CN110918097A - Cobalt-based catalyst for preparing high-carbon hydrocarbon by photo-thermal catalysis of carbon monoxide hydrogenation and preparation method and application thereof - Google Patents
Cobalt-based catalyst for preparing high-carbon hydrocarbon by photo-thermal catalysis of carbon monoxide hydrogenation and preparation method and application thereof Download PDFInfo
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- CN110918097A CN110918097A CN201811117498.4A CN201811117498A CN110918097A CN 110918097 A CN110918097 A CN 110918097A CN 201811117498 A CN201811117498 A CN 201811117498A CN 110918097 A CN110918097 A CN 110918097A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 106
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 88
- 239000010941 cobalt Substances 0.000 title claims abstract description 88
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 44
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 38
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 35
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 33
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 25
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 72
- 230000003197 catalytic effect Effects 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 15
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 13
- 238000001228 spectrum Methods 0.000 claims abstract description 13
- 230000008859 change Effects 0.000 claims abstract description 10
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 10
- 238000005286 illumination Methods 0.000 claims abstract description 7
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 35
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 34
- 229960001545 hydrotalcite Drugs 0.000 claims description 34
- 239000002243 precursor Substances 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 20
- 239000000047 product Substances 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 15
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 14
- 150000001868 cobalt Chemical class 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 150000002430 hydrocarbons Chemical class 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 239000012043 crude product Substances 0.000 claims description 7
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical group C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 238000004817 gas chromatography Methods 0.000 claims description 5
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 239000012716 precipitator Substances 0.000 claims description 4
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical group [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 19
- 230000009467 reduction Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 230000001699 photocatalysis Effects 0.000 description 8
- 230000000630 rising effect Effects 0.000 description 8
- 238000003917 TEM image Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002135 nanosheet Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- -1 carbon hydrocarbons Chemical class 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011943 nanocatalyst Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052599 brucite Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
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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
- 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
- B01J23/75—Cobalt
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/043—Catalysts; their physical properties characterised by the composition
- C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
- C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an application of a cobalt-based catalyst for preparing high-carbon hydrocarbon by photo-thermal catalytic carbon monoxide hydrogenation in photo-thermal catalytic Fischer-Tropsch reaction, wherein the cobalt-based catalyst is added into a closed reaction kettle which can pass light, diluted synthesis gas is introduced to carry out full-spectrum illumination, and a gas chromatograph is adopted to detect the change of a product along with time; the synthetic gas comprises CO and H2And N2Wherein said CO, H2And N2In a volume ratio of 20:60: 20. The catalyst provided by the invention is low in cost, convenient to prepare, simple in process and convenient for large-scale production, the prepared cobalt-based catalyst is used for the photothermal catalysis Fischer-Tropsch reaction for the first time, and high-carbon hydrocarbon in the product has high selectivity, so that the process is expected to be applied to industrial production.
Description
Technical Field
The invention relates to the technical field of photo-thermal catalysis. More particularly, relates to a cobalt-based catalyst for preparing high-carbon hydrocarbon by photo-thermal catalysis of carbon monoxide hydrogenation, and a preparation method and application thereof.
Background
With the increasing world population and the increasing aggravation of energy and environmental problems, the development of a clean energy preparation technology is urgently needed. The reserves of fossil fuels are limited, and the combustion of fossil fuels releases a large amount of greenhouse gases and generates a large amount of gases polluting the environment, so that the development of a clean and sustainable energy path becomes a problem and a significant scientific strategy which are highly concerned by a plurality of researchers. Solar energy occupies an irreplaceable position in the future utilization and development of new energy due to the advantages of inexhaustibility, environmental protection, no pollution, recycling and the like. The Fischer-Tropsch synthesis is regarded as a traditional energy preparation technology, and how to drive the Fischer-Tropsch reaction by utilizing clean energy such as solar energy is a topic which needs to be discussed urgently. The Fischer-Tropsch reaction is carried out at high temperature and high pressure, and the high-temperature reaction accelerates the formation of carbon deposition and the inactivation of the catalyst caused by the sintering of the catalyst; meanwhile, the energy and the efficiency are extremely wasted, and how to drive the Fischer-Tropsch reaction under a milder condition is always the foremost and extremely challenging subject in the fields of catalysis and chemistry. The conversion of solar energy into chemical energy by means of solar-driven catalytic technology has been considered as one of the best ways to solve the future renewable energy sources.
