CN115301271B - Copper-cobalt alloy catalyst and preparation method and application thereof - Google Patents
Copper-cobalt alloy catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- RYTYSMSQNNBZDP-UHFFFAOYSA-N cobalt copper Chemical compound [Co].[Cu] RYTYSMSQNNBZDP-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910000531 Co alloy Inorganic materials 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000010949 copper Substances 0.000 claims abstract description 31
- 239000000243 solution Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000012266 salt solution Substances 0.000 claims abstract description 20
- 229910052802 copper Inorganic materials 0.000 claims abstract description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000005275 alloying Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000001879 copper Chemical class 0.000 claims abstract description 9
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- 239000013110 organic ligand Substances 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 13
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 11
- 230000032683 aging Effects 0.000 claims description 7
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 7
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- 238000000354 decomposition reaction Methods 0.000 claims description 5
- 238000003837 high-temperature calcination Methods 0.000 claims description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 4
- 150000003751 zinc Chemical class 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 150000001868 cobalt Chemical class 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 2
- 230000002431 foraging effect Effects 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 19
- 230000008569 process Effects 0.000 abstract description 13
- 230000015572 biosynthetic process Effects 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 8
- 238000012546 transfer Methods 0.000 abstract description 7
- 229910045601 alloy Inorganic materials 0.000 abstract description 5
- 239000000956 alloy Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000011946 reduction process Methods 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 51
- 238000006243 chemical reaction Methods 0.000 description 16
- 229910017052 cobalt Inorganic materials 0.000 description 10
- 239000010941 cobalt Substances 0.000 description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- 239000011261 inert gas Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 238000005054 agglomeration Methods 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000007664 blowing Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003892 spreading Methods 0.000 description 4
- 230000007480 spreading Effects 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- 229910017816 Cu—Co Inorganic materials 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- -1 antifreezes Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 229940011182 cobalt acetate Drugs 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012072 active phase Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
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- 239000013078 crystal Substances 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000284 resting effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/399—
-
- B01J35/615—
-
- B01J35/647—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
Abstract
The invention discloses a copper-cobalt alloy catalyst and a preparation method and application thereof, and belongs to the technical field of catalyst material preparation. The copper-cobalt alloy catalyst comprises: a Co-N-C carrier and metallic copper, wherein the metallic copper is loaded on the Co-N-C carrier. The preparation method of the copper-cobalt alloy catalyst comprises the following steps: mixing Co-N-C solution and copper salt solution uniformly, and standing to obtain Cu 2+ Co-N-C; the Cu is treated with 2+ separating/Co-N-C, drying, and then subjecting the Cu to a treatment 2+ And alloying the alloy with the alloy of Co and N-C to obtain the copper-cobalt alloy catalyst. The Co-N-C carrier with high specific surface area and porous structure is selected to be used for synthesizing the copper-cobalt alloy catalyst, and the carbon in the Co-N-C is used for directly reducing the adsorbed copper ions into metallic copper in combination with an in-situ reduction process, so that the formation of the copper-cobalt alloy is promoted, and Co and Cu are uniformly dispersed in the process, and the particle size is basically consistent, thereby being beneficial to mass transfer and heat transfer in the catalytic process.
Description
Technical Field
The invention belongs to the technical field of catalyst material preparation, and particularly relates to a copper-cobalt alloy catalyst and a preparation method and application thereof.
Background
The low-carbon alcohol (alcohol substance with carbon number of C1-C5) has important application value in the chemical industry field, can be directly used as high-quality fuel, and can also be added into fuel to improve the antiknock and antiknock properties of the fuel. In addition, the low-carbon alcohol can be used as a solvent and an additive in chemical production, and is also a production chemical raw material and a synthesis intermediate of chemicals such as cosmetics, antifreezes, fragrances, medicines and the like. In the production route of synthetic alcohols, synthesis gas (CO and H) is produced from coal, natural gas or renewable biomass 2 Is a mixture of (3)Gas synthesis), and the synthesis gas is converted into low-carbon alcohol under the action of a catalyst, thereby being an ideal synthesis route.
