CN114308093A - High-loaded nickel-based carbide catalyst, preparation method and application thereof - Google Patents

Abstract

The invention discloses a high-load nickel-based carbide catalyst, which is a coated interstitial carbide alloy catalyst; the molecular formula of the nickel-based catalyst is Ni₃MC_x/N_yO_zWherein M is metal, x is more than 0 and less than or equal to 1, and metal oxide N_yO_zIs a carrier; the metal M is alloyed with the metal Ni, C is an interstitial carbon atom, Ni₃MC_xThe carrier is a gap carbide alloy, and the gap carbide alloy is coated by the carrier. The high-load nickel-based carbide catalyst has good activity, stability and anti-carbon deposition performance. The invention also provides a preparation method and application of the high-load nickel-based carbide catalyst.

Description

High-loaded nickel-based carbide catalyst, preparation method and application thereof

technical field

The invention relates to the field of catalysts, in particular to a high-load nickel-based carbide catalyst and a preparation method and application thereof.

Background technique

Facing the current energy and environmental problems facing the world, vigorously developing new energy and reducing carbon emissions have become the direction of my country's efforts in environmental protection and energy application.

Methane (CH ₄ ) and carbon dioxide (CO ₂ ), as two main greenhouse gases and carbon-containing resources, have received extensive attention in recent years for their recycling, conversion and utilization. On the one hand, for the natural gas, coalbed methane and biogas that can be obtained directly, in addition to CH ₄ , it also contains a higher proportion of CO ₂ . In the traditional process, CO ₂ is removed through a pre-decarbonization step before methane enrichment. The process steps are complicated and the economic cost is high. On the other hand, with the development of modern industry, the concentration of carbon dioxide in the atmosphere continues to rise, from 280 ppm before the industrial revolution to 400 ppm in 2013 and 415 ppm in 2019. The global climate change caused by the continuous increase of CO ₂ concentration It has become one of the problems facing mankind today. Taking the steel industry as an example, its carbon emissions account for 7-9% of the global direct carbon emissions. Among them, the CH ₄ and CO ₂ contents in the tail gas such as coke oven gas, blast furnace gas and basic oxygen furnace gas are quite different. Compounding and utilizing these gases has become the key to reducing carbon emissions in the steel industry (Angew. Chem. Int. Ed., 2021, 60:11852–11857).

Dry methane reforming (DRM) technology has been widely studied because it can utilize both gases, _CH4 and _CO2 , and can convert these two typical greenhouse gases into syngas, an ideal feedstock gas for Fischer-Tropsch synthesis. While DRM is a strong endothermic reaction, its reaction needs to be carried out at a higher temperature, and the side reactions such as CH cracking and carbon monoxide ₍ CO) disproportionation at high temperature often lead to catalyst deactivation. On the other hand, when the _CO2 -rich feed gas, especially when the _CO2 / _CH4 content exceeds 1/1 of the stoichiometric ratio, the metal catalyst is easily oxidized by _CO2 , resulting in the reduction or even deactivation of the catalyst activity.

Compared with noble metal catalysts, nickel-based catalysts have been widely studied due to their high catalytic activity and low price. However, nickel-based catalysts are prone to carbon deposition under the reaction conditions, which leads to the reduction of catalyst activity and the blockage of the reactor, which in turn increases the production cost and increases the hidden danger of production safety (Appl. Catal. A: Gen., 2015, 495: 141- 151; J. Am. Chem. Soc., 017, 139: 1937-1949; Appl. Catal. B: Environ., 2019, 246: 221-231). Studies have shown that transition metal carbides, such as Mo ₂ C and other transition metal carbide catalysts, have good carbon deposition resistance in methane dry reforming because the incorporation of carbon atoms changes the electronic and geometric properties of metal atoms. However, in the reaction gas containing _CO , these metal carbides are rapidly oxidized, thereby deactivating the catalyst (Nat. Commun., 2020, 11:4072; Phys.Chem.Chem.Phys., 2020, 4: 4549–4554; Appl. Catal. A: Gen., 2003, 255:239–253). Therefore, the use of metal carbides for methane dry reforming often requires higher pressures or the addition of CO gas to the reaction gas. On the other hand, similar to Raney nickel, nickel-based catalysts with high loadings have unique advantages in industrial applications. However, for traditional supported catalysts, in order to ensure the dispersibility of catalyst active metals to maintain their catalytic performance, their supported catalysts The amount is generally controlled below 20wt%. Therefore, it is of great significance to synthesize a high-loaded Ni-based catalyst that can be used for _CO2 -rich feed gas, and has good anti-carbon deposition and anti-oxidation properties in the field of direct conversion and utilization of _CH4 and _CO2 .

