CN114522708B - Preparation method of porous aza-carbon material supported cobalt-based catalyst and application of porous aza-carbon material supported cobalt-based catalyst in CO hydrogenation reaction for preparing high-carbon alcohol - Google Patents
Preparation method of porous aza-carbon material supported cobalt-based catalyst and application of porous aza-carbon material supported cobalt-based catalyst in CO hydrogenation reaction for preparing high-carbon alcohol Download PDFInfo
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- CN114522708B CN114522708B CN202011321221.0A CN202011321221A CN114522708B CN 114522708 B CN114522708 B CN 114522708B CN 202011321221 A CN202011321221 A CN 202011321221A CN 114522708 B CN114522708 B CN 114522708B
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- methanol
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- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 26
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 26
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 19
- 239000010941 cobalt Substances 0.000 title claims abstract description 18
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 7
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims abstract description 130
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims abstract description 89
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 17
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 9
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 156
- 239000000243 solution Substances 0.000 claims description 81
- 239000007789 gas Substances 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 21
- 230000015572 biosynthetic process Effects 0.000 claims description 20
- 238000003786 synthesis reaction Methods 0.000 claims description 20
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 19
- 239000000725 suspension Substances 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 16
- 238000009210 therapy by ultrasound Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 150000001868 cobalt Chemical class 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 150000003751 zinc Chemical class 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 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
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- MVNQJLFBHVHULX-UHFFFAOYSA-L cobalt(2+);2-hydroxybutanedioate Chemical compound [Co+2].[O-]C(=O)C(O)CC([O-])=O MVNQJLFBHVHULX-UHFFFAOYSA-L 0.000 claims description 2
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims description 2
- SCNCIXKLOBXDQB-UHFFFAOYSA-K cobalt(3+);2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Co+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O SCNCIXKLOBXDQB-UHFFFAOYSA-K 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
- PFQLIVQUKOIJJD-UHFFFAOYSA-L cobalt(ii) formate Chemical compound [Co+2].[O-]C=O.[O-]C=O PFQLIVQUKOIJJD-UHFFFAOYSA-L 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 1
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 238000000197 pyrolysis Methods 0.000 abstract description 24
- 238000011065 in-situ storage Methods 0.000 abstract description 18
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 239000002243 precursor Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 239000010453 quartz Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 239000011701 zinc Substances 0.000 description 12
- 239000002244 precipitate Substances 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 8
- 229910018669 Mn—Co Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 229910017816 Cu—Co Inorganic materials 0.000 description 4
- 229910007966 Li-Co Inorganic materials 0.000 description 4
- 229910008295 Li—Co Inorganic materials 0.000 description 4
- 229910017313 Mo—Co Inorganic materials 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 150000003138 primary alcohols Chemical class 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- CRHLEZORXKQUEI-UHFFFAOYSA-N dialuminum;cobalt(2+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Co+2].[Co+2] CRHLEZORXKQUEI-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- JBFYUZGYRGXSFL-UHFFFAOYSA-N imidazolide Chemical compound C1=C[N-]C=N1 JBFYUZGYRGXSFL-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a preparation method of a porous aza-carbon material supported cobalt-based catalyst and application thereof in a reaction of preparing high-carbon alcohol by CO hydrogenation. The catalyst takes Co as an active center and takes Mn, cu, mo, ca, li and the like as auxiliary agents for doping. The catalyst is prepared by taking ZIF-8@ZIF-67 as a precursor as a template and carrying out pyrolysis on an isovolumetric impregnated metal auxiliary agent. Cobalt content is 20-50wt% and auxiliary agent content is 1-10wt%; the catalyst metal Co particles prepared by pyrolysis are more uniformly distributed, the load is high, an auxiliary agent exists on the surface of the material, the reduction rate is high, co2C is generated in situ in the reaction process, the catalyst has excellent catalytic performance, the catalyst activity is high, the selectivity of generating high-carbon alcohol by CO hydrogenation is high, and the stability is good.
Description
Technical Field
The invention relates to a technology for catalytic conversion of synthesis gas, and belongs to the field of energy and chemical industry. In particular to a catalyst for preparing mixed primary alcohol and liquid hydrocarbon by catalytic conversion of synthesis gas and a preparation method thereof. More specifically, relates to an auxiliary agent-cobalt@nitrogen doped carbon catalyst taking ZIF material as precursor, wherein the active component is Co 2 C and metal Co.
Background
The hydrogenation of carbon monoxide to produce clean fuels and high value-added chemicals is an effective method to replace petroleum-based routes, receiving a great deal of attention in recent years. The mixed primary alcohol comprises C 2 -C 5 Lower alcohols of (C) 5+ The higher alcohols of (2) have wide application, are important raw materials in chemical industry and pharmaceutical industry, and can be used as a plasticizer emulsifier of a detergent, etc.
