CN110270377B - Methane dry reforming nickel-based catalyst and preparation method and application thereof - Google Patents

Methane dry reforming nickel-based catalyst and preparation method and application thereof Download PDF

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CN110270377B
CN110270377B CN201910586784.3A CN201910586784A CN110270377B CN 110270377 B CN110270377 B CN 110270377B CN 201910586784 A CN201910586784 A CN 201910586784A CN 110270377 B CN110270377 B CN 110270377B
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nickel
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任花萍
丁思懿
田少鹏
朱敏
任诚诚
王凤
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Xijing University
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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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
    • B01J35/50—
    • 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
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0213—Complexes without C-metal linkages
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/847—Nickel
    • 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
    • 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 nickel-based catalyst for dry reforming of methaneA method for preparing an agent, the method comprising: (1) Mixing Ni (NO) 3 ) 2 ·6H 2 O, complexing agent and SiO 2 Grinding, putting into a sealed bottle, and reacting at 40-100 ℃; (2) Roasting the reactant in the step (1), heating to 300-800 ℃, roasting, granulating, and screening particles of 40-60 meshes to obtain the nickel-based catalyst with the Ni load of 5-20%. Wherein the complexing agent is any one of citric acid, trimesic acid, urea, glycine and nicotinic acid; the complexing agent, ni (NO) 3 ) 2 ·6H 2 O and SiO 2 In a molar ratio of 1 to 6:1: (3-20). The method provided by the invention has the advantages that the high-activity and high-stability nickel-based catalyst for preparing the synthesis gas by dry reforming of methane is prepared, the preparation method is simple, the industrialization is easy to realize, and the preparation cost of the catalyst is reduced.

Description

Methane dry reforming nickel-based catalyst and preparation method and application thereof
Technical Field
The invention relates to a nickel-based catalyst, in particular to a methane dry reforming nickel-based catalyst and a preparation method and application thereof.
Background
With the growing awareness of the greenhouse effect, CO, one of the strongest greenhouse gases 2 Capture and efficient utilization of the same has attracted increasing attention. Wherein, CO 2 Combined with cleaning of natural gas or coal bed gas (methane as the main constituent) 4 The art of producing syngas by Dry Reforming (DRM) has received significant attention. DRM process except for simultaneous utilization of CO 2 And CH 4 The two greenhouse gases have great significance on the emission reduction of the greenhouse gases, and the H of the produced synthesis gas 2 the/CO is less than or equal to 1, and can be used as raw material gas for synthesizing carbonyl and organic oxygen-containing compounds and synthesizing long-chain hydrocarbons through Fischer-Tropsch (FT) synthesis reaction. More importantly, with other CO 2 Compared with the conversion utilization technology, the DRM is expected to be directly applied to the CH 4 With CO in the flue gas 2 Reforming reaction ofWithout the need for CO in the flue gas 2 And (4) performing pre-separation. Thus, an industrialization process to accelerate the DRM reaction is for realizing CO 2 The emission reduction and the efficient utilization have important application values. Studies have shown that catalyst deactivation by coke deposition and sintering is a bottleneck for industrial application of DRM. Therefore, a great deal of research has been conducted around the stability of the catalyst.
Although the catalytic activity and the carbon deposit resistance of noble metals such as Pt and Rh are obviously superior to those of Ni, the Ni-based catalyst is optimal in comprehensive consideration of the catalytic performance and the economical efficiency. Therefore, research to improve the catalytic performance of Ni-based catalysts in DRM reactions is required.
Disclosure of Invention
The invention aims to provide a methane dry reforming nickel-based catalyst, a preparation method and application thereof, the catalyst solves the problem that the existing catalyst is easy to inactivate due to carbon deposition and sintering, the high-activity and high-stability methane dry reforming synthesis gas nickel-based catalyst is prepared by the method, the preparation method is simple, industrialization is easy to realize, and the catalyst manufacturing cost is reduced.
In order to achieve the above object, the present invention provides a method for preparing a nickel-based catalyst for dry reforming of methane, the method comprising:
(1) Mixing Ni (NO) 3 ) 2 ·6H 2 O, complexing agent and SiO 2 Grinding, putting into a sealed bottle, and reacting at 40-100 ℃;
(2) Roasting the reactant in the step (1), heating to 300-800 ℃, roasting, granulating, and screening particles of 40-60 meshes to obtain the nickel-based catalyst with the Ni load of 5-20%.
