CN114887625A - Fe-based metal organic framework material derived catalyst and preparation method and application thereof - Google Patents
Fe-based metal organic framework material derived 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 69
- 239000000463 material Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 138
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 28
- 238000011068 loading method Methods 0.000 claims abstract description 25
- 229910001428 transition metal ion Inorganic materials 0.000 claims abstract description 21
- 150000002500 ions Chemical class 0.000 claims abstract description 19
- 238000003763 carbonization Methods 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 47
- 238000001035 drying Methods 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 19
- 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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 13
- 238000010000 carbonizing Methods 0.000 claims description 9
- 238000007598 dipping method Methods 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims 1
- 238000009795 derivation Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 9
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 39
- 239000007789 gas Substances 0.000 description 22
- 239000011734 sodium Substances 0.000 description 22
- 230000003197 catalytic effect Effects 0.000 description 20
- 239000007864 aqueous solution Substances 0.000 description 17
- 238000005470 impregnation Methods 0.000 description 16
- 238000003756 stirring Methods 0.000 description 16
- 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
- 239000002245 particle Substances 0.000 description 12
- 230000009467 reduction Effects 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000001816 cooling Methods 0.000 description 10
- 239000012621 metal-organic framework Substances 0.000 description 9
- 229910052786 argon Inorganic materials 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 229910052723 transition metal Inorganic materials 0.000 description 8
- 150000003624 transition metals Chemical class 0.000 description 8
- 229910003321 CoFe Inorganic materials 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000006004 Quartz sand Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000009471 action Effects 0.000 description 5
- 230000004913 activation Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000010335 hydrothermal treatment Methods 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 238000007873 sieving Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 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
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 241000282414 Homo sapiens Species 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002815 homogeneous catalyst Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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
- 238000004177 carbon cycle Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005034 decoration Methods 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
- 239000003502 gasoline Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000013384 organic framework Substances 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910000029 sodium carbonate 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
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 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
- 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
- 229910052802 copper Inorganic materials 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
- 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
- -1 ethanol Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 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
- 239000003345 natural gas Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 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
- 238000005457 optimization Methods 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
- 238000005120 petroleum cracking Methods 0.000 description 1
- 231100000719 pollutant Toxicity 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
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000010792 warming 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
- 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 a 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 combines Fe-MOFs with different metal active components to obtain the active component for CO 2 High-performance catalyst for preparing ethanol by catalytic hydrogenation and preparation of catalystSimple, low cost, and can realize CO 2 One-step catalytic hydrogenation is carried out to synthesize the ethanol with high selectivity. The invention opens up a new CO 2 The catalytic reaction path for preparing the 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 employs fossil fuels that have long been stored in the earth's crust in the form of coal, oil, and natural gas, and that maintain the natural carbon cycle of nature. With the increase of the world population and the shortage of fossil fuels, the carbon cycle changes and the CO in the atmosphere 2 Increase in concentration, etc. Carbon emissions and CO from the Earth before the human industry revolutionized 2 The storage of the gas is maintained in a dynamic equilibrium, but with the consumption of energy and CO 2 The increase in gas emissions results in an imbalance in the original carbon balance. Meanwhile, a series of problems such as 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. 2014 year global annual CO 2 Emissions are 39250 metric tons, with fossil fuel sources accounting for approximately 91% of human emissions.
Environmental problems we are facing at present include resource shortages and ecological destruction problems, whereas CO 2 Has rich carbon resource, is also the source of a plurality of chemical raw materials and is cheapThe price is easy to obtain. If hydrogen (H) can be produced electrolytically by means of alternative energy sources 2 ) Introducing CO 2 The catalytic conversion of the compound into high value-added chemicals has important significance for relieving global warming, improving ecological environment and solving the problem of increasingly exhausted fossil resources. At present, CO 2 In the preliminary stage, and C is synthesized by hydrogenation 2+ Hydrocarbons, particularly ethanol, having a higher octane number, are of increasing research interest.
