WO2021002224A1

WO2021002224A1 - Catalyst, reactor and method for producing hydrocarbon

Info

Publication number: WO2021002224A1
Application number: PCT/JP2020/024203
Authority: WO
Inventors: 康嗣橋本; 一則宮沢
Original assignee: Ｊｘｔｇエネルギー株式会社
Priority date: 2019-07-03
Filing date: 2020-06-19
Publication date: 2021-01-07
Also published as: JP2021010848A; JP7181161B2

Abstract

The present invention discloses a catalyst which contains: a copper-based catalyst element containing a copper component that is composed of at least one of copper metal and copper oxide; and an iron-based catalyst element containing an iron component that is composed of at least one of iron and iron oxide and an additive metal that is composed of at least one of an alkali metal and an alkaline earth metal. This catalyst is used for the purpose of producing a hydrocarbon from a starting material gas that contains hydrogen and at least one of carbon dioxide and carbon monoxide.

Description

Methods for producing catalysts, reactors, and hydrocarbons

The present invention relates to a catalyst, a reactor, and a method for producing a hydrocarbon.

As a method for effectively utilizing carbon dioxide contained in exhaust gas and the like, it has been studied to generate a liquid hydrocarbon having a high energy density from carbon dioxide and hydrogen in the presence of a catalyst (for example, Patent Document 1). Further, as a method for generating a liquid hydrocarbon from a raw material gas containing carbon monoxide and hydrogen, a Fischer-Tropsch (FT) reaction may be used (for example, Non-Patent Document 1).

Japanese Unexamined Patent Publication No. 7-80309

The cobalt-based catalyst usually used in the FT reaction selectively produces methane from carbon dioxide. Therefore, when a raw material containing carbon dioxide is used, methane is generated, and a liquid hydrocarbon cannot be obtained in a high yield.

The present invention provides a catalyst capable of producing a liquid hydrocarbon in a high yield from a raw material gas containing at least one of carbon dioxide or carbon monoxide and hydrogen.

The present invention contains a copper-based catalyst containing at least one of metallic copper or copper oxide, and an additive metal composed of at least one of iron or iron oxide and at least one of alkali metal or alkaline earth metal. The present invention relates to an iron-based catalyst and a catalyst containing. This catalyst is used to generate hydrocarbons from raw material gases containing at least one of carbon dioxide or carbon monoxide and hydrogen.

In another aspect, the present invention relates to a reactor used to generate a hydrocarbon from a raw material gas containing at least one of carbon dioxide or carbon monoxide and hydrogen. The reaction apparatus includes a reaction vessel having a gas inlet and a gas outlet, and a catalyst layer containing the catalyst. The catalyst layer is fixed in the reaction vessel. The catalyst layer has a first catalyst layer containing the copper-based catalyst body and a second catalyst layer containing the iron-based catalyst body, and the first catalyst layer from the gas inlet side in the reaction vessel. The catalyst layer and the second catalyst layer are laminated in this order. Alternatively, in the catalyst layer, the granular copper-based catalyst and the granular iron-based catalyst are mixed with each other, and the powder of the copper-based catalyst and the powder of the iron-based catalyst are mixed with each other. Granular molded materials may be formed by a powder mixture containing the powder of the copper-based catalyst and the powder of the iron-based catalyst.

Further, the present invention relates to a method for producing a hydrocarbon, which comprises producing a hydrocarbon from a raw material gas containing at least one of carbon dioxide or carbon monoxide and hydrogen in the presence of the above catalyst.

According to the present invention, a liquid hydrocarbon can be produced in a high yield from a raw material gas containing at least one of carbon dioxide or carbon monoxide and hydrogen.

It is a schematic diagram which shows one Embodiment of a reaction apparatus. It is a schematic diagram which shows one Embodiment of a reaction apparatus.