Wherein the complexing agent is any one of citric acid, trimesic acid, urea, glycine and nicotinic acid; the complexing agent, ni (NO) 3 ) 2 ·6H 2 O and SiO 2 In a molar ratio of 1 to 6:1: (3-20).
Preferably, in step (1), the milling time is 30min.
Preferably, in step (1), the reaction time is 10 to 48 hours.
Preferably, in the step (2), the roasting time is 3 to 5 hours.
Preferably, in step (2), the temperature increase rate is 5 ℃/min.
The invention also provides a nickel-based catalyst for dry reforming of methane, which is prepared by Ni (NO) 3 ) 2 ·6H 2 O, complexing agent and SiO 2 Grinding, sealing, heating at 40-100 ℃, roasting at 300-800 ℃, and sieving with a 40-60-mesh sieve to obtain the product; wherein the complexing agent is any one of citric acid, trimesic acid, urea, glycine and nicotinic acid; the complexing agent, ni (NO) 3 ) 2 ·6H 2 O and SiO 2 In a molar ratio of 1 to 6:1: (3-20); the Ni loading amount in the nickel-based catalyst is 5-20%.
The catalyst of the invention has an XRD characterization as shown in example 1 of fig. 1, and also has a TPR characterization as shown in example 1 of fig. 2.
Preferably, the catalyst is obtained by the preparation method of the methane dry reforming nickel-based catalyst.
Preferably, the catalyst is prepared by Ni (NO) 3 ) 2 ·6H 2 O, citric acid and SiO 2 Grinding, sealing, heating, reacting, roasting and sieving to obtain the product; wherein the citric acid and Ni (NO) are 3 ) 2 ·6H 2 O and SiO 2 In a molar ratio of 2:1:8 to 9.
Preferably, the catalyst is prepared by Ni (NO) 3 ) 2 ·6H 2 O, glycine and SiO 2 Grinding, sealing, heating, reacting, roasting and sieving to obtain the product; wherein, the glycine and Ni (NO) 3 ) 2 ·6H 2 O and SiO 2 In a molar ratio of 4:1:8 to 9.
The invention also provides the application of the methane dry reforming nickel-based catalyst, and the catalyst is used for catalytic reduction of methane dry reforming reaction.
The methane dry reforming nickel-based catalyst, the preparation method and the application thereof solve the problem that the existing catalyst is easy to inactivate due to carbon deposition and sintering, and have the following advantages:
(1) Hair brushThe nickel-based catalyst is prepared by taking nickel nitrate hexahydrate as a precursor of Ni, taking citric acid, trimesic acid, urea, glycine or nicotinic acid as a coordination agent, and taking SiO 2 The catalyst is a carrier, the nickel-based catalyst for preparing the synthesis gas by dry reforming of the methane with high activity and high stability is prepared, the preparation method is simple, the industrialization is easy to realize, and the preparation cost of the catalyst is reduced;
(2) The nickel-based catalyst avoids carbon deposition and sintering, and not only shows higher reaction activity (CH) 4 And CO 2 Conversion rate), CH 4 And CO 2 The conversion rates of the catalyst are respectively higher than 81% and 90%, and the catalyst simultaneously shows excellent stability, and the conversion rate is basically kept unchanged after the reaction is carried out for 20 hours, even after the reaction is carried out for 100 hours;
(3) Compared with the traditional isometric impregnation method and simple mixing, the catalyst prepared by the coordination-grinding method can obviously improve the dry reforming reaction performance, particularly the stability of the methane;
(4) The preparation method is simple and easy to operate, and the used coordination agent is cheap and easy to obtain and has good repeatability.
Drawings
Fig. 1 is an XRD characterization of the nickel-based catalysts prepared in example 1 and comparative example 1.
FIG. 2 is a TPR characterization of the nickel-based catalysts prepared in example 1 and comparative example 1.
