CN115555022A - Preparation method of catalyst for preparing hydrocarbon by carbon dioxide hydrogenation - Google Patents
Preparation method of catalyst for preparing hydrocarbon by carbon dioxide hydrogenation Download PDFInfo
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- CN115555022A CN115555022A CN202211217487.XA CN202211217487A CN115555022A CN 115555022 A CN115555022 A CN 115555022A CN 202211217487 A CN202211217487 A CN 202211217487A CN 115555022 A CN115555022 A CN 115555022A
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- carbon dioxide
- catalyst
- hydroxide
- iron
- mixture
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 55
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 55
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 44
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 29
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 28
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 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 64
- 229910052742 iron Inorganic materials 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 20
- 235000014413 iron hydroxide Nutrition 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims description 66
- 239000000203 mixture Substances 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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 31
- 239000002245 particle Substances 0.000 claims description 30
- 238000005303 weighing Methods 0.000 claims description 27
- 239000011148 porous material Substances 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 19
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 16
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 15
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims description 13
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 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
- 238000002156 mixing Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 241000219782 Sesbania Species 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
- 150000003839 salts Chemical class 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 238000004108 freeze drying Methods 0.000 claims description 7
- 235000011121 sodium hydroxide Nutrition 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
- 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
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 238000012216 screening Methods 0.000 claims description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 4
- 229960002089 ferrous chloride Drugs 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 159000000011 group IA salts Chemical class 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
- 239000012298 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
- 238000001027 hydrothermal synthesis Methods 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
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 239000003570 air Substances 0.000 claims description 2
- -1 alkali metal alkaline salt Chemical class 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
- 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
- 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 description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000001308 synthesis method Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims 2
- 238000007605 air drying Methods 0.000 claims 1
- 229910052786 argon Inorganic materials 0.000 claims 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical compound [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 17
- 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
- 239000013078 crystal Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 239000007789 gas Substances 0.000 description 10
- 239000012265 solid product Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 239000008187 granular material Substances 0.000 description 5
- 239000008240 homogeneous mixture Substances 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 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
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 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
- 238000001354 calcination Methods 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 229940044631 ferric chloride hexahydrate Drugs 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
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000009736 wetting 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
- 239000003513 alkali Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 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
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229940032296 ferric chloride Drugs 0.000 description 1
- 229960001781 ferrous sulfate Drugs 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
- 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
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 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
- 230000014759 maintenance of location Effects 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 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
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011946 reduction process Methods 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
- 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)
- Thermal Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of a catalyst for preparing hydrocarbon by carbon dioxide hydrogenation, which is characterized in that chemically synthesized iron oxide or hydroxide is subjected to high-temperature heat treatment, cooled and crushed, and then the iron-based catalyst for preparing the carbon dioxide hydrogenation is prepared by adopting a tabletting or extruding strip forming 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 single-pass conversion rate of the carbon dioxide hydrogenation to more than 40 percent, lower than 10 percent of the selectivity of methane and carbon monoxide and higher than the selectivity of long-chain hydrocarbons.
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 conversion of carbon dioxide into valuable chemicals can both mitigate the greenhouse effect and reduce the dependence on fossil fuels. In the utilization of carbon dioxide, the catalytic hydrogenation of carbon dioxide to generate hydrocarbon chemicals is the most feasible and most potential research direction, and if the catalytic hydrogenation is combined with 'green hydrogen' prepared by using renewable energy, the catalytic hydrogenation can be used as a source of hydrocarbon chemicals after fossil fuel is exhausted in the future, and can be used as an effective energy storage mode of renewable energy to realize green cycle of carbon.
