CN115301271A - 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 70
- RYTYSMSQNNBZDP-UHFFFAOYSA-N cobalt copper Chemical compound [Co].[Cu] RYTYSMSQNNBZDP-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910000531 Co alloy Inorganic materials 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000010949 copper Substances 0.000 claims abstract description 35
- 239000000243 solution Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 31
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 30
- 239000012266 salt solution Substances 0.000 claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
- 229910052802 copper Inorganic materials 0.000 claims abstract description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 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
- 238000001035 drying Methods 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 56
- 239000013110 organic ligand Substances 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 14
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 11
- 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
- 239000006185 dispersion Substances 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 6
- 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 6
- 238000000354 decomposition reaction Methods 0.000 claims description 6
- 238000003837 high-temperature calcination Methods 0.000 claims description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 5
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 5
- 150000003751 zinc Chemical class 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
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- 230000008569 process Effects 0.000 abstract description 14
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- 239000011261 inert gas Substances 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
- 238000005245 sintering Methods 0.000 description 7
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
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- 238000009210 therapy by ultrasound Methods 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
- 238000007605 air drying Methods 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 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
- 238000010494 dissociation reaction Methods 0.000 description 3
- 230000005593 dissociations Effects 0.000 description 3
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- 238000009835 boiling Methods 0.000 description 2
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- 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
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- 229910001092 metal group alloy Inorganic materials 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
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- 230000002195 synergetic effect Effects 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910017816 Cu—Co Inorganic materials 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
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
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- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
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Images
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- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- 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
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Abstract
The invention discloses a copper-cobalt alloy catalyst and a preparation method and application thereof, belonging to the technical field of catalyst material preparation. The copper-cobalt alloy catalyst comprises: the copper-based 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: uniformly mixing the Co-N-C solution with the copper salt solution, and standing to obtain Cu 2+ /Co-N-C; the Cu is added 2+ separating/Co-N-C, drying, and then allowing the Cu to react 2+ And performing/Co-N-C alloying to obtain the copper-cobalt alloy catalyst. The invention is provided withThe Co-N-C carrier with high specific surface area and porous structure is used for synthesizing the copper-cobalt alloy catalyst, and carbon in the Co-N-C is utilized to directly reduce the adsorbed copper ions into metal copper by combining an in-situ reduction process, so that the formation of the copper-cobalt alloy is promoted, the Co and the Cu are uniformly dispersed and the particle size is basically consistent in the process, and the mass transfer and the heat transfer in the catalysis process are facilitated.
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 (C1-C5 alcohol substance) has important application value in the chemical industry field, can be directly used as high-quality fuel, and can also be added into fuel oil to improve the anti-knock and anti-seismic properties of the fuel oil. In addition, the low-carbon alcohol can be used as a solvent and an additive in chemical production, and is also a chemical raw material and a synthetic intermediate for producing chemicals such as cosmetics, antifreeze, spice, medicines and the like. In the synthetic alcohol production route, synthesis gas (CO and H) is produced from coal, natural gas or renewable biomass 2 The mixed gas) is converted into low-carbon alcohol under the action of a catalyst, and is a more ideal synthetic route.
In the existing catalyst system, the copper-cobalt alloy metal catalyst has the advantages of low material cost, mild reaction conditions, high C2+ alcohol selectivity and the like, so that the copper-cobalt alloy metal catalyst is a catalyst system with research and application prospects. In a copper-cobalt bimetallic system, metal cobalt induces CO dissociation and generates carbon-carbon coupling to form a carbon chain, metal copper promotes the reaction of CO inserting into the carbon chain, namely, is responsible for introducing hydroxyl, and if C2+ alcohol is to be obtained (the economic value of the C2+ alcohol is higher), the synergistic effect of two active sites is needed. Since pure metals cobalt and copper as the catalyst active phases can only obtain hydrocarbons (methane, ethane, propane, etc.) and methanol, respectively, close contact between copper and cobalt or formation of an alloy phase is required, which is also considered to be the main active phase of the copper-cobalt catalyst. In addition, the grain size of the alloy is small enough to facilitate the full contact of the active sites and the reaction gas and improve the catalytic activity, and highly dispersed Cu-Co is sought after by the bimetallic catalyst system.
