CN114887625B - Fe-based metal organic framework material derivative catalyst and preparation method and application thereof - Google Patents
Fe-based metal organic framework material derivative catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- 239000013082 iron-based metal-organic framework Substances 0.000 title claims abstract description 73
- 239000000463 material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 136
- 238000011068 loading method Methods 0.000 claims abstract description 29
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 27
- 229910001428 transition metal ion Inorganic materials 0.000 claims abstract description 24
- 238000003763 carbonization Methods 0.000 claims abstract description 20
- 150000002500 ions Chemical class 0.000 claims abstract description 18
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims description 41
- 238000001035 drying Methods 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 18
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- 229910002651 NO3 Inorganic materials 0.000 claims description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 8
- 238000010000 carbonizing Methods 0.000 claims description 8
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 9
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 8
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 37
- 238000005470 impregnation Methods 0.000 description 29
- 239000011734 sodium Substances 0.000 description 26
- 230000003197 catalytic effect Effects 0.000 description 20
- 239000007789 gas Substances 0.000 description 18
- 239000007864 aqueous solution Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 14
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 12
- 238000003756 stirring Methods 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000012298 atmosphere Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 229910052786 argon Inorganic materials 0.000 description 8
- 239000012621 metal-organic framework Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- 229910052723 transition metal Inorganic materials 0.000 description 8
- 150000003624 transition metals Chemical class 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910003321 CoFe Inorganic materials 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000011049 filling Methods 0.000 description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000004913 activation Effects 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000012495 reaction gas Substances 0.000 description 5
- 238000007873 sieving Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000006004 Quartz sand Substances 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000002803 fossil fuel Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- 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 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- 229910017752 Cu-Zn Inorganic materials 0.000 description 1
- 229910017943 Cu—Zn Inorganic materials 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- BLJNPOIVYYWHMA-UHFFFAOYSA-N alumane;cobalt Chemical compound [AlH3].[Co] BLJNPOIVYYWHMA-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- PFWOQOGCSSAGBU-UHFFFAOYSA-N ethanol;octane Chemical compound CCO.CCCCCCCC PFWOQOGCSSAGBU-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 230000009466 transformation Effects 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of chemical catalysis, and particularly relates to a Fe-based metal organic framework material derivative catalyst, and a preparation method and application thereof. The catalyst provided by the invention is prepared by sequentially carrying out transition metal ion loading, carbonization and Na ion loading on an Fe-based metal organic framework material; the transition metal ions include one or more of Co ions, mn ions, zn ions, and Cu ions. The invention obtains the catalyst applicable to CO by combining Fe-MOFs with different metal active components 2 High-performance catalyst for preparing ethanol by catalytic hydrogenation, which has simple preparation and low cost and can realize CO 2 One-step catalytic hydrogenation to synthesize ethanol with high selectivity. The invention opens up a new CO 2 The catalytic reaction path for preparing ethanol by hydrogenation has higher economic value and social benefit.
Description
Technical Field
The invention belongs to the technical field of chemical catalysis, and particularly relates to a Fe-based metal organic framework material derivative catalyst, and a preparation method and application thereof.
Background
Energy production in modern society typically uses fossil fuels that are stored in the crust for a long period of time in the form of coal, oil, and gas, and maintain natural carbon circulation in nature. With the increase of world population and shortage of fossil fuel, carbon circulation changes and CO in the atmosphere are caused 2 Increasing concentration, etc. Before humans had revolutionized the industry, carbon emissions and CO from the earth 2 The gas is stored in dynamic balance, but with the consumption of energy and CO 2 The increase in gas emissions results in an inherent imbalance in carbon balance. At the same time, a series of problems of resource shortage, global climate change and the like are caused, and the diversity of organisms around the earth and the sustainable development of human beings are seriously influenced. Global year CO 2014 2 The emissions were 39250 metric tons, with fossil fuel emissions accounting for about 91% of human emissions.
The environmental problems we are facing at present include resource shortage and ecological destruction problems, whereas CO 2 The method has rich carbon resources, is also a source of a plurality of chemical raw materials and is cheap and easy to obtain. If hydrogen (H) can be electrolytically generated by means of alternative energy sources 2 ) CO is processed by 2 The catalytic conversion into high value-added chemicals has important significance for relieving global warming, improving ecological environment and solving the problem of increasingly exhausted fossil resources. CO at present 2 Is in the preliminary stage by addingSynthesis of C by hydrogen reaction 2+ Hydrocarbons, particularly higher octane ethanol, are of increasing research interest.
