CN113731422A - Preparation method of slurry bed methane synthesis catalyst - Google Patents

Preparation method of slurry bed methane synthesis catalyst Download PDF

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Publication number
CN113731422A
CN113731422A CN202010459855.6A CN202010459855A CN113731422A CN 113731422 A CN113731422 A CN 113731422A CN 202010459855 A CN202010459855 A CN 202010459855A CN 113731422 A CN113731422 A CN 113731422A
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preparation
catalyst
silicate
temperature
solution
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张�杰
蔡进
王金利
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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China Petroleum and Chemical Corp
Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
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    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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Abstract

The invention belongs to the technical field of catalysis, and particularly relates to a preparation method of a slurry bed methane synthesis catalyst. Preparing a modified nano-scale silicon-aluminum precursor by a sol-spray method through the synergistic effect of multiple metal components such as iron, copper, cobalt and the like to obtain a carrier with good specific surface area, pore volume and pore diameter; then loading the active component Ni on the carrier, using NaBH4And treating the solution to obtain a finished catalyst product. The methane synthesis catalyst prepared by the method is used in a slurry bed reactor, does not need to be reduced under hydrogen, and shows good activity and selectivity at a lower temperature, and meanwhile, the loss rate of active metal is low, and the stability is good.

Description

Preparation method of slurry bed methane synthesis catalyst
Technical Field
The invention belongs to the technical field of catalysis, and particularly relates to a preparation method of a slurry bed methane synthesis catalyst.
Background
Natural gas has been receiving much attention as a clean and efficient energy source. As a big coal country in China, the technology of preparing natural gas from coal not only can realize clean and efficient utilization of coal, but also can make up for the situation of insufficient natural gas in China.
The most central technology in the coal-to-natural gas technology is the methane synthesis technology, and the most central technology in the methane synthesis technology is the methane synthesis catalyst. Because the methanation reaction belongs to a strong exothermic reaction, the methanation reaction in the industry at present mostly adopts the form that a plurality of fixed bed reactors are connected in series, so a plurality of heat exchangers are needed to remove the heat generated by the reaction, and a circulating compressor is needed, so the process is relatively complex. Meanwhile, the catalyst has quite high requirements on high temperature resistance and carbon deposition resistance of the methane synthesis catalyst. The slurry bed reactor is a system which takes inert liquid with high heat conductivity coefficient as a medium and diffuses reaction heat in time to make the reaction process of the system close to constant temperature, and the slurry bed reactor can effectively avoid the problems of high-temperature sintering or carbon deposition of a catalyst in a fixed bed reactor and the like. However, the methane synthesis catalyst applied to the fixed bed reactor in the current industrial production cannot be well used in the slurry bed because the reaction temperature of the slurry bed is low (generally not more than 350 ℃) and the catalyst reacts in a liquid phase, so that the development of the slurry bed methane synthesis catalyst with good activity and high stability at low temperature is urgently needed.
Chinese patent CN103801304A describes a reduction-free slurry bed methanation catalyst, which adopts Ni-Al catalyst prepared by solution combustion method to react in the composition of inert liquid phase such as paraffin hydrocarbon, heat conducting oil, etc., the reaction temperature is 250-350 ℃, the reaction pressure is 0.5-6.0 Mpa, the CO conversion rate is more than 90.6%, and CH4The selectivity is more than 91.4%, but the stability data of the catalyst is not mentioned, and in addition, the method is carried out at high temperature, so that the characteristics of grain growth, agglomeration, nonuniform burning and the like are easily caused, and the large-scale industrial production is not easy to realize.
Chinese patent CN106563455A describes a Cu-based slurry bed methanation catalyst, the reaction temperature is 200-300 ℃, the reaction pressure is 0.1-8.0 Mpa, and CH4The selectivity is high and is 67.5-94.3%; but the CO conversion rate is low and is only 31.8-88.4%.
Chinese patent CN106492864A describes a preparation method of a methanation catalyst for synthesis gas, which uses raney alloy particles as active components and carbon composite as a carrier, and the prepared catalyst shows good catalytic activity in a fixed bed reaction, but the performance in a slurry bed reactor is not described in detail.