In the existing catalyst system, the copper-cobalt metal catalyst has the advantages of low material cost, mild reaction condition, high C2 < + > alcohol selectivity and the like, and is a catalyst system with very good research and application prospects. In a copper-cobalt bimetallic system, metallic cobalt induces CO dissociation and carbon-carbon coupling to form a carbon chain, metallic copper promotes the reaction of CO insertion into the carbon chain, namely, is responsible for introducing hydroxyl groups, and if C2+ alcohols (C2+ alcohols have higher economic value) are to be obtained, the synergistic effect of two active sites is required. The pure metals cobalt and copper are used as the catalyst active phases to obtain hydrocarbons (methane, ethane, propane, etc.) and methanol, respectively, so that intimate contact between copper and cobalt is required or an alloy phase is formed, which is also considered as the main active phase of the copper cobalt catalyst. In addition, the particle size of the alloy is small enough to facilitate the full contact between the active site and the reaction gas, and to improve the catalytic activity, highly dispersed Cu-Co is sought after by the bimetallic catalyst system.
At present, three routes for synthesizing copper-cobalt alloy catalysts are mainly adopted: one is to prepare a supported catalyst by an impregnation method, such as the one reported in patent document (CN 201410006546.8) by using SiO 2 Or ZrO(s) 2 Is used as a carrier, is impregnated with a mixed solution of copper ions, cobalt ions, citric acid and chelating agent, is dried and roasted to obtain a catalyst precursor, and the precursor is subjected to H 2 Or further reducing CO to finally obtain the Cu-Co supported bimetallic catalyst. The catalyst prepared by the scheme has the function of a carrier and good stability, but H is needed in the reduction process 2 Flammable and explosive gases such as CO and the like participate in high-temperature heat treatment, so that the requirement on the air tightness of equipment is high, and the difficulty of industrial production is increased. The second is to prepare a copper-cobalt catalyst by a coprecipitation method, for example, patent document (CN 200410082377.2) reports that potassium carbonate is added to an aqueous solution of copper ions and cobalt ions, the pH of the solution is controlled to form a precipitate, carbon nanotubes are introduced as a carrier in the process, and finally the copper-cobalt catalyst is obtained by heat treatment. However, the co-precipitation process tends to be difficult to control the two metal ionsThe simultaneous formation of the precipitate is disadvantageous for the formation of uniformly distributed active sites. Thirdly, a co-reduction method is adopted to prepare the copper-cobalt nano alloy, for example, patent literature (DOI https:// doi.org/10.1039/C3CY 00063J) reports that sodium borohydride is adopted as a reducing agent, and aqueous solution of sodium borohydride is directly dripped into ethylene glycol solution of copper ions and cobalt ions to reduce the copper ions and the cobalt ions into a metal state to form the nano alloy.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person of ordinary skill in the art.
Disclosure of Invention
In order to solve the technical problems of low active site, uneven dispersion and easy sintering of a copper-cobalt metal catalyst in the prior art, the invention provides a highly dispersed copper-cobalt alloy catalyst and a preparation method thereof, a Co-N-C catalyst and a preparation method of low-carbon alcohol.
The first aspect of the invention provides a highly dispersed copper-cobalt alloy catalyst comprising a Co-N-C support and metallic copper supported on the Co-N-C support.
In some embodiments, the copper-cobalt alloy catalyst is in a mesoporous structure; preferably, the pore diameter of the copper-cobalt alloy catalyst is 5-10 nm.
The second aspect of the invention provides a preparation method of a high-dispersion copper-cobalt alloy catalyst, which comprises the following steps:
mixing Co-N-C solution and copper salt solution uniformly, and standing to obtain Cu 2+ /Co-N-C；
The Cu is treated by 2+ separating/Co-N-C, drying, and then subjecting the Cu to a treatment 2+ alloying/Co-N-C to obtain the copper-cobalt alloy catalyst.
