CN112642439A - Preparation method of methanation catalyst for low-temperature slurry bed - Google Patents

Preparation method of methanation catalyst for low-temperature slurry bed Download PDF

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CN112642439A
CN112642439A CN201910965572.6A CN201910965572A CN112642439A CN 112642439 A CN112642439 A CN 112642439A CN 201910965572 A CN201910965572 A CN 201910965572A CN 112642439 A CN112642439 A CN 112642439A
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catalyst
solution
ruthenium
nickel
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CN112642439B (en
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张�杰
于杨
蔡进
王金利
黄先亮
吴学其
朱艳芳
徐本刚
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China Petroleum and Chemical Corp
Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
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    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • C07—ORGANIC CHEMISTRY
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Abstract

The invention belongs to the technical field of catalysis, and particularly relates to a preparation method of a methanation catalyst for a low-temperature slurry bed. The invention adopts a citric acid-gel method to prepare ZrO2The catalyst has the advantages of good dispersity, high airspeed and low temperature operation, difficult agglomeration, good stability and the like.

Description

Preparation method of methanation catalyst for low-temperature slurry bed
Technical Field
The invention belongs to the technical field of catalysis, and particularly relates to a preparation method of a methanation catalyst for a low-temperature slurry bed.
Background
Natural gas is a clean, safe and efficient high-quality energy, and with the rapid development of economy, the demand of natural gas is rapidly increased. The energy structure of China is characterized by rich coal, poor oil and less gas. Therefore, the technology for preparing the natural gas by the coal is vigorously developed, and the method has important significance for relieving the contradiction between supply and demand of the natural gas in China.
The coal-to-natural gas process mainly comprises four parts of coal gasification, conversion, purification and synthesis gas methanation. The key link is synthesis gas methanation. The methanation reaction is mainly a reaction for generating methane by CO hydrogenation, and belongs to a strong exothermic reaction with large adiabatic temperature rise. Therefore, the methanation process generally adopts a plurality of fixed bed reactors connected in series, and a plurality of heat exchangers are used for heat exchange to control the reaction heat, the process is complex, the energy consumption is high, the fixed bed reactors have poor heat transfer, the reaction heat is difficult to remove in time, and the problems of carbon deposition, sintering and the like of the catalyst are easily caused. Compared with the traditional fixed bed axial reactor, the slurry bed reactor has great advantages in reducing the temperature of the methane synthesis reaction, uses inert liquid as a reaction medium, can quickly transfer a large amount of heat generated in the reaction process, has the advantages of high thermal stability of a reaction system, easy realization of constant temperature operation and the like, and is beneficial to improving the balance conversion rate of CO and avoiding catalyst sintering and carbon deposition because the reaction temperature of the slurry bed is lower, but the traditional supported nickel-based methanation catalyst is used for the slurry bed methanation reaction at low temperature, and shows lower activity and CH4The selective and highly mobile nickel carbonyl species Ni (co) x forms on the catalyst surface, causing Ni particles to aggregate and grow, resulting in catalyst deactivation.