The ethanol can be mixed and dissolved with water and most organic compounds, is also an important chemical and clean energy, and has a wide application prospect. Such as: can replace fossil fuels such as gasoline and the like, and improve the energy structure; can be used as an oxygen increasing agent for fuel oxidation, and can increase oxygen content in the combustion process and reduce CO and CH x Discharging 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 could only be synthesized by fermentation, which was mainly obtained from sugars and starches by fermentation, which was time consuming and inefficient. The ethylene hydration method is synthesized by using ethylene obtained by petroleum cracking as a raw material, but the process flow is not suitable for large-scale application along with the reduction of fossil energy, and the methods for directly preparing ethanol by using coal chemical industry and synthesis gas have higher cost. CO2 2 The catalytic conversion of ethanol is considered to be one of the most promising ways at present, not only reducing atmospheric CO 2 The concentration of the carbon source can also relieve the problems of carbon balance unbalance, global greenhouse effect and the like, and has undoubtedly wide application prospect. In addition, the method aims at high emission CO of current refineries and coal-fired power plants 2 The unit faces the dilemma of energy conservation and emission reduction, and CO takes hydrogen-rich tail gas produced by refinery plants as hydrogen source 2 The technology for synthesizing the ethanol by hydrogenation is a feasible route in economic terms and has more important environmental and strategic meanings.
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 catalytic hydrogenation of CO2 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 bimetallic active sites to accomplish C-C chain propagation and CO 2 Partially reduced CO 2 The process for preparing ethanol by catalytic hydrogenation is more challenging. From a thermodynamic point of view, due to CO 2 The catalytic hydrogenation for preparing ethanol is an exothermic reaction with reduced gas molecules, so that the forward reaction is facilitated by high pressure and low temperature generally, and CO is used for preparing ethanol 2 The activation of the molecule needs to be carried out at a relatively high temperature, so that proper reaction conditions are very important.
Over the last few years, CO 2 The catalytic conversion of ethanol is mainly homogeneous catalysis, and the homogeneous catalyst which takes noble metal as an active center and is combined with organic ligand can efficiently activate CO 2 Molecular 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 view of the shortcomings of homogeneous catalysts, researchers have developed heterogeneous transition metal catalysts in recent years. Mn-Fe-Cd-Cu catalyst developed by Kyowa Chemical in 1942 and was used for CO 2 The catalytic conversion system successfully prepares ethanol, propanol and butanol. Tatsumi et al reported alkali modified Mo/SiO 2 Catalytic conversion of CO with catalyst 2 Synthesis of C1-C5 higher alcohols. Cu/Zn/ZrO modified by Guo et al with Fe 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 [0.24g/(mL.h)]. Subject group of Shoufeng harvest adopts hydrothermal synthesis method to prepare non-noble metal type cobalt-aluminium hydrotalcite catalyst (CoAlO) x ) Optimization of CoAlO at different Pre-reduction temperatures x Catalyst proves that Co can be used as metal active center to efficiently produce CO 2 Molecular and highly selective ethanol formation. Li et al prepared a K/Cu-Zn catalyst with highly dispersed active component and studied the catalyst in CO 2 Hydrogenation to C 2+ Catalytic performance in alcohol reaction systems, CO on the catalyst 2 The best condition for preparing the ethanol by hydrogenation is 350K, 6.0MPa and 5000 ml.h -1 And H 2 /CO 2 The selectivity to CO and ethanol under this condition reached 84.27 wt% and 7.56 wt%.
In summary, different catalysts can be selected to pass through different catalytic networksCO 2 The ethanol is prepared by catalytic conversion, however, the yield of the ethanol is low, the research on the reaction mechanism is not deep enough, and the real catalytic network is not clear. Therefore, the reaction mechanism thereof has been studied in an intensive manner to solve the above problems, and a novel CO has been constructed 2 Catalytic network for preparing ethanol by hydrogenation and simultaneously considering ethanol selectivity and CO 2 The conversion rate, which results in excellent ethanol per pass yield, is that CO is currently achieved 2 The development trend of the industrial application of the ethanol preparation by the hydroconversion is also a bottleneck which needs to be broken through urgently.
Disclosure of Invention
In view of the above, the present invention aims to provide a Fe-based metal-organic framework material derived catalyst, a preparation method and an application thereof, and the Fe-based metal-organic framework material derived catalyst provided by the present invention can be used as CO 2 Catalyst in the reaction of hydrogenation to prepare ethanol and has high CO content 2 Conversion and ethanol selectivity.