Chinese patent CN107029726A describes a Ni-based slurry bed methanation catalyst which is made of SiO2Is a carrier, the activity and the selectivity of which are both more than 90 percent, but the stability of the catalyst is not mentioned.
At present, in the aspect of a slurry bed methane synthesis catalyst, how to prepare a catalyst which has high low-temperature activity, good selectivity and good long-term reaction stability under a gas-liquid-solid three-phase condition is an important subject to be solved by researchers at present.
Disclosure of Invention
The purpose of the invention is as follows: provides a preparation method of a slurry bed methane synthesis catalyst. The problems of low activity, poor stability, large abrasion and the like of the traditional methane synthesis catalyst under the condition of gas-liquid-solid three phases with lower reaction temperature are solved; the problem that the catalyst needs to be reduced in a hydrogen atmosphere for a long time before hydroconversion is solved, and the production period of the natural gas is shortened.
The invention provides a preparation method of a slurry bed methane synthesis catalyst, which is characterized in that the catalyst is obtained by the following steps:
preparation of the carrier: dissolving pseudo-boehmite in water to prepare suspension; adding 1-8% of dilute nitric acid into the suspension under stirring to obtain alumina sol; fully mixing the silicate solution and the aluminum sol, and modulating the pH of the mixture by using alkali liquor to prepare silicon-aluminum sol; adding one or more of oxides of iron, copper, cobalt, cerium, magnesium and lanthanum into the materials, fully mixing and pulping, spray-drying, roasting at 600-900 ℃ for 3-5 h, crushing and tabletting to obtain the modified silicon-aluminum nano-scale composite carrier.
Preparation of active ingredients: dissolving Ni salt in water, and adding 0.05-0.2 mol/L NaOH solution to a pH value of 7-7.5 to obtain an impregnation solution rich in active components.
Preparation of the catalyst: controlling the temperature to be 50-70 ℃, and soaking the carrier in the impregnation liquid for 1.5-3 h in the same volume; at room temperature, NaBH was stirred while stirring4And adding the aqueous solution into the material, reducing for 1-2 h, taking out the impregnated catalyst precursor, washing with water, and drying to obtain a catalyst finished product.
In the steps, the molar ratio of Si to Al (one or more of Fe, Cu, Co, Ce, Mg and La) is 1: 0.9-1.5: 0.1-0.5.
In the step, the load amount of the active component Ni is 7-14% of the weight of the catalyst.
The preparation conditions of the alumina sol in the steps are that the stirring speed is 80-200 r/min, the temperature is controlled to be 40-60 ℃, and the treatment time is 0.5-1.5 h.
The preparation conditions of the aluminum-silicon sol in the steps are that the stirring speed is 150-280 r/min, the temperature is controlled at 60-80 ℃, the treatment time is 1-2 h, and the pH value is 7-9.
The silicate in the above step is one or more of sodium silicate, magnesium silicate, aluminum silicate, iron silicate, calcium silicate and potassium silicate.
The alkali solution in the above step is one or more of sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium carbonate, potassium hydroxide and potassium bicarbonate.
The carrier tablet in the above steps is formed into a size of phi 3 x 3 mm.
