Fischer-Tropsch constituent element nano particle with the reducing agent reduction; In gained Fischer-Tropsch constituent element nanoparticulate dispersion, add reducing agent, splash into copper salt solution then and carry out reduction reaction; Back centrifugation or magnetic separation are accomplished in reduction, and solid matter is with water, low mass molecule alcohol or washing with acetone, remove cleaning solvent after, drying promptly gets copper Quito metal nano catalyst.
IID, elder generation's reduction Fischer-Tropsch constituent element restore Cu, and step comprises:
Fischer-Tropsch constituent element salt is dissolved in forms solution in the solvent,, obtain Fischer-Tropsch constituent element nano particle with the reducing agent reduction; In gained Fischer-Tropsch constituent element nanoparticulate dispersion, add copper salt solution, splash into reducing agent then and carry out reduction reaction; Back centrifugation or magnetic separation are accomplished in reduction, and solid matter is with water, low mass molecule alcohol or washing with acetone, remove cleaning solvent after, drying promptly gets copper Quito metal nano catalyst.
Said while reducing process is that copper and Fischer-Tropsch constituent element are reduced simultaneously, and the step of this method comprises: mantoquita and Fischer-Tropsch constituent element salt are dissolved in form solution in the solvent, reduce with reducing agent; Back centrifugation or magnetic separation are accomplished in reduction, and solid matter is with water, low mass molecule alcohol or washing with acetone, remove cleaning solvent after, drying promptly gets copper Quito metal nano catalyst.
Among the preparation method of said copper-based nano-catalyst, used mantoquita is selected from following eight at least a in the mantoquita: stannous chloride (CuCl), anhydrous cupric chloride (CuCl
2), copper chloride dihydrate (CuCl
22H
2O), copper nitrate (Cu (NO
3)
23H
2O), anhydrous cupric sulfate (CuSO
4), cupric sulfate pentahydrate (CuSO
45H
2O), Schweinfurt green [Cu (AcO)
2H
2O] and acetylacetone copper [Cu (acac)
2].Said mantoquita concentration is pressed Cu
+And Cu
2+Total concentration is counted 0.001～10mol/L, is preferably 0.05～0.5mol/L.
Among the preparation method of said copper-based nano-catalyst, the solvent of used mantoquita and Fischer-Tropsch constituent element salt is selected from water, organic solvent or its mixed solvent.Wherein, said organic solvent is preferably methyl alcohol, ethanol, ethylene glycol, glycerine, 1, ammediol, 1,4-butanediol, polyethylene glycol-200 and polyethylene glycol-400.When solvent is selected ethylene glycol, glycerine, 1 for use, ammediol, 1 when 4-butanediol, Macrogol 200 and PEG400, does not add stabilizing agent in the solution; When solvent is selected water, methyl alcohol and ethanol for use, add stabilizing agent in the solution simultaneously.Used stabilizing agent is selected from polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), citric acid (CA), natrium citricum (Na
3-softex kw etc.), at least a in non-ionic surface active agent (comprising: tween, this class, F127, P123 etc.) or the betaines surfactant CA), soluble starch and cationic surfactant (comprising:.Used stabilizing agent (repeated fragment) is 400: 1～0: 1 with the mol ratio of catalyst metals.
Among the preparation method of said copper-based nano-catalyst, used reducing agent is selected from hydrogen (H
2), sodium borohydride (NaBH
4), potassium borohydride (KBH
4), lithium borohydride (LiBH
4), borine ether (BH
3OEt
2), amine borine (NH
3BH
3), borine oxolane (BH
3THF), diborane (B
2H
6), lithium aluminium hydride reduction (LiAlH
4), hydrazine hydrate (NH
2NH
2H
2O), dimethyl formamide (DMF), formaldehyde, formic acid, formates, organic amine (comprising: dimethylamine, diethylamine, cetylamine, octadecylamine etc.), dihydroxylic alcohols (comprising: ethylene glycol, 1; Ammediol, 1,4-butanediol etc.), at least a in polyalcohol (comprising: glycerine, glucitol etc.), polyhydroxy aldehyde (comprising: glucose, wood sugar, glyceraldehyde etc.), polyhydroxyketone (comprising: fructose, acetone glucose etc.), vitamin C, citric acid, citrate, lactic acid, lactate, tartaric acid or the tartrate.
Wherein, adopt NaBH
4, KBH
4, LiBH
4, NH
3BH
3, BH
3OEt
2, BH
3THF, B
2H
6, LiAlH
4Or NH
2NH
2H
2O when these strong reductants are reducing agent, can carry out reduction reaction under normal temperature, normal pressure;
When adopting DMF, formaldehyde, formic acid, formates, organic amine, dihydroxylic alcohols, polyalcohol, polyhydroxy aldehyde, polyhydroxyketone, vitamin C, citric acid, citrate, lactic acid, lactate, tartaric acid or tartrate to be reducing agent, reduction reaction is accomplished under 50 ℃～250 ℃ heating conditions;
Adopt H
2During for reducing agent, under 100～200 ℃, 0.1～4.0MPa condition, reduce.
Among the preparation method of said copper-based nano-catalyst, used Fischer-Tropsch constituent element salt is selected from single slaine or many metal mixed salt of ruthenium salt, molysite, cobalt salt and nickel salt.Said Fischer-Tropsch constituent element salinity is counted 0.001～10mol/L by metal cation total concentration, is preferably 0.05～0.5mol/L.
Concrete, ruthenium salt is selected from least a in following six kinds of ruthenium salt: ruthenic chloride (RuCl
3NH
2O), potassium ruthenate (K
2RuO
4H
2O), potassium perruthenate (KRuO
4), acetylacetone,2,4-pentanedione ruthenium [Ru (acac)
3], ruthenic acid tetrapropylammonium [N (C
3H
7)
4RuO
4], three (bipyridyl) ruthenic chloride { [Ru (bipy)
3] Cl
3.