In recent years, domestic research on low-temperature methanation of slurry bed is increasing, and most of the research focuses on supported catalystsThe research on the aspects of improving the preparation method or reaction process conditions and the like shows that the related catalyst has better activity, but the interaction force between the active component of the catalyst prepared by the method and the carrier is weaker, Ni crystal grains are easy to agglomerate on the surface of the carrier, the active component of the catalyst is easy to fall off from the surface of the carrier, the stability of the catalyst is reduced, and the deactivation is more serious at high airspeed. Chinese patent CN107029726A discloses a preparation method of a nano nickel-based CO methanation catalyst, which adopts an impregnation method, and comprises the following steps: the conversion rate of CO is 90-97% at 300-320 ℃ and 1.0-3.0 MPa, and CH4The selectivity is 91% -94%, but the stability of the catalyst is not involved. Aiming at the problems presented by the supported catalyst, a plurality of researchers adopt a sol-gel method to prepare the catalyst for the low-temperature methanation slurry bed, the method can realize the uniform mixing of the active components and carrier molecules in the gel forming process, the dispersibility of the active components is better, the particle size of the obtained catalyst is small, the specific surface area is large, and the activity and the stability of the catalyst are improved compared with the supported catalyst. However, the sol-gel method has some disadvantages that a large number of micropores exist in the gel, the pore size and the specific surface area are reduced due to a shrinkage effect generated during the drying process, the diffusion of reactants and products on the catalyst is limited, and the activity of the catalyst is reduced due to the reduction of active sites. Secondly, the gel aging process takes a long time, and the process of preparing the catalyst generally takes tens of days, which is not beneficial to industrial popularization. Chinese patent CN106563455B discloses a method for preparing CH by hydrogenation of Cu-based CO in slurry bed by adopting sol-gel method4Catalyst, under reaction conditions: at 250 ℃ and 4MPa, the CO conversion rate is 88.4 percent, and CH4The selectivity was 94.3% and the stability of the catalyst was not yet relevant.
Therefore, the research and preparation of a catalyst with a novel structure, which has good low-temperature activity, selectivity and stability at a higher space velocity, will be the key content of the low-temperature slurry bed methanation research.
Disclosure of Invention
The purpose of the invention is as follows: provides a preparation method of a bimetallic active site methanation catalyst of a low-temperature slurry bed. Solves the problems of low catalyst conversion rate, poor stability and the like under the conditions of lower reaction temperature and higher airspeed.
The invention has the main characteristics that:
Figure DEST_PATH_IMAGE002
preparation of ZrO by citric acid-gel method2A Ni-based catalyst precursor as a support;
Figure DEST_PATH_IMAGE004
adding noble metal ruthenium by an atomization spraying technology to prepare a Ru-Ni-based bimetallic active site low-temperature slurry bed methanation catalyst;
c. the catalyst has the advantages of good dispersity, high airspeed, low operation temperature, difficult agglomeration, good stability and the like.
The technical scheme is as follows: the purpose of the invention is realized by the following technical scheme.
The invention provides a preparation method of a methanation catalyst for a low-temperature slurry bed, which comprises the following steps:
(1) dissolving nickel nitrate and zirconium nitrate in water to prepare a mixed solution;
(2) dissolving citric acid in water to prepare a solution, and slowly adding the solution into the nickel-zirconium mixed solution under stirring;
(3) evaporating and dehydrating the nickel-zirconium citrate prepared in the step (2) in vacuum to obtain wet gel with higher viscosity;
(4) drying the wet gel obtained in the step (3) to obtain dry gel, and crushing and sieving the obtained dry gel to obtain a catalyst precursor;
(5) dissolving soluble salt of ruthenium in an organic solvent to prepare a solution, and uniformly spraying the ruthenium solution on the catalyst precursor obtained in the step (4) by adopting an atomization spraying technology;
(6) and drying, roasting and tabletting the obtained material to obtain a finished catalyst product.
Preferably, the molar ratio of Ni to Zr in the mixed solution in the step (1) is 1: 5-1: 12.
Preferably, the volume concentration of the citric acid solution in the step (2) is 0.1-0.3 g/ml, and the temperature is controlled at 30-60 ℃.
Preferably, a rotary evaporator is adopted in the step (3), and the rotary evaporation time is 3-8 h.
Preferably, a vacuum drying oven is adopted in the step (4), the drying temperature is 110-180 ℃, the drying time is 2-6 hours, and the catalyst precursor with the particle size of 40-80 meshes is obtained through sieving.
Preferably, the ruthenium salt in the step (5) is ruthenium trichloride, ruthenium acetate or ruthenium iodide; the organic solvent is ethanol or ethylene glycol, and the molar concentration of the organic solution is 0.002-0.005 mol/ml in terms of metal ruthenium.