A typical laboratory preparation procedure of the present invention is as follows:
1) dissolving 75-125 g of pseudo-boehmite in water to prepare a suspension; 2) controlling the stirring speed to be 80-200 r/min and the temperature to be 40-60 ℃, and adding 1-8% of dilute nitric acid into the suspension for treating for 0.5-1.5 h; 3) raising the temperature to 60-80 ℃, controlling the stirring speed to be 150-280 r/min, adding 100-280 g of one or more of sodium silicate, magnesium silicate, aluminum silicate, ferric silicate, calcium silicate and potassium silicate into the mixture for treatment for 1-2 h, and adjusting the pH value of the material to 7-9 by using one or more of sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium carbonate, potassium hydroxide and potassium bicarbonate; 4) adding 20-85 g of one or more oxides of iron, copper, cobalt, cerium, magnesium and lanthanum into the materials, fully mixing and pulping, spray-drying, roasting at 600-900 ℃ for 3-5 h, crushing and tabletting to obtain a modified silicon-aluminum nano-scale composite carrier; 5) mixing Ni (NO)3)2•6H2Dissolving O in water, preparing a solution with the concentration of 0.1-0.2 g/ml (calculated by Ni metal), adding 0.05-0.2 mol/L NaOH solution, and adjusting the pH value to 7-7.5 to obtain an active component impregnation solution; 6) soaking the molded carrier in the impregnating solution for 1.5-3 h at 50-70 ℃ in the same volume; 7) then the temperature is reduced to room temperature, and NaBH is stirred while the temperature is reduced to room temperature4Adding the aqueous solution into a carrier to reduce for 1-2 h; 8) and taking out the reduced catalyst precursor, washing with water, and drying to obtain a catalyst finished product with the Ni content of 7-14%.
The invention has the advantages of
1) The slurry bed methane synthesis catalyst prepared by the invention does not need to be reduced under hydrogen, has good activity and selectivity under lower reaction pressure, and simultaneously has low loss rate of active metal and good stability;
2) preparing a modified nano-scale silicon-aluminum precursor by a sol-spray method through the synergistic effect of multiple metal components such as iron, copper, cobalt and the like to obtain a carrier with good specific surface area, pore volume and pore diameter;
3) the metal Ni loading rate is low, the metal loss rate of the catalyst is low after the catalyst is used for a long time, and the stability is good;
4) before the catalyst is used, reduction and activation are not needed, the use cost of hydrogen in the reaction is reduced, and the production period of natural gas is shortened.
Detailed Description
The process of the present invention is described in detail below with reference to examples, but the examples are only illustrative and are not intended to limit the scope of the present invention.
Example 1
1) Dissolving 125g of pseudo-boehmite in water to prepare suspension; 2) controlling the stirring speed to be 200r/min and the temperature to be 60 ℃, and adding 8% dilute nitric acid into the suspension for treatment for 0.5 h; 3) raising the temperature to 80 ℃, controlling the stirring speed to be 280r/min, adding 140g of sodium silicate, 40g of aluminum silicate and 30g of calcium silicate into the mixture for treatment for 1 hour, and adjusting the pH value of the material to 8.5 by using a potassium hydroxide solution; 4) adding oxides of 8g of iron, 16g of copper and 7.5g of cobalt into the materials, fully mixing and pulping, spray-drying, roasting at 600 ℃ for 3 hours, crushing and tabletting to obtain a modified silicon-aluminum nano-scale composite carrier; 5) mixing Ni (NO)3)2•6H2Dissolving O in water, preparing a solution with the concentration of 0.1g/ml (calculated by Ni metal), and adding 0.05mol/L NaOH solution to adjust the pH value to 7 to obtain an active component impregnation solution; 6) soaking the molded carrier in the soaking solution at 70 deg.C for 1.5 h; 7) then the temperature is reduced to room temperature, and NaBH is stirred while the temperature is reduced to room temperature4Slowly adding the aqueous solution into the carrier to reduce for 1 h; 8) and taking out the reduced catalyst precursor, washing with water, and drying to obtain a catalyst finished product I with the Ni content of 7%.
