CN113522287A

CN113522287A - Carbon-supported metal catalyst with hierarchical pore structure, preparation method and application thereof

Info

Publication number: CN113522287A
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: Synfuels China Technology Co Ltd
Current assignee: Synfuels China Technology Co Ltd
Priority date: 2021-06-24
Filing date: 2021-06-24
Publication date: 2021-10-22
Anticipated expiration: 2041-06-24
Also published as: CN113522287B

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 active phase metal and a porous carbon carrier, wherein the porous carbon carrier has a hierarchical mesoporous structure formed by a carbon nanocage and graphene oxide, and the hierarchical mesoporous structure has specific hierarchical pore channel distribution; and wherein the active phase metal is encapsulated in the carbon nanocages, the carbon nanocages being located on the sheets of graphene oxide. The preparation method adopts active phase metal salt, organic ligand and graphene oxide to prepare the carbon-supported metal catalyst, so that metal nanoparticles can be effectively dispersed and sintering and aggregation of particles can be inhibited. The carbon-supported metal catalyst has excellent electronic characteristics, high hydrothermal stability, high activity and olefin selectivity, high mechanical strength, strong abrasion resistance, and the like when applied to a hydrocarbon synthesis reaction.

Description

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

Technical Field

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

Background

Carbon-coated metal nanoparticles are a novel composite material. The material has unique structural characteristics, namely, 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 nanoparticles to have better dispersibility, and avoids the problems of agglomeration and the like caused by interaction among the particles. Meanwhile, the unique electronic property of the graphene also endows the graphene-coated metal nanoparticles with excellent electromagnetic performance, and the graphene-coated metal nanoparticles have wide application in the technical fields of sensors, electromagnetic shielding, catalysis and the like.

CO hydrogenation or synthesis gas (containing CO and H)₂A small amount of CO₂Methane and N₂Mixed gas) to prepare the hydrocarbon compounds relates to a large class of typical heterogeneous catalytic reactions, including reactions such as Fischer-Tropsch synthesis, heterogeneous synthesis, preparation of aromatic hydrocarbons from synthesis gas, methanation and the like. Group VIIIB transition metals iron, cobalt, nickel and ruthenium and ZrO₂、ThO₂、CeO₂The metal oxides have catalytic activity for catalyzing the reaction of preparing hydrocarbons by CO hydrogenation. The reaction has the characteristics of high temperature (150-350 ℃), high pressure (10-50 bar) and strong heat release (165kJ/mol), and one main byproduct of the reaction is water. The reactors currently suitable for the CO hydrogenation reaction mainly comprise a fixed bed, a fixed fluidized bed and a gas-liquid-solid three-phase slurry bed. Therefore, CO hydrogenation catalysts experience very severe physical impact and chemical stress during the reaction, which requires the catalyst to have very high attrition resistance.

Typically some refractory oxides like silica, alumina and titania are used as supports for CO hydrogenation catalysts. However, these supports also bring about inevitable disadvantages to the catalyst, such as low thermal conductivity, poor hydrothermal stability, strong surface acidity, low mechanical strength and poor attrition resistance. Because the CO hydrogenation reaction is a strong exothermic reaction, the poor thermal conductivity of the catalyst can cause a large amount of reaction heat to be retained in the catalyst particles in the reaction process, so that the local reaction of the catalyst is over-temperature, the selectivity of a target product is poor, and the active phase of the catalyst is sintered to lose catalytic activity, so that the timely removal of a large amount of reaction heat released from the interior of the catalyst particles becomes very important. In addition, the high partial pressure of water in the CO hydrogenation reaction is also very fatal to the catalyst. The literature (Journal of the Chemical Society-Chemical Communications, 1984, 10, p. 629-630) reports that water has a very detrimental effect on alumina-supported catalysts, and at low temperatures, low water partial pressures, the alumina oxide partially converts to pseudo-water boehmite, which causes the catalyst to undergo pulverization. In addition, these refractory oxide supports or structural aids may interact strongly with the active phase metal components to form oxides (e.g., metal silicates, aluminates, or titanates) that are inactive in the fischer-tropsch synthesis.

In order to improve the activity and stability of CO hydrogenation catalysts, researchers have tried to use carbon materials as a carrier of the catalyst, such as activated carbon, nanofiber (CNF), Carbon Nanotube (CNT), graphene, carbon sphere, or glassy carbon. The conventional carbon-supported catalyst is generally prepared by impregnating a carbon material with gold. However, the interaction between the carbon carrier and the metal is weak, so that the particle distribution of the metal active phase in the catalyst is wide, and the active phase particles 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 WO2015/175759A1, disclose porous carbon-dispersed ultrafine iron carbide nanoparticle catalysts synthesized using iron carboxylate metal organic frameworks (iron-1, 3, 5-benzenetricarboxylate, iron-1, 4-benzenedicarboxylate or azobenzene tetracetate) as templates and furfuryl alcohol as an additional carbon source, with iron contents of up to 50 wt%. Pei et al (high Active and Selective Co-Based Fischer-Tropsch Catalysts Derived from Metal-Organic Frameworks, AIChE Journal,63 (2017)) 2944 disclose a completely reduced and Highly dispersed face-centered cubic cobalt nanoparticle carbon-supported catalyst prepared by a thermal decomposition method by using Co-MOF-74 as a precursor and adding ethyl orthosilicate as a silicon dopant.

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

Patent application CN107570155A of Chinese synthetic oil company discloses a method for preparing iron oxide/graphene oxide three-dimensional porous nano composite material by assembling iron oxide nano particles and graphene oxide through a hydrothermal synthesis method, and the iron oxide/graphene oxide three-dimensional porous nano composite material is applied to Fischer-Tropsch synthesis reaction and shows excellent reaction activity and operation stability. The iron oxide/graphene oxide three-dimensional composite material has excellent mechanical strength, but the sintering or agglomeration of metal particles cannot be effectively inhibited due to the large unit structure size of the graphene oxide, so that the metal active phase crystal grains of the catalyst grow in the reaction process.

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

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, and used it to catalyze a reaction of a gas containing CO and hydrogen to produce a hydrocarbon compound. The catalyst has greatly improved mechanical strength and metal particle sintering resistance, so that the catalytic efficiency of the catalyst is greatly improved, and the problems of poor stability, easy abrasion and the like of the conventional carbon-supported catalyst are solved.

