CN102500374B - 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
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- CN102500374B CN102500374B CN201110394867.6A CN201110394867A CN102500374B CN 102500374 B CN102500374 B CN 102500374B CN 201110394867 A CN201110394867 A CN 201110394867A CN 102500374 B CN102500374 B CN 102500374B
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- Prior art keywords
- copper
- catalyst
- tropsch
- fischer
- constituent element
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- 239000010949 copper Substances 0.000 title claims abstract description 129
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 80
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910052799 carbon Inorganic materials 0.000 title abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 74
- 150000001298 alcohols Chemical class 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 49
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 49
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 48
- 230000009467 reduction Effects 0.000 claims abstract description 47
- 230000008569 process Effects 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 136
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 87
- 239000000470 constituent Substances 0.000 claims description 63
- 229910052751 metal Inorganic materials 0.000 claims description 63
- 239000002184 metal Substances 0.000 claims description 63
- 238000006722 reduction reaction Methods 0.000 claims description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 58
- 239000000243 solution Substances 0.000 claims description 53
- 239000002904 solvent Substances 0.000 claims description 48
- 238000005406 washing Methods 0.000 claims description 46
- 239000007787 solid Substances 0.000 claims description 44
- 239000007789 gas Substances 0.000 claims description 42
- 239000003638 chemical reducing agent Substances 0.000 claims description 41
- 238000005119 centrifugation Methods 0.000 claims description 36
- 239000002105 nanoparticle Substances 0.000 claims description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 34
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims description 27
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 23
- 238000004140 cleaning Methods 0.000 claims description 21
- 239000006185 dispersion Substances 0.000 claims description 20
- 150000003839 salts Chemical class 0.000 claims description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 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
- 239000012266 salt solution Substances 0.000 claims description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 14
- 239000012046 mixed solvent Substances 0.000 claims description 14
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 12
- 150000001879 copper Chemical class 0.000 claims description 12
- 239000003381 stabilizer Substances 0.000 claims description 12
- 238000009938 salting Methods 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- 238000006073 displacement reaction Methods 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
- 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
- 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
- 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
- 229910052742 iron Inorganic materials 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
- 229910052759 nickel Inorganic materials 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
- 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
- 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
- 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
- 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
- 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
- 229920002565 Polyethylene Glycol 400 Polymers 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
- 229960003511 macrogol Drugs 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-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
- 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
- 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
- -1 diborane Substances 0.000 claims 1
- 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
- 238000006243 chemical reaction Methods 0.000 abstract description 45
- 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
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- PXRKCOCTEMYUEG-UHFFFAOYSA-N 5-aminoisoindole-1,3-dione Chemical compound NC1=CC=C2C(=O)NC(=O)C2=C1 PXRKCOCTEMYUEG-UHFFFAOYSA-N 0.000 description 3
- 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
- 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
- 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
- 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
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-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
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 1
- 239000004280 Sodium formate Substances 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
- 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
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 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
- 238000001035 drying Methods 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 class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 229940113115 polyethylene glycol 200 Drugs 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
- 238000012360 testing method Methods 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
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 ofly for prepared Catalysts and its preparation method and the application of higher alcohols by synthesis gas, particularly relate to a kind of copper-based nano-catalyst and method for making and application of preparing higher alcohols for the synthesis of gas.
Background technology
Higher alcohols refer generally to containing 6 monohydric alcohols more than carbon atom, and it is the raw material of synthetic surfactant, washing agent, plasticizer and other fine chemical product, has the advantages such as unit output value is high, added value is large.Preparing higher alcohols has two kinds of routes substantially, and first natural oil route be take animal and plant grease as raw material, standby by Hydrogenation, but the restriction that lacked by oil sources, large-scale production difficulty.Another is chemical synthesis route, has scale, is divided into by and large two kinds of ziegler process and oxo synthesis.Ziegler process be take ethene as raw material, and triethyl aluminum is 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 alpha-olefin, adopts cobalt-based or rhodium base catalyst, and preparation is than the higher alcohols of the many carbon atoms of alpha-olefin.Required alpha-olefin can make by ethylene oligomerization, oxidation of alkanes, wax cracking/methods such as oxidation, but oxo synthesis side reaction is many, and in product, branched-chain alcoho content is high, and biological degradability is poor.
Ziegler process or oxo synthesis are all large to oil product interdependency.Current petroleum resources are day by day in short supply, develop other fossil energy and are conducive to alleviate the dependence to petroleum resources as the efficient utilization of coal, natural gas etc.China Shi Yige big coal country, 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 efficiently utilizing coal resources.Because synthesis gas source is wide, from synthesis gas, directly prepare higher alcohols route short, products obtained therefrom higher alcohols added value is high, therefore this route is the method that has the synthesizing bigh carbon alcohol of economic worth, is also one of alternative of preparing of current higher alcohols.
Have at present the catalyst report of directly preparing mixed alcohol from synthesis gas, these catalyst can be classified as following four large classes generally:
(1) modified methanol synthetic catalyst (A-Cu-Zn/Al, A-Zn-Cr) adds alkali metal or Modified With Alkali-earth Compounds to obtain in methanol synthesis catalyst; Represent that patent has: EP 0034338A2 and US Patent 4513100.This class catalyst is developed by Italian Snam company and German Lugi company the earliest, and main alcohol product is methyl alcohol and isobutanol;
(2) modification fischer-tropsch synthetic catalyst (Cu-Co), represents that patent has: US Patent 4122110 and 4291126, GB Patent2118061 and 2158730; This class catalyst is proposed by France Petroleum Institute (IFP) the earliest, mainly for Cu-Co series; Main alcohol product is methyl alcohol and C
2～C
6straight chain n-alkanol;
(3) noble metal catalyst, the Rh of take is catalyst based as typical case, represents that patent has: US Patent 4014913 and 4096164; This type of catalyst ethanol is selectively high, but high because of its price, and total alcohol is selectively not high enough, therefore in recent years report less;
(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 by U.S. Dow company, proposed the earliest; Catalyst with base of molybdenum obtains researcher's attention because of its good anti-sulphur; But this catalyst promoter is easy to run off, and active and selectively unstable, the life-span falls short of, and CO in product
2content is high.