Preferably, the roasting temperature in the step (6) is 400-500 ℃.
A typical laboratory preparation procedure of the present invention is as follows: 1) dissolving 20-40 g of nickel nitrate and 300-340 g of zirconium nitrate in water to prepare a nickel-zirconium mixed solution; 2) dissolving citric acid in water to prepare a solution with the volume concentration of 0.1-0.3 g/ml; controlling the temperature to be 30-60 ℃ under stirring, and slowly adding the solution into the nickel-zirconium mixed solution; 3) putting the nickel zirconium citrate into a vacuum rotary evaporator to be treated for 3-8 hours to obtain wet gel; 4) drying the wet gel in a vacuum drying oven at 110-180 ℃ for 2-6 h, crushing and sieving to obtain a catalyst precursor of 40-80 meshes; 5) dissolving one of ruthenium trichloride, ruthenium acetate and ruthenium iodide in ethanol or ethylene glycol to prepare a ruthenium organic solution with the molar concentration of 0.002-0.005 mol/ml in terms of metal ruthenium, and then directly spraying 5-15 ml of the ruthenium organic solution on a catalyst precursor by adopting an atomization spraying technology; 6) And drying the obtained material, roasting at 400-500 ℃, and tabletting to obtain a catalyst finished product.
Advantageous effects
The low-temperature slurry bed bimetallic methanation catalyst prepared by the method has the characteristics of good low-temperature activity, high stability and the like at lower temperature and higher airspeed.
Detailed Description
The technical solution of the present invention is described in detail by the following specific examples, but the scope of the present invention is not limited to the examples. The reagents used in the examples of the present invention are all commercially available.
Example 1
1) Dissolving 20g of nickel nitrate and 300g of zirconium nitrate in water to prepare a nickel-zirconium mixed solution; 2) dissolving citric acid in water to prepare a solution with the volume concentration of 0.1 g/ml; the temperature is controlled at 40 ℃ under stirring, and the solution is slowly added into the nickel-zirconium mixed solution; 3) putting the nickel zirconium citrate into a vacuum rotary evaporator to be treated for 5 hours to obtain wet gel; 4) drying the wet gel in a vacuum drying oven at 150 ℃ for 5 hours, crushing and sieving to obtain a catalyst precursor of 40-80 meshes; 5) dissolving ruthenium trichloride in ethanol to prepare a ruthenium organic solution with the molar concentration of 0.002mol/ml in terms of metal ruthenium, and then directly spraying 10ml of the ruthenium organic solution on a catalyst precursor by adopting an atomization spraying technology; 6) drying the obtained material, roasting at 400 ℃, and tabletting to obtain the catalyst finished product I, Ni/Ru/ZrO2The mass ratio is 2:1: 42.5.
Example 2
1) Dissolving 40g of nickel nitrate and 340g of zirconium nitrate in water to prepare a nickel-zirconium mixed solution; 2) dissolving citric acid in water to prepare a solution with the volume concentration of 0.3 g/ml; the temperature is controlled at 60 ℃ under stirring, and the solution is slowly added into the nickel-zirconium mixed solution; 3) putting the nickel zirconium citrate into a vacuum rotary evaporator to be processed for 3 hours to obtain wet gel; 4) drying the wet gel in a vacuum drying oven at 180 ℃ for 2h, crushing and sieving to obtain a catalyst precursor of 40-80 meshes; 5) dissolving ruthenium acetate in ethylene glycol to prepare ruthenium organic solution with the molar concentration of 0.005mol/ml in terms of metal ruthenium, and then directly spraying 10ml of ruthenium organic solution on the catalyst precursor by adopting an atomization spraying technology; 6) drying the obtained material, roasting at 500 ℃, and tabletting to obtain a catalyst finished product II, Ni/Ru/ZrO2The ratio was 1.6:1: 19.3.