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 with a most probable pore size of 2-4nm, mesopores with a most probable pore size of 4-10nm, and mesopores with a most probable pore size of 15-22 nm; and wherein the active phase metal is encapsulated 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 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 pyrolyzing and carbonizing the molded 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 having a hierarchical pore structure as described above for catalyzing the reaction of a gas comprising CO and hydrogen to produce hydrocarbons.

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

1. according to the catalyst, 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 vermicular carbon nano tube, and the vermicular 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 the metal-organic framework or a carbon-containing gas in a carbon-containing atmosphere is used as a carbon source of a carbon nanocage (a precursor of a vermicular carbon nanotube). In the preparation process of the catalyst, a gas-phase carbon source is deposited and grown along the surface of the active-phase metal nanoparticles to form carbon nanocages and then vermicular carbon nanotubes, so that the active-phase metal nanoparticles can be effectively dispersed and sintering and aggregation of the particles can be inhibited.

3. The catalyst of the present invention has excellent electronic characteristic, physical and chemical wear resistance, high hydrothermal stability and high mechanical strength in the application of CO and hydrogen containing gas reaction to prepare hydrocarbon compound. The abundant hierarchical nano-pore structure of the catalyst according to the present invention can promote high dispersion of the active phase of the catalyst and diffusion of the reaction species, thereby allowing 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 spectrum of the MOFs/GO composite material precursor prepared in example 1 of the present invention.

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

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

Fig. 4 is an SEM photograph of the 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 the porous carbon support after removing metallic Fe ions from the porous carbon support supported Fe @ C catalyst prepared in example 1 of the present invention by washing with 0.5M dilute hydrochloric acid.

Fig. 7 is a BJH pore distribution plot 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 the porous carbon carrier after the Fe @ C catalyst supported by the porous carbon carrier prepared in example 1 of the present invention is washed and filtered with 0.5M diluted hydrochloric acid to remove the metal Fe ions.

Detailed Description

The solution of the invention will be illustrated below by means of an exemplary embodiment, but the scope of protection of the invention is not limited thereto.

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

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 nanocages, so that the dispersion degree 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 nanocage structure with a mesoscale (2-100nm), and the structure has the characteristic of being completely suitable for the metal nanoscale of the active phase of the heterogeneous catalyst, and is beneficial to the encapsulation and anchoring of metal particles and the diffusion of reactants, so that the catalyst has 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 100m²Per g, preferably 200m²A number of grams of water per gram, e.g. 200 to 285m²/g。

In a preferred embodiment, the mass ratio of the active phase metal to the porous carbon support may be (0.1-200): 100, preferably (1-70): 100, and may be, 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 a further preferred embodiment, 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, and may be, for example, 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 the step (1) above, the metal-organic framework/graphene oxide composite precursor is prepared according to the following process:

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

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

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

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

(a') adding an organic ligand into 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 an 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 liquid;

(d') placing the sol 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: ferric nitrate or its hydrate (e.g., ferric nitrate nonahydrate), ferric chloride or its hydrate (e.g., ferric chloride hexahydrate), ferrous chloride, ferrous sulfate, ferrous acetate, iron (III) acetylacetonate, carbonyl iron, ferrocene, cobalt nitrate or its hydrate (e.g., cobalt nitrate hexahydrate), cobalt chloride, cobalt formate, cobalt acetate or its hydrate (e.g., cobalt acetate tetrahydrate), cobalt acetylacetonate, carbonyl cobalt, tris (ethylenediamine) cobalt (III) chloride trihydrate, nickel nitrate, nickel chloride, nickel sulfate, nickel acetate, nickel acetylacetonate, nickel carbonyl, ruthenium trichloride, ruthenium nitrate, triphenylphosphine carbonyl ruthenium chloride, ruthenium carbonyl chloride, ammonium ruthenium chloride, ruthenium nitrosyl nitrate, 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-benzenetricarboxylic acid, terephthalic acid, 2-methylimidazole, fumaric acid, azobenzenetetracarboxylic acid, amino-terephthalic acid, 2, 5-dihydroxyterephthalic acid, 1, 4-naphthalenedicarboxylic acid, 1, 5-naphthalenedicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, or the like.

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

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 should be noted that the solvents in the above steps (a) and (c) and the solvents in the above steps (a ') and (c ') and (d ') may be the same or different, and may be conventionally selected depending on 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 mixing graphene powder with NaNO₃Mixing in a beaker, adding concentrated sulfuric acid, and putting the beaker in an ice-water bath to be stirred and mixed; then KMnO is slowly added into the mixed solution₄Heating the ice water bath to 10 ℃, and stirring and mixing; then transferring the beaker into a warm water bath at 35 ℃, and continuing stirring when the reaction temperature in the beaker is increased to 35 ℃; under the condition of stirring, adding deionized water into a beaker at a constant speed to dilute the mixed solution, keeping aging for a certain time after the reaction temperature is raised to 98 ℃, then adding hydrogen peroxide into the beaker for oxidation, filtering the mixed solution after oxidation, and repeatedly washing the mixed solution by HCl and deionized water until the solution is neutral; and finally, adding deionized water into the washing product to form a suspension, and dispersing 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, or 50 mg/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 the graphene oxide sol or the organic ligand-graphene oxide solution in the following manner: mechanical stirring, magnetic stirring, ball milling and mixing, shearing and 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-benzenetricarboxylate (MIL-100), cobalt 1,3, 5-benzenetricarboxylate, nickel 1,3, 5-benzenetricarboxylate, ruthenium 1,3, 5-benzenetricarboxylate, zirconium 1,3, 5-benzenetricarboxylate, cerium 1,3, 5-benzenetricarboxylate, thorium 1,3, 5-benzenetricarboxylate, 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, Nickel azobenzene tetracarboxylic acid, ruthenium azobenzene tetracarboxylic acid, zirconium azobenzene tetracarboxylic acid, cerium azobenzene tetracarboxylic acid, thorium azobenzene tetracarboxylic acid, 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, iron-m-olefin-co-olefin-terephthalate, 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 steps (c) and (d'), the reaction temperature in the reaction kettle may be 100 to 180 ℃.