Example 2
1) 100g is simulatedDissolving boehmite in water to prepare suspension; 2) controlling the stirring speed to be 150r/min and the temperature to be 40 ℃, and adding 5% dilute nitric acid into the suspension for treatment for 1 h; 3) raising the temperature to 60 ℃, controlling the stirring speed to be 200r/min, adding 50g of magnesium silicate, 10g of ferric silicate, 35g of calcium silicate and 20g of potassium silicate into the mixture for treatment for 2 hours, and adjusting the pH value of the material to 7 by using a potassium carbonate solution; 4) adding oxides of 8g of copper, 8g of cobalt and 20g of cerium into the materials, fully mixing and pulping, spray-drying, roasting at 600 ℃ for 3 hours, crushing and tabletting to obtain a modified silicon-aluminum nano-scale composite carrier; 5) mixing Ni (NO)3)2•6H2Dissolving O in water, preparing a solution with the concentration of 0.2g/ml (calculated by Ni metal), adding 0.1mol/L NaOH solution to adjust the pH value to 7.5 to obtain an active component impregnation solution; 6) soaking the molded carrier in the soaking solution at 50 deg.C for 3 h; 7) then the temperature is reduced to room temperature, and NaBH is stirred while the temperature is reduced to room temperature4Slowly adding the aqueous solution into the carrier to reduce for 1.5 h; 8) and taking out the reduced catalyst precursor, washing with water and drying to obtain a catalyst finished product II with the Ni content of 14%.
Example 3
1) 75g of pseudo-boehmite is dissolved in water to prepare suspension; 2) controlling the stirring speed to be 80r/min and the temperature to be 40 ℃, and adding 2% dilute nitric acid into the suspension for treatment for 0.5 h; 3) raising the temperature to 70 ℃, controlling the stirring speed to be 150r/min, adding 50g of magnesium silicate, 10g of ferric silicate, 30g of calcium silicate and 25g of potassium silicate into the mixture for treatment for 1h, and adjusting the pH value of the material to 7.5 by using a sodium carbonate solution; 4) adding oxides of 10g of copper, 10g of cobalt and 10g of cerium into the materials, fully mixing and pulping, spray-drying, roasting at 700 ℃ for 2 hours, crushing and tabletting to obtain a modified silicon-aluminum nano-scale composite carrier; 5) mixing Ni (NO)3)2•6H2Dissolving O in water, preparing a solution with the concentration of 0.15g/ml (calculated by Ni metal), adding 0.05mol/L NaOH solution to adjust the pH value to 7.5 to obtain an active component impregnation solution; 6) soaking the molded carrier in the soaking solution at 50 deg.C for 2 h; 7) then the temperature is reduced to room temperature, and NaBH is stirred while the temperature is reduced to room temperature4Slowly adding the aqueous solution into the carrier to reduce for 1.5 h; 8) and taking out the reduced catalyst precursor, washing with water, and drying to obtain a catalyst finished product III with the Ni content of 10.5%.
Example 4
1) 75g of pseudo-boehmite is dissolved in water to prepare suspension; 2) controlling the stirring speed at 160r/min and the temperature at 50 ℃, and adding 6% dilute nitric acid into the suspension for treatment for 1 h; 3) raising the temperature to 80 ℃, controlling the stirring speed to be 200r/min, adding 40g of magnesium silicate, 30g of sodium silicate, 30g of aluminum silicate and 45g of potassium silicate into the mixture for treatment for 1h, and adjusting the pH value of the material to 8 by using a mixed solution of sodium hydroxide and potassium carbonate; 4) adding oxides of 10g of copper, 10g of cobalt, 10g of cerium and 15g of potassium into the materials, fully mixing and pulping, spray-drying, roasting at 900 ℃ for 2 hours, crushing and tabletting to obtain a modified silicon-aluminum nano-scale composite carrier; 5) mixing Ni (NO)3)2•6H2Dissolving O in water, preparing a solution with the concentration of 0.1g/ml (calculated by Ni metal), adding 0.2mol/L NaOH solution to adjust the pH value to 7.5 to obtain an active component impregnation solution; 6) soaking the molded carrier in the soaking solution at 60 deg.C for 2 h; 7) then the temperature is reduced to room temperature, and NaBH is stirred while the temperature is reduced to room temperature4Slowly adding the aqueous solution into the carrier to reduce for 0.5 h; 8) and taking out the reduced catalyst precursor, washing with water, and drying to obtain a catalyst finished product IV with the Ni content of 7%.