Hydrotalcite is a unique type of layered anionic compoundThe main layer board structure of the material is similar to brucite Mg (OH)2The laminate is octahedral MO6The edges are shared, metal ions occupy the center of an octahedron, and hydrotalcite has a plurality of applications in the aspects of catalysis, carriers and functional materials due to the adjustable element composition of a host laminate and the adjustability of an interlayer object. Hydrotalcite is used as a precursor, the lattice positioning effect and the structural topological transformation effect of the hydrotalcite are utilized, and the hydrotalcite is used as the precursor or a rigid and stable template through roasting reduction to induce confinement to form the cheap metal nano catalyst with high dispersibility and high loading, so that the hydrotalcite can replace the traditional noble metal catalyst and is expected to have good selectivity in the Fischer-Tropsch reaction.
Therefore, the invention provides the cobalt-based catalyst for preparing the high-carbon hydrocarbon by photo-thermally catalyzing the hydrogenation of the carbon monoxide, and the cobalt-based catalyst can be used for preparing the high-carbon hydrocarbon with high selectivity by photo-thermally catalyzing the hydrogenation of the carbon monoxide.
Disclosure of Invention
The invention aims to provide a cobalt-based catalyst for preparing high-carbon hydrocarbon by photo-thermal catalysis of carbon monoxide hydrogenation.
The invention also aims to provide a preparation method of the cobalt-based catalyst for preparing high-carbon hydrocarbon by photo-thermal catalysis of carbon monoxide hydrogenation.
The third purpose of the invention is to provide an application of the cobalt-based catalyst for preparing high-carbon hydrocarbon by photo-thermal catalysis of carbon monoxide hydrogenation.
The invention is based on the layered structure of hydrotalcite and the controllability of the proportion of divalent and trivalent metal ions of the laminate, prepares the cobalt-based catalyst with high load and high dispersibility by high-temperature reduction, and uses the catalyst for photo-thermal catalysis of Fischer-Tropsch reaction for the first time, and the product has higher high hydrocarbon selectivity.
In order to achieve the first purpose, the invention adopts the following technical scheme:
a cobalt-based catalyst for preparing high-carbon hydrocarbon by photo-thermal catalysis of carbon monoxide hydrogenation has a chemical formula of Co/Al2O3。
In order to achieve the second purpose, the invention adopts the following technical scheme:
the preparation method of the cobalt-based catalyst for preparing high-carbon hydrocarbon by photo-thermal catalytic carbon monoxide hydrogenation comprises the following steps:
1) preparing mixed metal salt solution: dissolving cobalt salt and aluminum salt in deionized water, adding a precipitator, adding the mixture into a hydrothermal kettle after the cobalt salt and the aluminum salt are fully dissolved, reacting at the temperature of 90-120 ℃, and crystallizing for 8-24 hours to obtain a crude product;
2) washing and drying the crude product obtained in the step 1) to obtain a precursor hydrotalcite material;
3) subjecting the precursor hydrotalcite material obtained in the step 2) to hydrogen-argon mixed gas atmosphere at the temperature of 2-5 ℃ per minute-1And raising the temperature to 600-700 ℃ at the heating rate, keeping the temperature for 2-5 h, switching to a nitrogen atmosphere after the temperature is raised, and naturally cooling to room temperature to obtain the cobalt-based catalyst for preparing the high-carbon hydrocarbon by the photo-thermal catalytic carbon monoxide hydrogenation.
Because the cobalt-based catalyst is an active phase for preparing high-carbon hydrocarbon in the Fischer-Tropsch reaction, alumina is a good carrier in the Fischer-Tropsch reaction, and because the hydrotalcite is used as a precursor, a cobalt salt is required to be used as a cobalt source, and an aluminum salt is used as an aluminum source. In addition, in the invention, the LDH precursor is directly reduced in a reducing atmosphere, and the LDH precursor is firstly calcined into an oxide and then reduced, and the catalytic effects of the catalysts obtained by the two methods are the same, so that the catalyst can be prepared by adopting a direct reduction method in the invention, and the operation steps are simplified.
Preferably, in the step 1), the concentration of the cobalt salt dissolved in the deionized water is 0.3-0.05 mol.L-1(ii) a The concentration of the aluminum salt dissolved in the deionized water is 0.3-0.05 mol.L-1(ii) a The molar concentration ratio of the cobalt salt to the aluminum salt is 0.5-2: 1.
