CN115555022B - Preparation method of catalyst for preparing hydrocarbon by hydrogenation of carbon dioxide - Google Patents
Preparation method of catalyst for preparing hydrocarbon by hydrogenation of carbon dioxide Download PDFInfo
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- CN115555022B CN115555022B CN202211217487.XA CN202211217487A CN115555022B CN 115555022 B CN115555022 B CN 115555022B CN 202211217487 A CN202211217487 A CN 202211217487A CN 115555022 B CN115555022 B CN 115555022B
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- carbon dioxide
- hydroxide
- manganese
- iron oxide
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 50
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 50
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 36
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 24
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 24
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 11
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 70
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910052742 iron Inorganic materials 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- 235000014413 iron hydroxide Nutrition 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims description 63
- 239000000203 mixture Substances 0.000 claims description 38
- 239000002245 particle Substances 0.000 claims description 34
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 239000011148 porous material Substances 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 22
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 13
- 238000005303 weighing Methods 0.000 claims description 13
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- 239000011572 manganese Substances 0.000 claims description 10
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 241000219782 Sesbania Species 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 238000004108 freeze drying Methods 0.000 claims description 7
- 238000003746 solid phase reaction Methods 0.000 claims description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- -1 alkali metal alkaline salt Chemical class 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 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 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 235000011181 potassium carbonates Nutrition 0.000 claims description 6
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 6
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- 229960002089 ferrous chloride Drugs 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 235000017550 sodium carbonate Nutrition 0.000 claims description 4
- 239000012300 argon atmosphere Substances 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 239000003570 air Substances 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 238000002386 leaching Methods 0.000 claims description 2
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical compound [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 claims description 2
- TYTHZVVGVFAQHF-UHFFFAOYSA-N manganese(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Mn+3].[Mn+3] TYTHZVVGVFAQHF-UHFFFAOYSA-N 0.000 claims description 2
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims 3
- ZWXOQTHCXRZUJP-UHFFFAOYSA-N manganese(2+);manganese(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Mn+2].[Mn+3].[Mn+3] ZWXOQTHCXRZUJP-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 16
- 238000001816 cooling Methods 0.000 abstract description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 7
- 238000001125 extrusion Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 abstract description 2
- 239000012265 solid product Substances 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000007789 gas Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000003828 vacuum filtration Methods 0.000 description 4
- 241000282326 Felis catus Species 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910001655 manganese mineral Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 159000000011 group IA salts Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- 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 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
-
- 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)
- Physics & Mathematics (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of a catalyst for preparing hydrocarbon by hydrogenation of carbon dioxide, which comprises the steps of performing high-temperature heat treatment on chemically synthesized iron oxide or hydroxide, cooling, crushing, and preparing an iron-based catalyst for hydrogenation of carbon dioxide by adopting a tabletting or extrusion molding method. The preparation method of the catalyst is simple and practical, and the raw material adaptability is wide. The high-temperature heat treatment can improve the grain size and the crystal structure of the iron oxide, improve the carbon dioxide hydrogenation activity and the activity stability of the iron-based catalyst, improve the carbon dioxide hydrogenation single pass conversion to more than 40%, and improve the selectivity of methane and carbon monoxide to be lower than 10% and the selectivity of long-chain hydrocarbon to be higher.
Description
Technical Field
The invention relates to the technical field of carbon dioxide hydrogenation, in particular to a preparation method of an iron-based catalyst for preparing hydrocarbon by carbon dioxide hydrogenation.
Background
The carbon dioxide is converted into valuable chemicals, which can not only relieve the greenhouse effect, but also reduce the dependence on fossil fuels. In carbon dioxide utilization, the catalytic hydrogenation of carbon dioxide to produce hydrocarbon chemicals is the most feasible and potential research direction, and if combined with the green hydrogen prepared by using renewable energy sources, the catalyst can be used as a source of hydrocarbon chemicals after the exhaustion of fossil fuel in the future and as an effective energy storage mode of renewable energy sources, so that the green cycle of carbon is realized.