At present, the hydrocarbon chemicals synthesized by carbon dioxide hydrogenation mainly have two reaction paths: one is to synthesize a methanol intermediate and then prepare hydrocarbon from methanol; the other is that carbon dioxide is firstly generated into carbon monoxide through reverse water gas Reaction (RWGS), and then hydrocarbon is generated through Fischer-Tropsch synthesis reaction of synthesis gas. The preparation of methanol by carbon dioxide hydrogenation has the defects of difficult realization of high methanol yield and relatively low efficiency, 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 iron-based catalyst can catalyze the reverse water gas reaction and has Fischer-Tropsch synthesis reaction activity, and the control of the preparation method of the catalyst can improve the carbon dioxide hydrogenation reaction activity and the selectivity of long-chain hydrocarbon products.
Most of the iron-based carbon dioxide hydrogenation catalysts reported in the literature at present are complicated in preparation method and poor in reproducibility, such as a supersaturated impregnation method in a research laboratory of the navy of the United states, a coprecipitation method in a large continuous chemical institute, an organic combustion method reported by the university of Oxford and the like. Iron-based catalysts need to have not only higher carbon dioxide hydrogenation activity but also good activity stability. The preparation method of the iron-based catalyst reported in the literature at present generally pursues to prepare nano iron-based oxide with fine particles, has poor thermal stability, has high activity due to high surface area 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 crystal grains, and the overall activity of the catalyst is influenced. And the iron-based oxide with too fine size is not suitable for preparing the catalyst for preparing the hydrocarbon by hydrogenating the carbon dioxide, and researches report that when the particle size is too small, the iron-based oxide can only catalyze the reverse water-gas shift reaction to generate the carbon monoxide, and the high coordination structure on the large particle is beneficial to the growth of the carbon chain, namely the iron-based catalyst with larger grain size is beneficial to the increase of the selectivity of the long-chain hydrocarbon and the reduction of the selectivity of the carbon monoxide serving as a byproduct.
Disclosure of Invention
The invention aims to provide a convenient and practical preparation method of an iron-based catalyst for preparing hydrocarbons by carbon dioxide hydrogenation, 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 chemically synthesized iron oxide or hydroxide to improve the grain size and the crystal structure stability of the iron oxide or hydroxide, and then prepares the iron-based carbon dioxide hydrogenation catalyst by the commonly used tabletting and extrusion molding method 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 by rich pore channel structures, and diffusion channels of reactants and products can be provided, thereby being beneficial to improving the utilization efficiency of active metals and improving the overall activity of the catalyst. The impregnation method is adopted to load the alkali salt or hydroxide auxiliary agent of the alkali metal, so that the uniform distribution of the alkali salt or hydroxide auxiliary agent on the active metal and the carrier alumina can be ensured, and the effect of promoting the carbon dioxide adsorption by the alkali auxiliary agent can be favorably exerted. The prepared catalyst shows good carbon dioxide hydrogenation reaction activity and good long-chain hydrocarbon selectivity in practical application.
The object of the invention is achieved by the following measures:
firstly, chemically synthesized iron oxide or hydroxide is subjected to high-temperature heat treatment in the air, nitrogen, helium or argon atmosphere at the temperature of 800-2000 ℃, and is crushed into fine powder with the particle diameter of 1-150 mu m after being cooled.
Then preparing the iron-based carbon dioxide hydrogenation catalyst by adopting a tabletting or extruding strip forming method:
(1) weighing 15-45 wt% of heat-treated iron oxide powder, 0-30 wt% of manganese oxide powder and 25-85 wt% of carrier alumina powder, mechanically mixing and stirring uniformly. Meanwhile, alkaline salt or hydroxide of alkali metal with the mass percent of 10-25% of the mixture is weighed to prepare aqueous solution, the aqueous solution is evenly added into the mixture, then the mixture is put into a cold trap of a freeze dryer to be frozen for 4-8 hours, and then the mixture is transferred into a drying chamber to be dried for 10-24 hours. And taking out the dried catalyst, grinding, tabletting and forming by using a tabletting machine under the pressure of 5-20 MPa, crushing and screening to obtain 10-20 mesh particles, thus obtaining the iron-based carbon dioxide hydrogenation catalyst.