Hereinafter, some embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

The catalyst according to one embodiment includes a copper-based catalyst and an iron-based catalyst as a solid substance different from the copper-based catalyst. The form of each catalyst is not particularly limited, and may be powder, for example, and is preferably a granular molded product made of agglomerates of powder. The shape of the catalyst body, which is a granular molded product, is not particularly limited, and for example, a columnar shape, a prismatic shape, a spherical shape, or an amorphous shape is preferable. The particle size (maximum width) of the granular molded product may be 1 mm or more and 50 mm or less. The particle size (maximum width) of the powder of the catalyst body may be 1 μm or more and less than 1000 μm.

The copper-based catalyst contains a copper component containing metallic copper, copper oxide, or both. While the copper-based catalyst functions as a catalyst, the copper-based catalyst usually contains at least metallic copper. Therefore, the catalyst is usually reduced before being used in the reaction. The copper-based catalyst before the reduction treatment often contains copper oxide (CuO).

The content of the copper component in the copper-based catalyst is 20 to 100 mass based on the total mass of the copper-based catalyst when the amount of the copper component contained in the copper-based catalyst is converted into the amount of metallic copper. May be%.

The copper-based catalyst may further contain zinc oxide (ZnO). Since the copper-based catalyst contains zinc oxide, liquid hydrocarbons can be produced more efficiently. When all the amounts of copper elements contained in the copper-based catalyst body are converted into the amount of copper oxide (CuO), the ratio of the amount of zinc oxide is 10 to 70 mass based on the total amount of copper oxide and zinc oxide. %, 10 to 50% by mass, 20 to 70% by mass, or 20 to 50% by mass.

The copper-based catalyst may further contain a carrier that supports a copper component. When the copper-based catalyst contains zinc oxide, zinc oxide is also usually supported on the carrier. The carrier is preferably alumina such as γ-alumina. The content of the carrier in the copper-based catalyst is, for example, 5 to 60% by mass, 5 to 50% by mass, and 5 to 40, based on the total of the copper content, zinc oxide content, and alumina content. It may be mass%, 10-60 mass%, 10-50 mass%, 10-40 mass%, 15-60 mass%, 15-50 mass%, or 15-40 mass%. The copper content here means an amount obtained by converting all the amounts of copper components contained in the copper-based catalyst body into the amount of metallic copper.

A copper-based catalyst containing a copper component and zinc oxide can be obtained, for example, by a method including producing a precipitate containing copper and zinc by a coprecipitation method and calcining the produced precipitate. .. Precipitates include, for example, copper and zinc hydroxides, carbonates or composite salts thereof. A copper-based catalyst containing a copper component, zinc oxide and a carrier can be obtained by forming a precipitate containing copper and zinc by a coprecipitation method from a solution containing a carrier (for example, alumina).

The fired body containing the copper component and zinc oxide formed by firing may be powdered, or the powder may be further molded to form a granular molded body. Examples of methods for molding powders include extrusion molding and tablet molding. A molded product can also be obtained by molding a mixture containing the powder of the fired product and carbon black.

The iron-based catalyst contains an iron component containing metallic iron, iron oxide, or both, and an additive metal composed of at least one of an alkali metal and an alkaline earth metal. While the iron-based catalyst functions as a catalyst, the iron-based catalyst usually contains at least metallic iron. Therefore, the catalyst is usually reduced before being used in the reaction. The iron-based catalyst before the reduction treatment usually contains iron oxide (for example, Fe ₃ O ₄ ).

The content of the iron component in the iron-based catalyst is 20 to 100 mass based on the mass of the entire iron-based catalyst when the amount of the iron component contained in the iron-based catalyst is converted into the amount of metallic iron. May be%.

The additive metal includes one or more arbitrarily selected from alkali metals and alkaline earth metals. For example, the additive metal may contain at least one selected from the group consisting of sodium, potassium and cesium. When the additive metal contains sodium, potassium, or cesium, liquid hydrocarbons can be produced more efficiently.