At present, two reaction paths exist for synthesizing hydrocarbon chemicals through carbon dioxide hydrogenation: one is to synthesize methanol intermediate first and then prepare hydrocarbon from methanol; the other is carbon dioxide, which is produced by reverse water gas Reaction (RWGS) to carbon monoxide, which is then synthesized by the fischer-tropsch synthesis of synthesis gas to hydrocarbons. Since the hydrogenation of carbon dioxide to prepare methanol is difficult to realize high methanol yield at present, the efficiency is relatively low, and the reverse water gas reaction-Fischer-Tropsch synthesis reaction path can obtain higher carbon dioxide hydrogenation conversion rate and hydrocarbon selectivity by optimizing a catalyst. Research shows that the common iron-based catalyst can catalyze the reverse water gas reaction and the Fischer-Tropsch synthesis reaction, and the control of the catalyst preparation method can improve the hydrogenation reaction activity of carbon dioxide and the selectivity of long-chain hydrocarbon products.
Most of the iron-based carbon dioxide hydrogenation catalysts reported in the current literature are complex in preparation method and poor in reproducibility, such as supersaturation impregnation method in the American naval research laboratory, coprecipitation method of colleges and universities, organic combustion method reported by oxford university and the like. The iron-based catalyst is required to have high carbon dioxide hydrogenation activity and good activity stability. The preparation method of the iron-based catalyst reported in the literature generally pursues the preparation of nano iron-based oxides with fine particles, has poor thermal stability, and has higher surface area and higher activity when in a powder state, but if the iron-based catalyst is prepared into a large-particle catalyst, the effective surface area of the catalyst is greatly reduced due to agglomeration and mutual covering among small grains, so that the overall activity of the catalyst is influenced. And the iron-based oxide with too small size is not suitable for preparing the catalyst for preparing hydrocarbon by hydrogenating carbon dioxide, and researches report that only the reverse water gas shift reaction can be catalyzed to generate carbon monoxide when the particles are too small, and the high coordination structure on the large particles is beneficial to carbon chain growth, namely the iron-based catalyst with larger grain size is beneficial to the increase of the selectivity of long-chain hydrocarbon and reduces the selectivity of byproduct carbon monoxide.
Disclosure of Invention
The invention aims to provide a convenient and practical preparation method of an iron-based catalyst for preparing hydrocarbon by hydrogenating carbon dioxide, which can solve the technical problems of poor activity reproducibility and activity stability of a catalyst for preparing carbon dioxide by using chemically synthesized iron oxide. The invention carries out high-temperature heat treatment on the chemically synthesized iron oxide or hydroxide to improve the grain size and the crystal structure stability of the chemically synthesized iron oxide or hydroxide, and then prepares the iron-based carbon dioxide hydrogenation catalyst by a tabletting and extrusion molding method commonly used in industry. The alumina with different pore volumes is used as a catalyst carrier, so that the mechanical strength of the catalyst can be improved, active metal components can be effectively separated, the effective surface area of the catalyst can be improved due to the rich pore channel structure, and a diffusion channel of reactants and products can be provided, so that the utilization efficiency of active metal is improved, and the overall activity of the catalyst is improved. The alkaline salt or hydroxide auxiliary agent of the alkali metal is loaded by adopting an impregnation method, so that the uniform distribution of the alkaline salt or hydroxide auxiliary agent on the active metal and the carrier alumina can be ensured, and the effect of the alkaline auxiliary agent on promoting carbon dioxide adsorption can be exerted. The prepared catalyst shows good carbon dioxide hydrogenation reaction activity and good long-chain hydrocarbon selectivity in practical application.
The aim of the invention is achieved by the following measures:
firstly, performing high-temperature heat treatment on chemically synthesized iron oxide or hydroxide in air, nitrogen, helium or argon atmosphere at 800-2000 ℃, cooling and crushing into fine powder with the particle diameter of 1-150 mu m.
