CN114377677A - Iron-based catalyst for preparing high-carbon hydrocarbon by light-driven catalytic carbon dioxide hydrogenation, and preparation method and application thereof - Google Patents
Iron-based catalyst for preparing high-carbon hydrocarbon by light-driven catalytic carbon dioxide hydrogenation, and preparation method and application thereof Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 173
- 239000003054 catalyst Substances 0.000 title claims abstract description 100
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 82
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 46
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 43
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 38
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 33
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 32
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 24
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 5
- 229910005084 FexOy Inorganic materials 0.000 claims abstract description 3
- 229910003112 MgO-Al2O3 Inorganic materials 0.000 claims abstract description 3
- 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 29
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 28
- 229960001545 hydrotalcite Drugs 0.000 claims description 28
- 239000002243 precursor Substances 0.000 claims description 28
- 239000000047 product Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 159000000003 magnesium salts Chemical class 0.000 claims description 14
- 239000012495 reaction gas Substances 0.000 claims description 13
- 238000001228 spectrum Methods 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 8
- 230000008859 change Effects 0.000 claims description 8
- 150000002505 iron Chemical class 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 239000012716 precipitator Substances 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 238000004817 gas chromatography Methods 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- 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
- 239000013078 crystal Substances 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 8
- -1 carbon hydrocarbon Chemical class 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 12
- 239000004202 carbamide Substances 0.000 description 12
- 230000009467 reduction Effects 0.000 description 10
- 238000003917 TEM image Methods 0.000 description 6
- 238000005286 illumination Methods 0.000 description 6
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 230000000630 rising effect Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000011068 loading method Methods 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
- 239000002135 nanosheet Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
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- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The invention discloses an iron-based catalyst for preparing high-carbon hydrocarbon by photo-driven catalytic carbon dioxide hydrogenation, wherein the chemical formula of the iron-based catalyst is Fe/FexOy/MgO‑Al2O3(ii) a Wherein x is 2 or 3, and y is 3 or 4. The catalyst is especially suitable for the reaction of preparing high carbon hydrocarbon by light-driven catalytic carbon dioxide hydrogenation, and in the reaction, the carbon dioxide has higher conversion rate and can be used for methane and C2‑C4The hydrocarbons all have higher selectivity. The invention also discloses a preparation method and application of the iron-based catalyst.
Description
Technical Field
The invention relates to the technical field of light-driven catalysis. More particularly, relates to an iron-based catalyst for preparing high-carbon hydrocarbons by light-driven catalytic carbon dioxide hydrogenation, and a preparation method and application thereof.
Background
With the increasing energy demand and fossil fuel consumption in recent years, a large amount of CO is generated2As fossil energyThe final products of the source combustion are discharged into the atmosphere, which aggravates global warming, sea level rise and the like, and seriously threatens the living environment of human beings. With CO2Is also a potential high-quality carbon source, and how to better utilize CO2Becoming particularly important, there is an urgent need to develop a clean technology for producing energy. 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. CO22The hydrogenation reaction is regarded as a traditional energy preparation technology, and how to drive the carbon dioxide hydrogenation reaction by utilizing clean energy such as solar energy is a topic which needs to be discussed urgently. The carbon dioxide hydrogenation 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; while being extremely wasteful in terms of both energy and efficiency, how to drive the reaction under milder conditions has been the leading and challenging topic of catalysis and chemistry.
Disclosure of Invention
The first purpose of the invention is to provide an iron-based catalyst for preparing high-carbon hydrocarbon by photo-driven catalytic carbon dioxide hydrogenation, which is especially suitable for the reaction of preparing high-carbon hydrocarbon by photo-driven catalytic carbon dioxide hydrogenation, wherein carbon dioxide has higher conversion rate and is used for methane and C2-C4The hydrocarbons all have higher selectivity.
The second purpose of the invention is to provide a preparation method of the iron-based catalyst for preparing high-carbon hydrocarbon by light-driven catalytic carbon dioxide hydrogenation.
The third purpose of the invention is to provide an application of the iron-based catalyst for preparing high-carbon hydrocarbon by light-driven catalytic carbon dioxide hydrogenation.