At present, there are three main routes for synthesizing copper-cobalt alloy catalysts: one is to prepare the supported catalyst by adopting an impregnation method, such as SiO adopted and reported in a patent document (CN 201410006546.8) 2 Or ZrO 2 Impregnating a carrier with a mixed solution of copper ions, cobalt ions, citric acid and a chelating agent, drying and roasting to obtain a catalyst precursor, and subjecting the precursor to H 2 Or further reducing CO to finally obtain the copper-cobalt loaded bimetallic catalyst. The catalyst prepared by the scheme has the function of a carrier and good stability, but H is required to be used in the reduction process 2 And combustible and explosive gases such as CO 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 method is to prepare a copper-cobalt catalyst by a coprecipitation method, for example, in patent document (CN 200410082377.2), it is reported that potassium carbonate is added into an aqueous solution of copper ions and cobalt ions, the pH value of the solution is controlled to form a precipitate, carbon nanotubes are introduced in the process as a carrier, and finally the copper-cobalt catalyst is obtained by heat treatment. However, the co-precipitation process is often difficult to control two metal ions to form precipitates simultaneously, which is not favorable for forming uniformly distributed active sites. The third is to adopt the co-reduction method to prepare the copper cobalt nano alloy, for example, patent literature (DOI https:// doi.org/10.1039/C3CY 00063J) reports that sodium borohydride is used as a reducing agent, and sodium borohydride aqueous solution is directly dripped into copper ion and cobalt ion ethylene glycol solution to reduce the copper ion and cobalt ion 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 skilled in the art.
Disclosure of Invention
In order to solve the technical problems of low active sites, nonuniform 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, and a preparation method of a Co-N-C catalyst and a preparation method of low-carbon alcohol.
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.
In some embodiments, the copper-cobalt alloy catalyst has a mesoporous structure; preferably, the pore diameter of the copper-cobalt alloy catalyst is 5 to 10nm.
The second aspect of the invention provides a preparation method of a high-dispersion copper-cobalt alloy catalyst, which comprises the following steps:
uniformly mixing the Co-N-C solution with the copper salt solution, and standing to obtain Cu 2+ /Co-N-C；
Mixing the above Cu 2+ separating/Co-N-C, drying, and then allowing the Cu to react 2+ The cobalt-copper alloy catalyst is obtained by/Co-N-C alloying.
In some embodiments, 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; preferably, the concentration of copper ions in the copper salt solution is 0.01 to 0.1mol/L.
In some embodiments, the standing time is 10 to 16 hours;
and/or the temperature of the alloying is 300-500 ℃.
In some embodiments, the method of preparing Co-N-C described above comprises: adding the organic ligand solution into the metal salt solution, stirring vigorously, 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;
and/or, the organic ligand is 2-methylimidazole; preferably, the mass ratio of the organic ligand to the total metal is 1.
In some embodiments, the standing and aging time is 10 to 15 hours;
and/or the temperature of the high-temperature calcination 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 preparing low carbon alcohol.
The fourth aspect of the present invention provides a method for producing a lower alcohol, comprising: 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 low-carbon alcohol.
Compared with the prior art, the invention achieves the following technical effects:
(1) The specific surface area of the cobalt-copper metal catalyst is large and reaches 450m 2 The pore size distribution of the catalyst is concentrated at about 7.5nm, which is beneficial to the full contact of gas molecules and active sites and the 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, the porous structure can effectively adsorb copper salt ions so as to improve the loading effect, and the pore channel structure avoids the 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 preparing low-carbon alcohol by catalyzing synthesis gas is higher. .
(2) The invention selects the Co-N-C carrier with high specific surface area and porous structure to be used for the synthesis of the copper-cobalt alloy catalyst, combines the in-situ reduction process, utilizes the carbon in the Co-N-C to directly reduce the adsorbed copper ions into the metal copper, promotes the formation of the copper-cobalt alloy, and compared with the traditional preparation method of introducing two metal precursors of copper and cobalt into the carrier at the same time, in the preparation process of the cobalt-copper metal catalyst disclosed by the invention, co and Cu are uniformly dispersed, the particle sizes are basically consistent, the agglomeration phenomenon is avoided, the mass transfer and heat transfer in the catalysis process are facilitated, and the sintering is not easy to occur.