Example 5
1) Dissolving 90g of pseudo-boehmite in water to prepare suspension; 2) controlling the stirring speed to be 150r/min and the temperature to be 60 ℃, and adding 6 percent dilute nitric acid into the suspension for treatment for 1.5 h; 3) raising the temperature to 70 ℃, controlling the stirring speed to be 200r/min, adding 280g of sodium silicate into the mixture for treatment for 1h, and adjusting the pH value of the material to 8 by using a potassium carbonate solution; 4) adding 16g of iron, 10g of cobalt, 20g of cerium and 30g of lanthanum oxide into the materials, fully mixing and pulping, spray-drying, roasting at 600 ℃ for 2 hours, crushing and tabletting to obtain a modified silicon-aluminum nano-scale composite carrier; 5) mixing Ni (NO)3)2•6H2Dissolving O in water, preparing a solution with the concentration of 0.12g/ml (calculated by Ni metal), adding 0.15mol/L NaOH solution to adjust the pH value to 7.5 to obtain an active component impregnation solution; 6) soaking the molded carrier in the soaking solution at 60 deg.C for 2 h; 7) then the temperature is reduced to room temperature, and NaBH is stirred while the temperature is reduced to room temperature4Slowly adding the aqueous solution into a carrier to reduce for 2 hours; 8) taking out the reduced catalyst precursor, washing with water,And drying to obtain the finished catalyst V with the Ni mass content of 8.4%.
Example 6
1) 75g of pseudo-boehmite is dissolved in water to prepare suspension; 2) controlling the stirring speed to be 100r/min and the temperature to be 40 ℃, and adding 4% dilute nitric acid into the suspension for treatment for 1.5 h; 3) raising the temperature to 60 ℃, controlling the stirring speed to be 150r/min, adding 116g of calcium silicate into the mixture for treatment for 1h, and adjusting the pH value of the material to 9 by using a potassium bicarbonate solution; 4) adding oxides of 10g of cobalt, 10g of cerium, 5g of magnesium and 30g of lanthanum into the materials, fully mixing and pulping, spray-drying, roasting at 700 ℃ for 3 hours, crushing and tabletting to obtain a modified silicon-aluminum nano-scale composite carrier; 5) mixing Ni (NO)3)2•6H2Dissolving O in water, preparing a solution with the concentration of 0.18g/ml (calculated by Ni metal), adding 0.2mol/L NaOH solution to adjust the pH value to 7.5 to obtain an active component impregnation solution; 6) soaking the molded carrier in the soaking solution at 60 deg.C for 2 h; 7) then the temperature is reduced to room temperature, and NaBH is stirred while the temperature is reduced to room temperature4Slowly adding the aqueous solution into a carrier to reduce for 2 hours; 8) and taking out the reduced catalyst precursor, washing with water and drying to obtain a finished catalyst VI with the Ni content of 12.6 percent.
Example 7
1) 75g of pseudo-boehmite is dissolved in water to prepare suspension; 2) controlling the stirring speed to be 150r/min and the temperature to be 60 ℃, and adding 2% dilute nitric acid into the suspension for treatment for 1.5 h; 3) raising the temperature to 80 ℃, controlling the stirring speed at 280r/min, adding 70g of calcium silicate, 10g of ferric silicate and 30g of potassium silicate into the mixture for treatment for 1 hour, and adjusting the pH value of the material to 7.5 by using a sodium hydroxide solution; 4) adding oxides of 8g of cobalt, 10g of copper, 10g of cerium and 5g of magnesium into the materials, fully mixing and pulping, spray-drying, roasting at 600 ℃ for 3 hours, crushing and tabletting to obtain a modified silicon-aluminum nano-scale composite carrier; 5) mixing Ni (NO)3)2•6H2Dissolving O in water, preparing a solution with the concentration of 0.18g/ml (calculated by Ni metal), adding 0.18mol/L NaOH solution to adjust the pH value to 7.5 to obtain an active component impregnation solution; 6) soaking the molded carrier in the soaking solution at 60 deg.C for 2 h; 7) then the temperature is reduced to room temperature, and NaBH is stirred while the temperature is reduced to room temperature4Slowly adding the aqueous solution into a carrier to reduce for 2 hours; 8) take out and returnWashing and drying the original catalyst precursor to obtain the finished catalyst VII with the Ni content of 12.6 percent by mass.