In order to achieve the first purpose, the invention adopts the following technical scheme:
an iron-based catalyst for preparing high-carbon hydrocarbon by carbon dioxide hydrogenation under light-driven catalysis, wherein the chemical formula of the iron-based catalyst is Fe/FexOy/MgO-Al2O3(ii) a Wherein,x is 2 or 3, and y is 3 or 4.
In order to achieve the second purpose, the invention adopts the following technical scheme:
a preparation method of an iron-based catalyst for preparing high-carbon hydrocarbon by light-driven catalytic carbon dioxide hydrogenation comprises the following steps:
1) preparing mixed metal salt solution: dissolving ferric salt, magnesium salt and aluminum salt in deionized water, adding a precipitator, adding the mixture into a hydrothermal kettle after full dissolution, reacting at the temperature of 90-130 ℃, and crystallizing for 8-24 hours to obtain a crude product;
2) washing and drying the crude product obtained in the step 1) to obtain a precursor hydrotalcite material;
3) subjecting the precursor hydrotalcite material obtained in the step 2) to a hydrogen-argon mixed gas atmosphere at a temperature of 1-5 ℃ per minute-1And raising the temperature to 300-700 ℃ 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 iron-based catalyst for preparing the high-carbon hydrocarbon by the light-driven catalytic carbon dioxide hydrogenation.
Because the iron-based catalyst is CO2The preparation of the active phase of the high carbon hydrocarbon in the hydrogenation process, the hydrotalcite is used as the precursor in the invention, so the iron salt is needed to be used as the iron source, and the hydrotalcite is used as the precursor in the invention, and the alumina is used in CO2The hydrogenation reaction is a good carrier, so 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.
Further, in the step 1), the concentration of the magnesium salt dissolved in the deionized water is 0.2-0.04 mol.L-1(ii) a The concentration of the ferric salt dissolved in the deionized water is 0.1-0.02 mol.L-1(ii) a The concentration of the aluminum salt dissolved in the deionized water is 0.1-0.02 mol.L-1(ii) a The molar ratio of the magnesium salt to the iron salt to the aluminum salt is 3-1: 1: 1; the magnesium salt is selected from one or more of magnesium nitrate, magnesium chloride or magnesium sulfate; the iron salt is selected from ferric nitrate and chlorineOne or more of iron sulfide or iron sulfate; the aluminum salt is selected from one or more of aluminum nitrate, aluminum chloride or aluminum sulfate;
the precipitator is sodium hydroxide, and the addition mole number of the precipitator is 2-8 times of the total mole number of magnesium salt, ferric salt and aluminum salt.
Further, in the step 2), the washing mode is washing for 3-6 times by using deionized water, the drying temperature is 40-90 ℃, and the drying time is 5-20 hours.
Further, in the step 2), the chemical formula of the precursor hydrotalcite material is [ Mg2+ 1-m-nFe3+ mAl3+ n(OH)2](m+n)+·(Ax-)(m+n)/x·yH2O, wherein m + 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-。
Further, in the step 3), the volume fraction of the hydrogen in the hydrogen-argon mixed gas is 10%.
In order to achieve the third purpose, the invention adopts the following technical scheme:
the iron-based catalyst according to the first object is applied to the reaction of preparing high-carbon hydrocarbon by catalyzing carbon dioxide hydrogenation under the light drive.
The invention is based on the layered structure of hydrotalcite and the controllable proportion of the divalent and trivalent metal ions of the laminate, prepares the iron-based catalyst with high load capacity and high dispersibility by high-temperature reduction, and uses the catalyst to catalyze CO in a light-driven manner for the first time2Hydrogenation reaction, and the product has high carbon hydrocarbon selectivity.
Further, the reaction is carried out under light conditions, preferably full spectrum light conditions.
Further, the application comprises the steps of:
adding the iron-based catalyst into a light-permeable closed reaction kettle, introducing diluted reaction gas, irradiating under the full-spectrum condition, and detecting the change of a product along with time by adopting gas chromatography;
wherein the diluted reaction gas comprises CO2、H2And Ar.