Ethanol can be mixed with water and most organic compounds, is also an important chemical and clean energy, and has a wide application prospect. Such as: the fuel can replace fossil fuels such as gasoline and the like, and the energy structure is improved; can be used as oxygen increasing agent for fuel oxidation, and can improve oxygen content in combustion process, and reduce CO and CH x Discharging the gas pollutants; can be used as a reaction raw material for synthesizing basic chemicals such as low-carbon olefin, aromatic hydrocarbon and the like. In the early days, ethanol can only be synthesized by a fermentation method, and is mainly obtained by taking saccharides and starch as raw materials through fermentation, and the method has long time consumption and low efficiency. The ethylene hydration method is synthesized by taking petroleum-cracked ethylene as a raw material, but along with the reduction of fossil energy sources, the process flow is not suitable for large-scale application, and meanwhile, the methods of coal chemical industry, direct ethanol preparation by synthesis gas and the like have higher cost. CO 2 Catalytic conversion of ethanol is considered to be one of the most promising ways at present, and not only can reduce CO in the atmosphere 2 The concentration of the carbon-rich alloy can also relieve the problems of unbalanced carbon balance, global warming effect and the like, and has wide application prospect. In addition, aiming at the high emission of CO of the current refinery, coal-fired power plant and the like 2 Energy conservation and emission reduction dilemma faced by units, and CO taking hydrogen-rich tail gas produced by refineries as hydrogen source 2 The hydrogenation technology for synthesizing ethanol is a feasible route economically and has more important environmental and strategic significance.
The ethanol has the advantages of high heat value, capability of being directly added into gasoline to improve the performance and quality of oil products, and the like, and the low-carbon alcohol prepared by CO2 catalytic hydrogenation is CO 2 One of the effective ways of transformation and utilization. Compared with the synthesis of CH 4 CO, meOH, requires a catalyst with a bimetallic active site to accomplish C-C chain growth and CO 2 Partially reduced CO 2 The process of preparing ethanol by catalytic hydrogenation is more challenging. From a thermodynamic point of view, due to CO 2 The catalytic hydrogenation to ethanol is an exothermic reaction with reduced gas molecules, so that the high pressure and low temperature are generally favorable for forward progress of the reaction, while CO 2 Activation of the molecule needs to be carried out at a relatively high temperature, so proper reactionThe conditions are important.
Over the past few years, CO 2 The catalytic conversion into ethanol is mainly homogeneous phase catalysis, and the homogeneous phase catalyst which takes noble metal as an active center and is combined with an organic ligand can efficiently activate CO 2 Molecules and high selectivity to ethanol. However, the high sensitivity of homogeneous catalysts to air makes the catalysts less stable and the expensive organic ligands limit their use in industry. In recent years, researchers have developed heterogeneous catalysts of transition metals to address the shortcomings of homogeneous catalysts. Mn-Fe-Cd-Cu catalyst was developed by Kyowa Chemical in 1942 and used for CO 2 The catalytic conversion system successfully prepares ethanol, propanol and butanol. Tatsumi et al report an alkali modified Mo/SiO 2 Catalytic conversion of CO by a catalyst 2 Synthesizing C1-C5 higher alcohol. Cu/Zn/ZrO modified with Fe by Guo et al 2 The catalyst is used in a catalytic hydrogenation reaction system, and aims to examine the influence of the structure and the reaction performance of the catalyst. When the Fe doping amount is 6%, C 2+ The space-time yield of alcohol reaches a maximum [0.24 g/(mL. H)]. Shore harvest subject group non-noble metal type cobalt aluminum hydrotalcite catalyst (CoAlO) prepared by hydrothermal synthesis method x ) Optimizing CoAlO at different pre-reduction temperatures x Catalyst, co as metal active center proved to be high-efficiency CO 2 Molecular and highly selective ethanol formation. Li et al prepared a K/Cu-Zn catalyst with a high dispersion of the active ingredient and studied the catalyst in CO 2 Hydrogenation for preparing C 2+ Catalytic performance in alcohol reaction System, CO on the catalyst 2 The optimal condition for preparing ethanol by hydrogenation is 350K,6.0MPa,5000 ml.h -1 And H 2 /CO 2 =3.0, under this condition the selectivity of CO and ethanol reached 84.27wt% and 7.56wt%.
In summary, different catalysts are selected to realize CO through different catalytic networks 2 The ethanol is prepared by catalytic conversion, however, the ethanol yield is low, the research on the reaction mechanism is not deep enough, and the actual catalytic network is not clear. Therefore, the reaction mechanism is studied deeply to construct a novel CO 2 Catalytic network for preparing ethanol by hydrogenation, and simultaneously taking ethanol selectivity and CO into consideration 2 TransformationThe method has the advantages of obtaining excellent single pass yield of the ethanol and realizing CO at present 2 The development trend of industrial application of ethanol production by hydroconversion is also a bottleneck which is urgently needed to break through.