Molysite is selected from following six kinds of molysite at least a: frerrous chloride (FeCl
24H
2O), Iron trichloride hexahydrate (FeCl
36H
2O), anhydrous ferric chloride (FeCl
3), ferrous sulfate (FeSO
47H
2O), ferric sulfate (Fe
2(SO
4)
39H
2O), ferric nitrate (Fe (NO
3)
39H
2O).
Cobalt salt is selected from least a in following five kinds of cobalt salts: cobalt chloride (CoCl
26H
2O), cobalt nitrate [Co (NO
3)
26H
2O], cobaltous sulfate (CoSO
47H
2O), cobalt acetate [Co (AcO)
24H
2O], ammonium cobaltous sulfate [(NH
4)
2Co (SO
4)
26H
2O].
Nickel salt is selected from least a in following five kinds of nickel salts: nickel chloride (NiCl
26H
2O), nickel nitrate [Ni (NO
3)
26H
2O], nickelous sulfate (NiSO
46H
2O), nickel acetate [Ni (AcO)
24H
2O], ammonium nickel sulfate [(NH
4)
2Ni (SO
4)
26H
2O].
Among the preparation method of said copper-based nano-catalyst, used low mass molecule alcohol comprises: methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, butanols, isobutanol, sec-butyl alcohol and the tert-butyl alcohol.Copper of the present invention Quito metal nano catalyst can be applicable in the synthesis gas preparation higher alcohols, and wherein, catalytic reaction condition is: the temperature of catalytic reaction is 150～320 ℃, is preferably 200～280 ℃; H
2With the CO stagnation pressure be 0.1～13MPa, be preferably 4～7MPa; In the catalytic reaction, H
2With the mol ratio of CO be 0.1～10, be preferably 1～3; Air speed (GHSV) is 100h
-1～100000h
-1, be preferably 1000h
-1～10000h
-1
Copper Quito metal nano catalyst of the present invention's preparation is the catalyst that contains copper component and at least a Fischer-Tropsch component on a kind of single nano particle simultaneously, can be used in the synthetic reaction by the synthesis gas preparation higher alcohols, and the present invention has following beneficial effect:
1) catalyst particle size is little, and specific surface is big, and utilization rate is high;
2) preparation process is simple, and is easy to operate, and finely regulating is easy between each component of catalyst, helps the adjusting to products distribution;
3) utilize copper of the present invention Quito metal nano catalyst to carry out the synthetic of synthesis gas preparation higher alcohols, through the component and the ratio thereof of control catalyst, the selectivity of the above alcohol of ethanol can reach more than the 95wt% the above higher alcohols (C of hexanol in the gained alcohol
6 +OH) selectivity can reach more than the 80wt%.
Description of drawings
Below in conjunction with the accompanying drawing and the specific embodiment the present invention is done further detailed explanation:
Accompanying drawing is that (Transmission electron microscopy, TEM) photo wherein, show among the figure that the nano particle about this catalyst is by 15nm is formed for the transmission electron microscope of typical catalyst.
The specific embodiment
Copper Quito metal nano catalyst of following examples preparation, particle diameter is 0.5～300nm, can be used for from the synthetic reaction of synthesis gas preparation higher alcohols, wherein, preferable particle size is the catalyst of 2～100nm.This catalyst is made up of copper and at least a Fischer-Tropsch constituent element, and the Fischer-Tropsch constituent element is selected from least a among Ru, Fe, Co and the Ni.This copper Quito metal nano catalyst can prepare by any one method in described displacement reaction method, step-by-step reduction method and the while reducing process.
Below in conjunction with specific embodiment the present invention is described.Following examples help to understand the present invention, but do not limit application of the present invention.
Embodiment 1
With Cu (NO
3)
23H
2O and Fe (NO
3)
39H
2O is dissolved in the ethylene glycol (EG) in Cu/Fe=3/2 ratio (mol ratio), and making total concentration of metal ions is 0.15mol/L, gets hybrid metal solution, the ice-water bath cooling.With excessive NaBH
4Be dissolved in H
2O and EG mixed solvent (H
2O and EG volume ratio are 1/5) in, splash into hybrid metal solution fast, drip to finish and stir 10min so that reduction is complete.Room temperature to be chilled to adds acetone diluted, centrifugation.The gained black solid with washing with acetone once with the deoxidized water washing once, again with washing with acetone twice, places 80 ℃ of baking ovens to be dried to bulk, changes N in the tube furnace then over to
2Protect following 300 ℃ of dry 1h, get catalyst.The reaction condition that carries out the synthesis gas preparation higher alcohols at fixed-bed catalytic reactor is following: 220 ℃, and H
2With the CO stagnation pressure be 6.0MPa, GHSV=6000h
-1, H
2/ CO (mol ratio)=2.Reaction result is listed in table 1.
Embodiment 2
With Cu (NO
3)
23H
2O and Fe (NO
3)
39H
2O is dissolved in the ethylene glycol (EG) in the Cu/Fe=3/1 ratio, and making total concentration of metal ions is 0.13mol/L, gets hybrid metal solution, the ice-water bath cooling.With excessive NaBH
4Be dissolved in H
2O and EG mixed solvent (H
2O and EG volume ratio are 1/5) in, splash into hybrid metal solution fast, drip to finish and stir 10min so that reduction is complete.Room temperature to be chilled to adds the deoxidized water dilution, centrifugation.The gained black solid with the deoxidized water washing once again with washing with alcohol once, is dried to bulk under the room temperature, changes N in the tube furnace then over to
2Protect following 150 ℃ of dry 1h, get catalyst.The reaction condition that carries out the synthesis gas preparation higher alcohols at fixed-bed catalytic reactor is following: 210 ℃, and H
2With the CO stagnation pressure be 6.0MPa, GHSV=6000h
-1, H
2/ CO=2.Reaction result is listed in table 1.
