Catalyst for carbon dioxide reduction and method for producing higher hydrocarbon
A carbon dioxide reduction catalyst with iron, gallium, and zinc enhances the conversion rate and production of hydrocarbons with 8 to 16 carbon atoms, addressing the inefficiencies in existing technologies and enabling efficient production of synthetic jet fuel.
Patent Information
- Application Number
- PCT/JP2024/026114
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- Filing Date
- 2024-07-22
- Publication Date
- 2026-01-29
AI Technical Summary
Existing technologies struggle to efficiently convert carbon dioxide into higher hydrocarbons, particularly those with 5 or more carbon atoms, which are needed for sustainable aviation fuel (SAF), and there is a need to increase the carbon dioxide conversion rate in hydrogenation reactions.
A carbon dioxide reduction catalyst comprising iron, gallium, and zinc as catalytic metals, with iron as the main component, and optionally sodium as a promoter, enhances the conversion rate and production of hydrocarbons with 8 to 16 carbon atoms by promoting the hydrogenation reaction of carbon dioxide and hydrogen.
The catalyst significantly increases the carbon dioxide conversion rate and production rate of hydrocarbons with 8 to 16 carbon atoms, enabling efficient production of synthetic jet fuel.
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Abstract
Description
Carbon dioxide reduction catalyst and method for producing higher hydrocarbons
[0001] The present invention relates to a carbon dioxide reduction catalyst and a method for producing higher hydrocarbons.
[0002] Efforts aimed at mitigating or reducing the impact of climate change have been ongoing, and toward this end, automobile exhaust gas regulations have been further advanced. In particular, there is a demand for reducing the amount of carbon dioxide emissions contained in exhaust gases from internal combustion engines. In recent years, technologies for producing fuel by subjecting carbon dioxide to a hydrogenation reaction have become known. For example, a catalyst composed of Cu, Zn, and alumina has been proposed as a catalyst for synthesizing methanol from a mixed gas of carbon dioxide and hydrogen (see Patent Document 1).
[0003] However, it is desired to be able to produce hydrocarbons having, for example, 5 or more carbon atoms that can be used as liquid fuels as fuels obtained by hydrogenating carbon dioxide. As a technology for achieving this, a method has been proposed in which potassium is used as a promoter for an Fe catalyst in a Fischer-Tropsch (FT) synthesis reaction to prepare highly branched products having 5 or more carbon atoms (see Patent Document 2).
[0004] Special Publication No. 45-16682 Special Publication No. 2005-537340
[0005] Meanwhile, in efforts to reduce carbon dioxide emissions, technology related to sustainable aviation fuel (SAF), which is an aviation fuel produced from biomass-derived raw materials or waste, or produced from hydrocarbons using carbon dioxide as a feed gas, has been attracting attention. It would be preferable if SAF could be produced directly from carbon dioxide using technology related to the hydrogenation reaction of carbon dioxide. The production of SAF requires an increase in the conversion rate of carbon dioxide to hydrocarbons, i.e., an increase in the reduction rate (conversion rate) of carbon dioxide.
[0006] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a carbon dioxide reduction catalyst that can increase the carbon dioxide conversion rate.
[0007] In order to achieve the above object, the present invention provides the following means: [1] A carbon dioxide reduction catalyst that reduces carbon dioxide by subjecting carbon dioxide and hydrogen to a hydrogenation reaction, the carbon dioxide reduction catalyst containing iron, gallium, and zinc as catalytic metals, with the iron being a main component of the catalytic metals.
[0008] The carbon dioxide reduction catalyst according to [1] contains iron, gallium, and zinc as catalytic metals, and is therefore capable of increasing the conversion rate of carbon dioxide in the hydrogenation reaction of carbon dioxide and hydrogen.
[0009] [2] The carbon dioxide reduction catalyst according to [1], which produces hydrocarbons by a hydrogenation reaction between carbon dioxide and hydrogen.
