KR19990024978A - Iron Supported Zeolite Catalysts for Hydrocarbon Production - Google Patents

Abstract

The present invention relates to an iron-supported zeolite catalyst for the production of hydrocarbons, and more particularly, using an ion-exchanged-Y zeolite as a support and preparing iron as a main catalyst to produce a hydrocarbon in the process of producing a hydrocarbon by a hydrogenation reaction of carbon dioxide. When used, the invention relates to an iron-supported zeolite catalyst for the production of hydrocarbons which is capable of significantly improving the conversion of carbon dioxide, olefin selectivity and the synthesis of selective C ₂₊ hydrocarbons.

Description

Iron Supported Zeolite Catalysts for Hydrocarbon Production

The present invention relates to an iron-supported zeolite catalyst for the production of hydrocarbons, and more particularly, using an ion-exchanged-Y zeolite as a support and preparing iron as a main catalyst to produce a hydrocarbon in the process of producing a hydrocarbon by a hydrogenation reaction of carbon dioxide. When used, the invention relates to an iron-supported zeolite catalyst for the production of hydrocarbons which is capable of significantly improving the conversion of carbon dioxide, olefin selectivity and synthesis of selective C ₂₊ hydrocarbons.

The global warming problem caused by rising concentrations of green house effect gases such as carbon dioxide and methane gas in the atmosphere is becoming a serious problem causing various effects on the earth. According to the IPCC (Intergovernmental Panel on Climate Change) report, which has accumulated up-to-date knowledge of global warming issues, the average temperature in the world will rise by about 0.3 ° C every 10 years in the 21st century if no special measures are taken. By 2025, it will rise by about 1 ° C, and by the end of the 21st century, it will be about 3 ° C. The recent adverse weather effects on the global environment, including extreme weather events that occur in various parts of the world, include damage to crops, changes in precipitation, destruction of ecosystems, and rising sea levels due to meteorological changes. Global warming is expected to threaten human survival someday.

The UN Convention on Climate Change was adopted at the United Nations Conference on Environment and Development in June 1992, and on March 21, 1994, the Convention entered into force to regulate the generation of greenhouse gases that affect global warming. These greenhouse gases have been greatly increased due to rapid industrial development, and there are various gases such as CO ₂ , CH ₄ , CFC, NO _x and SO _x . Among them, carbon dioxide is known to contribute more than 50% to the overall greenhouse effect, which is one of the most serious environmental pollution sources. Therefore, efforts to control or utilize the amount of carbon dioxide emitted in large quantities to the atmosphere are urgently required.

At present, the concentration of carbon dioxide in the atmosphere has increased from 280ppm to 353ppm before the Industrial Revolution. In order to prevent the increase of carbon dioxide concentration in the air, there are active measures to conserve the global environment by regulating the amount of fossil fuel used or the amount of carbon dioxide generated, along with active measures around the world. However, in the current industrial system, actual statistics show that 73% of the world's energy sources rely on fossil fuels such as oil and coal, so the use of fossil fuels and raw materials that generate carbon dioxide will continue to be quite long. As expected, fundamental blocking of the source of carbon dioxide is impossible at this point. Therefore, there is an urgent need to develop technologies to recycle carbon dioxide from burning fossil fuels into fuels or useful compounds.

Therefore, in order to reduce the emission of carbon dioxide, alternative alternative energy has been proposed along with the development of alternative clean energy that does not use fossil fuels, and the release and recycling of carbon dioxide released as a temporary or complementary measure. Accordingly, research on the recovery and recycling of carbon dioxide is actively being conducted worldwide.

Currently, various researches are being conducted on the recycling method of carbon dioxide. Among them, chemical immobilization by hydrogenation of carbon dioxide provides fuel and resources at the same time, thus maintaining the convenience of using fossil fuel without significantly changing the existing industrial system. The advantage is that you can. The fields most studied as chemical immobilization by hydrogenation of carbon dioxide include methanol synthesis and hydrogenation by hydrogenation.

Methanol synthesis has been actively studied and has made considerable progress, and has been put into practical use. However, due to the thermodynamic limitations of the synthesis, it is difficult to increase the conversion to methanol, and there is a problem in that the utility value as a fuel has limitations.

On the other hand, the synthesis of hydrocarbons not only receive much less thermodynamic restrictions than methanol, but also has the advantage that it can be replaced by the current energy source and raw materials of the petrochemical industry. There are two main methods of synthesizing hydrocarbons.