The diluted reaction gas is also the reaction gas (CO) containing the inert gas Ar2And H2)。
Further, the CO is2、H2And Ar in a volume ratio of 15:60: 25. CO at this ratio2Hydrogenation is more favorable for generating high carbon hydrocarbon, and CO2The conversion rate of (c) is not too low.
Furthermore, the addition amount of the iron-based catalyst is 20-120 mg/108ml of diluted reaction gas.
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:
in the iron-based catalyst provided by the invention, layered hydrotalcite is used as a precursor, the lattice positioning effect and the structural topology conversion effect of the layered hydrotalcite are utilized, and the layered hydrotalcite is used as the precursor or a rigid and stable template through high-temperature reduction to induce confinement to form the cheap metallic iron nano catalyst with high dispersibility and high loading. The iron-based catalyst can catalyze CO under the drive of light without adding an additional cocatalyst2Hydrogenation reaction to prepare high-selectivity high-carbon hydrocarbon and methane.
In the iron-based catalyst provided by the invention, the selectivity of the prepared iron-based catalyst in preparing high-carbon hydrocarbon through the photo-driven catalytic carbon dioxide hydrogenation reaction can be further improved by controlling the molar ratio of the precursor metal salt and the reduction temperature.
The invention realizes that the iron-based catalyst is used for photo-driving CO under photo-driving for the first time2The hydrogenation reaction is used for preparing high-carbon hydrocarbon with high selectivity, the high-carbon hydrocarbon in the product has high selectivity, and the selectivity of the high-carbon hydrocarbon can reach 52.9% under the better condition.
The iron-based catalyst has the advantages of low cost, simple preparation, simple process and easy large-scale production.
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 examples 1 to 3 of the present invention; curves a, b and c in the figure respectively correspond to XRD spectrograms of the iron-based catalysts prepared in examples 1-3.
Fig. 2A shows a transmission electron micrograph of the iron-based catalyst obtained in example 1 of the present invention.
Fig. 2B shows a transmission electron micrograph of the iron-based catalyst obtained in example 2 of the present invention.
Fig. 2C shows a transmission electron micrograph of the iron-based catalyst obtained in example 3 of the present invention.
Fig. 2D shows the XRD spectrum of the precursor hydrotalcite material (MgFeAl-LDH) obtained in step 2) of example 1 of the present invention.
FIG. 3 shows the photo-driven catalysis of CO by the iron-based catalyst obtained in example 2 of the present invention2And (4) a hydrogenation reaction performance diagram.
Fig. 4 shows the temperature profile of the iron-based catalyst system obtained in example 3 of the present invention measured with 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. Similar parts in the figures are denoted by the same reference numerals. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
Example 1
A preparation method of an iron-based catalyst for preparing high-carbon hydrocarbon by light-driven catalytic carbon dioxide hydrogenation comprises the following steps:
1) preparing mixed metal salt solution: dissolving 0.006mol of magnesium nitrate hexahydrate, 0.003mol of ferric nitrate nonahydrate and 0.003mol of aluminum nitrate nonahydrate in 60mL of deionized water; after adding 0.03mol of urea as precipitant, fully dissolving the urea, transferring the urea into a 50mL reaction kettle, and finally reacting the urea 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 400 ℃, the temperature is kept for 5 hours, and the temperature is switched to N after the temperature rising rate is finished2And naturally cooling to room temperature in the atmosphere to obtain the iron-based catalyst 1, which is marked as Fe-400.
The iron-based catalyst prepared by the method is applied to light-driven catalysis of CO2In the hydrogenation reaction, an iron-based catalyst is added into a light-permeable closed reaction kettle, and diluted reaction gas (CO) is introduced2：H2: ar 15:60:25, volume ratio), and measuring the catalyst activity and the selectivity of each product by adopting a gas chromatograph after full spectrum illumination for 2 hours, wherein the dosage of the iron-based catalyst is 100mg/108ml of diluted reaction gas.