Preferably, in step 1), the cobalt salt is cobalt nitrate, cobalt chloride or cobalt sulfate; the aluminum salt is aluminum nitrate, aluminum chloride or aluminum sulfate.
Preferably, in the step 1), the precipitant is hexamethylenetetramine, and the addition mole number of the precipitant is 1-8 times of the total mole number of the cobalt salt and the aluminum salt.
Preferably, in the step 2), the washing mode is washing with deionized water for 2-5 times, the drying temperature is 50-80 ℃, and the drying time is 6-20 h.
Preferably, in the step 2), the obtained precursor hydrotalcite material has a chemical formula of [ Co [ ]2+ 1-nAl3+ n(OH)2]n+·(Ax-)n/x·yH2O, wherein n is more than or equal to 0.2 and less than or equal to 0.33; x is the valence number of the anion; y is the quantity of crystal water, and the value range of y is 0.5-9; a. thex-Is NO3 -Or CO3 2-。
Preferably, in the step 3), the volume fraction of the hydrogen in the hydrogen-argon mixture gas is 10%.
Preferably, the salts and precipitant used are both analytically pure.
In order to achieve the third purpose, the invention adopts the following technical scheme:
an application of the cobalt-based photocatalyst for preparing high-carbon hydrocarbon by photo-thermal catalytic carbon monoxide hydrogenation in the photo-thermal catalytic Fischer-Tropsch reaction.
Preferably, the application is that a cobalt-based catalyst is added into a light-permeable closed reaction kettle, and N is introduced2The released synthesis gas is subjected to full-spectrum illumination, and the change of products along with time is detected by adopting gas chromatography; the synthetic gas comprises CO and H2And N2Wherein said CO, H2And N2In a volume ratio of 20:60: 20; the gas pressure in the closed reaction kettle is 0.1-0.18 MPa.
Control of CO and H2The ratio of (A) to (B) is 20:60, because the hydrogenation of CO at this ratio is more favorable for the formation of higher hydrocarbons, and the conversion of CO is not too low. The cobalt-based catalyst has good catalytic activity, can induce and catalyze the Fischer-Tropsch reaction at relatively low temperature by utilizing photo-heat, and avoids the formation of carbon deposition caused by high temperature and the inactivation caused by catalyst sintering.
In addition, unless otherwise specified, all starting materials for use in the present invention are commercially available, and any range recited herein includes any value between the endpoints and any subrange between the endpoints and any value between the endpoints or any subrange between the endpoints.
The invention has the following beneficial effects:
(1) the invention takes layered hydrotalcite as a precursor, utilizes the self lattice positioning effect and structural topology transformation effect thereof, and induces the confinement by taking the layered hydrotalcite as the precursor or a rigid and stable template through high-temperature reduction to form the cheap metal cobalt nano catalyst with high dispersity and high load.
(2) The invention can further improve the selectivity of the prepared cobalt-based catalyst in the preparation of high-carbon hydrocarbon by the photothermal catalytic Fischer-Tropsch reaction by controlling the molar ratio of the precursor metal salt and the reduction temperature.
(3) Under the condition of optimizing the catalyst preparation, the selectivity of the high-carbon hydrocarbon can reach 65.0 percent, and the invention realizes the preparation of the high-carbon hydrocarbon with high selectivity by adopting the cobalt-based catalyst under the drive of light for the first time.
(4) The cobalt-based catalyst has the advantages of low cost, simple preparation, simple process and easy large-scale production, is used for the photothermal catalysis Fischer-Tropsch reaction for the first time, has high selectivity for high-carbon hydrocarbon in the product, and is expected to be applied to industrial production.
Description of the drawings:
the following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 shows XRD spectra of products obtained in comparative example 1, comparative example 2 and example 1 of the present invention; curves a, b and c in the figure correspond to XRD spectra of the cobalt-based catalysts prepared in comparative example 1, comparative example 2 and example 1, respectively.
FIG. 2A shows a transmission electron micrograph of a cobalt-based catalyst obtained according to comparative example 1 of the present invention.
FIG. 2B shows a transmission electron micrograph of a cobalt-based catalyst obtained according to comparative example 2 of the present invention.
FIG. 2C shows a transmission electron micrograph of a cobalt-based catalyst obtained in example 1 of the present invention.
Figure 2D shows the XRD spectrum of the precursor hydrotalcite material (CoAl-LDH) obtained in step 2) of comparative example 1 of the present invention.
FIG. 3 shows a diagram of the photothermal catalytic Fischer-Tropsch reaction performance of the cobalt-based catalyst obtained in example 1 of the present invention.