Metal ions (e.g. Zn 2+ 、Co 2+ ) And organic ligands (imidazoles) can construct Zeolite Imidazolate Frameworks (ZIFs) with three-dimensional porous structures through coordination bonds. ZIFs have high porosity and surface area, and adjustable pore sizeThe catalyst has the advantages of chemical stability, chemical modification according to target requirements, abundant structure, high thermal stability and the like, and is widely applied to the fields of gas storage separation, photoelectrocatalysis and the like. ZIFs show great potential for CO adsorption separation. The preparation of high-activity high-selectivity carbon monoxide hydrogenation catalyst by carbonization pyrolysis with ZIFs as precursors has more design possibility than the traditional isovolumetric impregnation method and coprecipitation method. Of these, zinc-containing ZIF-8 and cobalt-containing ZIF-67 are two typical ZIFs materials, except for metal ions (Zn 2+ Or Co 2+ ) In addition, both have the same topology, similar unit cell parameters and the same organic ligands, and both have rich carbon and nitrogen content and high metal ion duty cycle. The ZIF-8@ZIF-67 material prepared by the method has relatively low preparation cost and good performance.
The aza-carbon cobalt-loaded catalyst prepared by pyrolysis of the zeolite imidazole skeleton has the characteristics that:
(1) The in-situ pyrolysis generates a carbon-nitrogen carrier, so that the metal Co is more uniformly distributed, more uniform in size and better in dispersity, and the migration and aggregation of the metal Co are inhibited due to the blocking of N and C after the coordination in the ZIF precursor is pyrolyzed, and the Co aggregation is further inhibited by the sublimation of Zn in the ZIF-8.
(2) The mass content of cobalt on the material is high and can reach about 30-50%;
(3) The catalyst after pyrolysis mainly exists in stable metal Co, and is self-reduced in pyrolysis, so that CO hydrogenation reaction can be directly carried out
(4) Co in the reaction is promoted by adding an auxiliary agent into the precursor 2 And C is generated in situ, so that CO non-dissociative adsorption is promoted, and the generation of mixed primary alcohol is promoted.
Patent CN105582970B reports a catalyst of low carbon mixed alcohol using synthesis gas as raw material and its preparation method. The carrier of the catalyst is SiO 2 Or Al 2 O 3 The active component is Co 2 C and metal Co, and the auxiliary agent is one or more of Ca, li, na, pt and Cu. Is prepared by an isovolumetric impregnation method, but the generation of cobalt aluminate spinel and silicon aluminum spinel is reduced due to the strong interaction between metal and carrierThe degree of reduction of the catalyst is low and further improvements are still needed.
Patent CN105582970B reports a catalyst for preparing low-carbon mixed alcohol and liquid hydrocarbon by catalytic conversion of synthesis gas and a preparation method thereof, and Co@Co prepared by pyrolysis carbonization is prepared by taking Co-MOF-71 as a sacrificial template and ethyl orthosilicate as a silicon source 2 And C, the catalyst adopts an organic metal framework structure to form nano composite particles, the distribution of alcohol is narrow, and the space-time yield of the alcohol is good. The acting force of the oxide as a carrier is improved, but the deactivated catalyst is difficult to reuse and is carbonized to generate Co 2 The catalytic activity is reduced by extremely easy carbon deposition in the process C, so that improvement is still needed.
Disclosure of Invention
The invention provides a preparation method of an auxiliary agent-cobalt@nitrogen doped carbon catalyst and application of the auxiliary agent-cobalt@nitrogen doped carbon catalyst in hydrogenation of carbon monoxide to generate high-value-added high-carbon alcohol.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the preparation method of the auxiliary agent-cobalt@nitrogen doped carbon catalyst comprises the following steps:
(1) Preparing ZIF-8@ZIF-67, namely growing ZIF-67 on the surface of the ZIF-8 by taking the ZIF-8 as a kernel to obtain ZIF-8@ZIF-67;
(2) Preparing an auxiliary agent-ZIF-8@ZIF-67, and loading auxiliary agent metal M, which comprises one or more than two of Mn, cu, mo, ca, li, on the ZIF-8@ZIF-67 by an isovolumetric impregnation method to obtain an auxiliary agent modified M-ZIF-8@ZIF-67;
(3) Calcining the auxiliary agent-ZIF-8@ZIF-67 under the protection of inert atmosphere gas to obtain an auxiliary agent-Co@PCN;
according to the invention, an auxiliary agent-ZIF-8@ZIF-67 with an auxiliary agent-doped core-shell structure is calcined, nitrogen-doped carbon generated by pyrolysis carbonization of the ZIF-67 serves as a hollow skeleton of a nano structure, zinc element in the ZIF-8 reacts to form a Zn simple substance and evaporates along with a shielding gas, agglomeration of Co nano particles is inhibited, and then the auxiliary agent-containing Co-loaded nitrogen-doped carbon catalyst (auxiliary agent-Co@PCN) is obtained. The preparation method is simple, the elements in the obtained material are uniformly distributed, the active center Co is self-reduced, the dispersity is high, and the load is high.