The content of the added metal in the iron-based catalyst is 0.2 to 40% by mass, 0.2 to 20% by mass, and 0.5 to 40 based on the amount of the portion of the iron-based catalyst other than the added metal. It may be% by mass or 0.5 to 20% by mass. When the added metal contains sodium, the sodium content in the iron-based catalyst is 0.2 to 20% by mass, 0.2 to 10% by mass, 0.5 to 20% by mass, or 0.5 to 10% by mass. It may be. When the added metal contains potassium, cesium or a combination thereof, the total content of potassium and cesium in the iron-based catalyst is 0.2 to 40% by mass, 0.2 to 20% by mass, 0.5 to 40. It may be% by mass or 0.5 to 20% by mass. When the content of the added metal is within the above range, the conversion rate of carbon dioxide or carbon monoxide tends to be further improved.

The iron-based catalyst body, for example, produces a precipitate of an iron compound containing trivalent iron and divalent iron from an aqueous solution containing Fe ³⁺ and Fe ²⁺ , and heats the precipitate to produce iron oxide. It can be obtained by a method including forming a warming body to be contained, attaching an aqueous solution containing an additive metal to the warming body, and then drying the aqueous solution containing the additive metal.

The heated body containing iron oxide may be powdered, or the powder may be further molded to form a granular molded body. Examples of methods for molding powders include extrusion molding and tablet molding. A molded product can also be obtained by molding a mixture containing the powder of the fired product and carbon black.

One embodiment of the method for producing a hydrocarbon comprises producing a hydrocarbon from a raw material gas containing at least one of carbon dioxide or carbon monoxide and hydrogen in the presence of the catalyst according to the above embodiment. .. A catalyst containing a combination of a copper-based catalyst and an iron-based catalyst, for example, has at least one of carbon dioxide or carbon monoxide as compared with a catalyst containing a composite oxide containing copper and iron and an alkali metal. Liquid hydrocarbons can be produced in high yield from raw material gas containing hydrogen. The raw material gas containing carbon dioxide and carbon monoxide may be, for example, a gas obtained by converting a part of carbon dioxide into carbon monoxide by an electrochemical reaction or a normal chemical reaction.

The catalyst according to this embodiment can be used, for example, to form a catalyst layer provided in a reaction apparatus for producing hydrocarbons. FIG. 1 is a schematic view showing an embodiment of a reactor. The reaction device 1 shown in FIG. 1 is a fixed-bed reaction device including a reaction vessel 3 which is a cylindrical reaction tube and a catalyst layer 10 fixed in the reaction vessel 3. The reaction vessel 3 has a gas inlet 3A provided at one end and a gas outlet 3B provided at the other end. A raw material gas containing at least one of carbon dioxide or carbon monoxide and hydrogen is introduced from the gas inlet 3A side. While the raw material gas flows through the reaction vessel 3 from the gas inlet 3A to the gas outlet 3B, a product containing a liquid hydrocarbon is produced in the presence of the catalyst layer 10. The product is typically discharged from the gas outlet 3B.

The catalyst layer 10 provided in the reaction apparatus 1 of FIG. 1 has a first catalyst layer 11 containing a copper-based catalyst and a second catalyst layer 12 containing an iron-based catalyst. The first catalyst layer 11 and the second catalyst layer 12 are laminated in this order from the gas inlet 3A side. The first catalyst layer 11 is formed, for example, by filling the reaction vessel 3 with a plurality of granular copper-based catalysts. The second catalyst layer 12 is formed, for example, by filling the reaction vessel 3 with a plurality of granular iron-based catalysts.

FIG. 2 is a schematic diagram showing another embodiment of the reactor. In the case of the reaction apparatus 1 shown in FIG. 2, a single catalyst layer 10 including a copper-based catalyst and an iron-based catalyst is provided. In the catalyst layer 10, a plurality of granular copper-based catalysts and a plurality of granular iron-based catalysts are mixed with each other. The catalyst layer 10 contains a powder of a copper-based catalyst and a powder of an iron-based catalyst, and these may be mixed with each other. The catalyst layer 10 may include a granular molded body formed by molding a powder mixture containing a powder of a copper-based catalyst and a powder of an iron-based catalyst.