In the mixed alcohol of above catalyst gained, higher alcohols content is very micro-, does not even have.
At present, relatively less for the catalyst research of directly being prepared higher alcohols by synthesis gas both at home and abroad.US Patent No. 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 reported for the synthetic CuCoMn of mixed alcohol and CuCoMg catalyst, and this catalyst adopts coprecipitation preparation, in gained alcohol, contains C
5-C
11higher alcohols, but content is all below 40wt%.Chinese patent CN 101310856B has reported that a kind of Co of take is as active component, higher alcohols synthetic catalyst that the active carbon of take is carrier and preparation method thereof, and this catalyst directly synthesizes C for CO hydrogenation one-step method
2-C
18straight chain higher alcohol.So far, utilize copper-based nano-catalyst to there is no bibliographical information by the direct highly selective synthesizing bigh carbon alcohol of synthesis gas.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of copper-based nano-catalyst and method for making and application of preparing higher alcohols for the synthesis of gas.
For solving the problems of the technologies described above, the copper-based nano-catalyst of preparing higher alcohols for the synthesis of gas of the present invention, it is a kind of copper Quito metal (Cu-M) nanocatalyst, by copper and at least one Fischer-Tropsch constituent element, formed, wherein, described Fischer-Tropsch constituent element is selected from least one in ruthenium (Ru), iron (Fe), cobalt (Co) and nickel (Ni).
In described 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 described copper-based nano-catalyst is 0.5～300nm, is preferably 2～100nm.
In addition, the invention also discloses a kind of preparation method who prepares the copper-based nano-catalyst of higher alcohols for the synthesis of gas, be selected from any one method in replacement method, step-by-step reduction method, while reducing process.
Described replacement method, first prepares by reduction the metal nanoparticle that metal active is high, then adds the metal salt solution that other metal active is lower, and both displacement reaction occur and obtain many metal nanos catalyst; Specifically can operate by following IA or IB:
IA, for the preparation of CuRu bimetal nano catalyst, step comprises:
Mantoquita is dissolved in solvent and forms solution, with reducing agent reduction, obtain copper nano particles; In gained copper nano particles dispersion liquid, add Fischer-Tropsch constituent element Ru salting liquid, carry out displacement reaction with Cu nano particle, reacted rear centrifugation, solid matter is with water, low mass molecule alcohol or acetone washing, remove after cleaning solvent, dry, obtain CuRu bimetal nano catalyst.
IB, for the preparation of the catalyst except CuRu bimetal nano catalyst, step comprises:
At least one Fischer-Tropsch constituent element salt containing in Fe, Co and Ni is dissolved in solvent and forms solution, with reducing agent reduction, obtain Fischer-Tropsch constituent element nano particle; In gained Fischer-Tropsch constituent element nanoparticulate dispersion, add copper salt solution, carry out displacement reaction with Fischer-Tropsch constituent element nano particle, rear centrifugation or magnetic have been reacted separated, solid matter is with water, low mass molecule alcohol or acetone washing, remove after cleaning solvent, dry, obtain copper Quito metal nano catalyst.
Described step-by-step reduction method, is that each metal component in catalyst is reduced successively, specifically can operate by following IIA, IIB, IIC or IID:
IIA, first reduce Cu, restore Fischer-Tropsch constituent element, step comprises:
Mantoquita is dissolved in solvent and forms solution, with reducing agent reduction, obtain copper nano particles; In gained copper nano particles dispersion liquid, add reducing agent, then splash into Fischer-Tropsch constituent element salting liquid and carry out reduction reaction; It is separated to have reduced rear centrifugation or magnetic, and solid matter, with water, low mass molecule alcohol or acetone washing, is removed after cleaning solvent, dry, obtains copper Quito metal nano catalyst.
IIB, first reduce Cu, restore Fischer-Tropsch constituent element, step comprises:
Mantoquita is dissolved in solvent and forms solution, with reducing agent reduction, obtain copper nano particles; In gained copper nano particles dispersion liquid, add Fischer-Tropsch constituent element salting liquid, then splash into reducing agent and carry out reduction reaction; It is separated to have reduced rear centrifugation or magnetic, and solid matter, with water, low mass molecule alcohol or acetone washing, is removed after cleaning solvent, dry, obtains copper Quito metal nano catalyst.
IIC, first reduce Fischer-Tropsch constituent element, restore Cu, step comprises:
Fischer-Tropsch constituent element salt is dissolved in solvent and forms solution, with reducing agent reduction, obtain Fischer-Tropsch constituent element nano particle; In gained Fischer-Tropsch constituent element nanoparticulate dispersion, add reducing agent, then splash into copper salt solution and carry out reduction reaction; It is separated to have reduced rear centrifugation or magnetic, and solid matter, with water, low mass molecule alcohol or acetone washing, is removed after cleaning solvent, dry, obtains copper Quito metal nano catalyst.
IID, first reduce Fischer-Tropsch constituent element, restore Cu, step comprises:
Fischer-Tropsch constituent element salt is dissolved in solvent and forms solution, with reducing agent reduction, obtain Fischer-Tropsch constituent element nano particle; In gained Fischer-Tropsch constituent element nanoparticulate dispersion, add copper salt solution, then splash into reducing agent and carry out reduction reaction; It is separated to have reduced rear centrifugation or magnetic, and solid matter, with water, low mass molecule alcohol or acetone washing, is removed after cleaning solvent, dry, obtains copper Quito metal nano catalyst.
Described while reducing process, is that copper and Fischer-Tropsch constituent element are reduced simultaneously, and the step of the method comprises: mantoquita and Fischer-Tropsch constituent element salt are dissolved in solvent and form solution, with reducing agent, reduce; It is separated to have reduced rear centrifugation or magnetic, and solid matter, with water, low mass molecule alcohol or acetone washing, is removed after cleaning solvent, dry, obtains copper Quito metal nano catalyst.
In the preparation method of described copper-based nano-catalyst, mantoquita used is selected from least one in mantoquita in following eight: 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].Described mantoquita concentration is pressed Cu
+and Cu
2+total concentration is counted 0.001～10mol/L, is preferably 0.05～0.5mol/L.
