CN113522287B

CN113522287B - Carbon-supported metal catalyst with hierarchical pore structure, preparation method and application thereof

Info

Publication number: CN113522287B
Application number: CN202110705497.7A
Authority: CN
Inventors: 张成华; 王虎林; 魏宇学; 马彩萍; 杨勇; 李永旺
Original assignee: Zhongke Synthetic Oil Technology Co Ltd
Current assignee: Zhongke Synthetic Oil Technology Co Ltd
Priority date: 2021-06-24
Filing date: 2021-06-24
Publication date: 2023-09-12
Anticipated expiration: 2041-06-24
Also published as: CN113522287A

Abstract

The invention relates to a carbon-supported metal catalyst with a hierarchical pore structure, a preparation method and application thereof. The carbon-supported metal catalyst comprises an active phase metal and a porous carbon carrier, wherein the porous carbon carrier is provided with a hierarchical mesoporous structure formed by a carbon nano cage and graphene oxide, and the hierarchical mesoporous structure is provided with specific hierarchical pore channel distribution; and wherein the active phase metal is coated in the carbon nanocages, the carbon nanocages being located on the sheets of graphene oxide. According to the preparation method, the carbon-supported metal catalyst is prepared by adopting the active phase metal salt, the organic ligand and the graphene oxide, so that metal nano particles can be effectively dispersed, and sintering and aggregation of the particles can be inhibited. When the carbon-supported metal catalyst is applied to hydrocarbon synthesis reaction, it has excellent electronic characteristics, high hydrothermal stability, high activity and olefin selectivity, high mechanical strength, strong abrasion resistance, and the like.

Description

Carbon-supported metal catalyst with hierarchical pore structure, preparation method and application thereof

Technical Field

The invention belongs to the field of nano catalyst material preparation, and in particular relates to a high-strength carbon-supported metal nano catalyst with a hierarchical pore structure, a preparation method thereof and application thereof in preparing hydrocarbon compounds by catalyzing CO and hydrogen-containing gas to react.

Background

The carbon-coated metal nanoparticle is a novel composite material. The material has the unique structural characteristics that transition metal nano particles are dispersed in an amorphous carbon matrix or graphene is tightly coated outside the metal nano particles to form a core-shell structure. The graphene coating layer enables the metal nano particles to be better in dispersibility, and the problems of agglomeration and the like caused by interaction among particles are avoided. Meanwhile, the unique electronic property of the graphene also endows the graphene coated metal nano particles with excellent electromagnetic performance, and the graphene coated metal nano particles have wide application in the technical fields of sensors, electromagnetic shielding, catalysis and the like.

CO hydrogenation or synthesis gas (containing CO and H) ₂ Small amount of CO ₂ Methane and N ₂ The mixture of (c) to produce hydrocarbon compounds involves a large class of typical heterogeneous catalytic reactions including fischer-tropsch synthesis, isomerisation synthesis, aromatics production from synthesis gas, methanation and the like. Group VIIIB transition metals iron, cobalt, nickel and ruthenium and ZrO ₂ 、ThO ₂ 、CeO ₂ The metal oxide has catalytic activity for catalyzing the reaction of preparing hydrocarbon by CO hydrogenation. The reaction has the characteristics of high temperature (150-350 ℃), high pressure (10-50 bar) and strong heat release (165 kJ/mol), and one main byproduct of the reaction is water. The existing reactor suitable for CO hydrogenation reaction mainly comprises a fixed bed, a fixed fluidized bed and a gas-liquid-solid three-phase slurry bed. Thus, CO hydrogenation catalysts experience very severe physical impact and chemical stress during the reaction, which requires the catalyst to have Very high abrasion resistance.

Typically, refractory oxides, such as silica, alumina, titania, and the like, are used as supports for the CO hydrogenation catalyst. However, these supports also bring about some unavoidable drawbacks to the catalyst, such as low thermal conductivity, poor hydrothermal stability, strong surface acidity, low mechanical strength, poor abrasion resistance, etc. Because the CO hydrogenation reaction is a strong exothermic reaction, a large amount of reaction heat is retained in the catalyst particles in the reaction process due to poor thermal conductivity of the catalyst, so that the partial reaction of the catalyst is over-temperature, the selectivity of target products is poor, and the catalyst active phase sintering can be seriously caused to lose the catalytic activity, so that the timely removal of a large amount of reaction heat released in the catalyst particles becomes very important. In addition, the high water partial pressure in the CO hydrogenation reaction is also very critical for the catalyst. The literature (Journal of the Chemical Society-Chemical Communications,1984, 10, pages 629-630) reports that water has a very detrimental effect on alumina-supported catalysts, and that at low temperatures and low water pressures the alumina support is partly converted to pseudoboehmite, which causes pulverization of the catalyst. In addition, these refractory oxide supports or structure aids also undergo strong interactions with the active phase metal components to form oxides (e.g., metal silicates, aluminates, titanates, etc.) that are inactive in the Fischer-Tropsch synthesis.

To improve the activity and stability of CO hydrogenation catalysts, researchers have attempted to use carbon materials, such as activated carbon, nanofibers (CNF), carbon Nanotubes (CNT), graphene, carbon spheres, or glassy carbon, as carriers for the catalyst. Conventional carbon supported catalysts are typically prepared by impregnating a metal with a carbon material. However, due to the weak interaction between the carbon support and the metal, the particles of the metal active phase in the catalyst are widely distributed, and the particles of the active phase are easy to sinter and aggregate in the thermal reaction process.

Recently, researchers have synthesized carbon matrix dispersed nano-metal catalysts using Metal Organic Frameworks (MOFs) as precursors. In one example, santos et al in patent WO2015/175759A1 disclose the synthesis of ultrafine iron carbide nanoparticle catalysts with an iron carboxylate metal organic framework (iron-1, 3, 5-benzenetricarboxylic acid, iron-1, 4-phthalate or azobenzene tetra-formate) as a template and furfuryl alcohol as an additional carbon source, with an iron content of up to 50wt%, porous carbon dispersion. The Pei et al (Highly Active and Selective Co-Based Fischer-Tropsch Catalysts Derived from Metal-Organic Frameworks, AIChE Journal,63 (2017) 2935-2944.) discloses a fully reduced, highly dispersed face-centered cubic cobalt nanoparticle carbon-supported catalyst prepared by a thermal decomposition process using Co-MOF-74 as a precursor and ethyl orthosilicate as a silicon dopant.

The MOFs-derived carbon supported catalysts described above generally have a high specific surface area, ultra-small metal particle size, excellent thermal stability, and excellent catalytic performance. However, such catalysts have the following significant drawbacks: loose structure, low mechanical strength, weak interaction among powder particles and difficult secondary forming.

Patent application CN107570155a of the middle-branch of academic or vocational study synthetic oil company discloses a three-dimensional porous iron oxide/graphene oxide nanocomposite material prepared by assembling iron oxide nanoparticles and graphene oxide by a hydrothermal synthesis method, and the three-dimensional porous iron oxide/graphene oxide nanocomposite material is applied to fischer-tropsch synthesis reaction, and shows excellent reactivity and operation stability. The three-dimensional composite material of the ferric oxide/the graphene oxide has excellent mechanical strength, but the sintering or agglomeration of metal particles cannot be effectively inhibited due to the large structural size of the graphene oxide unit, so that the crystal grains of the metal active phase grow up in the reaction process of the catalyst.

Therefore, there is a need in the art for catalysts prepared using MOFs as precursors to address the problems of sintering of the crystallites and mechanical attrition of the catalyst during the reaction.

Disclosure of Invention

In view of the above problems, the present inventors have studied to provide a high-strength active phase metal-porous carbon support nanocomposite catalyst having a hierarchical pore structure, which is used for catalyzing a reaction of a gas containing CO and hydrogen to produce a hydrocarbon compound. The catalyst has great improvement in mechanical strength and metal particle sintering resistance, so that the catalytic efficiency is greatly improved, and the problems of poor stability, easy abrasion and the like of the conventional carbon-supported catalyst are overcome.

In one aspect, the present invention provides a carbon supported metal catalyst having a hierarchical pore structure, the catalyst comprising:

an active phase metal; and

a porous carbon support having a hierarchical pore structure composed of carbon nanocages and graphene oxide, wherein the hierarchical pore structure has a distribution of hierarchical mesoporous channels selected from at least two of micro mesopores having a most probable pore diameter of 2 to 4nm, mesopores having a most probable pore diameter of 4 to 10nm, and mesopores having a most probable pore diameter of 15 to 22 nm; and wherein the active phase metal is coated in the carbon nanocages, the carbon nanocages being located on the sheets of graphene oxide.

In another aspect, the present invention also provides a method for preparing the above carbon-supported metal catalyst having a hierarchical pore structure, wherein the method comprises:

(1) Mixing an active phase metal salt, an organic ligand and graphene oxide to prepare a metal organic framework/graphene oxide composite material precursor;

(2) Molding the composite material precursor to obtain a molded composite material; and

(3) And carrying out pyrolysis and carbonization on the formed composite material in an inert atmosphere or a carbon-containing atmosphere to obtain the carbon-supported metal catalyst.

In a further aspect, the present invention provides the use of a carbon supported metal catalyst as described above having a hierarchical pore structure for catalyzing the reaction of a CO and hydrogen containing gas to produce hydrocarbon compounds.

The scheme of the invention can at least realize the following beneficial effects, but is not limited to the following:

1. the active phase metal in the catalyst is coated in a discontinuous or independent porous carbon nano cage cavity, the porous carbon nano cage containing the active phase metal further forms an amorphous worm-shaped carbon nano tube, and the worm-shaped carbon nano tube is generated on a graphene oxide nano sheet layer and is further assembled with graphene oxide into a particle-shaped porous carbon carrier.

2. In the preparation method of the catalyst according to the present invention, an active phase metal organic framework compound grown on a lamellar structure of graphene oxide is used as a metal source in the catalyst, and carbon contained in a carbon or a carbon-containing gas in a carbon-containing atmosphere contained in the metal organic framework is used as a carbon source for a carbon nanocage (vermiform carbon nanotube precursor). During the catalyst preparation process, the gas phase carbon source is deposited and grown along the surface of the active phase metal nanoparticles to form carbon nanocages and then vermiform carbon nanotubes, which can effectively disperse the active phase metal nanoparticles and inhibit sintering and aggregation of the particles.