Then adopting a tabletting or extrusion molding method to prepare the iron-based carbon dioxide hydrogenation catalyst:
(1) weighing 15-45% of heat-treated iron oxide powder, 0-30% of manganese oxide powder and 25-85% of carrier alumina powder, mechanically mixing and uniformly stirring. And simultaneously weighing 10-25% of alkali metal alkaline salt or hydroxide by mass percent of the mixture, preparing into aqueous solution, uniformly adding the aqueous solution into the mixture, then placing the mixture into a cold trap of a freeze dryer for cooling for 4-8 hours, and then transferring the mixture into a drying chamber for drying for 10-24 hours. Taking out the dried catalyst, grinding, tabletting and forming by a tablet press under the pressure of 5-20 MPa, crushing and screening out 10-20 mesh particles, and obtaining the iron-based carbon dioxide hydrogenation catalyst.
(2) Weighing 15-45% of heat-treated iron oxide powder and 0-30% of manganese oxide powder by mass percent to prepare a uniform mixture A, weighing 25-85% of aluminum oxide powder by mass percent, and adding or not adding 2-5% of sesbania powder to prepare a uniform mixture B. Uniformly adding a dilute nitric acid solution with the mass concentration of 3-5% and 70-120% of the mass of aluminum oxide into the mixture B, fully and uniformly mixing, adding the mixture A, fully and uniformly mixing, extruding into a cylindrical strip with the diameter of 1.0-2.0mm, naturally airing, drying at 120 ℃ for 3h, roasting at 350-550 ℃ for 2-8h, and taking out to prepare the formed particles with the length of 2-3 mm. Weighing 10-25% of alkali metal alkaline salt or hydroxide by mass percent of the formed particles, preparing into aqueous solution, and adding the formed particles to completely and uniformly wet the formed particles. Freeze drying for 10-24h; or naturally airing, and drying at 120 ℃ for 3 hours; or roasting for 2-8 hours at 350-550 ℃ to obtain the iron-based carbon dioxide hydrogenation catalyst.
The iron oxide or hydroxide synthesis methods include, but are not limited to: solid phase reaction, precipitation, hydrothermal synthesis. The solid phase reaction method is that ferrous salt and ferric salt are mixed and grinded firstly, wherein the ferrous salt accounts for 0-50% of the mole percentage, and the ferric salt accounts for 50-100% of the mole percentage; then adding alkali metal hydroxide with the total mole number of 2.5-3 times of ferrous salt and ferric salt, continuously mixing and grinding, and leaching the solid phase reaction product by deionized water to obtain the iron oxide or hydroxide. The ferrous and ferric salts include, but are not limited to: ferrous chloride, ferrous sulfate, ferric chloride, and ferric nitrate.
The manganese oxide is one or more than two of natural or chemically synthesized manganese dioxide, manganese sesquioxide, manganous oxide and manganese monoxide, and comprises one or more than two of natural pyrolusite, brown manganese ore and square manganese ore, wherein the mass percentage of manganese is 60-77%, and the particle diameter is 1-150 mu m. The alumina as carrier has pore volume of 0.2-0.6cm 3 Alumina/g and pore volume of 0.8-1.2cm 3 One or two of the aluminum oxides per gram are combined, and the mass ratio of the aluminum oxides to the aluminum oxides is preferably 1:1-1:5. The alkali metal alkaline salt or hydroxide is one or more of potassium carbonate, potassium bicarbonate, potassium hydroxide, sodium carbonate, sodium bicarbonate and sodium hydroxide.
The beneficial effects of the invention are as follows:
(1) The preparation method of the iron-based catalyst for preparing hydrocarbon by hydrogenation of carbon dioxide is simple and practical, has wide raw material adaptability and is easy to realize industrially;
(2) The problems of poor activity reproducibility and activity stability of the chemically synthesized iron-based oxide catalyst can be solved by simple high-temperature heat treatment, the carbon dioxide conversion rate can reach more than 40% under proper reaction conditions, and the selectivity of long-chain hydrocarbon is better.
Detailed Description
The invention will be further described with reference to the following specific embodiments, without limiting the scope of the invention to the following examples.