Embodiment 3
With Cu (NO
3)
23H
2O and Fe (NO
3)
39H
2O is dissolved in the ethylene glycol (EG) in the Cu/Fe=3/1 ratio, and making total concentration of metal ions is 0.13mol/L, gets hybrid metal solution, the ice-water bath cooling.With excessive NaBH
4Be dissolved in H
2O and EG mixed solvent (H
2O and EG volume ratio are 1/5) in, splash into hybrid metal solution fast, drip to finish and stir 10min so that reduction is complete.Room temperature to be chilled to adds the deoxidized water dilution, centrifugation.The gained black solid is with deoxidized water washing 2 times, with washing with alcohol 3 times, is dried to bulk under the room temperature again, changes N in the tube furnace then over to
2Protect following 150 ℃ of dry 2h, get catalyst.The reaction condition that carries out the synthesis gas preparation higher alcohols at fixed-bed catalytic reactor is following: 240 ℃, and H
2With the CO stagnation pressure be 6.0MPa, GHSV=6000h
-1, H
2/ CO=2.Reaction result is listed in table 1.
Embodiment 4
With Cu (NO
3)
23H
2O and Fe (NO
3)
39H
2O is dissolved in the ethylene glycol (EG) in the Cu/Fe=1/3 ratio, and making total concentration of metal ions is 0.13mol/L, gets hybrid metal solution, the ice-water bath cooling.With excessive NaBH
4Be dissolved in H
2O and EG mixed solvent (H
2O and EG volume ratio are 1/5) in, splash into hybrid metal solution fast, drip to finish and stir 10min so that reduction is complete.Room temperature to be chilled to adds the deoxidized water dilution, centrifugation.The gained black solid is with deoxidized water washing 2 times, with washing with alcohol 2 times, is dried to bulk under the room temperature again, changes N in the tube furnace then over to
2Protect following 150 ℃ of dry 2h, get catalyst.
Ultrasonic being scattered in of the catalyst that takes a morsel is used for transmission electron microscope (TEM) test in the ethanol, test result shows that gained nanocatalyst grain diameter is 15 ± 3nm, and the TEM photo is seen Figure of description.
The reaction condition that carries out the synthesis gas preparation higher alcohols at fixed-bed catalytic reactor is following: 260 ℃, and H
2With the CO stagnation pressure be 6.0MPa, GHSV=6000h
-1, H
2/ CO=2.Reaction result is listed in table 1.
Embodiment 5
With Cu (NO
3)
23H
2O and Fe (NO
3)
39H
2O is dissolved in the ethylene glycol (EG) in the Cu/Fe=10/1 ratio, and making total concentration of metal ions is 0.05mol/L, gets hybrid metal solution, the ice-water bath cooling.With excessive NaBH
4Be dissolved in H
2O and EG mixed solvent (H
2O and EG volume ratio are 1/5) in, splash into hybrid metal solution fast, drip to finish and stir 10min so that reduction is complete.Room temperature to be chilled to adds the deoxidized water dilution, centrifugation.The gained black solid is with deoxidized water washing 2 times, with washing with alcohol 2 times, is dried to bulk under the room temperature again, changes N in the tube furnace then over to
2Protect following 150 ℃ of dry 2h, get catalyst.The reaction condition that carries out the synthesis gas preparation higher alcohols at fixed-bed catalytic reactor is following: 240 ℃, and H
2With the CO stagnation pressure be 6.0MPa, GHSV=10000h
-1, H
2/ CO=2.Reaction result is listed in table 1.
Embodiment 6
With Cu (NO
3)
23H
2O and Fe (NO
3)
39H
2O is dissolved in the ethylene glycol (EG) in the Cu/Fe=1/10 ratio, and making total concentration of metal ions is 0.5mol/L, gets hybrid metal solution, the ice-water bath cooling.With excessive NaBH
4Be dissolved in H
2O and EG mixed solvent (H
2O and EG volume ratio are 1/5) in, splash into hybrid metal solution fast, drip to finish and stir 10min so that reduction is complete.Room temperature to be chilled to adds the deoxidized water dilution, centrifugation.The gained black solid is with deoxidized water washing 2 times, again with washing with alcohol 2 times, and N
2Protection drying at room temperature down becomes block, changes N in the tube furnace then over to
2Protect following 150 ℃ of dry 2h, get catalyst.The reaction condition that carries out the synthesis gas preparation higher alcohols at fixed-bed catalytic reactor is following: 220 ℃, and H
2With the CO stagnation pressure be 6.0MPa, GHSV=1000h
-1, H
2/ CO=2.Reaction result is listed in table 1.
Embodiment 7
With Cu (NO
3)
23H
2O and Co (NO
3)
26H
2O is dissolved in the ethylene glycol (EG) in the Cu/Co=10/1 ratio, and making total concentration of metal ions is 0.2mol/L, gets hybrid metal solution, the ice-water bath cooling.With excessive NaBH
4Be dissolved in H
2Among the O, splash into hybrid metal solution fast, drip to finish and stir 10min so that reduction is complete.Room temperature to be chilled to adds the deoxidized water dilution, centrifugation.The gained black solid is with deoxidized water washing 2 times, with washing with alcohol 2 times, is dried to bulk under the room temperature again, changes N in the tube furnace then over to
2Protect following 150 ℃ of dry 2h, get catalyst.The reaction condition that carries out the synthesis gas preparation higher alcohols at fixed-bed catalytic reactor is following: 240 ℃, and H
2With the CO stagnation pressure be 6.0MPa, GHSV=6000h
-1, H
2/ CO=2.Reaction result is listed in table 1.