3. The catalyst according to the invention exhibits excellent electronic properties, physicochemical abrasion resistance, high hydrothermal stability and high mechanical strength in the application of hydrocarbon compounds produced by the reaction of gases containing CO and hydrogen. The rich hierarchical nano-pore structure of the catalyst can promote the high dispersion of the active phase of the catalyst and the diffusion of reaction species, thereby leading the catalyst to have excellent catalytic reaction performance: high activity, low methane selectivity, high olefin selectivity, and long operating life.

Drawings

FIG. 1 is an XRD pattern of MOFs/GO composite precursors prepared in example 1 of the present invention.

FIG. 2 is an SEM photograph of a precursor of MOFs/GO composite prepared in example 1 of the present invention.

FIG. 3 is an XRD pattern of a porous carbon support-supported Fe@C catalyst prepared in example 1 of the present invention.

FIG. 4 is an SEM photograph of a porous carbon support-supported Fe@C catalyst prepared in example 1 of the present invention.

Fig. 5 is a TEM photograph of a porous carbon support-supported fe@c catalyst prepared in example 1 of the present invention.

FIG. 6 is a TEM photograph of a porous carbon support prepared in example 1 of the present invention, after the Fe@C catalyst supported by the porous carbon support has been subjected to washing filtration with 0.5M dilute hydrochloric acid to remove metallic Fe ions.

FIG. 7 is a BJH pore distribution diagram of a porous carbon support-supported Fe@C catalyst prepared in example 1 of the present invention.

FIG. 8 is a BJH pore distribution diagram of a porous carbon support prepared in example 1 of the present invention, after metal Fe ions are removed by washing with 0.5M dilute hydrochloric acid.

Detailed Description

Hereinafter, aspects of the present invention will be described by way of exemplary embodiments, but the scope of the present invention is not limited thereto.

In the present invention, the terms "graphene oxide sol" and "graphene oxide hydrosol" are used interchangeably unless otherwise indicated.

In one embodiment, the present invention relates to a carbon supported metal catalyst having a hierarchical pore structure, the catalyst comprising:

an active phase metal; and

In the invention, the active phase metal is coated in the carbon nanocage, so that the dispersity of the active phase metal is higher, and the catalyst can show good catalyst activity when catalyzing CO hydrogenation. In the invention, the porous carbon carrier has a hierarchical mesoporous nano cage structure with mesoscale (2-100 nm), and the structure has the characteristics of being completely suitable for the nano scale of active phase metal of heterogeneous catalyst, and is beneficial to the encapsulation, anchoring and reactant diffusion of metal particles, so that the catalyst shows higher activity, higher olefin selectivity and the like.

In a further preferred embodiment, the active phase metal may be at least one of iron, cobalt, nickel, ruthenium, zirconium, cerium, thorium, or indium, but is not limited thereto.

In a preferred embodiment, the specific surface area of the catalyst is not less than 100m ² /g, preferably 200m ² Above/g, e.g. 200-285 m ² /g。

In a preferred embodiment, the mass ratio of the active phase metal to the porous carbon support may be (0.1 to 200): 100, preferably (1 to 70): 100, for example 65.6:100, 38.3:100, 51.6:100, 1.3:100, 58.8:100, 67.1:100 or 4.8:100.

In a preferred embodiment, the catalyst further comprises a promoter metal.

In further preferred embodiments, the promoter metal may be at least one of manganese, chromium, zinc, molybdenum, copper, platinum, palladium, rhodium, iridium, gold, silver, magnesium, calcium, strontium, barium, sodium, or potassium; preferably, the promoter metal may be at least one of manganese, chromium, zinc, copper, platinum, palladium, silver, magnesium, calcium, strontium, sodium or potassium.

In a further preferred embodiment, the mass ratio of the promoter metal to the porous carbon support may be (0.002 to 40): 100, preferably (5 to 30): 100, for example may be 5.8:100 or 27.2:100.

In one embodiment, the present invention relates to a method of preparing the above carbon supported metal catalyst having a hierarchical pore structure, wherein the method comprises:

In a preferred embodiment, in step (1) above, the metal organic framework/graphene oxide composite precursor is prepared according to the following procedure:

(a) Adding active phase metal salt and an organic ligand into a solvent to obtain a metal organic framework material precursor solution;

(b) Adding the metal organic framework material precursor solution into graphene oxide sol for mixing to obtain mixed solution;

(c) And (3) placing the mixed solution into a reaction kettle for reaction, and cooling, washing with a solvent, filtering and drying after the reaction to obtain the precursor of the metal-organic framework/graphene oxide composite material.

As an alternative embodiment, in the step (1) above, the metal-organic framework/graphene oxide composite precursor is prepared according to the following procedure:

(a') adding an organic ligand to a solvent to obtain an organic ligand precursor solution;

(b') adding the organic ligand precursor solution into graphene oxide sol for mixing to obtain an organic ligand-graphene oxide solution;

(c') adding active phase metal salt into a solvent to obtain an active phase metal salt solution, and adding the active phase metal salt solution into the organic ligand-graphene oxide solution to obtain sol-like liquid;

And (d') placing the sol-like liquid into a reaction kettle for reaction, and cooling, washing with a solvent, filtering and drying after the reaction to obtain the precursor of the metal-organic framework/graphene oxide composite material.

In a preferred embodiment, the active phase metal salt may be at least one selected from the group consisting of: iron nitrate or a hydrate thereof (e.g. iron nitrate nonahydrate), iron chloride or a hydrate thereof (e.g. iron chloride hexahydrate), iron chloride, iron sulfate, iron acetate, iron (III) acetylacetonate, iron carbonyl, ferrocene, cobalt nitrate or a hydrate thereof (e.g. cobalt nitrate hexahydrate), cobalt chloride, cobalt formate, cobalt acetate or a hydrate thereof (e.g. cobalt acetate tetrahydrate), cobalt acetylacetonate, cobalt carbonyl, tris (ethylenediamine) cobalt (III) chloride trihydrate, nickel nitrate, nickel chloride, nickel sulfate, nickel acetate, nickel acetylacetonate, nickel carbonyl, ruthenium trichloride, ruthenium nitrate, triphenylphosphine ruthenium carbonyl chloride, ammonium ruthenate, ruthenium nitrosylnitrate, zirconyl nitrate, zirconium oxychloride, zirconium nitrate, zirconium chloride, zirconium sulfate, cerium nitrate, cerium chloride, cerium sulfate, thorium nitrate, thorium chloride, indium nitrate, indium chloride, indium sulfate.

In a preferred embodiment, the organic ligand may be at least one of levulinic acid, lauric acid, oxalic acid, citric acid, 1,3, 5-benzene tricarboxylic acid, terephthalic acid, 2-methylimidazole, fumaric acid, azobenzene tetracarboxylic acid, amino-terephthalic acid, 2, 5-dihydroxyterephthalic acid, 1, 4-naphthalene dicarboxylic acid, 1, 5-naphthalene dicarboxylic acid, 2, 6-naphthalene dicarboxylic acid, or the like.

In a preferred embodiment, the mass ratio of the active phase metal salt to the organic ligand may be (30 to 400): 100, for example, (30 to 300): 100.

In a further preferred embodiment, the solvent may be one or more of water, methanol, methylamine, dimethylamine, N-dimethylformamide, N-methylformamide, formamide, ethanol, ethylene glycol, diethyl ether, ethylamine, acetonitrile, acetamide, propanol, acetone, propionitrile, tetrahydrofuran, dioxane, butanol, pyridine, morpholine, quinoline, toluene, xylene, heptane, but is not limited thereto. It is to be noted that the solvent in the above steps (a) and (c), the solvent in the above steps (a ') and (c ') and (d ') may be the same or different, and may be conventionally selected according to the corresponding active phase metal salt and organic ligand.

In the above preparation method, the graphene oxide sol may be prepared according to a conventional Hummers method: firstly, drying graphene powder in a drying oven; then the graphene powder and NaNO are mixed ₃ Mixing in a beaker, adding concentrated sulfuric acid, and placing the beaker in an ice-water bath for stirring and mixing; then KMnO was slowly added to the mixture ₄ Stirring and mixing the ice water bath at the temperature of 10 ℃; then transferring the beaker into a warm water bath at 35 ℃, and continuously stirring when the reaction temperature in the beaker is increased to 35 ℃; adding deionized water into a beaker at a constant speed under stirring to dilute the mixed solution, keeping aging for a certain time when the reaction temperature is raised to 98 ℃, adding hydrogen peroxide into the beaker for oxidation, filtering the mixed solution after oxidation, and repeatedly washing with HCl and deionized waterUntil the solution is neutral; and finally adding deionized water into the washing product to form suspension, and dispersing the suspension by using ultrasonic waves to obtain brown graphene oxide hydrosol.

In a preferred embodiment, the graphene oxide sol may have a mass volume concentration of 1 to 50mg/mL, for example, 1mg/mL, 5mg/mL, 10mg/mL, 20mg/mL, 30mg/mL, 40mg/mL, 50mg/mL.

In a preferred embodiment, the metal organic framework material precursor solution, the organic ligand precursor solution, and the active phase metal salt solution may be mixed with graphene oxide sol or the organic ligand-graphene oxide solution in the following manner: mechanical stirring, magnetic stirring, ball milling mixing, shearing emulsifying and ultrasonic mixing.