Disclosure of Invention
Accordingly, the present invention is directed to provide a catalyst derived from Fe-based metal organic framework material, and a preparation method and application thereof, wherein the catalyst derived from Fe-based metal organic framework material can be used as CO 2 Catalyst in hydrogenation ethanol preparation reaction and has higher CO 2 Conversion and ethanol selectivity.
The invention provides an Fe-based metal organic framework material derivative catalyst which is prepared by sequentially carrying out transition metal ion loading, carbonization and Na ion loading on an Fe-based metal organic framework material;
the transition metal ions include one or more of Co ions, mn ions, zn ions, and Cu ions.
In the catalyst provided by the present invention, the source of the Fe-based metal organic framework material (Fe-MOFs) is not particularly limited, and may be generally commercially available or prepared according to a method well known to those skilled in the art, and the present invention is preferably prepared according to the following method:
mixing an iron source compound and terephthalic acid in a liquid medium, and heating for reaction to obtain the Fe-based metal organic framework material.
In the preparation method of the Fe-MOFs provided by the invention, the iron source compound is preferably FeCl 3 ·6H 2 O; the molar ratio of Fe in the iron source compound to terephthalic acid is preferably 3: (4-6), more preferably 3:5; the liquid medium is preferably N, N-Dimethylformamide (DMF).
In the above preparation method of Fe-MOFs provided by the present invention, the specific mixing process preferably includes: the solution of terephthalic acid was added dropwise to the solution of the iron source compound under stirring.
In the preparation method of the Fe-MOFs provided by the invention, the heating mode of the reaction is preferably hydrothermal; the temperature of the reaction is preferably 80 to 180 ℃, more preferably 110 ℃; the reaction time is preferably 24 to 48 hours, more preferably 36 hours.
In the above-mentioned Fe-MOFs production method provided by the present invention, after the heating reaction is completed, the obtained reaction product is preferably centrifugally washed and dried. Wherein the temperature of the drying is preferably 60-100 ℃, more preferably 60 ℃; the drying time is preferably 6 to 24 hours, more preferably 24 hours.
In the catalyst provided by the invention, the transition metal ions are preferably loaded by a solution impregnation mode, and the solution used for impregnation is a solution containing a transition metal source compound, preferably an aqueous solution containing the transition metal source compound; the transition metal source compound is preferably a nitrate of a transition metal, including but not limited to Cu (NO) 3 ) 2 ·3H 2 O、Mn(NO 3 ) 2 ·4H 2 O、Zn(NO 3 ) 2 ·6H 2 O and Co (NO) 3 ) 2 ·6H 2 One or more of O; the aqueous solution preferably further contains ethanol, and the ethanol is preferably used in an amount of 5-70 wt%, more preferably 20wt%, based on the total mass of water and ethanol; the impregnation mode is preferably equal volume impregnation; the temperature of the impregnation is preferably 15 to 35 ℃, more preferably 25 ℃ (room temperature). In the invention, after the impregnation is finished, the drying is also needed; the drying mode is preferably drying; the temperature of the drying is preferably 60-100 ℃, more preferably 60 ℃; the drying time is preferably 6 to 24 hours, more preferably 24 hours.
In the catalyst provided by the invention, the loading of the transition metal ions is preferably 0.1-20 wt%, and specifically can be 0.1wt%, 0.5wt%, 1wt%, 2wt%, 5wt%, 7wt%, 10wt%, 12wt%, 15wt%, 17wt% or 20wt%, wherein the loading refers to the percentage mass of the transition metal ions loaded to the whole catalyst. In the present invention, the loading amount of the transition metal ion can be adjusted by adjusting the amount of the transition metal source compound used in the impregnation of the solution.
In the catalyst provided by the invention, the carbonization temperature is preferably 500-800 ℃, more preferably 550 ℃; the carbonization time is preferably 1 to 6 hours, more preferably 3 hours; the carbonization is preferably carried out in a protective gas atmosphere; the shielding gas is preferably nitrogen.
In the catalyst provided by the invention, the Na ions are preferably loaded by a solution impregnation mode, and the solution used for impregnation is a solution containing a Na source compound, preferably an aqueous solution containing the Na source compound; the Na source compound is preferably sodium carbonate; the aqueous solution preferably further contains ethanol, and the ethanol is preferably used in an amount of 5-70 wt%, more preferably 20wt%, based on the total mass of water and ethanol; the impregnation mode is preferably equal volume impregnation; the temperature of the impregnation is preferably 15 to 35 ℃, more preferably 25 ℃ (room temperature). In the invention, after the impregnation is finished, the drying is also needed; the drying mode is preferably drying; the temperature of the drying is preferably 60-100 ℃, more preferably 60 ℃; the drying time is preferably 6 to 24 hours, more preferably 24 hours.