The invention provides a Fe-based metal organic framework material deriving catalyst, which is prepared by sequentially carrying out transition metal ion loading, carbonization and Na ion loading on a 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 materials (Fe-MOFs) is not particularly limited, and may be generally commercially available or prepared according to methods 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 phase 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 the terephthalic acid is preferably 3: (4-6), more preferably 3: 5; the liquid phase medium is preferably N, N-Dimethylformamide (DMF).
In the preparation method of Fe-MOFs provided by the present invention, the specific process of mixing preferably comprises: a solution of terephthalic acid was added dropwise to a solution of the iron source compound with stirring.
In the preparation method of Fe-MOFs provided by the invention, the heating mode of the reaction is preferably hydrothermal; the reaction temperature is preferably 80-180 ℃, and more preferably 110 ℃; the reaction time is preferably 24-48 h, and more preferably 36 h.
In the preparation method of Fe-MOFs provided by the invention, after the heating reaction is finished, the obtained reaction product is preferably subjected to centrifugal washing and drying. Wherein the drying temperature is preferably 60-100 ℃, and more preferably 60 ℃; the drying time is preferably 6-24 h, and more preferably 24 h.
In the catalyst provided by the invention, the transition metal ions are preferably supported by a solution impregnation method, 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 dosage of the ethanol is preferably 5-70 wt% of the total mass of the water and the ethanol, and more preferably 20 wt%; the impregnation mode is preferably equal-volume impregnation; the dipping temperature is preferably 15-35 ℃, and more preferably 25 ℃ (room temperature). In the invention, after the impregnation is finished, drying is also needed; the drying mode is preferably drying; the drying temperature is preferably 60-100 ℃, and more preferably 60 ℃; the drying time is preferably 6-24 h, and more preferably 24 h.
In the catalyst provided by the invention, the loading amount of the transition metal ions is preferably 0.1-20 wt%, and specifically may be 0.1 wt%, 0.5 wt%, 1 wt%, 2 wt%, 5 wt%, 7 wt%, 10 wt%, 12 wt%, 15 wt%, 17 wt% or 20 wt%, and the loading amount refers to the percentage mass of the loaded transition metal ions in the entire 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 solution impregnation.
In the catalyst provided by the invention, the carbonization temperature is preferably 500-800 ℃, and more preferably 550 ℃; the carbonization time is preferably 1-6 h, and more preferably 3 h; the carbonization is preferably carried out in a protective gas atmosphere; the protective 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 dosage of the ethanol is preferably 5-70 wt% of the total mass of the water and the ethanol, and more preferably 20 wt%; the impregnation mode is preferably equal-volume impregnation; the dipping temperature is preferably 15-35 ℃, and more preferably 25 ℃ (room temperature). In the invention, after the impregnation is finished, drying is also needed; the drying mode is preferably drying; the drying temperature is preferably 60-100 ℃, and more preferably 60 ℃; the drying time is preferably 6-24 h, and more preferably 24 h.
In the catalyst provided by the invention, the loading amount of the Na ions is preferably 0.1-5 wt%, and specifically may be 0.1 wt%, 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt% or 5 wt%, and the loading amount refers to the percentage mass of the loaded Na ions in the whole catalyst. In the present invention, the amount of Na ions supported can be adjusted by adjusting the amount of Na source compound used in the solution impregnation.
In the catalyst provided by the invention, the particle size of the catalyst is preferably 10-100 meshes, and more preferably 20-40 meshes.
The invention also provides a preparation method of the Fe-based metal organic framework material derived catalyst, which comprises the following steps:
a) dipping the Fe-based metal organic framework material in a transition metal ion solution, drying and carbonizing to obtain a transition metal ion-loaded carbonized Fe-based metal organic framework material;
b) and (3) dipping the transition metal ion-loaded Fe-based metal organic framework carbide material in a 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 step a), the source of the Fe-based metal organic framework materials (Fe-MOFs) is not particularly limited, and may be generally commercially available or prepared according to methods well known to those skilled in the art, and is preferably prepared according to the above-described method of the present invention, and will not be described herein again.