FIG. 4 shows a temperature change curve of a cobalt-based catalyst system obtained in example 1 of the present invention and a temperature change curve of a cobalt-based catalyst system without addition of the cobalt-based catalyst system, which were measured using an internal thermocouple.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below with reference to preferred embodiments and the accompanying drawings. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
In the present invention, the preparation methods are all conventional methods unless otherwise specified. The starting materials used are available from published commercial sources unless otherwise specified, and the percentages are by mass unless otherwise specified.
Example 1
A preparation method of a cobalt-based catalyst for preparing high-carbon hydrocarbon by photo-thermal catalysis of carbon monoxide hydrogenation comprises the following steps:
1) preparing mixed metal salt solution: 0.01mol of cobalt nitrate hexahydrate and 0.01mol of aluminum nitrate nonahydrate are dissolved in 40mL of deionized water, fully dissolved by adding 0.013mol of precipitator-hexamethylenetetramine, transferred to a 50mL reaction kettle, and finally reacted in an oven for 24 hours at 120 ℃.
2) After the reaction is finished, centrifugally washing the hydrotalcite by deionized water for 3 times, and drying the hydrotalcite in an oven at 80 ℃ for 12 hours to obtain the precursor hydrotalcite material.
3) The hydrotalcite material obtained above was mixed with hydrogen and argon (10% H)2V/v) at 5 ℃ min-1The temperature rising rate is increased to 700 ℃, the temperature is kept for 5 hours, and the N is switched after the temperature rising rate is finished2And naturally cooling to room temperature in the atmosphere. Thus obtaining the cobalt-based catalyst 1 which is marked as Co-700.
The cobalt-based catalyst prepared by the method is applied to the photo-thermal catalytic Fischer-Tropsch reaction and is added into a reaction kettle with the volume of 100ml100mg of cobalt-based catalyst, diluted Synthesis gas (CO: H)2：N2Is 20:60: 20) the pressure in the container is 0.18MPa, the container is illuminated by full spectrum light, and the product is detected to change along with the time by adopting gas chromatography. The catalyst activity was measured.
Meanwhile, an internal thermocouple is adopted in the system to detect the change of the temperature of the surface of the catalyst along with the illumination time in situ. The catalyst prepared in this example was characterized:
FIG. 1, curve c shows the XRD spectrum of the cobalt-based catalyst prepared in example 1, from which a phase in which elemental cobalt is present can be obtained; FIG. 2C is a transmission electron micrograph of a cobalt-based catalyst obtained in example 1. FIG. 3 is a diagram showing the performance of the photothermal catalytic Fischer-Tropsch reaction of the cobalt-based catalyst obtained in example 1; fig. 4 is a graph illustrating a temperature change curve of the cobalt-based photothermal catalyst system obtained in example 1 of the present invention measured using an internal thermocouple.
As seen from FIG. 2C, at this temperature, a large amount of elemental cobalt is reduced on the surface of the catalyst, resulting in a high density and high loading of the cobalt-based catalyst dispersed in Al2O3On the nano-sheet. Table 1 shows the catalytic performance after 1 hour, the conversion rate of CO is 35.4%, and the selectivity of higher hydrocarbon is 65.0%. FIG. 3 is a graph showing the performance under flow conditions, from which it can be concluded that the CO conversion and the selectivity for higher hydrocarbons can be maintained at relatively high levels over time, indicating that the catalyst has good stability. FIG. 4 is a graph showing the time-dependent temperature variation of the surface of the catalyst in situ by using an internal thermocouple, and it can be seen that the temperature of the system can be raised to 107 ℃ by light irradiation without the catalyst, and after the catalyst is added, the temperature of the surface of the catalyst can be raised instantly, and finally can reach and balance about 210 ℃.
TABLE 1 Co-700 light and heat catalytic Properties Table
Examples 2 and 3
The influence of the temperature rise of the precursor hydrotalcite material on the performance of the cobalt-based catalyst is examined, namely the preparation method is the same as the example 1, except that the temperature reached by the temperature rise of the precursor hydrotalcite material in the step 3) is changed, the obtained product is subjected to the photocatalytic Fischer-Tropsch reaction, the reaction steps are the same as the example 1, and the results are shown in Table 2:
TABLE 2 catalysis results of different cobalt-based catalysts
| Example numbering | Temperature (. degree.C.) | Conversion rate of CO | CH4Selectivity of (2) | C2-C4Selectivity of hydrocarbon | C5+Selectivity of (2) |
| 2 | 600 | 31.5 | 41.5 | 37.0 | 21.5 |
| 3 | 650 | 34.9 | 35.9 | 32.1 | 32.0 |
The results show that the light-driven Fischer-Tropsch reaction is adopted, the CO has higher conversion rate, the aim of preparing high-carbon hydrocarbon with high selectivity is fulfilled, and compared with the traditional thermal catalysis Fischer-Tropsch reaction under a high-temperature and high-pressure system, the solar energy is effectively utilized, so that the environment protection is facilitated.