SUMMARY OF THE INVENTION

Therefore, the purpose of the present invention is to provide a high-load nickel-based carbide catalyst and its preparation method and application in order to solve the above-mentioned problems.

The invention provides a high-load nickel-based carbide catalyst, which is a clad-type interstitial carbide alloy catalyst;

The molecular formula of the high-loaded nickel-based carbide catalyst is Ni ₃ MC _x /N _y O _z , wherein M is a metal, 0<x≤1, and the metal oxide N _y O _z is a carrier;

Metal M and metal Ni form an alloy, C is an interstitial carbon atom, Ni ₃ MC _x is an interstitial carbide alloy, and the carrier coats the interstitial carbide alloy.

Further, 0.25≤x≤0.8.

Further, the Ni content is 40-60 wt %.

Further, the M is at least one of Al, Zn, In, Ga, Mg, and Ca;

The metal oxide N _y O _z is at least one of Al ₂ O ₃ , ZrO ₂ , Fe ₂ O ₃ and CeO ₂ .

Further, the carrier fully coats or partially coats the interstitial carbide alloy.

The present invention also provides a method for preparing a high-load nickel-based carbide catalyst, comprising:

Configuring a metal M precursor: the metal M precursor is obtained by mixing a soluble salt containing metal element M, a solvent and an organic ligand, and stirring and centrifuging to obtain the metal M precursor;

Synthesis of metal oxide precursors: Mix the soluble salt containing Ni ²⁺ and the soluble salt containing metal element N to obtain solution A, dissolve the metal M precursor to obtain solution B, and then mix solution A and solution B and carry out water treatment. The thermal reaction obtains a hydrothermal product, and the metal oxide precursor is obtained after washing and roasting the hydrothermal product;

Reduction: reducing the oxide precursor with hydrogen to obtain a reduced product; and

Carbonization: The reduction product is carbonized with a mixture of _CH4 and _CO2 to obtain the desired catalyst.

Further, the M is Al, the solvent is at least one of methanol solution, urea solution, and ammonia solution, and the organic ligand is 2-methylimidazole, ethylenediaminetetraacetic acid, 2-mercaptobutyl At least one of dicarboxylic acid and terephthalic acid.

Further, the temperature of the hydrothermal reaction is 100-150° C., and the time is 12-36 h.

Further, the reduction temperature is 400-600°C, and the carbonization temperature is 450-650°C.

The present invention also provides the application of a high-load nickel-based carbide catalyst, and the above-mentioned high-load nickel-based carbide catalyst is applied to methane dry reforming.

The above technical scheme of the present invention can synthesize a high-loaded core-shell nickel-based carbide catalyst, which not only solves the problem of easy oxidation and deactivation of the catalyst in _CO2 -rich gas, but also improves the stability of the catalyst and practicability, it also ensures high methane and carbon dioxide activation ability, and can well adapt to the reaction environment of various proportions of _CO2 -rich methane and carbon dioxide mixed gas atmosphere and high temperature reaction environment, so it is especially suitable for application Methane dry reforming. In addition, the C atoms generated by methane cracking are stored in the interstitial sites of the metal alloy, and carbon monoxide is generated by reacting with carbon dioxide, thereby avoiding the coupling of carbon-carbon bonds, and avoiding the carbon deposition path of the methane dry reforming reaction. The catalyst has good anti-carbon performance.

Description of drawings

In order to make the content of the present invention easier to understand clearly, the present invention will be described in further detail below according to specific embodiments of the present invention and in conjunction with the accompanying drawings, wherein

FIG. 1 is the XRD pattern of the Al precursor in experimental group 1.

FIG. 2 is a SEM image of the Al precursor in experimental group 1.

3 is the XRD pattern of NiO/Al ₂ O ₃ in experimental group 2.

FIG. 4 is the BET diagram of NiO/Al ₂ O ₃ in experimental group 2.

FIG. 5 is the XRD pattern of Ni ₃ AlC _0.5 /Al ₂ O ₃ in experimental group 3. FIG.

FIG. 6 is a TEM image of Ni ₃ AlC _0.5 /Al ₂ O ₃ in experimental group 3. FIG.

FIG. 7 is the catalyst stability test chart of test groups 1, 6, and 7. FIG.

FIG. 8 is the XRD pattern of the catalyst after the stability test of test group 1. FIG.