In the preparation method of described copper-based nano-catalyst, the solvent of mantoquita used and Fischer-Tropsch constituent element salt is selected from water, organic solvent or its mixed solvent.Wherein, described organic solvent is preferably methyl alcohol, ethanol, ethylene glycol, glycerine, 1,3-PD, BDO, polyethylene glycol-200 and PEG-4000.When solvent is selected ethylene glycol, glycerine, 1,3-PD, BDO, Macrogol 200 and PEG400, in solution, do not add stabilizing agent; When solvent is selected water, methyl alcohol and ethanol, in solution, add stabilizing agent simultaneously.Stabilizing agent used is selected from polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), citric acid (CA), natrium citricum (Na
3-CA), soluble starch and cationic surfactant (comprising: at least one softex kw etc.), in non-ionic surface active agent (comprising: tween, this class, F127, P123 etc.) or betaines surfactant.Stabilizing agent used (repeated fragment) is 400: 1～0: 1 with the mol ratio of catalyst metals.
In the preparation method of described copper-based nano-catalyst, reducing agent used 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, BDO etc.), at least one 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 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;
While 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 completes under 50 ℃～250 ℃ heating conditions;
Adopt H
2during for reducing agent, under 100～200 ℃, 0.1～4.0MPa condition, reduce.
In the preparation method of described copper-based nano-catalyst, Fischer-Tropsch constituent element salt used is selected from individual metal salt or many metal mixed salt of ruthenium salt, molysite, cobalt salt and nickel salt.Described Fischer-Tropsch constituent element salinity, counts 0.001～10mol/L by metal cation total concentration, is preferably 0.05～0.5mol/L.
Concrete, ruthenium salt is selected from least one 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 least one in following six kinds of molysite: 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 one 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 one 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].
In the preparation method of described copper-based nano-catalyst, low mass molecule alcohol used 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 to synthesis gas and prepares in higher alcohols, and wherein, catalytic reaction condition is: the temperature of catalytic reaction is 150～320 ℃, is preferably 200～280 ℃; H
2with CO stagnation pressure be 0.1～13MPa, be preferably 4～7MPa; In 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 prepared by the present invention is on a kind of single nano particle, to contain the catalyst of copper component and at least one Fischer-Tropsch component simultaneously, and in the synthetic reaction that can be used for preparing higher alcohols by synthesis gas, and the present invention has following beneficial effect:
1) catalyst particle size is little, and specific surface is large, and utilization rate is high;
2) preparation process is simple, easy to operate, and between catalyst components, finely regulating is easy, is conducive to the adjusting that product is distributed;
3) utilize copper of the present invention Quito metal nano catalyst to carry out synthesis gas and prepare the synthetic of higher alcohols, by controlling component and the ratio thereof of catalyst, in gained alcohol the above alcohol of ethanol selectively can reach 95wt% more than, the above higher alcohols (C of hexanol
6 +oH) selectively can reach 80wt% more than.
Accompanying drawing explanation
Below in conjunction with accompanying drawing and the specific embodiment, the present invention is further detailed explanation:
Accompanying drawing is transmission electron microscope (Transmission electron microscopy, the TEM) photo of typical catalyst, wherein, shows that this catalyst is comprised of the nano particle of 15nm left and right in figure.
The specific embodiment
Copper Quito metal nano catalyst prepared by following examples, particle diameter is 0.5～300nm, can be used for preparing the synthetic reaction of higher alcohols from synthesis gas, wherein, the catalyst that preferable particle size is 2～100nm.This catalyst is comprised of copper and at least one Fischer-Tropsch constituent element, and Fischer-Tropsch constituent element is selected from least one in Ru, Fe, Co and Ni.This copper Quito metal nano catalyst, can prepare by any one method in described replacement method, step-by-step reduction method and while reducing process.
Below in conjunction with specific embodiment, the present invention is described.Following examples contribute to understand the present invention, but do not limit application of the present invention.
Embodiment 1
By Cu (NO
3)
23H
2o and Fe (NO
3)
39H
2o is dissolved in ethylene glycol (EG) in Cu/Fe=3/2 ratio (mol ratio), and making total concentration of metal ions is 0.15mol/L, obtains hybrid metal solution, and ice-water bath is cooling.By excessive NaBH
4be dissolved in H
2o and EG mixed solvent (H
2o and EG volume ratio are 1/5) in, splash into fast hybrid metal solution, drip to finish and stir 10min so that reduction is complete.Room temperature to be chilled to, adds acetone diluted, centrifugation.Gained black solid with acetone washing once, with deoxidized water washing once, then with acetone washed twice, is placed in 80 ℃ of baking ovens and is dried to bulk, then proceeds to N in tube furnace
2protect lower 300 ℃ of dry 1h, obtain catalyst.At fixed-bed catalytic reactor, carrying out synthesis gas, to prepare the reaction condition of higher alcohols as follows: 220 ℃, and H
2with CO stagnation pressure be 6.0MPa, GHSV=6000h
-1, H
2/ CO (mol ratio)=2.Reaction result is listed in table 1.
Embodiment 2
By Cu (NO
3)
23H
2o and Fe (NO
3)
39H
2o is dissolved in ethylene glycol (EG) in Cu/Fe=3/1 ratio, and making total concentration of metal ions is 0.13mol/L, obtains hybrid metal solution, and ice-water bath is cooling.By excessive NaBH
4be dissolved in H
2o and EG mixed solvent (H
2o and EG volume ratio are 1/5) in, splash into fast hybrid metal solution, drip to finish and stir 10min so that reduction is complete.Room temperature to be chilled to, adds deoxidized water dilution, centrifugation.Gained black solid washs once with deoxidized water, then with ethanol washing once, under room temperature, is dried to bulk, then proceeds to N in tube furnace
2protect lower 150 ℃ of dry 1h, obtain catalyst.At fixed-bed catalytic reactor, carrying out synthesis gas, to prepare the reaction condition of higher alcohols as follows: 210 ℃, and H
2with CO stagnation pressure be 6.0MPa, GHSV=6000h
-1, H
2/ CO=2.Reaction result is listed in table 1.