The first method is a two-step synthesis method of synthesizing methanol by converting carbon dioxide and synthesizing a hydrocarbon compound through a continuous reaction of the produced methanol [Japanese Patent Laid-Open No. 11-190,638; 120,191], and the second method is to directly synthesize hydrocarbons by reacting carbon dioxide with hydrogen [G, A, Somorjai, J. Catal, 52, 291 (1978); C. H. Bartholomew., J. Catal, 52, 291 (1978); M. D. Lee, Bull. Chem. Soc. Jpn., 62, 2756 (1989).

In fact, the study of synthesizing hydrocarbon compounds through the continuous reaction of methanol is very similar to synthesizing methanol from the synthesis gas of carbon monoxide and hydrogen and shows high catalytic activity under low pressure conditions of CuO / ZnO / Al ₂ O Many studies using ₃ catalyst systems have been reported [GCChichen, CMHay, HDVandervell, KCWaugh, J. Catal., 103, 79 (1987)].

However, the method of synthesizing hydrocarbons from carbon dioxide mainly has a carbon number of 1, using catalysts such as iron and cobalt, which are used in Fischer-Tropsch reactions producing gasoline and waxes from existing syngas. Although methane can be synthesized, synthesis with hydrocarbons having 2 or more carbon atoms is not known. It is thought that carbon dioxide is inhibited from carbon chain growth due to the dilution of catalyst surface oxygen due to the high oxygen concentration at the surface of the catalyst, unlike the case of carbon monoxide, which is synthesized from chain growth of catalyst surface carbon. .

Meanwhile, as a method for synthesizing a compound having two or more carbon atoms from carbon dioxide, a direct method of inducing a Fischer-Tropsch reaction using a catalyst such as iron and cobalt and an activity of synthesizing methanol from carbon dioxide are shown. A stepwise method using a hybrid catalyst composed of a catalyst and a catalyst showing high activity in the synthesis of gasoline from methanol and methanol (Methanol-To-Gasoline, MTG) has been proposed.

However, the conversion of carbon dioxide from high-value hydrocarbons such as olefins and gasoline, which is a direct method by conventional methods, has a technical problem that the growth of carbon chain is suppressed due to the dilution of catalytic surface oxygen. The countermeasure that there was was necessary.

The present invention uses an alkali metal such as lithium, sodium, potassium, rubidium as a cocatalyst in the hydrogenation of carbon dioxide as a co-catalyst in order to solve the above problems in the conventional method for producing a hydrocarbon by the hydrogenation reaction of carbon dioxide and ion to the alkali metal Iron-supported catalyst using exchanged-Y zeolite as a support, which has high catalytic activity and olefin selectivity in the preparation of hydrocarbons and newly improved iron-supported zeolite catalyst for hydrocarbon production to synthesize hydrocarbons having 2 or more carbon atoms. The purpose is to provide.

The present invention is characterized in that an iron-supported zeolite catalyst for producing hydrocarbons, in which iron is supported as a main catalyst in a zeolite carrier ion-exchanged with an alkali metal as a promoter and reduced and activated in a catalyst for hydrocarbon production using iron.

In addition, the present invention is a method for producing a hydrocarbon using a catalyst from carbon dioxide, carbon dioxide and hydrogen on the iron-supported zeolite catalyst under the reaction temperature of 200 to 500 ℃ and reaction pressure of 1 to 50 atm: 1: 1.0 Another aspect of the present invention is a method for producing a hydrocarbon in which a mixed gas mixed at a volume ratio of -5.0 is introduced at a space velocity of 1000 to 2000 ml / (g-catalyst / hour) to perform hydrogenation of carbon dioxide.

The present invention will be described in more detail as follows.

In the present invention, zeolite used as a support for constituting the catalyst system has not been precedent for its application because it not only lowers the adsorption amount of carbon dioxide due to its strong acidity but also hinders the growth of surface carbon. However, in the present invention, in order to solve this problem, the acidity of the support and the overall catalyst system was controlled by ion exchange of alkali metal to zeolite, and at the same time, alkali metal acted as a promoter to improve the chain growth and olefin selectivity of surface carbon. I found it effective. In general, alkali metals have different electron donating abilities, which can be used to control the distribution of products.