FIG. 9 is an air TG graph of the catalyst after the stability test of test group 1. FIG.

Detailed ways

The following embodiments are only preferred technical solutions of the present invention, and are not intended to limit the present invention. Various modifications and variations of the present invention are possible for those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Example 1

A preparation method of a high-load nickel-based carbide catalyst comprises:

Step S1: configuring metal M precursor: mixing a soluble salt containing metal element M, a solvent and an organic ligand, and stirring and centrifuging to obtain the metal M precursor;

Step S2: Synthesize metal oxide precursors: Mix the soluble salt containing Ni ²⁺ and the soluble salt containing metal element N to obtain solution A, dissolve the metal M precursor to obtain solution B, and then mix solution A and solution B Then, performing a hydrothermal reaction to obtain a hydrothermal product, and washing and calcining the hydrothermal product to obtain the metal oxide precursor;

Step S3: reduction: reducing the oxide precursor with hydrogen to obtain a reduction product; and

Step S4: Carbonization: carbonize the reduced product with a mixture of CH ₄ and CO ₂ to obtain the desired catalyst.

The preparation method of the nickel-based catalyst realizes that the C atoms generated by methane cracking are stored in the interstitial sites of the metal alloy, and the carbon monoxide is generated by reacting with carbon dioxide, thereby avoiding the coupling of carbon-carbon bonds, and avoiding the methane dry reforming reaction. Therefore, the prepared nickel-based catalyst has good anti-carbon deposition performance. And it solves the problem that the catalyst is easily oxidized and deactivated in CO ₂ -rich gas, improves the stability and practicability of the catalyst, and also ensures high methane and carbon dioxide activation capacity, and can be well adapted to a variety of The reaction environment and the high temperature reaction environment of the methane-carbon dioxide mixed gas atmosphere rich in _CO2 .

In step S1, the metal element M may be at least one of Al, Zn, In, Ga, Mg, and Ca, preferably Al.

The soluble salt containing metal element M can be at least one of nitrate solution, acetate solution, and sulfate solution, that is, when M is Al, it can be one of aluminum nitrate, aluminum acetate, aluminum sulfate or A mixture of several; the solubility of the soluble salt is preferably 0.1–0.5 mol/L.

The solvent can be at least one of methanol solution, urea solution, and ammonia solution. The organic ligand can be at least one of 2-methylimidazole, ethylenediaminetetraacetic acid, 2-mercaptosuccinic acid, and terephthalic acid. When M is Al, the solvent is preferably methanol solution, and the organic ligand is preferably terephthalic acid.

The specific step S1 may be as follows: the aluminum nitrate solution, the methanol solution and the phthalic acid are mixed and stirred for 12 h, and then the metal Al precursor is obtained by means of centrifugation and filtration.

In step S2, the soluble salt of Ni ²⁺ can be at least one of nitrate solution, acetate solution, and sulfate solution, and the metal element N can be at least one of Al, Zr, Fe, Ce, and metal The soluble salt of element N may be at least one of nitrate solution, acetate solution and sulfate solution. It can be understood that when M is Al, N is preferably Al, which can not only reduce the types of raw materials, but also ensure the stability of the final catalyst. Further, the molar ratio of nickel ions to aluminum ions is 1-5:1, and the total The concentration is preferably 0.5-1.5 mol/L.

Preferably, the metal M precursor is dissolved in a sodium carbonate solution, and further, the concentration of the sodium carbonate solution is 0.5-1.5 mol/L.

The temperature of the hydrothermal reaction is preferably 100-150° C., and the hydrothermal time is preferably 12-36 h.

The roasting temperature is preferably 400-800°C, and the time is preferably 3-8h.

Step S2 may specifically be: mixing nickel nitrate solution and aluminum nitrate solution to obtain solution A, dissolving the metal Al precursor to obtain solution B, then mixing solution A and solution B uniformly, stirring for 30 min, and performing water treatment at 120 ° C. The hydrothermal product was obtained by thermal reaction for 12 h, the obtained hydrothermal product was washed by centrifugation, and calcined at 600° C. for 5 h to obtain the metal oxide precursor NiO/Al ₂ O ₃ .

In step S3, the reduction temperature is preferably 400-600°C, and the reduction time is preferably 1-5h. Further, the reduction temperature is 550°C, and the reduction time is 2h. The hydrogen concentration in the reducing environment is preferably 10%-100%.