In a preferred embodiment, in the steps (c) and (d'), the drying may be performed under vacuum or an inert atmosphere. In a more preferred embodiment, the degree of vacuum of the vacuum is 0.1 to 0.005 Pa. 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 the step of adding a promoter metal salt, wherein the promoter metal salt may be added by mixing the promoter metal salt with the active phase metal salt, the organic ligand and the graphene oxide in step (1); or adding the assistant metal salt to the metal organic framework/graphene oxide composite precursor obtained in the step (1) before the step (2) to obtain an assistant metal-added composite precursor.

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

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

As an example of an impregnation method, the promoter metal may be added to the metal organic framework/graphene oxide composite precursor by a co-impregnation or stepwise impregnation method at a suitable temperature, for example, room temperature (e.g., 15 ℃ to 40 ℃). The preparation method comprises the steps of weighing the metal organic framework/graphene oxide composite precursor and the assistant metal salt according to the composition proportion of the catalyst, dissolving the assistant metal salt in a solvent to form an impregnation solution, and then impregnating the impregnation solution on the metal organic framework/graphene oxide composite precursor. An exemplary step impregnation method is to dissolve the promoter metal salts separately in a solvent to form separate impregnation solutions and then impregnate the carbon-containing precursor step by step. The impregnation may be an equal volume impregnation or an excess impregnation. The isovolumetric impregnation means that the volume of the impregnation solution is equal to the saturated water absorption volume of the carrier; by excess impregnation is meant that the volume of impregnating solution is greater than the saturated water absorption volume of the support. The solvent can 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, and the like.

In a preferred embodiment, in the step (2), the molding may be direct tablet molding, or may be molding using cellulose ether, phenol resin, acrylic resin, epoxy resin, melamine resin, urea resin, or polyurethane as a binder. The forming method can be selected from compression forming, rotation forming, extrusion forming, forming in oil, forming in water or spray drying forming and the like. The shape of the formed composite material can be granular, microspherical, flaky, strip-shaped, columnar, annular, porous flaky or clover-shaped.

Herein, the cellulose ether is a cellulose substituted with a functional group, preferably selected from the group consisting of carboxylic acid groups, hydroxyl groups, alkyl functional groups, preferably selected from the group consisting of 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 average relative molecular weight of the phenolic resin is 500-1000. 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 preferable example, the epoxy resin is a polymer of 2, 2-bis (4-hydroxyphenyl) propane and epichlorohydrin, and the average relative molecular weight of the epoxy resin is 500-2000. As a preferable example, the melamine resin is a polymer of melamine and formaldehyde, and the relative molecular weight of the melamine resin is 1000-3000. Herein, the urea-formaldehyde resin is a polymer of urea and formaldehyde. Preferably, the average relative molecular weight of the urea resin is 500-1000. The polyurethane is a polymer of diisocyanate and hydroxyl-terminated polyester or hydroxyl-terminated polyether. Preferably, the relative molecular weight of the polyurethane is 1000-4000. 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 the group consisting of nitrogen, helium, argon, xenon, and radon. In a preferred embodiment, the carbon-containing atmosphere may be a mixed gas of a carbon-containing gas and an inert gas. Preferably, the carbon-containing gas is methane, ethane, ethylene, acetylene, propane, propylene, CO and/or syngas. Further preferably, the volume concentration of the carbon-containing gas in the carbon-containing atmosphere is 0.5% to 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 or carbon-containing atmosphere are key operations for forming carbon nanocage coating structures. In the above-mentioned method for preparing the catalyst, the pyrolysis and carbonization mean that both the pyrolysis of the MOF and the carbonization of the metal occur. Preferably, the pyrolysis and carbonization are carried out at a temperature of 350 ℃ to 1100 ℃ (e.g., 450 ℃ to 700 ℃) for 1 to 10 hours (e.g., 3 to 10 hours).

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

As a preferred example, the CO and hydrogen containing gas may be syngas. As a preferable example, the carbon-supported metal catalyst having a hierarchical pore structure of the present invention may be directly used in a reaction for catalytically producing hydrocarbon compounds from synthesis gas; or the catalyst is reduced in a reducing atmosphere before being used for the reaction of producing hydrocarbon compounds by the catalysis of synthesis gas. The reducing atmosphere may be a pure hydrogen atmosphere, a CO atmosphere, a syngas atmosphere, an ammonia atmosphere, a diluted hydrogen atmosphere, a diluted CO atmosphere, a diluted syngas atmosphere, a diluted ammonia atmosphere. H in syngas₂The volume ratio to CO is 0.01:1 to 1000:1 (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 atmospheres₂And/or CH₄The volume concentration of the reducing gas in each of the diluted reducing atmospheres is greater than 10%, preferably greater than 25%, more preferably 50%, even more preferably 75%, and most preferably greater than 90%. The carbon-supported metal catalyst is subjected to reduction treatment to form a reduced catalyst with a certain degree of reduction (i.e., the percentage of metal phase and metal carbide in the total active phase metal), and the degree of reduction of the obtained reduced catalyst is preferably 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 and hydrogen containing gas may be carried out in one or more fixed bed reactors, microchannel reactors, continuously stirred slurry bed tank reactors, jet circulation reactors, slurry bubble column reactors or fluidized bed reactors.

