KR102217720B1 - Metanation catalyst with high hydrostability and the method for preparing thereof - Google Patents

Abstract

The present invention relates to a catalyst for synthesizing methane having excellent durability and a method for preparing the same, and more particularly, to CO, CO ₂ And a catalyst for synthesizing methane from syngas containing H ₂ , comprising: a carrier; And iron (Fe), calcium (Ca), or a combination thereof supported on the carrier. Nickel (Ni); And a catalyst for synthesizing methane including magnesium (Mg) and a method for preparing the same.
According to the present invention, since the catalyst has excellent durability even in a high temperature environment of 700° C. or higher exposed to moisture, and has a high carbon dioxide conversion rate, modification of the catalyst and deterioration of properties do not occur under conditions including high temperature and high pressure steam. Therefore, the process efficiency of methane synthesis can be improved.

Description

Methanation catalyst with high hydrostability and the method for preparing thereof having excellent moisture durability

The present invention relates to a catalyst for synthesizing methane having excellent durability and a method for producing the same, and more particularly, to a synthesis gas comprising carbon monoxide, carbon dioxide and hydrogen together with an excessive amount of steam. It relates to a nickel-based catalyst and a method for preparing the same.

Methane is the simplest alkane compound as a compound with a molecular formula of CH ₄ and is also a main component of natural gas. The bonding angle of methane is 109.5 degrees, and when one methane molecule is burned by oxygen, one carbon dioxide (CO ₂ ) molecule and two water molecules (H ₂ O) are produced. Methane is attracting attention as a fuel because it is relatively abundant among alkanes.

Meanwhile, methane as described above may be synthesized from synthesis gas, and the synthesis gas refers to a mixture gas of hydrogen (H ₂ ), carbon dioxide (CO ₂ ), and carbon monoxide (CO). Looking at the generation process, it is generated by reforming a liquid hydrocarbon compound or natural gas through an oxidizing agent, or through a gasification process of biomass such as coal or wood chips.

Synthetic gas generated in this way is mainly used to synthesize compounds such as ammonia, methanol, and methane, and recently, the synthesis of next generation synthetic fuels such as Fischer-Tropsch synthesis or DME (Di-Methyl-Ether). The importance is increasing as an intermediate raw material gas in the manufacturing process.

The reaction for synthesizing methane by reacting carbon monoxide (CO), carbon dioxide (CO ₂ ) and hydrogen (H ₂ ) is as follows.

CO + 3H ₂ → CH ₄ + H ₂ O (Reaction heat: 206kJ/mol) ... Reaction Formula 1

CO ₂ + 4H ₂ → CH ₄ + 2H ₂ O (Reaction heat: 165kJ/mol) ... Reaction Formula 2

Referring to Reaction Schemes 1 and 2, when carbon monoxide or carbon dioxide and hydrogen react to synthesize methane (CH ₄ ), a lot of heat is generated, and the temperature inside the catalyst and the reactor rises to a high temperature of about 600°C or higher. . Therefore, in the case of the methane synthesis catalyst, high temperature durability that can withstand a temperature of at least 600°C is required to withstand high heat generated during the synthesis reaction.

As a method for solving the problem caused by such a high exothermic reaction, there is a method of cooling the heat generated during the methane synthesis reaction by injecting water with high heat capacity in a vapor state together with reaction gases such as carbon monoxide, carbon dioxide and hydrogen (US 1974). -503684, etc.). However, for this, a catalyst that does not deteriorate and does not deteriorate in properties under high temperature and high pressure conditions including steam is required.

Meanwhile, in the case of a general methane synthesis process, a high concentration of methane is finally synthesized using a method of increasing the methane conversion rate step by step by constructing a multistage reaction system due to high reaction heat. At this time, since water and carbon monoxide generated during methane synthesis in each step of the reaction react to produce some carbon dioxide, the use of a catalyst having a high conversion rate of carbon dioxide at the rear end of the multistage reactor is advantageous to increase process efficiency.

Therefore, it is expected to be useful in related fields when a catalyst having excellent durability at a high temperature of 700° C. or higher and without deterioration and deterioration in properties is developed under high temperature and high pressure conditions including steam.

One aspect of the present invention is to provide a catalyst that performs an effective methane synthesis reaction even under high temperature and high pressure conditions including a large amount of steam.

