CN114377677B - Iron-based catalyst for preparing high-carbon hydrocarbon by catalyzing carbon dioxide hydrogenation through light drive, and preparation method and application thereof - Google Patents
Iron-based catalyst for preparing high-carbon hydrocarbon by catalyzing carbon dioxide hydrogenation through light drive, and preparation method and application thereof Download PDFInfo
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- CN114377677B CN114377677B CN202011123432.3A CN202011123432A CN114377677B CN 114377677 B CN114377677 B CN 114377677B CN 202011123432 A CN202011123432 A CN 202011123432A CN 114377677 B CN114377677 B CN 114377677B
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 179
- 239000003054 catalyst Substances 0.000 title claims abstract description 104
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 84
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 44
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 38
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 30
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 30
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 25
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000000126 substance Substances 0.000 claims abstract description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 5
- 239000002243 precursor Substances 0.000 claims description 27
- 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 claims description 25
- 229960001545 hydrotalcite Drugs 0.000 claims description 24
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 15
- 230000003197 catalytic effect Effects 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 159000000003 magnesium salts Chemical class 0.000 claims description 14
- 238000001228 spectrum Methods 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 239000012495 reaction gas Substances 0.000 claims description 11
- 230000008859 change Effects 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000004817 gas chromatography Methods 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- 102000020897 Formins Human genes 0.000 claims description 2
- 108091022623 Formins Proteins 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- 239000012716 precipitator Substances 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 8
- 238000006555 catalytic reaction Methods 0.000 description 9
- 230000009467 reduction Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000005286 illumination Methods 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 6
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 150000002505 iron Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 2
- 239000002060 nanoflake Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 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
- 241000282414 Homo sapiens Species 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000036962 time dependent 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
- B01J23/78—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 alkali- or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
-
- 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)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses an iron-based catalyst for preparing high-carbon hydrocarbon by catalyzing carbon dioxide hydrogenation through light driving, wherein the chemical formula of the iron-based catalyst is Fe/Fe x O y /MgO‑Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the Where x=2 or 3 and y=3 or 4. The catalyst is especially suitable for the reaction of preparing high-carbon hydrocarbon by catalyzing the hydrogenation of carbon dioxide through light drive, and in the reaction, the carbon dioxide has higher conversion rate and is suitable for methane and C 2 ‑C 4 Hydrocarbons have high selectivity. The invention also discloses a preparation method and application of the iron-based catalyst.
Description
Technical Field
The invention relates to the technical field of optical drive catalysis. More particularly, relates to an iron-based catalyst for preparing high-carbon hydrocarbon by catalyzing hydrogenation of carbon dioxide through light driving, and a preparation method and application thereof.
Background
In recent years, with the increasing energy demand and fossil fuel consumption, a large amount of CO 2 The final product of fossil energy combustion is discharged into the atmosphere, so that global warming, sea level rising and the like are aggravated, and the living environment of human beings is seriously threatened. CO at the same time 2 Is also a potential high-quality carbon source, and can better utilize CO 2 It becomes particularly important, and therefore, there is an urgent need for developing a clean technology for preparing energy. The solar energy has the advantages of inexhaustible, environment-friendly, pollution-free, recyclable and the like, and occupies an irreplaceable position in the future new energy utilization and development. CO 2 The hydrogenation reaction is a traditional technology for preparing energy, and how to utilize clean energy such as solar energy to drive the hydrogenation reaction of carbon dioxide is an urgent topic to be studied. The hydrogenation of carbon dioxide is carried out at high temperature and high pressure, and the high temperature reaction accelerates the formation of carbon deposit and the deactivation of the catalyst caused by the sintering of the catalyst; at the same time from the energy and efficiency aspectsIs extremely wasteful, and how to drive the reaction under milder conditions has been the forefront and challenge of the catalytic and chemical fields.
Disclosure of Invention
A first object of the present invention is to provide an iron-based catalyst for the hydrogenation of carbon dioxide to higher hydrocarbons, which is particularly suitable for use in a reaction for the hydrogenation of carbon dioxide to higher hydrocarbons, which has a high conversion rate of carbon dioxide and is relatively high for methane and C 2 -C 4 Hydrocarbons have high selectivity.