Preferably, step (1) is specifically as follows:
1) First, ZIF-8 was prepared: and respectively dissolving the soluble zinc salt and the 2-methylimidazole in the methanol and ethanol equal volume solutions to obtain a first solution and a second solution. Rapidly adding the second solution into the first solution, carrying out ultrasonic treatment, stirring, centrifugal separation, washing and drying to obtain ZIF-8 crystals;
2) Subsequently, ZIF-8@ZIF-67 was prepared: and dispersing the dried ZIF-8 in methanol to obtain a ZIF-8 suspension. Dissolving soluble cobalt salt and 2-methylimidazole in the same volume of solution such as methanol and ethanol respectively to obtain solution three and solution four, mixing the solution three and the solution four, rapidly adding into ZIF-8 suspension, standing by ultrasound, centrifuging, separating, washing, and drying to obtain ZIF-8@ZIF-67.
Further preferably, in step 1), the soluble zinc salt comprises one or more of zinc nitrate, zinc sulfate or zinc acetate; the mole ratio of the soluble zinc salt to the 2-methylimidazole is 1:2-5; after the solution II is rapidly added into the solution I, the ultrasonic treatment is carried out for 0.5 to 1 hour, the stirring time is 20 to 40 hours, the centrifugal speed is 7000 to 13000r/min, the solution II is washed by methanol for 3 to 5 times, and the drying temperature is 50 to 100 ℃; in the step 2), the soluble cobalt salt comprises one or more than two of cobalt formate, cobalt acetate, cobalt nitrate, cobalt oxalate, cobalt sulfate, cobalt citrate and cobalt malate; ZIF-8, soluble cobalt salt and 2-methylimidazole in an amount of 0.5g:0.03-0.05mol:0.1 to 0.25mol; adding the solution IV into the mixed solution, performing ultrasonic treatment for 0.5-2h, standing for 20-40h, centrifuging at 7000-13000r/min, washing with methanol for 3-5 times, and drying at 50-100deg.C.
Preferably, step (2) is specifically as follows: grinding the dried ZIF-8@ZIF-67 crystal into powder, dissolving auxiliary salt in a mixed solution of methanol and water, soaking the ZIF-8@ZIF-67 in an equal volume, and drying to obtain the auxiliary-ZIF-8@ZIF-67.
Further preferred is a process for the preparation of a promoter-cobalt @ nitrogen doped carbon catalyst, characterized in that the promoter metal comprises Mn, cu, mo, ca, li and the soluble promoter salt comprises one or more of formate, acetate, nitrate, chloride, sulfate, citrate; the proportion of the methanol and water mixed solution is 1:1-2; ZIF-8@ZIF-67 and a soluble auxiliary salt in an amount ratio of 1g:0.001-0.02mol; the drying temperature is 50-100 ℃.
Preferably, step (3) is specifically as follows: calcining the auxiliary agent-ZIF-8@ZIF-67 for 1-3 hours at 600-1000 ℃ by taking argon, nitrogen or helium as a shielding gas; cooling the calcined material to obtain an auxiliary agent-Co@PCN; the temperature rising rate before calcination is not more than 5 ℃/min.
The auxiliary agent-cobalt@nitrogen doped carbon catalyst prepared by the preparation method is applied to the hydrogenation of CO to generate mixed primary alcohol.
The catalyst is applied to preparing high-carbon alcohol by taking synthesis gas as raw material and is characterized in that H in the synthesis gas 2 The volume ratio of the catalyst to CO is 1-3, the reaction temperature is 200-300 ℃, the reaction pressure is 1-5MPa, and the total space velocity of the reaction is 20-60L/h/g-catalyst.
The catalyst metal Co particles prepared by pyrolysis are more uniformly distributed, the load is high, an auxiliary agent exists on the surface of the material, the reduction rate is high, and Co is generated in situ in the reaction process 2 And C, the catalyst has excellent catalytic performance, high catalyst activity, high selectivity of high-carbon alcohol generated by CO hydrogenation and good stability.
The beneficial effects of the invention are as follows: the invention promotes in-situ Co by adding metal auxiliary agent 2 C is generated, and a ZIF structure is designed, and partial space limiting effect is still reserved after pyrolysis, so that better catalytic performance, stability and high-carbon alcohol selectivity are achieved in the hydrogenation reaction of carbon monoxide.
Detailed Description
The invention is further illustrated by the following examples, but is not limited to the examples listed.