Due to the large surface area and the dispersibility of the zeolite, iron, which is a catalytically active metal, is evenly supported on the surface of the zeolite in a uniform size, thereby increasing the activity of the catalyst. As a side effect, alkali metals are supported by ion-exchange, which is more evenly dispersed on the surface than impregnated, and due to sintering at the surface of the catalyst generated during high temperature reduction There is an advantage that the surface area reduction phenomenon is reduced.

According to the present invention, in order to maximize the increase in the amount of chemisorption of carbon dioxide in the hydrogenation of carbon dioxide, the amount of alkali metal applied to the zeolite is Fischer-Tropsch reaction (alkali metal: atomic ratio of iron = 1: 1: Unlike 10), it greatly exceeds the range as a cocatalyst. However, when excessively excessive, the surface area of iron, which is a catalytically active metal, is reduced due to the migration of alkali metals on the zeolite surface. Therefore, it is found that the adsorption amount of carbon dioxide decreases when it exceeds the supported amount (alkaline metal: iron = 1: 2 atomic ratio) [Glen Connell, JA Dumesic, J. catal., 92, 17 (1985). ; P. H. Choi, K. W. Jun, S. J. Lee, M. J. Choi, K. W. Lee, Catal. Letters, 40, 115 (1996)]. Thus, when the alkali metal is supported on the zeolite by ion exchange, the above problems may be solved as the alkali metal is immobilized on the catalyst surface due to the interaction for achieving an electrostatic equilibrium with the support.

The present invention will be described in more detail based on the preparation of the catalyst as follows.

The first process is to prepare a zeolite.

Zeolite can be used in addition to the Y-type and X-type, even when the X-type can be used to obtain the same effect. Synthesis method can be synthesized by the synthesis method disclosed in US Patent No. 3,130,009.

The production process will be described taking Y-type zeolite as an example.

The composition ratio of zeolite and sodium is as shown in Equation 1 below.

However, (alpha) is 2.4-7.0, (beta) is 6.1-10, (gamma) is 95-280.

As a second process, Li-Y, Na-Y, K-Y, and Rb-Y zeolites are synthesized by ion-exchanging the respective alkali metals using the Na-Y zeolite prepared as a parent.

As a starting material for ion exchange, Na-Y zeolite synthesized by the above method is used. To synthesize a lithium-substituted zeolite, the synthesized Na-Y zeolite was added to a 0.5 M LiNO ₃ solution (eg, 250 mL) and ion-exchanged several times, for example, three times at 80 to 85 ° C. for 10 to 12 hours. Prepare a Li-Y zeolite.

In addition, zeolites ion-exchanged with K ⁺ and Rb ⁺ , respectively, are also prepared by the same method as for preparing a lithium-substituted zeolite. Na-Y zeolite is added to a 0.5M KNO ₃ , 0.5M RbNO ₃ solution and then 80 to KY and Rb-Y zeolites were prepared by ion exchange several times at 85 ° C. for 10 to 12 hours.

As a third process, a catalyst in which iron is immersed is prepared by using the zeolite ion-exchanged with the alkali metal as a carrier and iron as a catalyst.

First, an aqueous salt solution containing iron is prepared, and the pH of this solution is maintained at 1 to 3 to prevent precipitation of iron, and then impregnated in the Y zeolite carrier ion-exchanged with alkali metal prepared by the above method.

Then, the fourth process is drying and firing.

Drying and baking are dried at 100-150 degreeC for 12 hours, and baked at 450-550 degreeC for 12 to 24 hours, and an iron supported zeolite catalyst is manufactured. At this time, the iron-containing salt is used one selected from iron chloride, iron nitrate, iron sulfate, iron acetate and iron oxalate, the iron immersion content is preferably contained 10 to 30% by weight based on the carrier.

If the iron immersion content is less than 10% by weight, there is a problem in the catalytic activity, and if it exceeds 30% by weight, there is a problem in the degree of dispersion on the catalyst surface. In addition, when the pH is out of the above range, a phenomenon occurs in which iron is precipitated before being supported on the carrier.

The iron-supported zeolite catalyst prepared as described above should be subjected to an appropriate pre-reaction treatment. The pre-reaction treatment consists of a reduction process and an activation process of the catalyst.

First, the reduction of the catalyst is a process of flowing hydrogen to the catalyst for 12 to 16 hours at a flow rate of 1,000 to 2,000 ml / g-catalyst and time at a temperature of 1 to 20 atm and 250 to 600 ° C. Iron oxide is changed into a metal state.