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, and more preferably an aqueous solution of a nitrate salt of a transition metal ion, wherein the nitrate salt includes 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 70 wt%, more preferably 20 wt%, 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 dipping temperature is preferably 15-35 ℃, and more preferably 25 ℃ (room temperature).
In the preparation method provided by the invention, in the step a), the drying mode is preferably drying; the drying temperature is preferably 60-100 ℃, and more preferably 60 ℃; the drying time is preferably 6-24 h, and more preferably 24 h.
In the preparation method provided by the invention, in the step a), the carbonization temperature is preferably 500-800 ℃, and more preferably 550 ℃; the carbonization time is preferably 1-6 h, and more preferably 3 h; the carbonization is preferably carried out in a protective gas atmosphere; the protective 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 70 wt%, more preferably 20 wt%, 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 dipping temperature is preferably 15-35 ℃, and more preferably 25 ℃ (room temperature).
In the preparation method provided by the invention, in the step b), the drying mode is preferably drying; the drying temperature is preferably 60-100 ℃, and more preferably 60 ℃; the drying time is preferably 6-24 h, and more preferably 24 h.
In the preparation method provided by the invention, the method preferably further comprises crushing and granulating the dried Fe-based metal organic framework material derived catalyst to obtain a catalyst product with a required particle size.
The invention also provides CO 2 The method for directly synthesizing the 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 prepared by the technical scheme or the Fe-based metal organic framework material derivative catalyst prepared by the preparation method of 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; said H 2 The reduction treatment activation is preferably carried out in a fixed bed reactor; said H 2 The temperature for reduction treatment activation is preferably 200-400 ℃, and more preferably 400 ℃; said H 2 The time for the reduction treatment and activation is preferably 1-6 h, and more preferably 4 h; said H 2 Reduction treatment of activated H 2 The flow rate is preferably 10 to 200mL/min, and more preferably 60 mL/min.
In the invention providedIn the alcohol synthesis process, the CO 2 And H 2 Is 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; the Ar preferably accounts for Ar, CO and CO 2 And H 2 2-8% of the volume of the mixed gas, more preferably 5%; the CO preferably accounts for Ar, CO and CO 2 And H 2 2-8% of the volume of the mixed gas, more preferably 5%.
In the ethanol synthesis method provided by the invention, the mixing reaction is preferably carried out in a fixed bed reactor; the temperature of the mixing reaction is preferably 300-400 ℃, and more preferably 320 ℃; the pressure intensity of the mixing reaction is preferably 3-8 MPa, and more preferably 5 MPa.
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 combines Fe-MOFs with different metal active components to obtain the active component for CO 2 The high-performance catalyst for preparing ethanol by catalytic hydrogenation has simple preparation and low cost, and can realize CO 2 One-step catalytic hydrogenation is carried out to synthesize the ethanol with high selectivity. The experimental results show that: the Fe-based metal organic framework material derived catalyst provided by the invention is applied to CO 2 In the performance test of ethanol preparation by hydrogenation, CO 2 The highest conversion rate reaches 48.9 percent, the highest ethanol selectivity reaches 20.8 percent, the highest CO conversion rate reaches 79.3 percent, and the catalyst can efficiently catalyze CO 2 Hydrogenation reaction and conversion of the product into high value-added chemical ethanol, and the conversion rate of the main byproduct CO is high. The technical scheme provided by the invention opens up a new CO 2 The catalytic reaction path for preparing the ethanol by hydrogenation has higher economic value and social benefit.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
1) Sequentially loading Zn source nitrate (Zn (NO) on Fe-based metal organic framework materials (Fe-MOFs) 3 ) 2 ·6H 2 O), carbonization and Na-supporting 2 CO 3 The 2% Na-ZnFe @ C catalyst is obtained, and the specific preparation process is as follows:
2.703g of FeCl 2 .6H 2 Dissolving O (3mmol) in 30mL DMF, and stirring for 30min to obtain solution A; 0.83g of terephthalic acid (5mmol) is dissolved in 30mL of DMF to prepare a solution B; dropwise adding the solution B into the solution A under the stirring state, stirring for 30min, transferring into a 100mL hydrothermal kettle, and carrying out hydrothermal treatment at 110 ℃ for 36 h; after natural cooling, centrifugally separating the product, washing with water and ethanol for 3 times respectively, and then drying in a vacuum oven at 80 ℃ for 12h to obtain Fe-MOFs;
0.247g of Zn (NO) is taken 3 ) 2 ·6H 2 Dissolving O (0.83mmol) which is a Zn source in 1.5g of aqueous solution (containing 0.3g of ethanol), impregnating 1.2g of Fe-MOFs in an equal volume, and drying in a vacuum oven at 60 ℃ overnight to obtain a Zn ion-loaded Fe-based metal organic framework material (ZnFe-MOFs);
and carbonizing the obtained ZnFe-MOFs in a tubular furnace in a nitrogen atmosphere at 550 ℃ for 3 hours. Naturally cooling to room temperature to obtain a Zn ion-loaded Fe-based metal carbide organic framework material (ZnFe @ C);
collecting 0.023g of Na 2 CO 3 (0.22mmol) of a source of Na dissolved in 1.25g of aqueous solution (containing 0.25g of ethanol) 0.5g of ZnFe @ C was impregnated with equal volume and dried in a vacuum oven overnight at 60 ℃ to give a 2% Na-ZnFe @ C catalyst with 10 wt% Zn loading and 2 wt% Na loading.