[0010] The carbon dioxide reduction catalyst according to [2] contains iron, gallium, and zinc as catalytic metals, and is therefore capable of increasing the conversion rate of carbon dioxide to hydrocarbons through a hydrogenation reaction between carbon dioxide and hydrogen.
[0011] [3] The carbon dioxide reduction catalyst according to [1] or [2], wherein the gallium content is greater than the zinc content.
[0012] The carbon dioxide reduction catalyst according to [3] contains iron as a main catalytic metal component, and contains gallium and zinc as auxiliary catalysts in that order of content, thereby improving the basicity of iron and enabling the promotion of upgrading of hydrocarbons produced by the hydrogenation reaction of carbon dioxide and hydrogen.
[0013] [4] The carbon dioxide reduction catalyst according to any one of [1] to [3], wherein the content of the zinc relative to the catalytic metal is 5 to 15 mass%.
[0014] The carbon dioxide reduction catalyst according to [4] has a zinc content relative to the catalyst metal within a specific range, thereby making it possible to increase the production rate of hydrocarbons having 8 to 16 carbon atoms.
[0015] [5] The carbon dioxide reduction catalyst according to any one of [1] to [4], wherein the content of the zinc relative to the catalytic metal is 9 to 11 mass%.
[0016] The carbon dioxide reduction catalyst according to [5] has a more limited zinc content relative to the catalytic metal than the carbon dioxide reduction catalyst according to [4]. This makes it possible to further increase the production rate of hydrocarbons having 8 to 16 carbon atoms.
[0017] [6] The carbon dioxide reduction catalyst according to any one of [1] to [5], further containing sodium as an auxiliary catalyst in addition to the catalytic metal.
[0018] The carbon dioxide reduction catalyst according to [6] further contains sodium as an auxiliary catalyst in addition to the catalytic metal, which can further improve the basicity of iron, thereby further increasing the production rate of hydrocarbons having 8 to 16 carbon atoms.
[0019] [7] A method for producing higher hydrocarbons, comprising producing hydrocarbons having 8 to 16 carbon atoms from a feed gas containing carbon dioxide and hydrogen, using the carbon dioxide reduction catalyst according to any one of [1] to [6].
[0020] The method for producing higher hydrocarbons according to [7] uses the carbon dioxide reduction catalyst according to any one of [1] to [6]. This makes it possible to increase the carbon dioxide conversion rate in the hydrogenation reaction of carbon dioxide and hydrogen, and to increase the production rate of hydrocarbons having 8 to 16 carbon atoms. This makes it possible to increase the production rate of hydrocarbons having 8 to 16 carbon atoms, which are the main components of synthetic jet fuel, and to efficiently produce synthetic jet fuel.
[0021] The carbon dioxide reduction catalyst of the present invention can increase the carbon dioxide conversion rate, and the method for producing higher hydrocarbons of the present invention can efficiently produce synthetic jet fuels such as SAF.
[0022] 1 is a conceptual diagram showing an embodiment of a fuel synthesis device using a carbon dioxide reduction catalyst according to the present invention; FIG. 2 is a conceptual diagram showing another embodiment of a fuel synthesis device using a carbon dioxide reduction catalyst according to the present invention; FIG. 3 is a conceptual diagram showing the relationship between the amount of Zn added in the carbon dioxide reduction catalyst according to the examples and comparative examples of the present invention and the CO 2 1 is a graph showing the relationship between the amount of Zn added and the conversion rate of C in Examples and Comparative Examples. 8 -C 161 is a graph showing the relationship between the amount of Zn added and the selectivity of hydrocarbons in Examples and Comparative Examples. 8 -C 16 1 is a graph showing the relationship between the rate of hydrocarbon production and the Fe content of Fe atoms in Example 3 and Comparative Example 1. 5 C 2 10 is a graph showing state ratios.
[0023] Preferred embodiments of the present invention will now be described in detail.