Example 8
1) Dissolving 80g of pseudo-boehmite in water to prepare suspension; 2) controlling the stirring speed to be 100r/min and the temperature to be 50 ℃, and adding 4% dilute nitric acid into the suspension for treatment for 1.5 h; 3) raising the temperature to 80 ℃, controlling the stirring speed to be 200r/min, adding 30g of magnesium silicate, 65g of aluminum silicate and 50g of potassium silicate into the mixture for treatment for 2 hours, and adjusting the pH value of the material to 8 by using a sodium carbonate solution; 4) adding 30g of iron and 10g of cerium oxide into the materials, fully mixing and pulping, spray-drying, roasting at 600 ℃ for 3h, crushing and tabletting to obtain a modified silicon-aluminum nano-scale composite carrier; 5) mixing Ni (NO)3)2•6H2Dissolving O in water, preparing a solution with the concentration of 0.16g/ml (calculated by Ni metal), adding 0.18mol/L NaOH solution to adjust the pH value to 7.5 to obtain an active component impregnation solution; 6) soaking the molded carrier in the soaking solution at 50 deg.C for 1 h; 7) then the temperature is reduced to room temperature, and NaBH is stirred while the temperature is reduced to room temperature4Slowly adding the aqueous solution into the carrier to reduce for 1.5 h; 8) and taking out the reduced catalyst precursor, washing with water, and drying to obtain a catalyst finished product VIII with the Ni mass content of 11.2%.
Example 9
1) Dissolving 120g of pseudo-boehmite in water to prepare suspension; 2) controlling the stirring speed to be 200r/min and the temperature to be 60 ℃, and adding 4% dilute nitric acid into the suspension for treatment for 1.5 h; 3) raising the temperature to 80 ℃, controlling the stirring speed at 280r/min, adding 30g of ferric silicate, 5g of calcium silicate, 65g of aluminum silicate and 50g of potassium silicate into the mixture for treatment for 2 hours, and adjusting the pH value of the material to 8 by using a sodium carbonate solution; 4) adding 10g of cerium oxide into the materials, fully mixing and pulping, spray-drying, roasting at 800 ℃ for 1h, crushing and tabletting to obtain a modified silicon-aluminum nano-scale composite carrier; 5) mixing Ni (NO)3)2•6H2Dissolving O in water, preparing a solution with the concentration of 0.16g/ml (calculated by Ni metal), adding 0.15mol/L NaOH solution to adjust the pH value to 7.5 to obtain an active component impregnation solution; 6) soaking the molded carrier in the soaking solution at 50 deg.C for 1 h; 7) then the temperature is reduced to room temperature, and NaBH is stirred while the temperature is reduced to room temperature4Slowly adding the aqueous solutionReducing in a carrier for 1.5 h; 8) and taking out the reduced catalyst precursor, washing with water and drying to obtain a finished catalyst product IX with the Ni mass content of 11.2%.
Comparative example 1
1) 100g of alumina was dissolved in water to prepare a suspension: 2) treating the suspension with sodium bicarbonate solution, drying, pulverizing, and molding to obtain carrier; 3) immersing the carrier in Ni (NO) at 60 deg.C3)2For 2 hours in the solution of (1); 4) drying, washing and roasting to obtain a catalyst precursor; 5) the catalyst precursor is reduced for 5 hours at 300 ℃ in a hydrogen atmosphere to obtain a comparative catalyst A rich in an active component Ni with the mass fraction of 12%.
Comparative example 2
1) A solution was prepared by dissolving 7g of nickel nitrate, 60g of aluminum nitrate, 2g of ferric nitrate, and 5g of urea in 100ml of water: 2) pouring the solution into a ceramic evaporating dish under a hydrogen-nitrogen reducing atmosphere, heating and igniting the solution by microwave, and collecting the rest powder after burning; 3) the powder was ground and granulated to obtain comparative catalyst B rich in active component Ni with a mass fraction of 14%.