The second object of the invention is to provide a preparation method of the iron-based catalyst for preparing high-carbon hydrocarbon by catalyzing carbon dioxide hydrogenation through light driving.
The third object of the invention is to provide an application of an iron-based catalyst for preparing high-carbon hydrocarbon by catalyzing hydrogenation of carbon dioxide through light driving.
In order to achieve the first object, the present invention adopts the following technical scheme:
an iron-based catalyst for preparing high-carbon hydrocarbon by catalyzing carbon dioxide hydrogenation through light drive, wherein the chemical formula of the iron-based catalyst is Fe/Fe x O y /MgO-Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the Where x=2 or 3 and y=3 or 4.
In order to achieve the second object, the present invention adopts the following technical scheme:
the preparation method of the iron-based catalyst for preparing the high-carbon hydrocarbon by catalyzing the hydrogenation of the carbon dioxide through the light drive comprises the following steps:
1) Preparing a mixed metal salt solution: dissolving ferric salt, magnesium salt and aluminum salt in deionized water, adding a precipitator, adding the mixture into a hydrothermal kettle after the mixture is fully dissolved, reacting at 90-130 ℃, and crystallizing for 8-24 hours to obtain a crude product;
2) Washing and drying the crude product obtained in the step 1) to obtain a precursor hydrotalcite material;
3) The precursor hydrotalcite material obtained in the step 2) is mixed with hydrogen and argon in the atmosphere at the temperature of 1-5 ℃ for min -1 Heating to 300-700 deg.c for 2-5 hr and switching to nitrogenAnd naturally cooling to room temperature in the gas atmosphere to obtain the light-driven iron-based catalyst for preparing high-carbon hydrocarbon by catalyzing the hydrogenation of carbon dioxide.
Since the iron-based catalyst is CO 2 In the hydrogenation process, the active phase of high-carbon hydrocarbon is prepared, and because hydrotalcite is used as a precursor in the invention, ferric salt is required to be used as an iron source, and because hydrotalcite is used as a precursor and alumina is used in CO 2 Is a good carrier in hydrogenation reaction, so that aluminum salt is used as an aluminum source. In addition, in the invention, the precursor of LDH is directly reduced in a reducing atmosphere, and the catalyst obtained by the two methods is calcined into oxide and then reduced, so that the catalytic effect of the catalyst obtained by the two methods is the same, the catalyst can be prepared by adopting a direct reduction method, and the operation steps are simplified.
Further, in the step 1), the concentration of the magnesium salt dissolved in deionized water is 0.2 to 0.04 mol.L -1 The method comprises the steps of carrying out a first treatment on the surface of the The concentration of the ferric salt dissolved in deionized water is 0.1 to 0.02 mol.L -1 The method comprises the steps of carrying out a first treatment on the surface of the The concentration of the aluminum salt dissolved in deionized water is 0.1 to 0.02 mol.L -1 The method comprises the steps of carrying out a first treatment on the surface of the The molar ratio of the magnesium salt to the ferric salt to the aluminum salt is 3-1:1:1; the magnesium salt is selected from one or more of magnesium nitrate, magnesium chloride or magnesium sulfate; the ferric salt is selected from one or more of ferric nitrate, ferric chloride or ferric sulfate; the aluminum salt is one or more selected from aluminum nitrate, aluminum chloride or aluminum sulfate;
the precipitant is sodium hydroxide, and the added mole number of the precipitant is 2-8 times of the mole total number of magnesium salt, ferric salt and aluminum salt.
Further, in the step 2), the washing mode is to wash 3-6 times by deionized water, the drying temperature is 40-90 ℃, and the drying time is 5-20 h.
Further, in step 2), the precursor hydrotalcite material has the chemical formula [ Mg ] 2+ 1-m-n Fe 3+ m Al 3+ n (OH) 2 ] (m+n)+ ·(A x- ) (m+n)/x ·yH 2 O, wherein 0.2.ltoreq.m+n.ltoreq.0.33; x is the valence number of the anion; y is the quantity of crystal water, and the value range of y is 0.5-9; a is that x- Is NO 3 - Or CO 3 2- 。
Further, in the step 3), the volume fraction of hydrogen in the hydrogen-argon mixture is 10%.
