Catalyst for direct hydrogenation of carbon dioxide, method for producing same, and method for preparing hydrocarbon compound using same

Abstract

The present invention relates to a catalyst useful for a direct hydrogenation reaction of carbon dioxide, a method for producing same, and a method for preparing a hydrocarbon compound using same, and provides a metal-oxide-based catalyst comprising an oxide-based support and catalyst particles containing iron supported on the support, a method for producing same, and a method for preparing a hydrocarbon compound using same.

Description

Carbon dioxide direct hydrogenation catalyst, preparation method thereof, and preparation method of hydrocarbon compound using same

[0001] [Cross-reference with related applications]

[0002] This application claims the benefit of priority to Korean Patent Application No. 10-2023-0119552, filed September 8, 2023, the entire disclosure of which is incorporated herein by reference.

[0003] [Technical Field]

[0004] The present invention relates to a catalyst useful for direct hydrogenation of carbon dioxide, a method for producing the same, and a method for producing a hydrocarbon compound through direct hydrogenation of carbon dioxide using the same.

[0005]

[0006] Coal and oil are fossil fuels that account for more than 50% of total energy and have been used as important energy sources for mankind for the past several centuries. During various energy conversion processes, mankind has emitted thermodynamically stable carbon dioxide without any separate post-treatment process.

[0007] However, as it has recently become known that carbon dioxide is the main greenhouse gas that contributes to 55% of global warming, various technologies for removing carbon dioxide have been proposed, and among these, technologies that use catalysts to hydrogenate carbon dioxide and convert it into high value-added chemical fuels such as alpha olefins or liquid fuels such as gasoline and diesel are the most preferred because they are easy to technically link with existing industrial processes, have a large market for the products produced, and can easily process large amounts of carbon dioxide.

[0008] Carbon dioxide conversion technology is a technology that converts carbon dioxide, the most stable carbon compound, into other useful compounds. For example, there is a technology that converts carbon dioxide into carbon monoxide, methanol, and hydrocarbon compounds through carbon dioxide hydrogenation.

[0009] The hydrogenation reaction of carbon dioxide generally consists of a first stage in which carbon dioxide supplied as a reactant is converted into carbon monoxide through the reverse water gas shift (RWGS) reaction, and a second stage in which the produced carbon monoxide is converted into hydrocarbons by combining with hydrogen through the Fischer-Tropsch (FTS) reaction.

[0010] At this time, the reverse water gas shift reaction of the first stage is an endothermic reaction and can be expressed by the following equation 1.

[0011] [Formula 1]

[0012]

[0013] The reverse water gas shift reaction in the first stage is a reversible reaction and can be carried out under conditions that provide partial conversion of carbon dioxide and hydrogen.

[0014] Carbon monoxide produced in the first stage undergoes a Fischer-Tropsch synthesis (FTS) reaction in the second stage, and the Fischer-Tropsch synthesis reaction is exothermic and can be expressed by the following equation 2.

[0015] [Formula 2]

[0016] 1) If the product is paraffin:

[0017] 2) If the product is an olefin:

[0018] Although the reverse water gas shift reaction in the first stage and the Fischer-Tropsch synthesis reaction in the second stage are sometimes configured as separate processes and connected, the reverse water gas shift reaction in the first stage is an endothermic reaction that requires a high reaction temperature to secure a high conversion rate, which reduces the energy efficiency of the overall conversion process. Therefore, research is being conducted on a direct carbon dioxide hydrogenation reaction that can perform the reverse water gas shift reaction in the first stage and the Fischer-Tropsch synthesis reaction in the second stage simultaneously using a single catalyst and process.

[0019] This direct hydrogenation reaction of carbon dioxide, in which the reverse water gas shift reaction and the Fischer-Tropsch synthesis reaction are performed simultaneously in one catalyst and process, is an exothermic reaction and can be expressed by the following equation 3.

[0020] [Formula 3]

[0021] 1) If the product is paraffin:

[0022] 2) If the product is an olefin:

[0023] In particular, when the heat of reaction accumulates inside the catalyst particle during the Fischer-Tropsch synthesis reaction, the selectivity for the hydrocarbon to be synthesized decreases and the catalyst deteriorates. Therefore, it is very important to quickly remove the heat of reaction from the catalyst particle. Accordingly, when forming a fixed catalyst layer, a method of appropriately controlling the reactivity was performed by including a certain amount of inert support or forming a catalyst layer by mixing arbitrary inert particles with the catalyst particles.

[0024] However, when using an inert support, since the support itself is a porous material, there is a problem that the catalytic material permeates the inside of the support, causing a catalytic reaction to occur inside, making it difficult to control the exothermic reaction inside. In addition, when using inert particles physically mixed with catalytic particles, uniform mixing is difficult, causing the catalytic material to clump together, causing a problem that the reaction occurs unevenly.

[0025] In addition, slurry reactions such as fluidized bed reactions are effective in terms of heat control and reaction efficiency, but in this case, securing the mechanical properties of the catalyst is necessary, and a method of adding a structural promoter to the catalyst has been performed. However, when an inactive structural promoter is added, the content of the active component decreases, and there is a serious problem of a decrease in the carbon dioxide conversion rate due to a decrease in the active component.

[0026] [Prior Art Literature]

[0027] [Patent Document]

[0028] (Patent Document 1) KR 10-1405090 B1 (June 2, 2014)

[0029]

[0030] The present invention is intended to solve the above problems, and aims to provide a catalyst useful for direct hydrogenation of carbon dioxide, which has high reaction activity by including a high content of catalytically active component and has excellent specific surface area and mechanical properties by including a structural co-catalyst component.

[0031] In addition, the present invention aims to provide a method for producing the catalyst.

[0032] In addition, the present invention aims to provide a method for producing a hydrocarbon compound including a direct hydrogenation reaction step of carbon dioxide in the presence of the catalyst.

[0033]

[0034] To solve the above problem, the present invention provides a catalyst, a method for producing the same, and a method for producing a hydrocarbon compound.

[0035] (1) The present invention relates to a metal-oxide catalyst, comprising: an oxide-based carrier; and catalyst particles containing iron supported on the carrier, wherein the surface area of ​​the catalyst is 1 m 2 A catalyst is provided having an iron content of 5 mg to 15 mg.

[0036] (2) The present invention provides a catalyst according to (1) above, which contains iron in an amount of 50 wt% or more and 65 wt% or less based on 100 wt% of the total catalyst.