(2) Weighing 15-45% by mass of the heat-treated iron oxide powder and 0-30% by mass of manganese oxide powder to prepare a uniform mixture A, weighing 25-85% by mass of alumina powder, and adding or not adding 2-5% by mass of sesbania powder to prepare a uniform mixture B. Uniformly adding a dilute nitric acid solution with the mass concentration of 3-5% and the mass of 70-120% of that of the alumina into the mixture B, fully and uniformly mixing and stirring, then adding the mixture A, fully and uniformly mixing and stirring, extruding into cylindrical strips with the diameter of 1.0-2.0mm, naturally drying, 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. And weighing alkaline salt or hydroxide of alkali metal with the mass percent of 10-25% of the formed particles, preparing into aqueous solution, and adding the aqueous solution into the formed particles to completely and uniformly wet the formed particles. Then freeze-drying for 10-24h; or naturally drying, and drying at 120 deg.C for 3 hr; or roasting at 350-550 ℃ for 2-8h to obtain the iron-based carbon dioxide hydrogenation catalyst.
The iron oxide or hydroxide synthesis method includes but is not limited to: solid phase reaction method, precipitation method, hydrothermal synthesis method. The solid phase reaction method is that ferrous salt and ferric salt are mixed and ground, wherein the molar percentage of the ferrous salt is 0-50%, and the molar percentage of the ferric salt is 50-100%; then adding alkali metal hydroxide with the total mole number of 2.5-3 times of that of the ferrous salt and the ferric salt, continuously mixing and grinding, and leaching the solid-phase reaction product with 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, ferric nitrate.
The manganese oxide is one or more of natural or chemically synthesized manganese dioxide, manganic oxide and manganese monoxide, and comprises one or more of natural pyrolusite, hausmannite, limonite and manganosite, wherein the mass percentage of the manganese is 60-77%, and the particle diameter is 1-150 mu m. The carrier alumina has a pore volume of 0.2-0.6cm 3 Alumina per gram and pore volume of 0.8-1.2cm 3 One or two of the alumina or the alumina and the alumina are preferably 1:1-1:5 in mass ratio. 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 invention has the beneficial effects that:
(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 through simple high-temperature heat treatment, the carbon dioxide conversion rate can reach over 40 percent under proper reaction conditions, and the selectivity of long-chain hydrocarbon is good.
Detailed Description
The invention will now be further described with reference to specific embodiments, without limiting the scope of the invention to the following examples.
The catalyst adopted by the invention is evaluated as follows:
and (3) carrying out reaction evaluation of catalytic hydrogenation of carbon dioxide by adopting a fixed bed reactor, wherein the filling amount of the catalyst is 20mL, the reaction product is condensed at 2 ℃, a liquid hydrocarbon product and water are taken, and the per-pass conversion rate of the carbon dioxide is estimated according to the generation amount of the water. The content of the gas phase product which can not be condensed is analyzed by an on-line gas chromatography which is provided with a TCD detector and a FID detector, and the selectivity of carbon monoxide, methane and low-carbon hydrocarbon is obtained by adopting a nitrogen internal standard method.
Before the carbon dioxide hydrogenation reaction is carried out, the catalyst needs to be reduced and carbonized firstly. The reduction process specifically comprises the following steps: introducing hydrogen into the reactor, pressurizing to 2-4MPa, adjusting the space velocity of the hydrogen to 200-600 mL/(h.g cat), heating to 350-450 ℃ at the speed of 1 ℃/min, and continuously reducing for 4-10 hours. The carbonization process specifically 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.
And (3) adjusting reaction conditions to carry out carbon dioxide hydrogenation after carbonization: retention of 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 the reaction device is controlled to be 2 ℃ by adopting a low-temperature thermostatic bath. After a reaction time of 24h, the condensed liquid hydrocarbon product and water were taken off while the composition of the non-condensable gases was analysed by on-line chromatography.