In the catalyst provided by the invention, the loading of the Na ions is preferably 0.1-5 wt%, and specifically can be 0.1wt%, 0.5wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt%, 3.5wt%, 4wt%, 4.5wt% or 5wt%, wherein the loading refers to the percentage mass of the loaded Na ions in the whole catalyst. In the present invention, the Na ion loading can be adjusted by adjusting the amount of Na source compound used in the impregnation of the solution.
In the catalyst provided by the present invention, the particle diameter of the catalyst is preferably 10 to 100 mesh, more preferably 20 to 40 mesh.
The invention also provides a preparation method of the Fe-based metal organic framework material derivative catalyst, which comprises the following steps:
a) Dipping the Fe-based metal organic framework material in a transition metal ion solution, drying, carbonizing to obtain a carbonized Fe-based metal organic framework material loaded with transition metal ions;
b) And immersing the carbonized Fe-based metal organic framework material loaded with the transition metal ions in Na ion solution, and drying to obtain the Fe-based metal organic framework material derivative catalyst.
In the preparation method provided by the present invention, in the step a), the source of the Fe-based metal organic framework material (Fe-MOFs) is not particularly limited, and may be generally commercially available or prepared according to a method well known to those skilled in the art, preferably prepared according to the method described above in the present invention, and will not be described herein.
In the preparation method provided by the invention, in the step a), the transition metal ion solution is a solution containing a transition metal source compound, preferably an aqueous solution containing a transition metal source compound, more preferably an aqueous nitrate solution of transition metal ions, wherein the nitrate comprises but is not limited to Cu (NO) 3 ) 2 ·3H 2 O、Mn(NO 3 ) 2 ·4H 2 O、Zn(NO 3 ) 2 ·6H 2 O and Co (NO) 3 ) 2 ·6H 2 One or more of O; the aqueous solution preferably further contains ethanol, and the amount of ethanol is preferably 5 to 70wt%, more preferably 20wt%, based on the total mass of water and ethanol.
In the preparation method provided by the invention, in the step a), the impregnation mode is preferably equal volume impregnation; the temperature of the impregnation is preferably 15 to 35 ℃, more preferably 25 ℃ (room temperature).
In the preparation method provided by the invention, in the step a), the drying mode is preferably drying; the temperature of the drying is preferably 60-100 ℃, more preferably 60 ℃; the drying time is preferably 6 to 24 hours, more preferably 24 hours.
In the preparation method provided by the invention, in the step a), the carbonization temperature is preferably 500-800 ℃, more preferably 550 ℃; the carbonization time is preferably 1 to 6 hours, more preferably 3 hours; the carbonization is preferably carried out in a protective gas atmosphere; the shielding gas is preferably nitrogen.
In the preparation method provided by the invention, in the step b), the Na ion solution is a solution containing a Na source compound, preferably an aqueous solution containing the Na source compound; the Na source compound is preferably sodium carbonate; the aqueous solution preferably further contains ethanol, and the amount of ethanol is preferably 5 to 70wt%, more preferably 20wt%, based on the total mass of water and ethanol.
In the preparation method provided by the invention, in the step b), the impregnation mode is preferably equal volume impregnation; the temperature of the impregnation is preferably 15 to 35 ℃, more preferably 25 ℃ (room temperature).
In the preparation method provided by the invention, in the step b), the drying mode is preferably drying; the temperature of the drying is preferably 60-100 ℃, more preferably 60 ℃; the drying time is preferably 6 to 24 hours, more preferably 24 hours.
In the preparation method provided by the invention, the method preferably further comprises the steps of crushing and granulating the Fe-based metal organic framework material derived catalyst obtained after drying to obtain a catalyst product with the required particle size.
The invention also provides a CO 2 The method for directly synthesizing ethanol by hydrogenation comprises the following steps:
in the presence of a catalyst, CO 2 And H 2 Mixing and reacting to obtain ethanol;
the catalyst is the Fe-based metal organic framework material derivative catalyst according to the technical scheme or the Fe-based metal organic framework material derivative catalyst prepared by the preparation method according to the technical scheme.
In the ethanol synthesis method provided by the invention, the catalyst is preferably subjected to H before use 2 Reduction treatment and activation; the H is 2 The reduction treatment activation is preferably carried out in a fixed bed reactor; the H is 2 The temperature of the reduction treatment activation is preferably 200 to 400 ℃, more preferably 400 ℃; the H is 2 The time for the activation of the reduction treatment is preferably 1 to 6 hours, more preferably 4 hours; the H is 2 Reduction treatment of activated H 2 The flow rate is preferably 10 to 200mL/min, more preferably 60mL/min.
In the ethanol synthesis method provided by the invention, the CO 2 And H 2 Preferably 1: (2-5), more preferably 1:3.8.