Comparative example 1
A preparation method of a cobalt-based catalyst for preparing high-carbon hydrocarbon by photo-thermal catalysis of carbon monoxide hydrogenation comprises the following steps:
1) preparing mixed metal salt solution: dissolving 0.01mol of cobalt nitrate hexahydrate and 0.01mol of aluminum nitrate nonahydrate in 40mL of deionized water; after adding 0.013mol of hexamethylenetetramine as precipitant and fully dissolving, transferring the solution into a 50mL reaction kettle, and finally reacting in an oven for 24h at 120 ℃.
2) After the reaction is finished, centrifugally washing the crude product for 3 times by using deionized water, and drying in an oven at 80 ℃ for 12 hours after the reaction is finished to obtain the precursor hydrotalcite material.
3) The hydrotalcite material obtained above was mixed with hydrogen and argon (10% H)2V/v) at 5 ℃ min-1The temperature rising rate is increased to 450 ℃, the temperature is kept for 5 hours, and the N is switched after the temperature rising rate is finished2And naturally cooling to room temperature in the atmosphere to obtain the cobalt-based catalyst 2, which is marked as Co-450.
The cobalt-based catalyst prepared by the method is applied to the photo-thermal catalysis Fischer-Tropsch reaction, 100mg of the cobalt-based catalyst is added into a closed reaction kettle with the light-permeable volume of 100ml, and diluted synthesis gas (CO: H) is introduced2：N2Is 20:60: 20) and the pressure in the container is 0.18MPa, and after full-spectrum illumination is carried out for 1h, the activity of the catalyst and the selectivity of each product are determined by adopting gas chromatography.
In fig. 1, curve a is an XRD spectrum of the cobalt-based catalyst prepared in comparative example 1. FIG. 2A is a transmission electron micrograph of a cobalt-based catalyst obtained in comparative example 1. Figure 2D is an XRD spectrum of the precursor hydrotalcite material (CoAl-LDH) obtained in step 2 of comparative example 1.
As can be seen from FIG. 2D, under these conditionsThe synthesized precursor forms a good hydrotalcite structure, and characteristic peaks of (003), (006) and (009) are obvious. At the reduction temperature, as shown by the a-curve in FIG. 1, weak Co appears3O4No obvious elemental cobalt is reduced; as seen from FIG. 2A, Co was reduced at this temperature3O4High density high loading of dispersed in Al2O3On the nano-sheet. From Table 3, it is understood that the CO conversion rate after 1 hour is 17.4%, and a large amount of high carbon hydrocarbons with a very small amount of methane are produced.
TABLE 3 Co-450 photocatalytic Performance Table
Comparative example 2
A preparation method of a cobalt-based catalyst for preparing high-carbon hydrocarbon by photo-thermal catalysis of carbon monoxide hydrogenation comprises the following steps:
1) preparing mixed metal salt solution: 0.01mol of cobalt nitrate hexahydrate and 0.01mol of aluminum nitrate nonahydrate are dissolved in 40mL of deionized water, fully dissolved by adding 0.013mol of precipitator-hexamethylenetetramine, transferred to a 50mL reaction kettle, and finally reacted in an oven for 24 hours at 120 ℃.
2) After the reaction is finished, centrifugally washing the hydrotalcite by deionized water for 3 times, and drying the hydrotalcite in an oven at 80 ℃ for 12 hours to obtain the precursor hydrotalcite material.
3) The hydrotalcite material obtained above was mixed with hydrogen and argon (10% H)2V/v) at 5 ℃ min-1The temperature rising rate is increased to 550 ℃, the temperature is kept for 5 hours, and the N is switched after the temperature rising rate is finished2And naturally cooling to room temperature in the atmosphere. Thus obtaining the cobalt-based catalyst 3 which is marked as Co-550.