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

For example, when the catalyst is a cobalt on carbon catalyst, H in the syngas₂The volume ratio of the carbon dioxide to CO is 1.0: 1-3.0: 1, preferably 1.5: 1-2.5: 1, and most preferably 1.8: 1-2.2: 1. The reaction pressure is 1.0 to 6.0MPa, preferably 1.5 to 4.5MPa, and most preferably 2.0 to 3.0 MPa. The reaction temperature is 180-280 ℃, preferably 200-260 ℃, and most preferably 220-240 ℃. When the reaction is carried out in a continuous reaction process, the weight hourly space velocity of the reaction is 100-25000 NL/Kg/h, preferably 1000-20000 NL/Kg/h, and most preferably 5000-15000 NL/Kg/h. Alternatively, when the catalyst is a carbon-supported iron catalyst, H in the syngas₂The volume ratio of the carbon dioxide to CO is 0.5: 1-3.0: 1, preferably 1.0: 1-2.5: 1, more preferably 1.2: 1-2.2: 1, and most preferably 1.5: 1-2.0: 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, and most preferably 2.5 to 4.0 MPa. The reaction temperature is 220-350 ℃, preferably 240-330 ℃, and most preferably 260-300 ℃. When the reaction is carried out in a continuous reaction process, the weight hourly space velocity of the reaction is 100-60000 NL/Kg/h, preferably 1000-40000 NL/Kg/h, and most preferably 10000-20000 NL/Kg/h. Alternatively, when the catalyst is a ruthenium on carbon catalyst, the H in the synthesis gas₂The volume ratio of the carbon dioxide to CO is 0.5: 1-3.0: 1, preferably 1.0: 1-2.5: 1, more preferably 1.2: 1-2.2: 1, and most preferably 1.5: 1-2.0: 1. The reaction pressure is 1.0 to 10.0MPa, preferably 2.5 to 7.5MPa, more preferably 3.0 to 6.0MPa, and most preferably 3.5 to 5.0 MPa. The reaction temperature is 120-280 ℃, preferably 150-240 ℃ and optimally 180-220 ℃. When the reaction is carried out in a continuous reaction process, the weight hourly space velocity of the reaction is 100-10000 NL/Kg/h, preferably 500-8000 NL/Kg/h, and most preferably 1000-5000 NL/Kg/h. Alternatively, when the catalyst is a nickel on carbon catalyst, the H in the syngas₂The volume ratio of the carbon dioxide to CO is 1.5: 1-4.0: 1, preferably 2.0: 1-3.0: 1, and more preferably 2.5: 1-3.0: 1. The reaction pressure is 0.5 to 3.0MPa, preferably 1.0 to 2.5MPa, more preferably 1.0 to 2.0MPa, and most preferably 1.0 to 1.5 MPa. The reaction temperature is 250-600 ℃, preferably 300-500 ℃,The optimum temperature is 350-450 ℃. When the reaction is carried out in a continuous reaction process, the weight hourly space velocity of the reaction is 1000-10000 NL/Kg/h, preferably 2000-8000 NL/Kg/h, and most preferably 3000-5000 NL/Kg/h. Alternatively, when the catalyst is a carbon-supported zirconium catalyst, a carbon-supported cerium catalyst, a carbon-supported thorium catalyst, a carbon-supported indium catalyst, H in the synthesis gas₂The volume ratio of the carbon dioxide to CO is 0.5: 1-3.0: 1, preferably 0.7: 1-2.5: 1, more preferably 1.0: 1-2.0: 1, and most preferably 1.0: 1-1.5: 1. The reaction pressure is 2.0 to 10.0MPa, preferably 3.0 to 8.5MPa, more preferably 5.0 to 8.0MPa, and most preferably 6.0 to 8.0 MPa. The reaction temperature is 320-600 ℃, preferably 350-500 ℃, and most preferably 380-450 ℃. When the reaction is carried out in a continuous reaction process, the weight hourly space velocity of the reaction is 100 to 5000NL/Kg/h, preferably 500 to 3000NL/Kg/h, and most preferably 1000 to 2000 NL/Kg/h.

The exemplary embodiment of the present invention has the following features: the catalyst has large specific surface area (not less than 100 m)²(g), ultra-small active phase metal or metal oxide grain size (3-7 nm), and high mechanical strength (abrasion index is 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 comparable to catalysts prepared by direct chemical synthesis or comprise a conventional Support (SiO)₂Or Al₂O₃) 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 synthesis gas catalytic reactions.

Exemplary aspects of the present invention may be illustrated by 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 metal on carbon 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 metal on carbon catalyst of

paragraph

1 or 2, wherein the specific surface area of the catalyst is not less than 100m²/g。

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

5. The metal on carbon 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 carrier is (0.002-40): 100.

8. A method of preparing the metal on carbon catalyst with a hierarchical pore structure of any 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 process:

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

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

(a') adding the organic ligand into 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 liquid;

11. The method of any of paragraphs 8-10, wherein the active phase metal salt is at least one selected from the group consisting of: iron nitrate or its hydrate, iron chloride or its hydrate, ferrous chloride, ferrous sulfate, ferrous acetate, iron (III) acetylacetonate, iron carbonyl, ferrocene, cobalt nitrate or its hydrate, cobalt chloride, cobalt formate, cobalt acetate or its hydrate, 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, ruthenium carbonyl chloride, ruthenium ammonium chloride, ruthenium nitrosyl nitrate, zirconyl nitrate, zirconium oxychloride, zirconium nitrate, zirconium chloride, zirconium sulfate, cerium nitrate, 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-benzenetricarboxylic acid, terephthalic acid, 2-methylimidazole, fumaric acid, azobenzenetetracarboxylic acid, amino-terephthalic acid, 2, 5-dihydroxyterephthalic acid, 1, 4-naphthalenedicarboxylic acid, 1, 5-naphthalenedicarboxylic acid, or 2, 6-naphthalenedicarboxylic acid.

13. The method according to any one of paragraphs 8 to 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 of paragraphs 9-14, wherein the graphene oxide sol has a mass-to-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 the graphene oxide sol or the organic ligand-graphene oxide solution in the following manner: mechanical stirring, magnetic stirring, ball milling mixing, shearing emulsification or ultrasonic mixing.

17. The method of any of paragraphs 8-16, wherein the metal-organic framework is selected from the group consisting of: iron 1,3, 5-benzenetricarboxylate, cobalt 1,3, 5-benzenetricarboxylate, nickel 1,3, 5-benzenetricarboxylate, ruthenium 1,3, 5-benzenetricarboxylate, zirconium 1,3, 5-benzenetricarboxylate, cerium 1,3, 5-benzenetricarboxylate, thorium 1,3, 5-benzenetricarboxylate, 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, cerium fumarate, thorium fumarate, iron azobenzene tetracarboxylic acid, cobalt azobenzene tetracarboxylic acid, nickel azobenzene tetracarboxylic acid, ruthenium azobenzene tetracarboxylic acid, zirconium azobenzene tetracarboxylic acid, iron, Cerium azobenzene tetracarboxylic acid, thorium azobenzene tetracarboxylic acid, 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, cobalt (III) amide, ruthenium (III) amide, cobalt (III) amide, nickel (III) amide, cobalt (III) amide, ruthenium (III) amide, cobalt (III) amide, ruthenium (III) amide, cobalt (III) amide (IV) amide (III), 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 or thorium 2, 6-naphthalenedicarboxylate.