Embodiment 8
With Co (NO
3)
26H
2O is that 0.13mol/L is dissolved in the deionized water by concentration of cobalt ions, and adding PVP is a stabilizing agent, makes mol ratio=20 of PVP/Co, gets cobalt salt solution, the ice-water bath cooling.With excessive NaBH
4Be dissolved in H
2Among the O, splash into cobalt liquor fast, drip to finish and stir 10min so that reduction is complete.Room temperature to be chilled to, strong magnetic separates.Solid dispersed is in deionized water, and making metal concentration is 0.2mol/L, gets cobalt nano-particle (Co NPs) dispersion liquid.Amount by Cu/Co=1/2 is the Cu (NO of 0.1mol/L with concentration
3)
23H
2The O aqueous solution slowly splashes in the gained Co NPs dispersion liquid, drip to finish stirs 30min so that displacement reaction is complete, and strong magnetic separates, and the gained black solid is with deoxidized water washing 1 time, with washing with alcohol 2 times, is dried to bulk under the room temperature again, changes N in the tube furnace then over to
2Protect following 150 ℃ of dry 2h, get catalyst.The reaction condition that carries out the synthesis gas preparation higher alcohols at fixed-bed catalytic reactor is following: 220 ℃, and H
2With the CO stagnation pressure be 6.0MPa, GHSV=6000h
-1, H
2/ CO=2.Reaction result is listed in table 1.
Embodiment 9
With Cu (NO
3)
23H
2O is that 0.13mol/L is dissolved among the PEG-200 by copper ion concentration, gets copper salt solution, the ice-water bath cooling.With excessive NH
3BH
4The aqueous solution splashes into copper solution fast, drips to finish to stir 10min so that reduction is complete.Remaining NH
3BH
4Remove with acetone, then by the amount of Cu/Co=2/1 to wherein adding the Co (NO that concentration is 0.13mol/L
3)
26H
2O PEG-200 solution stirs, with excessive NH
3BH
4The aqueous solution splashes into wherein fast, drips to finish to stir 10min so that reduction is complete.Add the deoxidized water dilution, strong magnetic separates, and the gained black solid is with deoxidized water washing 3 times, with washing with alcohol 2 times, is dried to bulk under the room temperature again, changes N in the tube furnace then over to
2Protect following 150 ℃ of dry 2h, get catalyst.The reaction condition that carries out the synthesis gas preparation higher alcohols at fixed-bed catalytic reactor is following: 240 ℃, and H
2With the CO stagnation pressure be 6.0MPa, GHSV=6000h
-1, H
2/ CO=2.Reaction result is listed in table 1.
Embodiment 10
With Cu (NO
3)
23H
2O is that 0.13mol/L is dissolved among the PEG-200 by copper ion concentration, gets copper salt solution, the ice-water bath cooling.With excessive NH
3BH
4The aqueous solution splashes into copper solution fast, drips to finish to stir 10min so that reduction is complete.Add excessive NH
3BH
4, then by the amount of Cu/Co=2/1 to wherein splashing into the Co (NO that concentration is 0.13mol/L
3)
26H
2O PEG-200 solution drips to finish and stirs 10min so that reduction is complete.Add the deoxidized water dilution, strong magnetic separates, and the gained black solid is with deoxidized water washing 3 times, with washing with alcohol 2 times, is dried to bulk under the room temperature again, changes N in the tube furnace then over to
2Protect following 150 ℃ of dry 2h, get catalyst.The reaction condition that carries out the synthesis gas preparation higher alcohols at fixed-bed catalytic reactor is following: 240 ℃, and H
2With the CO stagnation pressure be 6.0MPa, GHSV=6000h
-1, H
2/ CO=2.Reaction result is listed in table 1.
Embodiment 11
With NiCl
26H
2O is that 0.15mol/L is dissolved in H by nickel ion concentration
2In O-EG (1: the 1) mixed solvent, get nickel salt solution, add a small amount of tetraethyl ammonium hydroxide and transfer to alkalescence.With excess hydrazine hydrate (NH
2NH
2H
2O) splash into wherein, stir, immerse in 60～80 ℃ of oil baths and react 2h.Add excess hydrazine hydrate, then by the amount of Cu/Ni=1/3 to wherein adding the CuCl that concentration is 0.15mol/L
22H
2O H
2O-EG (1: 1) mixed solvent solution, stirring reaction 1h.Shift out oil bath, be chilled to room temperature, strong magnetic separates, and the gained solid is with deoxidized water washing 2 times, with washing with alcohol 2 times, is dried to bulk under the room temperature again, changes N in the tube furnace then over to
2Protect following 150 ℃ of dry 2h, get catalyst.The reaction condition that carries out the synthesis gas preparation higher alcohols at fixed-bed catalytic reactor is following: 260 ℃, and H
2With the CO stagnation pressure be 6.0MPa, GHSV=6000h
-1, H
2/ CO=2.Reaction result is listed in table 1.
Embodiment 12
With NiCl
26H
2O is that 0.15mol/L is dissolved in H by nickel ion concentration
2In O-EG (1: the 1) mixed solvent, get nickel salt solution, add a small amount of tetraethyl ammonium hydroxide and transfer to alkalescence.With excess hydrazine hydrate (NH
2NH
2H
2O) splash into wherein, stir, immerse in 60～80 ℃ of oil baths and react 2h.Shift out oil bath, be chilled to room temperature, strong magnetic separates, and solid dispersed is in H
2In O-EG (1: the 1) mixed solvent, making metal concentration is 0.15mol/L.By the amount of Cu/Ni=1/3 to wherein adding the CuCl that concentration is 0.15mol/L
22H
2O H
2O-EG (1: 1) mixed solvent solution adds a small amount of tetraethyl ammonium hydroxide and transfers to alkalescence.Splash into excess hydrazine hydrate (NH
2NH
2H
2O), stir stirring reaction 1h under the room temperature.Shift out oil bath, be chilled to room temperature, strong magnetic separates, and the gained solid is with deoxidized water washing 2 times, with washing with alcohol 2 times, is dried to bulk under the room temperature again, changes N in the tube furnace then over to
2Protect following 150 ℃ of dry 2h, get catalyst.The reaction condition that carries out the synthesis gas preparation higher alcohols at fixed-bed catalytic reactor is following: 260 ℃, and H
2With the CO stagnation pressure be 6.0MPa, GHSV=6000h
-1, H
2/ CO=2.Reaction result is listed in table 1.
