Catalyst body, method for producing catalyst body, method for producing fuel, and gas phase reaction device

Abstract

A catalyst body comprising: an amorphous support that is a single body containing a composite oxide that includes elemental aluminum and elemental silicon; and elemental copper that is dispersed in the support. A gas phase reaction device comprising: a reactor that forms a gas flow path; and a catalyst body that is provided in the reactor.

Description

Catalyst, method for producing a catalyst, method for producing fuel, and gas-phase reactor

[0001] This disclosure relates to a catalyst, a method for producing a catalyst, a method for producing a fuel containing dimethyl ether, and a gas-phase reactor.

[0002] Dimethyl ether (hereinafter sometimes referred to as "DME") is expected to be a next-generation clean fuel that can replace liquefied petroleum gas or diesel fuel. To date, the inventors have proposed a catalyst for directly synthesizing DME from carbon oxides and hydrogen (Patent Document 1).

[0003] Japanese Patent Publication No. 2014-054607, U.S. Patent No. 12275004, Chinese Patent Application Publication No. 101157040, Japanese Patent Publication No. 2010-115628, Japanese Patent Publication No. 2014-054607

[0004] One aspect of this disclosure relates to a catalyst that can efficiently produce a material containing dimethyl ether that can be used as a fuel through the reaction of carbon oxides and hydrogen.

[0005] This disclosure includes: [1] A catalyst comprising: an amorphous carrier which is a single entity comprising a composite oxide comprising aluminum and silicon elements; and copper elements dispersed within the carrier. [2] The catalyst according to [1], wherein the catalyst further comprises one or more co-catalyst elements selected from the group consisting of gallium, zirconium, lanthanum, zinc, cerium, yttrium, manganese, and iron elements, and the co-catalyst elements are dispersed within the carrier. [3] Al ２ O ３ The amount of aluminum element in the catalyst, converted to mass, is W1, and SiO ２The catalyst according to [1] or [2], wherein when the amount of silicon element in the catalyst converted to an amount is W2, the ratio of W2 to the sum of W1 and W2 is 25% by mass or more and 98% by mass or less. [4] The catalyst according to any one of [1] to [3], which is a fuel production catalyst for producing a fuel containing dimethyl ether by the reaction of carbon oxide and hydrogen. [4'] Use or application of the catalyst according to any one of [1] to [3] for producing a fuel containing dimethyl ether by the reaction of carbon oxide and hydrogen. [5] A method for producing a catalyst, comprising: preparing a sol-like dispersion containing an aluminum element, a silicon element, copper ions, and a solvent; removing the solvent from the dispersion to form a gel; and firing the gel to form a catalyst containing a copper element, wherein the preparation of the dispersion comprises: forming a mixture containing an aluminum compound containing an aluminum element, a silicon compound containing a silicon element, and a solvent, wherein one of the aluminum compound or the silicon compound is a hydrolyzable compound; forming a sol-like dispersion from the mixture by hydrolysis of the hydrolyzable compound; and adding a copper element to the dispersion; or forming a mixture containing an aluminum compound containing an aluminum element, a silicon compound containing a silicon element, a copper element, and a solvent, wherein one of the aluminum compound or the silicon compound is a hydrolyzable compound; and forming a sol-like dispersion from the mixture by hydrolysis of the hydrolyzable compound.[6] The dispersion further comprises one or more co-catalyst elements selected from the group consisting of gallium, zirconium, lanthanum, zinc, cerium, yttrium, manganese, and iron, and preparation of the dispersion comprises forming a mixture comprising an aluminum compound containing an aluminum element, a silicon compound containing a silicon element, and a solvent, wherein one of the aluminum compound or the silicon compound is a hydrolyzable compound; forming a sol-like dispersion from the mixture by hydrolysis of the hydrolyzable compound; and adding a copper element and the co-catalyst element to the dispersion; or the method according to [5], comprising forming a mixture comprising an aluminum compound containing an aluminum element, a silicon compound containing a silicon element, a copper element, the co-catalyst element, and a solvent, wherein one of the aluminum compound or the silicon compound is a hydrolyzable compound; and forming a dispersion from the mixture by hydrolysis of the hydrolyzable compound. [7] A method for producing a fuel containing dimethyl ether, comprising generating dimethyl ether by the reaction of a carbon oxide and hydrogen in the presence of a catalyst according to any one of [1] to [3]. [8] A gas-phase reactor comprising a reactor forming a gas flow path and a catalyst according to any one of [1] to [3] provided in the reactor. [9] The gas-phase reactor according to [8], wherein the reactor further comprises an FT catalyst that promotes the Fischer-Tropsch reaction, and the FT catalyst is provided downstream of the catalyst in the gas flow path.

[0006] A material containing dimethyl ether that can be used as fuel can be efficiently produced by the reaction of carbon oxides and hydrogen.

[0007] It is a schematic diagram showing an example of a gas-phase reaction apparatus. It is a schematic diagram showing an example of a gas-phase reaction apparatus. It is a graph showing the production rate of DME in the synthesis test of DME and methanol. It is a graph showing the relationship between the production rate of DME and the reaction temperature. It is a graph showing the relationship between the production rate of methanol and the reaction temperature. It is a graph showing the relationship between the total production rate of DME and methanol and the reaction temperature. It is a graph showing the relationship between the production rate of DME and the reaction temperature. It is a graph showing the relationship between the production rate of methanol and the reaction temperature. It is an example of an X-ray diffraction pattern of a catalyst body.

