CN113171790B - CH (physical channel) 4 -CO 2 Reforming catalyst and process for producing the same - Google Patents

CH (physical channel) 4 -CO 2 Reforming catalyst and process for producing the same Download PDF

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CN113171790B
CN113171790B CN202110526728.8A CN202110526728A CN113171790B CN 113171790 B CN113171790 B CN 113171790B CN 202110526728 A CN202110526728 A CN 202110526728A CN 113171790 B CN113171790 B CN 113171790B
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cobalt
nitrogen
catalyst
carbon material
mixture
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CN113171790A (en
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孙映晖
许瞳
梁海欧
柳欢
孙炜岩
李艳
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Inner Mongolia University of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention discloses a CH 4 ‑CO 2 Reforming catalyst and preparation method thereof, relating to CH 4 ‑CO 2 Mixing a carbon material and a nitrogen-containing precursor, and then placing the mixture in a high-temperature roasting furnace to roast at 650-850 ℃ to obtain a nitrogen-modified carbon material; soaking the obtained nitrogen modified carbon material in a cobalt salt solution, and adding an auxiliary agent in the soaking process; carbonizing the impregnated cobalt-containing carbon material at high temperature, introducing carbon-containing gas during carbonization for 3-8 h, and naturally cooling to obtain CH 4 ‑CO 2 A reforming catalyst. The catalyst prepared by the method has better catalytic activity and thermal stability. In addition, the addition of the active metal precursor cobalt and the auxiliary agent can directionally and accurately regulate and control the microstructure of the cobalt carbide active phase and the exposure of a specific crystal face, expose more crystal faces which are beneficial to the catalytic activity of the reforming reaction on the surface of the catalyst, and improve the catalytic performance of the catalyst.

Description

CH (physical channel) 4 -CO 2 Reforming catalyst and process for producing the same
Technical Field
The invention relates to CH 4 -CO 2 Reforming catalysis technical field, in particular to CH 4 -CO 2 Reforming catalyst and a preparation method thereof.
Background
CH 4 And CO 2 As a main component of greenhouse gases, it has a great influence on the environment. CH (CH) 4 -CO 2 The reforming reaction not only can comprehensively utilize CH 4 、CO 2 The two greenhouse gases, and the product is H 2 And C, the product can be directly used as raw material gas for Fischer-Tropsch synthesis to synthesize hydrocarbons with longer carbon chains.
CH 4 -CO 2 The reforming reaction is a strongly endothermic reaction and needs to be carried out at a relatively high temperature, and the conversion of the reaction gas and the selectivity of the product are greatly affected by the reaction temperature. The high reaction temperature and the sintering of carbon deposit and active metal generated by the side reactions such as methane cracking, carbon monoxide disproportionation and the like are the main causes of catalyst deactivation.
Disclosure of Invention
In order to solve the above problems, the present invention provides a CH 4 -CO 2 The method takes a nitrogen modified carbon material as a carrier to load active metal cobalt and an auxiliary agent, and then obtains CH by high-temperature carbonization of carbon-containing gas 4 -CO 2 A reforming catalyst.
Further, the nitrogen-modified carbon material is obtained by mixing a carbon material with a nitrogen-containing precursor and then modifying the mixture at a high temperature in an inert gas atmosphere.
Further, the mass ratio of the carbon material to the nitrogen-containing precursor is 0.5: 1-1: 1.
furthermore, the nitrogen-containing precursor is any one or a mixture of two or more of melamine, dicyandiamide, aniline and pyrrole.
Further, the carbon-containing gas is CO and CH 4 、C 2 H 2 、C 2 H 4 Any one or a mixture of two or more of them.
Furthermore, the auxiliary agent is one of Mn salt, Na salt and Li salt.
Furthermore, the raw material of the metal cobalt is one of cobalt nitrate, cobalt acetate and cobalt chloride.
Further, the method specifically comprises:
s1: mixing a carbon material and a nitrogen-containing precursor, and then placing the mixture in a high-temperature roasting furnace to roast at 650-850 ℃ to obtain a nitrogen-modified carbon material;
s2: soaking the nitrogen modified carbon material obtained in the step S1 in a cobalt salt solution, and adding an auxiliary agent in the soaking process;
s3: carbonizing the cobalt-containing carbon material impregnated in the step S2 at high temperature, introducing carbon-containing gas into the carbonization process for 3-8 h, and naturally cooling to obtain CH 4 -CO 2 A reforming catalyst.