Example 3
1) Dissolving 30g of nickel nitrate and 300g of zirconium nitrate in water to prepare a nickel-zirconium mixed solution; 2) dissolving citric acid in water to prepare a solution with the volume concentration of 0.2 g/ml; the temperature is controlled to be 30 ℃ under stirring, and the solution is slowly added into the nickel-zirconium mixed solution; 3) putting the nickel zirconium citrate into a vacuum rotary evaporator for treatment for 6 hours to obtain wet gel; 4) will wetDrying the gel in a vacuum drying oven at 110 ℃ for 6h, crushing and sieving to obtain a catalyst precursor of 40-80 meshes; 5) dissolving ruthenium iodide in ethylene glycol to prepare a ruthenium organic solution with the molar concentration of 0.002mol/ml in terms of metal ruthenium, and then directly spraying 15ml of ruthenium organic solution on a catalyst precursor by adopting an atomization spraying technology; 6) drying the obtained material, roasting at 500 ℃, and tabletting to obtain a catalyst finished product III, Ni/Ru/ZrO2The ratio was 2:1: 28.4.
Example 4
1) Dissolving 20g of nickel nitrate and 320g of zirconium nitrate in water to prepare a nickel-zirconium mixed solution; 2) dissolving citric acid in water to prepare a solution with the volume concentration of 0.3 g/ml; the temperature is controlled at 60 ℃ under stirring, and the solution is slowly added into the nickel-zirconium mixed solution; 3) putting the nickel zirconium citrate into a vacuum rotary evaporator for treatment for 6 hours to obtain wet gel; 4) drying the wet gel in a vacuum drying oven at 140 ℃ for 4 hours, crushing and sieving to obtain a catalyst precursor of 40-80 meshes; 5) dissolving ruthenium trichloride in ethanol to prepare a ruthenium organic solution with the molar concentration of 0.003mol/ml based on metal ruthenium, and then directly spraying 10ml of the ruthenium organic solution on a catalyst precursor by adopting an atomization spraying technology; 6) drying the obtained material, roasting at 500 ℃, and tabletting to obtain a catalyst finished product IV, Ni/Ru/ZrO2The ratio was 1.3:1: 30.3.
Example 5
1) Dissolving 40g of nickel nitrate and 320g of zirconium nitrate in water to prepare a nickel-zirconium mixed solution; 2) dissolving citric acid in water to prepare a solution with the volume concentration of 0.2 g/ml; the temperature is controlled to be 30 ℃ under stirring, and the solution is slowly added into the nickel-zirconium mixed solution; 3) putting the nickel zirconium citrate into a vacuum rotary evaporator for treatment for 4 hours to obtain wet gel; 4) drying the wet gel in a vacuum drying oven at 180 ℃ for 3h, crushing and sieving to obtain a catalyst precursor of 40-80 meshes; 5) dissolving ruthenium iodide in ethylene glycol to prepare a ruthenium organic solution with the molar concentration of 0.005mol/ml in terms of metal ruthenium, and then directly spraying 10ml of the ruthenium organic solution on a catalyst precursor by adopting an atomization spraying technology; 6) drying the obtained material, roasting at 450 ℃, and tabletting to obtain a catalyst finished product V, Ni/Ru/ZrO2The ratio was 1.6:1: 18.2.
Example 6
1) Dissolving 35g of nickel nitrate and 340g of zirconium nitrate in water to prepare a nickel-zirconium mixed solution; 2) dissolving citric acid in water to prepare a solution with the volume concentration of 0.3 g/ml; the temperature is controlled at 60 ℃ under stirring, and the solution is slowly added into the nickel-zirconium mixed solution; 3) putting the nickel zirconium citrate into a vacuum rotary evaporator to be treated for 5 hours to obtain wet gel; 4) drying the wet gel in a vacuum drying oven at 150 ℃ for 6 hours, crushing and sieving to obtain a catalyst precursor of 40-80 meshes; 5) dissolving ruthenium trichloride in ethanol to prepare a ruthenium organic solution with the molar concentration of 0.002mol/ml in terms of metal ruthenium, and then directly spraying 15ml of the ruthenium organic solution on a catalyst precursor by adopting an atomization spraying technology; 6) drying the obtained material, roasting at 400 ℃, and tabletting to obtain a catalyst finished product VI, Ni/Ru/ZrO2The ratio was 2.3:1: 32.2.