In addition, in order to show high activity of the catalyst in the conversion reaction of carbon dioxide to hydrocarbons, a catalyst is activated. The catalyst is activated at a temperature of 10 to 50 atm and at a temperature of 200 to 500 ° C. for 1: 20 After flowing the mixed gas mixed at a volume ratio of 1 to 2 hours at a flow rate of 1,000 to 2,000 ml / (g-catalyst and hour) for 1 to 2 hours, inertness such as argon and helium at a temperature of 1 to 20 atm and 200 to 500 ° C The gas is flowed for 1 to 2 hours while flowing the catalyst at a flow rate of 1,000 to 1,800 ml / (g-catalyst / hour) to activate the reaction.

The catalyst that has undergone the reduction and activation of such a catalyst is present in the carbonized state of the mixed metal to effectively activate the carbon dioxide.

On the other hand, the method for producing a hydrocarbon using the iron-supported zeolite according to the present invention as described above is as follows.

In converting a mixed gas of carbon dioxide and hydrogen according to the present invention into a hydrocarbon in the presence of a catalyst, one of the reactor selected from a fixed gas phase fixed bed reactor, a fluidized bed reactor, and a liquid slurry type reactor may be used. As the reaction conditions, carbon dioxide and hydrogen, which are raw materials, are mixed at a volume ratio of 1: 1.0 to 5.0. The reaction temperature is 200 to 500 ° C., the reaction pressure is 1 to 80 atmospheres, and the space velocity is hydrogenated to carbon dioxide at 1,000 to 2,000 ml / g-catalyst / hour to produce a hydrocarbon.

At this time, if the volume ratio of the mixed gas is out of the above range, high conversion cannot be expected. If the reaction temperature is less than 200 ° C., the reaction rate is insufficient and the conversion rate is low. If the reaction temperature exceeds 500 ° C., small molecules are not produced. It is advantageous that a large amount of methane is produced, thus _reducing the selectivity of C ₂₊ . In addition, if the reaction pressure is less than 1 atm, the reaction rate is too slow and a large amount of by-product methane is produced. If the pressure exceeds 80 atm, problems in the reaction operation may occur. And if the space velocity is out of the above range, a problem about the conversion rate occurs due to the change of the conditions for the contact time.

As described above, the iron-supported zeolite catalyst according to the present invention is used for the catalytic reduction reaction of carbon dioxide with hydrogen, and is made of metal on the zeolite support through the reduction process of the catalyst with hydrogen, and mixed gas of carbon dioxide and hydrogen Through activation process, it is made of carbonized metal.

Under the above reaction conditions, a hydrocarbon according to the present invention was prepared by catalytic reduction of carbon dioxide with hydrogen, which improved carbon dioxide conversion, olefin selectivity, and selective C ₂₊ hydrocarbon compared to the hydrocarbon prepared by the conventional method. It shows synthesis.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to Examples.

Production Example

Na-Y zeolite was prepared by the synthesis method disclosed in U.S. Patent No. 3,130,009, and the zeolites in the form of Li ⁺ , K ⁺ , Rb ⁺ substituted 10 g of Na-Y zeolite synthesized above were 0.5M LiNO ₃ , KNO ₃ , 250 mL of RbNO ₃ solution was added and ion-exchanged three times at 85 ° C. for 12 hours to prepare Li-Y, KY, and Rb-Y zeolites. The zeolite of the hydrogen-substituted form was added to 250 mL of 0.5 M NH ₄ NO ₃ solution and ion-exchanged three times at 85 ° C. for 12 hours to form NH ₄ -Y zeolite at 120 ° C. After drying for 12 hours and calcining at 350 ° C. for 12 hours, HY zeolite was prepared through deammoniation.

Example 1

In order to make a catalyst system in which the Li-Y zeolite carrier prepared in the above preparation was impregnated with 20% by weight, 5.4 g of Fe (NO ₃ ) ₃ .9H ₂ O was completely dissolved in water to make the total solution 60 ml. Then 4 g of Li-Y zeolite was added to the aqueous solution of iron nitrate prepared above. At this time, the pH was maintained at 2.0. The solution was slowly evaporated while maintaining the resulting aqueous solution at 60-80 ° C. with vigorous stirring. Then, after drying for 12 hours at 120 ℃ baked for 12 hours at 450 ℃ to prepare an iron supported zeolite catalyst.