In the catalyst layer 10, the amount of the iron-based catalyst may be larger than the amount of the copper-based catalyst. For example, the mass ratio of the amount of the iron-based catalyst to the amount of the copper-based catalyst may be 0.5 to 20, 0.5 to 10, 1.0 to 20 or 1.0 to 10. When the mass ratio of the amount of the iron-based catalyst to the amount of the copper-based catalyst is within the above range, the conversion rate of carbon dioxide or carbon monoxide tends to be further improved.

The method for producing a hydrocarbon using the reaction apparatus exemplified in FIGS. 1 and 2 is to reduce the catalyst contained in the catalyst layer 10 and to put carbon dioxide or carbon monoxide in the reaction vessel 3. It may include flowing a raw material gas containing at least one of hydrogen from the gas inlet 3A toward the gas outlet 3B, thereby producing a hydrocarbon from the raw material gas. The ratio of carbon dioxide and hydrogen in the raw material gas is adjusted in consideration of the stoichiometric ratio of the reaction and the like. In the raw material gas, carbon dioxide: hydrogen (molar ratio) may be 1: 0.5 to 1: 5.

The catalyst is reduced by, for example, circulating a reducing gas containing hydrogen in the reaction tube. The catalyst layer 10 may be heated during the reduction treatment. The heating temperature for the reduction treatment is, for example, 100 to 400 ° C.

The catalyst layer 10 may be heated while the reaction for producing hydrocarbons from the raw material gas is allowed to proceed. The heating temperature for the reaction is, for example, 200-400 ° C.

The raw material gas may contain only one of carbon dioxide and carbon monoxide, or may be a mixed gas containing carbon dioxide and carbon monoxide.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

(Example 1)
1. 1. Preparation of catalyst Preparation of copper-based catalyst 5.0 g of γ-alumina (BK-105, manufactured by Sumitomo Chemical Co., Ltd.) was suspended in 1.0 L of pure water by stirring with a homomixer. To the formed suspension, quickly add 300 mL of an aqueous solution containing 31.7 g of copper nitrate hydrate (manufactured by Nakarai Reagent) and 38.1 g of zinc nitrate hydrate (manufactured by Nakarai Reagent) at room temperature, and then at room temperature. The suspension was stirred for an additional hour. Then, while continuing stirring with a homomixer, 300 mL of an aqueous solution containing 35.0 g of sodium carbonate (manufactured by Wako Pure Chemical Reagent Co., Ltd.) was added dropwise at room temperature at a dropping rate of 5 mL / min using a roller pump. The suspension containing the precipitate formed by dropping was aged by leaving it at 35 ° C. for 24 hours. The supernatant was removed from the aged suspension by decanting and the remaining precipitate was diluted again with water. This decanting and diluting operation was repeated 4 times. Then, the precipitate was taken out by suction filtration, suspended in pure water again, and then the operation of taking out the precipitate by suction filtration was repeated four times, whereby the precipitate was thoroughly washed with water. The resulting precipitate was dried by heating at 120 ° C. for 24 hours. The dried precipitate is prepared in the order of 150 ° C. for 1 hour, 200 ° C. for 1 hour, 250 ° C. for 1 hour, 300 ° C. for 1 hour, 350 ° C. for 1 hour, and 400 ° C. for 4 hours under air circulation. It was fired by heating. By firing, a black powder which is a copper-based catalyst containing a copper component and zinc oxide was obtained. This black powder was pulverized in a mortar. By molding the obtained fine powder at a pressure of 40 MPa, a copper-based catalyst body, which is a columnar molded body having a diameter of 2 mm and a height of 2 mm, was obtained.