[0037] (3) In the present invention, in the above (1) or (2), the specific surface area of ​​the catalyst is 50 m 2 / g to 100 m 2 / g provides a catalyst.

[0038] (4) The present invention provides a catalyst in any one of the above (1) to (3), wherein the oxide-based carrier is at least one selected from the group consisting of SiO2, Al2O3, and zeolite.

[0039] (5) The present invention provides a catalyst according to any one of the above (1) to (4), wherein the iron is in the hematite phase.

[0040] (6) The present invention provides a catalyst in which, in any one of the above (1) to (5), the iron is activated by at least one selected from the group consisting of magnetite, iron carbide, and metallic iron (Fe).

[0041] (7) The present invention provides a catalyst according to any one of the above (1) to (6), wherein the catalyst particles further include a co-catalyst metal, and the co-catalyst metal is at least one selected from the group consisting of copper, potassium, and sodium.

[0042] (8) The present invention provides a catalyst in which, in any one of the above (1) to (7), the catalyst particles further include at least one co-catalyst metal selected from the group consisting of copper, potassium, and sodium, and the co-catalyst metal is included in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the catalyst.

[0043] (9) The present invention provides a catalyst for direct hydrogenation of carbon dioxide in any one of the above (1) to (8).

[0044] (10) The present invention comprises a step (S1) of preparing iron-oxide-based catalyst particles; a step (S2) of supporting a promoter metal on the catalyst particles; and a step (S3) of drying and calcining, wherein the step (S1) comprises a step (S1-1) of preparing a first solution having an iron weight concentration of 20 g / L to 100 g / L by dissolving an iron precursor in a solvent, and introducing and dispersing an oxide-based carrier into the first solution to prepare a second solution; a step (S1-2) of stirring the second solution to increase the temperature to 40°C to 90°C, and adding a precipitant aqueous solution to prepare a precipitate including iron-oxide-based supported particles; and a step (S1-3) of washing and filtering the precipitate and then drying it, wherein the oxide-based carrier in the step (S1-1) has a surface area of ​​1 m of the oxide-based carrier. 2 A method for producing a catalyst according to any one of the above (1) to (9), wherein the content of iron is introduced in an amount of 10 mg to 150 mg, and the co-catalyst metal is supported in an amount such that the weight ratio of iron / co-catalyst metal is 5 to 15 in the step (S2).

[0045] (11) The present invention provides a method for producing a catalyst, wherein in the step (S1-2), the precipitant aqueous solution contains a precipitant at a weight concentration of 50 g / L to 250 g / L, and the precipitant is at least one selected from the group consisting of sodium carbonate, ammonium carbonate, ammonia water, and sodium hydroxide.

[0046] (12) The present invention provides a method for producing a catalyst, wherein, in step (S1-2), a precipitant aqueous solution is added until the pH in the reactor becomes 7 to 8 in (10) or (11).

[0047] (13) The present invention provides a method for producing a catalyst, wherein the iron precursor is at least one selected from the group consisting of iron nitrate, iron sulfate, iron acetate, iron chloride, iron bromide, iron iodide, and iron hydrates, in any one of (10) to (12).

[0048] (14) The present invention provides a method for producing a catalyst, wherein in any one of the above (10) to (13), the stirring in the above step (S1-2) is performed at a speed of 100 rpm to 1000 rpm.

[0049] (15) The present invention provides a method for producing a catalyst, wherein, in any one of the above (10) to (14), stirring is further performed for 0.5 to 24 hours after completion of addition of the precipitant aqueous solution in the step (S1-2).

[0050] (16) The present invention provides a method for producing a catalyst, wherein in any one of the above (10) to (15), the co-catalyst metal in the step (S2) is at least one selected from the group consisting of copper, potassium, and sodium.

[0051] (17) The present invention provides a method for producing a catalyst, wherein the step (S2) is performed by an incipient wetness impregnation method in any one of the above (10) to (16).

[0052] (18) The present invention provides a method for producing a catalyst, wherein in any one of the above (10) to (17), drying in the above steps (S1-3) and (S3) is performed at 100°C to 200°C for 5 to 24 hours, respectively.

[0053] (19) The present invention provides a method for producing a catalyst, wherein in any one of the above (10) to (18), calcination in the step (S3) is performed by heat treatment at a temperature of 200°C to 600°C for 1 hour to 12 hours.

[0054] (20) The present invention provides a method for producing a hydrocarbon compound, which comprises a step of direct hydrogenation of carbon dioxide in the presence of a catalyst as described in any one of (1) to (9) above.

[0055]

[0056] The catalyst according to the present invention has a high catalytic reaction activity by containing a high content of iron, which is a catalytic component, and having a specific surface area and iron content per catalyst surface area within a specific range, and has excellent carbon dioxide conversion rate and turnover frequency (TOF), as well as excellent selectivity for high value-added C5 or higher hydrocarbon compounds.

[0057] In addition, the method for manufacturing a catalyst according to the present invention can manufacture a catalyst having a specific surface area and an iron content per surface area within a specific range while including iron within a specific range by controlling the ratio of an oxide-based carrier and an iron precursor to support iron on the carrier, drying the carrier, and then supporting a co-catalyst metal thereon at a controlled ratio.

[0058] In addition, the method for producing hydrocarbons according to the present invention can be more useful for producing hydrocarbon compounds of C5 or higher because it has excellent carbon dioxide conversion rate and TOF while also having high selectivity for hydrocarbon compounds of C5 or higher by using the catalyst.

[0059]

[0060] Terms or words used in this specification and claims should not be interpreted as limited to their usual or dictionary meanings, but should be interpreted as meanings and concepts that conform to the technical idea of ​​the present invention, based on the principle that the inventor can appropriately define the concept of the term to explain his or her own invention in the best way.

[0061]

[0062] The present invention provides a catalyst useful for direct hydrogenation of carbon dioxide, particularly a Fischer-Tropsch synthesis reaction, a method for producing the same, and a method for producing a hydrocarbon compound using the same.

[0063] Hereinafter, the present invention will be described in more detail.

[0064]

[0065] catalyst

[0066] The present invention provides a catalyst having excellent catalytic activity while being supported on a carrier and having excellent specific surface area and mechanical properties.

[0067] According to one embodiment of the present invention, the catalyst comprises a metal-oxide-based catalyst, an oxide-based carrier; and catalyst particles containing iron supported on the carrier, and the surface area of ​​the catalyst is 1 m 2 It is characterized by a content of iron of 5 mg to 15 mg per day.