Embodiment 3
By Cu (NO
3)
23H
2o and Fe (NO
3)
39H
2o is dissolved in ethylene glycol (EG) in Cu/Fe=3/1 ratio, and making total concentration of metal ions is 0.13mol/L, obtains hybrid metal solution, and ice-water bath is cooling.By excessive NaBH
4be dissolved in H
2o and EG mixed solvent (H
2o and EG volume ratio are 1/5) in, splash into fast hybrid metal solution, drip to finish and stir 10min so that reduction is complete.Room temperature to be chilled to, adds deoxidized water dilution, centrifugation.Gained black solid washs 2 times with deoxidized water, then with ethanol washing 3 times, under room temperature, is dried to bulk, then proceeds to N in tube furnace
2protect lower 150 ℃ of dry 2h, obtain catalyst.At fixed-bed catalytic reactor, carrying out synthesis gas, to prepare the reaction condition of higher alcohols as follows: 240 ℃, and H
2with CO stagnation pressure be 6.0MPa, GHSV=6000h
-1, H
2/ CO=2.Reaction result is listed in table 1.
Embodiment 4
By Cu (NO
3)
23H
2o and Fe (NO
3)
39H
2o is dissolved in ethylene glycol (EG) in Cu/Fe=1/3 ratio, and making total concentration of metal ions is 0.13mol/L, obtains hybrid metal solution, and ice-water bath is cooling.By excessive NaBH
4be dissolved in H
2o and EG mixed solvent (H
2o and EG volume ratio are 1/5) in, splash into fast hybrid metal solution, drip to finish and stir 10min so that reduction is complete.Room temperature to be chilled to, adds deoxidized water dilution, centrifugation.Gained black solid washs 2 times with deoxidized water, then with ethanol washing 2 times, under room temperature, is dried to bulk, then proceeds to N in tube furnace
2protect lower 150 ℃ of dry 2h, obtain catalyst.
Ultrasonic being scattered in ethanol of the catalyst that takes a morsel tested for transmission electron microscope (TEM), and test result shows that gained nanocatalyst grain diameter is 15 ± 3nm, and Figure of description is shown in by TEM photo.
At fixed-bed catalytic reactor, carrying out synthesis gas, to prepare the reaction condition of higher alcohols as follows: 260 ℃, and H
2with CO stagnation pressure be 6.0MPa, GHSV=6000h
-1, H
2/ CO=2.Reaction result is listed in table 1.
Embodiment 5
By Cu (NO
3)
23H
2o and Fe (NO
3)
39H
2o is dissolved in ethylene glycol (EG) in Cu/Fe=10/1 ratio, and making total concentration of metal ions is 0.05mol/L, obtains hybrid metal solution, and ice-water bath is cooling.By excessive NaBH
4be dissolved in H
2o and EG mixed solvent (H
2o and EG volume ratio are 1/5) in, splash into fast hybrid metal solution, drip to finish and stir 10min so that reduction is complete.Room temperature to be chilled to, adds deoxidized water dilution, centrifugation.Gained black solid washs 2 times with deoxidized water, then with ethanol washing 2 times, under room temperature, is dried to bulk, then proceeds to N in tube furnace
2protect lower 150 ℃ of dry 2h, obtain catalyst.At fixed-bed catalytic reactor, carrying out synthesis gas, to prepare the reaction condition of higher alcohols as follows: 240 ℃, and H
2with CO stagnation pressure be 6.0MPa, GHSV=10000h
-1, H
2/ CO=2.Reaction result is listed in table 1.
Embodiment 6
By Cu (NO
3)
23H
2o and Fe (NO
3)
39H
2o is dissolved in ethylene glycol (EG) in Cu/Fe=1/10 ratio, and making total concentration of metal ions is 0.5mol/L, obtains hybrid metal solution, and ice-water bath is cooling.By excessive NaBH
4be dissolved in H
2o and EG mixed solvent (H
2o and EG volume ratio are 1/5) in, splash into fast hybrid metal solution, drip to finish and stir 10min so that reduction is complete.Room temperature to be chilled to, adds deoxidized water dilution, centrifugation.Gained black solid washs 2 times with deoxidized water, then with ethanol washing 2 times, N
2the lower drying at room temperature of protection becomes block, then proceeds to N in tube furnace
2protect lower 150 ℃ of dry 2h, obtain catalyst.At fixed-bed catalytic reactor, carrying out synthesis gas, to prepare the reaction condition of higher alcohols as follows: 220 ℃, and H
2with CO stagnation pressure be 6.0MPa, GHSV=1000h
-1, H
2/ CO=2.Reaction result is listed in table 1.
Embodiment 7
By Cu (NO
3)
23H
2o and Co (NO
3)
26H
2o is dissolved in ethylene glycol (EG) in Cu/Co=10/1 ratio, and making total concentration of metal ions is 0.2mol/L, obtains hybrid metal solution, and ice-water bath is cooling.By excessive NaBH
4be dissolved in H
2in O, splash into fast hybrid metal solution, drip to finish and stir 10min so that reduction is complete.Room temperature to be chilled to, adds deoxidized water dilution, centrifugation.Gained black solid washs 2 times with deoxidized water, then with ethanol washing 2 times, under room temperature, is dried to bulk, then proceeds to N in tube furnace
2protect lower 150 ℃ of dry 2h, obtain catalyst.At fixed-bed catalytic reactor, carrying out synthesis gas, to prepare the reaction condition of higher alcohols as follows: 240 ℃, and H
2with CO stagnation pressure be 6.0MPa, GHSV=6000h
-1, H
2/ CO=2.Reaction result is listed in table 1.
Embodiment 8
By Co (NO
3)
26H
2o is that 0.13mol/L is dissolved in deionized water by concentration of cobalt ions, and adding PVP is stabilizing agent, makes mol ratio=20 of PVP/Co, obtains cobalt salt solution, and ice-water bath is cooling.By excessive NaBH
4be dissolved in H
2in O, splash into fast cobalt liquor, drip to finish and stir 10min so that reduction is complete.Room temperature to be chilled to, strong magnetic is separated.Solid is scattered in deionized water, and making metal concentration is 0.2mol/L, obtains cobalt nano-particle (Co NPs) dispersion liquid.Cu (the NO that is 0.1mol/L by concentration by the amount of Cu/Co=1/2
3)
23H
2the O aqueous solution slowly splashes in gained Co NPs dispersion liquid, and a complete 30min that stirs is so that displacement reaction is complete, and strong magnetic is separated, and gained black solid washs 1 time with deoxidized water, then washs 2 times with ethanol, under room temperature, is dried to bulk, then proceeds to N in tube furnace
2protect lower 150 ℃ of dry 2h, obtain catalyst.At fixed-bed catalytic reactor, carrying out synthesis gas, to prepare the reaction condition of higher alcohols as follows: 220 ℃, and H
2with CO stagnation pressure be 6.0MPa, GHSV=6000h
-1, H
2/ CO=2.Reaction result is listed in table 1.