FIG. 3 shows a nickel-based catalyst CH prepared in example 1 4 With CO 2 Curve of conversion (d) as a function of reaction time.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
A method of preparing a methane dry reforming nickel-based catalyst, comprising:
(1) According to the loading of metallic Ni of 10 percent, 0.55g of Ni (NO) 3 ) 2 ·6H 2 O (0.0019 mol, MW 290.81 g/mol), 0.80g citric acid (0.0038 mol 6 H 8 O 7 ·H 2 O, molecular weight 210.14 g/mol) (complexing agent and Ni (NO) 3 ) 2 ·6H 2 The molar ratio of O is 2: 1) And 1.00g SiO 2 (0.017 mol, MW 60.084 g/mol) (SiO 2 With Ni (NO) 3 ) 2 ·6H 2 The molar ratio of O is 9: 1) Putting into a mortar, fully grinding for 30min, then putting into a sealed bottle, and reacting for 24h at 80 ℃;
(2) Transferring the reactant of the step (1) into a crucible, heating to 500 ℃ at a heating rate of 5 ℃/min, roasting for 4 hours, tabletting, granulating, screening particles of 40-60 meshes, to obtain 10% of Ni-citric acid/SiO 2 A catalyst.
Comparative example 1
Essentially the same as in example 1, except that: without adding citric acid, obtaining 10% of Ni/SiO 2 A catalyst.
As shown in fig. 1, in order to characterize XRD of the nickel-based catalysts prepared in example 1 and comparative example 1, it can be seen from fig. 1 that the diffraction peak intensity of the catalyst prepared in example 1 is significantly lower than that of comparative example 1, and the corresponding half-peak width is also significantly wider, which all indicate that the particle size of nickel oxide on the nickel-based catalyst prepared in example 1 is smaller, thereby alleviating the carbon deposit, which also explains the reason for having better DRM reaction activity and stability.
As shown in fig. 2, for the TPR characterization of the nickel-based catalysts prepared in example 1 and comparative example 1, it can be seen from fig. 2 that the catalyst prepared in example 1 has a significant reduction peak at a high temperature of 450-600 ℃ in addition to the reduction peak at 400 ℃ compared to comparative example 1, indicating that the nickel oxide on the catalyst prepared in example 1 is more difficult to reduce, which indicates that the nickel oxide on the catalyst prepared in example 1 has stronger interaction with the carrier, thereby inhibiting the sintering of the nickel particles and thus prolonging the life of the catalyst.
Example 2
A method of preparing a methane dry reforming nickel-based catalyst, substantially as in example 1, except that:
in step (1), ni (NO) 3 ) 2 ·6H 2 The amount of O was 0.26g (0.00089 mol, MW 290.81 g/mol) and the amount of urea (0.0053 mol, MW 60.06 g/mol) was 0.32g, i.e. the complexing agent and Ni (NO) 3 ) 2 ·6H 2 The molar ratio of O is 6:1,SiO 2 With Ni (NO) 3 ) 2 ·6H 2 The molar ratio of O is 19:1; reacting for 12 hours at 40 ℃ in a sealed bottle;
in the step (2), heating to 700 ℃ and calcining for 3 hours, tabletting, granulating, screening 40 to 60 mesh granules, obtaining 5% Ni-Urea/SiO 2 A catalyst.
Example 3
A method of preparing a methane dry reforming nickel-based catalyst, substantially the same as in example 1, except that:
in step (1), ni (NO) 3 ) 2 ·6H 2 The amount of O is 0.87g (0.0030 mol, MW 290.81 g/mol) and the amount of glycine (MW 75.07 g/mol) is 0.45g, i.e. the coordinating agent and Ni (NO) 3 ) 2 ·6H 2 The molar ratio of O is 2:1,SiO 2 With Ni (NO) 3 ) 2 ·6H 2 The molar ratio of O is 6:1; reacting for 12 hours at 100 ℃ in a sealed bottle;
in the step (2), the mixture is heated to 600 ℃ and roasted for 4 hours, and then the mixture is tabletted, granulated and screened into 40-60 mesh granules, thereby obtaining the 15% of Ni-glycine/SiO 2 A catalyst.