The cobalt-based catalyst prepared by the method is applied to the photo-thermal catalysis Fischer-Tropsch reaction, 100mg of the cobalt-based catalyst is added into a reaction kettle with the volume of 100ml, and diluted synthesis gas (CO: H) is introduced2：N2Is 20:60: 20) the pressure in the container is 0.18 MPa. After full spectrum illumination reaction, gas chromatography is adopted to detect the productThe time is changed. The catalyst activity was measured.
Meanwhile, an internal thermocouple is adopted in the system to detect the change of the temperature of the surface of the catalyst along with the illumination time in situ. The catalyst prepared in this example was characterized:
curve b in FIG. 1 is the XRD spectrum of the cobalt-based catalyst prepared in comparative example 2; FIG. 2B is a transmission electron micrograph of a cobalt-based catalyst obtained in comparative example 2; .
When the reduction is carried out at the reduction temperature of the embodiment, the XRD spectrum of the final product is shown as a curve b in figure 1, and no elemental cobalt on the surface of the catalyst is reduced, and the cobalt is still Co3O4Phase (c); from FIG. 2B, the reduced Co at this temperature3O4Supported on Al2O3On the nano-sheet. After the catalyst is irradiated for 1 hour in a full spectrum, the catalytic activity and the selectivity of the catalyst are shown in table 4.
TABLE 4 Co-550 photo-thermal catalysis Performance Table
Comparative example 3
A cobalt-based catalyst was prepared in the same manner as in example 1, except that 0.01mol of cobalt nitrate hexahydrate in step 1) was replaced with 0.01mol of nickel nitrate hexahydrate.
The products are all methane and high carbon hydrocarbon is not obtained by carrying out the light Fischer-Tropsch reaction.
Comparative example 4
A cobalt-based catalyst was prepared in the same manner as in comparative example 1 except that,
step 3), heating the precursor hydrotalcite material to 600 ℃, keeping the temperature for 4 hours, naturally cooling to room temperature to obtain mixed metal oxide, and then putting the mixed metal oxide in hydrogen-argon mixed gas (10% H)2V/v) at 5 ℃ min-1The temperature rising rate is increased to 450 ℃, the temperature is kept for 5 hours, and the N is switched after the temperature rising rate is finished2And naturally cooling to room temperature in the atmosphere to obtain the cobalt-based catalyst.
The cobalt-based catalyst was subjected to the photo-driven Fischer-Tropsch reaction, and the results were the same as those of the comparative example 1, i.e., Table 3, but the process was not as complicated as the direct reduction process of the present invention.
From the results of comparative examples 1 to 4, it was found that the replacement of the cobalt-based catalyst with nickel-based catalysis, or the reduction of the temperature in step 3 of the preparation of the cobalt-based catalyst, resulted in a substantial reduction, or even complete absence, of the higher hydrocarbons in the fischer-tropsch reaction product.
Examples 4 and 5
The influence of the molar ratio of the cobalt salt to the aluminum salt on the performance of the cobalt-based catalyst was examined, i.e., the preparation method was the same as in example 1, except that the molar concentration ratio of the cobalt salt to the aluminum salt in step 1) was changed, the obtained product was subjected to the photocatalytic fischer-tropsch reaction, the reaction steps were the same as in example 1, and the results are shown in table 5:
TABLE 5 catalysis results of different cobalt-based catalysts
| Example numbering | Molar ratio of concentration | Conversion rate of CO | CH4Selectivity of (2) | C2-C4Selectivity of hydrocarbon | C5+ selectivity |
| 1 | 1:1 | 35.4 | 35.0 | 31.7 | 33.3 |
| 4 | 0.5:1 | 6.0 | 34.3 | 36.6 | 29.1 |
| 5 | 2:1 | 47.0 | 52.1 | 33.7 | 14.2 |
The results show that: and when Co: the conversion rate of CO and the selectivity of higher hydrocarbons are highest when Al is 1: 1.