Embodiment 13
With RuCl
3NH
2O is that 0.05mol/L is dissolved in the ethylene glycol (EG) by ruthenium ion concentration, and EG is reducing agent simultaneously, gets the ruthenium salting liquid, immerses in 200 ℃ of oil baths and reacts 30min.Shift out oil bath, be chilled to room temperature, by the amount of Cu/Ru=1/3 to wherein adding the CuCl that concentration is 0.05mol/L
22H
2O EG solution stirs, and immerses in 180 ℃ of oil baths and reacts 1h.Shift out oil bath, be chilled to room temperature, add acetone diluted, centrifugation, the gained solid washs 3 times with acetone-alcohol mixeding liquid, is dried to bulk under the room temperature, changes N in the tube furnace then over to
2Protect following 150 ℃ of dry 2h, get catalyst.The reaction condition that carries out the synthesis gas preparation higher alcohols at fixed-bed catalytic reactor is following: 200 ℃, and H
2With the CO stagnation pressure be 6.0MPa, GHSV=6000h
-1, H
2/ CO=2.Reaction result is listed in table 1.
Embodiment 14
With RuCl
3NH
2O, CuCl
22H
2O, NiCl
26H
2O is that 0.09mol/L, Cu/Ru/Ni=4/1/4 are dissolved in the ethylene glycol (EG) by total concentration of metal ions, and EG is reducing agent simultaneously, gets hybrid metal solution, immerses in 200 ℃ of oil baths and reacts 1h.Shift out oil bath, be chilled to room temperature, add acetone diluted, centrifugation, the gained solid washs 3 times with acetone-alcohol mixeding liquid, is dried to bulk under the room temperature, changes N in the tube furnace then over to
2Protect following 150 ℃ of dry 2h, get catalyst.The reaction condition that carries out the synthesis gas preparation higher alcohols at fixed-bed catalytic reactor is following: 240 ℃, and H
2With the CO stagnation pressure be 6.0MPa, GHSV=6000h
-1, H
2/ CO=2.Reaction result is listed in table 1.
Embodiment 15
With Cu (NO
3)
23H
2O, Co (NO
3)
26H
2O, Fe (NO
3)
39H
2O is that 0.16mol/L, Cu/Co/Fe=2/1/1 are dissolved among the EG by total concentration of metal ions, gets hybrid metal solution, the ice-water bath cooling.With excessive NaBH
4Be dissolved in H
2Among the O, splash into hybrid metal solution fast, drip to finish and stir 10min so that reduction is complete.Room temperature to be chilled to adds the deoxidized water dilution, and strong magnetic separates.The gained black solid is with deoxidized water washing 2 times, with washing with alcohol 2 times, is dried to bulk under the room temperature again, changes N in the tube furnace then over to
2Protect following 150 ℃ of dry 2h, get catalyst.The reaction condition that carries out the synthesis gas preparation higher alcohols at fixed-bed catalytic reactor is following: 240 ℃, and H
2With the CO stagnation pressure be 6.0MPa, GHSV=6000h
-1, H
2/ CO=2.Reaction result is listed in table 1.
Embodiment 16
With Cu (NO
3)
23H
2O, Co (NO
3)
26H
2O, Fe (NO
3)
39H
2O is that 0.16mol/L, Cu/Co/Fe=6/1/1 are dissolved among the EG by total concentration of metal ions, gets hybrid metal solution, the ice-water bath cooling.With excessive NaBH
4Be dissolved in H
2Among the O, splash into hybrid metal solution fast, drip to finish and stir 10min so that reduction is complete.Room temperature to be chilled to adds the deoxidized water dilution, centrifugation.The gained black solid is with deoxidized water washing 2 times, with washing with alcohol 2 times, is dried to bulk under the room temperature again, changes N in the tube furnace then over to
2Protect following 150 ℃ of dry 2h, get catalyst.The reaction condition that carries out the synthesis gas preparation higher alcohols at fixed-bed catalytic reactor is following: 240 ℃, and H
2With the CO stagnation pressure be 6.0MPa, GHSV=6000h
-1, H
2/ CO=2.Reaction result is listed in table 1.
Table 1 embodiment result
Embodiment 17
With potassium ruthenate (K
2RuO
4H
2O) with Cu (OAc)
2H
2O is that 0.002mol/L, Cu/Ru=1/1 are dissolved in the deionized water by total concentration of metal ions, and adding citric acid (CA) is stabilizing agent, makes the total metal ion of CA/=400/1, gets mixed solution.Mixed solution is changed in the autoclave, with hydrogen reducing, at 0.1MPa H
2Pressure, 100 ℃ of following reaction 4h.Cooling, centrifugalize after the pressure release, the gained black solid is with deoxidized water washing 2 times, with methanol wash 2 times, is dried to bulk under the room temperature again, changes N in the tube furnace then over to
2Protect following 150 ℃ of dry 2h, get catalyst.
This catalyst, the reaction condition that carries out the synthesis gas preparation higher alcohols at fixed-bed catalytic reactor can be: 150 ℃, H
2With the CO stagnation pressure be 0.1MPa, GHSV=100h
-1, H
2/ CO=0.1.