Preparation of iron-based catalysts 15.8 g of iron trichloride / hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) and 6.3 g of iron dichloride / tetrahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) in 75 mL of pure water and 35% hydrochloric acid. It was dissolved in a 2.5 mL mixed solution with stirring at 60 ° C. 336 mL of 5% aqueous ammonia was added dropwise to the dissolved solution while maintaining the temperature at 60 ° C., and then the solution was stirred for 1 hour. A precipitate formed in the solution. The supernatant was removed by a decant operation, and the remaining precipitate was filtered while being washed with 400 mL of pure water. The resulting precipitate was dried by heating at 70 ° C. for 6 hours. The obtained black powder was pulverized in a mortar. The fine powder was molded at a pressure of 40 MPa to obtain a cylindrical molded body containing Fe ₃ O ₄ having a diameter of 2 mm and a height of 2 mm. 10 g of this molded product was impregnated with an aqueous solution containing 0.17 g of sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and 4.63 g of pure water, and the aqueous solution impregnated in the molded product was dried by heating at 60 ° C. for 18 hours. An iron-based catalyst body, which is a molded product containing an iron-based catalyst (NaFe ₃ O ₄ ), was obtained. The ratio of sodium to Fe ₃ O ₄ is calculated to be about 1% by weight.

2. 2. Reduction treatment of evaluation catalyst A fixed-bed reaction tube with an inner diameter of 1.27 cm is sequentially filled with 0.5 g of a columnar copper-based catalyst and 3.5 g of a columnar iron-based catalyst, and is placed on the gas inlet side of the reaction tube. The copper-based catalyst and the iron-based catalyst were arranged in this order from (upstream side). Subsequently, the temperature of the catalyst was raised from room temperature to 150 ° C. over 1 hour while circulating a flowing gas composed of 1% by volume of hydrogen and nitrogen in the reaction tube at a flow rate of 200 Ncc / min under atmospheric pressure. While maintaining the temperature at 150 ° C., the concentration of hydrogen contained in the circulating gas was changed in the order of 2% by volume, 10% by volume, 20% by volume, 50% by volume, and 100% by volume. After changing to a distribution gas (hydrogen gas) having a hydrogen concentration of 100% by volume, the distribution state was maintained for 2 hours. Then, while continuing the flow of hydrogen gas, the temperature of the catalyst was raised to 350 ° C. at a rate of 200 ° C./hour and maintained at 350 ° C. for 7 hours to reduce the catalyst.

Reaction test After the reduction treatment, the temperature of the catalyst was lowered to 320 ° C. while hydrogen gas was circulated at a flow rate of 200 Ncc / min. After the temperature was lowered, the pressure of the flowing gas was increased to 0.8 MPa. After pressurization, carbon dioxide was added at a flow rate of 67 Ncc / min, and a raw material gas composed of hydrogen and carbon dioxide was circulated in the reaction tube for 6 hours (gas space velocity: 4000 Ncc · g-cat-1h ^-1 ). The liquid material spilled from the reaction tube was collected during 6 hours. In addition, the gas flowing out of the reaction tube was collected for 5 minutes immediately before the end of the test. The oil content of the supernatant of the liquid material was analyzed by a gas chromatograph / flame ionization detector (GC-FID). Gas was analyzed by gas chromatograph / thermal conductivity detector (GC-TCD) and flame ionization detector (GC-FID). From the analysis results, the yield of the product with respect to the amount of carbon dioxide in the raw material gas was determined.

(Example 2)
1.0 g of a columnar copper-based catalyst and 3.0 g of a columnar iron-based catalyst were uniformly mixed. The resulting catalyst mixture was filled into a fixed bed reaction tube. After that, the reduction treatment of the catalyst and the subsequent reaction test were carried out by the same operation as in Example 1.

(Example 3)
A columnar molded body containing Fe ₃ O ₄ was prepared in the same manner as in the iron-based catalyst body of Example 1. Fe ₃ O ₄ and sodium were added in the same procedure as in Example 1 except that 10 g of the molded product was impregnated with an aqueous solution containing 0.35 g of sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and 4.45 g of pure water. An iron-based catalyst containing the mixture was prepared. The ratio of sodium to Fe ₃ O ₄ in the obtained iron-based catalyst is calculated to be about 2% by mass. The reduction treatment of the catalyst and the subsequent reaction test were carried out by the same method as in Example 1 except that this iron-based catalyst was used in combination with the same copper-based catalyst as in Example 1.