[0068] In addition, the catalyst contains iron in an amount of 50 wt% or more and 65 wt% or less based on 100 wt% of the total catalyst, and has a specific surface area of ​​50 m 2 / g to 100 m 2 It could be / g.

[0069]

[0070] The hydrogenation reaction of carbon dioxide generally consists of a first stage in which carbon dioxide supplied as a reactant is converted into carbon monoxide through the reverse water gas shift (RWGS) reaction, and a second stage in which the produced carbon monoxide is converted into hydrocarbons by combining with hydrogen through the Fischer-Tropsch synthesis reaction (FTS).

[0071] In particular, a method of adding a structural promoter (support) to the catalyst has been performed to control the heat of reaction and improve the mechanical properties inside the catalyst particles during the Fischer-Tropsch synthesis reaction. However, when an inert structural promoter is added, the content of the catalyst active component decreases, and there is a serious problem of a decrease in the carbon dioxide conversion rate due to the decrease in the active component.

[0072] In addition, when the reverse water gas shift reaction in the first stage and the Fischer-Tropsch synthesis reaction in the second stage are performed continuously as separate processes, there is a problem that the energy efficiency of the entire conversion process is reduced because the reverse water gas shift reaction in the first stage is an endothermic reaction that requires a high reaction temperature to secure a high conversion rate. Therefore, research is being conducted on a carbon dioxide direct hydrogenation reaction that can perform the reverse water gas shift reaction in the first stage and the Fischer-Tropsch synthesis reaction in the second stage simultaneously in a single catalyst and process, and the development of such a catalyst is necessary.

[0073]

[0074] According to one embodiment of the present invention, the catalyst has a high content of iron in the form of catalyst particles supported on an oxide-based carrier as a structural promoter, and has a specific surface area and iron content per surface area within a specific range, thereby having high catalytic reaction activity in a process of simultaneously performing a Fischer-Tropsch synthesis reaction and a reverse water gas shift reaction and a Fischer-Tropsch synthesis reaction, and has excellent carbon dioxide conversion rate and turnover frequency (TOF), as well as excellent selectivity for high value-added C5 or higher hydrocarbon compounds.

[0075]

[0076] The catalyst according to one embodiment of the present invention is a metal-oxide-based supported catalyst, comprising an oxide-based carrier and catalyst particles supported on the carrier, wherein the catalyst particles contain iron. In addition, the iron may be in the hematite phase.

[0077] In addition, the catalyst is activated through pretreatment before being used in the direct hydrogenation reaction of carbon dioxide, and at this time, the iron can be activated by one or more selected from the group consisting of magnetite, iron carbide, and metallic iron (Fe).

[0078] As another example, the iron in the catalyst may be included in the catalyst in the form of hematite and then activated through pretreatment to one or more selected from the group consisting of magnetite, iron carbide, and metallic iron (Fe).

[0079] In addition, the catalyst contains iron in an amount of 50 wt% or more and 65 wt% or less based on 100 wt% of the total catalyst, and the specific surface area of ​​the catalyst is 50 m 2 / g to 100 m 2 / g, and the catalyst surface area is 1 m 2The content of iron per unit may be 5 mg to 15 mg. Specifically, the iron is included in an amount of 55 wt% to 60 wt% based on 100 wt% of the total catalyst, and the specific surface area of ​​the catalyst is 52 m 2 / g to 70 m 2 / g, and the catalyst surface area is 1 m 2 The content of iron per molecule may be 8 mg to 12 mg. In this case, when producing a hydrocarbon compound through direct hydrogenation of carbon dioxide using the catalyst, the catalytically active component is sufficient, so that the catalytic reaction activity is excellent, while the selectivity for hydrocarbon compounds of C5 or higher and the carbon dioxide conversion rate are excellent.

[0080] The above oxide-based carrier serves to improve the mechanical strength and specific surface area of ​​the catalyst as a structural cocatalyst, and specifically may be at least one selected from the group consisting of SiO2, Al2O3, and zeolite.

[0081] In addition, the oxide-based carrier may be SiO2 or Al2O3, taking into account that it does not adversely affect the performance and physico-chemical properties of the catalyst due to the interaction with the catalyst component and the improvement of the mechanical strength and specific surface area of ​​the catalyst.

[0082] The above catalyst particles may further include a co-catalyst metal as needed, and the co-catalyst metal may be at least one selected from the group consisting of copper, potassium, and sodium.

[0083] In addition, the catalyst particles may further include at least one selected from the group consisting of copper, potassium, and sodium, and may include the co-catalyst metal in an amount of 0.1 to 20 parts by weight, specifically 1 to 20 parts by weight, based on 100 parts by weight of the catalyst.

[0084] In addition, when two or more of the above-mentioned co-catalyst metals are included, the two or more co-catalyst metals may be included in the same amount.

[0085] If the catalyst particles contain more copper, the reducing power of the catalyst can be further increased, and if the catalyst particles contain more potassium, the basicity of the catalyst surface can be increased, and it can be more advantageous in improving the selectivity for hydrocarbon compounds having a C5 or higher content.

[0086]

[0087] Method for manufacturing a catalyst

[0088] The present invention provides a method for producing the above catalyst.

[0089] According to one embodiment of the present invention, the method for producing the catalyst comprises the steps of (S1) producing iron-oxide-based catalyst particles; (S2) supporting a promoter metal on the catalyst particles; and (S3) drying and calcining, wherein the step (S1) comprises the steps of: dissolving an iron precursor in a solvent to produce a first solution having an iron weight concentration of 20 g / L to 100 g / L; introducing and dispersing an oxide-based carrier into the first solution to produce a second solution; stirring the second solution to raise its temperature to 40°C to 90°C, and adding a precipitant aqueous solution to produce a precipitate including iron-oxide-based carrier particles; and washing and filtering the precipitate and then drying it (S1-3), wherein the oxide-based carrier in the step (S1-1) has a surface area of ​​1 m of the oxide-based carrier. 2 It is characterized in that the content of iron per unit is introduced in an amount of 10 mg to 150 mg, and in the step (S2), the co-catalyst metal is loaded in an amount such that the weight ratio of iron / co-catalyst metal is 5 to 15.

[0090]

[0091] Hereinafter, the manufacturing method of the above catalyst is explained in more detail step by step.