In the ethanol synthesis method provided by the invention, the mixing reaction is preferably carried out in the presence of Ar and CO; ar preferably accounts for Ar, CO and CO 2 And H 2 2-8% by volume of the mixed gas, more preferably 5%; the CO preferably accounts for Ar, CO and CO 2 And H 2 The volume of the mixed gas is 2 to 8%, more preferably 5%.
In the ethanol synthesis method provided by the invention, the mixed reaction is preferably performed in a fixed bed reactor; the temperature of the mixing reaction is preferably 300-400 ℃, more preferably 320 ℃; the pressure of the mixing reaction is preferably 3 to 8MPa, more preferably 5MPa.
Compared with the prior art, the invention provides a Fe-based metal organic framework material derived catalyst, and a preparation method and application thereof. The invention obtains the catalyst applicable to CO by combining Fe-MOFs with different metal active components 2 High-performance catalyst for preparing ethanol by catalytic hydrogenation, which has simple preparation and low cost and can realize CO 2 One-step catalytic hydrogenation to synthesize ethanol with high selectivity. The experimental results show that: the Fe-based metal organic framework material derivative catalyst provided by the invention is used in CO 2 In the performance test of preparing ethanol by hydrogenation, CO 2 The highest conversion rate reaches 48.9%, the highest ethanol selectivity reaches 20.8%, and the highest CO conversion rate reaches 79.3%, so that the catalyst can efficiently catalyze CO 2 Hydrogenation reaction and conversion to ethanol, which is a high value-added chemical, and the conversion rate of CO, which is a main byproduct, is high. The technical proposal provided by the invention opens up a new CO 2 The catalytic reaction path for preparing ethanol by hydrogenation has higher economic value and social benefit.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
1) Sequentially loading Fe-based metal organic framework materials (Fe-MOFs) with Zn source nitrate (Zn (NO) 3 ) 2 ·6H 2 O), carbonization and loading Na 2 CO 3 2% Na-ZnFe@C catalyst is obtained, and the specific preparation process is as follows:
2.703g FeCl 2 .6H 2 O (3 mmol) was dissolved in 30mL DMF and stirred for 30min to prepare solution A; 0.83g of terephthalic acid (5 mmol) was dissolved in 30mL of DMF to prepare solution B; dropwise adding the solution B into the solution A under stirring, stirring for 30min, transferring into a 100mL hydrothermal kettle, and hydrothermal treating at 110 ℃ for 36h; after natural cooling, centrifugally separating the product, washing the product with water and ethanol for 3 times respectively, and then drying the product in a vacuum oven at 80 ℃ for 12 hours to obtain Fe-MOFs;
0.247g Zn (NO) 3 ) 2 ·6H 2 O (0.83 mmol) is taken as a Zn source, is dissolved in 1.5g of aqueous solution (containing 0.3g of ethanol), is subjected to isovolumetric impregnation on 1.2g of Fe-MOFs, and is dried in a vacuum oven at 60 ℃ overnight to obtain Fe-based metal organic framework material (ZnFe-MOFs) loaded with Zn ions;
and carbonizing the obtained ZnFe-MOFs in a tube furnace under the nitrogen atmosphere, wherein the carbonization temperature is controlled to be 550 ℃, and the time is 3 hours. Naturally cooling to room temperature to obtain carbonized Fe-based metal organic framework material (ZnFe@C) loaded with Zn ions;
0.023g of Na 2 CO 3 (0.22 mmol) was a Na source, dissolved in 1.25g of an aqueous solution (containing 0.25g of ethanol), 0.5g of ZnFe@C was subjected to isovolumetric impregnation, and dried overnight at 60℃in a vacuum oven to give a 2% Na-ZnFe@C catalyst wherein the loading of Zn was 10wt% and the loading of Na was 2wt%.
2) 2% Na-ZnFe@C as catalyst for catalyzing CO 2 The hydrogenation reaction comprises the following specific experimental processes:
tabletting 2% Na-ZnFe@C catalyst under 20MPa, crushing, sieving and granulating, wherein the particle size is 20-40 meshes;
weighing 0.1g of granulated 2% Na-ZnFe@C and 1g of quartz sand, fully mixing, filling into a fixed bed reactor (with the inner diameter of 6 mm), and firstly, filling into a reactor at 400 ℃ H 2 Reducing for 4h, H under atmosphere 2 The flow rate is 60mL/min; the temperature was then reduced to 320℃at the reaction temperature, and the gas was switched to the reaction gas (5% Ar, 5% CO, 18.74% CO) 2 、71.26％H 2 ) And at back pressureThe reaction was started after the pressure was raised to the target pressure (5 MPa) by the valve. Specific catalytic CO 2 The hydrogenation reaction results are shown in Table 1 below:
TABLE 1 catalytic CO of example 1 2 Hydrogenation reaction results
Others a : propanol, butanol, and the like.