The catalyst used in the invention is evaluated as follows:
and (3) carrying out reaction evaluation of carbon dioxide catalytic hydrogenation by adopting a fixed bed reactor, wherein the catalyst filling amount is 20mL, condensing reaction products at the temperature of 2 ℃, taking liquid hydrocarbon products and water, and estimating the carbon dioxide single pass conversion rate according to the water production amount. The non-condensable gas phase products were analyzed for content by on-line gas chromatography with TCD and FID detectors and selectivity to carbon monoxide, methane and lower hydrocarbons was obtained by using the nitrogen internal standard method.
Before the hydrogenation reaction of carbon dioxide, the catalyst needs to be reduced and carbonized first. The reduction process specifically comprises the following steps: the reactor is filled with hydrogen gas to be pressurized to 2-4MPa, the space velocity of the hydrogen gas is regulated to be 200-600 mL/(h.g cat), the temperature is raised to 350-450 ℃ at the speed of 1 ℃/min, and the reduction is continued for 4-10 hours. The carbonization process comprises the following steps: reducing the temperature of the reactor to 100 ℃ after hydrogen reduction, introducing carbon dioxide, and adjusting H 2 /CO 2 The molar ratio is 2.0-4.0, the total gas space velocity is 500-800 mL/(h.g cat), the pressure is kept at 2-4MPa, and the temperature is raised to 250-350 ℃ at the speed of 1 ℃/min for carbonization for 4-10 hours.
After carbonization, adjusting reaction conditions to hydrogenate carbon dioxide: hold H 2 /CO 2 The molar ratio is 2.0-4.0, the reaction temperature is 250-350 ℃, the pressure is 2-4MPa, 10mL/min of high-purity nitrogen is introduced as internal standard gas, the total gas space velocity is 500-1000 mL/(h.g cat), and the temperature of a condensing tank, a high-pressure separating tank and a low-pressure separating tank in a reaction device is controlled to be 2 ℃ by adopting a low-temperature constant-temperature tank. After 24 hours of reaction duration, condensed liquid hydrocarbon product and water were taken up while the non-condensable gas composition was analyzed by on-line chromatography.
Example 1
96g of ferric trichloride hexahydrate (0.355 mol, 64.4 mol percent) and 39g of ferrous chloride tetrahydrate (0.196 mol, 35.6 mol percent) are weighed, mixed and ground, then 81.75g of potassium hydroxide (1.457 mol) is added, mixed and ground until all the solid product turns into black, the solid product is transferred to a buchner funnel which is subjected to vacuum filtration, and the solid product is leached with deionized water for more than 6 times while the solid product is subjected to vacuum filtration. And (3) heating the black solid product with water removed to 1000 ℃ at a speed of 1 ℃/min in a muffle furnace for 4 hours under the nitrogen atmosphere, cooling and crushing the black solid product into iron oxide powder A with a particle diameter of 1-150 mu m.
Example 2
81.4g of ferric trichloride hexahydrate (0.301 mol, 54.6 mol percent) and 69.5g of ferrous sulfate heptahydrate (0.250 mol, 45.4 mol percent) are weighed, mixed and ground, then 56.12g of sodium hydroxide (1.403 mol) is added, mixed and ground until all the solid product turns black, the solid product is transferred to a buchner funnel which is subjected to vacuum filtration, and the solid product is leached with deionized water for more than 6 times while the solid product is subjected to vacuum filtration. And (3) heating the black solid product with water removed to 1500 ℃ at a speed of 1 ℃/min in a muffle furnace under helium atmosphere for 2 hours, cooling and crushing the black solid product into iron oxide powder B with a particle diameter of 1-150 mu m.