Embodiment 18
With acetylacetone,2,4-pentanedione ruthenium [Ru (acac)
3] and acetylacetone copper; By total concentration of metal ions is 20mol/L, Cu/Ru=1/1; Be dissolved in the ethanol-water mixed solvent (ethanol and water volume ratio are 1/1); The adding mol ratio is that 1: 1 soluble starch and softex kw (CTAB) is stabilizing agent, makes stabilizing agent/total metal ion=200/1, gets mixed solution.Mixed solution is changed in the autoclave, with hydrogen reducing, at 4MPa H
2Pressure, 200 ℃ of following reaction 12h.Cooling, centrifugalize after the pressure release, the gained black solid is with deoxidized water washing 2 times, with washed with isopropyl alcohol 2 times, is dried to bulk under the room temperature again, changes N in the tube furnace then over to
2Protect following 150 ℃ of dry 2h, get catalyst.
This catalyst, the reaction condition that carries out the synthesis gas preparation higher alcohols at fixed-bed catalytic reactor can be: 320 ℃, H
2With the CO stagnation pressure be 13MPa, GHSV=100000h
-1, H
2/ CO=10.
Embodiment 19
With ammonium cobaltous sulfate [(NH
4)
2Co (SO
4)
26H
2O], three (bipyridyl) ruthenic chloride { [Ru (bipy)
3] Cl
3And cupric sulfate pentahydrate (CuSO
45H
2O), be that 5mol/L, Cu/Co/Ru=1/50/50 are dissolved in the glycerine by total concentration of metal ions, get mixed solution.Mixed solution is changed in the autoclave, with hydrogen reducing, at 2MPa H
2Pressure, 150 ℃ of following reaction 4h.Cooling, centrifugalize after the pressure release, the gained black solid is with deoxidized water washing 1 time, and with washing with alcohol 1 time, again with butanols washing 2 times, vacuum drying becomes block under the room temperature, changes N in the tube furnace then over to
2Protect following 150 ℃ of dry 2h, get catalyst.
This catalyst, the reaction condition that carries out the synthesis gas preparation higher alcohols at fixed-bed catalytic reactor can be: 280 ℃, H
2With the CO stagnation pressure be 1MPa, GHSV=500h
-1, H
2/ CO=1.
Embodiment 20
With ammonium nickel sulfate [(NH
4)
2Ni (SO
4)
26H
2O], ruthenic acid tetrapropylammonium [N (C
3H
7)
4RuO
4], ferric sulfate (Fe
2(SO
4)
39H
2O), ammonium cobaltous sulfate [(NH
4)
2Co (SO
4)
26H
2O] and cupric sulfate pentahydrate (CuSO
45H
2O) be 0.505mol/L, Cu/Ni/Ru/Fe/Co=100/0.25/0.25/0.25/0.25 by total metal concentration; Be dissolved in 1; In the 4-butanediol, get hybrid metal solution, in this mixed solution, adding excessive mol ratio is 1: 1: 1: the mixed liquor of 1 DMF, diethylamine, tartaric acid and glucose; Under 50 ℃ of heating conditions, reaction reduction 18h.
Cooling back centrifugation, gained black solid be with deoxidized water washing 1 time, and with methanol wash 1 time, again with isobutanol washing 2 times, vacuum drying becomes block under the room temperature, changes N in the tube furnace then over to
2Protect following 150 ℃ of dry 2h, get catalyst.
This catalyst, the reaction condition that carries out the synthesis gas preparation higher alcohols at fixed-bed catalytic reactor can be: 300 ℃, H
2With the CO stagnation pressure be 4MPa, GHSV=50000h
-1, H
2/ CO=3.
Embodiment 21
With copper chloride dihydrate (CuCl
22H
2O) with cobaltous sulfate (CoSO
47H
2O) be that 0.1mol/L, Cu/Co=5/1 are dissolved in the ethylene glycol (EG) by total metal concentration, add 1mol/L NaOH EG solution, make the total metal ion of NaOH/=10/1, get mixed solution.In this mixed solution, add excessive sodium formate (HCOONa), 250 ℃ of reaction reduction 8h.
Cooling back centrifugation, gained black solid be with deoxidized water washing 2 times, with washing with alcohol 2 times, is dried to bulk under the room temperature again, changes N in the tube furnace then over to
2Protect following 150 ℃ of dry 2h, get catalyst.
This catalyst, the reaction condition that carries out the synthesis gas preparation higher alcohols at fixed-bed catalytic reactor can be: 180 ℃, H
2With the CO stagnation pressure be 7MPa, GHSV=20000h
-1, H
2/ CO=1.5.
Embodiment 22
Change the reduction temperature among the embodiment 21 into 180 ℃, other conditions are the same with embodiment 21, the catalyst that finally obtains, and the reaction condition that carries out the synthesis gas preparation higher alcohols at fixed-bed catalytic reactor can be: 160 ℃, H
2With the CO stagnation pressure be 10MPa, GHSV=200h
-1, H
2/ CO=5.
Claims (15)
1. copper-based nano-catalyst that is used for the synthesis gas preparation higher alcohols; It is characterized in that: said catalyst is a kind of copper Quito metal nano catalyst; Be made up of copper and at least a Fischer-Tropsch constituent element, wherein, said Fischer-Tropsch constituent element is selected from least a in ruthenium, iron, cobalt and the nickel.
2. catalyst as claimed in claim 1 is characterized in that: the particle diameter of said copper-based nano-catalyst is 0.5～300nm; The mol ratio of said copper and Fischer-Tropsch constituent element is 0.01～100.
3. catalyst as claimed in claim 2 is characterized in that: the particle diameter of said copper-based nano-catalyst is 2～100nm; The mol ratio of said copper and Fischer-Tropsch constituent element is 0.1～10.