In some embodiments, the concentration of the Co-N-C solution is from 0.0005 to 0.001g/mL;
and/or the copper salt is selected from one or more of copper nitrate, copper chloride and copper acetate; preferably, the concentration of copper ions in the copper salt solution is 0.01 to 0.1mol/L.
In some embodiments, the time of the standing is 10 to 16 hours;
and/or the alloying temperature is 300-500 ℃.
In some embodiments, the method for preparing Co-N-C comprises: adding the organic ligand solution into the metal salt solution, vigorously stirring, standing for aging, and calcining at high temperature for decomposition to obtain the Co-N-C powder.
In some embodiments, the metal salt solution is a mixed solution of cobalt salt and zinc salt; preferably, the concentration of the metal ions in the metal salt solution is 0.01 to 0.1mol/L; more preferably, the molar ratio of zinc ions to cobalt ions in the metal salt solution is 1:0.1-1;
and/or, the organic ligand is 2-methylimidazole; preferably, the total mass ratio of the organic ligand to the metal is 1:0.05-0.1.
In some embodiments, the above-described resting aging time is from 10 to 15 hours;
and/or the high-temperature calcination temperature is 700-900 DEG C
The third aspect of the invention provides an application of the copper-cobalt alloy catalyst or the copper-cobalt alloy catalyst obtained by the preparation method in preparation of low-carbon alcohol.
The fourth aspect of the present invention provides a method for preparing a lower alcohol, comprising: and adding the copper-cobalt alloy catalyst or the copper-cobalt alloy catalyst prepared by any one of the preparation methods into a reactant, and catalyzing to obtain the low-carbon alcohol.
Compared with the prior art, the invention has the following technical effects:
(1) The cobalt-copper metal catalyst has larger specific surface area which reaches 450m 2 The pore size distribution of the catalyst is concentrated at about 7.5nm, which is favorable for the full contact of gas molecules and active sites and the performance of mass and heat transfer process of catalytic reaction,thereby effectively improving the conversion rate of CO and the selectivity of low-carbon alcohol; the Co-N-C carrier has highly dispersed Co active sites, and the porous structure can effectively adsorb copper salt ions so as to improve the loading effect, and the pore channel structure also avoids agglomeration sintering phenomenon of nano particles in the high-temperature alloying process, so that the dispersibility of the active sites is further improved, and the catalytic activity of the finally obtained copper-cobalt alloy sample for catalyzing synthesis gas to prepare low-carbon alcohol is higher. .
(2) The Co-N-C carrier with high specific surface area and porous structure is selected to be used for synthesizing the copper-cobalt alloy catalyst, and the carbon in the Co-N-C is used for directly reducing the adsorbed copper ions into metal copper in combination with an in-situ reduction process to promote the formation of copper-cobalt alloy.
(3) The preparation of Co-N-C generally requires pyrolysis, cobalt is often agglomerated and sintered to cause active site loss, zn salt (zinc nitrate, zinc chloride and the like) is introduced in the synthesis process in order to solve the problem of Co species agglomeration, zn can also react with organic ligands to form MoFs materials, the boiling point of Zn is lower, zn and the organic ligands are decomposed and volatilized together in the high-temperature heat treatment process, the agglomeration of cobalt is inhibited, the stable existence of highly dispersed cobalt sites in Co-N-C is ensured, and meanwhile, the preparation of the Co-N-C is beneficial to forming a high specific surface and a porous structure.
(4) The method is simple, safe, environment-friendly and easy to implement, and is suitable for large-scale industrial production.
Drawings
FIG. 1 is an SEM image of a sample CuCoNC-1 prepared according to example 1 of the present invention;
FIG. 2 is an enlarged SEM image of sample CuCoNC-1 prepared in example 1 of the present invention;
FIG. 3 is an XRD pattern of sample CuCoNC-1 prepared in example 1 of the present invention.
Detailed Description
The technical scheme of the invention is described below through specific embodiments with reference to the accompanying drawings. It is to be understood that the reference to one or more steps of the invention does not exclude the presence of other methods and steps before or after the combination of steps, or that other methods and steps may be interposed between the explicitly mentioned steps. It should also be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Unless otherwise indicated, the numbering of the method steps is for the purpose of identifying the method steps only and is not intended to limit the order of arrangement of the method steps or to limit the scope of the invention, which relative changes or modifications may be regarded as the scope of the invention which may be practiced without substantial technical content modification.