(3) The preparation of Co-N-C generally needs high-temperature pyrolysis, which often causes cobalt agglomeration and sintering to cause active site loss, in order to solve the problem of Co species agglomeration, zn salt (zinc nitrate, zinc chloride and the like) is introduced in the synthesis process of the Co-N-C disclosed by the invention, zn can also react with an organic ligand to form a MoFs material, the boiling point of Zn is lower, zn and the organic ligand 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 the Co-N-C is ensured, and the high specific surface and the porous structure are favorably formed.
(4) The method is simple, safe, environment-friendly, easy to implement and suitable for large-scale industrial production.
Drawings
FIG. 1 is an SEM image of a sample CuCoNC-1 prepared in example 1 of the present invention;
FIG. 2 is an enlarged SEM image of a sample CuCoNC-1 prepared in example 1 of the present invention;
FIG. 3 is an XRD pattern of a sample CuCoNC-1 prepared in example 1 of the present invention.
Detailed Description
The technical scheme of the invention is explained by specific embodiments in the following with reference to the attached drawings. It is to be understood that one or more of the steps referred to in the present application do not exclude the presence of other methods or steps before or after the combination of steps, or that other methods or steps may be intervening between those steps specifically referred to. It should also be understood that these examples are intended only to illustrate the invention and are not intended to limit the scope of the invention. Unless otherwise indicated, the numbering of the method steps is only for the purpose of identifying the method steps, and is not intended to limit the arrangement order of each method or the scope of the implementation of the present invention, and changes or modifications of the relative relationship thereof may be regarded as the scope of the implementation of the present invention without substantial technical change.
The raw materials and apparatuses used in the examples are not particularly limited in their sources, and may be purchased from the market or prepared according to a conventional method 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 the mass and heat transfer in the catalytic process are facilitated, and the sintering phenomenon is not easy to occur.
The copper-cobalt alloy catalyst is of a mesoporous structure; preferably, the pore diameter of the copper-cobalt alloy catalyst is 5 to 10nm. The mesoporous structure has large specific surface area, is beneficial to the full contact between gas molecules and active sites, and further improves the mass transfer and heat transfer processes of 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, etc., the zinc salt can be zinc nitrate, zinc chloride, etc., and the solvent can be ethanol. The concentration of the metal ions in the salt solution is 0.01-0.1 mol/L, and the molar ratio of zinc ions to cobalt ions is 1. The zinc salt can form a metal organic framework compound (MoFs) together with cobalt and an organic ligand in the reaction, the boiling point of zinc is low, the zinc salt can be decomposed and volatilized with C, H in the organic ligand in the later heat treatment process, only Co, C and other elements are left, and the 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 used solvent is ethanol, and the mass ratio of the organic ligand to the total metal is 1. 2-methylimidazole is effective in neutralizing Co 2+ Form bidentate coordination, and the price is low, is favorable to the volume production preparation of sample
(3) The organic ligand solution is added into the metal salt solution, because the reaction process is rapid, a large amount of crystal nuclei can be formed at the moment of contact of the two solutions, and a large amount of heat is released, which is not beneficial to the uniformity of the product and the controllability of the reaction, the two solutions are fully mixed and uniformly dispersed by violent stirring in a low-temperature environment, the nucleation reaction rate of the MoFs is delayed, the low-temperature environment is kept and the violent stirring is carried out for a period of time, the reaction is uniformly and stably carried out, the low-temperature environment can be realized by placing the reaction container in an ice-water bath mode or other modes capable of reducing the temperature, then the reaction container is kept still for aging, the aging time is controlled within the range of 10-15 hours, and the reaction is fully carried out.
(4) 5363 and centrifuging the sample after Chen Huajie bundle, adding ethanol to wash for several times, removing redundant 2-methylimidazole and precursor salt, and blowing and drying at 50-70 ℃.
(5) And flatly spreading the obtained solid powder at the bottom of the crucible, transferring the solid powder to a tubular furnace, introducing inert gas for protection, and carrying out high-temperature calcination decomposition at 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, copper salt can be cupric nitrate, cupric chloride, cupric 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 1.5-5.
(7) Mixing the two solutions, performing ultrasonic treatment to uniformly disperse the two solutions, stirring the two solutions for a period of time, and standing the mixture for 12 to 24 hours to ensure that the Co-N-C porous structure can fully adsorb Cu 2+ And (4) carrying out suction filtration and separation on the ions, and carrying out air blast drying at 50-70 ℃.