Example 1
96g of ferric chloride hexahydrate (0.355 mol, 64.4 mol%) and 39g of ferrous chloride tetrahydrate (0.196 mol, 35.6 mol%) were weighed, mixed and ground, then 81.75g of potassium hydroxide (1.457 mol) was added, mixed and ground continuously until the mixture became a black solid product, and the black solid product was transferred to a buchner funnel with vacuum filtration and rinsed with deionized water for more than 6 times while vacuum filtration was performed. Heating the black solid product without water content to 1000 deg.C under nitrogen atmosphere in muffle furnace at 1 deg.C/min for 4h, cooling, and pulverizing into iron oxide powder A with particle diameter of 1-150 μm.
Example 2
81.4g of ferric chloride hexahydrate (0.301 mol, mol percent 54.6%) and 69.5g of ferrous sulfate heptahydrate (0.250 mol, mol percent 45.4%) were weighed, mixed and ground, then 56.12g of sodium hydroxide (1.403 mol) were added, mixed and ground continuously until all the mixture became a black solid product, which was transferred to a buchner funnel of vacuum filtration, and rinsed with deionized water for more than 6 times while vacuum filtration was performed. Heating the black solid product without water content to 1500 ℃ at the speed of 1 ℃/min in a muffle furnace under the atmosphere of helium for 2h, cooling and crushing the black solid product into iron oxide powder B with the particle diameter of 1-150 mu m.
Example 3
89.2g of ferric chloride hexahydrate (0.330 mol, mole percent 59.9%) and 43.94g of ferrous chloride tetrahydrate (0.221 mol, mole percent 40.1%) were weighed into a large beaker, 500mL of deionized water and 5mL of 12mol/L concentrated hydrochloric acid were added, dissolved with stirring and warmed to 70 ℃. 85.0g of potassium hydroxide (1.515 mol) was weighed into 750mL of water, added dropwise to the above iron salt mixed solution, and the pH of the solution was continuously monitored using an acidimeter. When the pH value of the solution rises to about 10, the addition of the potassium hydroxide solution is stopped, and the solution is kept at 70 ℃ for 1h. A portion of the supernatant was decanted and the remaining solution and solid precipitate were transferred to an average of 5 250mL hydrothermal kettles and sealed. And (3) putting the hydrothermal kettle into a 160 ℃ oven for hydrothermal treatment for 12h, taking out, cooling, opening the kettle, performing suction filtration and washing, heating the black solid product without water to 1200 ℃ for heat treatment for 4h 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 iron nitrate nonahydrate (0.551 mol) was weighed into a large beaker, 500mL of deionized water and 5mL of 12mol/L concentrated hydrochloric acid were added, dissolved with stirring, and the temperature was raised 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 acidimeter. When the pH value of the solution rises 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 without water to 800 ℃ at the speed of 1 ℃/min in a muffle furnace in the hollow atmosphere for 6h, cooling and crushing into iron oxide powder D with the particle diameter of 1-150 mu m.
Example 5
Weighing 7.05g of iron oxide powder A,5.70g of chemically synthesized commercial manganese dioxide powder with the mass percentage of 98 percent and 3.45g of manganese dioxide powder with the pore volume of 0.2-0.6cm 3 Alumina powder per g and 13.80g of pore volume 0.8-1.2cm 3 The alumina powder per gram is fully stirred and evenly mixed. 4.50g of potassium carbonate are weighed out and dissolved in 14mL of water, and the solution is added uniformly to the mixture until complete wetting. And freeze-drying the soaked sample for 16h, tabletting by using a tabletting machine under the pressure of 10MPa, crushing and screening the tabletted product to obtain 10-20 meshes of catalyst particles, and thus obtaining the iron-based carbon dioxide hydrogenation catalyst.
Example 6
Weighing 7.05g of iron oxide powder B,4.65g of square manganese ore powder (manganese content 76 wt.%), and 3.66g of manganese ore powder with pore volume of 0.2-0.6cm 3 Alumina powder per g and 14.64g of pore volume 0.8-1.2cm 3 The alumina powder per gram is fully stirred and evenly mixed. 6.00g of potassium bicarbonate was weighed into 15mL of water and the solution was added uniformly to the mixture until completely wetted. And freeze-drying the soaked sample for 18h, tabletting by using a tabletting machine under the pressure of 10MPa, crushing and screening the tabletted product to obtain 10-20 meshes of catalyst particles, and thus obtaining the iron-based carbon dioxide hydrogenation catalyst.