Example 1
1. Preparation of ZIF-8 Zn (NO 3 ) 2 ·6H 2 O (5.95 g,0.02 mol) and 2-methylimidazole (6.16 g,0.075 mol) were dissolved in 150mL of an equal volume mixed solution of methanol and ethanol, respectively, to give a solution I and a solution II; then rapidly adding the second solution into the first solution, carrying out ultrasonic treatment for 30min, stirring for 24 hours at room temperature, centrifuging the white suspension at high speed (10000 r/min) and washing with MeOH for 3 times, and drying at 60 ℃ to obtain ZIF-8 crystals.
2. PreparationZIF-8@ZIF-67 ZIF-8 (0.5 g) was dispersed in 100mL of an equal volume of methanol and ethanol to form a white ZIF-8 suspension; co (NO) 3 ) 2 ·6H 2 O (5.82 g,0.02 mol) and 2-methylimidazole (6.16 g,0.075 mol) were dissolved in 100mL of equal volume solutions of methanol and ethanol, respectively, to give solution three and solution four; then adding the solution III into the ZIF-8 suspension rapidly to obtain a mixed solution; and rapidly adding the solution IV into the mixed solution, carrying out ultrasonic treatment for 1h, standing for 24h, centrifuging the light purple precipitate at high speed (10000 r/min), washing the precipitate with MeOH for several times, and drying the precipitate at 60 ℃ to obtain the ZIF-8@ZIF-67.
3. Preparation of Mn-ZIF-8@ZIF-67, mnC 4 H 6 O 4 ·4H 2 O (0.49 g, 0.002mol) is dissolved in 2g of methanol and 2g of aqueous solution, 2g of ZIF-8@ZIF-67 is immersed in the solution in equal volume, and the solution is dried at 100 ℃ to obtain Mn-ZIF-8@ZIF-67.
4. Mn-Co@PCN is prepared by placing 2g of Mn-ZIF-8@ZIF-67 in a quartz tube, passing through a tube furnace, and heating to 600 ℃ at a heating rate of 5 ℃/min in Ar atmosphere for in-situ pyrolysis for 2 hours to obtain Mn-Co@PCN.
The catalyst was used for the synthesis of gas (H) at a pressure of 3MPa, a temperature of 270℃and a space velocity of 30L/H/g-catalyst 2 The CO hydrogenation reaction was carried out with a CO volume ratio of 1) and the results are shown in Table 1 below.
Example 2
1. Preparation of ZIF-8 Zn (NO 3 ) 2 ·6H 2 O (5.95 g,0.02 mol) and 2-methylimidazole (8.21 g,0.1 mol) were dissolved in 200mL of an equal volume of methanol and ethanol, respectively, to give a first solution and a second solution; then rapidly adding the second solution into the first solution, carrying out ultrasonic treatment for 1h, stirring for 25h at room temperature, centrifuging the white suspension at high speed (10000 r/min) and washing with methanol for 3 times, and drying at 100 ℃ to obtain ZIF-8 crystals.
2. ZIF-8@ZIF-67 was prepared, and ZIF-8 (1.0 g) was dispersed in 150mL of an equal volume of methanol and ethanol to form a white ZIF-8 suspension; co (NO) 3 ) 2 ·6H 2 O (5.82 g,0.02 mol) and 2-methylimidazole (8.21 g,0.01 mol) were dissolved in 150mL of an equal volume solution of methanol and ethanol, respectively, to give a solution III and a solution IV; the solution III was then added rapidlyAdding into ZIF-8 suspension to obtain mixed solution; and rapidly adding the solution IV into the mixed solution, carrying out ultrasonic treatment for 2 hours, standing for 24 hours, centrifuging the light purple precipitate at high speed (10000 r/min), washing for 4 times by using methanol, and drying at 100 ℃ to obtain the ZIF-8@ZIF-67.
3. Preparation of Mn-ZIF-8@ZIF-67, mn (NO 3 ) 2 ·4H 2 O (0.5 g, 0.002mol) is dissolved in 2g of methanol and 2g of aqueous solution, 2g of ZIF-8@ZIF-67 is immersed in the solution in equal volume, and the solution is dried at 100 ℃ to obtain Mn-ZIF-8@ZIF-67.
4. Mn-Co@PCN is prepared by placing 2g of Mn-ZIF-8@ZIF-67 in a quartz tube, passing through a tube furnace, and heating to 700 ℃ at a heating rate of 5 ℃/min in Ar atmosphere for in-situ pyrolysis for 3 hours to obtain Mn-Co@PCN.
The catalyst was used for the synthesis of gas (H) at a pressure of 3MPa, a temperature of 300℃and a space velocity of 50L/H/g-catalyst 2 The CO hydrogenation reaction was carried out with a CO volume ratio of 3), and the results are shown in Table 1 below.