The raw materials and instruments used in the examples are not particularly limited in their sources, and may be purchased on the market or prepared according to conventional methods well known to those skilled in the art.
The invention provides a high-dispersion copper-cobalt alloy catalyst, which comprises a Co-N-C carrier and metallic copper, wherein the metallic copper is loaded on the Co-N-C carrier. The Co-N-C carrier has highly dispersed Co active sites, and the loaded copper is highly dispersed on the Co-N-C carrier, so that mass and heat transfer in the catalytic process are facilitated, and sintering phenomenon is not easy to occur.
The copper-cobalt alloy catalyst has a mesoporous structure; preferably, the pore diameter of the copper-cobalt alloy catalyst is 5-10 nm. The mesoporous structure has large specific surface area, is favorable for full contact between gas molecules and active sites, and further improves the mass and heat transfer process of the catalytic reaction, thereby effectively improving the conversion rate of CO and the selectivity of low-carbon alcohol.
The invention also provides a preparation method of the high-dispersion copper-cobalt alloy catalyst, which comprises the following steps:
(1) Preparing a metal salt solution:
the cobalt salt can be cobalt nitrate, cobalt chloride, cobalt acetate and the like, the zinc salt can be zinc nitrate, zinc chloride and the like, and the solvent used is ethanol. The concentration of the metal ions in the salt solution is 0.01-0.1 mol/L, and the mol ratio of zinc to cobalt ions is 1:0.1-1. Zinc salt and cobalt can form a metal organic framework compound (MoFs) together in the reaction, the boiling point of zinc is lower, and zinc can be decomposed and volatilized together with C, H in the organic ligand in the post heat treatment process, only elements such as Co and C are left, and agglomeration and sintering of cobalt species in Co-N-C can be effectively inhibited.
(2) Preparing an organic ligand solution:
the organic ligand is 2-methylimidazole, the solvent used is ethanol, and the mass ratio of the organic ligand to the total metal is 1:0.05-0.1. 2-methylimidazole is effective and Co 2+ Form bidentate coordination, and the price is low, which is beneficial to the mass production and preparation of samples
(3) The organic ligand solution is added into the metal salt solution, and as the reaction process is rapid, a large amount of crystal nuclei can be formed in the moment of contact of the two solutions, and a large amount of heat is released, which is unfavorable for the uniformity of the product and the controllability of the reaction, so that the organic ligand solution is fully and uniformly mixed and dispersed under a low-temperature environment, the nucleation reaction rate of MoFs is delayed, the low-temperature environment is maintained and the violent stirring is carried out for a period of time, the uniform and stable reaction is carried out, the low-temperature environment can be realized by placing a reaction container in an ice-water bath or other cooling modes, then standing and aging are carried out, the aging time is controlled within the range of 10-15h, and the reaction is enabled to be full.
(4) And (3) centrifugally separating the aged sample, adding ethanol for washing for a plurality of times, removing redundant 2-methylimidazole and precursor salt, and drying by blowing at 50-70 ℃.
(5) Spreading the obtained solid powder at the bottom of a crucible, transferring the solid powder into a tube furnace, introducing inert gas for protection, and calcining and decomposing at a high temperature of 700-900 ℃ to obtain a Co-N-C powder sample.
(6) 0.05g of Co-N-C powder is taken and dispersed in ethanol solution to prepare copper salt solution, wherein copper salt can be copper nitrate, copper chloride, copper acetate and the like, the concentration range of copper ions is 0.01-0.1 mol/L, the used solvent is water, and the volume ratio of ethanol to water is 1:0.5-5.
(7) Mixing the two solutions, performing ultrasonic treatment to uniformly disperse the two solutions, stirring for a period of time, and standing for 12-24 h to enable the porous structure of Co-N-C to fully adsorb Cu 2+ Ion, suction filtration and separation, and blast drying at 50-70 ℃.