Another aspect of the present invention is to provide a method of preparing a catalyst having excellent moisture durability as described above.

According to one aspect of the present invention, CO, CO ₂ And a catalyst for synthesizing methane from syngas containing H ₂ , comprising: a carrier; And iron (Fe), calcium (Ca), or a combination thereof supported on the carrier. Nickel (Ni); And magnesium (Mg), a catalyst for methane synthesis is provided.

The catalyst, 20 to 85 parts by weight of a carrier per 100 parts by weight of the total catalyst; And iron (Fe) 0 to 10 parts by weight, calcium (Ca) 0 to 10 parts by weight, or a combination thereof; 20 to 40 parts by weight of nickel; And it is preferable to include more than 0 20 parts by weight of magnesium.

The carrier is preferably alumina, silica, or a combination thereof.

According to another aspect of the invention, dispersing the catalyst precursor in water; Heating the catalyst precursor dispersed in water; Introducing aqueous ammonia to induce precipitation; Removing moisture from the precipitated catalyst to obtain a solid content; Removing a basic component from the solid content using distilled water; Drying; And there is provided a method for producing a methane synthesis catalyst comprising the step of heat treatment.

The catalyst precursor is a carrier precursor; And an iron (Fe) precursor, a calcium (Ca) precursor, or a combination thereof supported on the carrier. Nickel (Ni) precursor; And a magnesium (Mg) precursor.

The carrier precursor is preferably aluminum nitrate 9 hydrate ((Al ₂ NO ₃ ) ₃ 9H ₂ O), tetraethyl orthosilicate (Si(OC ₂ H ₅ ) ₄ ) or a combination thereof.

The nickel precursors include nickel nitrate hexahydrate (Ni(NO ₃ ) ₂ ·6H ₂ O), nickel acetate tetrahydrate ((CH ₃ CO ₂ ) ₂ Ni·4H ₂ O), nickel chloride hexahydrate (NiCl ₂ ·6H ₂ O) and nickel carbonate tetrahydrate (NiCO ₃ ·2Ni(OH) ₂ ·4H2O) is preferably selected from the group consisting of.

The magnesium precursor is magnesium nitrate hexahydrate (Mg(NO ₃ ) _2· 6H ₂ O), magnesium acetate tetrahydrate ((CH ₃ CO ₂ ) ₂ Mg·4H ₂ O), magnesium chloride hexahydrate (MgCl ₂ ·6H ₂ O) and magnesium carbonate ((MgCO ₃ ) ₄ Mg(OH) ₂ ·5H ₂ O) is preferably selected from the group consisting of.

The calcium precursor is calcium nitrate tetrahydrate (Ca(NO ₃ ) ₂ ·4H ₂ O), calcium chloride dihydrate (CaCl ₂ ·2H ₂ O), calcium acetate (Ca(CH ₃ COO) ₂ ·2H ₂ O), calcium hydroxide It is preferably selected from the group consisting of (Ca(OH) ₂ ) and calcium carbonate (CaCO ₃ ).

The iron precursors are ferrous nitrate 9 hydrate (Fe(NO ₃ ) ₂ ·9H ₂ O), ferrous chloride tetrahydrate (FeCl ₂ ·4H ₂ O), ferric chloride hexahydrate (FeCl ₃ ·6H ₂ O) and ferrous sulfate 7 It is preferably selected from the group consisting of hydrates (FeSO ₄ ·7H ₂ O).

The heating step is preferably carried out at a temperature of 50 to 60 ℃.

The step of inducing the precipitation is preferably performed at pH 9 to pH 10.

The step of removing the basic component is preferably performed so that the pH of the recovered distilled water is 7 to 8.

The drying step is preferably carried out at a temperature of 190 to 250 ℃.

The heat treatment step is preferably carried out at a temperature of 700 to 900 ℃.

According to the present invention, since the catalyst has excellent durability even in a high temperature environment of 700° C. or higher exposed to moisture, and has a high carbon dioxide conversion rate, modification of the catalyst and deterioration of properties do not occur under conditions including high temperature and high pressure steam. Therefore, the process efficiency of methane synthesis can be improved.

1 is a graph showing the result of measuring the conversion rate of carbon monoxide and hydrogen of the catalyst of Comparative Example 1 according to whether or not steam is included.
FIG. 2 is a graph showing the results of measuring the conversion rates of carbon monoxide and hydrogen of the catalysts disclosed in Comparative Examples 1 and 1 to 4 under a steam condition.

Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings. However, embodiments of the present invention may be modified in various other forms, and the scope of the present invention is not limited to the embodiments described below.

The present invention is a synthesis gas that is obtained through gasification such as coal or biomass, or from a by-product gas such as petrochemical industry, that is, CO, CO ₂ And a catalyst used in a method of synthesizing methane, which is a main component of natural gas, using an H ₂ mixed gas, and a method for producing the same.

According to the invention CO, CO ₂ And a catalyst for synthesizing methane from syngas containing H ₂ , wherein the catalyst includes a carrier; And iron (Fe), calcium (Ca), or a combination thereof supported on the carrier. Nickel (Ni); And magnesium (Mg).

In more detail, the catalyst, 20 to 85 parts by weight of a carrier per 100 parts by weight of the total catalyst; And iron (Fe) 0 to 10 parts by weight, calcium (Ca) 0 to 10 parts by weight, or a combination thereof; 20 to 40 parts by weight of nickel; And it is preferable to include more than 0 20 parts by weight of magnesium.

In the present invention, the iron (Fe), calcium (Ca) or a combination thereof; Nickel (Ni); And in magnesium (Mg), iron (Fe), calcium (Ca) or a combination thereof is additionally included along with nickel and magnesium, and only when the composition of the above components is satisfied, the effect of the present invention can be obtained. I can. More preferably, the component is iron (Fe) 0 to 10 parts by weight, calcium (Ca) 0 to 10 parts by weight, or a combination thereof.

On the other hand, when nickel is contained in an amount of less than 20 parts by weight per 100 parts by weight of the total catalyst, the CO ₂ conversion rate is lowered and the catalyst efficiency is lowered, and when nickel exceeds 40 parts by weight per 100 parts by weight of the total catalyst, a sintering phenomenon occurs. Thus reducing the life of the catalyst there is a problem.

Meanwhile, the magnesium is preferably contained in an amount of more than 0 and 20 or less by weight per 100 parts by weight of the total catalyst. When magnesium contains more than 20 parts by weight per 100 parts by weight of the total catalyst, the CO conversion rate is lowered.

In the present invention, based on 100 parts by weight of the total catalyst, the remaining content is the content of the carrier. Preferably, the carrier is included in an amount of 20 to 85 parts by weight per 100 parts by weight of the total catalyst.

The carrier may be alumina, silica, or a combination thereof.

On the other hand, the catalyst of the present invention as described above comprises the steps of dispersing a catalyst precursor in water; Heating the catalyst precursor dispersed in water; Inducing precipitation by adding aqueous ammonia: removing moisture from the precipitated catalyst to obtain a solid content; Removing a basic component from the solid content using distilled water; Drying; And it may be prepared by a method comprising the step of heat treatment.

In the present invention, the catalyst precursor is a carrier precursor; And an iron (Fe) precursor, a calcium (Ca) precursor, or a combination thereof supported on the carrier. Nickel (Ni) precursor; And a magnesium (Mg) precursor.

In the method for preparing the catalyst of the present invention, details related to the catalyst, such as specific components and contents of the catalyst, are as described above with respect to the catalyst.

The carrier precursor is preferably aluminum nitrate 9 hydrate ((Al ₂ NO ₃ ) ₃ 9H ₂ O), tetraethyl orthosilicate (Si(OC ₂ H ₅ ) ₄ ) or a combination thereof.

The nickel precursors include nickel nitrate hexahydrate (Ni(NO ₃ ) ₂ ·6H ₂ O), nickel acetate tetrahydrate ((CH ₃ CO ₂ ) ₂ Ni·4H ₂ O), nickel chloride hexahydrate (NiCl ₂ ·6H ₂ O) and nickel carbonate tetrahydrate (NiCO ₃ ·2Ni(OH) ₂ ·4H2O) is preferably selected from the group consisting of.

The magnesium precursor is magnesium nitrate hexahydrate (Mg(NO ₃ ) ₂ ·6H ₂ O), magnesium acetate tetrahydrate ((CH ₃ CO ₂ ) ₂ Mg·4H ₂ O), magnesium chloride hexahydrate (MgCl ₂ ·6H ₂ O) and magnesium carbonate ((MgCO ₃ ) ₄ Mg(OH) ₂ ·5H ₂ O) is preferably selected from the group consisting of.