Curve a in fig. 1 is the XRD spectrum of the iron-based catalyst prepared in example 1. Fig. 2A is a transmission electron micrograph of the iron-based catalyst obtained in example 1. Fig. 2D is an XRD spectrum of the precursor hydrotalcite material (MgFeAl-LDH) obtained in step 2 of example 1.
As can be seen from fig. 2D, under these conditions, the synthesized precursor forms a good hydrotalcite structure, and characteristic peaks of (003), (006) and (009) are evident. At the reduction temperature, as shown by a curve in fig. 1, a weak elemental Fe peak appears, indicating that elemental Fe is reduced; from FIG. 2A, it can be seen that Fe is dispersed in Al at a high density and a high loading amount after reduction at this temperature2O3On the nano-sheet. From Table 1, it can be seen that CO was present after 2 hours2The conversion rate of the catalyst can reach 17.8 percent, and the selectivity of the high-carbon hydrocarbon can reach 38.6 percent.
TABLE 1Fe-400 light-driven catalysis Performance Table
Example 2
A preparation method of an iron-based catalyst for preparing high-carbon hydrocarbon by light-driven catalytic carbon dioxide hydrogenation comprises the following steps:
1) preparing mixed metal salt solution: dissolving 0.006mol of magnesium nitrate hexahydrate, 0.003mol of ferric nitrate nonahydrate and 0.003mol of aluminum nitrate nonahydrate in 60mL of deionized water; after adding 0.03mol of urea as precipitant, fully dissolving the urea, transferring the urea into a 50mL reaction kettle, and finally reacting the urea in an oven for 24h 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 500 ℃, the temperature is kept for 5 hours, and the temperature is switched to N after the temperature is up2And naturally cooling to room temperature in the atmosphere. The iron-based catalyst 2 is obtained and recorded as Fe-500.
The iron-based catalyst prepared by the method is applied to light-driven catalysis of CO2In the hydrogenation reaction, an iron-based catalyst is added into a reaction kettle, and diluted synthesis gas (CO) is introduced2：H2：N215:60:25, volume ratio). And (3) full spectrum illumination, and detecting the change of the product with time by adopting gas chromatography, wherein the dosage of the iron-based catalyst is 100mg/108ml of diluted reaction gas. The catalyst activity was measured.
Meanwhile, an internal thermocouple is adopted in the system to detect the change of the temperature of the surface of the catalyst along with the illumination time in situ. The catalyst prepared in this example was characterized:
FIG. 1, curve b shows the XRD spectrum of the iron-based catalyst prepared in example 2; FIG. 2B is a TEM image of the Fe-based catalyst obtained in example 2; FIG. 3 is the Fe-based photo-driven CO obtained in example 22Performance maps of the hydrogenation reactions; FIG. 4 is a graph showing the temperature change of the iron-based catalyst system obtained in example 2 of the present invention measured by an internal thermocouple.
FIG. 3 is a graph showing the performance under flow conditions, from which it can be concluded that the conversion of CO2 and the selectivity of 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 110 ℃ 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 to about 275 ℃.
When the reduction is carried out at the reduction temperature in the embodiment, the XRD spectrogram of the final product is shown as a curve b in figure 1, and obvious elemental iron appears on the surface of the catalyst; as shown in FIG. 2B, the elemental Fe after reduction at this temperature is supported on Al2O3On the nano-sheet. After the catalyst is irradiated for 2 hours in a full spectrum, the catalytic activity and the selectivity are shown in the table II.
TABLE 2Fe-500 light-driven catalysis Performance Table
Example 3
A preparation method of an iron-based catalyst for preparing high-carbon hydrocarbon by light-driven catalytic carbon dioxide hydrogenation comprises the following steps:
1) preparing mixed metal salt solution: dissolving 0.006mol of magnesium nitrate hexahydrate, 0.003mol of ferric nitrate nonahydrate and 0.003mol of aluminum nitrate nonahydrate in 60mL of deionized water; after adding 0.03mol of urea as precipitant, fully dissolving the urea, transferring the urea into a 50mL reaction kettle, and finally reacting the urea in an oven for 24h 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 rise rate is increased to 600 ℃, the temperature is kept for 5 hours, and the N is switched after the temperature rise rate is over2And naturally cooling to room temperature in the atmosphere. To obtain the iron-based catalystReagent 3, noted as Fe-600.