Embodiment 9
By Cu (NO
3)
23H
2o is that 0.13mol/L is dissolved in PEG-200 by copper ion concentration, obtains copper salt solution, and ice-water bath is cooling.By 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
4with acetone, remove, then by the amount of Cu/Co=2/1, adding wherein concentration is the Co (NO of 0.13mol/L
3)
26H
2o PEG-200 solution, stirs, by excessive NH
3bH
4the aqueous solution splashes into wherein fast, drips to finish to stir 10min so that reduction is complete.Add deoxidized water dilution, strong magnetic is separated, and gained black solid washs 3 times with deoxidized water, then with ethanol washing 2 times, under room temperature, is dried to bulk, then proceeds to N in tube furnace
2protect lower 150 ℃ of dry 2h, obtain catalyst.At fixed-bed catalytic reactor, carrying out synthesis gas, to prepare the reaction condition of higher alcohols as follows: 240 ℃, and H
2with CO stagnation pressure be 6.0MPa, GHSV=6000h
-1, H
2/ CO=2.Reaction result is listed in table 1.
Embodiment 10
By Cu (NO
3)
23H
2o is that 0.13mol/L is dissolved in PEG-200 by copper ion concentration, obtains copper salt solution, and ice-water bath is cooling.By 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, splash into wherein 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 deoxidized water dilution, strong magnetic is separated, and gained black solid washs 3 times with deoxidized water, then with ethanol washing 2 times, under room temperature, is dried to bulk, then proceeds to N in tube furnace
2protect lower 150 ℃ of dry 2h, obtain catalyst.At fixed-bed catalytic reactor, carrying out synthesis gas, to prepare the reaction condition of higher alcohols as follows: 240 ℃, and H
2with CO stagnation pressure be 6.0MPa, GHSV=6000h
-1, H
2/ CO=2.Reaction result is listed in table 1.
Embodiment 11
By NiCl
26H
2o is that 0.15mol/L is dissolved in H by nickel ion concentration
2in O-EG (1: 1) mixed solvent, obtain nickel salt solution, add a small amount of tetraethyl ammonium hydroxide to be adjusted to alkalescence.By 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, adding wherein concentration is the CuCl of 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 is separated, and gained solid washs 2 times with deoxidized water, then with ethanol washing 2 times, under room temperature, is dried to bulk, then proceeds to N in tube furnace
2protect lower 150 ℃ of dry 2h, obtain catalyst.At fixed-bed catalytic reactor, carrying out synthesis gas, to prepare the reaction condition of higher alcohols as follows: 260 ℃, and H
2with CO stagnation pressure be 6.0MPa, GHSV=6000h
-1, H
2/ CO=2.Reaction result is listed in table 1.
Embodiment 12
By NiCl
26H
2o is that 0.15mol/L is dissolved in H by nickel ion concentration
2in O-EG (1: 1) mixed solvent, obtain nickel salt solution, add a small amount of tetraethyl ammonium hydroxide to be adjusted to alkalescence.By 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 is separated, and solid is scattered in H
2in O-EG (1: 1) mixed solvent, making metal concentration is 0.15mol/L.By the amount of Cu/Ni=1/3, adding wherein concentration is the CuCl of 0.15mol/L
22H
2o H
2o-EG (1: 1) mixed solvent solution, adds a small amount of tetraethyl ammonium hydroxide to be adjusted to alkalescence.Splash into excess hydrazine hydrate (NH
2nH
2h
2o), stir, stirring reaction 1h under room temperature.Shift out oil bath, be chilled to room temperature, strong magnetic is separated, and gained solid washs 2 times with deoxidized water, then with ethanol washing 2 times, under room temperature, is dried to bulk, then proceeds to N in tube furnace
2protect lower 150 ℃ of dry 2h, obtain catalyst.At fixed-bed catalytic reactor, carrying out synthesis gas, to prepare the reaction condition of higher alcohols as follows: 260 ℃, and H
2with CO stagnation pressure be 6.0MPa, GHSV=6000h
-1, H
2/ CO=2.Reaction result is listed in table 1.
Embodiment 13
By RuCl
3nH
2o is that 0.05mol/L is dissolved in ethylene glycol (EG) by ruthenium ion concentration, and EG is reducing agent simultaneously, obtains 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, adding wherein concentration is the CuCl of 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, gained solid, with acetone-alcohol mixeding liquid washing 3 times, is dried to bulk under room temperature, then proceeds to N in tube furnace
2protect lower 150 ℃ of dry 2h, obtain catalyst.At fixed-bed catalytic reactor, carrying out synthesis gas, to prepare the reaction condition of higher alcohols as follows: 200 ℃, and H
2with CO stagnation pressure be 6.0MPa, GHSV=6000h
-1, H
2/ CO=2.Reaction result is listed in table 1.
Embodiment 14
By RuCl
3nH
2o, CuCl
22H
2o, NiCl
26H
2o is that 0.09mol/L, Cu/Ru/Ni=4/1/4 are dissolved in ethylene glycol (EG) by total concentration of metal ions, and EG is reducing agent simultaneously, obtains 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, gained solid, with acetone-alcohol mixeding liquid washing 3 times, is dried to bulk under room temperature, then proceeds to N in tube furnace
2protect lower 150 ℃ of dry 2h, obtain catalyst.At fixed-bed catalytic reactor, carrying out synthesis gas, to prepare the reaction condition of higher alcohols as follows: 240 ℃, and H
2with CO stagnation pressure be 6.0MPa, GHSV=6000h
-1, H
2/ CO=2.Reaction result is listed in table 1.