In step S4, the carbonization temperature is preferably 450-650°C, and the carbonization time is preferably 1-5h. Further, the carbonization temperature is 500°C, and the carbonization time is preferably 2h.

Embodiment 2

A nickel-based catalyst can be prepared by the method for preparing a nickel-based catalyst provided in Embodiment 1, and the nickel-based catalyst is a coated interstitial carbide alloy catalyst;

The molecular formula of the high-loaded nickel-based carbide catalyst is Ni ₃ MC _x /N _y O _z , wherein M is a metal, 0<x≤1, and the metal oxide N _y O _z is a carrier;

Metal M and metal Ni form an alloy, C is an interstitial carbon atom, Ni ₃ MC _x is an interstitial carbide alloy, and the carrier coats the interstitial carbide alloy.

As a coated catalyst, the coating form of the catalyst can be fully coated or partially coated, that is, the carrier is fully coated or partially coated with the interstitial carbide alloy. Preferably, the nickel-based catalyst has The cover form is full cover. Preferably, the coating thickness is 2-10 nm, and the particle size of the interstitial carbide alloy is 5-100 nm.

Preferably, 0.25≤x≤0.8, and the Ni content is 40-60wt%.

The M may be at least one of Al, Zn, In, Ga, Mg, and Ca, more preferably Al. The metal oxide N _y O _z may be at least one of Al ₂ O ₃ , ZrO ₂ , Fe ₂ O ₃ , and CeO ₂ , and is more preferably Al ₂ O ₃ .

In some specific embodiments, the molecular formula of the nickel-based catalyst is Ni ₃ AlC _0.5 /Al ₂ O ₃ .

Embodiment 3

An application of a high-loading nickel-based carbide catalyst, the high-loading nickel-based carbide catalyst provided in Example 2 is applied to methane dry reforming.

Embodiment 4

A method for producing synthesis gas by dry reforming of methane. Under the conditions of producing synthesis gas by dry reforming of methane, methane and carbon dioxide are contacted and reacted with the high-load nickel-based carbide catalyst provided in Example 2.

Preferably, the contacting reaction is carried out in a fixed bed reactor. The reaction conditions are that the ratio between _CH4 and _CO2 is 1:1-4, the reaction temperature is 450-650°C, and the reaction pressure is normal pressure. The atmospheric pressure here refers to one atmospheric pressure, that is, 1 bar.

Some specific experimental groups and test/characterization results are provided below

Experimental group 1

Dissolve 1.02 g of terephthalic acid and 1.20 g of Al(NO ₃ ) ₃ ·9H ₂ O in 40 mL of methanol solution, rinse the wall of the beaker with 32 mL of terephthalic acid solution, stir at room temperature for 12 h, and then centrifuge and wash the solution. way to obtain the Al precursor.

Experimental group 2

5.81g Ni(NO ₃ ) ₂ ·6H ₂ O and 1.88g Al(NO ₃ ) ₃ ·9H ₂ O were dissolved in 20mL of distilled water and stirred for 20min; 2g of the Al precursor prepared in experimental group 1 was dissolved in 0.75 g M sodium carbonate solution; and the above two solutions were mixed uniformly and stirred at room temperature for 30min. Subsequently, the above solution was transferred to a 100 mL autoclave and reacted at 120 °C for 12 h to obtain the product. The product was centrifuged, washed, and calcined at 600° C. for 5 h to obtain the metal oxide precursor NiO/Al ₂ O ₃ .

Experimental group 3

The NiO/Al ₂ O ₃ obtained in experimental group 2 was reduced with hydrogen at 550 °C for 2 h, and carbonized with CH ₄ /CO ₂ mixture at 500 ° C for 2 h to obtain a metal alloy interstitial carbide catalyst Ni ₃ AlC _0.5 /Al ₂ O ₃ .

The following tests/characterizations are performed for the above experimental groups

1. Al precursor obtained for experimental group 1

FIG. 1 is the XRD pattern of the Al precursor in experimental group 1. This indicates that the reaction between Al and the organic framework has occurred, and the Al precursor has been successfully prepared.

FIG. 2 is a SEM image of the Al precursor in experimental group 1. This indicates the morphological features of the Al precursor.

2. The metal oxide precursor NiO/Al ₂ O ₃ obtained for experimental group 2.

3 is the XRD pattern of NiO/Al ₂ O ₃ in experimental group 2. The figure illustrates that the NiO/Al ₂ O ₃ catalyst after calcination is mainly NiO and amorphous Al ₂ O ₃ .