In order to solve the problems, the invention also provides a catalyst which is prepared by the method.
The invention has the beneficial effects that:
the catalyst prepared by the method has better catalytic activity and thermal stability. In addition, the addition of the active metal precursor cobalt and the auxiliary agent can directionally and accurately regulate and control the microstructure of the cobalt carbide active phase and the exposure of a specific crystal face, expose more crystal faces which are beneficial to the catalytic activity of the reforming reaction on the surface of the catalyst, and greatly improve the catalytic performance of the catalyst.
In addition to the above-described objects, features and advantages, the present invention has other objects, features and advantages. The present invention will be described in further detail below.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
CH (physical channel) 4 -CO 2 The method takes a nitrogen modified carbon material as a carrier to load active metal cobalt and an auxiliary agent, and then obtains CH by high-temperature carbonization of carbon-containing gas 4 -CO 2 A reforming catalyst.
The carbon material adopted by the invention can be biomass active carbon, carbon nano tubes and graphene, and because the carbon material has a larger specific surface area and an abundant pore structure, the dispersibility of active metal cobalt on the surface of the carbon material can be improved, so that the metal agglomeration is reduced, the active metal can be limited in pore channels by the abundant pore structure, and the sintering resistance of the active metal in the catalyst is further improved by inhibiting the metal sintering.
The invention also introduces nitrogen atoms into the carbon material, and aims to improve the electronic characteristics, surface acidity and alkalinity and the like of the carbon material, thereby accelerating the electron transfer in the reforming reaction process, improving the reaction rate, improving the surface acidity and alkalinity, facilitating the rapid adsorption of reaction gas, further improving the reaction rate, and effectively promoting the adsorption performance of carbon material carriers on active metals and improving the stability and the dispersibility of active metal cobalt by nitrogen-containing functional groups such as pyrrole, pyridine and the like doped into the carbon material.
The catalyst of the invention takes transition metal cobalt as active metal, and can adopt cobalt nitrate, cobalt acetate or cobalt chloride as an example, carbon-containing gas such as CO and CH is introduced in the high-temperature carbonization process of the catalyst 4 、C 2 H 4 、C 2 H 2 In such a way that carbon atoms enter into the gaps of the metallic cobalt crystal lattice, the formed cobalt carbide has the properties of transition metal, covalent solid and ion crystal at the same time. In addition, electrons are transferred from the transition metal to the carbon atom in the cobalt carbide, and thus the cobalt carbide exhibits a good electron transfer performance. During the process of forming carbide, the carbon atoms enter into the gaps of the metal crystal lattice, so that the metal crystal lattice expands to increase the metal bond distance, so that the catalytic performance of the cobalt carbide is better than that of the metal cobalt, and the cobalt carbide has higher selectivity and resistance to poisoning. The catalyst of the invention shows better catalytic performance in various reactions.
In addition, metal additives such as Mn salt, Na salt and Li salt are added in the preparation process of the catalyst, and the addition of the additives has certain influence on the catalytic performance of the cobalt carbide. The addition of different assistants mainly carries out directional regulation and control on crystal faces of different active phases of cobalt carbide generated in the carbonization process of the catalyst, so that more active crystal faces which are beneficial to reforming reaction are exposed on the surface of the catalyst. In addition, the addition of the auxiliary agent has great influence on the dispersibility of the cobalt carbide active phase on the surface of the carrier and the interaction strength between the cobalt carbide active phase and the carrier.
The nitrogen-modified carbon material is obtained by mixing a carbon material with a nitrogen-containing precursor and then modifying the mixture at a high temperature in an inert gas atmosphere.
In particular, the method comprises the following steps of,
s1: according to the mass ratio of 0.5: 1-1: 1, weighing a carbon material and a nitrogen-containing precursor, mixing and placing the mixture in a high-temperature roasting furnace for roasting, introducing inert gas in the roasting process, wherein the roasting temperature is 650-850 ℃, the heating rate of the furnace body is 3-8 ℃/min, and the nitrogen-containing precursor is any one or a mixture of two or more of melamine, dicyandiamide, aniline and pyrrole.