The calcium precursor is calcium nitrate tetrahydrate (Ca(NO ₃ ) ₂ ·4H ₂ O), calcium chloride dihydrate (CaCl ₂ ·2H ₂ O), calcium acetate (Ca(CH ₃ COO) ₂ ·2H ₂ O), calcium hydroxide It is preferably selected from the group consisting of (Ca(OH) ₂ ) and calcium carbonate (CaCO ₃ ).

The iron precursors are ferrous nitrate 9 hydrate (Fe(NO ₃ ) ₂ ·9H ₂ O), ferrous chloride tetrahydrate (FeCl ₂ ·4H ₂ O), ferric chloride hexahydrate (FeCl ₃ ·6H ₂ O) and ferrous sulfate 7 It is preferably selected from the group consisting of hydrates (FeSO ₄ ·7H ₂ O), but is not particularly limited thereto.

In the step of dispersing the precursor in water, the amount of water for dispersion is not particularly limited, and an appropriate amount of water for sufficient dispersion may be used. However, it is preferable to use 3 to 5 times of water based on the weight of the total catalyst precursor.

When the dispersion of the catalyst precursor is completed, a step of heating the dispersed catalyst precursor is performed, and the heating step is preferably performed at a temperature of 50 to 60°C.

Then, ammonia water is added to induce precipitation, and the step of inducing precipitation is preferably performed at a pH of 9 to 10. When the above pH range is satisfied, a high metal crystallinity can be obtained.

Although the ammonia water used in the step of inducing the precipitation is not particularly limited, it is preferable to use ammonia water having a concentration of about 30 wt%, and the step of inducing the precipitation is more preferably carried out with stirring.

After the precipitation is generated by the step of inducing the affinity, the step of aging by raising the temperature may be additionally performed. The aging step is preferably carried out over 2 hours to 6 hours at a temperature of 80 to 100 ℃. When the aging step is completed, the temperature is cooled to room temperature.

Subsequently, a step of obtaining a solid content is performed by removing moisture from the precipitated catalyst. The process of removing the moisture is not particularly limited, but a solid content may be obtained, for example, by removing the water through a filter. The filter that can be used at this time is not particularly limited, but, for example, a polypropylene (PP) or polyester-based filter cloth having excellent basic resistance and high temperature stability of 100° C. or higher may be used.

Thereafter, the step of removing the base component from the solid content is performed using distilled water, and the step of removing the base component is preferably performed so that the pH of the recovered distilled water is 7 to 8. That is, it is preferable to remove the base component by flowing distilled water into the solid content, and if the base component is not sufficiently removed, the properties of the catalyst may be deteriorated.

The solid content from which the base is removed may be obtained as a final catalyst through a drying step and a heat treatment step.

The drying step is preferably performed at a temperature of 190 to 250°C, and when the temperature of the drying step is less than 190°C, there is a problem that drying is not sufficiently performed, and when the drying step exceeds 250°C There is a concern that catalyst properties may be modified. The drying step is more preferably carried out at 200 to 220 ℃.

On the other hand, the step of the heat treatment is preferably carried out at a temperature of 700 to 900 ℃, if the temperature of the heat treatment step is less than 700 ℃ sintering is not sufficiently performed, the catalytic activity may be reduced, and the heat treatment step is 900 If it exceeds ℃, there is a concern that sintering of the catalyst occurs and the catalyst properties are deformed. The heat treatment step is more preferably carried out at 700 to 800 ℃.

Furthermore, the step of reducing the catalyst may be performed subsequent to the heat treatment step. Nickel in the catalyst obtained after the heat treatment exists in the form of nickel oxide, and nickel oxide can be converted to nickel by performing the reduction step of the catalyst. The step of reducing the catalyst is preferably carried out for 4 to 8 hours at a temperature of 400 to 800 ℃.

Hereinafter, the present invention will be described in more detail through specific examples. The following examples are only examples to aid understanding of the present invention, and the scope of the present invention is not limited thereto.