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

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

20. The method of paragraph 19, wherein the vacuum is in the range of 0.1 to 0.005 Pa.

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

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

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

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 impregnation method.

26. The method according to any one of paragraphs 8 to 25, wherein in the step (2), the molding is direct tablet molding or molding using cellulose ether, phenol 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 is by a method selected from compression molding, rotational molding, extrusion molding, in-oil molding, in-water molding, or spray drying molding.

28. The method of paragraph 26, wherein the binder comprises 0% to 20% by mass of the metal organic framework/graphene oxide composite precursor.

29. The method as set forth in 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 of any 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 volume concentration of the carbon-containing gas in the carbon-containing atmosphere is between 0.5% and 100%.

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

35. Use of a metal on carbon catalyst with a hierarchical pore structure as described in any of paragraphs 1 to 7 for catalyzing a reaction of a gas comprising CO and hydrogen to produce hydrocarbons.

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

37. The use of paragraph 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, continuously stirred slurry bed tank reactors, jet circulation reactors, slurry bubble column reactors, or fluidized bed reactors.

39. The use as in 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 as claimed in any of paragraphs 35-39, wherein the reaction is carried out as a continuous reaction process with a reaction weight hourly space velocity of from 100 to 60000 NL/Kg/h.

The experimental procedures used in the following examples are all conventional procedures unless otherwise specified. Materials, reagents and the like used in the following examples are commercially available unless otherwise specified. The graphene oxide hydrosols in the following examples 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 iron nitrate nonahydrate and 12.7g of 1,3, 5-benzenetricarboxylic acid (H) were weighed₃BTC), dissolving the above materials in 325g of deionized water, mixing and stirring until the materials are completely dissolved to obtain a precursor solution of the MOFs synthetic material. And dropwise adding the precursor solution into 350mL and 10mg/mL graphene oxide hydrosol, and stirring and mixing to obtain a stable and uniform suspension.

And pouring the suspension into a 1L hydrothermal reaction kettle, reacting for 24h at 120 ℃, naturally cooling to room temperature, alternately washing with deionized water and ethanol for 5 times, performing suction filtration to obtain a MOFs/GO composite, and finally drying in a vacuum (0.1Pa) oven at 60 ℃ for 12h to obtain a MOFs/GO composite precursor, wherein the texture properties of the precursor are listed in Table 1. The XRD spectrum and the scanning electron microscope image of the MOFs/GO composite precursor prepared in this example are respectively shown in fig. 1 and fig. 2, which shows that a typical metal organic framework material Fe-MIL-100 structure exists in the composite precursor, and the metal organic framework material is uniformly dispersed on the graphene oxide sheet.

Directly tabletting and molding the MOFs/GO composite material precursor, crushing the mixture into particles of 20-40 meshes, and then carrying out particle size reduction at 2 vol% C₂H₂/98vol％N₂Pyrolyzing and carbonizing at 500 ℃ for 5h in airflow to obtain the Fe @ C catalyst with a hierarchical pore structure. The catalyst comprises the following elements in percentage by mass: Fe/C65.6: 100, texture properties are listed in table 1.

The XRD pattern of the Fe @ C catalyst prepared in this example is shown in FIG. 3As shown, the diffraction peaks broadened between 20 ° to 30 ° in 2 θ correspond to the signals of graphene oxide and amorphous carbon in the catalyst; the series of diffraction peaks of 2 theta at the positions of 44.1 degrees, 46.6 degrees, 47.7 degrees, 50.4 degrees, 51.4 degrees, 52.5 degrees, 52.8 degrees, 53.9 degrees, 57.3 degrees and 57.9 degrees are corresponding to theta-Fe₃C. SEM photographs of the Fe @ C catalyst prepared in this example are shown in fig. 4, which consists of lamellar graphene oxide and vermicular particles, which are hollow tubular structures. In the Fe @ C catalyst, the Fe particle size is between 5 and 10nm and is uniformly distributed in the carbon carrier, as shown in FIG. 5. The Fe @ C catalyst was treated with 0.5M dilute hydrochloric acid aqueous solution for 24 hours, and then repeatedly filtered and washed with deionized water to completely remove Fe element, and a carbon carrier, labeled C-1, was obtained, and its texture properties are shown in Table 1. The TEM photograph of the carbon carrier is shown in FIG. 6, the carbon carrier is a hollow spherical structure, the outer diameter of the carbon sphere is between 8nm and 20nm, and the diameter of the cavity is between 5 nm and 10 nm. 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 a typical hierarchical pore structure. The BJH pore distribution curve of the carbon carrier after 0.5M dilute hydrochloric acid washing and filtering is shown in figure 8, and two most probable pore distribution peaks exist at the pore diameters of 3.8nm and 24.6nm, which indicates that the pore distribution of the carbon carrier is a hierarchical pore structure.

And (3) testing CO hydrogenation performance: 2g of the catalyst was diluted with 2mL of silicon carbide and mixed well, and the mixture was placed in a fixed bed reactor having an inner diameter of 10mm and a constant temperature zone length of 50 mm. Catalyst at 98 vol% H₂Reducing the mixture in a reducing atmosphere of 2 vol% CO at 350 ℃ for 24 hours, and cooling the mixture to 220 ℃. Then 63 vol% H₂Introducing the synthesis gas of 37 vol% CO into a reactor, wherein the pressure is 2.0MPa, the temperature of the reactor is increased to 280 ℃ according to the heating rate of 0.1 ℃/min, the reaction space velocity is adjusted to 12000NL/Kg/h, and the reaction is kept 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

Weighing422.8g of ferric chloride hexahydrate and 149.2g of terephthalic acid (H)₂BDC) and dissolving the materials in 3935g N, N-Dimethylformamide (DMF), mixing and stirring until the materials are completely dissolved to obtain a precursor solution of the MOFs (Fe-BDC) synthetic material. And dropwise adding the precursor solution into 1.7L of 50mg/mL graphene oxide hydrosol, stirring and mixing to obtain a stable and uniform suspension. And uniformly placing the suspension in a 5L hydrothermal reaction kettle, reacting for 18h 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 with absolute ethyl alcohol according to the mass ratio of 1:2, stirring to form slurry suspension, and then carrying out N treatment at 160 DEG C₂Spray drying is carried out under the condition of atmosphere and 0.2MPa to obtain the precursor of the Fe-BDC/GO composite material, and the texture properties of the precursor are shown in Table 1.