2) 2% Na-ZnFe @ C as catalyst for catalyzing CO 2 The hydrogenation reaction comprises the following specific experimental processes:
tabletting the 2% Na-ZnFe @ C catalyst under 20MPa, and then crushing, sieving and granulating to obtain particles with the particle size of 20-40 meshes;
0.1g of granulated 2% Na-ZnFe @ C and 1g of stone are weighedAfter thoroughly mixing the quartz sand, the mixture was packed in a fixed bed reactor (inner diameter 6mm), first at 400 ℃ in H 2 Reduction for 4H under atmosphere 2 The flow rate is 60 mL/min; the temperature was then reduced to a reaction temperature of 320 ℃ and the gases switched to reaction gases (5% Ar, 5% CO, 18.74% CO) 2 、71.26％H 2 ) And the reaction was started after increasing the pressure to a target pressure (5MPa) under the action of a back pressure valve. Specific catalytic CO 2 The hydrogenation results are shown in table 1 below:
table 1 catalytic CO of example 1 2 Result of hydrogenation reaction
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 The 2% Na-Fe @ C catalyst is obtained, and the specific preparation process is as follows:
2.703g of FeCl 2 .6H 2 Dissolving O (3mmol) in 30mL DMF, and stirring for 30min to obtain solution A; 0.83g of terephthalic acid (5mmol) is dissolved in 30mL of DMF to prepare a solution B; dropwise adding the solution B into the solution A under the stirring state, stirring for 30min, transferring into a 100mL hydrothermal kettle, and carrying out hydrothermal treatment at 110 ℃ for 36 h; after natural cooling, centrifugally separating the product, washing with water and ethanol for 3 times respectively, and then drying in a vacuum oven at 80 ℃ for 12h to obtain Fe-MOFs;
and carbonizing the obtained Fe-MOFs in a tubular furnace in a nitrogen atmosphere, wherein the carbonizing temperature is controlled to be 550 ℃ and the time is 3 h. Naturally cooling to room temperature to obtain a Fe-carbide-based metal organic framework material (Fe @ C);
collecting 0.023g of Na 2 CO 3 (0.22mmol) of Na as source was dissolved in 1.25g of aqueous solution (containing 0.25g of ethanol), 0.5g of Fe @ C was impregnated in equal volume and dried in a vacuum oven overnight at 60 ℃ to give 2% Na-Fe @ C catalyst.
2) 2% Na-Fe @ C as catalyst for catalyzing CO 2 Hydrogenation reaction, apparatusThe experimental procedure was as follows:
tabletting 2% of Na-Fe @ C catalyst under 20MPa, and then crushing, sieving and granulating to obtain particles with the particle size of 20-40 meshes;
0.1g of granulated 2% Na-Fe @ C was weighed, thoroughly mixed with 1g of quartz sand, and then charged into a fixed bed reactor (inner diameter 6mm), first at 400 ℃ in H 2 Reduction for 4H under atmosphere 2 The flow rate is 60 mL/min; the temperature was then reduced to a reaction temperature of 320 ℃ and the gases switched to reaction gases (5% Ar, 5% CO, 18.74% CO) 2 、71.26％H 2 ) And the reaction was started after increasing the pressure to a target pressure (5MPa) under the action of a back pressure valve. Specific catalytic CO 2 The hydrogenation results are shown in table 2 below:
table 2 catalytic CO of comparative example 1 2 Result of hydrogenation reaction
Others a : propanol, butanol, and the like.