[0024] [Carbon dioxide reduction catalyst] The carbon dioxide reduction catalyst of this embodiment is a catalyst that reduces carbon dioxide by subjecting carbon dioxide and hydrogen to a hydrogenation reaction. In addition, the carbon dioxide reduction catalyst of this embodiment is a catalyst that can produce hydrocarbons by subjecting carbon dioxide and hydrogen to a hydrogenation reaction. In particular, the carbon dioxide reduction catalyst of this embodiment can increase the production rate of hydrocarbons having 8 to 16 carbon atoms compared to conventional catalysts. In this specification, "higher hydrocarbons" refers to hydrocarbons having 8 or more carbon atoms. Hydrocarbons having 8 to 16 carbon atoms fall under the category of higher hydrocarbons.
[0025] The carbon dioxide reduction catalyst of this embodiment contains iron (Fe), gallium (Ga), and zinc (Zn) as catalytic metals, with iron being the main component of the catalytic metal. Here, "mainly containing iron" means that the iron content is 50 mass% or more relative to the total mass of the catalytic metals in the carbon dioxide reduction catalyst.
[0026] The carbon dioxide reduction reaction using the carbon dioxide reduction catalyst according to this embodiment is carried out by H 2 (hydrogen) and CO 2 (carbon dioxide) mixed gas as raw material, 2 This is the so-called direct FT synthesis reaction, in which hydrocarbons are produced by carrying out, in a single stage, a reverse water-gas shift reaction in which CO is reduced to CO (carbon monoxide), and an FT synthesis reaction in which CO is converted into hydrocarbons. The carbon dioxide reduction catalyst according to this embodiment contributes to both the reverse water-gas shift reaction and the FT synthesis reaction. In addition, it can also be used in the so-called direct FT synthesis reaction.
[0027] Iron is contained as a catalytic metal in the carbon dioxide reduction catalyst and may be a compound such as an oxide, carbonate compound, nitrate compound, or sulfate compound, with an oxide being preferred. Two or more of these compounds may be contained. Furthermore, iron is more preferably contained in the catalytic metal as an iron-gallium composite oxide containing iron and gallium. Use of a catalytic metal containing an iron-gallium composite oxide can promote the growth of hydrocarbon carbon chains compared to compounds such as iron oxide.
[0028] The iron content relative to the total mass of catalytic metals in the carbon dioxide reduction catalyst is 50 mass % or more, preferably 50 to 75 mass %, and more preferably 60 to 70 mass %, calculated as metal atoms. By setting the iron content within the above range, the carbon dioxide conversion rate in the hydrogenation reaction of carbon dioxide and hydrogen can be further increased.
[0029] The gallium contained in the catalytic metal according to this embodiment may be, like iron, in the form of a compound such as an oxide, a carbonate compound, a nitrate compound, or a sulfate compound, and is preferably an oxide. Two or more of these compounds may be contained. Gallium is more preferably contained in the catalytic metal as an iron-gallium composite oxide containing iron and gallium.
[0030] The gallium content relative to the total mass of the catalytic metals in the carbon dioxide reduction catalyst is preferably 10 to 30 mass%, and more preferably 20 to 30 mass%, calculated as metal atoms. When the gallium content is within the above range, the catalytic activity of the carbon dioxide reduction catalyst can be further enhanced.
[0031] In the catalytic metal, the content of gallium is preferably greater than the content of zinc, which will be described later. In the carbon dioxide reduction catalyst of this embodiment, both gallium and zinc function as auxiliary catalysts. By including gallium and zinc in order of decreasing content as auxiliary catalysts, the basicity of iron can be improved, and the upgrading of hydrocarbons produced by the hydrogenation reaction of carbon dioxide and hydrogen can be promoted.
[0032] Zinc is contained as a catalytic metal in the carbon dioxide reduction catalyst, and like iron, it may be in the form of an oxide, a carbonate compound, a nitrate compound, a sulfate compound, or the like, and is preferably an oxide. Zinc is more preferably contained in the catalytic metal as an iron-gallium-zinc composite oxide containing iron and gallium.