In order to achieve the third object, the present invention adopts the following technical scheme:
the use of the iron-based catalyst according to the first object above in a light-driven catalytic carbon dioxide hydrogenation reaction for preparing higher hydrocarbons.
The invention prepares the high-load and high-dispersivity iron-based catalyst by high-temperature reduction based on the layered structure of hydrotalcite and the proportion adjustability of the divalent and trivalent metal ions of the laminate, and drives the catalyst to catalyze CO for the first time 2 Hydrogenation reaction, and the product has higher high-carbon hydrocarbon selectivity.
Further, the reaction is carried out under light conditions, preferably under full spectrum conditions.
Further, the application comprises the steps of:
adding the iron-based catalyst into a light-permeable closed reaction kettle, introducing diluted reaction gas, illuminating under the condition of full spectrum, and detecting the change of a product along with time by adopting gas chromatography;
wherein the diluted reaction gas comprises CO 2 、H 2 And Ar.
Diluted reactant gas, i.e. reactant gas containing inert gas Ar (CO 2 And H 2 )。
Further, the CO 2 、H 2 And Ar in a volume ratio of 15:60:25. CO at this ratio 2 Hydrogenation is more beneficial to the generation of higher hydrocarbons, and CO 2 The conversion rate of (2) is not too low.
Further, the addition amount of the iron-based catalyst is 20-120 mg/108ml diluted reaction gas.
In addition, unless otherwise specified, all raw materials used in the present invention are commercially available, and any ranges recited in the present invention include any numerical value between the end values and any sub-range constituted by any numerical value between the end values or any numerical value between the end values.
The beneficial effects of the invention are as follows:
in the iron-based catalyst provided by the invention, layered hydrotalcite is used as a precursor, and the layered hydrotalcite is used as a precursor or a rigid and stable template through high-temperature reduction by utilizing the lattice positioning effect and the structural topology conversion effect of the layered hydrotalcite, so that the metal iron nano catalyst with high dispersibility and high load type low cost is formed by inducing the confinement. The iron-based catalyst can catalyze CO under the driving of light without adding any auxiliary catalyst 2 Hydrogenation reaction to produce high-selectivity high-carbon hydrocarbon and methane.
According to the iron-based catalyst provided by the invention, the selectivity of the prepared iron-based catalyst in the light-driven catalytic carbon dioxide hydrogenation reaction for preparing high-carbon hydrocarbon can be further improved by controlling the molar ratio of the precursor metal salt and the reduction temperature.
The invention adopts the iron-based catalyst for light driving CO under the light driving for the first time 2 The hydrogenation reaction is used for preparing high-selectivity high-carbon hydrocarbon, the high-carbon hydrocarbon in the product has high selectivity, and the selectivity of the high-carbon hydrocarbon under the better condition can reach 52.9 percent, so the discovery is expected to be applied to industrial production.
The iron-based catalyst has the advantages of low cost, simple and convenient preparation and simple process, and is easy for mass production.
Drawings
The following describes the embodiments of the present invention in further detail with reference to the drawings.
FIG. 1 shows XRD patterns of the products obtained in examples 1 to 3 of the present invention; curves a, b, and c in the figure correspond to XRD patterns of the iron-based catalysts prepared in examples 1 to 3, respectively.
Fig. 2A shows a transmission electron microscopic view of the iron-based catalyst obtained in example 1 of the present invention.
Fig. 2B shows a transmission electron microscopic view of the iron-based catalyst obtained in example 2 of the present invention.
Fig. 2C shows a transmission electron microscopic view of the iron-based catalyst obtained in example 3 of the present invention.
Fig. 2D shows the XRD spectrum of the precursor hydrotalcite material (MgFeAl-LDH) obtained in step 2) in example 1 of the present invention.
FIG. 3 shows the light-driven catalysis of CO by the iron-based catalyst obtained in example 2 of the present invention 2 Hydrogenation reaction performance diagram.