Example 2
1) Sequentially loading Cu source nitrate (Cu (NO)) on Fe-based metal organic framework materials (Fe-MOFs) 3 ) 2 ·3H 2 O), carbonization and Na-supporting 2 CO 3 The 2% Na-CuFe @ C catalyst is obtained, and the specific preparation process is as follows:
2.703g of FeCl 2 .6H 2 Dissolving O (3mmol) in 30mL DMF, and stirring for 30min to obtain solution A; 0.83g of terephthalic acid (5mmol) is dissolved in 30mL of DMF to prepare a solution B; dropwise adding the solution B into the solution A under the stirring state, stirring for 30min, transferring into a 100mL hydrothermal kettle, and carrying out hydrothermal treatment at 110 ℃ for 36 h; after natural cooling, centrifugally separating the product, washing with water and ethanol for 3 times respectively, and then drying in a vacuum oven at 80 ℃ for 12h to obtain Fe-MOFs;
0.200g of Cu (NO) was taken 3 ) 2 ·3H 2 O (0.83mmol) as Cu source dissolved in 1.5g of water solution (containing 0.3g of ethanol), 1.2g of Fe-MOFs was immersed in the solution in equal volume, and dried in a vacuum oven at 60 ℃ overnight to obtain Fe-based metalloorganorganics loaded with Cu ionsFramework materials (CuFe-MOFs);
and carrying out carbonization treatment on the obtained CuFe-MOFs in a tubular furnace in a nitrogen atmosphere, wherein the carbonization temperature is controlled to be 550 ℃ and the time is 3 h. Naturally cooling to room temperature to obtain a Cu ion-loaded Fe-based metal carbide organic framework material (CuFe @ C);
collecting 0.023g of Na 2 CO 3 (0.22mmol) of a source of Na dissolved in 1.25g of aqueous solution (containing 0.25g of ethanol) 0.5g of CuFe @ C was impregnated in equal volume and dried in a vacuum oven overnight at 60 ℃ to give a 2% Na-CuFe @ C catalyst with 10 wt% Cu loading and 2 wt% Na loading.
2) 2% Na-CuFe @ C as catalyst for catalyzing CO 2 The hydrogenation reaction comprises the following specific experimental processes:
tabletting 2% of Na-CuFe @ C catalyst under 20MPa, and then crushing, sieving and granulating to obtain particles with the particle size of 20-40 meshes;
0.1g of granulated 2% Na-CuFe @ C and 1g of quartz sand are weighed, mixed thoroughly, and then filled in a fixed bed reactor (inner diameter 6mm), and the mixture is firstly put in a 400 ℃ H 2 Reduction for 4H under atmosphere 2 The flow rate is 60 mL/min; the temperature was then reduced to a reaction temperature of 320 ℃ and the gases switched to reaction gases (5% Ar, 5% CO, 18.74% CO) 2 、71.26％H 2 ) And the reaction was started after increasing the pressure to a target pressure (5MPa) under the action of a back pressure valve. Specific catalytic CO 2 The hydrogenation results are shown in table 3 below:
table 3 catalytic CO of example 2 2 Result of hydrogenation reaction
Others a : propanol, butanol, and the like.