(Example 4)
A columnar molded body containing Fe ₃ O ₄ was prepared in the same manner as in the iron-based catalyst body of Example 1. Fe ₃ O ₄ and sodium were added to 10 g of the molded product by the same procedure as in Example 1 except that 0.70 g of sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and 4.10 g of pure water were impregnated with the aqueous solution. An iron-based catalyst containing the mixture was prepared. The ratio of sodium to Fe ₃ O ₄ in the obtained iron-based catalyst is calculated to be about 4% by mass. The reduction treatment of the catalyst and the subsequent reaction test were carried out by the same method as in Example 1 except that this iron-based catalyst was used in combination with the same copper-based catalyst as in Example 1.

(Example 5)
A columnar molded body containing Fe ₃ O ₄ was prepared in the same manner as in the iron-based catalyst body of Example 1. The second catalyst molded product was subjected to the same procedure as in Example 1 except that 10 g of this molded product was impregnated with an aqueous solution containing 1.05 g of sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and 3.75 g of pure water. Was produced. The ratio of sodium to Fe ₃ O ₄ in the obtained second catalyst is calculated to be about 6% by weight. The reduction treatment of the catalyst and the subsequent reaction test were carried out by the same method as in Example 1 except that this iron-based catalyst was used in combination with the same copper-based catalyst as in Example 1.

(Example 6)
A columnar molded body containing Fe ₃ O ₄ was prepared in the same manner as in the iron-based catalyst body of Example 1. Fe ₃ O ₄ and sodium were added in the same procedure as in Example 1 except that 10 g of the molded product was impregnated with an aqueous solution containing 1.39 g of sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and 3.41 g of pure water. An iron-based catalyst containing the mixture was prepared. The ratio of sodium to Fe ₃ O ₄ in the obtained iron-based catalyst is calculated to be about 8% by mass. The reduction treatment of the catalyst and the subsequent reaction test were carried out by the same method as in Example 1 except that this iron-based catalyst was used in combination with the same copper-based catalyst as in Example 1.

(Example 7)
Using the same catalyst as in Example 4, the reaction test was carried out in the same manner as in Example 4 except that the hydrogen flow rate was changed to 400 Ncc / min and the carbon dioxide flow rate was changed to 134 Ncc / min.

(Example 8)
A columnar molded body containing Fe ₃ O ₄ was prepared in the same manner as in the iron-based catalyst body of Example 1. By impregnating 10 g of this molded body with an aqueous solution containing 0.64 g of potassium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and 4.18 g of pure water, the aqueous solution impregnated in the molded body is dried by heating at 60 ° C. for 18 hours. , Fe ₃ O ₄ and potassium-containing iron-based catalyst was prepared. The ratio of potassium to Fe ₃ O ₄ is calculated to be about 4% by weight. The reduction treatment of the catalyst and the subsequent reaction test were carried out by the same method as in Example 7 except that this iron-based catalyst was used in combination with the same copper-based catalyst as in Example 1.

(Example 9)
A columnar molded body containing Fe ₃ O ₄ was prepared in the same manner as in the iron-based catalyst body of Example 1. By impregnating 10 g of this molded body with an aqueous solution containing 1.28 g of potassium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and 3.52 g of pure water, the aqueous solution impregnated in the molded body is dried by heating at 60 ° C. for 18 hours. , Fe ₃ O ₄ and potassium-containing iron-based catalyst was prepared. The ratio of potassium to Fe ₃ O ₄ is calculated to be about 8% by weight. The reduction treatment of the catalyst and the subsequent reaction test were carried out by the same method as in Example 7 except that this iron-based catalyst was used in combination with the same copper-based catalyst as in Example 1.

(Example 10)
A columnar molded body containing Fe ₃ O ₄ was prepared in the same manner as in the iron-based catalyst body of Example 1. By impregnating 10 g of the molded product with an aqueous solution containing 0.45 g of cesium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and 4.35 g of pure water, the aqueous solution impregnated in the molded product is dried by heating at 60 ° C. for 18 hours. , Fe ₃ O ₄ and cesium-containing iron-based catalyst was prepared. The ratio of cesium to Fe ₃ O ₄ is calculated to be about 4% by mass. The reduction treatment of the catalyst and the subsequent reaction test were carried out by the same method as in Example 7 except that this iron-based catalyst was used in combination with the same copper-based catalyst as in Example 1.