Fig. 4 shows a temperature change curve under the iron-based catalyst system obtained in example 3 of the present invention using an internal thermocouple.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be further described with reference to preferred embodiments and the accompanying drawings. Like parts in the drawings are denoted by the same reference numerals. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and that this invention is not limited to the details given herein.
Example 1
The preparation method of the iron-based catalyst for preparing the high-carbon hydrocarbon by catalyzing the hydrogenation of the carbon dioxide through the light drive comprises the following steps:
1) Preparing a mixed metal salt solution: 0.006mol of magnesium nitrate hexahydrate, 0.003mol of ferric nitrate nonahydrate, and 0.003mol of aluminum nitrate nonahydrate were dissolved in 60mL of deionized water; after adding 0.03mol of urea as a precipitant, the solution is fully dissolved and then transferred into a 50mL reaction kettle, and finally reacted for 24 hours in an oven at 120 ℃.
2) And after the reaction is finished, centrifugally washing the crude product with deionized water for 3 times, and drying the crude product in an oven at 80 ℃ for 12 hours after the completion of the reaction to obtain the precursor hydrotalcite material.
3) The hydrotalcite material obtained above was mixed with hydrogen argon (10% H) 2 V/v) at 5℃min in an atmosphere -1 Heating to 400 deg.C, maintaining at the temperature for 5 hr, and switching to N 2 And naturally cooling to room temperature in the atmosphere to obtain the iron-based catalyst 1, which is marked as Fe-400.
The iron-based catalyst prepared by the method is applied to photo-driven CO catalysis 2 In hydrogenation reaction, iron-based catalyst is added into a light-permeable closed reaction kettle, and diluted reaction gas (CO) is introduced 2 ：H 2 : ar=15: 60:25, volume ratio), all-optical is performedAfter 2 hours of spectrum illumination, the activity of the catalyst and the selectivity of each product are measured by adopting gas chromatography, wherein the dosage of the iron-based catalyst is 100mg/108ml diluted reaction gas.
Curve a in fig. 1 is the XRD spectrum of the iron-based catalyst prepared in example 1. Fig. 2A is a transmission electron microscopic view of the iron-based catalyst obtained in example 1. Fig. 2D is an XRD spectrum of the precursor hydrotalcite material (MgFeAl-LDH) obtained in step 2 of example 1.
As can be seen from fig. 2D, under this condition, the synthesized precursor forms a very good hydrotalcite structure with (003), (006) and (009) characteristic peaks apparent. At the reduction temperature, as shown by the curve a in fig. 1, a weak peak of elemental Fe appears indicating that elemental Fe is reduced; from FIG. 2A, fe with high density and high loading after reduction at this temperature is dispersed in Al 2 O 3 On the nanoflakes. As can be seen from Table 1, CO after 2 hours 2 The conversion rate of (C) can reach 17.8% and the selectivity of high-carbon hydrocarbon can reach 38.6%.
TABLE 1Fe-400 optical drive catalysis performance table
Example 2
The preparation method of the iron-based catalyst for preparing the high-carbon hydrocarbon by catalyzing the hydrogenation of the carbon dioxide through the light drive comprises the following steps:
1) Preparing a mixed metal salt solution: 0.006mol of magnesium nitrate hexahydrate, 0.003mol of ferric nitrate nonahydrate, and 0.003mol of aluminum nitrate nonahydrate were dissolved in 60mL of deionized water; after adding 0.03mol of urea as a precipitant, the solution is fully dissolved and then transferred into a 50mL reaction kettle, and finally reacted for 24 hours in an oven at 120 ℃.
2) And after the reaction is finished, centrifugally washing for 3 times by using deionized water, and drying in an oven at 80 ℃ for 12 hours after the completion of the reaction to obtain the precursor hydrotalcite material.
3) The hydrotalcite material obtained above was mixed with hydrogen argon (10% H) 2 V/v) at 5℃min in an atmosphere -1 The temperature rise rate is raised to 500 ℃, and the temperature is kept at the temperatureHolding for 5h, and switching to N after finishing 2 And naturally cooling to room temperature in the atmosphere. The iron-based catalyst 2 was obtained and was designated Fe-500.