Example 3
1) Sequentially loading Co source nitrate (Co (NO) on Fe-based metal organic framework materials (Fe-MOFs) 3 ) 2 ·6H 2 O), carbonization and Na-supporting 2 CO 3 The 2% Na-CoFe @ C catalyst is obtained, and the specific preparation process is as follows:
2.703g of FeCl 2 .6H 2 Dissolving O (3mmol) in 30mL DMF, and stirring for 30min to obtain solution A; 0.83g of terephthalic acid (5mmol) is dissolved in 30mL of DMF to prepare a solution B; dropwise adding the solution B into the solution A under the stirring state, stirring for 30min, transferring into a 100mL hydrothermal kettle, and carrying out hydrothermal treatment at 110 ℃ for 36 h; after natural cooling, centrifugally separating the product, washing with water and ethanol for 3 times respectively, and then drying in a vacuum oven at 80 ℃ for 12h to obtain Fe-MOFs;
0.242g of Co (NO) was taken 3 ) 2 ·6H 2 Dissolving O (0.83mmol) serving as a Co source in 1.5g of aqueous solution (containing 0.3g of ethanol), impregnating 1.2g of Fe-MOFs in an equal volume, and drying in a vacuum oven at 60 ℃ overnight to obtain a Co ion-loaded Fe-based metal organic framework material (CoFe-MOFs);
and carbonizing the obtained CoFe-MOFs in a tubular furnace in a nitrogen atmosphere, wherein the carbonization temperature is controlled to be 550 ℃ and the time is 3 h. Naturally cooling to room temperature to obtain a Co ion-loaded Fe-based metal organic framework material (CoFe @ C);
collecting 0.023g of Na 2 CO 3 (0.22mmol) of a source of Na dissolved in 1.25g of an aqueous solution (containing 0.25g of ethanol) 0.5g CoFe @ C was impregnated in equal volume and dried in a vacuum oven at 60 ℃ overnight to give a 2% Na-CoFe @ C catalyst with 10 wt% Co and 2 wt% Na loading.
2) 2% Na-CoFe @ C as catalyst for catalyzing CO 2 The hydrogenation reaction comprises the following specific experimental processes:
tabletting 2% of Na-CoFe @ C catalyst under 20MPa, and then crushing, sieving and granulating to obtain particles with the particle size of 20-40 meshes;
0.1g of granulated 2% Na-CoFe @ C was weighed, thoroughly mixed with 1g of quartz sand, and then charged into a fixed bed reactor (inner diameter 6mm), first at 400 ℃ in H 2 Reduction for 4H under atmosphere 2 The flow rate is 60 mL/min; the temperature was then reduced to a reaction temperature of 320 ℃ and the gases switched to reaction gases (5% Ar, 5% CO, 18.74% CO) 2 、71.26％H 2 ) And the reaction was started after increasing the pressure to a target pressure (5MPa) under the action of a back pressure valve. Specific catalytic CO 2 Hydrogenation reaction knotThe results are shown in Table 4 below:
table 4 catalytic CO of example 3 2 Result of hydrogenation reaction
Others a : propanol, butanol, and the like.
Example 4
1) Sequentially loading Mn source nitrate (Mn (NO) on Fe-based metal organic framework materials (Fe-MOFs) 3 ) 2 ·4H 2 O), carbonization and Na-supporting 2 CO 3 The 2% Na-MnFe @ C catalyst is obtained, and the specific preparation process is as follows:
2.703g of FeCl 2 .6H 2 Dissolving O (3mmol) in 30mL DMF, and stirring for 30min to obtain solution A; 0.83g of terephthalic acid (5mmol) is dissolved in 30mL of DMF to prepare a solution B; dropwise adding the solution B into the solution A under the stirring state, stirring for 30min, transferring into a 100mL hydrothermal kettle, and carrying out hydrothermal treatment at 110 ℃ for 36 h; after natural cooling, centrifugally separating the product, washing with water and ethanol for 3 times respectively, and then drying in a vacuum oven at 80 ℃ for 12h to obtain Fe-MOFs;
0.208g of Mn (NO) was taken 3 ) 2 ·4H 2 Dissolving O (0.83mmol) serving as a Mn source in 1.5g of aqueous solution (containing 0.3g of ethanol), impregnating 1.2g of Fe-MOFs in an equal volume, and drying in a vacuum oven at 60 ℃ overnight to obtain a Mn ion-loaded Fe-based metal organic framework material (MnFe-MOFs);
and carbonizing the obtained MnFe-MOFs in a tube furnace in a nitrogen atmosphere, wherein the carbonizing temperature is controlled to be 550 ℃ and the time is 3 h. Naturally cooling to room temperature to obtain a Mn ion-loaded Fe-based metal organic framework material (MnFe @ C);
collecting 0.023g of Na 2 CO 3 (0.22mmol) of a source of Na dissolved in 1.25g of aqueous solution (containing 0.25g of ethanol) 0.5g of MnFe @ C was impregnated with equal volume and dried in a vacuum oven overnight at 60 ℃ to give a 2% Na-MnFe @ C catalyst with 10 wt% Mn loading and 2 wt% Na loading.