Weighing 2.3g of manganese nitrate hexahydrate, 0.3g of copper nitrate and 1.3g of potassium nitrate, dissolving the mixture in 15ml of deionized water to prepare a solution, uniformly mixing the solution with the Fe-BDC/GO composite precursor, drying to obtain the composite precursor added with the auxiliary metal, tabletting and molding the precursor, crushing the precursor into particles of 20-40 meshes, and then placing the particles in a condition of 5 vol% CO/95 vol% N₂Pyrolyzing and carbonizing at 700 ℃ for 3h in airflow to obtain the FeMnCuK @ C catalyst with a hierarchical pore structure. The catalyst comprises the following elements in percentage by mass: Fe/Mn/Cu/K/C38.3: 3.4:0.7:1.7:100, with texture properties as listed in table 1. The FeMnCuK @ C catalyst was treated with 0.5M dilute hydrochloric acid aqueous solution for 24 hours, and then repeatedly filtered and washed with deionized water to completely remove the metal elements, and a carbon carrier, labeled C-2, was obtained, and its texture properties are listed 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 indicates that the pore distribution of the catalyst and the carbon carrier is 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) are weighed out₂BDC) and adding the mixture into 58g tetrahydrofuran to obtain terephthalic acid precursor suspension; and dropwise adding the obtained terephthalic acid precursor suspension into 340mL and 20mg/mL graphene oxide sol, and uniformly stirring and mixing to obtain the terephthalic acid-graphene oxide colloidal solution. Weighing 134g of cobalt acetate tetrahydrate, dissolving the cobalt acetate tetrahydrate in 50g of deionized water, and mixing and stirring until the cobalt acetate is completely dissolved to obtain a cobalt precursor solution; and dropwise adding the obtained cobalt precursor solution into the terephthalic acid-graphene oxide colloidal solution, and stirring and mixing to form stable and uniform sol liquid.

Pouring the sol liquid into a 1L hydrothermal reaction kettle, reacting for 72h at 110 ℃, naturally cooling to room temperature, washing for 3 times with deionized water, washing for 3 times with ethanol, performing suction filtration to obtain a Co-MOFs/GO compound, and finally drying in a vacuum (0.1Pa) oven at 60 ℃ for 12 h. The precursor of the Co-MOFs/GO composite material is obtained, and the texture properties of the precursor are listed 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, molding, ventilating and drying at normal temperature, crushing into particles of 20-40 meshes, and then adding 8 vol% C₂H₄Pyrolyzing and carbonizing at 550 ℃ for 3h in 92 vol% Ar gas flow to obtain the Co @ C catalyst with a hierarchical pore structure. The catalyst had an elemental mass composition of Co/C51.6: 100 and its texture properties are listed in table 1. The Co @ C catalyst was treated with 0.5M dilute hydrochloric acid aqueous solution for 24 hours, and then repeatedly filtered and washed with deionized water to completely remove the metal elements, and a carbon support, labeled C-3, was obtained, the texture properties of which are listed in table 1. As shown in Table 1, the Co @ C catalyst and the C-3 carrier both have two most probable pore distribution peaks, indicating that the pore distribution of the catalyst and the carbon carrier are both hierarchical mesoporous structures.

And (3) testing CO hydrogenation performance: 2g of the Co @ C catalyst is diluted and mixed uniformly by 2mL of silicon carbide, and the mixture is placed in a fixed bed reactor with the inner diameter of 10mm and the constant temperature section length of 50mmIn (1). Catalyst in H₂Reducing for 36 hours at 350 ℃ in the atmosphere, and cooling to 180 ℃. Then 63 vol% H₂Introducing the synthesis gas of 37 vol% CO into the reactor, wherein the pressure is 2.0MPa, the temperature of the reactor is increased to 220 ℃ according to the heating rate of 0.1 ℃/min, the reaction space velocity is adjusted to 5000NL/Kg/h, and the reaction is kept 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 (38% by weight Ru content) and 16.6g of terephthalic acid (H) were weighed out₂BDC), they were dissolved in a mixed solvent of 12.4g of ethylene glycol and 580g N, N-Dimethylformamide (DMF), and stirred and mixed until they were completely dissolved, to obtain a precursor solution. And 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.

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

Mixing and stirring a Ru-MOFs/GO composite material precursor, 70 wt% of phenolic resin ethanol sol and anhydrous ethanol according to the mass ratio of 1:0.15:5 to form a slurry suspension, and then carrying out N treatment at 160 DEG C₂Spray drying under the atmosphere and 0.2MPa to form the Ru-MOFs/GO composite material.

And pyrolyzing and carbonizing the formed Ru-MOFs/GO composite material in Ar airflow at 450 ℃ for 8h to obtain the Ru @ C catalyst with a hierarchical pore structure. The catalyst comprises the following elements in percentage by mass: Ru/C ═ 1.3:100, and the texture properties are listed in table 1. The Ru @ C catalyst was treated with 0.5M dilute hydrochloric acid aqueous solution for 24 hours, and then repeatedly filtered and washed with deionized water to completely remove the metal elements, and a carbon carrier, labeled C-4, was obtained, and its texture properties are listed in table 1. As shown in Table 1, the Ru @ C catalyst and the C-4 carrier both have two most probable pore distribution peaks, which indicates that the pore distribution of the catalyst and the carbon carrier are both hierarchical mesoporous structures.