Comparative example 3
1) 100g of silicon carbide and 200g of nickel-aluminum alloy powder are fully and mechanically mixed: 2) tabletting and forming the materials, and carbonizing the materials in a high-temperature electric furnace for 3 hours; 3) and adding NaOH solution into the carbonized material, and activating at 80 ℃ for 5h to obtain a comparative catalyst C rich in active component Ni with the mass fraction of 14%.
Comparative example 4
1) Kneading silicon dioxide, aluminum oxide and silica sol together to extrude into strips; 2) drying, roasting and forming to obtain a carrier; 3) immersing the carrier in Ni (NO) at 60 deg.C3)2Soaking in the solution for 1 h; 4) drying, washing and roasting to obtain a catalyst precursor; 5) the catalyst precursor is reduced for 3h at 450 ℃ in a hydrogen atmosphere to obtain a comparative catalyst D rich in 8 mass percent of active component Ni.
Comparative example 5
1) Kneading silica sol and alumina together to extrude into strips; 2) drying, roasting and forming to obtain a carrier; 3) immersing the carrier in Ni (NO)3)2Soaking in the solution for 2 h;4) drying, washing and roasting to obtain a catalyst precursor; 5) the catalyst precursor is reduced for 4 hours at 400 ℃ in a hydrogen atmosphere to obtain a comparative catalyst E which is rich in an active component Ni with the mass fraction of 12%.
Evaluation of catalyst Performance
The catalysts I to IX and the comparative examples A to E were packed in a slurry bed reactor at a temperature of 280 ℃ and a pressure of 2.0 MPa at a space velocity of 3000h-1Paraffin is liquid medium, stirring speed is 750r/min, H2Samples were taken at 50h and 300h for analysis at/CO = 3.
Figure DEST_PATH_IMAGE002
As can be seen from the reaction data in the table, the catalysts I to IX prepared by the method show good CO conversion rate and CH after 50h and 300h4The selectivity and the stability are ensured, and the loss rate of Ni active metal is lower than 0.02 per mill; although the comparative examples A to E show good conversion rate and selectivity within 50 hours, the conversion rate and the selectivity are greatly reduced after 300 hours of reaction, and the fact that the catalyst is poor in qualitative property after long-time operation under the condition of a slurry bed and the loss rate of Ni active metal reaches 0.3-1.2 per thousand is proved.

Claims (10)

1. A preparation method of a slurry bed methane synthesis catalyst is characterized in that the catalyst is obtained by the following steps:
(1) preparation of the carrier:
a. dissolving pseudo-boehmite in water to prepare suspension;
b. adding 1-8% of dilute nitric acid into the suspension liquid obtained in the step a under stirring to obtain aluminum sol;
c. fully stirring and mixing the silicate solution and the aluminum sol, and modulating the pH of the mixture by using alkali liquor to prepare silicon-aluminum sol;
d. c, adding the material obtained in the step c into one or more of oxides of iron, copper, cobalt, cerium, magnesium and lanthanum, and fully mixing and pulping;
e. d, spray drying, roasting, crushing and tabletting the material obtained in the step d to obtain a modified silicon-aluminum nano-scale composite carrier;
(2) preparation of active ingredients:
f. dissolving Ni salt in water, adding NaOH solution to adjust the pH value to obtain impregnation liquid rich in active components;
(3) preparation of the catalyst:
g. soaking the carrier obtained in the step e in the soaking solution prepared in the step f in the same volume;
h. at room temperature, NaBH was slowly added with stirring4And g, adding the aqueous solution into the material obtained in the step g for reduction, taking out the impregnated catalyst precursor, washing with water, and drying to obtain a catalyst finished product.
2. The preparation method according to claim 1, wherein the molar ratio of Si to Al to X is 1: 0.9-1.5: 0.1-0.5, wherein X is one or more of Fe, Cu, Co, Ce, Mg and La.
3. The preparation method according to claim 1, wherein the loading amount of the active component Ni is 7-14% of the weight of the catalyst.