Comparative example 1
1) Sequentially carbonizing Fe-based metal organic framework materials (Fe-MOFs) and loading Na 2 CO 3 2% of Na-Fe@C catalyst is obtained, and the specific preparation process is as follows:
2.703g FeCl 2 .6H 2 O (3 mmol) was dissolved in 30mL DMF and stirred for 30min to prepare solution A; 0.83g of terephthalic acid (5 mmol) was dissolved in 30mL of DMF to prepare solution B; dropwise adding the solution B into the solution A under stirring, stirring for 30min, transferring into a 100mL hydrothermal kettle, and hydrothermal treating at 110 ℃ for 36h; after natural cooling, centrifugally separating the product, washing the product with water and ethanol for 3 times respectively, and then drying the product in a vacuum oven at 80 ℃ for 12 hours to obtain Fe-MOFs;
and carbonizing the Fe-MOFs in a tube furnace under the nitrogen atmosphere, wherein the carbonization temperature is controlled to be 550 ℃, and the carbonization time is 3 hours. Naturally cooling to room temperature to obtain carbonized Fe-based metal organic framework material (Fe@C);
0.023g of Na 2 CO 3 (0.22 mmol) as Na source, dissolved in 1.25g of aqueous solution (containing 0.25g of ethanol), 0.5g of Fe@C was subjected to isovolumetric impregnation and dried overnight in a vacuum oven at 60℃to give 2% Na-Fe@C catalyst.
2) 2% Na-Fe@C as catalyst for catalyzing CO 2 The hydrogenation reaction comprises the following specific experimental processes:
tabletting 2% Na-Fe@C catalyst under 20MPa, crushing, sieving and granulating, wherein the particle size is 20-40 meshes;
weighing 0.1g of granulated 2% Na-Fe@C and 1g of quartz sand, fully mixing, and filling into a fixed bed reactor (with an inner diameter of 6 mm)First at 400 ℃ H 2 Reducing for 4h, H under atmosphere 2 The flow rate is 60mL/min; the temperature was then reduced to 320℃at the reaction temperature, and the gas was switched to the reaction gas (5% Ar, 5% CO, 18.74% CO) 2 、71.26％H 2 ) And the reaction was started after the pressure was raised to the target pressure (5 MPa) by the back pressure valve. Specific catalytic CO 2 The hydrogenation reaction results are shown in Table 2 below:
table 2 catalytic CO of comparative example 1 2 Hydrogenation reaction results
Others a : propanol, butanol, and the like.
Example 2
1) Sequentially loading Cu source nitrate (Cu (NO) into Fe-based metal organic frameworks (Fe-MOFs) 3 ) 2 ·3H 2 O), carbonization and loading Na 2 CO 3 The 2% Na-CuFe@C catalyst is obtained, and the specific preparation process is as follows:
2.703g FeCl 2 .6H 2 O (3 mmol) was dissolved in 30mL DMF and stirred for 30min to prepare solution A; 0.83g of terephthalic acid (5 mmol) was dissolved in 30mL of DMF to prepare solution B; dropwise adding the solution B into the solution A under stirring, stirring for 30min, transferring into a 100mL hydrothermal kettle, and hydrothermal treating at 110 ℃ for 36h; after natural cooling, centrifugally separating the product, washing the product with water and ethanol for 3 times respectively, and then drying the product in a vacuum oven at 80 ℃ for 12 hours to obtain Fe-MOFs;
0.200g Cu (NO) 3 ) 2 ·3H 2 O (0.83 mmol) is used as a Cu source, is dissolved in 1.5g of aqueous solution (containing 0.3g of ethanol), is subjected to isovolumetric impregnation on 1.2g of Fe-MOFs, and is dried in a vacuum oven at 60 ℃ overnight to obtain Fe-based metal organic framework materials (CuFe-MOFs) loaded with Cu ions;
and carbonizing the obtained CuFe-MOFs in a tube furnace under the nitrogen atmosphere, wherein the carbonization temperature is controlled to be 550 ℃, and the time is 3 hours. Naturally cooling to room temperature to obtain carbonized Fe-based metal organic framework material (CuFe@C) loaded with Cu ions;
0.023g of Na 2 CO 3 (0.22 mmol) was a Na source, dissolved in 1.25g of an aqueous solution (containing 0.25g of ethanol), subjected to isovolumetric impregnation with 0.5g of CuFe@C, and dried overnight at 60℃in a vacuum oven to give a 2% Na-CuFe@C catalyst having a Cu loading of 10wt% and a Na loading of 2wt%.