Example 4
A method of preparing a methane dry reforming nickel-based catalyst, substantially the same as in example 1, except that:
in step (1), ni (NO) 3 ) 2 ·6H 2 The dosage of O is 0.26g (0.00089 mol, molecular weight is 290.81 g/mol) and the dosage of nicotinic acid (molecular weight is 123.11 g/mol), namely the dosage of the coordination agent and Ni (NO) 3 ) 2 ·6H 2 The molar ratio of O is 5:1,SiO 2 With Ni (NO) 3 ) 2 ·6H 2 The molar ratio of O is 19:1; reacting for 36 hours at 50 ℃ in a sealed bottle;
in the step (2), the mixture is heated to 800 ℃ and roasted for 3 hours, and then the mixture is tableted, granulated and screened into 40 to 60 mesh granules, thereby obtaining 5% of Ni-nicotinic acid/SiO 2 A catalyst.
Example 5
A method of preparing a methane dry reforming nickel-based catalyst, substantially the same as in example 1, except that:
in step (1), ni (NO) 3 ) 2 ·6H 2 The dosage of O is 0.87g (0.0030 mol, the molecular weight is 290.81 g/mol) and the dosage of trimesic acid (the molecular weight is 210.14 g/mol) is 0.63g, namely the coordination agent and Ni (NO) 3 ) 2 ·6H 2 The molar ratio of O is 1:1,SiO 2 With Ni (NO) 3 ) 2 ·6H 2 The molar ratio of O is 6:1; reacting for 24 hours at 90 ℃ in a sealed bottle;
in the step (2), heating to 400 ℃ and calcining for 5 hours, tabletting, granulating, screening 40 to 60 mesh granules, to obtain 15% Ni-trimesic acid/Al 2 O 3 A catalyst.
Example 6
A method of preparing a methane dry reforming nickel-based catalyst, substantially the same as in example 1, except that:
in step (1), ni (NO) 3 ) 2 ·6H 2 The amount of O is 1.24g (0.0043 mol, MW 290.81 g/mol) and the amount of urea is 0.77g, i.e. the complexing agent and Ni (NO) 3 ) 2 ·6H 2 The molar ratio of O is 3:1,SiO 2 With Ni (NO) 3 ) 2 ·6H 2 The molar ratio of O is 4:1; reacting for 48 hours at 70 ℃ in a sealed bottle;
in step (2), heating to 500 deg.C, roasting for 5h, tabletting, granulating, sieving 40-60 mesh granules to obtain 20% Ni-urea/Al 2 O 3 A catalyst.
Example 7
A method of preparing a methane dry reforming nickel-based catalyst, substantially the same as in example 1, except that:
in step (1), the amount of glycine used was 0.57g, i.e., complexing agent and Ni (NO) 3 ) 2 ·6H 2 The molar ratio of O is 4:1; reaction at 70 ℃ in a sealed flask48h; reacting for 12 hours at 70 ℃ in a sealed bottle;
in the step (2), the mixture is heated to 600 ℃ and roasted for 4 hours, and then the mixture is tabletted, granulated and screened into 40-60 mesh granules, thereby obtaining the content of 10% of Ni-glycine/Al 2 O 3 A catalyst.
Example 8
A method of preparing a methane dry reforming nickel-based catalyst, substantially the same as in example 1, except that:
in step (1), ni (NO) 3 ) 2 ·6H 2 O in an amount of 0.26g (0.00089 mol, MW 290.81 g/mol), citric acid (C) 6 H 8 O 7 ·H 2 O) in an amount of 0.19g, i.e., the complexing agent and Ni (NO) 3 ) 2 ·6H 2 The molar ratio of O is 1:1,SiO 2 With Ni (NO) 3 ) 2 ·6H 2 The molar ratio of O is 19:1; reacting for 48 hours at 60 ℃ in a sealed bottle;
in the step (2), the mixture is heated to 300 ℃ and roasted for 5 hours, and then the mixture is tableted, granulated and screened into 40 to 60 mesh granules, thereby obtaining 5% of Ni-citric acid/Al 2 O 3 A catalyst.
The nickel-based catalysts prepared in examples 1 to 8 and comparative example 1 of the present invention were subjected to the evaluation of the reaction performance of the synthesis gas prepared by dry reforming of methane, and the specific experimental conditions were as follows:
0.10g of nickel-based catalyst (the catalyst was diluted with 5 times the volume of quartz sand) was placed in a fixed bed reactor, and 20% by volume of H was introduced under normal pressure 2 /N 2 The total flow rate is 50 mL/min -1 At 4 ℃ in min -1 The temperature rise rate of (2) is increased from room temperature to 700 ℃, and the reduction is carried out for 2.0h.