The iron-based catalyst prepared by the method is applied to light-driven catalysis of CO2During the reaction, an iron-based catalyst is added into a reaction kettle, and diluted reaction gas (CO) is introduced2：H2: ar 15:60:25, volume ratio). And (3) full spectrum illumination, and detecting the change of the product with time by adopting gas chromatography, wherein the dosage of the iron-based catalyst is 100mg/108ml of diluted reaction gas. The catalyst activity was measured.
Meanwhile, an internal thermocouple is adopted in the system to detect the change of the temperature of the 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 3, from which a phase in which elemental iron is present can be obtained; fig. 2C is a transmission electron micrograph of the iron-based catalyst obtained in example 3. FIG. 3 shows that the iron-based catalyst obtained in example 3 catalyzes CO in a photo-driven manner2Performance maps of the hydrogenation reactions; FIG. 4 is a graph showing the temperature change of the iron-based photo-driven catalyst system obtained in example 2 of the present invention measured by an internal thermocouple.
TABLE 3Fe-600 photo-driven catalytic Performance Table
In summary, the prior art is based on CO2The main route for preparing high-carbon hydrocarbon is to use iron-based catalyst to apply traditional thermal catalysis, and the condition is mostly carried out in a high-temperature high-pressure system; compared with the prior art, the invention adopts light to drive CO for the first time2The hydrogenation reaction is more beneficial to environmental protection and effectively utilizes solar energy.
Examples 4 to 7
The influence of the temperature rise of the precursor hydrotalcite material on the performance of the iron-based catalyst is examined, namely the preparation method is the same as the example 1, and the difference is only that the temperature reached by the temperature rise of the precursor hydrotalcite material in the step 3) is changed, and the obtained product is subjected to CO illumination2Hydrogenation reaction, hydrolysis reactionThe procedure is as in example 1, and the results are shown in Table 4:
TABLE 4 catalysis results of different iron-based catalysts
| Example numbering | Temperature (. degree.C.) | CO2Conversion rate of | CH4Selectivity of (2) | C2-C4Selectivity of hydrocarbon | C5+ selectivity |
| 1 | 400 | 17.8 | 61.4 | 34.3 | 4.3 |
| 4 | 500 | 50.1 | 47.1 | 46.6 | 6.3 |
| 5 | 550 | 59.2 | 58.9 | 37.2 | 3.9 |
| 6 | 600 | 76.9 | 70.0 | 28.2 | 1.8 |
| 7 | 700 | 73.1 | 78.7 | 20.7 | 0.6 |
The results show that: the selectivity of the product is greatly influenced by the difference of the temperature reached by the precursor temperature rise, and the selectivity of the high-carbon hydrocarbon is the maximum at 500 ℃ and CO is generated2Has high conversion rate.
Examples 8 to 9
The influence of the molar ratio of the magnesium salt, the iron salt and the aluminum salt on the performance of the iron-based catalyst is examined, namely the preparation method is the same as the example 2, and the difference is only that the molar ratio of the magnesium salt, the iron salt and the aluminum salt in the step 1) is changed while the total molar ratio of the iron salt, the magnesium salt and the aluminum salt in the step 1) is kept unchanged, and the obtained product is subjected to photocatalysis CO by light2Hydrogenation, the reaction procedure is the same as in example 1, and the results are shown in Table 5:
TABLE 5 catalysis results of different iron-based catalysts
| Example numbering | Molar ratio of | CO2Conversion rate of | CH4Selectivity of (2) | C2-C4Selectivity of hydrocarbon | C5+ |
| 2 | 2:1:1 | 50.1 | 47.1 | 46.6 | 6.3 |
| 8 | 2:2:1 | 59.8 | 57.3 | 40.6 | 2.1 |
| 9 | 2:3:1 | 62.3 | 68.1 | 30.7 | 1.2 |
The results show that: as the molar ratio of magnesium salt, iron salt and aluminum salt is changed, the ratio to CO is changed2Conversion rate of (2) and selectivity of productAll had a great impact, and when Mg: fe: al: when it is 2:1:1, CO2The conversion rate of (a) is relatively moderate and the selectivity of higher hydrocarbons is highest.