Example 3
1. Preparation of ZIF-8 Zn (NO 3 ) 2 ·6H 2 O (5.95 g,0.02 mol) and 2-methylimidazole (8.21 g,0.1 mol) were dissolved in 200mL of an equal volume of methanol and ethanol, respectively, to give a first solution and a second solution; then rapidly adding the second solution into the first solution, carrying out ultrasonic treatment for 0.5h, stirring for 30h at room temperature, centrifuging the white suspension at high speed (11000 r/min) and washing with methanol for 4 times, and drying at 80 ℃ to obtain ZIF-8 crystals.
2. ZIF-8@ZIF-67 was prepared, and ZIF-8 (1.0 g) was dispersed in 150mL of an equal volume of methanol and ethanol to form a white ZIF-8 suspension; co (NO) 3 ) 2 ·6H 2 O (5.82 g,0.02 mol) and 2-methylimidazole (8.21 g,0.1 mol) were dissolved in 150mL of an equal volume solution of methanol and ethanol, respectively, to give a solution III and a solution IV; then adding the solution III into the ZIF-8 suspension rapidly to obtain a mixed solution; and rapidly adding the solution IV into the mixed solution, carrying out ultrasonic treatment for 1.5h, standing for 24h, centrifuging the light purple precipitate at high speed (12000 r/min), washing with methanol for 4 times, and drying at 100 ℃ to obtain the ZIF-8@ZIF-67.
3. Preparation of Cu-ZIF-8@ZIF-67, cu (NO 3 ) 2 (0.38g，0002 mol) was dissolved in 2g of methanol and 2g of an aqueous solution, and 2g of ZIF-8@ZIF-67 was immersed in an equal volume and dried at 100℃to obtain Cu-ZIF-8@ZIF-67.
4. Preparation of Cu-Co@PCN 2g of Cu-ZIF-8@ZIF-67 were placed in a quartz tube through a tube furnace at N 2 Heating to 900 ℃ at a heating rate of 3 ℃/min in the atmosphere, and carrying out in-situ pyrolysis for 1h to obtain the Cu-Co@PCN.
The catalyst was used for the synthesis of gas (H) at a pressure of 3MPa, a temperature of 280℃and a space velocity of 40L/H/g-catalyst 2 The CO hydrogenation reaction was carried out with a CO volume ratio of 3), and the results are shown in Table 1 below.
Example 4
1. Preparation of ZIF-8 Zn (NO 3 ) 2 ·6H 2 O (5.95 g,0.02 mol) and 2-methylimidazole (6.16 g,0.075 mol) were dissolved in 150mL of equal volume solution of methanol and ethanol, respectively, to give solution I and solution II; then rapidly adding the second solution into the first solution, carrying out ultrasonic treatment for 1h, stirring for 15h at room temperature, centrifuging the white suspension at high speed (9000 r/min) and washing with methanol for 5 times, and drying at 100 ℃ to obtain ZIF-8 crystals.
2. ZIF-8@ZIF-67 was prepared, and ZIF-8 (0.5 g) was dispersed in 100mL of an equal volume of methanol and ethanol to form a white ZIF-8 suspension; co (NO) 3 ) 2 ·6H 2 O (5.82 g,0.02 mol) and 2-methylimidazole (8.21 g,0.1 mol) were dissolved in 150mL of an equal volume solution of methanol and ethanol, respectively, to give a solution III and a solution IV; then adding the solution III into the ZIF-8 suspension rapidly to obtain a mixed solution; and rapidly adding the solution IV into the mixed solution, carrying out ultrasonic treatment for 2 hours, standing for 24 hours, centrifuging the light purple precipitate at high speed (8000 r/min), washing for 4 times by using methanol, and drying at 100 ℃ to obtain the ZIF-8@ZIF-67.
3. Preparation of Cu-ZIF-8@ZIF-67, cuSO 4 (0.61 g, 0.004mol) is dissolved in 2g of methanol and 2g of water solution, and 2g of ZIF-8@ZIF-67 is immersed in the solution in an equal volume and dried at 100 ℃ to obtain the Cu-ZIF-8@ZIF-67.
4. Preparing Cu-Co@PCN, placing 2g of Cu-ZIF-8@ZIF-67 in a quartz tube, passing through a tube furnace, heating to 800 ℃ in the He atmosphere at the heating rate of 4 ℃/min, and carrying out in-situ pyrolysis for 2 hours to obtain the Cu-Co@PCN.
The catalyst was used for the synthesis of gas (H) at a pressure of 3MPa, a temperature of 300℃and a space velocity of 20L/H/g-catalyst 2 The CO hydrogenation reaction was carried out with a CO volume ratio of 2) and the results are shown in Table 1 below.
Example 5
1. ZIF-8@ZIF-67 was prepared in the same manner as in example 1.
2. Preparation of Mo-ZIF-8@ZIF-67, mo (NO 3 ) 3 ·5H 2 O (0.89 g, 0.002mol) is dissolved in 2g of methanol and 2g of aqueous solution, 2g of ZIF-8@ZIF-67 is immersed in the solution in equal volume, and the solution is dried at 100 ℃ to obtain the Mo-ZIF-8@ZIF-67.