4. the preparation method who is used for the copper-based nano-catalyst of synthesis gas preparation higher alcohols as claimed in claim 1 is characterized in that: any one method that is selected from displacement reaction method, step-by-step reduction method, the while reducing process prepares;
Wherein, said displacement reaction method, operate by following IA or IB:
IA, mantoquita is dissolved in forms solution in the solvent,, obtain copper nano particles with the reducing agent reduction; In gained copper nano particles dispersion liquid, add Fischer-Tropsch constituent element Ru salting liquid, carry out displacement reaction, centrifugation after reaction is accomplished with the Cu nano particle; Solid matter is with water, low mass molecule alcohol or washing with acetone; After removing cleaning solvent, drying promptly gets CuRu bimetal nano catalyst;
IB, will contain at least a Fischer-Tropsch constituent element salt among Fe, Co and the Ni and be dissolved in and form solution in the solvent,, obtain Fischer-Tropsch constituent element nano particle with the reducing agent reduction; In gained Fischer-Tropsch constituent element nanoparticulate dispersion, add copper salt solution; Carry out displacement reaction with Fischer-Tropsch constituent element nano particle; Back centrifugation or magnetic separation are accomplished in reaction, and solid matter is with water, low mass molecule alcohol or washing with acetone, remove cleaning solvent after; Drying promptly gets copper Quito metal nano catalyst;
Said step-by-step reduction method, operate by following IIA, IIB, IIC or IID:
IIA, mantoquita is dissolved in forms solution in the solvent,, obtain copper nano particles with the reducing agent reduction; In gained copper nano particles dispersion liquid, add reducing agent, splash into Fischer-Tropsch constituent element salting liquid then and carry out reduction reaction; Back centrifugation or magnetic separation are accomplished in reduction, and solid matter is with water, low mass molecule alcohol or washing with acetone, remove cleaning solvent after, drying promptly gets copper Quito metal nano catalyst;
IIB, mantoquita is dissolved in forms solution in the solvent,, obtain copper nano particles with the reducing agent reduction; In gained copper nano particles dispersion liquid, add Fischer-Tropsch constituent element salting liquid, splash into reducing agent then and carry out reduction reaction; Back centrifugation or magnetic separation are accomplished in reduction, and solid matter is with water, low mass molecule alcohol or washing with acetone, remove cleaning solvent after, drying promptly gets copper Quito metal nano catalyst;
IIC, Fischer-Tropsch constituent element salt is dissolved in forms solution in the solvent,, obtain Fischer-Tropsch constituent element nano particle with the reducing agent reduction; In gained Fischer-Tropsch constituent element nanoparticulate dispersion, add reducing agent, splash into copper salt solution then and carry out reduction reaction; Back centrifugation or magnetic separation are accomplished in reduction, and solid matter is with water, low mass molecule alcohol or washing with acetone, remove cleaning solvent after, drying promptly gets copper Quito metal nano catalyst;
IID, Fischer-Tropsch constituent element salt is dissolved in forms solution in the solvent,, obtain Fischer-Tropsch constituent element nano particle with the reducing agent reduction; In gained Fischer-Tropsch constituent element nanoparticulate dispersion, add copper salt solution, splash into reducing agent then and carry out reduction reaction; Back centrifugation or magnetic separation are accomplished in reduction, and solid matter is with water, low mass molecule alcohol or washing with acetone, remove cleaning solvent after, drying promptly gets copper Quito metal nano catalyst;
Said while reducing process, step comprises: mantoquita and Fischer-Tropsch constituent element salt are dissolved in form solution in the solvent, reduce with reducing agent; Back centrifugation or magnetic separation are accomplished in reduction, and solid matter is with water, low mass molecule alcohol or washing with acetone, remove cleaning solvent after, drying promptly gets copper Quito metal nano catalyst.
5. method as claimed in claim 4; It is characterized in that: among the preparation method of said copper-based nano-catalyst, used mantoquita is selected from following eight at least a in the mantoquita: stannous chloride, anhydrous cupric chloride, copper chloride dihydrate, copper nitrate, anhydrous cupric sulfate, cupric sulfate pentahydrate, Schweinfurt green and acetylacetone copper;
Said mantoquita concentration is pressed Cu
+And Cu
2+Total concentration is counted 0.001～10mol/L.
6. method as claimed in claim 5 is characterized in that: said mantoquita concentration is pressed Cu
+And Cu
2+Total concentration is counted 0.05～0.5mol/L.
7. method as claimed in claim 4 is characterized in that: among the preparation method of said copper-based nano-catalyst, the solvent of used mantoquita and Fischer-Tropsch constituent element salt is selected from water, organic solvent or its mixed solvent.
8. method as claimed in claim 7 is characterized in that: said organic solvent is methyl alcohol, ethanol, ethylene glycol, glycerine, 1, ammediol, 1,4-butanediol, polyethylene glycol-200 and polyethylene glycol-400;
When solvent is selected ethylene glycol, glycerine, 1 for use, ammediol, 1 when 4-butanediol, Macrogol 200 and PEG400, does not add stabilizing agent in the solution;
When solvent is selected water, methyl alcohol and ethanol for use, add stabilizing agent in the solution simultaneously, the mol ratio of this stabilizing agent and catalyst metals is 400: 1～0: 1; Wherein, stabilizing agent is selected from least a in polyvinylpyrrolidone, polyethylene glycol, citric acid, natrium citricum, soluble starch, cationic surfactant, non-ionic surface active agent or the betaines surfactant.
9. method as claimed in claim 4; It is characterized in that: among the preparation method of said copper-based nano-catalyst, used reducing agent is selected from least a in hydrogen, sodium borohydride, potassium borohydride, lithium borohydride, borine ether, amine borine, borine oxolane, diborane, lithium aluminium hydride reduction, hydrazine hydrate, dimethyl formamide, formaldehyde, formic acid, formates, organic amine, dihydroxylic alcohols, polyalcohol, polyhydroxy aldehyde, polyhydroxyketone, vitamin C, citric acid, citrate, lactic acid, lactate, tartaric acid or the tartrate;
Wherein, organic amine comprises: dimethylamine, diethylamine, cetylamine, octadecylamine;
Dihydroxylic alcohols comprises: ethylene glycol, 1, ammediol, 1,4-butanediol;
Polyalcohol comprises: glycerine, glucitol;
Polyhydroxy aldehyde comprises: glucose, wood sugar, glyceraldehyde;
Polyhydroxyketone comprises: fructose, acetone glucose.