[0092] (S1) Step

[0093] The above step (S1) is a step for producing iron-oxide catalyst particles in which iron, which is a catalytically active component, is supported on an oxide-based carrier, and can be performed by the steps of: dissolving an iron precursor in a solvent to produce a first solution having an iron weight concentration of 20 g / L to 100 g / L; adding and dispersing an oxide-based carrier into the first solution to produce a second solution; stirring the second solution to raise the temperature to 40°C to 90°C and adding a precipitant aqueous solution to produce a precipitate including iron-oxide-based supported particles; and washing and filtering the precipitate and then drying it (S1-3).

[0094]

[0095] The above step (S1-1) is a preliminary step for producing a precipitate, which is an iron-oxide catalyst cake, by carrying iron, which is a catalytically active component derived from the iron precursor, on the carrier by co-precipitation reaction of an iron precursor and an oxide-based carrier. The step is performed by dissolving the iron precursor in a solvent to produce a first solution having an iron weight concentration of 20 g / L to 100 g / L, and adding and dispersing an oxide-based carrier in the first solution to produce a second solution.

[0096] Specifically, the first solution is obtained by dissolving an iron precursor in a solvent. At this time, the iron precursor may be used without particular limitation as long as it is widely used in the art, but may be, for example, at least one selected from the group consisting of iron nitrate, iron sulfate, iron acetate, iron chloride, iron bromide, iron iodide, and hydrates thereof. Specifically, the iron precursor may be at least one selected from iron nitrate, iron chloride, iron sulfate, iron acetate, and hydrates thereof.

[0097] Additionally, the solvent used in the first solution may be at least one selected from distilled water, ethanol, methanol, and acetone, and specifically may be distilled water.

[0098]

[0099] In addition, the second solution is prepared by adding and dispersing an oxide-based carrier into the first solution, and at this time, the oxide-based carrier may be at least one selected from the group consisting of SiO2, Al2O3, and zeolite.

[0100] In addition, when preparing the second solution, the oxide-based carrier has an oxide-based carrier surface area of ​​1 m 2 It may be injected in an amount such that the content of iron per unit is 10 mg to 150 mg. Specifically, the oxide-based carrier has a surface area of ​​1 m 2 It may be administered in an amount such that the iron content per tablet is 15 mg to 130 mg, 20 mg to 100 mg, or 25 mg to 80 mg.

[0101]

[0102] The above step (1-2) is a step of producing a precipitate, which is an iron-oxide catalyst cake, by performing a co-precipitation reaction between an iron precursor and an oxide-based carrier to support iron, which is a catalytically active component derived from the iron precursor, on the carrier. This step can be performed by heating the second solution to 40°C to 90°C while stirring and adding a precipitant aqueous solution. The stirring can be performed at a speed of 100 rpm to 1000 rpm. If the precipitant aqueous solution is added while stirring under the above conditions, the oxide-based carrier can be uniformly dispersed in the solution, so that iron, which is a catalytically active component, can be evenly precipitated on the surface of the oxide-based carrier, thereby obtaining iron-oxide-based catalyst particles having a uniform composition.

[0103] In addition, the precipitant aqueous solution may be added until the pH in the reactor becomes 7 to 8, and may be stirred for 0.5 to 24 hours after the addition is completed. At this time, the stirring may be performed while maintaining the stirring speed and temperature when the precipitant aqueous solution is added.

[0104] As another example, the step (S1-2) may be performed by heating the second solution in the reactor to 40°C to 90°C while stirring at a speed of 100 rpm to 1000 rpm, adding a precipitant aqueous solution until the pH in the reactor becomes 7 to 8, and further stirring for 0.5 to 24 hours while maintaining the speed and temperature after completion of the addition.

[0105] The above precipitant aqueous solution contains a precipitant at a weight concentration of 50 g / L to 250 g / L, and the precipitant may be at least one selected from the group consisting of sodium carbonate, ammonium carbonate, ammonia water, and sodium hydroxide.

[0106]

[0107] The above step (S1-2) is a step for separating and obtaining iron-oxide catalyst particles from the manufactured precipitate, and can be performed by filtering, washing, and drying the precipitate.

[0108] The above filtration and washing may be performed according to a method widely known in the art, and the drying may be performed so that the sediment is completely dried, for example, at 100°C to 200°C for 5 to 24 hours.

[0109]

[0110] (S2) Step

[0111] The above step (S2) is a step for further supporting a promoter metal component, and can be performed by supporting the promoter metal on the iron-oxide-based catalyst particles manufactured in the above step (S1), and the promoter metal can be supported in an amount such that the weight ratio of iron / promoter metal is 5 to 15. In addition, the promoter metal can be at least one selected from the group consisting of copper, potassium, and sodium, and in this case, the supporting of the promoter metal in the above step (S2) can be performed by an incipient wetness impregnation method.

[0112] Here, the initial wetness impregnation method may be performed in the same manner as a method widely known in the art, and for example, the steps of pulverizing iron-oxide catalyst particles to obtain powder and measuring pore volume; adding and mixing a promoter metal precursor aqueous solution to the powder; and drying may be performed sequentially. At this time, the promoter metal precursor aqueous solution is added in an amount equal to the pore volume or an integer multiple thereof, and when added in an integer multiple thereof, the adding and drying may be repeated a number of times equal to the integer multiple thereof.

[0113] The above-mentioned co-catalyst metal precursor aqueous solution is a solution in which a co-catalyst metal precursor is dissolved in distilled water, and the co-catalyst metal precursor may be at least one selected from the group consisting of nitrate, sulfate, acetate, chloride, bromide, iodide, and hydrates thereof of the co-catalyst metal.

[0114] Specifically, when the above-mentioned catalyst metal is copper, the copper precursor may be at least one selected from the group consisting of copper nitrate, copper chloride, copper acetate, copper sulfate, and hydrates thereof, and more specifically, may be copper nitrate hydrate.

[0115] In addition, when the above-mentioned catalyst metal is potassium, the potassium precursor may be at least one selected from the group consisting of potassium nitrate, potassium chloride, potassium carbonate, potassium acetate, and potassium sulfate, and more specifically, may be potassium nitrate.

[0116] In addition, when the above-mentioned catalyst metal is sodium, the sodium precursor may be at least one selected from the group consisting of sodium nitrate, sodium chloride, sodium carbonate, sodium acetate, and sodium sulfate, and more specifically, may be sodium carbonate.

[0117]

[0118] (S3) Step

[0119] The above step (S3) is a step for manufacturing a catalyst in the form of oxide catalyst particles through heat treatment, which can be performed by drying and calcination. The drying can be performed at 100°C to 200°C for 5 to 24 hours, and the calcination can be performed by heat treatment at a temperature of 200°C to 600°C for 1 to 12 hours. If drying and calcination are performed under the above conditions, the iron component in the catalyst can be completely oxidized to obtain a catalyst in the form of hematite, and impurities such as moisture, nitrogen oxides, and chloride remaining in the catalyst can be removed.