Examples 10 to 12
The influence of the synthesis temperature of the precursor on the performance of the iron-based catalyst is examined, namely the preparation method is the same as the example 2, and the difference is only that the reaction temperature of the oven in the step 1) is changed, and the obtained product is subjected to photocatalysis CO2Hydrogenation, the reaction procedure is the same as in example 2, and the results are shown in Table 6:
TABLE 6 catalysis results of different iron-based catalysts
The results show that: in the invention, CO is treated when the synthesis temperature of the precursor is changed2The conversion of (a) and the selectivity of the product have no significant influence.
Examples 13 to 15
The influence of the crystallization time on the performance of the iron-based catalyst is examined, namely the preparation method is the same as the example 2, but the difference is that the crystallization time in the step 1) is changed, and the obtained product is subjected to light-catalyzed CO2Hydrogenation, the reaction procedure is the same as in example 1, and the results are shown in Table 7:
TABLE 7 catalysis results of different iron-based catalysts
| Example numbering | Crystallization time (h) | CO2Conversion rate of | CH4Selectivity of (2) | C2-C4Selectivity of hydrocarbon | C5+ |
| 2 | 24 | 50.1 | 47.1 | 46.6 | 6.3 |
| 13 | 10 | 49.8 | 45.5 | 47.9 | 6.6 |
| 14 | 15 | 52.2 | 49.9 | 48.0 | 2.1 |
| 15 | 20 | 49.5 | 48.9 | 46.3 | 4.8 |
The results show that: in the invention, the crystallization time of hydrotalcite is changed to CO when a precursor is synthesized2The conversion rate and the selectivity of the product do not have a great influence.
Examples 16 to 18
The influence of the addition of the precipitating agent on the performance of the iron-based catalyst is examined, namely the preparation method is the same as that of example 2, except that the addition of the precipitating agent in the step 1) is changed, and the obtained product is subjected to photocatalysis by light for CO2Hydrogenation, the reaction procedure is the same as in example 2, and the results are shown in Table 8:
TABLE 8 catalysis results of different iron-based catalysts
The results show that: in the invention, the amount of the precipitator is changed while the CO is treated2The conversion rate and the selectivity of the product do not have a great influence.
Examples 19 to 20
The influence of the drying temperature on the performance of the iron-based catalyst is examined, namely the preparation method is the same as that of example 2, except that the drying temperature in the step 2) is changed, and the obtained product is subjected to light-driven catalysis CO2The hydrogenation and hydrolysis steps were the same as in example 1, and the results are shown in Table 9:
TABLE 9 catalysis results of different iron-based catalysts
The results show that: in the invention, the drying temperature of the precursor is changed while CO is treated2The conversion rate and the selectivity of the product do not have a great influence.
Examples 21 to 22
The influence of the drying time on the performance of the iron-based catalyst was examined, namely the preparation method was the same as example 2 except that the drying time in step 2) was changed, and the obtained product was subjected to photocatalytic CO2Hydrogenation, the reaction procedure is the same as in example 2, and the results are shown in Table 10:
TABLE 10 catalysis results of different iron-based catalysts
The results show that: in the invention, CO is treated when the drying time of the precursor is changed2The conversion rate and the selectivity of the product do not have a great influence.
Comparative example 1
An iron-based catalyst was prepared in the same manner as in example 1, except that 0.003mol of ferric nitrate nonahydrate was replaced with 0.003mol of nickel nitrate hexahydrate in step 1).
CO is illuminated2The products of the hydrogenation reaction are all methane, and high carbon hydrocarbon is not obtained.