2) 2% Na-CuFe@C as catalyst for catalyzing CO 2 The hydrogenation reaction comprises the following specific experimental processes:
tabletting 2% Na-CuFe@C catalyst under 20MPa, crushing, sieving and granulating, wherein the particle size is 20-40 meshes;
weighing 0.1g of granulated 2% Na-CuFe@C and 1g of quartz sand, fully mixing, filling into a fixed bed reactor (with the inner diameter of 6 mm), and firstly, filling into a reactor at 400 ℃ H 2 Reducing for 4h, H under atmosphere 2 The flow rate is 60mL/min; the temperature was then reduced to 320℃at the reaction temperature, and the gas was switched to the reaction gas (5% Ar, 5% CO, 18.74% CO) 2 、71.26％H 2 ) And the reaction was started after the pressure was raised to the target pressure (5 MPa) by the back pressure valve. Specific catalytic CO 2 The hydrogenation reaction results are shown in Table 3 below:
TABLE 3 catalytic CO of example 2 2 Hydrogenation reaction results
Others a : propanol, butanol, and the like.
Example 3
1) Sequentially loading Co source nitrate (Co (NO) into Fe-based metal organic frameworks (Fe-MOFs) 3 ) 2 ·6H 2 O), carbonization and loading Na 2 CO 3 2% of Na-CoFe@C catalyst was obtained, and the specific preparation process was as follows:
2.703g FeCl 2 .6H 2 O (3 mmol) was dissolved in 30mL DMF and stirred for 30min to prepare solution A; 0.83g of terephthalic acid (5 mmol) was dissolved in 30mL of DMF to prepare solution B; dropwise adding the solution B into the solution A under stirring, stirring for 30min, transferring into a 100mL hydrothermal kettle, and hydrothermal treating at 110 ℃ for 36h; natural natureAfter cooling, centrifugally separating the product, washing the product with water and ethanol for 3 times respectively, and then drying the product in a vacuum oven at 80 ℃ for 12 hours to obtain Fe-MOFs;
0.242g Co (NO) 3 ) 2 ·6H 2 O (0.83 mmol) is used as a Co source, is dissolved in 1.5g of aqueous solution (containing 0.3g of ethanol), is subjected to isovolumetric impregnation on 1.2g of Fe-MOFs, and is dried in a vacuum oven at 60 ℃ overnight to obtain Fe-based metal organic framework material (CoFe-MOFs) loaded with Co ions;
the obtained CoFe-MOFs were carbonized in a tube furnace under nitrogen atmosphere at 550℃for 3 hours. Naturally cooling to room temperature to obtain a carbonized Fe-based metal organic framework material (CoFe@C) loaded with Co ions;
0.023g of Na 2 CO 3 (0.22 mmol) was a Na source, dissolved in 1.25g of an aqueous solution (containing 0.25g of ethanol), and after isovolumetric impregnation of 0.5g of CoFe@C and drying overnight at 60℃in a vacuum oven, a 2% Na-CoFe@C catalyst was obtained, wherein the Co loading was 10wt% and the Na loading was 2wt%.
2) 2% Na-CoFe@C as catalyst for catalyzing CO 2 The hydrogenation reaction comprises the following specific experimental processes:
tabletting 2% Na-CoFe@C catalyst under 20MPa, crushing, sieving and granulating, wherein the particle size is 20-40 meshes;
weighing 0.1g of granulated 2% Na-CoFe@C and 1g of quartz sand, fully mixing, filling into a fixed bed reactor (with an inner diameter of 6 mm), and firstly carrying out H at 400 DEG C 2 Reducing for 4h, H under atmosphere 2 The flow rate is 60mL/min; the temperature was then reduced to 320℃at the reaction temperature, and the gas was switched to the reaction gas (5% Ar, 5% CO, 18.74% CO) 2 、71.26％H 2 ) And the reaction was started after the pressure was raised to the target pressure (5 MPa) by the back pressure valve. Specific catalytic CO 2 The hydrogenation reaction results are shown in Table 4 below:
TABLE 4 catalytic CO of example 3 2 Hydrogenation reaction results
Others a : propanol, butanol, and the like.