In a preferred embodiment, the metal-organic framework may be selected from, but is not limited to: iron 1,3, 5-benzenetricarboxylic acid (MIL-100), cobalt 1,3, 5-benzenetricarboxylic acid, nickel 1,3, 5-benzenetricarboxylic acid, ruthenium 1,3, 5-benzenetricarboxylic acid, zirconium 1,3, 5-benzenetricarboxylic acid, cerium 1,3, 5-benzenetricarboxylic acid, thorium 1,3, 5-benzenetricarboxylic acid, iron 1, 4-terephthalate (MIL-101), cobalt 1, 4-terephthalate, nickel 1, 4-terephthalate, ruthenium 1, 4-terephthalate, zirconium 1, 4-terephthalate (UIO-66), cerium 1, 4-terephthalate, thorium 1, 4-terephthalate, iron fumarate, cobalt fumarate, nickel fumarate, ruthenium fumarate, zirconium fumarate, cerium fumarate, thorium fumarate, iron azobenzene tetracarboxylic acid, cobalt azobenzene tetracarboxylic acid, nickel azobenzene tetracarboxylic acid, ruthenium azobenzene tetracarboxylic acid, zirconium azobenzene tetracarboxylic acid cerium azoxyphthalate, thorium azoxybenzoate, iron amino-terephthalate, cobalt amino-terephthalate, nickel amino-terephthalate, ruthenium amino-terephthalate, zirconium amino-terephthalate, cerium amino-terephthalate, thorium amino-terephthalate, iron 2, 5-dihydroxyterephthalate, cobalt 2, 5-dihydroxyterephthalate, nickel 2, 5-dihydroxyterephthalate, ruthenium 2, 5-dihydroxyterephthalate, zirconium 2, 5-dihydroxyterephthalate, cerium 2, 5-dihydroxyterephthalate, thorium 2, 5-dihydroxyterephthalate, iron 1, 4-naphthalenedicarboxylate, cobalt 1, 4-naphthalenedicarboxylate, nickel 1, 4-naphthalenedicarboxylate, ruthenium 1, 4-naphthalenedicarboxylate, zirconium 1, 4-naphthalenedicarboxylate, cerium 1, 4-naphthalenedicarboxylate, thorium 1, 4-naphthalenedicarboxylate, iron 1, 5-naphthalenedicarboxylate, cobalt 1, 5-naphthalenedicarboxylate, nickel 1, 5-naphthalenedicarboxylate, ruthenium 1, 5-naphthalenedicarboxylate, zirconium 1, 5-naphthalenedicarboxylate, cerium 1, 5-naphthalenedicarboxylate, thorium 1, 5-naphthalenedicarboxylate, iron 2, 6-naphthalenedicarboxylate, cobalt 2, 6-naphthalenedicarboxylate, nickel 2, 6-naphthalenedicarboxylate, ruthenium 2, 6-naphthalenedicarboxylate, zirconium 2, 6-naphthalenedicarboxylate, cerium 2, 6-naphthalenedicarboxylate, thorium 2, 6-naphthalenedicarboxylate, and the like.

In a preferred embodiment, in the step (c) and the step (d'), the reaction temperature in the reaction vessel may be 100 to 180 ℃.

In a preferred embodiment, in said step (c) and step (d'), said drying may be performed under vacuum or under an inert atmosphere. In a further preferred embodiment, the vacuum is a vacuum degree of 0.1 to 0.005Pa. In a further preferred embodiment, the inert atmosphere is nitrogen, argon or helium. In a further preferred embodiment, the temperature of the drying may be 60 ℃ to 180 ℃.

In a preferred embodiment, the above method for preparing a carbon-supported metal catalyst having a hierarchical pore structure further comprises a step of adding an auxiliary metal salt, wherein the auxiliary metal salt may be added by mixing the auxiliary metal salt with the active phase metal salt, the organic ligand and the graphene oxide in step (1); or the auxiliary metal salt can be added to the metal organic framework/graphene oxide composite material precursor obtained in the step (1) before the step (2) is carried out, so as to obtain the composite material precursor added with the auxiliary metal.

In a further preferred embodiment, the auxiliary metal salt may be any one or more selected from the group consisting of: manganese nitrate or a hydrate thereof (e.g., manganese nitrate hexahydrate), manganese chloride, manganese acetate, manganese acetylacetonate, manganese carbonyl, zinc nitrate or a hydrate thereof (e.g., zinc nitrate hexahydrate), zinc chloride, zinc acetate, zinc acetylacetonate, chromium nitrate, ammonium molybdate, platinum nitrate, nitrosodiammonium platinum, palladium nitrate, palladium acetate, triphenylphosphine palladium, silver nitrate, silver acetate, silver carbonate, magnesium nitrate, magnesium acetate, calcium nitrate, calcium acetate, strontium nitrate, strontium acetate, sodium nitrate, sodium acetate, sodium hydroxide, sodium carbonate, sodium bicarbonate, copper nitrate, potassium hydroxide, potassium carbonate, potassium bicarbonate, and potassium acetate.

In a further preferred embodiment, the additive metal salt may be added to the metal organic framework/graphene oxide composite precursor by impregnation.

As an example of an impregnation method, the additive metal may be added to the metal organic framework/graphene oxide composite precursor by co-impregnation or stepwise impregnation at a suitable temperature, for example, room temperature (e.g., 15 to 40 ℃). The method for co-impregnation comprises weighing the metal-organic framework/graphene oxide composite material precursor and the auxiliary metal salt according to the composition ratio of the catalyst, dissolving the auxiliary metal salt in a solvent to form an impregnation solution, and then impregnating the impregnation solution on the metal-organic framework/graphene oxide composite material precursor. An exemplary step impregnation method is to separately dissolve the promoter metal salt in a solvent to form separate impregnation solutions, and then step impregnate the carbonaceous precursor. The impregnation may be either equal volume impregnation or excessive impregnation. Equal volume impregnation means that the volume of the impregnating solution is equal to the saturated water absorption volume of the support; excess impregnation means that the volume of the impregnating solution is greater than the saturated water absorption volume of the support. The solvent may be water, methanol, methylamine, dimethylamine, N-dimethylformamide, N-methylformamide, formamide, ethanol, ethylene glycol, diethyl ether, ethylamine, acetonitrile, acetamide, propanol, acetone, propionitrile, tetrahydrofuran, dioxane, butanol, pyridine, morpholine, quinoline, toluene, xylene, heptane, or a mixture of one or more thereof.

In a preferred embodiment, in the step (2), the molding may be direct compression molding, or may be molding using cellulose ether, phenolic resin, acrylic resin, epoxy resin, melamine resin, urea resin, polyurethane as a binder. The molding method can be selected from compression molding, rotation molding, extrusion molding, oil molding, water molding, spray drying molding, and the like. The shape of the shaped composite material can be granular, microsphere, sheet, strip, column, ring, porous sheet or clover.

Herein, the cellulose ether is a cellulose substituted with functional groups, preferably selected from carboxylic acid groups, hydroxyl groups, alkyl functional groups, and combinations thereof, and alkyl functional groups preferably selected from methyl, ethyl, propyl, and combinations thereof. As a preferred example, the cellulose ether may be at least one selected from the group consisting of carboxyethyl cellulose, carboxymethyl hydroxyethyl cellulose, carboxyethyl hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxymethyl cellulose, hydroxypropyl cellulose, hydroxymethyl-methyl cellulose, hydroxymethyl-ethyl cellulose, hydroxyethyl-ethyl cellulose, methyl cellulose, ethyl cellulose, propyl cellulose, ethyl-carboxymethyl cellulose, hydroxy-ethyl cellulose and hydroxy-ethyl-propyl cellulose.

Herein, the phenolic resin is a polymer of phenol and formaldehyde. Preferably, the phenolic resin has an average relative molecular weight of 500 to 1000. As a preferable example, the acrylic resin is a polymer of methyl acrylate, ethyl acrylate, n-butyl acrylate, methyl methacrylate, and n-butyl methacrylate, and has an average relative molecular weight of 1000 to 3000. As a preferred example, the epoxy resin is a polymer of 2, 2-bis (4-hydroxyphenyl) propane and cyclopropane having an average relative molecular weight of 500 to 2000. As a preferred example, the melamine resin is a polymer of melamine and formaldehyde, and has a relative molecular weight of 1000 to 3000. Herein, the urea-formaldehyde resin is a polymer of urea and formaldehyde. Preferably, the urea-formaldehyde resin has an average relative molecular weight of 500 to 1000. The polyurethane is a polymer of diisocyanate and hydroxyl-terminated polyester or hydroxyl-terminated polyether. Preferably, the polyurethane has a relative molecular weight of 1000 to 4000. The diisocyanate is 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate and a mixture thereof; the hydroxyl-terminated polyester is a liquid oligomer of terephthalic acid and ethylene glycol, and the relative molecular weight of the hydroxyl-terminated polyester is 500-2000; the hydroxyl-terminated polyether is an oligomer of ethylene oxide, propylene oxide or tetrahydrofuran, and the relative molecular weight of the hydroxyl-terminated polyether is 500-2000.

In a further preferred embodiment, the mass of the binder is 0% to 20%, for example 15% to 20% of the mass of the metal organic framework/graphene oxide composite precursor.

In a preferred embodiment, in the step (3), the inert atmosphere is at least one selected from nitrogen, helium, argon, xenon and radon. In a preferred embodiment, the carbon-containing atmosphere may be a mixture of a carbon-containing gas and an inert gas. Preferably, the carbon-containing gas is methane, ethane, ethylene, acetylene, propane, propylene, CO and/or synthesis gas. Further preferably, the volume concentration of the carbon-containing gas in the carbon-containing atmosphere is 0.5% -100%, such as 2%, 5%, 8%. Further preferably, the inert gas may be at least one selected from the group consisting of nitrogen, helium, argon, xenon, and radon.

Pyrolysis and carbonization in an inert atmosphere or a carbon-containing atmosphere are key operations in forming carbon nanocage cladding structures. In the above catalyst preparation method, the pyrolysis and carbonization means both pyrolysis of MOF and carbonization of metal. Preferably, the pyrolysis and carbonization temperatures are from 350 ℃ to 1100 ℃ (e.g., 450 ℃ to 700 ℃) for a period of time ranging from 1 to 10 hours (e.g., 3 to 10 hours).

In one embodiment, the present invention relates to the use of a carbon supported metal catalyst having a hierarchical pore structure as described above for catalyzing the reaction of a CO and hydrogen containing gas to produce hydrocarbon compounds.