FIG. 4 is the BET diagram of NiO/Al ₂ O ₃ in experimental group 2. The figure illustrates the pore structure and specific surface area of the catalyst. The pore size distribution map shows that the catalyst has abundant mesoporous structure.

Table 1 shows the specific surface area, average pore diameter, and pore volume of the metal oxide precursors in experimental group 2.

Table 1

Table 2 shows the metal content of the metal oxide precursors in experimental group 2.

Table 2

3. The metal alloy interstitial carbide catalyst Ni ₃ AlC _0.5 /Al ₂ O 3 obtained for the experimental group ₃

FIG. 5 is the XRD pattern of Ni ₃ AlC _0.5 /Al ₂ O ₃ in experimental group 3. FIG. It can be seen from the figure that the characteristic diffraction peaks of Ni ₃ AlC _0.5 appear at 2θ of 43.3°, 50.4° and 74.0°, indicating that the catalyst Ni ₃ AlC _0.5 /Al ₂ O ₃ has been successfully prepared. The characteristic diffraction peaks of Al ₂ O ₃ were not obtained due to the low crystallinity of the oxide, which could not be detected by XRD.

FIG. 6 is a TEM image of Ni ₃ AlC _0.5 /Al ₂ O ₃ in experimental group 3. FIG. As can be seen from this figure, the catalysis is a core-shell structure, ie, about 2 nm of Al ₂ O ₃ shells are wrapped around about 80 nm of Ni ₃ AlC _0.5 .

Stability testing of catalysts:

Test group 1

A fixed bed reactor was used to investigate the performance of the catalysts prepared in experimental group 3. The fixed bed reactor has an outer diameter of 12 mm, an inner diameter of 8 mm and a length of 450 mm. The reactants and products were detected by gas chromatograph equipped with TCD detector and soap bubble flowmeter.

Reaction conditions: 0.1g of catalyst was mixed with 1g of quartz sand to fill the constant temperature zone of the fixed-bed reactor, heated to 500°C under Ar, and then switched to a mixed gas of _CH4 / _CO2 =1/1, the flow rate was 60mL/min, and the reaction was carried out. The pressure is normal pressure. The atmospheric pressure here refers to one atmospheric pressure, that is, 1 bar.

Test group 2-5

The difference from test group 1 is that the temperature is raised to 450°C, 550°C, 600°C, and 650°C under Ar.

Test group 6

The difference from test group 1 is: CH ₄ /CO ₂ =1/2.

Test group 7

The difference from test group 1 is: CH ₄ /CO ₂ =1/4.

Test Group 8-11

The difference from test group 7 is that the temperature is raised to 450°C, 550°C, 600°C, and 650°C under Ar.

FIG. 7 is the catalyst stability test chart of test groups 1, 6, and 7. FIG. The catalyst has no obvious deactivation in the 100h test, indicating that the catalyst has good stability in the atmosphere of CH ₄ /CO ₂ =1/1, 1/2, and 1/4.

According to the test data of test groups 1-5, Table 3 is obtained:

Table 3 Effects of different reaction temperatures on the dry reforming of methane on Ni ₃ AlC _0.5 /Al ₂ O ₃ metal alloy interstitial carbide catalysts when CH ₄ /CO ₂ =1/1

It can be seen from Table 3 that the catalyst synthesized by the present invention has a good conversion rate of methane and carbon dioxide at a lower temperature. The methane conversion and carbon dioxide conversion can reach 57.1% and 69.2% conversion at 650°C, respectively.

According to the test data of test groups 7-11, Table 4 is obtained:

Table 4 Effects of different reaction temperatures on the dry reforming of methane on Ni ₃ AlC _0.5 /Al ₂ O ₃ metal alloy interstitial carbide catalysts when CH ₄ /CO ₂ = 1/4

It can be seen from Table 4 that the catalysts synthesized in the examples of the present invention have good conversion rates of methane and carbon dioxide at lower temperatures. The methane conversion and carbon dioxide conversion can reach 91.6% and 42.5% conversion at 650°C, respectively.

Further characterization of catalysts after stability testing in Test Group 1

FIG. 8 is the XRD pattern of the catalyst after the stability test of test group 1, and Al ₂ O ₃ is an amorphous substance. The spectrum shows that there are no diffraction peaks of carbon species, indicating that the catalyst has good anti-carbon performance. And compared with the XRD pattern of the catalyst before the stability test (Figure 6), it can be seen that the two are consistent, indicating that the catalyst has high stability.