4. The preparation method according to claim 1, wherein the stirring speed in the preparation step b is 80-200 r/min, the temperature is controlled at 40-60 ℃, and the treatment time is 0.5-1.5 h; and c, the stirring speed in the step c is 150-280 r/min, the temperature is controlled at 60-80 ℃, the treatment time is 1-2 h, and the pH value is 7-9.
5. The method according to claim 1, wherein the silicate in step c is one or more selected from sodium silicate, magnesium silicate, aluminum silicate, iron silicate, calcium silicate and potassium silicate; the alkali liquor is one or more of sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium carbonate, potassium hydroxide and potassium bicarbonate.
6. The preparation method according to claim 1, wherein the roasting temperature in the preparation step e is 600-900 ℃ and the roasting time is 3-5 h.
7. The method of claim 1, wherein the carrier sheet is formed to have a dimension Φ 3 x 3mm in the step e.
8. The method according to claim 1, wherein the NaOH solution in the step f has a concentration of 0.05 to 0.2mol/L and a pH of 7 to 7.5.
9. The method according to claim 1, wherein the temperature in the step g is controlled to be 50-70 ℃ and the dipping time is 1.5-3 h.
10. The method according to claim 1, wherein the reduction time in the preparation step h is 1 to 2 hours.
CN202010459855.6A 2020-05-27 2020-05-27 Preparation method of slurry bed methane synthesis catalyst Pending CN113731422A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116459837A (en) * 2023-04-28 2023-07-21 山东理工大学 Nickel oxide/pseudo-boehmite catalyst and preparation method and application thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3988262A (en) * 1974-07-03 1976-10-26 Haldor Topsoe A/S Methanation catalyst and process for preparing the catalyst
CN102690157A (en) * 2012-06-05 2012-09-26 中国科学院山西煤炭化学研究所 Process for synthesizing methane through synthesis gas
CN102872875A (en) * 2012-09-19 2013-01-16 太原理工大学 Slurry bed methanation catalyst, preparing method and application
CN104056641A (en) * 2014-07-08 2014-09-24 赛鼎工程有限公司 Preparation method and application of slurry reactor sulfur-resistant methanation Raney nickel catalyst
CN104353463A (en) * 2014-11-04 2015-02-18 赛鼎工程有限公司 Anti-carbon synthesis gas methanation catalyst, preparation method and application thereof
CN110026197A (en) * 2019-02-28 2019-07-19 山西潞安矿业(集团)有限责任公司 Ni-based methanation catalyst and its controllable type solution combustion the preparation method and application
CN110624537A (en) * 2018-06-25 2019-12-31 中国石油化工股份有限公司 Preparation method of phthalate hydrogenation catalyst

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3988262A (en) * 1974-07-03 1976-10-26 Haldor Topsoe A/S Methanation catalyst and process for preparing the catalyst
CN102690157A (en) * 2012-06-05 2012-09-26 中国科学院山西煤炭化学研究所 Process for synthesizing methane through synthesis gas
CN102872875A (en) * 2012-09-19 2013-01-16 太原理工大学 Slurry bed methanation catalyst, preparing method and application
CN104056641A (en) * 2014-07-08 2014-09-24 赛鼎工程有限公司 Preparation method and application of slurry reactor sulfur-resistant methanation Raney nickel catalyst
CN104353463A (en) * 2014-11-04 2015-02-18 赛鼎工程有限公司 Anti-carbon synthesis gas methanation catalyst, preparation method and application thereof
CN110624537A (en) * 2018-06-25 2019-12-31 中国石油化工股份有限公司 Preparation method of phthalate hydrogenation catalyst
CN110026197A (en) * 2019-02-28 2019-07-19 山西潞安矿业(集团)有限责任公司 Ni-based methanation catalyst and its controllable type solution combustion the preparation method and application

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116459837A (en) * 2023-04-28 2023-07-21 山东理工大学 Nickel oxide/pseudo-boehmite catalyst and preparation method and application thereof
CN116459837B (en) * 2023-04-28 2024-02-02 山东理工大学 Nickel oxide/pseudo-boehmite catalyst and preparation method and application thereof

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