S2: weighing cobalt salt, illustratively, cobalt nitrate, cobalt acetate or cobalt chloride, preparing the cobalt salt solution, then dipping the nitrogen-containing precursor baked in the step S1 in the cobalt salt solution, performing ultrasonic treatment in the dipping process to fully fill the cobalt salt in the precursor, adding a certain amount of assistant in the dipping process, illustratively, one of Mn salt, Na salt and Li salt, and adding the assistant to adjust the exposure degree of different active phase crystal faces of cobalt carbide.
S3: carbonizing the cobalt-containing carbon material impregnated in the step S2 at 650-850 deg.C, introducing carbon-containing gas during carbonization for 3-8 h, and naturally cooling to obtain CH 4 -CO 2 Reforming catalyst, wherein the carbon-containing gas is CO and CH 4 、C 2 H 2 、C 2 H 4 Any one or a mixture of two or more of them.
Example 1
Step 1: mixing 5g of biomass activated carbon of 100-120 meshes with dicyandiamide of the same mass, placing the mixture in a roasting furnace, introducing nitrogen, heating the mixture from room temperature to 750 ℃, heating the mixture at the rate of 5 ℃/min, and roasting the mixture in nitrogen atmosphere for 3h to obtain the nitrogen modified activated carbon.
Step 2: dissolving active metal cobalt nitrate and an auxiliary agent sodium carbonate with a certain mass in 30mL of water, soaking 5g of the nitrogen modified activated carbon prepared in the step 1 in the mixed solution of the cobalt nitrate and the sodium carbonate, starting an ultrasonic vibration instrument in the soaking process, setting the ultrasonic time for 30min, and soaking at the ultrasonic frequency of 35kHz for 6h at normal temperature. Wherein, the active metal cobalt accounts for 4 wt% of the total mass of the catalyst, and the auxiliary agent accounts for 2 wt% of the total mass of the catalyst.
And step 3: the impregnated sample of step 2 was placed in an oven and dried overnight at 100 ℃. And (3) placing the dried sample in a carbonization furnace, introducing methane gas, setting the temperature rise rate of the carbonization furnace to be 5 ℃/min, setting the carbonization temperature to be 850 ℃, and carbonizing for 5 hours to obtain the required cobalt carbide-containing catalyst.
Example 2
Step 1: mixing 5g of biomass activated carbon of 100-120 meshes with dicyandiamide of the same mass, placing the mixture in a roasting furnace, introducing argon, heating the mixture from room temperature to 750 ℃, setting the heating rate to be 5 ℃/min, and roasting the mixture for 3h in argon atmosphere to obtain the nitrogen modified activated carbon.
Step 2: and (2) adding 30mL of deionized water into cobalt nitrate and manganese nitrate with certain mass for dissolving, soaking the nitrogen modified carbon material obtained in the step (1) in a mixed solution of the cobalt nitrate and the manganese nitrate, starting an ultrasonic vibration instrument in the soaking process, setting the ultrasonic time for 30min, setting the ultrasonic frequency to 35kHz, and soaking for 6h at normal temperature. Wherein, the active metal cobalt accounts for 4 wt% of the total mass of the catalyst, and the auxiliary agent accounts for 2 wt% of the total mass of the catalyst.
And step 3: the impregnated sample was placed in an oven and dried overnight at 100 ℃. And (3) placing the dried sample in a carbonization furnace, introducing methane gas, setting the temperature rise rate of the carbonization furnace to be 5 ℃/min, setting the carbonization temperature to be 850 ℃, and carbonizing for 5 hours to obtain the required cobalt carbide-containing catalyst.
Example 3
Step 1: taking 5g of carbon nano tube, adding 30mL of deionized water into a certain mass of cobalt acetate and sodium carbonate for dissolving, directly soaking the carbon nano tube in a mixed solution of the cobalt acetate and the sodium carbonate, starting an ultrasonic vibration instrument in the soaking process, setting the ultrasonic time for 30min, setting the ultrasonic frequency to be 35kHz, and soaking for 6h at normal temperature. The active metal cobalt accounts for 4 wt% of the total mass of the catalyst, and the auxiliary agent accounts for 2 wt% of the total mass of the catalyst.