[0033] When zinc is contained in the carbon dioxide reduction catalyst together with iron and gallium, it is possible to form the acidic reaction intermediate CH 2 The content of zinc relative to the total mass of catalytic metals in the carbon dioxide reduction catalyst is preferably 5 to 15 mass %, more preferably 9 to 11 mass %, calculated as metal atoms. When the content of zinc is equal to or greater than the lower limit, CO 2 The conversion rate is improved and the intermediate CH 2 When the zinc content is equal to or less than the upper limit, it is possible to suppress a decrease in activity due to zinc covering the reactive sites of iron.
[0034] The carbon dioxide reduction catalyst of this embodiment preferably further contains sodium (Na) in addition to the catalytic metal. Sodium functions as a co-catalyst (promoter) together with the catalytic metal containing iron, gallium, and zinc. Sodium acts to convert carbon dioxide into sodium carbonate (Na 2 CO 3 ) promotes the reverse shift reaction in which carbon monoxide is produced from hydrogen and carbon dioxide, thereby further increasing the carbon dioxide conversion rate. Sodium is preferably present on the surface of the composite oxide in the form of an oxide or the like, separate from the composite oxide. By being present on the surface of the composite oxide, sodium functions as a surface catalyst. The carbon dioxide reduction catalyst may contain an alkali metal such as lithium (Li), potassium (K), rubidium (Rb), or cesium (Cs) in place of or together with sodium.
[0035] When the carbon dioxide reduction catalyst of this embodiment contains sodium, the content of sodium relative to the total mass of the catalytic metal in the carbon dioxide reduction catalyst is preferably 0.5 to 2.0 mass%, and more preferably 0.5 to 1.5 mass%, calculated as metal atoms. When the sodium content is equal to or greater than the above-mentioned lower limit, the basicity of the carbon dioxide reduction catalyst can be increased, and the efficiency of producing hydrocarbons having 8 to 16 carbon atoms can be sufficiently improved. When the sodium content is equal to or less than the above-mentioned upper limit, the adverse effects caused by sodium covering the iron reaction sites can be avoided, the production of carbon monoxide as a by-product can be suppressed, and a decrease in catalytic activity can be prevented.
[0036] The carbon dioxide reduction catalyst of this embodiment may be, for example, a powder of catalytic metal, or a pellet-shaped molded body formed by pressure molding of catalytic metal. Alternatively, the catalyst may be supported on a known catalyst carrier such as silica. In addition to the above, the carbon dioxide reduction catalyst of this embodiment may contain inevitable impurities that are mixed in during the catalyst production process, etc., but it is preferable that the carbon dioxide reduction catalyst contain as few impurities as possible.
[0037] [Method for producing carbon dioxide reduction catalyst] The method for producing the carbon dioxide reduction catalyst of this embodiment preferably includes a coprecipitation step and an impregnation step.
[0038] <Coprecipitation Step> The coprecipitation step is a step of extracting a catalyst precursor precipitate by coprecipitation from an aqueous solution in which a predetermined amount of iron nitrate and at least one of gallium nitrate and zinc nitrate are dissolved in distilled water. The coprecipitation step forms at least one of iron-gallium composite oxide, iron-zinc composite oxide, and iron-gallium-zinc composite oxide. In the coprecipitation step, a precipitation solution is preferably obtained by adding a urea aqueous solution dropwise to the aqueous solution containing iron and at least one of gallium and zinc. The precipitate is then separated from the precipitation solution by filtration, washing, or the like, and dried to obtain a catalyst precursor precipitate (iron-gallium composite oxide, iron-zinc composite oxide, iron-gallium-zinc composite oxide).
[0039] <Impregnation Step> The impregnation step is a step of dropping an aqueous solution containing Na onto the precipitate obtained by the coprecipitation step, drying for a predetermined time, and firing the obtained powder at a predetermined temperature. The impregnation step allows the Na compound to be unevenly distributed near the surface of the composite oxide. Examples of the aqueous solution containing Na include NaNO 3 (sodium nitrate) aqueous solution. 3 The aqueous solution can be added dropwise under ultrasonic vibration. This allows the Na compound to be uniformly distributed near the surface of the composite oxide. The firing temperature can be, for example, 500 to 600°C, and the firing time can be 3 to 5 hours.