Comparative example 2
An iron-based catalyst was prepared in the same manner as in example 1 except that,
step 3), heating the precursor hydrotalcite material to 500 ℃, keeping the temperature for 4 hours, naturally cooling to room temperature to obtain mixed metal oxide, and then putting the mixed metal oxide in hydrogen-argon mixed gas (10% H)2V/v) at 5 ℃ min-1The temperature rising rate is increased to 400 ℃, the temperature is kept for 5 hours, and the temperature is switched to N after the temperature rising rate is finished2And naturally cooling to room temperature in the atmosphere to obtain the iron-based catalyst.
Subjecting the iron-based catalyst to photo-driving CO2The hydrogenation reaction results are the same as the catalytic performance under the conditions of example 1, i.e. table 1, but the method is complicated and is not as simple as the direct reduction operation step of the invention.
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. The iron-based catalyst for preparing high-carbon hydrocarbon by using light-driven catalytic carbon dioxide hydrogenation is characterized in that the chemical formula of the iron-based catalyst is Fe/FexOy/MgO-Al2O3(ii) a Wherein x is 2 or 3, and y is 3 or 4.
2. The method of preparing an iron-based catalyst according to claim 1, comprising the steps of:
1) preparing mixed metal salt solution: dissolving ferric salt, magnesium salt and aluminum salt in deionized water, adding a precipitator, adding the mixture into a hydrothermal kettle after full dissolution, reacting at the temperature of 90-130 ℃, and crystallizing for 8-24 hours to obtain a crude product;
2) washing and drying the crude product obtained in the step 1) to obtain a precursor hydrotalcite material;
3) subjecting the precursor hydrotalcite material obtained in the step 2) to a hydrogen-argon mixed gas atmosphere at a temperature of 1-5 ℃ per minute-1And raising the temperature to 300-700 ℃ 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 iron-based catalyst for preparing the high-carbon hydrocarbon by the light-driven catalytic carbon dioxide hydrogenation.
3. The method according to claim 2, wherein the concentration of the magnesium salt dissolved in the deionized water in step 1) is 0.2 to 0.04 mol-L-1(ii) a The concentration of the ferric salt dissolved in the deionized water is 0.1-0.02 mol.L-1(ii) a The concentration of the aluminum salt dissolved in the deionized water is 0.1-0.02 mol.L-1(ii) a The molar ratio of the magnesium salt to the iron salt to the aluminum salt is 3-1: 1: 1; the magnesium salt is selected from one or more of magnesium nitrate, magnesium chloride or magnesium sulfate; the ferric salt is selected from one or more of ferric nitrate, ferric chloride or ferric sulfate; the aluminum salt is selected from one or more of aluminum nitrate, aluminum chloride or aluminum sulfate;
the precipitator is sodium hydroxide, and the addition mole number of the precipitator is 2-8 times of the total mole number of magnesium salt, ferric salt and aluminum salt.
4. The method according to claim 2, wherein in the step 2), the washing is performed by washing with deionized water for 3-6 times, the drying temperature is 40-90 ℃, and the drying time is 5-20 h.
5. The method according to claim 2, wherein in step 2), the precursor hydrotalcite material has a chemical formula of [ Mg2+ 1-m-nFe3+ mAl3+ n(OH)2](m+n)+·(Ax-)(m+n)/x·yH2O, wherein m + 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-。
6. The method according to claim 2, wherein the volume fraction of hydrogen in the mixed hydrogen-argon gas in step 3) is 10%.
7. The use of the iron-based catalyst of claim 1 in the photo-driven catalytic hydrogenation of carbon dioxide to produce higher hydrocarbons.
8. Use according to claim 7, wherein the reaction is carried out under light conditions, preferably full spectrum light conditions.
9. The application according to claim 7, characterized in that it comprises the following steps:
adding the iron-based catalyst into a light-permeable closed reaction kettle, introducing diluted reaction gas, irradiating under the full-spectrum condition, and detecting the change of a product along with time by adopting gas chromatography;
wherein the diluted reaction gas comprises CO2、H2And Ar.
10. The use of claim 9, wherein the iron-based catalyst is added in an amount of 20-120 mg/108ml diluted reaction gas;
preferably, the CO is2、H2And Ar in a volume ratio of 15:60: 25.
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