Example 7
1) Dissolving 25g of nickel nitrate and 330g of zirconium nitrate in water to prepare a nickel-zirconium mixed solution; 2) dissolving citric acid in water to prepare a solution with the volume concentration of 0.1 g/ml; the temperature is controlled at 60 ℃ under stirring, and the solution is slowly added into the nickel-zirconium mixed solution; 3) putting the nickel zirconium citrate into a vacuum rotary evaporator to be treated for 5 hours to obtain wet gel; 4) drying the wet gel in a vacuum drying oven at 180 ℃ for 6 hours, crushing and sieving to obtain a catalyst precursor of 40-80 meshes; 5) dissolving ruthenium trichloride in ethylene glycol to prepare a ruthenium organic solution with the molar concentration of 0.004mol/ml in terms of metal ruthenium, and then directly spraying 15ml of ruthenium organic solution on a catalyst precursor by adopting an atomization spraying technology; 6) drying the obtained material, roasting at 500 ℃, and tabletting to obtain a catalyst finished product VII, Ni/Ru/ZrO2The ratio was 0.8:1: 15.6.
Example 8
1) Dissolving 40g of nickel nitrate and 300g of zirconium nitrate in water to prepare a nickel-zirconium mixed solution; 2) dissolving citric acid in water to prepare a solution with the volume concentration of 0.2 g/ml; the temperature is controlled at 60 ℃ under stirring, and the solution is slowly added into the nickel-zirconium mixed solution; 3) putting the nickel zirconium citrate into a vacuum rotary evaporator to be processed for 3 hours to obtain wet gel; 4) drying the wet gel in a vacuum drying oven at 180 ℃ for 2h, crushing and sieving to obtain the catalyst of 40-80 meshesAn oxidant precursor; 5) dissolving ruthenium iodide in ethanol to prepare a ruthenium organic solution with the molar concentration of 0.005mol/ml based on metal ruthenium, and then directly spraying 10ml of the ruthenium organic solution on a catalyst precursor by adopting an atomization spraying technology; 6) drying the obtained material, roasting at 500 ℃, and tabletting to obtain a catalyst finished product VIII, Ni/Ru/ZrO2The ratio was 1.6:1: 17.0.
Example 9
1) Dissolving 30g of nickel nitrate and 300g of zirconium nitrate in water to prepare a nickel-zirconium mixed solution; 2) dissolving citric acid in water to prepare a solution with the volume concentration of 0.3 g/ml; the temperature is controlled at 50 ℃ under stirring, and the solution is slowly added into the nickel-zirconium mixed solution; 3) putting the nickel zirconium citrate into a vacuum rotary evaporator for treatment for 4 hours to obtain wet gel; 4) drying the wet gel in a vacuum drying oven at 110 ℃ for 2h, crushing and sieving to obtain a catalyst precursor of 40-80 meshes; 5) dissolving ruthenium acetate in ethanol to prepare ruthenium organic solution with the molar concentration of 0.003mol/ml based on metal ruthenium, and then directly spraying 15ml of ruthenium organic solution on a catalyst precursor by adopting an atomization spraying technology; 6) drying the obtained material, roasting at 450 deg.C, tabletting to obtain catalyst finished product IX, Ni/Ru/ZrO2The ratio was 1.3:1: 18.9.