Example 2

In order to make the catalyst system impregnated with 20% by weight in the Na-Y zeolite carrier prepared in the above preparation, 5.4 g of Fe (NO ₃ ) ₃ .9H ₂ O was completely dissolved in water to make the total solution 60 ml. 4 g of Na-Y zeolite was added to the aqueous solution of iron nitrate prepared above. At this time, the pH was maintained at 2.0 and the same procedure as in Example 1 to prepare an iron-supported zeolite catalyst.

Example 3

KY g of Fe (NO ₃ ) ₃ .9H ₂ O was completely dissolved in water to make the catalyst system impregnated with 20% by weight in the KY zeolite carrier prepared in Preparation Example, and the total solution was adjusted to 60 ml. 4 g of zeolite was added to the aqueous solution of iron nitrate prepared above. At this time, the pH was maintained at 2.0 and the same procedure as in Example 1 to prepare an iron-supported zeolite catalyst.

Example 4

In order to make a catalyst system in which 20% of the Rb-Y zeolite carrier prepared in the above preparation was impregnated by weight ratio, 5.4 g of Fe (NO ₃ ) ₃ .9H ₂ O was completely dissolved in water to make the total solution 60 ml. 4 g of Rb-Y zeolite was then added to the aqueous solution of iron nitrate prepared above. At this time, the pH was maintained at 2.0 and the same procedure as in Example 1 to prepare an iron-supported zeolite catalyst.

Comparative Example 1

In order to make the catalyst system impregnated with 20% by weight in the HY zeolite carrier prepared in the preparation example, 5.4 g of Fe (NO ₃ ) ₃ .9H ₂ O was completely dissolved in water, and the total solution was adjusted to 60 ml. 4 g of zeolite was added to the aqueous solution of iron nitrate prepared above. At this time, the pH was maintained at 2.0 and the same procedure as in Example 1 to prepare a catalyst.

Comparative Example 2

To make the iron catalyst without carrier, 4.0 g of Fe (NO ₃ ) ₃ · 9H ₂ O was taken and completely dissolved in water, and the total solution was adjusted to 100 ml. At this time, the pH was maintained at 1.0. While maintaining the resulting aqueous solution at 50-60 ° C. while stirring, 0.3 M ammonia water was titrated at a rate of 150 ml / h until the pH of the whole solution reached 6.0-8.5, and then the precipitated solution was stirred for another 1 hour. Filtration and washing with high tertiary distilled water were repeated several times. Then, the catalyst was prepared by drying in an air atmosphere at 450 ° C. for 12 hours after drying at 120 ° C. for 24 hours.

Experimental Example

0.5 g of the catalysts prepared in Examples 1 to 4 and Comparative Examples 1 and 2 were taken and reduced in a fixed bed reactor under a hydrogen stream of 450 ° C. and 2,000 ml / (g-catalyst · hour) for 16 hours. Subsequently, a mixed gas (volume ratio of hydrogen / carbon dioxide = 3) was flowed into the catalyst for 1 hour at a flow rate of 1800 ml / (g-catalyst / hour) at 10 atm and 300 ° C, and then helium gas was flowed at a temperature of 10 atm and 300 ° C. It was activated by flowing the catalyst for 1 hour at a flow rate of 1,200 mL / (g-catalyst / hour). The hydrogenation reaction was then carried out by contacting the catalyst with a mixture gas of carbon dioxide and hydrogen (volume ratio of H ₂ / CO ₂ = 3) at 10 atm and 300 ° C. at a flow rate of 1,800 ml / g-catalyst.

After 12 hours of contact, the same concentration of product was obtained and the reaction proceeded for 48 hours. The results obtained at this time are shown in Table 1 below.

division catalyst Conversion rate (C mol%) Hydrocarbon yield (C mol%) Hydrocarbon Distribution (C mol%) Olefin Selectivity (C mol%) C ₁ C ₂ C ₃ C ₄ C ₅₊ Example 1 Fe / Li-Y 26.8 20.1 16.8 11.4 16.4 12.7 42.7 64.7 Example 2 Fe / Na-Y 30.2 26.8 12.3 10.2 17.8 14.6 45.1 75.4 Example 3 Fe / K-Y 27.3 22.5 10.6 10.0 16.0 13.4 50.9 81.0 Example 4 Fe / Rb-Y 28.5 24.6 9.3 9.8 15.3 12.8 52.8 85.6 Comparative Example 1 Fe / H-Y 10.2 7.7 72.6 15.2 7.7 3.0 1.5 0.4 Comparative Example 2 Fe ₂ O ₃ 15.2 12.2 47.0 19.9 14.5 8.8 9.8 1.5

As shown in Table 1, it can be seen that the iron-supported zeolite catalysts prepared in Examples 1 to 4 according to the present invention are particularly excellent in activity compared to the catalysts prepared in Comparative Examples 1 to 2. In the hydrogenation reaction of carbon dioxide, many researches up to now have focused only on potassium as a promoter, but in the present invention, a high promoter effect is obtained by ion-exchanging not only potassium but also alkali metals such as lithium, sodium, and rubidium to zeolite. I could see that.