[0040] [Fuel synthesis device] When a carbon dioxide reduction reaction is carried out using the carbon dioxide reduction catalyst according to this embodiment, for example, a fuel synthesis device can be used. FIG. 1 is a conceptual diagram that schematically shows one embodiment of a fuel synthesis device that uses the carbon dioxide reduction catalyst according to this embodiment. As shown in FIG. 1, the fuel synthesis device 1 of this embodiment includes a catalyst reaction vessel 20, a catalyst reaction vessel 30, and a water trap unit 40. The catalyst reaction vessel 20 and the catalyst reaction vessel 30 are connected by a flow path L. The water trap unit 40 is connected to the flow path L.
[0041] <Catalyst Reaction Vessel> The carbon dioxide reduction catalyst (C1) of this embodiment, which contains iron, gallium, and zinc as catalytic metals, is placed in the catalyst reaction vessel 20. The carbon dioxide reduction catalyst (C2) of this embodiment, which contains iron, gallium, and zinc as catalytic metals, similar to the catalyst reaction vessel 20, is placed in the catalyst reaction vessel 30.
[0042] There are no particular limitations on the configuration of the catalyst reactor 20 and the catalyst reactor 30, and any known configuration can be applied. For example, a fixed-bed flow-type reactor in which a flow path having a predetermined shape is filled with a powdery, granular, or pellet-like catalyst or a carrier carrying the catalyst can be mentioned.
[0043] <Water Trap Unit> The water trap unit 40 removes water from the fluid supplied to the carbon dioxide reduction catalyst. This makes it possible to shift the chemical equilibrium in the carbon dioxide reduction reaction by the carbon dioxide reduction catalyst in the direction of increasing the number of carbon atoms in hydrocarbons. This makes it possible to improve the yield of hydrocarbons with 8 to 16 carbon atoms.
[0044] The fuel synthesizer may be a fuel synthesizer 1' as shown in Fig. 2, in which a water trap unit 40' is connected to a catalyst reaction vessel 20'. The catalyst reaction vessel 20' and the water trap unit 40' shown in Fig. 2 are similar to the catalyst reaction vessel 20 and the water trap unit 40 described above, respectively.
[0045] [Method for Producing Higher Hydrocarbons] The method for producing higher hydrocarbons according to the present embodiment is not particularly limited as long as it uses the carbon dioxide reduction catalyst according to the present embodiment, and examples include a method for producing hydrocarbons having 8 to 16 carbon atoms from a feed gas containing carbon dioxide and hydrogen.
[0046] The method for producing higher hydrocarbons according to this embodiment uses the carbon dioxide reduction catalyst according to this embodiment. This increases the carbon dioxide conversion rate in the hydrogenation reaction of carbon dioxide and hydrogen, and increases the production rate of hydrocarbons having 8 to 16 carbon atoms. As a result, it increases the production rate of hydrocarbons having 8 to 16 carbon atoms, which are the main components of synthetic jet fuels such as SAF, and allows for efficient production of synthetic jet fuel.
[0047] The present invention is not limited to the above-described embodiment, and includes modifications and improvements within the scope of achieving the object of the present invention.
[0048] Examples of the present invention will be described below, but the present invention is not limited to the following examples.