As a preferred example, the CO and hydrogen containing gas may be synthesis gas. As a preferred example, the carbon-supported metal catalyst having a hierarchical pore structure of the present invention may be directly used in a reaction for preparing hydrocarbon compounds by catalyzing synthesis gas; or the catalyst is reduced in a reducing atmosphere in advance before being used for the reaction of preparing hydrocarbon compounds by catalyzing synthesis gas. The reducing atmosphere may be a pure hydrogen atmosphere, a CO atmosphere, a synthesis gas atmosphere, an ammonia atmosphere, a diluted hydrogen atmosphere, a diluted CO atmosphere, a diluted synthesis gas atmosphere, a diluted ammonia atmosphere. H in synthesis gas ₂ The volume ratio of the catalyst to CO is 0.01:1 to1000:1 (e.g., 0.5:1 to 3.0:1, preferably 1.0:1 to 2.5:1, more preferably 1.2:1 to 2.2:1, most preferably 1.5:1 to 2.0:1). The diluted reducing atmospheres can further contain nitrogen, argon, helium and CO besides the corresponding reducing atmospheres ₂ And/or CH ₄ The volume concentration of the reducing gas in each of the diluted reducing atmospheres is more than 10%, preferably more than 25%, more preferably 50%, even more preferably 75%, and most preferably more than 90%. The carbon supported metal catalyst is reduced to produce a reduced catalyst having a degree of reduction (i.e., metal phase, metal carbide as a percentage of total active phase metal), preferably the degree of reduction of the resulting reduced catalyst is at least greater than 60%, preferably greater than 75%, and most preferably greater than 85%.

In a preferred embodiment, the reaction of the CO and hydrogen containing gas can be carried out as a continuous or batch reaction process.

In a preferred embodiment, the reaction of the CO with hydrogen-containing gas may be carried out in one or more fixed bed reactors, microchannel reactors, continuously stirred slurry tank reactors, jet loop reactors, slurry bubble column reactors or fluidised bed reactors.

In a preferred embodiment, the reaction pressure of the CO with the hydrogen-containing gas is 1.0 to 6.0MPa and the temperature is 100℃to 500 ℃ (e.g., 200℃to 400 ℃). Preferably, the reaction is carried out as a continuous reaction process with a reaction weight hourly space velocity of from 100 to 60000NL/Kg/h (e.g. from 2000 to 12000 NL/Kg/h).

For example, when the catalyst is a carbon-supported cobalt catalyst, H in the synthesis gas ₂ The volume ratio of the catalyst to CO is 1.0:1-3.0:1, preferably 1.5:1-2.5:1, and optimally 1.8:1-2.2:1. The reaction pressure is 1.0-6.0 MPa, preferably 1.5-4.5 MPa, most preferably 2.0-3.0 MPa. The reaction temperature is 180 to 280 ℃, preferably 200 to 260 ℃, and most preferably 220 to 240 ℃. When the reaction is carried out as a continuous reaction process, the weight hourly space velocity of the reaction is from 100 to 25000NL/Kg/h, preferably from 1000 to 20000NL/Kg/h, most preferably from 5000 to 15000NL/Kg/h. Alternatively, when the catalyst is a carbon-supported iron catalyst, H in the synthesis gas ₂ The volume ratio of the catalyst to CO is 0.5:1-3.0:1, and the catalyst is excellent1.0:1 to 2.5:1, more preferably 1.2:1 to 2.2:1, most preferably 1.5:1 to 2.0:1. The pressure of the reaction is preferably 1.0 to 6.0MPa, preferably 1.5 to 5.5MPa, more preferably 2.0 to 5.0MPa, most preferably 2.5 to 4.0MPa. The reaction temperature is 220 to 350 ℃, preferably 240 to 330 ℃, and most preferably 260 to 300 ℃. When the reaction is carried out as a continuous reaction process, the weight hourly space velocity of the reaction is from 100 to 60000NL/Kg/h, preferably from 1000 to 40000NL/Kg/h, most preferably from 10000 to 20000NL/Kg/h. Alternatively, when the catalyst is a carbon-supported ruthenium catalyst, H in the synthesis gas ₂ The volume ratio to CO is 0.5:1 to 3.0:1, preferably 1.0:1 to 2.5:1, more preferably 1.2:1 to 2.2:1, most preferably 1.5:1 to 2.0:1. The pressure of the reaction is 1.0 to 10.0MPa, preferably 2.5 to 7.5MPa, more preferably 3.0 to 6.0MPa, most preferably 3.5 to 5.0MPa. The reaction temperature is 120 to 280 ℃, preferably 150 to 240 ℃, and most preferably 180 to 220 ℃. When the reaction is carried out as a continuous reaction process, the weight hourly space velocity of the reaction is from 100 to 10000NL/Kg/h, preferably from 500 to 8000NL/Kg/h, most preferably from 1000 to 5000NL/Kg/h. Alternatively, when the catalyst is a carbon supported nickel catalyst, H in the synthesis gas ₂ The volume ratio to CO is 1.5:1 to 4.0:1, preferably 2.0:1 to 3.0:1, more preferably 2.5:1 to 3.0:1. The pressure of the reaction is 0.5 to 3.0MPa, preferably 1.0 to 2.5MPa, more preferably 1.0 to 2.0MPa, most preferably 1.0 to 1.5MPa. The reaction temperature is 250 to 600 ℃, preferably 300 to 500 ℃, and most preferably 350 to 450 ℃. When the reaction is carried out as a continuous reaction process, the weight hourly space velocity of the reaction is from 1000 to 10000NL/Kg/h, preferably from 2000 to 8000NL/Kg/h, most preferably from 3000 to 5000NL/Kg/h. Or when the catalyst is a carbon-supported zirconium catalyst, a carbon-supported cerium catalyst, a carbon-supported thorium catalyst or a carbon-supported indium catalyst, H in the synthesis gas ₂ The volume ratio to CO is 0.5:1 to 3.0:1, preferably 0.7:1 to 2.5:1, more preferably 1.0:1 to 2.0:1, most preferably 1.0:1 to 1.5:1. The pressure of the reaction is 2.0 to 10.0MPa, preferably 3.0 to 8.5MPa, more preferably 5.0 to 8.0MPa, most preferably 6.0 to 8.0MPa. The reaction temperature is 320 to 600 ℃, preferably 350 to 500 ℃, and most preferably 380 to 450 ℃. When the reaction is carried out as a continuous reaction process, the weight hourly space velocity of the reaction is from 100 to 5000NL/Kg/h, preferably from 500 to 3000NL/Kg/h, most preferably from 1000 to 2000NL/Kg/h.

The exemplary scheme of the invention has the following characteristics: the catalyst has a higherLarge specific surface area (not less than 100m ² Per g), ultra-small active phase metal or metal oxide grain size (3-7 nm), high mechanical strength (wear index 1-2.0%. H ^-1 ) Hierarchical mesoporous channels and excellent stability; the catalysts of the present disclosure, when applied to fischer-tropsch synthesis reactions, are superior to catalysts prepared by direct chemical synthesis or comprise conventional supports (SiO ₂ Or Al ₂ O ₃ ) The catalyst has better CO and hydrogen conversion activity, hydrocarbon compound selectivity and high-temperature stability; the catalyst of the present disclosure also has excellent attrition resistance when used in a syngas catalytic reaction.

Exemplary embodiments of the present invention may be described in the following numbered paragraphs, but the scope of the present invention is not limited thereto:

1. a carbon supported metal catalyst having a hierarchical pore structure, the catalyst comprising:

an active phase metal; and

2. The carbon-supported metal catalyst of paragraph 1 wherein the active phase metal is at least one of iron, cobalt, nickel, ruthenium, zirconium, cerium, thorium, or indium.

3. The carbon-supported metal catalyst as in paragraph 1 or 2, wherein the specific surface area of the catalyst is not less than 100m ² /g。

4. The carbon-supported metal catalyst as in any one of paragraphs 1-3, wherein the mass ratio of the active phase metal to the porous carbon support is (0.1-200): 100.

5. The carbon supported metal catalyst of any of paragraphs 1-4, wherein the catalyst further comprises a promoter metal.

6. The carbon-supported metal catalyst of paragraph 5 wherein the promoter metal is at least one of manganese, chromium, zinc, molybdenum, copper, platinum, palladium, rhodium, iridium, gold, silver, magnesium, calcium, strontium, barium, sodium, or potassium.

7. The carbon-supported metal catalyst according to paragraph 5 or 6, wherein the mass ratio of the promoter metal to the porous carbon support is (0.002 to 40): 100.

8. A method of preparing the carbon supported metal catalyst having a hierarchical pore structure of any one of paragraphs 1-7, wherein the method comprises:

9. The method of paragraph 8, wherein in step (1), the metal-organic framework/graphene oxide composite precursor is prepared according to the following procedure:

(a) Adding the active phase metal salt and the organic ligand into a solvent to obtain a metal organic framework material precursor solution;

10. The method of paragraph 8, wherein in step (1), the metal-organic framework/graphene oxide composite precursor is prepared according to the following procedure:

(a') adding the organic ligand to a solvent to obtain an organic ligand precursor solution;

(c') adding the active phase metal salt into a solvent to obtain an active phase metal salt solution, and adding the active phase metal salt solution into the organic ligand-graphene oxide solution to obtain a sol-like liquid;

11. The method of any one of paragraphs 8-10, wherein the active phase metal salt is at least one selected from the group consisting of: iron nitrate or a hydrate thereof, iron chloride, iron sulfate, iron acetate, iron (III) acetylacetonate, iron carbonyl, ferrocene, cobalt nitrate or a hydrate thereof, cobalt chloride, cobalt formate, cobalt acetate or a hydrate thereof, cobalt acetylacetonate, cobalt carbonyl, cobalt (III) tri (ethylenediamine) chloride trihydrate, nickel nitrate, nickel chloride, nickel sulfate, nickel acetate, nickel acetylacetonate, nickel carbonyl, ruthenium trichloride, ruthenium nitrate, triphenylphosphine ruthenium carbonyl chloride, ammonium ruthenate, ruthenium nitrosylnitrate, zirconyl nitrate, zirconium oxychloride, zirconium nitrate, zirconium chloride, zirconium sulfate, cerium nitrate, cerium chloride, cerium sulfate, thorium nitrate, thorium chloride, indium nitrate, indium chloride, indium sulfate.

12. The method of any of paragraphs 8-11, wherein the organic ligand is at least one of levulinic acid, lauric acid, oxalic acid, citric acid, 1,3, 5-benzene tricarboxylic acid, terephthalic acid, 2-methylimidazole, fumaric acid, azobenzene tetracarboxylic acid, amino-terephthalic acid, 2, 5-dihydroxyterephthalic acid, 1, 4-naphthalene dicarboxylic acid, 1, 5-naphthalene dicarboxylic acid, or 2, 6-naphthalene dicarboxylic acid.