Subsequently, H is turned off 2 Continuing to introduce N 2 At 2 ℃ min -1 The temperature is raised to 750 ℃ at the temperature raising rate, and the reaction gas (CH) is switched to after the temperature is stable 4 With CO 2 Mixed gas of (1: 1) by volume), CH 4 With CO 2 The total amount of (B) is 100 mL/min -1 CO at P =1.0atm, T =750 deg.C 2 /CH 4 =1.0, space velocity =60000mL · g -1 ·h -1 Reacting under the condition that the gas after the reaction is prepared from Zhejiang Fuli GC9720 IIThe chromatograph (the chromatographic columns are 5A and PQ columns) of the type thermal conductivity cell detector is used for detection and analysis, and the experimental results are shown in Table 1.
TABLE 1 methane-carbon dioxide reforming reaction Performance of the nickel-based catalysts of inventive examples 1-8
Figure BDA0002114760090000071
As shown in Table 1, the nickel-based catalysts prepared by the method have high dry reforming reaction activity of methane, CH 4 With CO 2 The conversion rates of the catalyst are respectively higher than 81 percent and 90 percent, and the Ni/SiO prepared by simple grinding without adding a complexing agent 2 Catalyst (comparative example 1) after 20h reaction, CH 4 With CO 2 The conversion of (a) decreased from 83.6% and 92.1% to 10.7% and 21.3%, respectively. Compared with comparative example 1, the stability of the nickel-based catalyst prepared by adopting the coordination-grinding method is obviously improved, and CH is reacted for 20 hours 4 With CO 2 The conversion of (a) remains substantially unchanged.
The catalyst prepared in example 1 was used as a representative, and the dry reforming reaction life of methane of the catalyst was examined, and it can be seen from FIG. 3 that the catalyst has a high dry reforming reaction performance of methane, and CH thereof was observed after 100 hours of reaction 4 With CO 2 The conversion of (a) remains substantially unchanged.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. Various modifications and alterations to this invention will become apparent to those skilled in the art upon reading the foregoing description. Accordingly, the scope of the invention should be determined from the following claims.

Claims (9)

1. A method for preparing a methane dry reforming nickel-based catalyst, the method comprising:
(1) Mixing Ni (NO) 3 ) 2 ·6H 2 O, complexing agent and SiO 2 Grinding, filling into a sealed bottle, and reacting at 40 to 100 ℃;
(2) Heating the reactant in the step (1) to 300 to 800 ℃, roasting, granulating, and screening particles of 40 to 60 meshes to obtain a nickel-based catalyst with the Ni load of 5 to 20 percent;
wherein the complexing agent is any one of citric acid, trimesic acid, urea, glycine and nicotinic acid; the complexing agent, ni (NO) 3 ) 2 ·6H 2 O and SiO 2 Is 1~6:1: (3 to 20).
2. The method for preparing a methane dry reforming nickel-based catalyst according to claim 1, wherein the grinding time is 30min in the step (1).
3. The method for preparing the nickel-based catalyst for dry reforming of methane according to claim 1, wherein the reaction time in step (1) is 10 to 48h.
4. The method for preparing the nickel-based catalyst for dry reforming of methane according to claim 1, wherein the calcination time in step (2) is 3 to 5 hours.
5. The method for preparing a nickel-based catalyst for dry reforming of methane according to claim 1, wherein the temperature increase rate in the step (2) is 5 ℃/min.
6. A methane dry reforming nickel-based catalyst, characterized in that it is obtained by the method for the preparation of a methane dry reforming nickel-based catalyst according to any one of claims 1 to 5.
7. The methane dry reforming nickel-based catalyst of claim 6, wherein the citric acid, ni (NO), is 3 ) 2 ·6H 2 O and SiO 2 In a molar ratio of 2:1:8~9.
8. The nickel-based catalyst for dry reforming of methane according to claim 6, wherein the nickel-based catalyst is characterized by being prepared by using a nickel-based catalyst for dry reforming of methaneThen, the glycine and Ni (NO) 3 ) 2 ·6H 2 O and SiO 2 In a molar ratio of 4:1:8~9.
9. Use of a methane dry reforming nickel-based catalyst according to any one of claims 6-8 for catalysing the reaction of methane dry reforming to synthesis gas.
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