[0049] [Preparation of Carbon Dioxide Reduction Catalyst] <Example 1> Iron nitrate (Fe(NO)) as a catalytic metal of a carbon dioxide reduction catalyst 3 ) 3 ・9H 2 O) and zinc nitrate (Zn(NO) 3 ) 2 ・6H2 O) and gallium nitrate (Ga(NO) 3 ) 3 ・6H 2 O) were weighed out so that the mass ratio of Fe:Zn:Ga was 14.2:1.0:4.8 in terms of metal atoms, and dissolved in distilled water to obtain an aqueous solution. Next, urea (CH 4 N 2 An aqueous solution of iron, zinc, and gallium was added dropwise at 2 ml / min and the pH was fixed at 8.5 (25°C), thereby obtaining a precipitate solution containing iron, zinc, and gallium as a precipitate. Next, the precipitate solution was aged at room temperature (25°C) for 24 hours, and then the precipitate was separated by repeated filtration and washing. The separated precipitate was dried at 60°C for 12 hours to obtain an iron-gallium-zinc catalyst precursor (Fe-Ga-Zn catalyst precursor). Sodium nitrate (NaNO) was added to the above Fe-Ga-Zn catalyst precursor. 3 An aqueous solution of 1.0% by mass of Na, calculated as metal atoms, was added dropwise to the catalyst under 92 kHz ultrasonic vibration. The catalyst was then dried under a vacuum of 5000 Pa for 1 hour, and further dried at 60°C under normal pressure for 12 hours to obtain a powder. The obtained powder was calcined at 550°C for 4 hours to obtain a carbon dioxide reduction catalyst according to Example 1 (hereinafter also simply referred to as "catalyst").
[0050] Examples 2 to 5 Catalysts were prepared in the same manner as in Example 1, except that the amounts of iron, gallium, and zinc nitrates were adjusted so that the content of zinc as the catalytic metal was 7.5% by mass (Example 2), 10% by mass (Example 3), 12.5% by mass (Example 4), and 15% by mass (Example 5), respectively.
[0051] Comparative Example 1 A catalyst was prepared in the same manner as in Example 1, except that zinc nitrate was not used as the catalytic metal, and iron nitrate and gallium nitrate were weighed out so that the mass ratio of Fe:Ga was 3:1 in terms of metal atoms.
[0052] The contents of catalytic metals and sodium (surface catalyst) in the catalysts of Examples 1 to 5 and Comparative Example 1 are shown in Table 1. In Table 1, the numbers in parentheses after the element names represent mass % in terms of metal atoms relative to the total mass of catalytic metals. In Table 1, "-" means that the element is not contained.
[0053]
[0054] [Evaluation] Using the carbon dioxide reduction catalysts of the above examples and comparative examples, a carbon dioxide reduction reaction was carried out in the following manner. A fixed-bed flow-type reactor was used, and the reaction gas was CO 2 0.28NL / h, H 2 0.84NL / h(CO 2 / H 2 W / F (catalyst weight / gas flow rate) was 5.0 g·h / mol, and space velocity SV (Space Velocity) was 5,000 h -1 The reaction conditions were a temperature of 380°C, a pressure of 3 MPa, and a reaction time of 4 hours. The gas components after the catalytic reaction were qualitatively and quantitatively analyzed by online gas chromatography (Shimadzu, GC-2014AT, detector: thermal conductivity detector (TCD)) and a flame ionization detector (FID) (Shimadzu, GC-2014AF). The liquid components after the catalytic reaction were also qualitatively and quantitatively analyzed by offline gas chromatography (Shimadzu, GC-2014AF, detector: flame ionization detector (FID)).
[0055] (CO 2 Conversion rate) CO by the above carbon dioxide reduction reaction 2 The conversion rate of CO was calculated by the following formula (1). The results are shown in Figure 3. 2 The improvement in conversion rate was confirmed. 2 Conversion rate (%) = (CO before reaction 2 concentration)-(CO after reaction 2 concentration) / (CO before reaction 2 Concentration)×100…(1)
[0056] (C 8-16 Selectivity) of hydrocarbons having 8 to 16 carbon atoms (C 8-16The selectivity of CO was calculated by the following formula (2). The results are shown in Figure 4. It was confirmed that the addition of Zn improved the selectivity. 2 The CO adsorbed on the catalyst due to the improved conversion rate 2 increases, and the intermediate CH 2 It is believed that the amount of C increased, the carbon chain grew, and the selectivity improved. 8-16 Selectivity (%) = (C 8-16 (concentration of contained components) / ((CO before reaction 2 concentration)-(CO after reaction 2 Concentration))×100…(2)
[0057] (C 8-16 Production rate (yield) of hydrocarbons having 8 to 16 carbon atoms (C 8-16 The CO 2 production rate was calculated using the following formula (3). The results are shown in Figure 5. 2 Conversion rate and C 8-16 Selectivity improved, C 8-16 The production rate was improved. 8-16 Production rate (%) = CO 2 Conversion rate x C 8-16 Selection rate / 100...(3)
[0058] In FIG. 5, the C content of Zn is 5, 7.5, 10, 12.5, and 15 mass%. 8-16 The generation rate was approximated by least squares. The approximate formula obtained is shown in the following formula (4): (C 8-16 Generation rate (%)) = 0.0336x 4 -1.3345x 3 +18.754x 2 -109.39x+244.87...(4)
[0059] In the above formula (4), x means the Zn content (% by mass). From the above formula (4), C of Comparative Example 1, which has a Zn content of 0% by mass, 8-16 C exceeding production rate (%) 8-16 The Zn content in the catalyst metal that gave the production rate (%) was calculated to be 7.4 to 12.3 mass %.