Example 3
89.2g of ferric trichloride hexahydrate (0.330 mol, 59.9 mole percent) and 43.94g of ferrous chloride tetrahydrate (0.221 mol, 40.1 mole percent) were weighed into a beaker, 500mL of deionized water and 5mL of concentrated hydrochloric acid 12mol/L were added, stirred for dissolution and warmed to 70 ℃. 85.0g of potassium hydroxide (1.515 mol) was weighed into 750mL of water, added dropwise to the above-described iron salt mixed solution, and the pH of the solution was continuously monitored using an acidometer. Stopping adding potassium hydroxide solution when the pH value of the solution is raised to about 10, and keeping at 70 ℃ for 1h. Part of the supernatant was decanted and the remaining solution and solid precipitate were transferred on average to 5 250mL hydrothermal kettles and sealed. Putting the hydrothermal kettle into a 160 ℃ oven for hydrothermal treatment for 12 hours, taking out, cooling, opening the kettle, carrying out suction filtration and washing, heating the black solid product with water removed to 1200 ℃ for 4 hours at the speed of 1 ℃/min in an argon atmosphere in a muffle furnace, cooling, and crushing into iron oxide powder C with the particle diameter of 1-150 mu m.
Example 4
222.6g of ferric nitrate nonahydrate (0.551 mol) was weighed into a beaker, 500mL of deionized water and 5mL of 12mol/L concentrated hydrochloric acid were added, dissolved with stirring and warmed to 70 ℃. 70.0g of sodium hydroxide (1.750 mol) was weighed into 850mL of water, added dropwise to the ferric nitrate solution, and the pH of the solution was continuously monitored using an acidometer. When the pH value of the solution is raised to about 10, the addition of the sodium hydroxide solution is stopped, and the solution is kept at 70 ℃ for 1h. Cooling the solution, filtering, washing, heating the solid product with water removed to 800 ℃ at a speed of 1 ℃/min in a muffle furnace for 6 hours, cooling, and crushing into iron oxide powder D with a particle diameter of 1-150 mu m.
Example 5
7.05g of iron oxide powder A,5.70g of chemically synthesized commercial manganese dioxide powder with the mass percentage content of 98 percent and 3.45g of pore volume of 0.2-0.6cm are weighed 3 Alumina powder/g and pore volume of 13.80g0.8-1.2cm 3 And (3) per gram of alumina powder, and fully stirring and uniformly mixing. 4.50g of potassium carbonate was weighed out and dissolved in 14mL of water, and the solution was added uniformly to the above mixture until completely wetted. Freeze-drying the impregnated sample for 16h, tabletting under the pressure of 10MPa by a tabletting machine, crushing and sieving the tabletting to obtain 10-20-mesh catalyst particles, and obtaining the iron-based carbon dioxide hydrogenation catalyst.
Example 6
7.05g of iron oxide powder B,4.65g of square manganese mineral powder (manganese mass percentage content is 76%) and 3.66g of pore volume of 0.2-0.6cm are weighed 3 Alumina powder/g and pore volume of 0.8-1.2cm at 14.64g 3 And (3) per gram of alumina powder, and fully stirring and uniformly mixing. 6.00g of potassium bicarbonate was weighed out and dissolved in 15mL of water, and the solution was added uniformly to the above mixture until it was completely wetted. Freeze-drying the impregnated sample for 18h, tabletting under the pressure of 10MPa by a tabletting machine, crushing and sieving the tabletting to obtain 10-20-mesh catalyst particles, and obtaining the iron-based carbon dioxide hydrogenation catalyst.
Example 7
Weighing 35.5g of iron oxide powder A and 28.5g of pyrolusite powder (manganese mass percentage content is 62%) to prepare a uniform mixture A; weighing 17.2g of the mixture, and the pore volume is 0.2-0.6cm 3 Alumina powder/g and pore volume of 0.8-1.2cm in 68.8g 3 Per gram of alumina powder and 5g of sesbania powder. 90g of dilute nitric acid solution with the mass concentration of 4.0% is weighed, added into the mixture B dropwise and stirred uniformly, then added into the mixture A and mixed uniformly, extruded and kneaded twice in a strip extruder, and extruded into strips with the diameter of 1.6 mm. Naturally airing, drying at 120 ℃ for 3 hours, roasting at 450 ℃ for 4 hours, and taking out to prepare the formed particles with the length of 2-3 mm. Weighing 50g of baked formed particles and 10.0g of potassium hydroxide, dissolving the potassium hydroxide in 14mL of water, uniformly soaking, and freeze-drying for 14h to obtain the iron-based carbon dioxide hydrogenation catalyst.