Step 2: and (3) placing the impregnated sample in an oven, drying at 100 ℃ overnight, placing the dried sample in a carbonization furnace, introducing ethylene gas, setting the temperature rise rate of the carbonization furnace at 5 ℃/min, setting the carbonization temperature at 800 ℃, and carbonizing for 5 hours to obtain the required cobalt carbide-containing catalyst.
Example 4
Step 1: mixing 5g of graphene with melamine with the same mass, placing the mixture in a roasting furnace, introducing nitrogen, heating the mixture from room temperature to 850 ℃, setting the heating rate to be 5 ℃/min, and roasting the mixture for 3h in nitrogen atmosphere to obtain the nitrogen modified graphene.
Step 2: dissolving cobalt acetate and manganese nitrate with certain mass in 30mL of deionized water, soaking the carbon material in a mixed solution of the cobalt acetate and the manganese nitrate, starting an ultrasonic vibration instrument during the soaking process, setting the ultrasonic time for 30min, setting the ultrasonic frequency to be 35kHz, and soaking for 6h at normal temperature. Wherein, the active metal cobalt accounts for 4 wt% of the total mass of the catalyst, and the auxiliary agent accounts for 2 wt% of the total mass of the catalyst.
And step 3: the impregnated sample of step 2 was placed in an oven and dried overnight at 100 ℃. And (3) placing the dried sample in a carbonization furnace, introducing mixed gas of ethylene and acetylene, setting the temperature rise rate of the carbonization furnace to be 5 ℃/min, setting the carbonization temperature to be 850 ℃, and carbonizing for 5 hours to obtain the required catalyst containing the cobalt carbide.
Example 5
Step 1: mixing 5g of 100-120 mesh biomass activated carbon, 5g of aniline and 5g of pyrrole, placing the mixture in a roasting furnace, introducing nitrogen, heating the mixture to 650 ℃ from room temperature, heating the mixture at the rate of 5 ℃/min, and roasting the mixture in nitrogen atmosphere for 3h to obtain the nitrogen modified activated carbon.
Step 2: and (2) adding 30mL of deionized water into cobalt chloride and lithium carbonate with certain mass for dissolving, soaking 5g of the nitrogen-modified carbon material prepared in the step (1) into the mixed solution of the cobalt chloride and the lithium carbonate, starting an ultrasonic vibration instrument in the soaking process, setting the ultrasonic time to be 30min, setting the ultrasonic frequency to be 35kHz, and soaking for 6h at normal temperature. Wherein, the active metal cobalt accounts for 4 wt% of the total mass of the catalyst, and the auxiliary agent accounts for 2 wt% of the total mass of the catalyst.
And step 3: the impregnated sample of step 2 was placed in an oven and dried overnight at 100 ℃. And (3) putting the dried sample into a carbonization furnace, introducing carbon monoxide gas, setting the temperature rise rate of the carbonization furnace to be 5 ℃/min, setting the carbonization temperature to be 650 ℃, and carbonizing for 5 hours to obtain the required catalyst containing cobalt carbide.
Example 6
Step 1: mixing 5g of biomass activated carbon of 100-120 meshes with 10g of dicyandiamide, placing the mixture in a roasting furnace, introducing nitrogen, heating the mixture from room temperature to 700 ℃, heating the mixture at the rate of 5 ℃/min, and roasting the mixture in nitrogen atmosphere for 3h to obtain the nitrogen modified activated carbon.
And 2, step: dissolving cobalt acetate and manganese nitrate with certain mass in 30mL of deionized water, soaking 5g of the nitrogen-modified carbon material prepared in the step 1 in the mixed solution of the cobalt acetate and the manganese nitrate, starting an ultrasonic vibrator during the soaking process, setting the ultrasonic frequency to be 35kHz, and soaking for 6 hours at normal temperature. Wherein, the active metal cobalt accounts for 4 wt% of the total mass of the catalyst, and the auxiliary agent accounts for 2 wt% of the total mass of the catalyst.