Example 7
Weighing 35.5g of iron oxide powder A and 28.5g of pyrolusite powder (the manganese content is 62 mass%) to prepare a uniform mixture A; weighing 17.2g of the mixture with the pore volume of 0.2-0.6cm 3 Alumina powder per g and 68.8g of pore volume of 0.8-1.2cm 3 A homogeneous mixture B was prepared from alumina powder/g, and sesbania powder 5 g. Weighing 90g of dilute nitric acid solution with the mass concentration of 4.0%, dropwise adding the dilute nitric acid solution into the mixture B, uniformly stirring, adding the mixture A, uniformly mixing, extruding and kneading twice in a strip extruding machine, and extruding into strips with the diameter of 1.6 mm. Naturally drying, drying at 120 deg.C for 3 hr, baking at 450 deg.C for 4 hr, and taking out to obtain 2-3mm long molded granule. Weighing 50g of roasted molded 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 chemically synthesized mass percent are weighedPreparing a uniform mixture A from commercial manganese monoxide powder with the content of 99 percent; weighing 30.0g of the mixture with the pore volume of 0.2-0.6cm 3 Alumina powder per gram and 60.0g of pore volume 0.8-1.2cm 3 Alumina powder/g, and sesbania powder 4g were made into a homogeneous mixture B. 100g of dilute nitric acid solution with the mass concentration of 3.5% is weighed, is dropwise added into the mixture B and is uniformly stirred, then the mixture A is added and is uniformly mixed, and the mixture A is firstly extruded and kneaded twice in a strip extruding machine and is extruded into strips with the diameter of 1.8 mm. Naturally drying, drying at 120 deg.C for 3 hr, calcining at 400 deg.C for 6 hr, and taking out to obtain 2-3mm long molded granule. Weighing 50g of roasted molded particles and 7.5g of sodium carbonate, dissolving the sodium carbonate in 15mL of water, uniformly soaking, naturally airing, and drying at 120 ℃ for 3h to obtain the iron-based carbon dioxide hydrogenation catalyst.
Example 9
Weighing 49.0g of iron oxide powder C and 15.0g of black manganese ore powder (the mass percentage of manganese is 70%) to prepare a uniform mixture A; weighing 43.0g of pore volume 0.2-0.6cm 3 Alumina powder and 43.0g of pore volume of 0.8-1.2cm 3 A homogeneous mixture B was prepared from alumina powder/g, and sesbania powder 7.5 g. Weighing 90g of dilute nitric acid solution with the mass concentration of 4.5%, dropwise adding the dilute nitric acid solution into the mixture B, uniformly stirring, adding the mixture A, uniformly mixing, extruding and kneading twice in a strip extruding machine, and extruding into strips with the diameter of 1.8 mm. Naturally drying, drying at 120 deg.C for 3 hr, baking at 350 deg.C for 6 hr, and taking out to obtain 2-3mm long molded granule. Weighing 50g of roasted molded particles and 11.0g of sodium bicarbonate, dissolving the sodium bicarbonate in 14mL of water, uniformly soaking, naturally airing, drying at 120 ℃ for 3h, and roasting at 350 ℃ for 4h to obtain the iron-based carbon dioxide hydrogenation catalyst.