Embodiment 15
By 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 in EG by total concentration of metal ions, obtains hybrid metal solution, and ice-water bath is cooling.By excessive NaBH
4be dissolved in H
2in O, splash into fast hybrid metal solution, drip to finish and stir 10min so that reduction is complete.Room temperature to be chilled to, adds deoxidized water dilution, and strong magnetic is separated.Gained black solid washs 2 times with deoxidized water, then with ethanol washing 2 times, under room temperature, is dried to bulk, then proceeds to N in tube furnace
2protect lower 150 ℃ of dry 2h, obtain catalyst.At fixed-bed catalytic reactor, carrying out synthesis gas, to prepare the reaction condition of higher alcohols as follows: 240 ℃, and H
2with CO stagnation pressure be 6.0MPa, GHSV=6000h
-1, H
2/ CO=2.Reaction result is listed in table 1.
Embodiment 16
By 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 in EG by total concentration of metal ions, obtains hybrid metal solution, and ice-water bath is cooling.By excessive NaBH
4be dissolved in H
2in O, splash into fast hybrid metal solution, drip to finish and stir 10min so that reduction is complete.Room temperature to be chilled to, adds deoxidized water dilution, centrifugation.Gained black solid washs 2 times with deoxidized water, then with ethanol washing 2 times, under room temperature, is dried to bulk, then proceeds to N in tube furnace
2protect lower 150 ℃ of dry 2h, obtain catalyst.At fixed-bed catalytic reactor, carrying out synthesis gas, to prepare the reaction condition of higher alcohols as follows: 240 ℃, and H
2with 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
By potassium ruthenate (K
2ruO
4h
2o) with Cu (OAc)
2h
2o is that 0.002mol/L, Cu/Ru=1/1 are dissolved in deionized water by total concentration of metal ions, and adding citric acid (CA) is stabilizing agent, makes total metal ion=400/1 of CA/, obtains mixed solution.Mixed solution is proceeded in autoclave, with hydrogen reducing, at 0.1MPa H
2at pressure, 100 ℃, react 4h.Centrifugation after cooling, pressure release, gained black solid is with deoxidized water washing 2 times, then with methanol wash 2 times, under room temperature, is dried to bulk, then proceeds to N in tube furnace
2protect lower 150 ℃ of dry 2h, obtain catalyst.
This catalyst, carries out synthesis gas at fixed-bed catalytic reactor and prepares the reaction condition of higher alcohols and can be: 150 ℃, H
2with CO stagnation pressure be 0.1MPa, GHSV=100h
-1, H
2/ CO=0.1.
Embodiment 18
By acetylacetone,2,4-pentanedione ruthenium [Ru (acac)
3] and acetylacetone copper, by total concentration of metal ions, be 20mol/L, Cu/Ru=1/1, be dissolved in ethanol-water mixed solvent (ethanol and water volume ratio are 1/1), adding mol ratio is that soluble starch and the softex kw (CTAB) of 1: 1 is stabilizing agent, make stabilizing agent/total metal ion=200/1, obtain mixed solution.Mixed solution is proceeded in autoclave, with hydrogen reducing, at 4MPa H
2at pressure, 200 ℃, react 12h.Centrifugation after cooling, pressure release, gained black solid is with deoxidized water washing 2 times, then with washed with isopropyl alcohol 2 times, under room temperature, is dried to bulk, then proceeds to N in tube furnace
2protect lower 150 ℃ of dry 2h, obtain catalyst.
This catalyst, carries out synthesis gas at fixed-bed catalytic reactor and prepares the reaction condition of higher alcohols and can be: 320 ℃, H
2with CO stagnation pressure be 13MPa, GHSV=100000h
-1, H
2/ CO=10.
Embodiment 19
By 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), by total concentration of metal ions, be that 5mol/L, Cu/Co/Ru=1/50/50 are dissolved in glycerine, obtain mixed solution.Mixed solution is proceeded in autoclave, with hydrogen reducing, at 2MPa H
2at pressure, 150 ℃, react 4h.Centrifugation after cooling, pressure release, gained black solid is with deoxidized water washing 1 time, and with ethanol washing 1 time, then with butanols washing 2 times, under room temperature, vacuum drying becomes block, then proceeds to N in tube furnace
2protect lower 150 ℃ of dry 2h, obtain catalyst.
This catalyst, carries out synthesis gas at fixed-bed catalytic reactor and prepares the reaction condition of higher alcohols and can be: 280 ℃, H
2with CO stagnation pressure be 1MPa, GHSV=500h
-1, H
2/ CO=1.
Embodiment 20
By 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) by total metal concentration, be 0.505mol/L, Cu/Ni/Ru/Fe/Co=100/0.25/0.25/0.25/0.25, be dissolved in 1, in 4-butanediol, obtain hybrid metal solution, it to adding excessive mol ratio in this mixed solution, it is 1: 1: 1: the mixed liquor of 1 DMF, diethylamine, tartaric acid and glucose, under 50 ℃ of heating conditions, reaction reduction 18h.
Cooling rear centrifugation, gained black solid is with deoxidized water washing 1 time, and with methanol wash 1 time, then with isobutanol washing 2 times, under room temperature, vacuum drying becomes block, then proceeds to N in tube furnace
2protect lower 150 ℃ of dry 2h, obtain catalyst.
This catalyst, carries out synthesis gas at fixed-bed catalytic reactor and prepares the reaction condition of higher alcohols and can be: 300 ℃, H
2with CO stagnation pressure be 4MPa, GHSV=50000h
-1, H
2/ CO=3.
Embodiment 21
By copper chloride dihydrate (CuCl
22H
2o) with cobaltous sulfate (CoSO
47H
2o) by total metal concentration, be that 0.1mol/L, Cu/Co=5/1 are dissolved in ethylene glycol (EG), add 1mol/L NaOH EG solution, make total metal ion=10/1 of NaOH/, obtain mixed solution.In this mixed solution, add excessive sodium formate (HCOONa), 250 ℃ of reaction reduction 8h.
Cooling rear centrifugation, gained black solid washs 2 times with deoxidized water, then with ethanol washing 2 times, under room temperature, is dried to bulk, then proceeds to N in tube furnace
2protect lower 150 ℃ of dry 2h, obtain catalyst.