(Example 11)
A columnar molded body containing Fe ₃ O ₄ was prepared in the same manner as in the iron-based catalyst body of Example 1. By impregnating 10 g of the molded product with an aqueous solution containing 0.90 g of cesium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and 3.90 g of pure water, the aqueous solution impregnated in the molded product is dried by heating at 60 ° C. for 18 hours. , Fe ₃ O ₄ and cesium-containing iron-based catalyst was prepared. The ratio of cesium to Fe ₃ O ₄ is calculated to be about 8% by mass. The reduction treatment of the catalyst and the subsequent reaction test were carried out by the same method as in Example 7 except that this iron-based catalyst was used in combination with the same copper-based catalyst as in Example 1.

(Example 12)
A columnar molded body containing Fe ₃ O ₄ was prepared in the same manner as in the iron-based catalyst body of Example 1. By impregnating 10 g of the molded product with an aqueous solution containing 1.35 g of cesium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and 3.45 g of pure water, the aqueous solution impregnated in the molded product is dried by heating at 60 ° C. for 18 hours. , Fe ₃ O ₄ and cesium-containing iron-based catalyst was prepared. The ratio of cesium to Fe ₃ O ₄ is calculated to be about 12% by mass. The reduction treatment of the catalyst and the subsequent reaction test were carried out by the same method as in Example 7 except that this iron-based catalyst was used in combination with the same copper-based catalyst as in Example 1.

(Example 13)
A columnar molded body containing Fe ₃ O ₄ was prepared in the same manner as in the iron-based catalyst body of Example 1. By impregnating 10 g of the molded product with an aqueous solution containing 1.80 g of cesium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and 3.00 g of pure water, the aqueous solution impregnated in the molded product is dried by heating at 60 ° C. for 18 hours. , Fe ₃ O ₄ and cesium-containing iron-based catalyst was prepared. The ratio of cesium to Fe ₃ O ₄ is calculated to be about 16% by mass. The reduction treatment of the catalyst and the subsequent reaction test were carried out by the same method as in Example 7 except that this iron-based catalyst was used in combination with the same copper-based catalyst as in Example 1.

(Comparative Example 1)
34.6 g of iron nitrate nineahydrate and 2.3 g of copper nitrate trihydrate were dissolved in distilled water to prepare a 100 mL solution in total. Subsequently, while maintaining the temperature at 70 ° C., 5% aqueous ammonia was added dropwise until pH = 8. The dropping amount was 212 mL. After further stirring the solution at room temperature for 15 hours, the resulting precipitate was removed by filtration and washed with distilled water. The precipitate was dried by heating at 120 ° C. for 6 hours. The obtained powder (8 g) was impregnated with an aqueous solution containing 0.55 g of sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and 3 g of pure water, and dried at 60 ° C. for 18 hours. Then, the powder was calcined at 350 ° C. for 3 hours to obtain an iron-copper catalyst containing iron, copper and sodium. The ratio of sodium to the iron-copper catalyst is calculated to be about 4% by weight. The obtained powder was molded at a pressure of 40 MPa to obtain a molded body of a columnar iron-copper catalyst having a diameter of 2 mm and a height of 2 mm. 4.0 g of this iron-copper catalyst molded product was filled in a fixed bed type reaction tube. After that, the reduction treatment of the catalyst and the subsequent reaction test were carried out by the same operation as in Example 1.

(Comparative Example 2)
Only 4.0 g of the iron-based catalyst was filled in the fixed-bed reaction tube, and the copper-based catalyst was not used. After that, the reduction treatment of the catalyst and the subsequent reaction test were carried out by the same operation as in Example 1.

(Comparative Example 3)
A columnar molded body containing Fe ₃ O ₄ was prepared in the same manner as in the iron-based catalyst body of Example 1. This molded product was filled in a fixed bed type reaction tube together with a copper-based catalyst without being impregnated with an aqueous solution of sodium hydroxide. After that, the reduction treatment of the catalyst and the subsequent reaction test were carried out by the same operation as in Example 1.