(8) Putting 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 and 1.34g of zinc nitrate were weighed and dissolved in 200mL of ethanol. Weighing 3.3g of 2-methylimidazole, and dissolving in 200mL of ethanol; adding an organic ligand solution into a metal salt solution, fully mixing and uniformly dispersing the organic ligand solution by vigorous stirring, keeping an ice water bath and vigorous stirring for a period of time, and then standing and aging for 10 hours; 5363 centrifuging the sample after Chen Huajie, washing with ethanol for several times to remove redundant 2-methylimidazole and precursor salt, and air-drying at 60 deg.C; spreading the obtained solid powder at the bottom of a crucible, transferring the crucible to a tubular furnace, introducing inert gas argon for protection, and carrying out high-temperature calcination decomposition at 900 ℃ to obtain a Co-N-C powder sample; taking Co-N-0.05g of C powder is 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 the two solutions for a period of time, and standing the mixture overnight to ensure that the Co-N-C porous structure can fully adsorb Cu 2+ Separating ions by suction filtration, and drying by blowing at 50 ℃; and putting the obtained solid in a crucible, introducing inert gas for protection, and alloying at the high temperature of 400 ℃ to finally obtain the copper-cobalt alloy catalyst which is marked as CuCoNC-1.
Fig. 1 is an electron microscope scanning result of the sample, and it can be seen from the figure that the particle size of the sample is about 200nm, the size is uniform, no obvious sintering agglomeration phenomenon occurs, and the particles are stacked to form a multi-gap structure, which is beneficial to mass and heat transfer in the catalysis process and promotes the reaction. Fig. 2 is an XRD peak of the sample, and it can be seen that a broad peak at 25.7 ° belongs to a diffraction peak of carbon, while diffraction peaks at 44.4 °, 51.4 °, and 75.9 ° correspond to metallic cobalt, and no obvious diffraction peak of Cu is found, indicating that Cu is highly dispersed in the catalyst and no larger Cu metal nanoparticles are formed.
Subjecting the sample to N 2 Adsorption and desorption tests, 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 showed that the specific surface area of the sample was large (450.6 m) 2 The pore size distribution of the catalyst is concentrated at about 7.5nm, which shows that the catalyst belongs to a mesoporous material, and the existence of mesopores is beneficial to the full contact of gas molecules and active sites and the mass and heat transfer process 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
Weighing 0.24g of cobalt chloride and 0.3g of zinc nitrate, and dissolving in 200mL of ethanol; weighing 2.5g of 2-methylimidazole, and dissolving in 200mL of ethanol; will haveAdding the organic ligand solution into the metal salt solution, fully mixing and uniformly dispersing the organic ligand solution by vigorous stirring, keeping an ice water bath and vigorous stirring for a period of time, and then standing and aging for 12 hours; 5363 centrifuging the sample after Chen Huajie, washing with ethanol for several times, removing excessive 2-methylimidazole and precursor salt, and air-drying at 60 deg.C; spreading the obtained solid powder at the bottom of a crucible, transferring the crucible to a tubular furnace, introducing inert gas argon for protection, and carrying out high-temperature calcination decomposition at 700 ℃ to obtain a Co-N-C powder sample; taking 0.05g of Co-N-C powder, dispersing in 20mL of ethanol solution, weighing 0.1g of copper chloride, and dissolving in 20mL of pure water; mixing the two solutions, performing ultrasonic treatment to uniformly disperse the two solutions, stirring the two solutions for a period of time, and standing the mixture overnight to ensure that the Co-N-C porous structure can fully adsorb Cu 2+ Separating ions by suction filtration, and drying by blowing at 50 ℃; and putting the obtained solid in a crucible, introducing inert gas for protection, and alloying at the 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, stirring vigorously to mix the organic ligand solution and the metal salt solution uniformly, keeping an ice water bath and stirring vigorously for a period of time, and then standing and aging for 15 hours; 5363 centrifuging the sample after Chen Huajie, washing with ethanol for several times, removing excessive 2-methylimidazole and precursor salt, and air-drying at 50 deg.C; flatly paving the obtained solid powder at the bottom of a crucible, transferring the solid powder to a tubular furnace, introducing inert gas argon for protection, and carrying out high-temperature calcination decomposition at 800 ℃ to obtain a Co-N-C powder sample; taking 0.05g of Co-N-C powder, dispersing in 20mL of ethanol solution, weighing 1.0g of copper acetate, and dissolving in 100mL of pure water; mixing the two solutions, performing ultrasonic treatment to uniformly disperse the two solutions, stirring the two solutions for a period of time, and standing the mixture overnight to enable the Co-N-C porous structure to fully adsorb Cu 2+ Separating ions by suction filtration, and drying by blowing at 70 ℃; placing the obtained solid in a crucible, introducing inert gas for protection, and heating at 500 deg.CAnd (4) alloying at high temperature to finally obtain the copper-cobalt alloy catalyst, which is recorded as CuCoNC-3.