The iron-based catalyst prepared by the method is applied to photo-driven CO catalysis 2 In the hydrogenation reaction, an iron-based catalyst is added into a reaction kettle, and diluted synthesis gas (CO) is introduced 2 ：H 2 ：N 2 =15: 60:25, volume ratio). And (3) full spectrum illumination, and detecting the change of a product with time by adopting gas chromatography, wherein the dosage of the iron-based catalyst is 100mg/108ml diluted reaction gas. The catalyst activity was measured.
Meanwhile, an internal thermocouple is adopted in the system to detect the change of the temperature of the catalyst surface along with the illumination time in situ. Characterization of the catalyst prepared in this example:
curve b in fig. 1 is the XRD spectrum of the iron-based catalyst prepared in example 2; FIG. 2B is a transmission electron microscopic view of the iron-based catalyst obtained in example 2; FIG. 3 is an iron-based photo-driven CO obtained in example 2 2 Performance diagram of hydrogenation reaction; FIG. 4 is a graph showing the temperature change in the iron-based catalyst system obtained in example 2 of the present invention using an internal thermocouple.
FIG. 3 is a graph showing the performance of the catalyst under flowing conditions, and the graph shows that the conversion rate of CO2 and the selectivity of high-carbon hydrocarbon can be maintained at a relatively high level along with the time, so that the catalyst has good stability. Fig. 4 shows a time-dependent curve of the temperature of the catalyst surface of the system detected in situ by using an internal thermocouple, and it is known that the temperature of the system can be raised to 110 ℃ by illumination without catalyst, and after the catalyst is added, the temperature of the catalyst surface is raised instantaneously, and finally the temperature can reach and be balanced at about 275 ℃.
The reduction is carried out at the reduction temperature of the embodiment, the XRD spectrum of the final product is shown as a b curve in figure 1, and obvious elemental iron appears on the surface of the catalyst; as seen from FIG. 2B, the elemental Fe reduced at this temperature is supported on Al 2 O 3 On the nanoflakes. The catalytic activity and selectivity of the catalyst after 2h of full spectrum irradiation are shown in Table II.
TABLE 2Fe-500 optical drive catalysis performance table
Example 3
The preparation method of the iron-based catalyst for preparing the high-carbon hydrocarbon by catalyzing the hydrogenation of the carbon dioxide through the light drive comprises the following steps:
1) Preparing a mixed metal salt solution: 0.006mol of magnesium nitrate hexahydrate, 0.003mol of ferric nitrate nonahydrate, and 0.003mol of aluminum nitrate nonahydrate were dissolved in 60mL of deionized water; after adding 0.03mol of urea as a precipitant, the solution is fully dissolved and then transferred into a 50mL reaction kettle, and finally reacted for 24 hours in an oven at 120 ℃.
2) And after the reaction is finished, centrifugally washing for 3 times by using deionized water, and drying in an oven at 80 ℃ for 12 hours after the completion of the reaction to obtain the precursor hydrotalcite material.
3) The hydrotalcite material obtained above was mixed with hydrogen argon (10% H) 2 V/v) at 5℃min in an atmosphere -1 Heating to 600 deg.C, maintaining at the temperature for 5 hr, and switching to N 2 And naturally cooling to room temperature in the atmosphere. The iron-based catalyst 3 was obtained and was designated Fe-600.
The iron-based catalyst prepared by the method is applied to photo-driven CO catalysis 2 In the reaction, an iron-based catalyst is added into a reaction kettle, and diluted reaction gas (CO) is introduced 2 ：H 2 : ar=15: 60:25, volume ratio). And (3) full spectrum illumination, and detecting the change of a product with time by adopting gas chromatography, wherein the dosage of the iron-based catalyst is 100mg/108ml diluted reaction gas. The catalyst activity was measured.