13. The method of any one of paragraphs 8-12, wherein the mass ratio of the active phase metal salt to the organic ligand is (30-400): 100.

14. The method of any of paragraphs 9-13, wherein the solvent is one or more of water, methanol, methylamine, dimethylamine, N-dimethylformamide, N-methylformamide, formamide, ethanol, ethylene glycol, diethyl ether, ethylamine, acetonitrile, acetamide, propanol, acetone, propionitrile, tetrahydrofuran, dioxane, butanol, pyridine, morpholine, quinoline, toluene, xylene, heptane.

15. The method of any one of paragraphs 9-14, wherein the graphene oxide sol has a mass volume concentration of 1-50 mg/mL.

16. The method of any of paragraphs 9-15, wherein the metal organic framework material precursor solution, the organic ligand precursor solution, and the active phase metal salt solution are mixed with graphene oxide sol or the organic ligand-graphene oxide solution by: mechanical stirring, magnetic stirring, ball milling mixing, shear emulsification or ultrasonic mixing.

17. The method of any one of paragraphs 8-16, wherein the metal-organic framework is selected from the group consisting of: iron 1,3, 5-benzenetricarboxylic acid, cobalt 1,3, 5-benzenetricarboxylic acid, nickel 1,3, 5-benzenetricarboxylic acid, ruthenium 1,3, 5-benzenetricarboxylic acid, zirconium 1,3, 5-benzenetricarboxylic acid, cerium 1,3, 5-benzenetricarboxylic acid thorium, iron 1, 4-terephthalate, cobalt 1, 4-terephthalate, nickel 1, 4-terephthalate, ruthenium 1, 4-terephthalate, zirconium 1, 4-terephthalate, cerium 1, 4-terephthalate, thorium 1, 4-terephthalate, iron fumarate, cobalt fumarate, nickel fumarate, ruthenium fumarate, zirconium fumarate, cerium fumarate, thorium fumarate, iron azobenzoate, cobalt azobenzoate, nickel azobenzoate, ruthenium azobenzoate, zirconium azobenzoate, cerium azobenzoate, thorium azobenzoate, iron amino-terephthalate cobalt amino-terephthalate, nickel amino-terephthalate, ruthenium amino-terephthalate, zirconium amino-terephthalate, cerium amino-terephthalate, thorium amino-terephthalate, iron 2, 5-dihydroxyterephthalate, cobalt 2, 5-dihydroxyterephthalate, nickel 2, 5-dihydroxyterephthalate, ruthenium 2, 5-dihydroxyterephthalate, zirconium 2, 5-dihydroxyterephthalate, cerium 2, 5-dihydroxyterephthalate, thorium 2, 1, 4-iron naphthalene dicarboxylate, cobalt 1, 4-naphthalene dicarboxylate, nickel 1, 4-naphthalene dicarboxylate, ruthenium 1, 4-naphthalene dicarboxylate, zirconium 1, 4-naphthalene dicarboxylate, cerium 1, 4-naphthalene dicarboxylate, thorium 1, 5-naphthalene dicarboxylate, cobalt 1, 5-naphthalene dicarboxylate, nickel 1, 5-naphthalene dicarboxylic acid, nickel 1, 4-naphthalene dicarboxylic acid, ruthenium 1, 5-naphthalenedicarboxylate, zirconium 1, 5-naphthalenedicarboxylate, cerium 1, 5-naphthalenedicarboxylate, thorium 1, 5-naphthalenedicarboxylate, iron 2, 6-naphthalenedicarboxylate, cobalt 2, 6-naphthalenedicarboxylate, nickel 2, 6-naphthalenedicarboxylate, ruthenium 2, 6-naphthalenedicarboxylate, zirconium 2, 6-naphthalenedicarboxylate, cerium 2, 6-naphthalenedicarboxylate or thorium 2, 6-naphthalenedicarboxylate.

18. The method according to any one of paragraphs 9 to 17, wherein, in the steps (c) and (d'), the reaction temperature in the reaction vessel is 100℃to 180 ℃.

19. The method of any one of paragraphs 9-17, wherein in the steps (c) and (d'), the drying is performed under vacuum or an inert atmosphere.

20. The method of paragraph 19, wherein the vacuum has a vacuum level of 0.1 to 0.005Pa.

21. The method of paragraph 19, wherein the inert atmosphere is nitrogen, argon, or helium.

22. The method of any one of paragraphs 9-21, wherein, in the steps (c) and (d'), the drying temperature is 60℃to 180 ℃.

23. The method of any one of paragraphs 8-22, wherein the method further comprises the step of adding an auxiliary metal salt, wherein the auxiliary metal salt is added by mixing the auxiliary metal salt with the active phase metal salt, organic ligand and graphene oxide in step (1); or before the step (2), adding the auxiliary metal salt into the metal organic framework/graphene oxide composite material precursor obtained in the step (1) to obtain the composite material precursor added with the auxiliary metal.

24. The method of paragraph 23, wherein the promoter metal salt is one or more selected from the group consisting of: manganese nitrate or a hydrate thereof, manganese chloride, manganese acetate, manganese acetylacetonate, manganese carbonyl, zinc nitrate or a hydrate thereof, zinc chloride, zinc acetate, zinc acetylacetonate, chromium nitrate, ammonium molybdate, platinum nitrate, nitrosodiammonium platinum, palladium nitrate, palladium acetate, triphenylphosphine palladium, silver nitrate, silver acetate, silver carbonate, magnesium nitrate, magnesium acetate, calcium nitrate, calcium acetate, strontium nitrate, strontium acetate, sodium nitrate, sodium acetate, sodium hydroxide, sodium carbonate, sodium bicarbonate, copper nitrate, potassium hydroxide, potassium carbonate, potassium bicarbonate, and potassium acetate.

25. The method of paragraph 23 or 24, wherein the promoter metal salt is added to the metal organic framework/graphene oxide composite precursor by an immersion method.

26. The method according to any one of paragraphs 8-25, wherein in step (2), the molding is direct compression molding or molding using cellulose ether, phenolic resin, acrylic resin, epoxy resin, melamine resin, urea resin, polyurethane as a binder.

27. The method of any of paragraphs 8-26, wherein the shaping method is selected from compression shaping, rotational shaping, extrusion shaping, in-oil shaping, in-water shaping, or spray drying shaping.

28. The method of paragraph 26, wherein the mass of the binder is between 0% and 20% of the mass of the metal organic framework/graphene oxide composite precursor.

29. The method of any one of paragraphs 8-28, wherein in step (3), the inert atmosphere is at least one selected from the group consisting of nitrogen, helium, argon, xenon, and radon.

30. The method according to any one of paragraphs 8-28, wherein in step (3), the carbon-containing atmosphere is a mixture of a carbon-containing gas and an inert gas.

31. The method of paragraph 30, wherein the carbon-containing gas is methane, ethane, ethylene, acetylene, propane, propylene, CO, and/or syngas.

32. The method of paragraph 30 or 31, wherein the inert gas is at least one selected from the group consisting of nitrogen, helium, argon, xenon, and radon.

33. The method of any of paragraphs 30-32, wherein the carbon-containing gas is present in the carbon-containing atmosphere at a volume concentration of 0.5% to 100%.

34. The method of any of paragraphs 8-33, wherein the pyrolysis and carbonization are at a temperature of 350℃to 1100℃for a period of 1 to 10 hours.

35. Use of the carbon-supported metal catalyst having a hierarchical pore structure of any one of paragraphs 1-7 for catalyzing a reaction of a gas comprising CO and hydrogen to produce hydrocarbon compounds.

36. The use of paragraph 35 wherein the CO and hydrogen containing gas is syngas.

37. The use of paragraphs 35 or 36 wherein the reaction is carried out as a continuous or batch reaction process.

38. The use of any of paragraphs 35-37, wherein the reaction is carried out in one or more fixed bed reactors, microchannel reactors, continuous stirred slurry tank reactors, jet loop reactors, slurry bubble column reactors, or fluidized bed reactors.

39. The use of any of paragraphs 35-38, wherein the reaction is at a pressure of 1.0 to 6.0MPa and a temperature of 100 to 500 ℃.

40. The use of any of paragraphs 35-39 wherein the reaction is conducted as a continuous reaction process with a reaction weight hourly space velocity of 100 to 60000NL/Kg/h.

The experimental methods used in the following examples are conventional methods unless otherwise specified. Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified. The graphene oxide hydrosols in the examples below were prepared according to the conventional Hummers method.

Examples

Example 1: fe@C catalyst prepared from Fe-MOFs/GO and CO hydrogenation performance thereof

36.8g of ferric nitrate nonahydrate and 12.7g of 1,3, 5-benzenetricarboxylic acid (H) were weighed out ₃ BTC), they were dissolved in 325g of deionized water, mixed and stirred until they were completely dissolved, to obtain MOFs synthesis material precursor solution. Will be put onThe precursor solution is dropwise added into 350mL and 10mg/mL graphene oxide hydrosol for stirring and mixing, so that stable and uniform suspension is obtained.

Pouring the suspension into a 1L hydrothermal reaction kettle, reacting for 24 hours at the temperature of 120 ℃, naturally cooling to room temperature, alternately washing for 5 times by using deionized water and ethanol, suction-filtering to obtain MOFs/GO compound, and finally drying in a vacuum (0.1 Pa) oven at the temperature of 60 ℃ for 12 hours to obtain MOFs/GO compound material precursors, wherein the texture properties of the MOFs/GO compound material precursors are shown in Table 1. The XRD patterns and scanning electron microscope patterns of the MOFs/GO composite material precursor prepared in the embodiment are shown in fig. 1 and 2, respectively, and it can be seen that typical metal-organic framework material Fe-MIL-100 structures exist in the composite material precursor, and the metal-organic framework material is uniformly dispersed on the graphene oxide sheets.

Directly tabletting and shaping the precursor of the MOFs/GO composite material, crushing into particles with 20-40 meshes, and then carrying out compression molding on the particles at 2vol%C ₂ H ₂ /98vol％N ₂ Pyrolyzing and carbonizing for 5h at 500 ℃ in the air flow to obtain the Fe@C catalyst with a hierarchical pore structure. The catalyst comprises the following elements in mass: fe/c=65.6:100, the texture properties of which are listed in table 1.