Example 8
36.5g of iron oxide powder B and 23.5g of commercially available manganese monoxide powder with 99 mass percent of chemical synthesis are weighed to prepare a uniform mixture A; weighing 30.0g of the porous material with the pore volume of 0.2-0.6cm 3 Alumina powder per gram and 60.0g pore volume of 0.8-1.2cm 3 Alumina powder/g and 4g fieldThe cyanine powder is prepared into a uniform mixture B. 100g of dilute nitric acid solution with the mass concentration of 3.5% is weighed, added into the mixture B dropwise and stirred uniformly, then added into the mixture A and mixed uniformly, extruded and kneaded twice in a strip extruder, and extruded into strips with the diameter of 1.8 mm. Naturally airing, drying at 120 ℃ for 3 hours, roasting at 400 ℃ for 6 hours, and taking out to prepare the formed particles with the length of 2-3 mm. 50g of baked formed particles and 7.5g of sodium carbonate are weighed, sodium carbonate is dissolved in 15mL of water, and after uniform impregnation, the mixture is naturally dried and dried at 120 ℃ for 3 hours, so that the iron-based carbon dioxide hydrogenation catalyst is obtained.
Example 9
49.0g of iron oxide powder C and 15.0g of black manganese mineral powder (manganese mass percentage content is 70%) are weighed to prepare a uniform mixture A; 43.0g of pore volume of 0.2-0.6cm is weighed 3 Alumina powder per gram and pore volume of 0.8-1.2cm in 43.0g 3 Per gram of alumina powder and 7.5g of sesbania powder. 90g of dilute nitric acid solution with the mass concentration of 4.5% is weighed, added into the mixture B dropwise and stirred uniformly, then added into the mixture A and mixed uniformly, extruded and kneaded twice in a strip extruder, and extruded into strips with the diameter of 1.8 mm. Naturally airing, drying at 120 ℃ for 3 hours, roasting at 350 ℃ for 6 hours, and taking out to prepare the formed particles with the length of 2-3 mm. Weighing 50g of baked formed particles and 11.0g of sodium bicarbonate, dissolving the sodium bicarbonate in 14mL of water, naturally airing after uniform impregnation, drying at 120 ℃ for 3 hours, and baking at 350 ℃ for 4 hours to obtain the iron-based carbon dioxide hydrogenation catalyst.
Example 10
31.0g of iron oxide powder D and 31.0g of brown manganese mineral powder (67% of manganese mass percent) are weighed to prepare a uniform mixture A; 22.0g of pore volume of 0.2-0.6cm is weighed 3 Alumina powder/g and 66.0g pore volume 0.8-1.2cm 3 Per gram of alumina powder and 6g of sesbania powder. 95g of dilute nitric acid solution with the mass concentration of 3.5% is weighed, added into the mixture B dropwise and stirred uniformly, then added into the mixture A and mixed uniformly, extruded and kneaded twice in a strip extruder, and then extruded into strips with the diameter of 1.8 mm. Naturally airing, drying at 120 ℃ for 3 hours, roasting at 400 ℃ for 6 hours, and taking out to prepare the formed particles with the length of 2-3 mm. 50g of the calcined shaped granules and 5.5g of sodium hydroxide were weighed and dissolved in 1And (3) in 5mL of water, uniformly soaking, naturally airing, drying at 120 ℃ for 3h, and roasting at 400 ℃ for 4h to obtain the iron-based carbon dioxide hydrogenation catalyst.