Example 4
1) Sequentially loading Mn source nitrate (Mn (NO) into Fe-based metal organic frameworks (Fe-MOFs) 3 ) 2 ·4H 2 O), carbonization and loading Na 2 CO 3 2% of Na-MnFe@C catalyst is obtained, and the specific preparation process is as follows:
2.703g FeCl 2 .6H 2 O (3 mmol) was dissolved in 30mL DMF and stirred for 30min to prepare solution A; 0.83g of terephthalic acid (5 mmol) was dissolved in 30mL of DMF to prepare solution B; dropwise adding the solution B into the solution A under stirring, stirring for 30min, transferring into a 100mL hydrothermal kettle, and hydrothermal treating at 110 ℃ for 36h; after natural cooling, centrifugally separating the product, washing the product with water and ethanol for 3 times respectively, and then drying the product in a vacuum oven at 80 ℃ for 12 hours to obtain Fe-MOFs;
0.208g Mn (NO) 3 ) 2 ·4H 2 O (0.83 mmol) is taken as Mn source, dissolved in 1.5g of aqueous solution (containing 0.3g of ethanol), and 1.2g of Fe-MOFs are subjected to isovolumetric impregnation and dried overnight at 60 ℃ in a vacuum oven, so that Fe-based metal organic framework material (MnFe-MOFs) loaded with Mn ions is obtained;
and carbonizing the obtained MnFe-MOFs in a tube furnace under the nitrogen atmosphere, wherein the carbonization temperature is controlled to be 550 ℃, and the carbonization time is 3 hours. Naturally cooling to room temperature to obtain carbonized Fe-based metal organic framework material (MnFe@C) loaded with Mn ions;
0.023g of Na 2 CO 3 (0.22 mmol) was a Na source, dissolved in 1.25g of an aqueous solution (containing 0.25g of ethanol), and after isovolumetric impregnation of 0.5g of MnFe@C and drying overnight at 60℃in a vacuum oven, a 2% Na-MnFe@C catalyst was obtained, wherein the loading of Mn was 10wt% and the loading of Na was 2wt%.
2) 2% Na-MnFe@C as catalyst for catalyzing CO 2 The hydrogenation reaction comprises the following specific experimental processes:
tabletting 2% of Na-MnFe@C catalyst under 20MPa, crushing, sieving and granulating, wherein the particle size is 20-40 meshes;
weighing 0.1g of granulated 2% Na-MnFe@C and 1g of quartz sandAfter thorough mixing, the mixture was packed in a fixed bed reactor (inner diameter: 6 mm), and was first subjected to H at 400 ℃ 2 Reducing for 4h, H under atmosphere 2 The flow rate is 60mL/min; the temperature was then reduced to 320℃at the reaction temperature, and the gas was switched to the reaction gas (5% Ar, 5% CO, 18.74% CO) 2 、71.26％H 2 ) And the reaction was started after the pressure was raised to the target pressure (5 MPa) by the back pressure valve. Specific catalytic CO 2 The hydrogenation reaction results are shown in Table 5 below:
TABLE 5 catalytic CO of example 4 2 Hydrogenation reaction results
Others a : propanol, butanol, and the like.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (8)
1. Fe-based metal organic framework material derived catalyst as CO 2 The application of the catalyst for directly synthesizing ethanol by hydrogenation is characterized in that the catalyst for deriving Fe-based metal organic framework material is prepared by the following steps:
a) Dipping the Fe-based metal organic framework material in a transition metal ion solution, drying, carbonizing to obtain a carbonized Fe-based metal organic framework material loaded with transition metal ions;
the transition metal ions are Zn ions;
b) And immersing the carbonized Fe-based metal organic framework material loaded with the transition metal ions in Na ion solution, and drying to obtain the Fe-based metal organic framework material derivative catalyst.
2. The use according to claim 1, wherein the loading of the transition metal ions is 0.1-20 wt%.
3. The use according to claim 1, wherein the Na ion loading is 0.1-5 wt%.
4. The use according to claim 1, wherein in step a) the transition metal ion solution is an aqueous nitrate solution of transition metal ions.
5. The use according to claim 1, wherein in step a) the carbonization temperature is 500-800 ℃; and the carbonization time is 1-6 hours.
6. The use according to claim 1, wherein in step a) the Fe-based metal organic framework material is prepared according to the following method:
mixing an iron source compound and terephthalic acid in a liquid medium, and heating for reaction to obtain the Fe-based metal organic framework material.
7. CO (carbon monoxide) 2 The method for directly synthesizing ethanol by hydrogenation comprises the following steps:
in the presence of a catalyst, CO 2 And H 2 Mixing and reacting to obtain ethanol;
the catalyst is an Fe-based metal organic framework material derivative catalyst, and the Fe-based metal organic framework material derivative catalyst is prepared according to the following steps:
a) Dipping the Fe-based metal organic framework material in a transition metal ion solution, drying, carbonizing to obtain a carbonized Fe-based metal organic framework material loaded with transition metal ions;
the transition metal ions are Zn ions;
b) And immersing the carbonized Fe-based metal organic framework material loaded with the transition metal ions in Na ion solution, and drying to obtain the Fe-based metal organic framework material derivative catalyst.
8. The method of claim 7, wherein the temperature of the mixing reaction is 300-400 ℃; the pressure intensity of the mixing reaction is 3-8 MPa.
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