(8) And placing the obtained solid in a crucible, introducing inert gas for protection, and alloying at 300-500 ℃ to finally obtain the high-dispersion copper-cobalt alloy catalyst.
Example 1: preparation method of copper-cobalt alloy catalyst
The preparation method comprises the following steps: 0.29g of cobalt nitrate, 1.34g of zinc nitrate was weighed out and dissolved in 200mL of ethanol. 3.3g of 2-methylimidazole is weighed and dissolved in 200mL of ethanol; adding an organic ligand solution into a metal salt solution, fully and uniformly mixing and dispersing the solution by intense stirring, keeping an ice water bath and intense stirring for a period of time, and standing and aging for 10 hours; centrifuging the aged sample, adding ethanol for washing for several times, removing excessive 2-methylimidazole and precursor salt, and drying by air blast at 60 ℃; spreading the obtained solid powder at the bottom of a crucible, transferring to a tube furnace, introducing inert gas argon for protection, and performing high-temperature calcination decomposition at 900 ℃ to obtain a Co-N-C powder sample; 0.05g of Co-N-C powder is taken and dispersed in 20mL of ethanol solution, 0.5g of copper nitrate is weighed and dissolved in 60mL of pure water; mixing the two solutions, performing ultrasonic treatment to uniformly disperse the two solutions, stirring for a period of time, and standing overnight to enable the porous structure of Co-N-C to fully adsorb Cu 2+ Ion, then separating by suction filtration, and drying by blowing at 50 ℃; putting the obtained solid in a crucible, introducing inert gas for protection, alloying at a high temperature of 400 ℃, and finally obtaining the copper-cobalt alloy catalyst which is named as CuCoNC-1.
Fig. 1 shows the scanning result of the electron microscope of the sample, and the particle size of the sample is about 200nm, the sample is uniform in size, no obvious sintering agglomeration phenomenon occurs, and the particles are piled up to form a multi-void structure, so that mass and heat transfer in the catalysis process are facilitated, and the reaction is promoted. Fig. 2 shows XRD peaks of the sample, and shows that broad peaks at 25.7 ° belong to diffraction peaks of carbon, while diffraction peaks at 44.4 °, 51.4 °, 75.9 ° correspond to metallic cobalt, no obvious diffraction peak of Cu is found, indicating that Cu is highly dispersed in the catalyst, and no larger Cu metal nanoparticle is formed.
N is carried out on the sample 2 The adsorption and desorption tests were carried out, and the results are shown in Table 1.
TABLE 1N of sample CuCoNC-1 prepared in example 1 2 Adsorption and desorption test results
As can be seen from Table 1, the test results show that the specific surface area of the sample is large (450.6 m 2 And the pore size distribution of the catalyst is concentrated at about 7.5nm, which indicates that the catalyst belongs to mesoporous materials, and the existence of mesopores is favorable for the full contact of gas molecules and active sites and the implementation of mass and heat transfer processes of catalytic reaction, thereby effectively improving the conversion rate of CO and the selectivity of low-carbon alcohol.
Example 2: preparation method of copper-cobalt alloy catalyst
0.24g of cobalt chloride and 0.3g of zinc nitrate are weighed and dissolved in 200mL of ethanol; 2.5g of 2-methylimidazole is weighed and dissolved in 200mL of ethanol; adding the organic ligand solution into the metal salt solution, fully and uniformly mixing and dispersing the organic ligand solution by intense stirring, keeping an ice water bath and intense stirring for a period of time, and standing and aging for 12 hours; centrifuging the aged sample, adding ethanol for washing for several times, removing excessive 2-methylimidazole and precursor salt, and drying by air blast at 60 ℃; spreading the obtained solid powder at the bottom of a crucible, transferring to a tube furnace, introducing inert gas argon for protection, and performing high-temperature calcination decomposition at 700 ℃ to obtain a Co-N-C powder sample; 0.05g of Co-N-C powder is taken and dispersed in 20mL of ethanol solution, 0.1g of copper chloride is weighed and dissolved in 20mL of pure water; mixing the two solutions, performing ultrasonic treatment to uniformly disperse the two solutions, stirring for a period of time, and standing overnight to enable the porous structure of Co-N-C to fully adsorb Cu 2+ Ion, then separating by suction filtration, and drying by blowing at 50 ℃; and (3) placing the obtained solid in a crucible, introducing inert gas for protection, and alloying at a high temperature of 300 ℃ to finally obtain the copper-cobalt alloy catalyst, which is marked as CuCoNC-2.