This catalyst, carries out synthesis gas at fixed-bed catalytic reactor and prepares the reaction condition of higher alcohols and can be: 180 ℃, H
2with CO stagnation pressure be 7MPa, GHSV=20000h
-1, H
2/ CO=1.5.
Embodiment 22
Change the reduction temperature in embodiment 21 into 180 ℃, other conditions are the same with embodiment 21, and the catalyst finally obtaining carries out synthesis gas at fixed-bed catalytic reactor and prepares the reaction condition of higher alcohols and can be: 160 ℃, and H
2with CO stagnation pressure be 10MPa, GHSV=200h
-1, H
2/ CO=5.
Claims (14)
1. a copper-based nano-catalyst of preparing higher alcohols for the synthesis of gas, it is characterized in that: described catalyst is a kind of copper Quito metal nano catalyst, copper and at least one Fischer-Tropsch constituent element, consist of, wherein, described Fischer-Tropsch constituent element is selected from least one in ruthenium, iron, cobalt and nickel;
The particle diameter of described copper-based nano-catalyst is 0.5～300nm; The mol ratio of described copper and Fischer-Tropsch constituent element is 0.01～100;
Described catalyst is to be prepared by any one method being selected from replacement method, step-by-step reduction method, while reducing process;
Wherein, described replacement method, operates by following IA or IB:
IA, mantoquita is dissolved in and in solvent, forms solution, with reducing agent reduction, obtain copper nano particles; In gained copper nano particles dispersion liquid, add Fischer-Tropsch constituent element Ru salting liquid, carry out displacement reaction with Cu nano particle, reacted rear centrifugation, solid matter is with water, low mass molecule alcohol or acetone washing, remove after cleaning solvent, dry, obtain CuRu bimetal nano catalyst
;
IB, at least one the Fischer-Tropsch constituent element salt containing in Fe, Co and Ni is dissolved in solvent and forms solution, with reducing agent reduction, obtain Fischer-Tropsch constituent element nano particle; In gained Fischer-Tropsch constituent element nanoparticulate dispersion, add copper salt solution, carry out displacement reaction with Fischer-Tropsch constituent element nano particle, rear centrifugation or magnetic have been reacted separated, solid matter is with water, low mass molecule alcohol or acetone washing, remove after cleaning solvent, dry, obtain copper Quito metal nano catalyst;
Described step-by-step reduction method, operates by following IIA, IIB, IIC or IID:
IIA, mantoquita is dissolved in and in solvent, forms solution, with reducing agent reduction, obtain copper nano particles; In gained copper nano particles dispersion liquid, add reducing agent, then splash into Fischer-Tropsch constituent element salting liquid and carry out reduction reaction; It is separated to have reduced rear centrifugation or magnetic, and solid matter, with water, low mass molecule alcohol or acetone washing, is removed after cleaning solvent, dry, obtains copper Quito metal nano catalyst;
IIB, mantoquita is dissolved in and in solvent, forms solution, with reducing agent reduction, obtain copper nano particles; In gained copper nano particles dispersion liquid, add Fischer-Tropsch constituent element salting liquid, then splash into reducing agent and carry out reduction reaction; It is separated to have reduced rear centrifugation or magnetic, and solid matter, with water, low mass molecule alcohol or acetone washing, is removed after cleaning solvent, dry, obtains copper Quito metal nano catalyst;
IIC, Fischer-Tropsch constituent element salt is dissolved in and in solvent, forms solution, with reducing agent reduction, obtain Fischer-Tropsch constituent element nano particle; In gained Fischer-Tropsch constituent element nanoparticulate dispersion, add reducing agent, then splash into copper salt solution and carry out reduction reaction; It is separated to have reduced rear centrifugation or magnetic, and solid matter, with water, low mass molecule alcohol or acetone washing, is removed after cleaning solvent, dry, obtains copper Quito metal nano catalyst;
IID, Fischer-Tropsch constituent element salt is dissolved in and in solvent, forms solution, with reducing agent reduction, obtain Fischer-Tropsch constituent element nano particle; In gained Fischer-Tropsch constituent element nanoparticulate dispersion, add copper salt solution, then splash into reducing agent and carry out reduction reaction; It is separated to have reduced rear centrifugation or magnetic, and solid matter, with water, low mass molecule alcohol or acetone washing, is removed after cleaning solvent, dry, obtains copper Quito metal nano catalyst;
Described while reducing process, step comprises: mantoquita and Fischer-Tropsch constituent element salt are dissolved in solvent and form solution, with reducing agent, reduce; It is separated to have reduced rear centrifugation or magnetic, and solid matter, with water, low mass molecule alcohol or acetone washing, is removed after cleaning solvent, dry, obtains copper Quito metal nano catalyst.
2. catalyst as claimed in claim 1, is characterized in that: the particle diameter of described copper-based nano-catalyst is 2～100nm
;the mol ratio of described copper and Fischer-Tropsch constituent element is 0.1～10.