The results shown in Table 1 show that the C ₅₊ hydrocarbon and olefin selectivity gradually increased as the electron donating degree of the alkali metal increased, and this phenomenon was closely related to the basicity of the catalyst system. Therefore, the distribution of hydrocarbons can be seen because the electron donating ability of the alkali metal itself is different at the same time to control the acidity of the carrier, which is valuable from the viewpoint of selectively synthesizing high value-added compounds industrially. Can be said to be large.

As described above, the iron-supported zeolite catalyst according to the present invention uses a -Y zeolite ion-exchanged with an alkali metal as a carrier and is supported by iron, thereby supporting the carrier due to the difference in electron donating ability of each alkali metal. It can be seen that the basicity of the catalyst system can be easily controlled and the adsorption amount of carbon dioxide can also be controlled, thereby facilitating the selective synthesis of hydrocarbons, and the ion-exchanged alkali metal controls the basicity of the catalyst system. It acts as a catalyst to increase the activity of the catalyst and the selectivity of olefins.

In addition, iron and alkali metals present on the surface have a relatively strong interaction with the zeolite carrier, and thus can be uniformly distributed on the catalyst surface, thereby preventing sintering on the catalyst surface resulting from the high temperature reduction process. As a result, it is possible to increase the activity of the catalyst by preventing the reduction of the surface area of the catalyst.

Claims (9)

A catalyst for producing a hydrocarbon using iron, wherein the iron-supported zeolite catalyst for producing hydrocarbons is characterized in that iron is supported as a main catalyst on a zeolite carrier ion-exchanged with an alkali metal as a promoter and is reduced and activated. The iron-supported zeolite catalyst for producing hydrocarbons according to claim 1, wherein the alkali metal used as the cocatalyst is lithium, sodium, potassium or rubidium. The iron-supported zeolite catalyst for producing hydrocarbons according to claim 1, wherein the zeolite used as the support is X type or Y type. The iron-supported zeolite catalyst for producing a hydrocarbon according to claim 1, wherein the iron is supported in an iron aqueous salt solution selected from iron chloride, iron nitrate, iron sulfate, iron acetate, and iron oxalate. The iron-supported zeolite catalyst for producing hydrocarbons according to claim 1, wherein the iron is contained in an amount of 5 to 50% by weight based on the total iron-supported zeolite catalyst. The hydrocarbon as claimed in claim 1, wherein the reduction is performed by flowing hydrogen for 12 to 16 hours at a flow rate of 1,000 to 2,000 ml / (g-catalyst / hour) at a temperature of 1 to 20 atm and a temperature of 250 to 600 ° C. Iron-supported zeolite catalyst for preparation. The method according to claim 1, wherein the activation is performed at a flow rate of 1,000 to 2,000 ml / g-catalyst and time at a flow rate of 1:20 at a pressure of 10 to 50 atm and a temperature of 200 to 500 ° C. in a volume ratio of 1:20. After the passage of time, the iron-supported zeolite for hydrocarbon production, which was carried out by flowing an inert gas at a flow rate of 1,200 to 1,800 / (g-catalyst / hour) for 1 to 2 hours at a temperature of 1 to 20 atm and 100 to 500 ° C catalyst. In the method for producing a hydrocarbon by hydrogenation of carbon dioxide, carbon dioxide and hydrogen are 1: 1.0 to 1 at a reaction temperature of 200 to 500 ° C. and a reaction pressure of 1 to 50 atm under the iron-supported zeolite catalyst according to claim 1. Method for producing a hydrocarbon, characterized in that the hydrogenation reaction of carbon dioxide by introducing a mixed gas mixed at a volume ratio of 5.0 to 2,000 ml / (g-catalyst, time) at a space velocity. The method of claim 8, wherein the hydrogenation reaction is performed in a slurry slurry reactor, a gaseous fixed bed reactor, or a fluidized bed reactor.