(Comparative Example 4)
1.23 g of cobalt nitrate hexahydrate was dissolved in 1.50 g of pure water. The obtained aqueous solution was impregnated with 4 g of spherical alumina (KHA-24, manufactured by Sumitomo Chemical Co., Ltd.) and dried at 110 ° C. overnight. This impregnation and drying were repeated twice to obtain a cobalt-based catalyst (Al-supported Co-based catalyst) in which 12.5% by mass of cobalt was supported on an alumina carrier. The obtained cobalt-based catalyst was used instead of the iron-based catalyst, and the reduction treatment of the catalyst and the subsequent reaction test were carried out by the same operation as in Example 1 except that the heating temperature for the reduction treatment was changed to 400 ° C. Carried out.

Table 1 shows the yields of CO, CH ₄ , hydrocarbons having 2 to 4 carbon atoms (C2-C4) and hydrocarbons having 5 or more carbon atoms (C5 +). It was confirmed that the combination of the copper-based catalyst body and the iron-based catalyst body produces a liquid hydrocarbon having 5 or more carbon atoms in a high yield from carbon dioxide and hydrogen.

1 ... Reaction device, 3 ... Reaction vessel, 3A ... Gas inlet, 3B ... Gas outlet, 10 ... Catalyst layer, 11 ... First catalyst layer, 12 ... Second catalyst layer.

Claims

A copper-based catalyst containing a copper component consisting of at least one of metallic copper and copper oxide, and
An iron-based catalyst containing an iron component consisting of at least one of iron or iron oxide and an additive metal consisting of at least one of an alkali metal or an alkaline earth metal.
A catalyst used to generate hydrocarbons from a source gas containing at least one of carbon dioxide or carbon monoxide and hydrogen.
The catalyst according to claim 1, wherein the additive metal contains at least one selected from the group consisting of sodium, potassium, and cesium.
The catalyst according to claim 1 or 2, wherein the copper-based catalyst further contains zinc oxide.
The first catalyst layer containing the granular copper-based catalyst and the second catalyst layer containing the granular iron-based catalyst are laminated, and the raw material gas is introduced from the first catalyst layer side. , The catalyst according to any one of claims 1 to 3.
The granular copper-based catalyst and the granular iron-based catalyst are mixed with each other, the powder of the copper-based catalyst and the powder of the iron-based catalyst are mixed with each other, or the copper. The catalyst according to any one of claims 1 to 3, wherein a granular compact is formed by a powder mixture containing the powder of the system catalyst and the powder of the iron-based catalyst.
A reactor used to generate hydrocarbons from a raw material gas containing at least one of carbon dioxide or carbon monoxide and hydrogen.
The reactor
A reaction vessel with a gas inlet and a gas outlet,
A catalyst layer containing the catalyst according to any one of claims 1 to 3 and
With
The catalyst layer is fixed in the reaction vessel,
The catalyst layer has a first catalyst layer containing the copper-based catalyst body and a second catalyst layer containing the iron-based catalyst body, and the first catalyst layer from the gas inlet side in the reaction vessel. The catalyst layer and the second catalyst layer are laminated in this order.
A reactor used to generate hydrocarbons from a raw material gas containing at least one of carbon dioxide or carbon monoxide and hydrogen.
The reactor
A reaction vessel with a gas inlet and a gas outlet,
A catalyst layer containing the catalyst according to any one of claims 1 to 3 and
With
The catalyst layer is fixed in the reaction vessel,
In the catalyst layer, the granular copper-based catalyst and the granular iron-based catalyst are mixed with each other, and the powder of the copper-based catalyst and the powder of the iron-based catalyst are mixed with each other. A reactor in which a granular compact is formed by a powder mixture containing the powder of the copper-based catalyst and the powder of the iron-based catalyst.
Producing a hydrocarbon comprising producing a hydrocarbon from a raw material gas containing at least one of carbon dioxide or carbon monoxide and hydrogen in the presence of the catalyst according to any one of claims 1 to 3. how to.