And step 3: the impregnated sample from step 2 was placed in an oven and dried overnight at 100 ℃. The impregnated sample of step 2 was placed in an oven and dried overnight at 100 ℃. And (3) placing the dried sample in a roasting furnace, introducing nitrogen, setting the temperature rise rate of roasting at 5 ℃/min, setting the roasting temperature at 700 ℃, and roasting for 5 hours to obtain the required catalyst.
Example 7
The catalysts prepared in the above examples were tested to investigate the catalytic performance, and when the intake rates of methane and carbon dioxide are 60mL/min and the amount of the catalyst is 3g, the influence of the catalysts prepared in examples 1 to 6 on the conversion rates of methane and carbon dioxide was investigated, and the results are shown in tables 1 and 2, wherein in the preparation process of the catalyst, the catalytic activity of the catalyst modified by nitrogen doping and carbonized to form cobalt carbide is greatly improved and the influence of the addition of the auxiliary agent on the catalytic activity of the catalyst is larger as compared with the catalyst prepared by using different metal auxiliary agents (example 2), modifying without nitrogen doping (example 3), using different carbon material carriers (example 4), modifying with different nitrogen-doped precursors (example 5), and directly loading active metal cobalt (example 6), the catalytic activity of the catalyst added with the auxiliary agent Mn is improved greatly, and the catalytic activity of the catalyst added with the auxiliary agents Na and Li is slightly improved, which shows that the nitrogen doping modification and the addition of the auxiliary agent Mn have larger influence on the generation of the active center of the cobalt carbide.
TABLE 1 conversion of methane
Figure DEST_PATH_IMAGE001
TABLE 2 conversion of carbon dioxide
Figure 199658DEST_PATH_IMAGE002
As can be seen from tables 1 and 2, the catalyst prepared by the present invention has higher catalytic activity, while the catalyst of example 6 obtained by loading active metal Co only needs higher reaction temperature to achieve the same conversion rate; moreover, as can be seen from example 2, the promoter also has a significant effect on the catalytic performance of the catalyst, and the addition of the metal promoter Mn can greatly improve the catalytic activity of the catalyst compared with other metal promoters. Fully explaining: compared with other supported catalysts, the catalyst prepared by the method and using the carbon material as the carrier has the advantages that the reaction temperature required for achieving the same conversion rate is lower, and the energy required by the reaction is reduced.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (5)

1. CH (channel) 4 -CO 2 A method for preparing a reforming catalyst, characterized in that the method specifically comprises:
s1: mixing a carbon material and a nitrogen-containing precursor, and then placing the mixture in a high-temperature roasting furnace to roast at the temperature of 650-850 ℃ to obtain a nitrogen-modified carbon material, wherein the mass ratio of the carbon material to the nitrogen-containing precursor is (0.5: 1) - (1): 1;
s2: soaking the nitrogen modified carbon material obtained in the step S1 in a cobalt salt solution, and adding an auxiliary agent in the soaking process, wherein the auxiliary agent is any one of Mn salt, Na salt and Li salt;
s3: carrying out high-temperature carbonization on the cobalt-containing carbon material obtained by dipping in the step S2, and introducing carbon-containing gas in the carbonization process, wherein the carbon-containing gas is CO and CH 4 、C 2 H 2 、C 2 H 4 Carbonizing for 3-8 h to obtain CH after natural cooling 4 -CO 2 A reforming catalyst.
2. The CH of claim 1 4 -CO 2 The preparation method of the reforming catalyst is characterized in that the nitrogen-modified carbon material is obtained by mixing a carbon material with a nitrogen-containing precursor and then modifying the mixture at a high temperature in an inert gas atmosphere.
3. The CH of claim 2 4 -CO 2 The preparation method of the reforming catalyst is characterized in that the nitrogen-containing precursor is any one or a mixture of two or more of melamine, dicyandiamide, aniline and pyrrole.
4. The CH of claim 1 4 -CO 2 The preparation method of the reforming catalyst is characterized in that the cobalt salt solution is any one of cobalt nitrate, cobalt acetate and cobalt chloride.
5. A catalyst, characterized in that it is obtained by a process according to any one of claims 1 to 4.
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