Comparative example 1
The iron oxide prepared by the solid phase reaction method of example 1 was not subjected to high temperature heat treatment but was freeze-dried and then pulverized into fine powder having a particle diameter of 1 to 150. Mu.m. 7.05g of the iron oxide powder, 5.70g of chemically synthesized commercial manganese dioxide powder with the mass percentage content of 98 percent and 3.45g of pore volume of 0.2-0.6cm are weighed 3 Alumina powder/g and pore volume of 0.8-1.2cm of 13.80g 3 And (3) per gram of alumina powder, and fully stirring and uniformly mixing. 4.50g of potassium carbonate was weighed out and dissolved in 14mL of water, and the solution was added uniformly to the above mixture until completely wetted. And freeze-drying the impregnated sample for 16 hours, tabletting by a tabletting machine under the pressure of 10MPa, crushing and sieving the tabletting to obtain 10-20-mesh catalyst particles, and thus obtaining the comparative iron-based carbon dioxide hydrogenation catalyst.
Comparative example 2:
the iron oxide prepared in example 3 was not subjected to high temperature heat treatment but freeze-dried and then pulverized into fine powder having a particle diameter of 1 to 150. Mu.m. 36.5g of the iron oxide powder and 23.5g of a commercially available manganese monoxide powder having a mass percentage of 99% by chemical synthesis were weighed to prepare a homogeneous mixture A; weighing 30.0g of the porous material with the pore volume of 0.2-0.6cm 3 Alumina powder per gram and 60.0g pore volume of 0.8-1.2cm 3 Per gram of alumina powder and 4g of sesbania powder. 100g of dilute nitric acid solution with the mass concentration of 3.5% is weighed, added into the mixture B dropwise and stirred uniformly, then added into the mixture A and mixed uniformly, extruded and kneaded twice in a strip extruder, and extruded into strips with the diameter of 1.8 mm. Naturally airing, drying at 120 ℃ for 3 hours, roasting at 400 ℃ for 6 hours, and taking out to prepare the formed particles with the length of 2-3 mm. 50g of baked formed particles and 7.5g of potassium carbonate are weighed, the potassium carbonate is dissolved in 15mL of water, and the mixture is uniformly soaked, dried for 3 hours at 120 ℃ and baked for 4 hours at 400 ℃ to obtain the comparative iron-based carbon dioxide hydrogenation catalyst.
The following table is a comparative table of the results of activity evaluation of 20mL of the catalyst prepared in examples 5 to 10 and comparative examples 1 to 2, which was run continuously for 24 hours, including the amount of water produced by the reaction and calculatedCO out 2 Conversion of methane, carbon monoxide, C in the product 5 + The above liquid hydrocarbon yields. It can be seen that the iron oxide powder obtained by taking chemically synthesized iron oxide or hydroxide after high-temperature heat treatment is used as a raw material, the iron-based carbon dioxide hydrogenation catalyst is prepared by a simple tabletting or extrusion molding method, the single-pass conversion rate of carbon dioxide hydrogenation can reach more than 40%, the selectivity of methane and carbon monoxide in the product is lower than 10%, and the carbon dioxide hydrogenation conversion rate and the selectivity of long-chain hydrocarbon are higher than those of the iron-based catalyst prepared by the iron oxide or hydroxide which is not subjected to high-temperature heat treatment.