Examples 1-3 copper-cobalt metal alloys prepared therein were tested for catalytic activity
The results of the catalytic performance tests on three copper cobalt metal alloy samples prepared in examples 1-3 are shown in table 2.
Table 2 examples 1-3 catalytic activity of copper cobalt alloy catalysts
As can be seen from the table, the catalyst samples prepared by the invention have 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 C2+ OH percentage of the obtained low-carbon alcohol is higher than 77%, and basically no CO is generated 2 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 is loose in texture and has a high specific surface area (>450m 2 The/g) and more concentrated pore size distribution (7.5 nm) are ideal mesoporous materials, and meanwhile, the mesoporous materials have uniform microscopic size, the particle size is about 100-200 nm atmosphere, and no obvious agglomeration phenomenon exists.
Example 5: preparation method of low-carbon alcohol
A method for preparing a lower alcohol, comprising: the copper-cobalt metal catalyst obtained in example 1 was added to a catalytic unit and passed into synthesis gas (CO and H) 2 Mixed gas) at a certain temperature and pressure, maintaining constant temperature and constant pressure, and catalyzing CO dissociation hydrogenation, carbon chain growth, CO non-dissociation insertion and the like by the synergistic action of copper and cobalt active sites in the catalystThe final target product is low-carbon alcohol, and the by-products mainly comprise methane and CO 2 And a trace amount of H 2 O。
The foregoing description of specific exemplary embodiments of the invention has been presented for the 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 certain principles of the invention and its practical application to enable one skilled in the art to make and use various exemplary embodiments of the invention and various alternatives and 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 (10)
1. A highly dispersed copper-cobalt alloy catalyst, which is characterized by comprising a Co-N-C carrier and metallic copper, wherein the metallic copper is loaded on the Co-N-C carrier.
2. The copper-cobalt alloy catalyst according to claim 1, wherein the copper-cobalt alloy catalyst is a mesoporous structure; preferably, the pore diameter of the copper-cobalt alloy catalyst is 5-10 nm.
3. The preparation method of the high-dispersion copper-cobalt alloy catalyst is characterized by comprising the following steps of:
uniformly mixing the Co-N-C solution with the copper salt solution, and standing to obtain Cu 2+ /Co-N-C；
The Cu is added 2+ separating/Co-N-C, drying, and then allowing the Cu to react 2+ And carrying out/Co-N-C alloying to obtain the copper-cobalt alloy catalyst.
4. The method according to claim 3, 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; preferably, the concentration of copper ions in the copper salt solution is 0.01-0.1 mol/L.
5. The preparation method according to claim 3, wherein the standing time is 10 to 16 hours;
and/or the temperature of the alloying is 300-500 ℃.
6. The method according to claim 3, wherein the method for preparing Co-N-C comprises: and adding the organic ligand solution into a metal salt solution, stirring vigorously, standing for aging, and then calcining at high temperature for decomposition to obtain the Co-N-C powder.
7. The production method according to claim 6, wherein the metal salt solution is a mixed solution of a cobalt salt and a zinc salt; preferably, the concentration of the metal ions in the metal salt solution is 0.01-0.1 mol/L; more preferably, the molar ratio of zinc ions to cobalt ions in the metal salt solution is 1;
and/or the organic ligand is 2-methylimidazole; preferably, the mass ratio of the organic ligand to the total metal is 1.
8. The method according to claim 6, wherein the standing aging time is 10 to 15 hours;
and/or the temperature of the high-temperature calcination is 700-900 ℃.
9. Use of a copper-cobalt alloy catalyst according to any one of claims 1 to 2 or obtained by the preparation method according to claims 2 to 8 for preparing a lower alcohol.
10. A method for preparing a lower alcohol, comprising: adding the copper-cobalt alloy catalyst of claim 1 or 2 or the copper-cobalt alloy catalyst prepared by the preparation method of any one of claims 3 to 8 into reactants, and catalyzing to obtain low-carbon alcohol.
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