< Example >

Comparative example One

4 liters of distilled water, 396 g of nickel nitrate as a nickel precursor, 422 g of magnesium nitrate as a magnesium precursor, and 1709 g of ammonium nitrate as an alumina precursor were mixed and heated to 60°C. After adding 1.1 liters of 30wt% aqueous ammonia to the mixed solution, the mixture was stirred sufficiently, and then, ammonia water was added slowly, so that the pH of the mixed solution was 9 to 10. Subsequently, the temperature was raised to 90° C. and stirred for 2 hours. After that, the temperature was cooled to room temperature and the stirred solution was filtered to remove water to obtain a solid content, and further, the basic component inside the solid was removed with distilled water, and the pH of the distilled water recovered at this time was set to 7 to 8. Thereafter, the solid component from which the base component was removed was calcined at 500° C. for 6 hours to prepare a catalyst including 20 parts by weight of nickel and 10 parts by weight of magnesium.

Example One

20 weight of nickel in the same process as the process disclosed in Comparative Example 1, except that 29 g of an iron precursor was mixed together and 1671 g of ammonium nitrate was mixed in the manufacturing process of the catalyst disclosed in Comparative Example 1 Parts, 10 parts by weight of magnesium, and 1% by weight of iron were included to prepare a catalyst.

Example 2

In the process of manufacturing the catalyst disclosed in Comparative Example 1, 145 g of an iron precursor was mixed together, and 1519 g of ammonium nitrate was mixed, and 0 weight of calcium was carried out by the same process as the process disclosed in Comparative Example 1. A catalyst was prepared including parts, 20 parts by weight of nickel, 10 parts by weight of magnesium, and 5% by weight of iron.

Example 3

In the manufacturing process of the catalyst disclosed in Comparative Example 1, 145 g of an iron precursor and 118 g of a calcium precursor were mixed together, and 1313 g of ammonium nitrate was mixed, and the same process as the process disclosed in Comparative Example 1 was used. , 20 parts by weight of nickel, 10 parts by weight of magnesium, 5% by weight of iron, and 5% by weight of calcium were prepared to prepare a catalyst.

Example 4

In the manufacturing process of the catalyst disclosed in Comparative Example 1, except that 594 g of a nickel precursor, 145 g of an iron precursor, and 118 g of a calcium precursor were mixed together, and 938 g of ammonium nitrate was mixed, the process disclosed in Comparative Example 1 and By the same process, a catalyst was prepared including 30 parts by weight of nickel, 10 parts by weight of magnesium, 8% by weight of iron, and 8% by weight of calcium.

Experimental example One

The catalyst prepared in the comparative example contains only a gas containing 1/3 the ratio of CO/H _{2 as} a reaction gas after 5 hours reduction at 700° C. under a hydrogen atmosphere, and 45 vol% of CO and H ₂ In the case of additionally injecting steam (H ₂ O) into the reactor, the pressure was fixed to 20 bar and reacted.

At this time, a reaction experiment was performed while varying the reaction temperature from 250° C. to 450° C., and the composition of the reaction product was analyzed using a gas analyzer. CH ₄ or CO ₂ was generated by the reaction of CO and H ₂ , and the CO conversion rate according to the reaction temperature was calculated based on the consumption amount of CO, and the CO conversion rate result according to the steam atmosphere is shown in FIG. 1.

The results are shown in Fig. 1, and as can be seen in Fig. 1, in the case of the catalyst of Comparative Example 1, it can be confirmed that the CO conversion rate increases in the vicinity of 250°C in the condition where steam is not included, and at 220 to 250°C It means that the catalyst is active. On the other hand, it can be seen that the catalyst starts to show activity between about 270 to 300° C. under the condition including steam.

In this way, when the catalytic activity temperature is increased, the initial reaction temperature must be increased, and thus more energy is consumed, which in turn increases the operating cost of the process. Therefore, it is advantageous that the active temperature of the catalyst is low from the viewpoint of the efficiency and economy of the reaction.

Experimental example 2

The catalysts prepared in Comparative Examples 1 and 1 to 4 were reduced at 700° C. for 5 hours in a hydrogen atmosphere, and then a gas containing 1/3 of the ratio of CO/H _{2 as} a reaction gas and CO and H ₂ 45 vol % Steam (H ₂ O) was injected into the reactor and the pressure was fixed at 20 bar to react.

At this time, a reaction experiment was performed while varying the reaction temperature from 250° C. to 450° C., and the composition of the reaction product was analyzed using a gas analyzer. CH ₄ by the reaction of CO and H ₂ Alternatively, CO ₂ is generated, and the CO conversion rate according to the reaction temperature is calculated based on the consumption amount of CO, and the CO conversion rate result according to the catalyst composition is shown in FIG. 2.