Meanwhile, an internal thermocouple is adopted in the system to detect the change of the temperature of the catalyst surface along with the illumination time in situ. Characterization of the catalyst prepared in this example:
curve c in fig. 1 is the XRD spectrum of the cobalt-based catalyst prepared in example 3, from which the phase of elemental iron appears; FIG. 2C is an iron-based catalyst obtained in example 3Is a transmission electron microscope image of (a). FIG. 3 is an optically active CO catalysis with the iron-based catalyst obtained in example 3 2 Performance diagram of hydrogenation reaction; FIG. 4 is a graph showing the temperature change in the iron-based photo-driven catalyst system obtained in example 2 of the present invention using an internal thermocouple.
TABLE 3Fe-600 optical drive catalytic performance table
To sum up, the prior art uses CO 2 The main path for preparing the high-carbon hydrocarbon is to use an iron-based catalyst to apply traditional thermocatalysis, and the conditions are mostly carried out in a high-temperature and high-pressure system; compared with the prior art, the invention adopts light to drive CO for the first time 2 The hydrogenation reaction is more beneficial to environmental protection and effectively utilizes solar energy.
Examples 4 to 7
The influence of the temperature rise of the precursor hydrotalcite material on the performance of the iron-based catalyst is examined, namely the preparation method is the same as in example 1, except that the temperature reached by the temperature rise of the precursor hydrotalcite material in step 3) is changed, and the obtained product is subjected to illumination CO 2 Hydrogenation, hydrolysis procedure was as in example 1, and the results are shown in Table 4:
TABLE 4 catalytic results for different iron-based catalysts
| Examples numbering | Temperature (. Degree. C.) | CO 2 Is of the conversion rate of (2) | CH 4 Selectivity of (2) | C 2 -C 4 Hydrocarbon selectivity | C 5 Selectivity of + |
| 1 | 400 | 17.8 | 61.4 | 34.3 | 4.3 |
| 4 | 500 | 50.1 | 47.1 | 46.6 | 6.3 |
| 5 | 550 | 59.2 | 58.9 | 37.2 | 3.9 |
| 6 | 600 | 76.9 | 70.0 | 28.2 | 1.8 |
| 7 | 700 | 73.1 | 78.7 | 20.7 | 0.6 |
The results show that: the difference of the temperature reached by the temperature rise of the precursor has great influence on the selectivity of the product, the selectivity of the high-carbon hydrocarbon is the maximum at 500 ℃ and CO 2 Has high conversion rate.
Examples 8 to 9
The effect of the molar ratio of magnesium salt, iron salt and aluminum salt on the performance of the iron-based catalyst was examined, i.e., the preparation method was the same as in example 2, except that the total molar ratio of iron salt, magnesium salt and aluminum salt in step 1) was kept unchanged, the molar ratio of magnesium salt, iron salt and aluminum salt in step 1) was changed, and the resultant was subjected to photocatalytic CO 2 Hydrogenation reaction, the reaction procedure was as in example 1, and the results are shown in Table 5:
TABLE 5 catalytic results for different iron-based catalysts
| Examples numbering | Molar ratio of | CO 2 Is of the conversion rate of (2) | CH 4 Selectivity of (2) | C 2 -C 4 Hydrocarbon selectivity | C 5 Selectivity of + |
| 2 | 2:1:1 | 50.1 | 47.1 | 46.6 | 6.3 |
| 8 | 2:2:1 | 59.8 | 57.3 | 40.6 | 2.1 |
| 9 | 2:3:1 | 62.3 | 68.1 | 30.7 | 1.2 |
The results show that: with the change of the mole ratio of magnesium salt, ferric salt and aluminum salt, the catalyst is used for CO 2 Has a great influence on the conversion rate of the product and the selectivity of the product, and when Mg: fe: al: CO when=2:1:1 2 Relatively moderate conversion and highest selectivity to higher hydrocarbons.
Examples 10 to 12
The influence of the synthesis temperature of the precursor on the performance of the iron-based catalyst was examined, i.e., the preparation method was the same as example 2, except that the reaction temperature of the oven in step 1) was changed, and the obtained product was subjected to photo-catalytic CO 2 Hydrogenation reaction, the reaction procedure was as in example 2, and the results are shown in Table 6:
TABLE 6 catalytic results for different iron-based catalysts
The results show that: in the invention, CO is treated when the synthesis temperature of the precursor is changed 2 Has no obvious influence on the conversion rate of the product and the selectivity of the product.