Examples 6 to 8
The influence of the synthesis temperature of the precursor on the performance of the cobalt-based catalyst is examined, namely the preparation method is the same as that in example 1, except that the reaction temperature of the oven in the step 1) is changed, the obtained product is subjected to the photocatalytic Fischer-Tropsch reaction, the reaction steps are the same as those in example 1, and the results are shown in Table 6:
TABLE 6 catalysis results of different cobalt-based catalysts
| ExamplesNumbering | Temperature of Water bath (. degree.C.) | Conversion rate of CO | CH4Selectivity of (2) | C2-C4Selectivity of hydrocarbon | C5+ selectivity |
| 1 | 120 | 35.4 | 35.0 | 31.7 | 33.3 |
| 6 | 100 | 34.1 | 34.5 | 32.4 | 33.2 |
| 7 | 110 | 36.1 | 35.8 | 30.3 | 33.9 |
| 8 | 90 | 34.9 | 35.3 | 31.8 | 32.9 |
The results show that: the invention has no obvious influence on the conversion rate of CO and the selectivity of products when the synthesis temperature of the precursor is changed.
Examples 9 to 11
The influence of the crystallization time on the performance of the cobalt-based catalyst was examined, namely the preparation method was the same as example 1 except that the crystallization time in step 1) was changed, the obtained product was subjected to the photocatalytic fischer-tropsch reaction, the reaction steps were the same as example 1, and the results are shown in table 7:
TABLE 7 catalysis results of different cobalt-based catalysts
| Example numbering | Crystallization time (h) | Conversion rate of CO | CH4Selectivity of (2) | C2-C4Selectivity of hydrocarbon | C5+ selectivity |
| 1 | 24 | 35.4 | 35.0 | 31.7 | 33.3 |
| 9 | 10 | 34.2 | 35.5 | 32.5 | 32.0 |
| 10 | 15 | 37.3 | 34.9 | 31.0 | 34.1 |
| 11 | 20 | 34.7 | 34.5 | 31.7 | 33.8 |
The results show that: in the invention, the change of the crystallization time of the hydrotalcite during the synthesis of the precursor has little influence on the conversion rate of CO and the selectivity of the product.
Examples 12 to 14
The influence of the added amount of the precipitant on the performance of the cobalt-based catalyst was examined, that is, the preparation method was the same as example 1 except that the added amount of the precipitant in step 1) was changed, the obtained product was subjected to the photocatalytic fischer-tropsch reaction, the reaction steps were the same as example 1, and the results are shown in table 8:
TABLE 8 catalysis results of different cobalt-based catalysts
The results show that: the invention does not greatly affect the conversion rate of CO and the selectivity of products when the dosage of the precipitator is changed.
Examples 15 and 16
The effect of the drying temperature on the performance of the cobalt-based catalyst was examined, i.e., the preparation method was the same as example 1 except that the drying temperature in the step 2) was changed, the obtained product was subjected to the photocatalytic fischer-tropsch reaction, and the hydrolysis step was the same as example 1, and the results are shown in table 9:
TABLE 9 catalysis results of different cobalt-based catalysts
| Example numbering | Temperature for drying (. degree.C.) | Conversion rate of CO | CH4Selectivity of (2) | C2-C4Selectivity of (2) | C5+ selectivity |
| 1 | 80 | 35.4 | 35.0 | 31.7 | 33.3 |
| 15 | 60 | 33.9 | 32.8 | 31.6 | 34.6 |
| 16 | 70 | 36.9 | 36.3 | 31.2 | 32.5 |
The results show that: the invention has no great influence on the conversion rate of CO and the selectivity of products when the drying temperature of the precursor is changed.
Examples 17 and 18
The effect of the drying time on the performance of the cobalt-based catalyst was examined, i.e., the preparation method was the same as example 1 except that the drying time in the step 2) was changed, the obtained product was subjected to the photocatalytic fischer-tropsch reaction, the reaction procedure was the same as example 1, and the results are shown in table 10:
TABLE 10 catalysis results of different cobalt-based catalysts
| Example numbering | Time of drying (h) | Conversion rate of CO | CH4Selectivity of (2) | C2-C4Selectivity of (2) | C5+ selectivity |
| 1 | 12 | 35.4 | 35.0 | 31.7 | 33.3 |
| 17 | 6 | 36.2 | 32.6 | 31.9 | 35.5 |
| 18 | 20 | 36.5 | 37.1 | 31.8 | 31.1 |
The results show that: the invention does not have great influence on the conversion rate of CO and the selectivity of products when the drying time of the precursor is changed.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (10)
1. An application of a cobalt-based catalyst for preparing high-carbon hydrocarbon by photo-thermal catalysis of carbon monoxide hydrogenation in a photo-thermal catalysis Fischer-Tropsch reaction.