3. Mo-Co@PCN is prepared by placing 2g of Mo-ZIF-8@ZIF-67 in a quartz tube, passing through a tube furnace, heating to 800 ℃ at a heating rate of 4 ℃/min in He atmosphere, and carrying out in-situ pyrolysis for 2 hours to obtain the Mo-Co@PCN.
The catalyst was used for the synthesis of gas (H) at a pressure of 3MPa, a temperature of 300℃and a space velocity of 20L/H/g-catalyst 2 The CO hydrogenation reaction was carried out with a CO volume ratio of 2) and the results are shown in Table 1 below.
Example 6
1. ZIF-8@ZIF-67 was prepared in the same manner as in example 2.
2. Preparation of Mo-ZIF-8@ZIF-67, moCl 5 (1.092 g, 0.004mol) was dissolved in 2g of methanol and 2g of an aqueous solution, and 2g of ZIF-8@ZIF-67 was immersed in the solution at an equal volume and dried at 100℃to obtain Mo-ZIF-8@ZIF-67.
3. Preparation of Mo-Co@PCN 2g of Mo-ZIF-8@ZIF-67 were placed in a quartz tube through a tube furnace at N 2 And heating to 700 ℃ at a heating rate of 4 ℃/min in the atmosphere, and carrying out in-situ pyrolysis for 3.5h to obtain the Mo-Co@PCN.
The catalyst was used for the synthesis of gas (H) at a pressure of 3MPa, a temperature of 280℃and a space velocity of 40L/H/g-catalyst 2 The CO hydrogenation reaction was carried out with a CO volume ratio of 1) and the results are shown in Table 1 below.
Example 7
1. ZIF-8@ZIF-67 was prepared in the same manner as in example 3.
2. Preparation of Ca-ZIF-8@ZIF-67, caSO 4 (0.41 g, 0.003mol) is dissolved in 2g of methanol and 2g of aqueous solution, 2g of ZIF-8@ZIF-67 is immersed in the solution in equal volume, and the solution is dried at 100 ℃ to obtain the Ca-ZIF-8@ZIF-67.
3. Ca-Co@PCN is prepared by placing 2g of Ca-ZIF-8@ZIF-67 in a quartz tube, passing through a tube furnace, heating to 800 ℃ at a heating rate of 4 ℃/min in Ar atmosphere, and carrying out in-situ pyrolysis for 2 hours to obtain the Ca-Co@PCN.
The catalyst was used for the synthesis of gas (H) at a pressure of 3MPa, a temperature of 300℃and a space velocity of 40L/H/g-catalyst 2 The CO hydrogenation reaction was carried out with a CO volume ratio of 3), and the results are shown in Table 1 below.
The catalyst was used for the synthesis of gas (H) at a pressure of 3MPa, a temperature of 300℃and a space velocity of 40L/H/g-catalyst 2 The CO hydrogenation reaction was carried out with a CO volume ratio of 2) and the results are shown in Table 1 below.
Example 8
1. ZIF-8@ZIF-67 was prepared in the same manner as in example 4.
2. Preparation of Ca-ZIF-8@ZIF-67, caCl 2 (0.44 g,0.004 mol) is dissolved in 2g of methanol and 2g of water solution, 2g of ZIF-8@ZIF-67 is immersed in the solution in equal volume, and the solution is dried at 100 ℃ to obtain the Cu-ZIF-8@ZIF-67.
3. Ca-Co@PCN is prepared by placing 2g of Ca-ZIF-8@ZIF-67 in a quartz tube, passing through a tube furnace, heating to 800 ℃ at a heating rate of 4 ℃/min in Ar atmosphere, and carrying out in-situ pyrolysis for 2 hours to obtain the Ca-Co@PCN.
The catalyst was used for the synthesis of gas (H) at a pressure of 3MPa, a temperature of 280℃and a space velocity of 30L/H/g-catalyst 2 The CO hydrogenation reaction was carried out with a CO volume ratio of 2) and the results are shown in Table 1 below.
Example 9
1. ZIF-8@ZIF-67 was prepared in the same manner as in example 1.
2. Li-ZIF-8@ZIF-67 was prepared by dissolving LiCl (0.17 g,0.004 mol) in 2g of methanol and 2g of an aqueous solution, immersing 2g of ZIF-8@ZIF-67 in an equal volume, and drying at 100℃to obtain Li-ZIF-8@ZIF-67.
3. Li-Co@PCN is prepared by placing 2g of Li-ZIF-8@ZIF-67 in a quartz tube, passing through a tube furnace, and heating to 600 ℃ at a heating rate of 3 ℃/min in Ar atmosphere for in-situ pyrolysis for 3 hours to obtain the Li-Co@PCN.