Example 3: preparation method of copper-cobalt alloy catalyst
Weighing 0.5g of cobalt acetate and 2.78g of zinc chloride, and dissolving in 200mL of ethanol; weighing 6.5g of 2-methylimidazole, and dissolving in 200mL of ethanol; adding the organic ligand solution into the metal salt solution, fully and uniformly mixing and dispersing the organic ligand solution by intense stirring, keeping an ice water bath and intense stirring for a period of time, and standing and aging for 15 hours; centrifuging the aged sample, adding ethanol for washing for several times, removing excessive 2-methylimidazole and precursor salt, and drying by air blast at 50 ℃; spreading the obtained solid powder at the bottom of a crucible, transferring to a tube furnace, introducing inert gas argon for protection, and performing high-temperature calcination decomposition at 800 ℃ to obtain a Co-N-C powder sample; 0.05g of Co-N-C powder is taken and dispersed in 20mL of ethanol solution, 1.0g of copper acetate is weighed and dissolved in 100mL of pure water; mixing the two solutions, performing ultrasonic treatment to uniformly disperse the two solutions, stirring for a period of time, and standing overnight to enable the porous structure of Co-N-C to fully adsorb Cu 2+ Ion, then separating by suction filtration, and drying by blowing at 70 ℃; putting the obtained solid in a crucible, introducing inert gas for protection, alloying at a high temperature of 500 ℃, and finally obtaining the copper-cobalt alloy catalyst which is marked as CuCoNC-3.
Test of catalytic Activity of copper cobalt Metal alloys prepared in examples 1-3
The results of the catalytic performance tests of the three copper cobalt metal alloy samples prepared in examples 1-3 are shown in Table 2.
TABLE 2 catalytic Activity of copper cobalt alloy catalysts of examples 1-3
As can be seen from the table, the catalyst sample prepared by the invention has good catalytic performance, higher CO conversion rate and C2+OH selectivity, the CO conversion rate of the three examples is higher than 50%, and the ratio of C2+OH in the obtained low-carbon alcohol is higher than 77%, and the catalyst sample is basically free ofCO 2 The generation of the catalyst has better application prospect and development potential.
Example 4: co-N-C catalyst
A Co-N-C catalyst comprising the Co-N-C powder prepared in example 1. The Co-N-C powder has loose texture and high specific surface area>450m 2 And/g) and relatively concentrated pore size distribution (-7.5 nm), is an ideal mesoporous material, has uniform microscopic size and no obvious agglomeration phenomenon in the atmosphere of about 100-200 nm.
Example 5: preparation method of low-carbon alcohol
A method for preparing a lower alcohol, comprising: the copper-cobalt metal catalyst prepared in example 1 is added into a catalytic device, and the mixture is introduced into synthesis gas (CO and H 2 The mixed gas of (2) is applied with certain temperature and air pressure and kept at constant temperature and pressure, and two active sites of copper and cobalt in the catalyst act cooperatively to catalyze a series of reactions such as CO dissociative hydrogenation, carbon chain growth, CO non-dissociative insertion and the like, and finally the target product is low-carbon alcohol, and the byproducts mainly comprise methane and CO 2 Trace of H 2 O。
The foregoing descriptions of specific exemplary embodiments of the present invention are presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain the specific principles of the invention and its practical application to thereby enable one skilled in the art to make and utilize the invention in various exemplary embodiments and with various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (8)
1. A highly dispersed copper-cobalt alloy catalyst, characterized in that the copper-cobalt alloy catalyst comprises a Co-N-C support and metallic copper, the metallic copper being supported on the Co-N-C support;
the preparation method of the copper-cobalt alloy catalyst comprises the following steps:
mixing Co-N-C solution and copper salt solution uniformly, and standing to obtain Cu 2+ /Co-N-C；
The Cu is treated with 2+ separating/Co-N-C, drying, and then subjecting the Cu to a treatment 2+ Alloying Co-N-C to obtain the copper-cobalt alloy catalyst;
the preparation method of the Co-N-C comprises the following steps: adding an organic ligand solution into a metal salt solution, vigorously stirring, standing for aging, and then calcining at a high temperature for decomposition to obtain Co-N-C powder;
the metal salt solution is a mixed solution of cobalt salt and zinc salt.