[0060] (Zn and reactive intermediate Fe 5 C 2Next, the relationship between the presence or absence of Zn in the catalysts of Example 3 and Comparative Example 1 and the reaction intermediate Fe 5 C 2 The relationship between the ratio of Fe atoms and the ZnO content was investigated. The results are shown in Figure 6. The vertical axis of Figure 6 represents the ratio of Fe atoms to the ZnO content. 5 C 2 The horizontal axis of FIG. 6 indicates the presence or absence of Zn (comparative example 1 does not contain Zn, and example 3 contains Zn). 5 C 2 The ratio was measured using a Mössbauer spectrometer, and the radiation source was 57 A Co / Rh matrix was used. After performance evaluation, the catalyst was processed into a thin film and subjected to spectroscopic measurement. 3 O 4 , Fe 5 C 2 , Fe was calculated by fitting. From FIG. 6, when Zn is contained, the reaction intermediate Fe 5 C 2 Considering the results of Figures 3 to 5 together, it is clear that the addition of Zn to the catalyst metal 8 -C 16 The improvement of catalytic activity such as production rate is due to the reaction intermediate Fe 5 C 2 It is presumed that this is due to the large amount of
[0061] By using a carbon dioxide reduction (fuel synthesis) device filled with the carbon dioxide reduction catalyst of the present invention, it is possible to obtain a large amount of higher hydrocarbons having about 8 to 16 carbon atoms, which can be expected to be used to produce aviation fuel with a small input of energy.
[0062] REFERENCE SIGNS LIST 1, 1'... fuel synthesis device 20, 20'... catalytic reaction vessel 30... catalytic reaction vessel 40, 40'... water trap section L... flow path C1... carbon dioxide reduction catalyst C2... carbon dioxide reduction catalyst
Claims
1. A carbon dioxide reduction catalyst that reduces carbon dioxide by subjecting carbon dioxide and hydrogen to a hydrogenation reaction, the carbon dioxide reduction catalyst containing iron, gallium, and zinc as catalytic metals, with the iron being the main component of the catalytic metals.
2. The carbon dioxide reduction catalyst according to claim 1, which produces hydrocarbons by hydrogenating carbon dioxide and hydrogen.
3. The carbon dioxide reduction catalyst according to claim 1, wherein the content of said gallium is greater than the content of said zinc.
4. The carbon dioxide reduction catalyst according to claim 1, wherein the content of said zinc relative to said catalytic metal is 5 to 15 mass %.
5. The carbon dioxide reduction catalyst according to claim 1, wherein the content of said zinc relative to said catalytic metal is 9 to 11 mass %.
6. The carbon dioxide reduction catalyst according to claim 1, further comprising sodium as a co-catalyst in addition to the catalytic metal.
7. A method for producing higher hydrocarbons, which comprises producing hydrocarbons having 8 to 16 carbon atoms from a feed gas containing carbon dioxide and hydrogen using the carbon dioxide reduction catalyst according to any one of claims 1 to 6.
Citation Information
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