The XRD pattern of the Fe@C catalyst prepared in the example is shown in fig. 3, and diffraction peaks with the spread 2 theta between 20 degrees and 30 degrees correspond to signals of graphene oxide and amorphous carbon in the catalyst; the series of diffraction peaks of 2 theta at 44.1 deg., 46.6 deg., 47.7 deg., 50.4 deg., 51.4 deg., 52.5 deg., 52.8 deg., 53.9 deg., 57.3 deg., 57.9 deg., etc. are corresponding to theta-Fe ₃ And C. SEM photographs of the fe@c catalyst prepared in this example are shown in fig. 4, the fe@c catalyst consisting of lamellar graphene oxide and vermiform particles, the vermiform particles being hollow tubular structures. In the Fe@C catalyst, the Fe particles are 5-10nm in size and uniformly distributed in the carbon support, as shown in FIG. 5. After treating the Fe@C catalyst with a 0.5M dilute aqueous hydrochloric acid solution for 24 hours, repeatedly filtering and washing with deionized water to completely remove Fe element, a carbon carrier, labeled as C-1, can be obtained, and the texture properties are shown in Table 1. The TEM photograph of the carbon carrier is shown in figure 6, the carbon carrier is of a hollow spherical structure, the outer diameter of the carbon sphere is 8-20nm, The diameter of the cavity is 5-10nm. The BJH pore distribution curve of the Fe@C catalyst is shown in FIG. 7, three most probable pore distribution peaks exist at the pore diameters of 3.8nm, 7.7nm and 24.3nm, and the pore distribution in the catalyst is of a typical hierarchical pore structure. The BJH pore distribution curve of the carbon carrier after 0.5M dilute hydrochloric acid washing filtration is shown in figure 8, and two most probable pore distribution peaks exist at the pore diameters of 3.8nm and 24.6nm, which shows that the pore distribution of the carbon carrier is of a hierarchical pore structure.

CO hydrogenation performance test: 2g of the catalyst was taken, diluted and mixed uniformly with 2mL of silicon carbide, and placed in a fixed bed reactor having an inner diameter of 10mm and a constant temperature section length of 50 mm. Catalyst at 98vol% H ₂ Reducing in a reducing atmosphere of/2 vol% CO at 350 ℃ for 24 hours, and cooling to 220 ℃. Then 63vol% H ₂ A synthesis gas of/37 vol% CO was introduced into the reactor at a pressure of 2.0MPa, the temperature of the reactor was increased to 280℃at a rate of 0.1℃per minute, the space velocity of the reaction was adjusted to 12000NL/Kg/h, and the reaction was maintained for 128 hours. The composition of the reactor off-gas was analyzed by gas chromatography during the reaction and used to calculate the CO conversion, product selectivity and stability of the reaction. The results of the CO hydrogenation performance test are listed in table 2.

Example 2: feMnCuK@C catalyst prepared from Fe-MOFs/GO and CO hydrogenation performance thereof

422.8g of ferric chloride hexahydrate and 149.2g of terephthalic acid (H) were weighed out ₂ BDC), they were dissolved in 3935g of N, N-Dimethylformamide (DMF), mixed and stirred until they were completely dissolved, to give MOFs (Fe-BDC) synthesis material precursor solutions. The precursor solution is added into graphene oxide hydrosol with the concentration of 1.7L and the concentration of 50mg/mL drop by drop, and stirring and mixing are carried out, so that stable and uniform suspension is obtained. And uniformly placing the suspension into a 5L hydrothermal reaction kettle, reacting for 18 hours at 160 ℃, naturally cooling to room temperature, washing with deionized water for 3 times, washing with ethanol for 3 times, and performing suction filtration to obtain the Fe-BDC/GO compound. Mixing Fe-BDC/GO compound and absolute ethyl alcohol according to the mass ratio of 1:2, stirring to form slurry suspension, and then at 160 ℃ and N ₂ Spray drying was performed under an atmosphere of 0.2MPa to obtain Fe-BDC/GO composite precursors, the texture properties of which are shown in Table 1.

Weighing 2.3g of manganese nitrate hexahydrate, 0.3g of copper nitrate and 1.3g of potassium nitrate, dissolving in 15ml of deionized water to prepare a solution, uniformly mixing the solution with the Fe-BDC/GO composite material precursor, drying to obtain a composite material precursor added with additive metal, tabletting and forming the precursor, crushing the precursor into particles with 20-40 meshes, and then adding the particles into 5vol%CO/95vol%N ₂ Pyrolyzing and carbonizing for 3h at 700 ℃ in the air flow to obtain the FeMnCuK@C catalyst with a hierarchical pore structure. The catalyst comprises the following elements in mass: fe/Mn/Cu/K/c=38.3:3.4:0.7:1.7:100, the texture properties of which are listed in table 1. After the FeMnCuK@C catalyst was treated with a 0.5M dilute aqueous hydrochloric acid solution for 24 hours, the metal element was completely removed by repeated filtration with deionized water to obtain a carbon support, labeled C-2, whose texture properties are shown in Table 1. As shown in Table 1, the FeMnCuK@C catalyst and the C-2 carrier both have three most probable pore distribution peaks, which indicate that the pore distribution of the catalyst and the carbon carrier is of a hierarchical mesoporous structure.

The catalyst of this example was tested for CO hydrogenation performance as described in example 1, except that the catalytic reaction time was adjusted to 116 hours. The composition of the reactor off-gas was analyzed by gas chromatography during the reaction and used to calculate the CO conversion, product selectivity and stability of the reaction. The results of the CO hydrogenation performance test are listed in table 2.

Example 3: co@C catalyst prepared from Co-MOFs/GO and CO hydrogenation performance thereof

44.7g of terephthalic acid (H) was weighed out ₂ BDC) and adding the BDC) to 58g of tetrahydrofuran to obtain a terephthalic acid precursor suspension; and (3) dropwise adding the obtained terephthalic acid precursor suspension into 340mL and 20mg/mL graphene oxide sol, and uniformly stirring and mixing to obtain a terephthalic acid-graphene oxide colloidal solution. Weighing 134g of cobalt acetate tetrahydrate, dissolving the cobalt acetate tetrahydrate in 50g of deionized water, mixing and stirring until the cobalt acetate tetrahydrate is completely dissolved, and obtaining cobalt precursor solution; and (3) dropwise adding the obtained cobalt precursor solution into the terephthalic acid-graphene oxide colloid solution, and stirring and mixing to form stable and uniform sol-like liquid.

Pouring the sol liquid into a 1L hydrothermal reaction kettle, reacting for 72 hours at the temperature of 110 ℃, naturally cooling to room temperature, washing with deionized water for 3 times, washing with ethanol for 3 times, performing suction filtration to obtain Co-MOFs/GO compound, and finally drying in a vacuum (0.1 Pa) oven at the temperature of 60 ℃ for 12 hours. Co-MOFs/GO composite precursors were obtained with texture properties as set forth in Table 1.

Uniformly mixing the obtained Co-MOFs/GO composite material precursor and hydroxymethyl cellulose according to the mass ratio of 5:1, adding deionized water, kneading, extruding into strips, forming, ventilating and drying at normal temperature, crushing into particles of 20-40 meshes, and then adding the particles into a mixture of 8vol%C ₂ H ₄ Pyrolysis and carbonization for 3h at 550 ℃ in a 92vol% Ar gas stream gave a Co@C catalyst with a hierarchical pore structure. The elemental mass composition of the catalyst was Co/c=51.6:100, and the texture properties are listed in table 1. After the Co@C catalyst was treated with 0.5M dilute aqueous hydrochloric acid for 24 hours, the metal elements were removed completely by repeated filtration with deionized water to give a carbon support, labeled C-3, whose texture properties are shown in Table 1. As shown in Table 1, there are two most probable pore distribution peaks for both Co@C catalyst and C-3 support, indicating that the pore distribution of both catalyst and carbon support is a hierarchical mesoporous structure.

CO hydrogenation performance test: 2g of the Co@C catalyst was taken and diluted and mixed uniformly with 2mL of silicon carbide, and placed in a fixed bed reactor having an inner diameter of 10mm and a constant temperature section length of 50 mm. Catalyst at H ₂ Reducing at 350 deg.C for 36 hr, and cooling to 180 deg.C. Then 63vol% H ₂ A synthesis gas of/37 vol% CO was introduced into the reactor at a pressure of 2.0MPa, the temperature of the reactor was increased to 220℃at a rate of 0.1℃per minute, the reaction space velocity was adjusted to 5000NL/Kg/h, and the reaction was maintained for 115 hours. The composition of the reactor off-gas was analyzed by gas chromatography during the reaction and used to calculate the CO conversion, product selectivity and stability of the reaction. The results of the CO hydrogenation performance test are listed in table 2.

Example 4: ru@C catalyst prepared from Ru-MOFs/GO and CO hydrogenation performance thereof

5.56g of ruthenium trichloride (Ru content 38% by weight) and 16.6g of terephthalic acid (H) were weighed out ₂ BDC), dissolving them in a mixed solvent of 12.4g of ethylene glycol and 580g of N, N-Dimethylformamide (DMF), and mixing them with stirring until they are completely dissolved, to obtain a precursorA bulk solution. And (3) dropwise adding the precursor solution into 1.5L of 30mg/mL graphene oxide hydrosol, and stirring and mixing to obtain stable and uniform sol mixed liquid.

Pouring the mixed liquid into a 5L hydrothermal reaction kettle, reacting for 8 hours at the temperature of 130 ℃, naturally cooling to room temperature, washing with deionized water for 5 times, washing with ethanol for 3 times, and carrying out suction filtration and drying to obtain the Ru-MOFs/GO composite material precursor. The texture properties are listed in table 1.

Ru-MOFs/GO composite material precursor, 70wt% phenolic resin ethanol sol and absolute ethanol are mixed and stirred into slurry suspension according to the mass ratio of 1:0.15:5, and then the slurry suspension is prepared at 160 ℃ and N ₂ Spray drying is carried out under the condition of atmosphere and 0.2MPa to form, and the formed Ru-MOFs/GO composite material is obtained.