| Examples | Water (mL/24 h) | CO 2 Conversion (%) | CH 4 (％) | CO(％) | C 5 + (％) |
| Example 5 | 47.0 | 40.62 | 8.64 | 4.98 | 51.63 |
| Example 6 | 46.5 | 40.19 | 8.36 | 4.79 | 50.87 |
| Example 7 | 49.0 | 42.35 | 9.72 | 4.34 | 52.66 |
| Example 8 | 48.0 | 41.49 | 9.45 | 4.23 | 51.93 |
| Example 9 | 47.5 | 41.05 | 8.31 | 4.46 | 51.89 |
| Example 10 | 47.0 | 40.62 | 8.28 | 4.50 | 50.95 |
| Comparative example 1 | 26.0 | 22.47 | 17.55 | 10.16 | 20.75 |
| Comparative example 2 | 24.0 | 20.74 | 15.58 | 11.47 | 21.85 |
Claims (5)
1. The application of the catalyst in preparing hydrocarbon by hydrogenating carbon dioxide is characterized in that: the method for preparing the carbon dioxide hydrogenation catalyst comprises the following steps of:
(1) Performing heat treatment on iron oxide or hydroxide, performing heat treatment in air, nitrogen, helium or argon atmosphere at 800-2000 ℃, and then crushing into iron oxide powder with particle diameter of 1-150 mu m;
(2) The carbon dioxide hydrogenation catalyst is prepared by adopting the iron oxide powder through the following two methods:
(1) mechanically mixing 15% -45% of heat-treated iron oxide powder, 0% -30% of manganese oxide powder and 25% -85% of aluminum oxide in percentage by mass and uniformly stirring; weighing 10-25% of alkali metal alkaline salt or hydroxide by mass percent of the mixture, preparing into water solution, dripping the water solution into the mixture, and uniformly stirring, wherein the adding amount of water ensures that the mixture is completely and uniformly wetted; freeze-drying the mixture for 10-24h, grinding, tabletting, forming, crushing and screening to obtain the iron-based carbon dioxide hydrogenation catalyst;
(2) preparing a uniform mixture A from 15 to 45 mass percent of iron oxide powder and 0 to 30 mass percent of manganese oxide powder after heat treatment, and preparing a uniform mixture B from 25 to 85 mass percent of aluminum oxide with or without sesbania powder, wherein the adding proportion of the sesbania powder is 2 to 5 mass percent of the sum of the iron oxide powder, the manganese oxide powder and the aluminum oxide; adding 3-5% nitric acid solution into the mixture B, wherein the adding proportion of the nitric acid solution is 70-120% of the alumina mass, fully and uniformly mixing, adding the mixture A, fully mixing and stirring into a sticky dough, extruding into a cylindrical strip with the diameter of 1.0-2.0mm, naturally airing, drying at 120 ℃ for 3h, roasting at 350-550 ℃ for 2-8h, taking out, and preparing into 2-3mm long molded particles; weighing 10-25% of alkali metal alkaline salt or hydroxide by mass percent of the formed particles, preparing an aqueous solution, dripping the aqueous solution into the formed particles, and ensuring that the formed particles can be completely and uniformly wetted by the addition of water; freeze drying for 10-24h; or naturally airing, and drying at 120 ℃ for 3 hours; or roasting for 2-8 hours at 350-550 ℃ to obtain the carbon dioxide hydrogenation catalyst.
2. The use according to claim 1, characterized in that: the method for synthesizing the iron oxide or hydroxide comprises the following steps: solid phase reaction, precipitation, hydrothermal synthesis; the solid phase reaction method is that ferrous salt and ferric salt are mixed and grinded firstly, wherein the ferrous salt accounts for 0-50% of the mole percentage, and the ferric salt accounts for 50-100% of the mole percentage; then adding alkali metal hydroxide with the total mole number of 2.5-3 times of that of ferrous salt and ferric salt, continuously mixing and grinding, and leaching the solid-phase reaction product with deionized water to obtain iron oxide or hydroxide; the ferrous and ferric salts include: ferrous chloride, ferrous sulfate, ferric chloride, and ferric nitrate.
3. The use according to claim 1, characterized in that: the manganese oxide is one or more than two of natural or chemically synthesized manganese dioxide, manganese sesquioxide, manganous oxide and manganese monoxide, wherein the natural manganese oxide comprises one or more than two of pyrolusite, hausmannite, brown manganese ore and square manganese ore, the mass percentage of manganese is 60-77%, and the particle diameter is 1-150 mu m.
4. The use according to claim 1, characterized in that: the alumina has pore volume of 0.2-0.6cm 3 Alumina/g and pore volume of 0.8-1.2cm 3 One or two of the alumina/g, when the alumina/alumina composite is formed by two of the alumina composite, the mass ratio of the alumina to the alumina composite is 1:1-1:5.
5. Use according to claim 1 or 2, characterized in that: the alkali metal alkaline salt or hydroxide is one or more than two of potassium carbonate, potassium bicarbonate, potassium hydroxide, sodium carbonate, sodium bicarbonate and sodium hydroxide.
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