FIG. 9 is an air TG graph of the catalyst after the stability test of test group 1. FIG. The spectrum shows that there is an obvious weight loss peak below 200 °C, which is due to the removal of water adsorbed by the catalyst; the increase in mass at 200-400 °C is attributed to the oxidation of carbide metals in the catalyst; the weight loss above 400 °C is attributed to Mass loss due to oxidation of evolved carbon species in alloy catalysts. Therefore, the data also show that the catalyst has good resistance to carbon deposition.

To sum up, the nickel-based metal carbide interstitial catalyst prepared by the present invention can be very suitable for methane dry reforming reaction, and can adapt to different reactant ratios, and the CH ₄ /CO ₂ range is 1:1–1:4 . The catalyst in the present invention has good activity, stability and anti-carbon properties. In addition, compared to other carbide catalysts, the catalyst has good oxidation resistance in _CO2 -rich reaction gas. In addition, the catalyst of the present invention is simple in production, low in cost, and easy to realize industrialization.

It will be apparent to those skilled in the art that the present invention is not limited to the details of the above-described exemplary embodiments, but that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments are to be regarded in all respects as illustrative and not restrictive, and the scope of the invention is defined by the appended claims rather than the foregoing description, which are therefore intended to fall within the scope of the appended claims. All changes within the meaning and scope of the equivalents of , are included in the present invention.

In addition, it should be understood that although this specification is described in terms of embodiments, not each embodiment only includes an independent technical solution, and this description in the specification is only for the sake of clarity, and those skilled in the art should take the specification as a whole , the technical solutions in each embodiment can also be appropriately combined to form other implementations that can be understood by those skilled in the art.

Claims (10)

1. A high-load nickel-based carbide catalyst is characterized in that: it is a coated interstitial carbide alloy catalyst;

the molecular formula of the high-load nickel-based carbide catalyst is Ni₃MC_x/N_yO_zWherein M is metal, x is more than 0 and less than or equal to 1, and metal oxide N_yO_zIs a carrier;

the metal M is alloyed with the metal Ni, C is an interstitial carbon atom, Ni₃MC_xThe carrier is a gap carbide alloy, and the gap carbide alloy is coated by the carrier.

2. The high loading nickel-based carbide catalyst of claim 1, wherein: x is more than or equal to 0.25 and less than or equal to 0.8.

3. The high loading nickel-based carbide catalyst of claim 1, wherein: the Ni content is 40-60 wt%.

4. The high loading nickel-based carbide catalyst of claim 1, wherein: the M is at least one of Al, Zn, In, Ga, Mg and Ca;

the metal oxide N_yO_zIs Al₂O₃、ZrO₂、Fe₂O₃、CeO₂At least one of (1).

5. A high loading nickel based carbide catalyst according to any of claims 1 to 4, wherein: the carrier fully or partially coats the interstitial carbide alloy.

6. A preparation method of a high-load nickel-based carbide catalyst is characterized by comprising the following steps: the method comprises the following steps:

preparing a metal M precursor: mixing soluble salt containing metal element M, solvent and organic ligand, and then stirring and centrifuging to obtain a metal M precursor;

synthesizing a metal oxide precursor: will contain Ni²⁺Mixing the soluble salt and the soluble salt containing the metal element N to obtain a solution A, dissolving the metal M precursor to obtain a solution B, mixing the solution A and the solution B, carrying out hydrothermal reaction to obtain a hydrothermal product, and washing and roasting the hydrothermal product to obtain the metal oxide precursor;

reduction: reducing the oxide precursor by using hydrogen to obtain a reduction product; and

carbonizing: the reduction product is treated with CH₄And CO₂The mixed gas is carbonized to obtain the needed catalyst.

7. The method of preparing the high loading nickel-based carbide catalyst of claim 6, wherein: the M is Al, the solvent is at least one of methanol solution, urea solution and ammonia water solution, and the organic ligand is at least one of 2-methylimidazole, ethylenediamine tetraacetic acid, 2-mercaptosuccinic acid and terephthalic acid.

8. The method of preparing the high loading nickel-based carbide catalyst of claim 6, wherein: the temperature of the hydrothermal reaction is 100-150 ℃, and the time is 12-36 h.

9. A method of preparing a high loading nickel-based carbide catalyst according to any of claims 6 to 8, wherein: the reduction temperature is 400-600 ℃, and the carbonization temperature is 450-650 ℃.

10. The application of the high-load nickel-based carbide catalyst is characterized in that: use of the high loading nickel-based carbide catalyst as claimed in any of claims 1 to 5 in dry reforming of methane.

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