Comparative example 1
1) Dissolving 30g of nickel nitrate and 300g of aluminum nitrate in water to prepare a nickel-aluminum mixed solution; 2) dissolving citric acid in water to prepare a solution with the volume concentration of 0.2 g/ml; the temperature is controlled at 60 ℃ under stirring, and the solution is slowly added into the nickel-aluminum mixed solution; 3) putting the nickel aluminum citrate into a vacuum rotary evaporator to be processed for 3 hours to obtain wet gel; 4) drying the wet gel in a vacuum drying oven at 150 ℃ for 2h, crushing and sieving to obtain a catalyst precursor of 40-80 meshes; 5) dissolving ruthenium trichloride in ethanol to prepare a ruthenium organic solution with the molar concentration of 0.002mol/ml in terms of metal ruthenium, and then directly spraying 10ml of the ruthenium organic solution on a catalyst precursor by adopting an atomization spraying technology; 6) drying the obtained material, roasting at 450 ℃, and tabletting to obtain a comparative catalyst A, Ni/Ru/Al2O3The ratio was 3:1: 40.3.
Comparative example 2
1) 150g of pseudo-boehmite was dissolved in waterPreparing aluminum suspension; 2) slowly adding 1% dilute nitric acid into the aluminum suspension to prepare aluminum sol while stirring at 60 ℃; 3) drying the aluminum sol in a vacuum drying oven at 150 ℃ for 10h, crushing and sieving to obtain a carrier precursor of 40-80 meshes; 4) dissolving 20g of nickel nitrate in 50ml of water to prepare a nickel solution, dissolving ruthenium trichloride in ethanol to prepare 10ml of ruthenium organic solution with the molar concentration of 0.002mol/ml in terms of metal ruthenium, and then soaking the carrier precursor in the nickel-ruthenium mixed solution; 5) drying the obtained material, roasting at 450 ℃, and tabletting to obtain a comparative catalyst B, Ni/Ru/Al2O3The ratio was 2:1: 46.0.
Comparative example 3
1) Dissolving 30g of nickel nitrate and 300g of aluminum nitrate in water to prepare a nickel-aluminum mixed solution; 2) dissolving citric acid in water to prepare a solution with the volume concentration of 0.2 g/ml; the temperature is controlled at 60 ℃ under stirring, and the solution is slowly added into the nickel-aluminum mixed solution; 3) putting the nickel aluminum citrate into a vacuum rotary evaporator to be processed for 3 hours to obtain wet gel; 4) drying the wet gel in a vacuum drying oven at 150 ℃ for 2h, crushing and sieving to obtain a catalyst precursor of 40-80 meshes; 5) drying the obtained material, roasting at 450 ℃, and tabletting to obtain the comparative catalyst C, Ni/Al2O3The ratio was 6: 71.
Comparative example 4
1) Dissolving 150g of pseudo-boehmite in water to prepare suspension of aluminum; 2) slowly adding 1% dilute nitric acid into the aluminum suspension to prepare aluminum sol while stirring at 40 ℃; 3) drying the aluminum sol in a vacuum drying oven at 180 ℃ for 8h, crushing and sieving to obtain a carrier precursor of 40-80 meshes; 4) dissolving 25g of nickel nitrate in 50ml of water to prepare a nickel solution, and then soaking the carrier precursor in the nickel solution; 5) drying the obtained material, roasting at 450 ℃, and tabletting to obtain a comparative catalyst D, Ni/Al2O3The ratio is 5: 93.
Comparative example 5
1) Dissolving 30g of nickel nitrate and 300g of zirconium nitrate in water to prepare a nickel-zirconium mixed solution; 2) dissolving citric acid in water to prepare a solution with the volume concentration of 0.2 g/ml; the temperature is controlled at 60 ℃ under stirring, and the solution is slowly added into the nickel-zirconium mixed solution; 3) mixing nickel zirconium citrateAdding citrate into a vacuum rotary evaporator to be processed for 3h to obtain wet gel; 4) drying the wet gel in a vacuum drying oven at 150 ℃ for 2h, crushing and sieving to obtain a catalyst precursor of 40-80 meshes; 5) drying the obtained material, roasting at 450 ℃, and tabletting to obtain a comparative catalyst E, Ni/ZrO2The ratio was 6: 86.