2) Mixing 2% Na-MnFe @ CAs catalysts for catalyzing CO 2 The hydrogenation reaction comprises the following specific experimental processes:
tabletting 2% of Na-MnFe @ C catalyst under 20MPa, and then crushing, sieving and granulating to obtain particles with the particle size of 20-40 meshes;
0.1g of granulated 2% Na-MnFe @ C and 1g of quartz sand are weighed, fully mixed and filled into a fixed bed reactor (the inner diameter is 6mm), and the mixture is firstly put into a reactor at 400 ℃ in H 2 Reduction for 4H under atmosphere 2 The flow rate is 60 mL/min; the temperature was then reduced to a reaction temperature of 320 ℃ and the gases switched to reaction gases (5% Ar, 5% CO, 18.74% CO) 2 、71.26％H 2 ) And the reaction was started after increasing the pressure to a target pressure (5MPa) under the action of a back pressure valve. Specific catalytic CO 2 The hydrogenation results are shown in table 5 below:
table 5 catalytic CO of example 4 2 Result of hydrogenation reaction
Others a : propanol, butanol, and the like.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A Fe-based metal organic framework material derivation catalyst is prepared by sequentially carrying out transition metal ion loading, carbonization and Na ion loading on a Fe-based metal organic framework material;
the transition metal ions include one or more of Co ions, Mn ions, Zn ions, and Cu ions.
2. The Fe-based metal organic framework material derived catalyst as claimed in claim 1, wherein the transition metal ion loading is 0.1 to 20 wt%.
3. The Fe-based metal-organic framework material derived catalyst as claimed in claim 1, wherein the loading of Na ions is 0.1 to 5 wt%.
4. A method for preparing a Fe-based metal organic framework material derived catalyst as claimed in any one of claims 1 to 3, comprising the steps of:
a) dipping the Fe-based metal organic framework material in a transition metal ion solution, drying and carbonizing to obtain a transition metal ion-loaded carbonized Fe-based metal organic framework material;
b) and (3) dipping the transition metal ion-loaded Fe-based metal organic framework carbide material in a Na ion solution, and drying to obtain the Fe-based metal organic framework material derivative catalyst.
5. The method according to claim 4, wherein in the step a), the transition metal ion solution is an aqueous nitrate solution of transition metal ions.
6. The method according to claim 4, wherein the carbonization temperature in step a) is 500 to 800 ℃; the carbonization time is 1-6 h.
7. The method of claim 4, wherein in step a), the Fe-based metal-organic framework material is prepared by the following method:
mixing an iron source compound and terephthalic acid in a liquid phase medium, and heating for reaction to obtain the Fe-based metal organic framework material.
8. Fe-based metal organic framework material derived catalyst as claimed in any one of claims 1 to 3 or prepared by the preparation method as claimed in any one of claims 4 to 7 as CO 2 The application of the catalyst for directly synthesizing ethanol by hydrogenation.
9. CO (carbon monoxide) 2 The method for directly synthesizing the 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 as described in any one of claims 1 to 3 or the Fe-based metal organic framework material derivative catalyst prepared by the preparation method as described in any one of claims 4 to 7.
10. The method according to claim 9, 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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| CN115155590A (en) * | 2022-08-25 | 2022-10-11 | 南京工业大学 | Preparation method and application of catalyst suitable for preparing liquid hydrocarbon by carbon dioxide hydrogenation |
| CN115350706A (en) * | 2022-08-29 | 2022-11-18 | 南京信息工程大学 | CO (carbon monoxide) 2 Preparation method of three-element metal MOF (Metal organic framework) derivative catalyst for hydrogenation thermal catalysis |
| CN115350706B (en) * | 2022-08-29 | 2023-07-18 | 南京信息工程大学 | CO (carbon monoxide) 2 Preparation method of hydrogenation thermocatalytic ternary metal MOF derivative catalyst |
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