And (3) testing CO hydrogenation performance: 2g of the Ru @ C catalyst is diluted and mixed uniformly with 2mL of silicon carbide, and the mixture is placed in a fixed bed reactor with the inner diameter of 10mm and the constant-temperature section length of 50 mm. Catalyst in H₂Reducing for 5 hours at 250 ℃ in the atmosphere, and cooling to 180 ℃. Then 63 vol% H₂Introducing the synthesis gas of 37 vol% CO into the reactor, wherein the pressure is 2.0MPa, the temperature of the reactor is increased to 200 ℃ according to the heating rate of 0.1 ℃/min, the reaction space velocity is adjusted 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/GO₂@ C catalyst and CO hydrogenation performance thereof

5.0g of zirconyl nitrate and 3.6g of terephthalic acid (H) were weighed out₂BDC), they were dissolved in 189g of N, N-Dimethylformamide (DMF), and stirred and mixed until they were completely dissolved, to obtain a zirconium-terephthalic acid precursor solution. And dropwise adding the precursor solution into 500mL and 1mg/mL graphene oxide hydrosol, and stirring and mixing to obtain a stable and uniform suspension. And pouring the suspension into a 1L hydrothermal reaction kettle, reacting for 96h at 100 ℃, naturally cooling to room temperature, alternately washing for 5 times by using DMF and ethanol, carrying out suction filtration to obtain a Zr-MOFs/GO compound, and finally drying for 24h in a vacuum (0.01Pa) oven at 80 ℃. The Zr-MOFs/GO composite material precursor is obtained, and the texture properties of the precursor are listed in Table 1.

Directly tabletting and molding the obtained Zr-MOFs/GO composite material precursor, crushing the precursor into particles with 20-40 meshes, and then carrying out N₂Pyrolyzing and carbonizing at 550 deg.c for 10 hr to obtain ZrO with graded pore structure₂@ C catalyst. The catalyst comprises the following elements in percentage by mass: Zr/C67.1: 100, texture properties are listed in table 1. ZrO 2 is mixed with₂Treating the @ C catalyst with 1M hydrofluoric acid aqueous solution for 72 hours, and repeatedly filtering and washing with deionized water to completely remove the catalystMetallic elements, available carbon support, labeled C-5, with texture properties listed in table 1. As shown in Table 1, ZrO₂The @ C catalyst and the C-5 carrier both have two most probable pore distribution peaks, which indicates that the pore distribution of the catalyst and the carbon carrier is of a hierarchical mesoporous structure.

And (3) testing CO hydrogenation performance: 2g of the above-mentioned ZrO was taken₂The @ C catalyst was diluted with 2mL of silicon carbide and mixed well, and placed in a fixed bed reactor having an inner diameter of 10mm and a constant temperature section length of 50 mm. 50 vol% H₂Introducing 50 vol% CO synthesis gas into a reactor, wherein the pressure is 5.0MPa, the temperature of the reactor is increased to 400 ℃ according to the heating rate of 0.2 ℃/min, the reaction space velocity is adjusted to 2000NL/Kg/h, and the reaction is kept for 119 hours. The composition of the reactor off-gas was analyzed by gas chromatography during the reaction and used to calculate 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, and mixed and dissolved in 569g N, N-dimethylformamide to obtain a cobalt zinc-methylimidazole precursor solution. And dropwise adding the precursor solution into 50mL and 40mg/mL graphene oxide hydrosol, and stirring and mixing to obtain a stable and uniform suspension.

And pouring the suspension into a 1L hydrothermal reaction kettle, reacting for 12h at 180 ℃, naturally cooling to room temperature, alternately washing for 5 times by using DMF and ethanol, carrying out suction filtration to obtain a CoZn-ZIF/GO compound, and finally drying for 24h in a vacuum (0.005Pa) oven at 80 ℃. The precursor of the CoZn-ZIF/GO composite material is obtained, and the texture properties of the precursor are shown in Table 1.

Directly tabletting and molding the obtained ZnCo-ZIF/GO composite material precursor, crushing the precursor into particles of 20-40 meshes, and then adding N₂Pyrolyzing and carbonizing at 550 deg.c for 10 hr in gas flow to obtain CoZn @ C catalyst with hierarchical pore structure. The catalyst had an elemental mass composition of Co/Zn/C of 4.8:27.2:100 and its texture properties are listed in table 1. CoZn @ C catalyst was treated with 0.5M dilute aqueous hydrochloric acid for 24 hours and then deionizedRepeatedly filtering and washing the carbon support with water to completely remove metal elements to obtain the carbon support marked as C-6, wherein the texture properties of the carbon support 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 hierarchical mesoporous structure.

And (3) testing CO hydrogenation performance: 2g of the CoZn @ C catalyst was diluted with 2mL of silicon carbide and mixed well, and placed in a fixed bed reactor having an inner diameter of 10mm and a constant temperature zone length of 50 mm. Catalyst in H₂Reducing for 12 hours at 350 ℃ in the atmosphere, and cooling to 180 ℃. 67 vol% H₂Introducing 33% vol CO synthesis gas into a reactor, wherein the pressure is 2.0MPa, the temperature of the reactor is increased to 200 ℃ according to the heating rate of 0.2 ℃/min, the reaction space velocity is adjusted to 2000NL/Kg/h, and the reaction is kept for 110 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.

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.

295g of coconut shell activated carbon AC (20-40 meshes) is weighed, the mixed salt solution is slowly added into the AC carrier in batches by adopting an incipient wetness impregnation method, and the mixture is dried in an oven at 120 ℃; the above impregnation and drying process was repeated until all of the above mixed salt solution was completely impregnated on the AC support. Impregnating the AC carrier in N₂Roasting the mixture for 10 hours at 550 ℃ in airflow to obtain the FeMnCuK/AC catalyst. The catalyst comprises the following elements in percentage by mass: Fe/Mn/Cu/K/C29.5: 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 tested for CO hydrogenation performance 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 precursor and catalyst texture prepared in examples 1-7 and comparative example 1

Table 2 CO hydrogenation activity, hydrocarbon product selectivity and stability of catalysts prepared in examples 1-7 and comparative example 1

As shown in table 2, the porous carbon supported metal or metal oxide catalyst of the present invention exhibits very high CO hydrogenation activity, high hydrocarbon selectivity and excellent operation stability under typical CO catalytic hydrogenation reaction conditions of the corresponding metals. It is noted that the FeMnCuK @ C prepared in example 2 of the present invention also exhibits higher olefins and higher liquid hydrocarbons (C) than the coconut shell activated carbon-supported FeMnCuK/AC catalyst prepared in comparative example 1_5-11) And (4) selectivity. Therefore, 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 efficiently preparing high value-added hydrocarbon compounds by 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;

preferably, the specific surface area of the catalyst is not less than 100m²/g；

Preferably, the mass ratio of the active phase metal to the porous carbon carrier is (0.1-200): 100;

preferably, the catalyst further comprises a promoter metal; more preferably, 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; further preferably, the mass ratio of the auxiliary metal to the porous carbon carrier is (0.002-40): 100.