And pyrolyzing and carbonizing the formed Ru-MOFs/GO composite material in Ar gas flow at 450 ℃ for 8 hours to obtain the Ru@C catalyst with a hierarchical pore structure. The catalyst comprises the following elements in mass: ru/c=1.3:100, the texture properties are listed in table 1. After treating Ru@C catalyst with 0.5M dilute aqueous hydrochloric acid for 24 hours, repeatedly filtering and washing with deionized water to completely remove metal elements, a carbon carrier, labeled C-4, can be obtained, and the texture properties are shown in Table 1. As shown in Table 1, there are two most probable pore distribution peaks for both Ru@C catalyst and C-4 support, indicating that the pore distribution of both catalyst and carbon support is a hierarchical mesoporous structure.

CO hydrogenation performance test: 2g of the Ru@C catalyst was taken and diluted and mixed uniformly with 2mL of silicon carbide, and placed in a fixed bed reactor with an inner diameter of 10mm and a constant temperature section length of 50 mm. Catalyst at H ₂ Reducing for 5 hours at 250 ℃ in the atmosphere, and cooling to 180 ℃. Then 63vol% H ₂ A synthesis gas of/37 vol% CO is introduced into the reactor, the pressure is 2.0MPa, the temperature of the reactor is increased to 200 ℃ at a heating rate of 0.1 ℃/min, the reaction space velocity is regulated to 5000NL/Kg/h, and the reaction is kept for 109 hours. The composition of the reactor off-gas was analyzed by gas chromatography during the reaction and used to calculate the CO conversion, product selectivity and stability of the reaction. The results of the CO hydrogenation performance test are listed in table 2.

Example 5: zrO prepared from Zr-MOFs/GO ₂ Catalyst at C and CO hydrogenation performance thereof

5.0g of zirconyl nitrate and 3.6g of terephthalic acid (H) were weighed out ₂ BDC), they were dissolved in 189g of n, n-Dimethylformamide (DMF), and mixed with stirring until they were completely dissolved, to obtain a zirconium-terephthalic acid precursor solution. The precursor solution is added into 500mL and 1mg/mL graphene oxide hydrosol drop by drop, and stirred and mixed to obtain stable and uniform suspension. Pouring the suspension into a 1L hydrothermal reaction kettle, reacting for 96 hours at the temperature of 100 ℃, naturally cooling to room temperature, alternately washing for 5 times by using DMF and ethanol, carrying out suction filtration to obtain Zr-MOFs/GO compound, and finally drying in a vacuum (0.01 Pa) oven at the temperature of 80 ℃ for 24 hours. The Zr-MOFs/GO composite precursors were obtained and the texture properties are shown in Table 1.

Directly tabletting, shaping and crushing the obtained Zr-MOFs/GO composite material precursor into particles with 20-40 meshes, and then adding the particles into N ₂ Pyrolyzing and carbonizing for 10h at 550 ℃ in air flow to obtain ZrO with hierarchical pore structure ₂ Catalyst @ C. The catalyst comprises the following elements in mass: zr/c=67.1:100, the texture properties of which are listed in table 1. ZrO (ZrO) ₂ After 72 hours of treatment of catalyst @ C with 1M aqueous hydrofluoric acid, repeated filtration and washing with deionized water completely removed the metallic elements, a carbon support, labeled C-5, was obtained, the texture properties of which are shown in Table 1. As shown in Table 1, zrO ₂ Two most probable pore distribution peaks exist in the catalyst at the temperature of C and the C-5 carrier, which indicates that the pore distribution of the catalyst and the carbon carrier is of a hierarchical mesoporous structure.

CO hydrogenation performance test: 2g of the above ZrO were taken ₂ The @ C catalyst was diluted with 2mL of silicon carbide and mixed well and placed in a fixed bed reactor having an internal diameter of 10mm and a constant temperature section length of 50 mm. 50vol% H ₂ A synthesis gas of 50vol% CO was introduced into the reactor at a pressure of 5.0MPa, the temperature of the reactor was increased to 400℃at a heating rate of 0.2℃per minute, the reaction space velocity was adjusted to 2000NL/Kg/h, and the reaction was maintained for 119 hours. The composition of the reactor off-gas was analyzed by gas chromatography during the reaction and used to calculate the CO conversion, product selectivity and stability of the reaction. The results of the CO hydrogenation performance test are listed in table 2.

Example 6: coZn@C catalyst prepared from CoZn-MOFs/GO and CO hydrogenation performance thereof

7.2g of zinc nitrate hexahydrate, 1.4g of cobalt nitrate hexahydrate and 4.3g of 2-methylimidazole were weighed out respectively, and mixed and dissolved in 569g of N, N-dimethylformamide to obtain a cobalt zinc-methylimidazole precursor solution. The precursor solution is added into 50mL and 40mg/mL graphene oxide hydrosol drop by drop, and stirring and mixing are carried out at the same time, so as to obtain stable and uniform suspension.

Pouring the suspension into a 1L hydrothermal reaction kettle, reacting for 12 hours at 180 ℃, naturally cooling to room temperature, alternately washing for 5 times by using DMF and ethanol, performing suction filtration to obtain a CoZn-ZIF/GO compound, and finally drying in a vacuum (0.005 Pa) oven at 80 ℃ for 24 hours. A CoZn-ZIF/GO composite precursor was obtained with texture properties as set forth in table 1.

Directly tabletting, shaping and crushing the obtained ZnCo-ZIF/GO composite material precursor into particles with 20-40 meshes, and then adding the particles into N ₂ Pyrolyzing and carbonizing for 10 hours at 550 ℃ in the air flow to obtain the CoZn@C catalyst with a hierarchical pore structure. The elemental mass composition of the catalyst was Co/Zn/c=4.8:27.2:100, and the texture properties are listed in table 1. After the CoZn@C catalyst was treated with a 0.5M dilute aqueous hydrochloric acid solution for 24 hours, the metal element was completely removed by repeated filtration with deionized water to obtain a carbon support, labeled C-6, whose texture properties are shown in Table 1. As shown in Table 1, there are three most probable pore distribution peaks for both CoZn@C catalyst and C-6 support, indicating that the pore distribution of both catalyst and carbon support is a hierarchical mesoporous structure.

CO hydrogenation performance test: 2g of the CoZn@C catalyst was taken and diluted and mixed uniformly with 2mL of silicon carbide, and placed in a fixed bed reactor having an inner diameter of 10mm and a constant temperature section length of 50 mm. Catalyst at H ₂ Reducing for 12 hours at 350 ℃ in the atmosphere, and cooling to 180 ℃. 67vol% H ₂ The synthesis gas of/33%vol CO is introduced into the reactor, the pressure is 2.0MPa, the temperature of the reactor is increased to 200 ℃ at the heating rate of 0.2 ℃/min, the reaction space velocity is regulated to 2000NL/Kg/h, and the reaction is kept for 110 hours. Analysis of the composition of the reactor off-gas during the reaction by gas chromatography and calculation of the reactionCO conversion, product selectivity and stability. The results of the CO hydrogenation performance test are listed in table 2.

Comparative example 1: feMnCuK/AC catalyst prepared by conventional impregnation method and CO hydrogenation performance thereof

422.8g of ferric chloride hexahydrate, 2.3g of manganese nitrate hexahydrate, 0.3g of copper nitrate and 1.3g of potassium nitrate were weighed out and dissolved in 785g of deionized water to form a mixed salt solution.

Weighing 295g of coconut shell active carbon AC (20-40 meshes), slowly adding the mixed salt solution into the AC carrier in batches by adopting a incipient wetness impregnation method, and drying in an oven at 120 ℃; the above impregnation and drying process is repeated until all of the above mixed salt solution is impregnated onto the AC support. The impregnated AC carrier is put in N ₂ Roasting for 10 hours at 550 ℃ in air flow to obtain the FeMnCuK/AC catalyst. The catalyst comprises the following elements in mass: fe/Mn/Cu/K/c=29.5:2.6:0.5:1.3:100. The texture properties of the catalyst are listed in table 1.

The catalyst of this comparative example was subjected to CO hydrogenation performance testing as described in example 2. The composition of the reactor off-gas was analyzed by gas chromatography during the reaction and used to calculate the CO conversion, product selectivity and stability of the reaction. The results of the CO hydrogenation performance test are listed in table 2.

Table 1 properties, particle size and attrition index of the composite precursors and catalyst textures prepared in examples 1-7 and comparative example 1

TABLE 2 CO hydrogenation reactivity, hydrocarbon product selectivity and stability for the catalysts prepared in examples 1-7 and comparative example 1

As shown in table 2, the porous carbon-supported metal or metal oxide catalyst according to the present invention exhibits very high CO hydrogenation activity, high hydrocarbon selectivity and excellent running stability under typical CO catalytic hydrogenation reaction conditions of the corresponding metal. It is noted that FeMnCuK@C prepared in example 2 of the present invention also exhibits higher olefins and higher liquid hydrocarbons (C _5-11 ) Selectivity. From the results, the porous carbon-supported metal or metal oxide catalyst disclosed by the invention has stronger economic competitiveness and wide application prospect in the field of high-value-added hydrocarbon compounds with high efficiency in CO hydrogenation.

Claims

an active phase metal; and

2. The carbon supported metal catalyst of claim 1, wherein the active phase metal is at least one of iron, cobalt, nickel, ruthenium, zirconium, cerium, thorium, or indium.

3. The carbon-supported metal catalyst according to claim 1 or 2, wherein the specific surface area of the catalyst is not less than 100m ² /g。

4. The carbon-supported metal catalyst according to claim 1 or 2, wherein the mass ratio of the active phase metal to the porous carbon support is (0.1 to 200): 100.

5. The carbon supported metal catalyst of claim 1 or 2, wherein the catalyst further comprises a promoter metal.

6. The carbon supported metal catalyst of claim 5, wherein the promoter metal is at least one of manganese, chromium, zinc, molybdenum, copper, platinum, palladium, rhodium, iridium, gold, silver, magnesium, calcium, strontium, barium, sodium, or potassium.

7. The carbon-supported metal catalyst according to claim 5, wherein a mass ratio of the additive metal to the porous carbon support is (0.002-40): 100.