Examples 13 to 15
The influence of crystallization time on the performance of the iron-based catalyst was examined, i.e., the preparation method was the same as in example 2, except that the crystallization time in step 1) was changed, and the resultant was subjected to photocatalytic CO 2 Hydrogenation reaction, the reaction procedure was as in example 1, and the results are shown in Table 7:
TABLE 7 catalytic results for different iron-based catalysts
| Examples numbering | Crystallization time (h) | CO 2 Is of the conversion rate of (2) | CH 4 Selectivity of (2) | C 2 -C 4 Hydrocarbon selectivity | C 5 Selectivity of + |
| 2 | 24 | 50.1 | 47.1 | 46.6 | 6.3 |
| 13 | 10 | 49.8 | 45.5 | 47.9 | 6.6 |
| 14 | 15 | 52.2 | 49.9 | 48.0 | 2.1 |
| 15 | 20 | 49.5 | 48.9 | 46.3 | 4.8 |
The results show that: in the invention, the crystallization time of hydrotalcite is changed to CO when the precursor is synthesized 2 The conversion of (c) and the selectivity of the product are not very significant.
Examples 16 to 18
The effect of the amount of precipitant added on the performance of the iron-based catalyst was examined, i.e., the preparation method was the same as in example 2, except that the amount of precipitant added in step 1) was changed, and the resultant was subjected to photocatalytic CO 2 Hydrogenation reaction, the reaction procedure was as in example 2, and the results are shown in Table 8:
TABLE 8 catalytic results for different iron-based catalysts
The results show that: in the invention, CO is treated when the dosage of the precipitant is changed 2 The conversion of (c) and the selectivity of the product are not much affected.
Examples 19 to 20
The influence of the drying temperature on the performance of the iron-based catalyst was examined, i.e. the preparation method was the same as in example 2, except that the drying temperature in step 2) was changed and the resulting product was subjected to light-driven CO catalysis 2 Hydrogenation, hydrolysis procedure was as in example 1, and the results are shown in Table 9:
TABLE 9 catalytic results for different iron-based catalysts
The results show that: in the present invention, CO is treated when the drying temperature of the precursor is changed 2 The conversion of (c) and the selectivity of the product are not much affected.
Examples 21 to 22
The effect of drying time on the performance of the iron-based catalyst was examined, i.e. the preparation method was the same as in example 2, except that the drying time in step 2) was changed and the resulting product was subjected to photo-catalytic CO 2 Hydrogenation reaction, the reaction procedure was as in example 2, and the results are shown in Table 10:
TABLE 10 catalytic results for different iron-based catalysts
The results show that: CO is treated in the present invention when the amount of drying time of the precursor is changed 2 The conversion of (c) and the selectivity of the product are not much affected.
Comparative example 1
An iron-based catalyst was prepared in the same manner as in example 1 except that 0.003mol of ferric nitrate nonahydrate in step 1) was replaced with 0.003mol of nickel nitrate hexahydrate.
CO illumination 2 Hydrogenation reaction, the product is methane, and high-carbon hydrocarbon is not obtained.
Comparative example 2
An iron-based catalyst was prepared in the same manner as in example 1 except that,
heating the precursor hydrotalcite material in the step 3) to 500 ℃, keeping the temperature for 4 hours, naturally cooling to room temperature to obtain mixed metal oxide, and then putting the mixed metal oxide into hydrogen-argon mixed gas (10% H) 2 V/v) at 5℃min in an atmosphere -1 Heating to 400 deg.C, maintaining at the temperature for 5 hr, and switching to N 2 And naturally cooling to room temperature in the atmosphere to obtain the iron-based catalyst.
Photo-driven CO by using the iron-based catalyst 2 The hydrogenation reaction results are the same as the catalytic performance under the conditions of example 1, namely Table 1, but the method has complicated operation and is not as simple as the direct reduction operation step of the invention.
It should be understood that the foregoing examples of the present invention are provided merely for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention, and that various other changes and modifications may be made therein by one skilled in the art without departing from the spirit and scope of the present invention as defined by the appended claims.