10. method as claimed in claim 4; It is characterized in that: among the preparation method of said copper-based nano-catalyst; Used Fischer-Tropsch constituent element salt is selected from single slaine or many metal mixed salt of ruthenium salt, molysite, cobalt salt and nickel salt; Wherein, Fischer-Tropsch constituent element salinity is counted 0.001～10mol/L by the metal total ion concentration.
11. method as claimed in claim 10 is characterized in that: said Fischer-Tropsch constituent element salinity is counted 0.05～0.5mol/L by the metal total ion concentration.
12. method as claimed in claim 10 is characterized in that: said ruthenium salt is selected from least a in following six kinds of ruthenium salt: ruthenic chloride, potassium ruthenate, potassium perruthenate, acetylacetone,2,4-pentanedione ruthenium, ruthenic acid tetrapropylammonium, three (bipyridyl) ruthenic chloride;
Molysite is selected from following six kinds of molysite at least a: frerrous chloride, Iron trichloride hexahydrate, anhydrous ferric chloride, ferrous sulfate, ferric sulfate, ferric nitrate;
Cobalt salt is selected from least a in following five kinds of cobalt salts: cobalt chloride, cobalt nitrate, cobaltous sulfate, cobalt acetate, ammonium cobaltous sulfate;
Nickel salt is selected from least a in following five kinds of nickel salts: nickel chloride, nickel nitrate, nickelous sulfate, nickel acetate, ammonium nickel sulfate.
13. method as claimed in claim 4 is characterized in that: among the preparation method of said copper-based nano-catalyst, used low mass molecule alcohol comprises: methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, butanols, isobutanol, sec-butyl alcohol and the tert-butyl alcohol.
14. copper as claimed in claim 1 Quito metal nano Application of Catalyst is characterized in that: be applied in the synthesis gas preparation higher alcohols, wherein, catalytic reaction condition is: the temperature of catalytic reaction is 150～320 ℃; H
2With the CO stagnation pressure be 0.1～13MPa; H
2With the mol ratio of CO be 0.1～10; Air speed is 100～100000h
-1
15. application as claimed in claim 14 is characterized in that: the temperature of said catalytic reaction is 200～280 ℃; H
2With the CO stagnation pressure be 4～7MPa, H
2With the mol ratio of CO be 1～3, air speed is 1000～10000h
-1
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Cited By (13)
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| CN103084181A (en) * | 2013-01-17 | 2013-05-08 | 上海中科高等研究院 | Copper-based composite oxide catalyst as well as preparation method and application thereof |
| CN103084178A (en) * | 2013-01-17 | 2013-05-08 | 上海中科高等研究院 | Copper-contained hydrotalcite-based catalyst for preparing mixed alcohol by using synthesis gas as well as preparation method and application thereof |
| CN103263921A (en) * | 2013-06-04 | 2013-08-28 | 中国科学院山西煤炭化学研究所 | Metal/graphene catalyst and preparation method thereof |
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| CN103084181A (en) * | 2013-01-17 | 2013-05-08 | 上海中科高等研究院 | Copper-based composite oxide catalyst as well as preparation method and application thereof |
| CN103263921A (en) * | 2013-06-04 | 2013-08-28 | 中国科学院山西煤炭化学研究所 | Metal/graphene catalyst and preparation method thereof |
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| CN112619653B (en) * | 2020-04-01 | 2022-02-11 | 中国科学院山西煤炭化学研究所 | High-carbon alcohol catalyst for preparing detergent from synthetic gas and preparation method and application thereof |
| CN112619653A (en) * | 2020-04-01 | 2021-04-09 | 中国科学院山西煤炭化学研究所 | High-carbon alcohol catalyst for preparing detergent from synthetic gas and preparation method and application thereof |
| CN111569894A (en) * | 2020-06-05 | 2020-08-25 | 华东理工大学 | Supported Cu-Fe-based catalyst and preparation method and application thereof |
| CN111905747A (en) * | 2020-08-10 | 2020-11-10 | 中科合成油内蒙古有限公司 | Iron-based Fischer-Tropsch synthesis catalyst with non-carbide active phase as well as preparation method and application thereof |
| CN111905747B (en) * | 2020-08-10 | 2023-07-28 | 中科合成油内蒙古有限公司 | Iron-based Fischer-Tropsch synthesis catalyst with non-carbide active phase, and preparation method and application thereof |
| CN113981481A (en) * | 2021-09-27 | 2022-01-28 | 西安电子科技大学 | Preparation method and application of copper nanoparticle-loaded one-dimensional carbon-based nano material |
| CN113981481B (en) * | 2021-09-27 | 2022-10-14 | 西安电子科技大学 | Preparation method and application of copper nanoparticle-loaded one-dimensional carbon-based nano material |
| CN114345353A (en) * | 2021-12-16 | 2022-04-15 | 扬州大学 | For CO2Low-temperature copper-based core-shell catalyst for preparing methanol by hydrogenation and preparation method thereof |
| CN114345353B (en) * | 2021-12-16 | 2023-04-28 | 扬州大学 | For CO 2 Low-temperature copper-based core-shell catalyst for preparing methanol by hydrogenation and preparation method thereof |
| CN115635093A (en) * | 2022-09-16 | 2023-01-24 | 大连理工大学 | Preparation method, structure and application of superfine monometal or alloy nanoparticles synthesized by solid-state reduction of metal salt |
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