The catalyst was used for the synthesis of gas (H) at a pressure of 3MPa, a temperature of 300℃and a space velocity of 30L/H/g-catalyst 2 With CO in a volume ratio of 3), the result of the CO hydrogenation reaction is shown in Table 1 below。
Example 10
1. ZIF-8@ZIF-67 was prepared in the same manner as in example 2.
2. Preparation of Li-ZIF-8@ZIF-67 LiC 2 H 4 O 2 (0.26 g, 0.004mol) is dissolved in 2g of methanol and 2g of water solution, and 2g of ZIF-8@ZIF-67 is immersed in the solution in an equal volume and dried at 100 ℃ to obtain the Cu-ZIF-8@ZIF-67.
3. Preparation of Li-Co@PCN, 2g of Li-ZIF-8@ZIF-67 was placed in a quartz tube and passed through a tube furnace at N 2 Heating to 800 ℃ at a heating rate of 3.5 ℃/min in the atmosphere, and carrying out in-situ pyrolysis for 2 hours to obtain the Li-Co@PCN.
The catalyst was used for the synthesis of gas (H) at a pressure of 3MPa, a temperature of 280℃and a space velocity of 40L/H/g-catalyst 2 The CO hydrogenation reaction was carried out with a CO volume ratio of 1) and the results are shown in Table 1 below.
Comparative example 1
1. Preparation of ZIF-8 Zn (NO 3 ) 2 ·6H 2 O (5.95 g,0.02 mol) and 2-methylimidazole (6.16 g,0.075 mol) were dissolved in 150mL of methanol (MeOH) to give a first solution and a second solution, respectively; then adding the solution II into the solution I rapidly, stirring for 24 hours at room temperature, centrifuging the white suspension at high speed (10000 r/min) and washing with MeOH for several times, and vacuum drying at 60 ℃ to obtain ZIF-8 crystals.
2. Preparation of ZIF-8@ZIF-67: ZIF-8 (0.5 g) was dispersed in 100mL MeOH to form a white ZIF-8 suspension; co (NO) 3 ) 2 ·6H 2 O (5.82 g,0.02 mol) and 2-methylimidazole (6.16 g,0.075 mol) were dissolved in 100mL MeOH, respectively, to give solution three and solution four; then adding the solution III into the ZIF-8 suspension rapidly to obtain a mixed solution; and then adding the solution IV into the mixed solution rapidly, mixing and stirring for 24 hours at room temperature, centrifuging the light purple precipitate at high speed (10000 r/min), washing the precipitate with MeOH for a plurality of times, and drying the precipitate in vacuum at 60 ℃ to obtain the ZIF-8@ZIF-67.
3. Preparation of Co@PCN, placing 2.0g of ZIF-8@ZIF-67 in a quartz tube, passing through a tube furnace, heating to 800 ℃ at a heating rate of 5 ℃/min in Ar atmosphere, and carrying out in-situ pyrolysis for 2 hours to obtain the Co@PCN.
The catalyst is pressedSynthesis gas (H) with a force of 3MPa, a temperature of 270℃and a space velocity of 35L/H/g-catalyst 2 The CO hydrogenation reaction was carried out with a CO volume ratio of 2) and the results are shown in Table 1 below.
Comparative example 2
1. Preparing ZIF-67; co (NO) 3 ) 2 ·6H 2 O (5.82 g,0.02 mol) and 2-methylimidazole (6.16 g,0.075 mol) were dissolved in 100mL MeOH, respectively, to give solutions one and two; then the solution I was added to the solution II rapidly, and after mixing and stirring for 24 hours at room temperature, the purple precipitate was centrifuged at high speed (10000 r/min) and washed several times with MeOH and dried at 100℃to give ZIF-67.
3. Preparation of Mn-ZIF-67, mnC 4 H 6 O 4 ·4H 2 O (0.49 g, 0.002mol) was dissolved in 2g of methanol and 2g of aqueous solution, and 2g of ZIF-67 was immersed in the solution in equal volume and dried at 100℃to obtain Mn-ZIF-67.
4. Mn-Co@CN was prepared by placing 2.0g of Mn-ZIF-67 in a quartz tube, passing through a tube furnace, and heating to 700℃at a heating rate of 5℃per minute in an Ar atmosphere, and performing in-situ pyrolysis for 3 hours to obtain Mn-Co@CN.
The catalyst was used for the synthesis of gas (H) at a pressure of 3MPa, a temperature of 250℃and a space velocity of 35L/H/g-catalyst 2 The CO hydrogenation reaction was carried out with a CO volume ratio of 2) and the results are shown in Table 1 below.
Table 1 catalyst CO hydrogenation performance evaluation and product analysis.