[0120]

[0121] Method for producing hydrocarbon compounds

[0122] The present invention provides a method for producing a hydrocarbon compound from carbon dioxide using the above catalyst.

[0123] According to one embodiment of the present invention, a method for producing a hydrocarbon compound includes a step of directly hydrogenating carbon dioxide in the presence of the catalyst.

[0124] Here, the direct hydrogenation reaction of the carbon dioxide can be performed in the same manner as a method widely known in the art, except that the above-mentioned catalyst is used.

[0125] Specifically, the method for producing the hydrocarbon compound includes a step of loading a catalyst into a reactor and performing a reduction treatment under a hydrogen atmosphere; and a step of injecting a raw material gas and performing a direct hydrogenation reaction of carbon dioxide, wherein the direct hydrogenation reaction of carbon dioxide includes a reverse water gas shift (RWGS) reaction and a Fischer-Tropsch synthesis reaction (Fischer-Tropsch, FTS).

[0126] The above reduction treatment can be carried out by flowing hydrogen through the catalyst at 20 mL / g-catalyst / min to 100 mL / g-catalyst / min at 1 atm to 10 atm and 300°C to 500°C, and the carbon dioxide direct hydrogenation reaction can be carried out at 200°C to 500°C, the reaction pressure can be 1 atm to 100 atm, and the space velocity can be 100 h -1 20,000 h -1 It may be carried out in .

[0127] In addition, the above reaction can be performed without limitation in any reactor widely used in the art, such as a gaseous fixed bed reactor, a fluidized bed reactor, and a liquid slurry reactor.

[0128]

[0129] Example

[0130] Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement them. However, the present invention may be implemented in various different forms and is not limited to the embodiments described herein.

[0131]

[0132] Example 1

[0133] 395 m in the sedimentation reaction vessel 20.36 g of porous silica powder having a surface area of ​​ / g and 200 mL of a solution of iron nitrate hydrate (55.8 g / L) dissolved in distilled water were added and heated to 60°C while stirring at 400 rpm. At this time, the porous silica powder had a surface area of ​​1 m 2 The amount of iron per molecule was added to make the content of iron 78 mg. After the temperature of the solution reached 60℃, 180 g / L of ammonium carbonate aqueous solution was added at a rate of 2 mL / min using a syringe pump until the pH in the reactor became 7.0. After the addition was completed, the reactor was stirred at 400 rpm for 2 hours while maintaining 60℃ to produce a precipitate. After the precipitation was completed, the pH of the slurry was 7.4. The produced precipitate was separated from the solvent by filtration, washed with 2.5 L of distilled water, and dried at 110℃ for 12 hours (completely dry).

[0134] The iron content in the Fe-SiO2 powder obtained after drying was 60 wt%, and the iron content was adjusted by adding copper and potassium. An aqueous solution containing 153 g / L of copper nitrate hydrate and 153 g / L of potassium nitrate was added to the Fe-SiO2 powder so that the weight ratio of iron / (copper + potassium) was 6, thereby supporting copper and potassium. At this time, copper and potassium were supported in equal weights. After adding copper and potassium, the catalyst was manufactured by drying at 110°C for 12 hours and calcining at 400°C for 3 hours.

[0135]

[0136] Example 2

[0137] 200 m in the sedimentation reaction vessel 2 2.23 g of porous alumina (γ-Al2O3) powder with a surface area of ​​1 m / g and 200 mL of a solution of iron nitrate hydrate (55.8 g / L) dissolved in distilled water were added and heated to 60°C while stirring at 400 rpm. At this time, the porous alumina powder had a surface area of ​​1 m 2The amount of iron per molecule was added in an amount such that the content of iron per molecule was 25 mg. After the temperature of the solution reached 60°C, 180 g / L of ammonium carbonate aqueous solution was added at a rate of 2 mL / min using a syringe pump until the pH in the reactor became 7.0. After the addition was completed, the reactor was stirred at 400 rpm for 2 hours while maintaining 60°C to produce a precipitate. After the precipitation was completed, the pH of the slurry was 7.3. The produced precipitate was separated from the solvent by filtration, washed with 2.5 L of distilled water, and dried at 110°C for 12 hours (completely dry).

[0138] The iron content in the Fe-Al2O3 powder obtained after drying was 60 wt%, and the iron content was adjusted by adding copper and potassium. An aqueous solution containing 62 g / L of copper nitrate hydrate and 62 g / L of potassium nitrate was added to the Fe-Al2O3 powder so that the weight ratio of iron / (copper + potassium) was 10, thereby supporting copper and potassium. At this time, copper and potassium were supported in equal weights. After adding copper and potassium, the catalyst was manufactured by drying at 110°C for 12 hours and calcining at 400°C for 3 hours.

[0139]

[0140] Example 3

[0141] 395 m in the sedimentation reaction vessel 2 1.84 g of porous silica powder having a surface area of ​​ / g and 200 mL of a solution of iron nitrate hydrate (55.8 g / L) dissolved in distilled water were added and heated to 60°C while stirring at 400 rpm. At this time, the porous silica powder had a surface area of ​​1 m 2The amount of iron per molecule was added in an amount such that the content of iron per molecule was 15 mg. After the temperature of the solution reached 60°C, 180 g / L of ammonium carbonate aqueous solution was added at a rate of 2 mL / min using a syringe pump until the pH in the reactor became 7.0. After the addition was completed, the reactor was stirred at 400 rpm for 2 hours while maintaining 60°C to produce a precipitate. After the precipitation was completed, the pH of the slurry was 7.3. The produced precipitate was separated from the solvent by filtration, washed with 2.5 L of distilled water, and dried at 110°C for 12 hours (completely dry).

[0142] The iron content in the Fe-SiO2 powder obtained after drying was 63 wt%, and the iron content was adjusted by adding copper and potassium. An aqueous solution containing 153 g / L of copper nitrate hydrate and 153 g / L of potassium nitrate was added to the Fe-SiO2 powder so that the weight ratio of iron / (copper + potassium) was 5.5, thereby supporting copper and potassium. At this time, copper and potassium were supported in equal weights. After adding copper and potassium, the catalyst was manufactured by drying at 110°C for 12 hours and calcining at 400°C for 3 hours.