8. A method of preparing the carbon supported metal catalyst having a hierarchical pore structure of any one of claims 1-7, wherein the method comprises:

9. The method of claim 8, wherein in step (1), the metal-organic framework/graphene oxide composite precursor is prepared according to the following procedure:

10. The method of claim 8, wherein in step (1), the metal-organic framework/graphene oxide composite precursor is prepared according to the following procedure:

11. The method of any one of claims 8-10, wherein the active phase metal salt is at least one selected from the group consisting of: iron nitrate or a hydrate thereof, iron chloride, iron sulfate, iron acetate, iron (III) acetylacetonate, iron carbonyl, ferrocene, cobalt nitrate or a hydrate thereof, cobalt chloride, cobalt formate, cobalt acetate or a hydrate thereof, cobalt acetylacetonate, cobalt carbonyl, cobalt (III) tri (ethylenediamine) chloride trihydrate, nickel nitrate, nickel chloride, nickel sulfate, nickel acetate, nickel acetylacetonate, nickel carbonyl, ruthenium trichloride, ruthenium nitrate, triphenylphosphine ruthenium carbonyl chloride, ammonium ruthenate, ruthenium nitrosylnitrate, zirconyl nitrate, zirconium oxychloride, zirconium nitrate, zirconium chloride, zirconium sulfate, cerium nitrate, cerium chloride, cerium sulfate, thorium nitrate, thorium chloride, indium nitrate, indium chloride, indium sulfate.

12. The method of any one of claims 8-10, wherein the organic ligand is at least one of levulinic acid, lauric acid, oxalic acid, citric acid, 1,3, 5-benzene tricarboxylic acid, terephthalic acid, 2-methylimidazole, fumaric acid, azobenzene tetracarboxylic acid, amino-terephthalic acid, 2, 5-dihydroxyterephthalic acid, 1, 4-naphthalene dicarboxylic acid, 1, 5-naphthalene dicarboxylic acid, or 2, 6-naphthalene dicarboxylic acid.

13. The process according to any one of claims 8 to 10, wherein the mass ratio of the active phase metal salt to the organic ligand is (30 to 400): 100.

14. The method of claim 9 or 10, wherein the solvent is one or more of water, methanol, methylamine, dimethylamine, N-dimethylformamide, N-methylformamide, formamide, ethanol, ethylene glycol, diethyl ether, ethylamine, acetonitrile, acetamide, propanol, acetone, propionitrile, tetrahydrofuran, dioxane, butanol, pyridine, morpholine, quinoline, toluene, xylene, heptane.

15. The method of claim 9 or 10, wherein the graphene oxide sol has a mass volume concentration of 1-50 mg/mL.

16. The method of claim 9 or 10, wherein the metal organic framework material precursor solution, the organic ligand precursor solution, and the active phase metal salt solution are mixed with graphene oxide sol or the organic ligand-graphene oxide solution by: mechanical stirring, magnetic stirring, ball milling mixing, shear emulsification or ultrasonic mixing.

17. The method of any one of claims 8-10, wherein the metal-organic framework is selected from the group consisting of: iron 1,3, 5-benzenetricarboxylic acid, cobalt 1,3, 5-benzenetricarboxylic acid, nickel 1,3, 5-benzenetricarboxylic acid, ruthenium 1,3, 5-benzenetricarboxylic acid, zirconium 1,3, 5-benzenetricarboxylic acid, cerium 1,3, 5-benzenetricarboxylic acid thorium, iron 1, 4-terephthalate, cobalt 1, 4-terephthalate, nickel 1, 4-terephthalate, ruthenium 1, 4-terephthalate, zirconium 1, 4-terephthalate, cerium 1, 4-terephthalate, thorium 1, 4-terephthalate, iron fumarate, cobalt fumarate, nickel fumarate, ruthenium fumarate, zirconium fumarate, cerium fumarate, thorium fumarate, iron azobenzoate, cobalt azobenzoate, nickel azobenzoate, ruthenium azobenzoate, zirconium azobenzoate, cerium azobenzoate, thorium azobenzoate, iron amino-terephthalate cobalt amino-terephthalate, nickel amino-terephthalate, ruthenium amino-terephthalate, zirconium amino-terephthalate, cerium amino-terephthalate, thorium amino-terephthalate, iron 2, 5-dihydroxyterephthalate, cobalt 2, 5-dihydroxyterephthalate, nickel 2, 5-dihydroxyterephthalate, ruthenium 2, 5-dihydroxyterephthalate, zirconium 2, 5-dihydroxyterephthalate, cerium 2, 5-dihydroxyterephthalate, thorium 2, 1, 4-iron naphthalene dicarboxylate, cobalt 1, 4-naphthalene dicarboxylate, nickel 1, 4-naphthalene dicarboxylate, ruthenium 1, 4-naphthalene dicarboxylate, zirconium 1, 4-naphthalene dicarboxylate, cerium 1, 4-naphthalene dicarboxylate, thorium 1, 5-naphthalene dicarboxylate, cobalt 1, 5-naphthalene dicarboxylate, nickel 1, 5-naphthalene dicarboxylic acid, nickel 1, 4-naphthalene dicarboxylic acid, ruthenium 1, 5-naphthalenedicarboxylate, zirconium 1, 5-naphthalenedicarboxylate, cerium 1, 5-naphthalenedicarboxylate, thorium 1, 5-naphthalenedicarboxylate, iron 2, 6-naphthalenedicarboxylate, cobalt 2, 6-naphthalenedicarboxylate, nickel 2, 6-naphthalenedicarboxylate, ruthenium 2, 6-naphthalenedicarboxylate, zirconium 2, 6-naphthalenedicarboxylate, cerium 2, 6-naphthalenedicarboxylate or thorium 2, 6-naphthalenedicarboxylate.

18. The process of claim 9, wherein in step (c), the reaction temperature in the reaction vessel is 100 ℃ to 180 ℃.

19. The method of claim 10, wherein in the step (d'), the reaction temperature in the reaction vessel is 100 to 180 ℃.

20. The method of claim 9, wherein in step (c), the drying is performed under vacuum or an inert atmosphere.

21. The method of claim 10, wherein in the step (d'), the drying is performed under vacuum or an inert atmosphere.

22. The method of claim 20 or 21, wherein the vacuum has a vacuum level of 0.1 to 0.005Pa.

23. The method of claim 20 or 21, wherein the inert atmosphere is nitrogen, argon or helium.

24. The method of claim 9, wherein in the step (c), the drying temperature is 60 ℃ to 180 ℃.

25. The method of claim 10, wherein in the step (d'), the drying temperature is 60 ℃ to 180 ℃.

26. The method of any one of claims 8-10, wherein the method further comprises the step of adding an auxiliary metal salt, wherein the auxiliary metal salt is added by mixing the auxiliary metal salt with the active phase metal salt, organic ligand, and graphene oxide in the step (1); or before the step (2), adding the auxiliary metal salt into the metal organic framework/graphene oxide composite material precursor obtained in the step (1) to obtain the composite material precursor added with the auxiliary metal.

27. The method of claim 26, wherein the promoter metal salt is one or more selected from the group consisting of: manganese nitrate or a hydrate thereof, manganese chloride, manganese acetate, manganese acetylacetonate, manganese carbonyl, zinc nitrate or a hydrate thereof, zinc chloride, zinc acetate, zinc acetylacetonate, chromium nitrate, ammonium molybdate, platinum nitrate, nitrosodiammonium platinum, palladium nitrate, palladium acetate, triphenylphosphine palladium, silver nitrate, silver acetate, silver carbonate, magnesium nitrate, magnesium acetate, calcium nitrate, calcium acetate, strontium nitrate, strontium acetate, sodium nitrate, sodium acetate, sodium carbonate, sodium bicarbonate, copper nitrate, potassium carbonate, potassium bicarbonate, and potassium acetate.

28. The method of claim 26, wherein the additive metal salt is added to the metal organic framework/graphene oxide composite precursor by impregnation.

29. The method according to any one of claims 8 to 10, wherein in the step (2), the molding is direct compression molding or molding using cellulose ether, phenol resin, acrylic resin, epoxy resin, melamine resin, urea resin, polyurethane as a binder.

30. The method of any of claims 8-10, wherein the shaping method is selected from compression shaping, rotational shaping, extrusion shaping, in-oil shaping, in-water shaping, or spray drying shaping.

31. The method of claim 29, wherein the mass of the binder is 0% to 20% of the mass of the metal organic framework/graphene oxide composite precursor.

32. The method according to any one of claims 8 to 10, wherein in the step (3), the inert atmosphere is at least one selected from nitrogen, helium, argon, xenon and radon.

33. The method according to any one of claims 8 to 10, wherein in the step (3), the carbon-containing atmosphere is a mixture of a carbon-containing gas and an inert gas.

34. The method of claim 33, wherein the carbon-containing gas is methane, ethane, ethylene, acetylene, propane, propylene, CO, and/or syngas.

35. The method of claim 33, wherein the inert gas is at least one selected from the group consisting of nitrogen, helium, argon, xenon, and radon.

36. The method of claim 33, wherein the carbon-containing gas is present in the carbon-containing atmosphere at a volume concentration of 0.5% to 100%.

37. The method of any one of claims 8-10, wherein the pyrolysis and carbonization is at a temperature of 350 ℃ to 1100 ℃ for a time of 1 to 10 hours.

38. Use of a carbon-supported metal catalyst having a hierarchical pore structure according to any one of claims 1-7 for catalyzing a reaction of a CO and hydrogen containing gas to produce hydrocarbon compounds.

39. The use according to claim 38, wherein the CO and hydrogen containing gas is synthesis gas.

40. The use according to claim 38 or 39, wherein the reaction is carried out as a continuous or batch reaction process.

41. The use according to claim 38 or 39, wherein the reaction is carried out in one or more fixed bed reactors, microchannel reactors, continuously stirred slurry tank reactors, jet loop reactors, slurry bubble column reactors or fluidised bed reactors.

42. The use according to claim 38 or 39, wherein the reaction is carried out at a pressure of 1.0 to 6.0MPa and a temperature of 100 to 500 ℃.

43. The use according to claim 38 or 39, wherein the reaction is carried out as a continuous reaction process with a reaction weight hourly space velocity of 100 to 60000NL/Kg/h.