3. the preparation method who prepares the copper-based nano-catalyst of higher alcohols for the synthesis of gas as claimed in claim 1, is characterized in that: any one method being selected from replacement method, step-by-step reduction method, while reducing process is prepared;
Wherein, described replacement method, operates by following IA or IB:
IA, mantoquita is dissolved in and in solvent, forms solution, with reducing agent reduction, obtain copper nano particles; In gained copper nano particles dispersion liquid, add Fischer-Tropsch constituent element Ru salting liquid, carry out displacement reaction with Cu nano particle, reacted rear centrifugation, solid matter is with water, low mass molecule alcohol or acetone washing, remove after cleaning solvent, dry, obtain CuRu bimetal nano catalyst;
IB, at least one the Fischer-Tropsch constituent element salt containing in Fe, Co and Ni is dissolved in solvent and forms solution, with reducing agent reduction, obtain Fischer-Tropsch constituent element nano particle; In gained Fischer-Tropsch constituent element nanoparticulate dispersion, add copper salt solution, carry out displacement reaction with Fischer-Tropsch constituent element nano particle, rear centrifugation or magnetic have been reacted separated, solid matter is with water, low mass molecule alcohol or acetone washing, remove after cleaning solvent, dry, obtain copper Quito metal nano catalyst;
Described step-by-step reduction method, operates by following IIA, IIB, IIC or IID:
IIA, mantoquita is dissolved in and in solvent, forms solution, with reducing agent reduction, obtain copper nano particles; In gained copper nano particles dispersion liquid, add reducing agent, then splash into Fischer-Tropsch constituent element salting liquid and carry out reduction reaction; It is separated to have reduced rear centrifugation or magnetic, and solid matter, with water, low mass molecule alcohol or acetone washing, is removed after cleaning solvent, dry, obtains copper Quito metal nano catalyst;
IIB, mantoquita is dissolved in and in solvent, forms solution, with reducing agent reduction, obtain copper nano particles; In gained copper nano particles dispersion liquid, add Fischer-Tropsch constituent element salting liquid, then splash into reducing agent and carry out reduction reaction; It is separated to have reduced rear centrifugation or magnetic, and solid matter, with water, low mass molecule alcohol or acetone washing, is removed after cleaning solvent, dry, obtains copper Quito metal nano catalyst;
IIC, Fischer-Tropsch constituent element salt is dissolved in and in solvent, forms solution, with reducing agent reduction, obtain Fischer-Tropsch constituent element nano particle; In gained Fischer-Tropsch constituent element nanoparticulate dispersion, add reducing agent, then splash into copper salt solution and carry out reduction reaction; It is separated to have reduced rear centrifugation or magnetic, and solid matter, with water, low mass molecule alcohol or acetone washing, is removed after cleaning solvent, dry, obtains copper Quito metal nano catalyst;
IID, Fischer-Tropsch constituent element salt is dissolved in and in solvent, forms solution, with reducing agent reduction, obtain Fischer-Tropsch constituent element nano particle; In gained Fischer-Tropsch constituent element nanoparticulate dispersion, add copper salt solution, then splash into reducing agent and carry out reduction reaction; It is separated to have reduced rear centrifugation or magnetic, and solid matter, with water, low mass molecule alcohol or acetone washing, is removed after cleaning solvent, dry, obtains copper Quito metal nano catalyst;
Described while reducing process, step comprises: mantoquita and Fischer-Tropsch constituent element salt are dissolved in solvent and form solution, with reducing agent, reduce; It is separated to have reduced rear centrifugation or magnetic, and solid matter, with water, low mass molecule alcohol or acetone washing, is removed after cleaning solvent, dry, obtains copper Quito metal nano catalyst.
4. method as claimed in claim 3, it is characterized in that: in the preparation method of described copper-based nano-catalyst, mantoquita used is selected from least one in following eight kinds of mantoquitas: stannous chloride, anhydrous cupric chloride, copper chloride dihydrate, copper nitrate, anhydrous cupric sulfate, cupric sulfate pentahydrate, Schweinfurt green and acetylacetone copper;
Described mantoquita concentration is pressed Cu
+and Cu
2+total concentration is counted 0.001～10mol/L.
5. method as claimed in claim 4, is characterized in that: described mantoquita concentration is by Cu
+and Cu
2+total concentration is counted 0.05～0.5mol/L.
6. method as claimed in claim 3, is characterized in that: in the preparation method of described copper-based nano-catalyst, the solvent of mantoquita used and Fischer-Tropsch constituent element salt is selected from water, organic solvent or its mixed solvent.
7. method as claimed in claim 6, is characterized in that: described organic solvent is methyl alcohol, ethanol, ethylene glycol, glycerine, 1,3-PD, BDO, Macrogol 200 and PEG400;
When solvent is selected ethylene glycol, glycerine, 1,3-PD, BDO, Macrogol 200 and PEG400, in solution, do not add stabilizing agent; When solvent is selected water, methyl alcohol and ethanol, in solution, add stabilizing agent simultaneously;
The mol ratio of this stabilizing agent and catalyst metals is 400:1～0:1; Wherein, stabilizing agent is selected from least one in polyvinylpyrrolidone, polyethylene glycol, citric acid, natrium citricum, soluble starch, cationic surfactant, non-ionic surface active agent or betaines surfactant.
8. method as claimed in claim 3, it is characterized in that: in the preparation method of described copper-based nano-catalyst, reducing agent used is selected from least one 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 tartrate;
Wherein, organic amine, comprising: dimethylamine, diethylamine, cetylamine, octadecylamine;
Dihydroxylic alcohols, comprising: ethylene glycol, 1,3-PD, BDO;
Polyalcohol, comprising: glycerine, glucitol;
Polyhydroxy aldehyde, comprising: glucose, wood sugar, glyceraldehyde;
Polyhydroxyketone, comprising: fructose, acetone glucose.
9. method as claimed in claim 3, it is characterized in that: in the preparation method of described copper-based nano-catalyst, Fischer-Tropsch constituent element salt used is selected from individual metal salt 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 metal total ion concentration.
10. method as claimed in claim 9, is characterized in that: described Fischer-Tropsch constituent element salinity is counted 0.05～0.5mol/L by metal total ion concentration.
11. methods as claimed in claim 9, is characterized in that: described ruthenium salt is selected from least one 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 least one in following six kinds of molysite: frerrous chloride, Iron trichloride hexahydrate, anhydrous ferric chloride, ferrous sulfate, ferric sulfate, ferric nitrate;
Cobalt salt is selected from least one in following five kinds of cobalt salts: cobalt chloride, cobalt nitrate, cobaltous sulfate, cobalt acetate, ammonium cobaltous sulfate;
Nickel salt is selected from least one in following five kinds of nickel salts: nickel chloride, nickel nitrate, nickelous sulfate, nickel acetate, ammonium nickel sulfate.
12. methods as claimed in claim 3, is characterized in that: in the preparation method of described copper-based nano-catalyst, low mass molecule alcohol used, comprising: methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, butanols, isobutanol, sec-butyl alcohol and the tert-butyl alcohol.
13. application of preparing the copper-based nano-catalyst of higher alcohols for the synthesis of gas as claimed in claim 1, is characterized in that: be applied to synthesis gas and prepare in higher alcohols, wherein, catalytic reaction condition is: the temperature of catalytic reaction is 150～320 ℃; H
2with CO stagnation pressure be 0.1～13MPa; H
2with the mol ratio of CO be 0.1～10; Air speed is 100～100000h
-1.
14. application as claimed in claim 13, is characterized in that: the temperature of described catalytic reaction is 200～280 ℃; H
2with 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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