[0143]

[0144] Example 4

[0145] 395 m in the sedimentation reaction vessel 2 0.23 g of porous silica powder having a surface area of ​​ / g and 200 mL of a solution of iron nitrate hydrate (55.8 g / L) dissolved in distilled water were added and heated to 60°C while stirring at 400 rpm. At this time, the porous silica powder had a surface area of ​​1 m 2The amount of iron per molecule was added in an amount such that the content of iron per molecule was 121 mg. After the temperature of the solution reached 60°C, 180 g / L of ammonium carbonate aqueous solution was added at a rate of 2 mL / min using a syringe pump until the pH in the reactor became 7.0. After the addition was completed, the reactor was stirred at 400 rpm for 2 hours while maintaining 60°C to produce a precipitate. After the precipitation was completed, the pH of the slurry was 7.1. The produced precipitate was separated from the solvent by filtration, washed with 2.5 L of distilled water, and dried at 110°C for 12 hours (completely dry).

[0146] The iron content in the Fe-SiO2 powder obtained after drying was 69 wt%, and the iron content was adjusted by adding copper and potassium. An aqueous solution containing 15 g / L of copper nitrate hydrate and 15 g / L of potassium nitrate was added to the Fe-SiO2 powder so that the weight ratio of iron / (copper + potassium) was 13, thereby supporting copper and potassium. At this time, copper and potassium were supported in equal weights. After adding copper and potassium, the catalyst was manufactured by drying at 110°C for 12 hours and calcining at 400°C for 3 hours.

[0147]

[0148] Example 5

[0149] 395 m in the sedimentation reaction vessel 2 / g of porous silica powder and 200 mL of a solution of iron nitrate hydrate (55.8 g / L) dissolved in distilled water were added and heated to 60°C while stirring at 400 rpm. At this time, the porous silica powder had a surface area of ​​1 m 2The amount of iron per molecule was added to make 68 mg. After the temperature of the solution reached 60℃, 180 g / L of ammonium carbonate aqueous solution was added at a rate of 2 mL / min using a syringe pump until the pH in the reactor became 7.0. After the addition was completed, the reactor was stirred at 400 rpm for 2 hours while maintaining 60℃ to produce a precipitate. After the precipitation was completed, the pH of the slurry was 7.2. The produced precipitate was separated from the solvent by filtration, washed with 2.5 L of distilled water, and dried at 110℃ for 12 hours (completely dry).

[0150] The iron content in the Fe-SiO2 powder obtained after drying was 68 wt%, and the iron content was adjusted by adding copper and potassium. An aqueous solution containing 50 g / L of copper nitrate hydrate and 50 g / L of potassium nitrate was added to the Fe-SiO2 powder so that the weight ratio of iron / (copper + potassium) was 12, thereby supporting copper and potassium. At this time, copper and potassium were supported in equal weights. After adding copper and potassium, the catalyst was manufactured by drying at 110°C for 12 hours and calcining at 400°C for 3 hours.

[0151]

[0152] Comparative Example 1

[0153] 395 m in the sedimentation reaction vessel 2 10.4 g of porous silica powder having a surface area of ​​ / g and 200 mL of a solution of iron nitrate hydrate (27.9 g / L) dissolved in distilled water were added and heated to 60°C while stirring at 400 rpm. At this time, the porous silica powder had a surface area of ​​1 m 2The amount of iron per molecule was added in an amount such that the content of iron per molecule was 1.5 mg. After the temperature of the solution reached 60°C, 72 g / L of ammonium carbonate aqueous solution was added at a rate of 2 mL / min using a syringe pump until the pH in the reactor became 7.0. After the addition was completed, the reactor was stirred at 400 rpm for 2 hours while maintaining 60°C to produce a precipitate. After the precipitation was completed, the pH of the slurry was 7.5. The produced precipitate was separated from the solvent by filtration, washed with 2.5 L of distilled water, and completely dried at 110°C for more than 12 hours.

[0154] The iron content in the Fe-SiO2 powder obtained after drying was 30 wt%, and the iron content was adjusted by adding potassium. An aqueous solution containing 30 g / L of potassium carbonate was added to the Fe-SiO2 powder so that the iron / potassium weight ratio was 16, thereby supporting potassium. After adding potassium, the catalyst was manufactured by drying at 110°C for 12 hours and calcining at 400°C for 3 hours.

[0155]

[0156] Comparative Example 2

[0157] 395 m in the sedimentation reaction vessel 2 2.23 g of porous silica powder having a surface area of ​​ / g and 200 mL of a solution of iron nitrate hydrate (55.8 g / L) dissolved in distilled water were added and heated to 60°C while stirring at 400 rpm. At this time, the porous silica powder had a surface area of ​​1 m 2The amount of iron per molecule was added in an amount such that the content of iron per molecule was 13 mg. After the temperature of the solution reached 60°C, 144 g / L of ammonium carbonate aqueous solution was added at a rate of 2 mL / min using a syringe pump until the pH in the reactor became 7.0. After the addition was completed, the reactor was stirred at 400 rpm for 2 hours while maintaining 60°C to produce a precipitate. After the precipitation was completed, the pH of the slurry was 7.5. The produced precipitate was separated from the solvent by filtration, washed with 2.5 L of distilled water, and completely dried at 110°C for more than 12 hours.

[0158] The iron content in the Fe-SiO2 powder obtained after drying was 60 wt%, and the iron content was adjusted by adding copper and potassium. An aqueous solution containing 55 g / L of copper nitrate hydrate and 55 g / L of potassium nitrate was added to the Fe-SiO2 powder so that the iron / (copper + potassium) weight ratio was 10, thereby supporting copper and potassium. At this time, copper and potassium were supported in equal weights. After adding copper and potassium, the catalyst was manufactured by drying at 110°C for 12 hours and calcining at 400°C for 3 hours.

[0159]

[0160] Comparative Example 3

[0161] A 200 mL solution of iron nitrate hydrate (55.8 g / L) dissolved in distilled water was added to a precipitation reaction vessel and heated to 60°C while stirring at 400 rpm. After the temperature of the solution reached 60°C, 120 g / L of aqueous sodium hydroxide solution was added at a rate of 2 mL / min using a syringe pump until the pH in the reactor became 7.0. After the addition was completed, the reactor was maintained at 60°C and stirred at 400 rpm for an additional 2 hours to produce a precipitate. The pH of the slurry after the precipitation was completed was 7.9. The produced precipitate was separated from the solvent by filtration, washed with 2.5 L of distilled water, and completely dried at 110°C for more than 12 hours.