Example 10
Weighing 31.0g of iron oxide powder D and 31.0g of brown manganese ore powder (the manganese content is 67 mass percent) to prepare a uniform mixture A; weighing 22.0g of the mixture with pore volume of 0.2-0.6cm 3 Alumina powder per g and pore volume of 66.0g 0.8-1.2cm 3 Alumina powder/g, and sesbania powder 6g were made into a homogeneous mixture B. Weighing 95g of dilute nitric acid solution with the mass concentration of 3.5%, dropwise adding the dilute nitric acid solution into the mixture B, uniformly stirring, adding the mixture A, uniformly mixing, extruding and kneading twice in a strip extruding machine, and extruding into a product with the diameter of 1.8A strip of mm. Naturally drying, drying at 120 deg.C for 3 hr, calcining at 400 deg.C for 6 hr, and taking out to obtain 2-3mm long molded granule. Weighing 50g of roasted molded particles and 5.5g of sodium hydroxide, dissolving the sodium hydroxide in 15mL 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 in example 1 was not subjected to high temperature heat treatment, but was freeze-dried and pulverized into fine powder having a particle diameter of 1 to 150 μm. Weighing 7.05g of the iron oxide powder, 5.70g of chemically synthesized commercial manganese dioxide powder with the mass percentage of 98 percent, and 3.45g of manganese dioxide powder with the pore volume of 0.2-0.6cm 3 Alumina powder per g and 13.80g of pore volume 0.8-1.2cm 3 The alumina powder per gram is fully stirred and evenly mixed. 4.50g of potassium carbonate are weighed into 14mL of water and the solution is added uniformly to the mixture until complete wetting. And freeze-drying the soaked sample for 16h, tabletting by using a tabletting machine under the pressure of 10MPa, crushing and screening the tabletted product to obtain 10-20 meshes of catalyst particles, and thus obtaining the comparative iron-based carbon dioxide hydrogenation catalyst.
Comparative example 2:
the iron oxide prepared by the coprecipitation-hydrothermal synthesis method of example 3 was not subjected to a high-temperature heat treatment, but was freeze-dried and pulverized into fine powder having a particle diameter of 1 to 150 μm. Weighing 36.5g of the iron oxide powder and 23.5g of chemically synthesized commercial manganese monoxide powder with the mass percentage of 99 percent to prepare a uniform mixture A; weighing 30.0g of porous material with pore volume of 0.2-0.6cm 3 Alumina powder per gram and 60.0g of pore volume 0.8-1.2cm 3 Alumina powder/g, and sesbania powder 4g were made into a homogeneous mixture B. Weighing 100g of dilute nitric acid solution with the mass concentration of 3.5%, dropwise adding the dilute nitric acid solution into the mixture B, uniformly stirring, adding the mixture A, uniformly mixing, extruding and kneading twice in a strip extruding machine, and extruding into strips with the diameter of 1.8 mm. Naturally drying, drying at 120 deg.C for 3 hr, calcining at 400 deg.C for 6 hr, and taking out to obtain 2-3mm long molded granule. And weighing 50g of roasted molded particles and 7.5g of potassium carbonate, dissolving the potassium carbonate in 15mL of water, uniformly soaking, drying at 120 ℃ for 3 hours, and roasting at 400 ℃ for 4 hours to obtain the comparative iron-based carbon dioxide hydrogenation catalyst.
The following table is a comparative table of the activity evaluation results of 20mL of the catalysts prepared in examples 5 to 10 and comparative examples 1 to 2, which were continuously operated for 24 hours, including the amount of water produced by the reaction and the calculated CO 2 Conversion, and methane, carbon monoxide, C in the product 5 + The above liquid hydrocarbon yield. It can be seen that, the iron oxide powder obtained by high-temperature heat treatment of chemically synthesized iron oxide or hydroxide is used as a raw material to prepare the iron-based carbon dioxide hydrogenation catalyst by a simple tabletting or extruding strip forming 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 |
| Comparison ofExample 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 (6)
1. A preparation method of a catalyst for preparing hydrocarbon by carbon dioxide hydrogenation is characterized by comprising the following steps: the method is characterized in that the oxide or hydroxide of iron is subjected to heat treatment to prepare the carbon dioxide hydrogenation catalyst, and comprises the following steps:
(1) The iron oxide or hydroxide is heat treated and then pulverized into iron oxide powder having a particle diameter of 1 to 150 μm.