3. A method of preparing the metal on carbon catalyst with a hierarchical pore structure of claim 1 or 2, wherein the method comprises:

4. The method of claim 3, wherein, in the step (1), the metal-organic framework/graphene oxide composite precursor is prepared according to the following process:

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

or preferably, in the step (1), the metal-organic framework/graphene oxide composite precursor is prepared according to the following process:

5. The method of claim 3 or 4, wherein the active phase metal salt is at least one selected from the group consisting of: iron nitrate or a hydrate thereof, iron chloride or a hydrate thereof, ferrous chloride, ferrous sulfate, ferrous 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, tris (ethylenediamine) cobalt (III) chloride trihydrate, nickel nitrate, nickel chloride, nickel sulfate, nickel acetate, nickel acetylacetonate, nickel carbonyl, ruthenium trichloride, ruthenium nitrate, ruthenium carbonyl chloride, ruthenium chloride carbonyl, ruthenium ammonium chloride, ruthenium nitrosyl nitrate, 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;

preferably, the organic ligand is at least one of levulinic acid, lauric acid, oxalic acid, citric acid, 1,3, 5-benzenetricarboxylic acid, terephthalic acid, 2-methylimidazole, fumaric acid, azobenzene tetracarboxylic acid, amino-terephthalic acid, 2, 5-dihydroxyterephthalic acid, 1, 4-naphthalenedicarboxylic acid, 1, 5-naphthalenedicarboxylic acid or 2, 6-naphthalenedicarboxylic acid;

preferably, the mass ratio of the active phase metal salt to the organic ligand is (30-400): 100.

6. The process of claim 4 or 5, 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;

preferably, the mass volume concentration of the graphene oxide sol is 1-50 mg/mL;

preferably, the metal-organic framework material precursor solution, the organic ligand precursor solution and the active phase metal salt solution are mixed with the graphene oxide sol or the organic ligand-graphene oxide solution in the following manner: mechanical stirring, magnetic stirring, ball milling mixing, shearing emulsification or ultrasonic mixing.

7. The method of any one of claims 3-6, wherein the metal-organic framework is selected from: iron 1,3, 5-benzenetricarboxylate, cobalt 1,3, 5-benzenetricarboxylate, nickel 1,3, 5-benzenetricarboxylate, ruthenium 1,3, 5-benzenetricarboxylate, zirconium 1,3, 5-benzenetricarboxylate, cerium 1,3, 5-benzenetricarboxylate, thorium 1,3, 5-benzenetricarboxylate, 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, cerium fumarate, thorium fumarate, iron azobenzene tetracarboxylic acid, cobalt azobenzene tetracarboxylic acid, nickel azobenzene tetracarboxylic acid, ruthenium azobenzene tetracarboxylic acid, zirconium azobenzene tetracarboxylic acid, iron, Cerium azobenzene tetracarboxylic acid, thorium azobenzene tetracarboxylic acid, 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, cobalt (III) amide, ruthenium (III) amide, cobalt (III) amide, nickel (III) amide, cobalt (III) amide, ruthenium (III) amide, cobalt (III) amide, ruthenium (III) amide, cobalt (III) amide (IV) amide (III), 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 or thorium 2, 6-naphthalenedicarboxylate.

8. The process of any one of claims 4 to 7, wherein in steps (c) and (d'), the reaction temperature in the reaction kettle is from 100 ℃ to 180 ℃;

preferably, in said steps (c) and (d'), said drying is carried out under vacuum or inert atmosphere;

preferably, the vacuum degree of the vacuum is 0.1-0.005 Pa;

preferably, the inert atmosphere is nitrogen, argon or helium;

preferably, in the step (c) and the step (d'), the temperature of the drying is 60 ℃ to 180 ℃.

9. The method of any one of claims 3-8, wherein the method further comprises the step of adding a promoter metal salt, wherein the promoter metal salt is added by mixing the promoter metal salt with the active phase metal salt, organic ligand, and graphene oxide in step (1); or before the step (2), adding the assistant metal salt to the metal organic framework/graphene oxide composite precursor obtained in the step (1) to obtain an assistant metal-added composite precursor;

preferably, 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;

preferably, the auxiliary metal salt is added into the metal organic framework/graphene oxide composite material precursor through an impregnation method;

preferably, in the step (2), the molding is direct tablet molding or molding using cellulose ether, phenol resin, acrylic resin, epoxy resin, melamine resin, urea resin, polyurethane as a binder;

preferably, the forming method is selected from compression forming, rotation forming, extrusion forming, forming in oil, forming in water or spray drying forming;

preferably, the mass of the binder accounts for 0-20% of the mass of the metal organic framework/graphene oxide composite material precursor;

preferably, in the step (3), the inert atmosphere is at least one selected from the group consisting of nitrogen, helium, argon, xenon, and radon;

preferably, in the step (3), the carbon-containing atmosphere is a mixed gas of a carbon-containing gas and an inert gas; more preferably, the carbon-containing gas is methane, ethane, ethylene, acetylene, propane, propylene, CO and/or syngas; more preferably, the inert gas is at least one selected from the group consisting of nitrogen, helium, argon, xenon, and radon;

preferably, in the carbon-containing atmosphere, the volume concentration of the carbon-containing gas is 0.5-100%;

preferably, the temperature of pyrolysis and carbonization is 350-1100 ℃, and the time is 1-10 hours.

10. Use of the carbon supported metal catalyst with hierarchical pore structure of claim 1 or 2 for catalyzing a reaction of a gas containing CO and hydrogen to produce a hydrocarbon compound;

preferably, the CO and hydrogen containing gas is syngas;

preferably, the reaction is carried out as a continuous or batch reaction process;

preferably, the reaction is carried out in one or more fixed bed reactors, microchannel reactors, continuously stirred slurry bed tank reactors, jet circulation reactors, slurry bubble column reactors or fluidized bed reactors;

preferably, the pressure of the reaction is 1.0-6.0 MPa, and the temperature is 100-500 ℃;

preferably, the reaction is carried out in a continuous reaction process, and the weight hourly space velocity of the reaction is 100-60000 NL/Kg/h.