[0162] The iron content was controlled by adding sodium to the Fe powder obtained after drying. An aqueous solution containing 110 g / L of sodium carbonate was added to the Fe powder so that the iron / sodium weight ratio was 13, thereby supporting sodium. After adding sodium, the catalyst was manufactured by drying at 110°C for 12 hours and calcining at 400°C for 3 hours.

[0163]

[0164] Comparative Example 4

[0165] 200 m in the sedimentation reaction vessel 2 0.56 g of porous alumina (γ-Al2O3) powder with a specific surface area of ​​ / g and 200 mL of a solution of iron nitrate hydrate (55.8 g / L) in distilled water were added and heated to 60°C while stirring at 400 rpm. At this time, the porous alumina powder had a surface area of ​​1 m 2 The amount of iron per molecule was added in an amount such that the content of iron per molecule was 100 mg. After the temperature of the solution reached 60°C, 180 g / L of ammonium carbonate aqueous solution was added at a rate of 2 mL / min using a syringe pump until the pH in the reactor became 7.0. After the addition was completed, the reactor was stirred at 400 rpm for 2 hours while maintaining 60°C to produce a precipitate. After the precipitation was completed, the pH of the slurry was 7.1. The produced precipitate was separated from the solvent by filtration, washed with 2.5 L of distilled water, and dried at 110°C for 12 hours (completely dry).

[0166] The iron content in the Fe-Al2O3 powder obtained after drying was 67 wt%, and the iron content was adjusted by adding copper and potassium. An aqueous solution containing 50 g / L of copper nitrate hydrate and 50 g / L of potassium nitrate was added to the Fe-Al2O3 powder so that the weight ratio of iron / (copper + potassium) was 20, thereby supporting copper and potassium. At this time, copper and potassium were supported in equal weights. After adding copper and potassium, the catalyst was manufactured by drying at 110°C for 12 hours and calcining at 400°C for 3 hours.

[0167]

[0168] Experimental Example 1

[0169] The iron content (wt%), specific surface area, and iron content per catalyst surface area in each catalyst manufactured in the examples and comparative examples were measured, and the results are shown in Table 1 below.

[0170] (1) Iron content (wt%)

[0171] Iron content was measured using the ICP-OES method.

[0172] 0.01 g of each catalyst was aliquoted and placed in a container containing 1 mL of hydrochloric acid and hydrogen peroxide, and heated on a hot plate to dissolve. Then, two drops of a 50 wt% hydrofluoric acid solution were added to the container using a dropper, and 2 hours after the addition of the hydrofluoric acid solution, 0.1 mL of boric acid (57 g / L) was added, and the solution was allowed to stand for 12 hours to completely dissolve the catalyst. After confirming that the catalyst was completely dissolved and the solution was transparent, the solution was diluted with tertiary ultrapure water to prepare an analysis sample solution. The iron content in each sample was measured using iCAP PRO (ThermoFischer).

[0173]

[0174] (2) Specific surface area (m) 2 / g)

[0175] The specific surface area of ​​the catalysts was measured using a conventional nitrogen isothermal adsorption-desorption method based on the Brunauer-Emmett-Teller (BET) theory. Each catalyst was pretreated at 150°C for 3 h using BELPREP VAC II (MicrotracBEL), and then nitrogen isothermal adsorption-desorption results at 77 K (-196°C) were obtained using BELSORP MAX (MicrotracBEL). The specific surface area was calculated by applying the BET theory in the range of P / P0 (Relative Pressure) 0.05-0.35.

[0176]

[0177] (3) Iron content per surface area (mg / m) 2 )

[0178] Surface area 1 m 2 The iron content (mg) per unit was calculated using the following equation 4 from the iron content and specific surface area of ​​the catalyst.

[0179] [Formula 4]

[0180] Iron content per surface area (mg / m) 2 ) = [Iron content (wt%) / specific surface area (m 2 / g)]×1000 mg / g

[0181] Classification Fe content (wt%) Specific surface area (m 2 / g) Iron content per catalyst surface area (mg / m) 2 ) Example 157.2639.0 Example 257.35410.6 Example 353.1975.5 Example 464.75212.4 Example 563.95511.6 Comparative Example 130.22491.2 Comparative Example 257.01933.0 Comparative Example 368.13519.4 Comparative Example 464.84215.5

[0182] As shown in Table 1 above, it was confirmed that the catalysts manufactured in Examples 1 to 5 all had iron content, specific surface area, and iron content per catalyst surface area that met the specific ranges set forth in the present invention. On the other hand, Comparative Examples 1 to 4 did not meet all or two of the characteristics of iron content, specific surface area, and iron content per catalyst surface area.

[0183] Through this, it was confirmed that the iron content, specific surface area, and iron content per catalyst surface area, which are controlled to a specific range as suggested in the present invention, are characteristics that can be obtained by the manufacturing method suggested in the present invention, which controls the ratio of the oxide-based carrier and iron when supporting iron on the oxide-based carrier, or controls the co-catalyst metal at a measured weight ratio relative to iron.

[0184]

[0185] Experimental Example 2

[0186] The catalytic activity was confirmed by performing a direct hydrogenation reaction of carbon dioxide using the catalysts manufactured in the examples and comparative examples, and the results are shown in Table 2 below.

[0187] 0.5 g of each catalyst was charged into a fixed-bed tubular reactor (Stainless steel, 3 / 8 inch diameter), and the catalysts were activated by reduction treatment for 8 hours under a carbon monoxide atmosphere (>99.9 vol%) at 400°C before starting the reaction. Afterwards, the raw material gas (H2:CO2:N2=72:24:4 volume ratio) was introduced at a flow rate of 75 mL / min, and the reaction temperature and pressure were adjusted to 340°C and 20 bar, respectively. The reaction was performed while maintaining the same raw material gas flow rate, and the molar ratio of hydrogen to carbon dioxide in the raw material gas was 3, and nitrogen was added as an internal standard. During the 48-hour reaction, the gas phase reactants and products were analyzed by gas chromatography (GC), and the liquid phase products and byproducts were recovered in a cooling trap. The components of the liquid products were analyzed separately using GC. Fluid flow analysis before and after the reaction was performed through real-time measurements and changes in the concentration of nitrogen, an internal standard. Based on the results measured using GC, carbon dioxide (CO2) conversion, turnover frequency (TOF), and C5+ selectivity (%) were calculated.