(2) The carbon dioxide hydrogenation catalyst is prepared by the following two methods by using the iron oxide powder:
(1) according to the mass percentage, 15 to 45 percent of iron oxide powder after heat treatment, 0 to 30 percent of manganese oxide powder and 25 to 85 percent of aluminum oxide are mechanically mixed and evenly stirred. Weighing alkaline salt or hydroxide of alkali metal with the mass percent of 10-25% of the mixture, preparing water solution, dripping the water solution into the mixture, and uniformly stirring, wherein the adding amount of the water ensures that the mixture can be completely and uniformly wetted. And then freeze-drying the mixture for 10-24h, grinding, tabletting, forming, crushing and screening to obtain the iron-based carbon dioxide hydrogenation catalyst.
(2) According to the mass percentage, 15% -45% of the iron oxide powder and 0% -30% of the manganese oxide powder after heat treatment are prepared into a uniform mixture A, 25% -85% of the aluminum oxide is added or not added with sesbania powder to prepare a uniform mixture B, and the adding proportion of the sesbania powder is 2-5% of the mass sum of the iron oxide powder, the manganese oxide powder and the aluminum oxide. Adding 3-5% nitric acid solution into mixture B, adding 70-120% nitric acid solution, stirring, adding mixture A, stirring to obtain viscous dough, extruding into cylindrical strips with diameter of 1.0-2.0mm, air drying, drying at 120 deg.C for 3h, baking at 350-550 deg.C for 2-8h, and taking out to obtain 2-3mm long molded particles. And weighing alkaline salt or hydroxide of alkali metal with the mass percent of 10-25% of the formed particles, preparing water solution, and dropwise adding the water solution into the formed particles, wherein the addition of the water ensures that the formed particles can be completely and uniformly wetted. Then freeze-drying for 10-24h; or naturally drying the mixture for 3 hours at 120 ℃; or roasting at 350-550 ℃ for 2-8h to obtain the carbon dioxide hydrogenation catalyst.
2. The method for producing a hydrocarbon catalyst by hydrogenation of carbon dioxide according to claim 1, wherein: the iron oxide or hydroxide synthesis method includes but is not limited to: solid phase reaction method, precipitation method, hydrothermal synthesis method. The solid phase reaction method is to mix and grind ferrous salt and ferric salt, wherein the molar percentage of the ferrous salt is 0-50%, and the molar percentage of the ferric salt is 50-100%; then adding alkali metal hydroxide with the total molar number of ferrous salt and ferric salt being 2.5-3 times, continuously mixing and grinding, and leaching the solid phase reaction product with deionized water to obtain the oxide or hydroxide of the iron. The ferrous and ferric salts include, but are not limited to: ferrous chloride, ferrous sulfate, ferric chloride, ferric nitrate.
3. The method for producing a hydrocarbon catalyst by hydrogenation of carbon dioxide according to claim 1, wherein: the heat treatment of the iron oxide or hydroxide can be carried out in the atmosphere of air, nitrogen, helium or argon, and the heat treatment temperature is 800-2000 ℃.
4. The method for producing a hydrocarbon catalyst by hydrogenation of carbon dioxide according to claim 1, wherein: the manganese oxide is one or a combination of more than two of natural or chemically synthesized manganese dioxide, manganous oxide and manganese monoxide, the natural manganese oxide comprises one or a combination of more than two of pyrolusite, hausmannite, limonite and manganosite, wherein the mass percentage of manganese is 60-77%, and the particle diameter is 1-150 mu m.
5. The method for producing a hydrocarbon catalyst by hydrogenation of carbon dioxide according to claim 1, wherein: the alumina has a 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 or the alumina and the alumina are preferably 1:1-1:5 in mass ratio.
6. The method for producing a hydrocarbon catalyst by hydrogenation of carbon dioxide according to claim 1 or 2, wherein: the alkali metal alkaline salt or hydroxide is one or the combination of more than two of potassium carbonate, potassium bicarbonate, potassium hydroxide, sodium carbonate, sodium bicarbonate and sodium hydroxide.
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