Claims (11)
1. An iron-based catalyst for preparing high-carbon hydrocarbon by catalyzing carbon dioxide hydrogenation through light drive, which is characterized in that the chemical formula of the iron-based catalyst is Fe/Fe x O y /MgO-Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the Wherein x=2 or 3, y=3 or 4;
the preparation method of the iron-based catalyst comprises the following steps:
1) Preparing a mixed metal salt solution: dissolving ferric salt, magnesium salt and aluminum salt in deionized water, adding a precipitator, adding the mixture into a hydrothermal kettle after the mixture is fully dissolved, reacting at 90-130 ℃, and crystallizing for 8-24 hours to obtain a crude product;
2) Washing and drying the crude product obtained in the step 1) to obtain a precursor hydrotalcite material;
3) The precursor hydrotalcite material obtained in the step 2) is subjected to hydrogen-argon mixed gas atmosphere at the temperature of 1-5 ℃ for min -1 Heating to 300-700 ℃ at a heating rate, keeping for 2-5 h, switching to a nitrogen atmosphere after finishing, and naturally cooling to room temperature to obtain the light-driven iron-based catalyst for preparing high-carbon hydrocarbon by catalyzing carbon dioxide hydrogenation;
the molar ratio of the magnesium salt to the ferric salt to the aluminum salt is 3-1:1:1;
the precipitant is sodium hydroxide, and the added mole number of the precipitant is 2-8 times of the total mole number of the magnesium salt, the ferric salt and the aluminum salt.
2. The method according to claim 1, wherein in step 1), the concentration of the magnesium salt dissolved in deionized water is 0.2 to 0.04 mol.l -1 The method comprises the steps of carrying out a first treatment on the surface of the The concentration of the ferric salt dissolved in deionized water is 0.1-0.02 mol.L -1 The method comprises the steps of carrying out a first treatment on the surface of the The concentration of the aluminum salt dissolved in deionized water is 0.1-0.02 mol.L -1 The method comprises the steps of carrying out a first treatment on the surface of the The magnesium salt is selected from one or more of magnesium nitrate, magnesium chloride or magnesium sulfate; the ferric salt is selected from one or more of ferric nitrate, ferric chloride or ferric sulfate; the aluminum salt is selected from one or more of aluminum nitrate, aluminum chloride or aluminum sulfate.
3. The method according to claim 1, wherein in step 2), the washing is performed 3 to 6 times with deionized water, the drying temperature is 40 to 90 ℃, and the drying time is 5 to 20 hours.
4. The method of claim 1, wherein in step 2), the precursor hydrotalcite material has the chemical formula [ Mg 2+ 1-m-n Fe 3+ m Al 3+ n (OH) 2 ] (m+n)+ ·(A x- ) （m+n）/x ·yH 2 O, wherein 0.2.ltoreq.m+n.ltoreq.0.33; x is the valence number of the anion; y is the quantity of crystal water, and the value range of y is 0.5-9; a is that x- Is NO 3 - Or CO 3 2- 。
5. The method according to claim 1, wherein in the step 3), the volume fraction of hydrogen in the hydrogen-argon mixture is 10%.
6. Use of the iron-based catalyst according to claim 1 in a light-driven catalytic carbon dioxide hydrogenation reaction for preparing higher hydrocarbons.
7. The use according to claim 6, wherein the reaction is carried out under light conditions.
8. The use according to claim 7, wherein the reaction is carried out under full spectrum conditions under light.
9. The application according to claim 6, characterized in that it comprises the steps of:
adding the iron-based catalyst into a light-permeable closed reaction kettle, introducing diluted reaction gas, illuminating under the condition of full spectrum, and detecting the change of a product along with time by adopting gas chromatography;
wherein the diluted reaction gas comprises CO 2 、H 2 And Ar.
10. The use according to claim 9, wherein the iron-based catalyst is added in an amount of 20-120 mg/108ml diluted reaction gas.
11. The use according to claim 9, wherein the CO 2 、H 2 And Ar in a volume ratio of 15:60:25.
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