[0188] Iron content per surface area (mg / m) 2 )CO2 conversion rate (%)TOF (h) -1 )C5+ Selectivity (%)Example 19.0444.047Example 210.6454.154Example 35.5454.440Example 412.4463.754Example 511.6473.850Comparative Example 11.2122.14Comparative Example 23.0464.132Comparative Example 319.4423.255Comparative Example 415.5423.354

[0189] As shown in Table 2 above, it was confirmed that Examples 1 to 5 were superior to Comparative Examples 1 to 4 in terms of carbon dioxide (CO2) conversion, turnover frequency (TOF), and C5+ selectivity (%). Specifically, Examples 1 to 5 showed a significant increase of more than 10 times in C5+ selectivity (%) compared to Comparative Example 1, and also showed a significant increase of about 4 times and 2 times in carbon dioxide (CO2) conversion and turnover frequency (TOF). In addition, Examples 1 to 5 showed an improvement of about 1.25 times and 1.72 times in C5+ selectivity (%) compared to Comparative Example 2 in terms of carbon dioxide (CO2) conversion and turnover frequency (TOF).

[0190] In addition, Examples 1 to 5 showed improved carbon dioxide (CO2) conversion of about 5% to 12% while showing C5+ selectivity (%) equivalent to or slightly improved compared to Comparative Examples 3 and 4, and at the same time showed a significant improvement in turnover frequency (TOF) of about 6% to 30%.

[0191] At this time, Examples 1 to 5 have a catalyst surface area of ​​1 m 2 While the iron content per unit area is between 5 mg and 15.0 mg, the catalysts of Comparative Examples 1 and 2 have a surface area of ​​1 m 2 The density of the Fe site on the catalyst surface, which is the reaction active site, was very low compared to Examples 1 to 6, with the iron content being 1.2 mg and 3.0 mg, respectively, and in the case of Comparative Examples 3 and 4, the catalyst surface area was 1 m 2 The iron content per unit is 19.4 mg and 15.5 mg, but the specific surface area is 35 m 2 / g and 42 m 2 The available catalyst surface area was half that of Example 1.

[0192] From the above results, it was confirmed that a catalyst that satisfies the iron content, specific surface area, and iron content per catalyst surface area defined in the present invention has the effect of simultaneously improving carbon dioxide (CO2) conversion rate, turnover frequency (TOF), and C5+ selectivity (%).

Claims

1. In metal-oxide catalysts, An oxide-based carrier; and catalyst particles comprising iron supported on the carrier, Surface area of ​​the above catalyst 1 m 2 A catalyst having an iron content of 5 mg to 15 mg per molecule.

2. In paragraph 1, A catalyst comprising the iron in an amount of 50 wt% or more and 65 wt% or less based on 100 wt% of the total catalyst.

3. In paragraph 1, The specific surface area of ​​the above catalyst is 50 m 2 / g to 100 m 2 / g is the catalyst.

4. In paragraph 1, A catalyst wherein the above oxide-based carrier is at least one selected from the group consisting of SiO2, Al2O3, and zeolite.

5. In paragraph 1, The above catalyst is in the form of hematite.

6. In paragraph 1, A catalyst wherein the iron is activated by at least one selected from the group consisting of magnetite, iron carbides, and metallic iron (Fe).

7. In paragraph 1, The above catalyst particles further comprise a co-catalyst metal, A catalyst wherein the above-mentioned co-catalyst metal is at least one selected from the group consisting of copper, potassium, and sodium.

8. In paragraph 1, The above catalyst particles further comprise at least one co-catalyst metal selected from the group consisting of copper, potassium and sodium, A catalyst comprising the above-mentioned cocatalyst metal in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the catalyst.

9. In paragraph 1, A catalyst that is a catalyst for direct hydrogenation of carbon dioxide.

10. Step of manufacturing iron-oxide catalyst particles (S1); A step (S2) of supporting a co-catalyst metal on the above catalyst particles; and Including a step of firing after drying (S3), The above step (S1) is a step (S1-1) of preparing a first solution having an iron weight concentration of 20 g / L to 100 g / L by dissolving an iron precursor in a solvent, and introducing and dispersing an oxide-based carrier into the first solution to prepare a second solution; Step (S1-2) of heating the second solution to 40°C to 90°C while stirring and adding a precipitant aqueous solution to prepare a precipitate including iron-oxide catalyst particles; It includes a step (S1-3) of washing and filtering the above sediment and then drying it, In the above step (S1-1), the oxide carrier has an oxide carrier surface area of ​​1 m 2 Administer in an amount that contains 10 mg to 150 mg of iron per day, A method for producing a catalyst, wherein in the step (S2), the co-catalyst metal is supported in an amount such that the weight ratio of iron / co-catalyst metal is 5 to 15.

11. In paragraph 10, In the above step (S1-2), the precipitant aqueous solution contains the precipitant in a weight concentration of 50 g / L to 250 g / L, A method for producing a catalyst, wherein the above precipitant is at least one selected from the group consisting of sodium carbonate, ammonium carbonate, ammonia water, and sodium hydroxide.

12. In paragraph 10, A method for producing a catalyst, wherein in the above step (S1-2), a precipitant aqueous solution is added until the pH in the reactor becomes 7 to 8.

13. In paragraph 10, A method for producing a catalyst, wherein the iron precursor is at least one selected from the group consisting of iron nitrate, iron sulfate, iron acetate, iron chloride, iron bromide, iron iodide, and iron hydrates.

14. In paragraph 10, A method for producing a catalyst, wherein the stirring in the above step (S1-2) is performed at a speed of 100 rpm to 1000 rpm.

15. In paragraph 10, A method for producing a catalyst, wherein stirring is performed for 0.5 to 24 hours after the addition of the precipitant aqueous solution in the above step (S1-2).

16. In paragraph 10, A method for producing a catalyst, wherein in the above step (S2), the co-catalyst metal is at least one selected from the group consisting of copper, potassium, and sodium.

17. In paragraph 10, A method for manufacturing a catalyst, wherein the above step (S2) is performed using the incipient wetness impregnation method.

18. In paragraph 10, A method for producing a catalyst, wherein drying in the above steps (S1-3) and (S3) is performed at 100°C to 200°C for 5 to 24 hours, respectively.

19. In paragraph 10, (S3) A method for producing a catalyst, wherein the calcination is performed by heat treatment at a temperature of 200°C to 600°C for 1 to 12 hours.

20. A method for producing a hydrocarbon compound comprising a direct hydrogenation reaction step of carbon dioxide in the presence of the catalyst of paragraph 1.

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