From the physicochemical properties and catalytic properties of the catalysts in Table 1, it can be seen that: the method can be used for preparing the porous nitrogen-doped carbon-loaded metal cobalt and auxiliary agent nanoparticle catalyst, has excellent catalytic performance, and compared with the Co@PCN catalyst without the auxiliary agent, the M-Co@PCN catalyst has higher CO conversion rate and synthesizes C 2 + The selectivity of the higher alcohols is higher. The addition of the auxiliary agent has high reducibility and activity, and Co is generated in situ in the reaction process 2 C, promote C 2 + And (3) generating high-carbon alcohol. And ZIF-67 is adopted as the materialThe prepared M-Co@CN catalyst also has higher CO conversion rate and higher synthetic C compared with the M-Co@PCN catalyst 2 + Selectivity to higher alcohols. The method is mainly characterized in that Co nano particles are not easy to aggregate and sublimate due to the ZIFs framework structure and sublimation in the pyrolysis process of metal Zn in ZIF-8, and cobalt metal nano particles on the catalyst are uniformly distributed and have good dispersity.
Claims (4)
1. The application of a porous aza-carbon material supported cobalt-based catalyst in catalyzing CO hydrogenation to synthesize high-carbon alcohol is characterized in that the preparation method of the catalyst comprises the following steps:
(1) Taking ZIF-8 as an inner core, coating the outer surface of the ZIF-8 with ZIF-67, and preparing the ZIF-8@ZIF-67;
(2) Loading auxiliary metal M on ZIF-8@ZIF-67 by an isovolumetric impregnation method, wherein M is one or more than two selected from Mn, cu, mo, ca, li, so as to obtain auxiliary modified M-ZIF-8@ZIF-67;
(3) Calcining the auxiliary agent modified M-ZIF-8@ZIF-67 in the presence of inert atmosphere gas to obtain a porous aza-carbon material supported cobalt-based catalyst M-Co@PCN;
the specific preparation method of the ZIF-8@ZIF-67 in the step (1) is as follows:
1) Preparation of ZIF-8: dissolving soluble zinc salt and 2-methylimidazole in a solution of methanol and ethanol which are mixed in equal volume, carrying out ultrasonic treatment, stirring, centrifugal separation, washing and drying to obtain ZIF-8 crystals;
the soluble zinc salt is selected from one or more of zinc nitrate, zinc sulfate or zinc acetate; the mole ratio of the soluble zinc salt to the 2-methylimidazole is 1:2-5;
2) Preparation of ZIF-8@ZIF-67: dispersing the dried ZIF-8 in a solution of methanol and ethanol which are mixed in equal volume, and carrying out ultrasonic treatment to obtain ZIF-8 suspension; respectively dissolving soluble cobalt salt and 2-methylimidazole in a mixed solution with equal volume of methanol and ethanol, then adding the mixed solution into ZIF-8 suspension, carrying out ultrasonic standing, carrying out centrifugal separation, washing and drying to obtain ZIF-8@ZIF-67;
the soluble cobalt salt is selected from one or more of cobalt formate, cobalt acetate, cobalt nitrate, cobalt oxalate, cobalt sulfate, cobalt citrate and cobalt malate, and the dosage ratio of ZIF-8, soluble cobalt salt and 2-methylimidazole is 0.5g:0.03-0.05mol:0.1 to 0.25mol;
the preparation method of the M-ZIF-8@ZIF-67 in the step (2) comprises the following steps: grinding the dried ZIF-8@ZIF-67 crystal into powder, dissolving auxiliary salt in a mixed solution of methanol and water, soaking the ZIF-8@ZIF-67 in an equal volume, and drying to obtain M-ZIF-8@ZIF-67; the dosage ratio of ZIF-8@ZIF-67 to the soluble auxiliary salt is 1g:0.001-0.02mol;
the step (3) is specifically as follows: calcining the auxiliary agent modified M-ZIF-8@ZIF-67 at 600-1000 ℃ by taking argon, nitrogen or helium as inert atmosphere gas, wherein the inert atmosphere gas comprises 1-3 h; and cooling the calcined material to obtain the M-Co@PCN.
2. Use according to claim 1, characterized in that the ultrasound is 0.5-2h, the stirring time is 20-40h, the centrifugation speed is 7000-13000r/min, the washing is 3-5 times with methanol, and the drying temperature is 50-100 ℃.
3. The use according to claim 1, wherein the promoter metal M is selected from one or more of Mn, cu, mo, ca, li, and the soluble promoter salt is selected from one or more of formate, acetate, nitrate, chloride, sulfate, citrate of the metal M; the mass ratio of the methanol to the water in the mixed solution is 1:1-2; the drying temperature is 50-100 ℃.
4. The use according to claim 1, characterized in that: the catalyst is applied to preparing high-carbon alcohol by taking synthesis gas as raw material, and H in the synthesis gas 2 The volume ratio of the catalyst to CO is 1-3, the reaction temperature is 200-300 ℃, the reaction pressure is 1-5MPa, and the total space velocity of the reaction is 20-60L/h/g-catalyst.
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