Evaluation of catalyst Performance
Respectively crushing and sieving catalysts I to IX and comparative examples A to E, respectively filling 80 to 150-mesh samples into a slurry bed reactor for reduction for 5 hours, and then carrying out reaction, wherein the reaction medium is liquid paraffin, the reaction temperature is 250 ℃, the pressure is 3.0MPa, and the reaction pressure is H2The ratio of the carbon to the carbon monoxide is 3.0, and the air volume is 6000ml g-1·h-1(ii) a Samples were taken at 20h and 200h reaction times, respectively, and analyzed to obtain the results as shown in the following table.
TABLE 1 Activity of the catalysts of the examples and comparative examples in different periods of time
Figure DEST_PATH_IMAGE006
As can be seen from the reaction data in the table, the catalysts I to IX prepared by the method have the reaction temperature of 250 ℃, the pressure of 3.0MPa and the H2The ratio of the carbon to the oxygen is 3.0, and the space velocity is 6000ml g-1·h-1Under the condition, the CO conversion rate is between 84 and 93 percent, and the low-temperature conversion rate is good; the measured CO conversion rate data of 20h and 200h are reduced (wherein the IV conversion rate is slightly increased) but the fluctuation is small, and the catalyst stability is good; compared with the comparative example A, B, C, D, after the stability test of 200h, the CO conversion rate is obviously reduced, and the stability is poor; comparative example E, after 200h stability test, showed little change in CO conversion data but low initial low temperature conversion.

Claims (10)

1. A preparation method of a methanation catalyst for a low-temperature slurry bed is characterized in that the catalyst comprises the following steps:
a) dissolving nickel nitrate and zirconium nitrate in water to prepare a mixed solution;
b) dissolving citric acid in water to prepare a solution, and slowly adding the solution into the nickel-zirconium mixed solution under stirring;
c) evaporating and dehydrating the nickel-zirconium citrate in vacuum to obtain wet gel;
d) drying the obtained wet gel to obtain dry gel, and crushing and sieving the obtained dry gel to obtain a catalyst precursor;
e) dissolving soluble salt of ruthenium in an organic solvent to prepare a solution, and uniformly spraying the ruthenium solution on the catalyst precursor by adopting atomization spraying;
f) and drying, roasting and tabletting the obtained material to obtain a finished catalyst product.
2. The method according to claim 1, wherein the molar ratio of Ni to Zr in the mixed solution of nickel and zirconium in the step (a) is 1:5 to 1: 12.
3. The method according to claim 1, wherein the citric acid solution in the step (b) has a volume concentration of 0.1 to 0.3g/ml and a temperature of 30 to 60 ℃.
4. The method according to claim 1, wherein the rotary evaporator is used in the step (c), and the rotary evaporation time is 3-8 h.
5. The method according to claim 1, wherein the step (d) comprises a vacuum drying oven, wherein the temperature of the vacuum drying oven is 110-180 ℃ and the time is 2-6 hours, and the catalyst precursor is sieved to obtain a catalyst precursor of 40-80 meshes.
6. The method according to claim 1, wherein the ruthenium salt in the step (e) is ruthenium trichloride, ruthenium acetate, or ruthenium iodide.
7. The method according to claim 1, wherein the organic solvent in the step (e) is ethanol or ethylene glycol.
8. The method according to claim 1, wherein the organic solution in the step (e) has a molar concentration of 0.002 to 0.005mol/ml in terms of metallic ruthenium.
9. The method according to claim 1, wherein the calcination temperature in the step (f) is 400 to 500 ℃.
10. The use of the catalyst according to claim 1, characterized in that the catalyst is used in slurry bed methanation reactions under the following reaction conditions: the reaction medium is liquid paraffin, the reaction temperature is 250 ℃, the pressure is 3.0MPa, and H2The ratio of the carbon to the oxygen is 3.0, and the space velocity is 6000ml g-1·h-1。
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