2. Use according to claim 1, characterized in that saidThe method for preparing the cobalt-based catalyst for the high-carbon hydrocarbon by photo-thermal catalytic carbon monoxide hydrogenation for the photo-thermal catalytic Fischer-Tropsch reaction comprises the following steps: adding cobalt-based catalyst into a light-permeable closed reaction kettle, and introducing N2The diluted synthesis gas is subjected to full-spectrum illumination, and the change of a product along with time is detected by adopting a gas chromatography; the synthetic gas comprises CO and H2And N2Wherein said CO, H2And N2In a volume ratio of 20:60: 20.
3. The use of claim 1, wherein the cobalt-based catalyst for the photothermal catalytic hydrogenation of carbon monoxide to produce higher hydrocarbons has the formula Co/Al2O3。
4. The application of the catalyst as claimed in claim 1, wherein the preparation method of the cobalt-based catalyst for preparing high-carbon hydrocarbon by photo-thermal catalytic carbon monoxide hydrogenation comprises the following steps:
1) preparing mixed metal salt solution: dissolving cobalt salt and aluminum salt in deionized water, adding a precipitator, fully dissolving, transferring into a hydrothermal kettle, reacting at 90-120 ℃, and crystallizing for 8-24 hours to obtain a crude product;
2) washing and drying the crude product obtained in the step 1) to obtain a precursor hydrotalcite material;
3) subjecting the precursor hydrotalcite material obtained in the step 2) to hydrogen-argon mixed gas atmosphere at the temperature of 2-5 ℃ per minute-1The temperature is raised to 600-700 ℃ at the temperature raising rate, the temperature is kept for 2-5 hours, then the temperature is switched to a nitrogen atmosphere, and the temperature is naturally reduced to room temperature, so that the cobalt-based catalyst for preparing high-carbon hydrocarbon by photo-thermal catalytic carbon monoxide hydrogenation is obtained.
5. The cobalt-based catalyst for preparing high-carbon hydrocarbon by photo-thermal catalysis of carbon monoxide hydrogenation is characterized in that the chemical formula of the cobalt-based catalyst for preparing high-carbon hydrocarbon by photo-thermal catalysis of carbon monoxide hydrogenation is Co/Al2O3。
6. The method for preparing the cobalt-based catalyst for preparing the high-carbon hydrocarbon by the photothermal catalysis of the hydrogenation of the carbon monoxide as recited in claim 5, comprising the steps of:
1) preparing mixed metal salt solution: dissolving cobalt salt and aluminum salt in deionized water, adding a precipitator, fully dissolving, transferring into a hydrothermal kettle, reacting at 90-120 ℃, and crystallizing for 8-24 hours to obtain a crude product;
2) washing and drying the crude product obtained in the step 1) to obtain a precursor hydrotalcite material;
3) subjecting the precursor hydrotalcite material obtained in the step 2) to hydrogen-argon mixed gas atmosphere at the temperature of 2-5 ℃ per minute-1The temperature is raised to 600-700 ℃ at the temperature raising rate, the temperature is kept for 2-5 hours, then the temperature is switched to a nitrogen atmosphere, and the temperature is naturally reduced to room temperature, so that the cobalt-based catalyst for preparing high-carbon hydrocarbon by photo-thermal catalytic carbon monoxide hydrogenation is obtained.
7. The method according to claim 6, wherein in the step 1), the cobalt salt is dissolved in the deionized water to a concentration of 0.3 to 0.05 mol-L-1(ii) a The concentration of the aluminum salt dissolved in the deionized water is 0.3-0.02 mol.L-1(ii) a The molar concentration ratio of the cobalt salt to the aluminum salt is 0.5-2: 1; the cobalt salt is cobalt nitrate, cobalt chloride or cobalt sulfate; the aluminum salt is aluminum nitrate, aluminum chloride or aluminum sulfate; the precipitant is hexamethylenetetramine.
8. The preparation method according to claim 6, wherein in the step 2), the washing manner is washing with deionized water for 2-5 times, the drying temperature is 50-80 ℃, and the drying time is 6-20 h.
9. The method according to claim 6, wherein the precursor hydrotalcite material obtained in step 2) has a chemical formula of [ Co2+ 1-nAl3+ n(OH)2]n+·(Ax-)n/x·yH2O, wherein n is more than or equal to 0.2 and less than or equal to 0.33; x is the valence number of the anion; y is the quantity of crystal water, and the value range of y is 0.5-9; a. thex-Is NO3 -Or CO3 2-。
10. The method according to claim 6, wherein the volume fraction of hydrogen in the mixed hydrogen-argon gas in step 3) is 10%.
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