2. The copper-cobalt alloy catalyst according to claim 1, wherein the copper-cobalt alloy catalyst is of a mesoporous structure.
3. The copper-cobalt alloy catalyst according to claim 2, wherein the pore size of the copper-cobalt alloy catalyst is 5-10 nm.
4. The method for preparing a copper-cobalt alloy catalyst according to claim 1, wherein the concentration of the Co-N-C solution is 0.0005 to 0.001g/mL;
and/or the copper salt is selected from one or more of copper nitrate, copper chloride and copper acetate; the concentration of copper ions in the copper salt solution is 0.01-0.1 mol/L.
5. The method for preparing a copper-cobalt alloy catalyst according to claim 1, wherein the standing time is 10 to 16 hours;
and/or the alloying temperature is 300-500 ℃.
6. The method for preparing a copper-cobalt alloy catalyst according to claim 1, wherein the concentration of metal ions in the metal salt solution is 0.01 to 0.1mol/L; the molar ratio of zinc ions to cobalt ions in the metal salt solution is 1:0.1.
7. The method for preparing a copper-cobalt alloy catalyst according to claim 1, wherein the organic ligand is 2-methylimidazole; the total mass ratio of the organic ligand to the metal is 1:0.05-0.1.
8. The method for preparing a copper-cobalt alloy catalyst according to claim 1, wherein the standing aging time is 10 to 15 hours;
and/or the high-temperature calcination temperature is 700-900 ℃.
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| CN108963276A (en) * | 2018-06-27 | 2018-12-07 | 中国科学技术大学 | Non-precious metal catalyst and preparation method thereof for catalytic oxidation-reduction |
| CN110876955A (en) * | 2019-11-08 | 2020-03-13 | 天津大学 | Cobalt-copper bimetallic catalyst for directly preparing low-carbon alcohol from synthesis gas and preparation method thereof |
| CN113363516A (en) * | 2020-03-04 | 2021-09-07 | 香港科技大学 | Catalyst carrier, composite catalyst, preparation method thereof, fuel cell and application thereof |
| CN113371693A (en) * | 2021-06-09 | 2021-09-10 | 中钢集团南京新材料研究院有限公司 | Cobalt-nitrogen co-doped three-dimensional structure carbon material and preparation method and application thereof |
| CN114784297A (en) * | 2022-03-14 | 2022-07-22 | 北京理工大学 | Preparation method of monatomic cobalt ORR catalyst |
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| CN108963276A (en) * | 2018-06-27 | 2018-12-07 | 中国科学技术大学 | Non-precious metal catalyst and preparation method thereof for catalytic oxidation-reduction |
| CN110876955A (en) * | 2019-11-08 | 2020-03-13 | 天津大学 | Cobalt-copper bimetallic catalyst for directly preparing low-carbon alcohol from synthesis gas and preparation method thereof |
| CN113363516A (en) * | 2020-03-04 | 2021-09-07 | 香港科技大学 | Catalyst carrier, composite catalyst, preparation method thereof, fuel cell and application thereof |
| CN113371693A (en) * | 2021-06-09 | 2021-09-10 | 中钢集团南京新材料研究院有限公司 | Cobalt-nitrogen co-doped three-dimensional structure carbon material and preparation method and application thereof |
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