As can be seen in Figure 2, it can be seen that the catalysts of Examples 1 to 4 according to the present invention increase the CO conversion rate in the vicinity of 250° C. even in the condition containing steam, which means that the catalyst is active at 220 to 250° C. Means what you see.

Although the embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and variations are possible without departing from the technical spirit of the present invention described in the claims. It will be obvious to those of ordinary skill in the field.

Claims (15)

As a catalyst for synthesizing methane from syngas containing CO, CO ₂ and H ₂ ,
The catalyst may contain more than 0 to 10 parts by weight of iron (Fe) per 100 parts by weight of the total catalyst; 20 to 40 parts by weight of nickel (Ni); Greater than 0 to 20 parts by weight of magnesium (Mg); And the remainder of the carrier.
The method of claim 1, wherein the catalyst,
A catalyst for methane synthesis further comprising more than 0 to 10 parts by weight of calcium (Ca).
The catalyst for methane synthesis according to claim 1, wherein the carrier is alumina, silica, or a combination thereof.
Carrier precursors; And dispersing a catalyst precursor including an iron (Fe) precursor, a nickel (Ni) precursor, and a magnesium (Mg) precursor supported on the carrier in water.
Heating the catalyst precursor dispersed in water;
Introducing ammonia water to induce precipitation at pH 9 to pH 10;
Removing moisture from the precipitated catalyst to obtain a solid content;
Removing a basic component from the solid by using distilled water so that the recovered distilled water has a pH of 7 to 8;
Drying; And
Heat treatment step
Method for producing a methane synthesis catalyst comprising a.
The method of claim 4, wherein the catalyst precursor further comprises a calcium (Ca) precursor.
The method of claim 4, wherein the carrier precursor is aluminum nitrate 9 hydrate ((Al ₂ NO ₃ ) ₃ 9H ₂ O), tetraethyl orthosilicate (Si(OC ₂ H ₅ ) ₄ ) or a combination thereof. Manufacturing method.
The method of claim 4, wherein the nickel precursor is nickel nitrate hexahydrate (Ni(NO ₃ ) ₂ ·6H ₂ O), nickel acetate tetrahydrate ((CH ₃ CO ₂ ) ₂ Ni·4H ₂ O), nickel chloride hexahydrate (NiCl ₂ ·6H ₂ O) and nickel carbonate tetrahydrate (NiCO ₃ ·2Ni(OH) ₂ ·4H2O) A method for producing a methane synthesis catalyst selected from the group consisting of.
The method of claim 4, wherein the magnesium precursor is magnesium nitrate hexahydrate (Mg(NO ₃ ) ₂ ·6H ₂ O), magnesium acetate tetrahydrate ((CH ₃ CO ₂ ) ₂ Mg·4H ₂ O), and magnesium chloride hexahydrate (MgCl ₂ ·6H ₂ O) and magnesium carbonate ((MgCO ₃ ) ₄ Mg(OH) ₂ ·5H ₂ O) A method for producing a methane synthesis catalyst selected from the group consisting of.
The method of claim 5, wherein the calcium precursor is calcium nitrate tetrahydrate (Ca(NO ₃ ) ₂ ·4H ₂ O), calcium chloride dihydrate (CaCl ₂ ·2H ₂ O), and calcium acetate (Ca(CH ₃ COO) ₂ · 2H ₂ O), calcium hydroxide (Ca(OH) ₂ ) and calcium carbonate (CaCO ₃ ) A method for producing a methane synthesis catalyst selected from the group consisting of.
The method of claim 4, wherein the iron precursor is ferrous nitrate 9 hydrate (Fe(NO ₃ ) ₂ ·9H ₂ O), ferrous chloride tetrahydrate (FeCl ₂ ·4H ₂ O), ferric chloride hexahydrate (FeCl ₃ ·6H ₂ O) and ferrous sulfate heptahydrate (FeSO ₄ · 7H ₂ O) A method for producing a methane synthesis catalyst selected from the group consisting of.
The method of claim 4, wherein the heating is performed at a temperature of 50 to 60°C.
delete delete The method of claim 4, wherein the drying is performed at a temperature of 190 to 250°C.
The method of claim 4, wherein the heat treatment is performed at a temperature of 700 to 900°C.

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