[0008] The present invention is not limited to the following examples.

[0009] An example of the catalyst body according to the present disclosure includes a carrier containing a composite oxide containing an aluminum element and a silicon element, and a copper element dispersed in the carrier. The carrier can be a single body (for example, a granular body) integrally formed, rather than a mixture composed of a plurality of types of particles. Catalyst fine particles containing a copper element may be dispersed inside the carrier that is a single body. A catalyst body having such a structure can be formed by, for example, the sol-gel method described later.

[0010] The catalyst body according to the present disclosure can promote a reaction for generating DME from, for example, carbon oxides and hydrogen, mainly based on the catalytic activity of the copper element. The carbon oxides may include carbon dioxide and / or carbon monoxide. When the carbon oxide is carbon dioxide or carbon monoxide, in the presence of the catalyst body, DME can be efficiently generated mainly by the following reaction. The generated gas may also include methanol that has not been converted to DME by dehydration. A gas or liquid containing DME and methanol can also be used as a fuel. CO ２ + 3H ２ → CH ３ OH + H ２ O CO + 2H ２ → CH ３ OH 2CH ３ OH → CH ３ OCH ３ (DME) + H ２ O

[0011] Supports containing composite oxides of aluminum and silicon elements enable more efficient DME production compared to supports containing aluminum oxide but not silicon oxide. Supports with introduced silicon oxide have relatively high acidity, which is thought to contribute to the efficient production of DME. ２ When the acidity of the support decreases due to molecular adsorption or other factors, the generation of DME through methanol dehydration tends to become less efficient. It is thought that maintaining high acidity in the support facilitates efficient methanol dehydration. Gas containing a high proportion of DME, obtained through significant methanol dehydration, may be particularly advantageous as a fuel.

[0012] A composite oxide containing aluminum and silicon elements refers to all oxides containing aluminum oxide and silicon oxide. The composite oxide may also be aluminum silicate.

[0013] Al ２ O ３ The amount of aluminum element in the catalyst, converted to mass, is W1, and SiO ２ When the amount of silicon element in the catalyst converted to a certain amount is W2, the ratio of W2 to the sum of W1 and W2 may be 25% by mass or more and 98% by mass or less. When the ratio of W2 corresponding to the amount of silicon oxide is within this range, DME can be produced particularly efficiently and selectively. From a similar viewpoint, the ratio of W2 to the sum of W1 and W2 may be 30% by mass or more, 35% by mass or more, 40% by mass or more, 45% by mass or more, 50% by mass or more, or 55% by mass or more, and may be 95% by mass or less. W1 is the same amount of Al as the amount of aluminum element in the catalyst. ２ O ３ It is the mass of W2. W2 is SiO ２ The amount of silicon in the catalyst, converted to the same amount as the amount of SiO ２ It is the mass of.

[0014] Generally, catalyst supports are often crystalline, but the support according to this disclosure can be amorphous. However, the amorphous support according to this disclosure may also contain trace amounts of crystalline phase. In the X-ray diffraction pattern of the catalyst including the support, Al ２ O ３ SiO ２ If no peaks originating from the zeolite crystals are observed, or if they are extremely small, the support is considered amorphous. For example, if no peaks are observed at the reference 2θ value ± 1° for each of these crystals, or if peaks are observed but their peak heights are 10% or less of the peak heights originating from the Cu crystal at 2θ = 43.2° or nearby, or from the CuO crystal at 2θ = 35.6° or nearby, the support can be determined to be amorphous. Here, Al ２ O ３ The reference 2θ values ​​for the peaks originating from the crystal are 45.9° and 67.0°, and SiO ２ The reference 2θ values ​​for peaks originating from the crystals are 22.0°, 25.9°, and 27.8°, while the reference 2θ values ​​for peaks originating from the zeolite crystals are 7.9° and 23.0°. Peak height refers to the height from the baseline (the portion of the X-ray diffraction pattern where no peaks are observed).

[0015] Fine particles containing copper may be dispersed in the carrier. The amount of copper in the catalyst may be 5% by mass or more and 70% by mass or less relative to the mass of the catalyst. The amount of copper in the catalyst may be 10% by mass or more, 15% by mass or more, 20% by mass or more, 25% by mass or more, or 30% by mass or more, and may be 65% by mass or less, 60% by mass or less, 55% by mass or less, or 50% by mass or less. At least a portion of the copper may be contained in the carrier as an oxide. Before DME production using the catalyst, the catalyst may be subjected to a reduction treatment to reduce copper oxide and form metallic copper. The copper in the catalyst often forms crystals as metallic copper or copper oxide.

[0016] The catalyst may further contain one or more co-catalyst elements selected from the group consisting of gallium, zirconium, lanthanum, zinc, cerium, yttrium, manganese, and iron. These co-catalyst elements can contribute to the more efficient production of dimethyl ether and methanol by promoting the reaction that mainly produces methanol. The co-catalyst elements are also dispersed in the carrier. Fine particles containing the co-catalyst elements may be dispersed in the carrier. The fine particles containing the co-catalyst elements may be different particles from the fine particles containing copper. Alternatively, fine particles containing copper and co-catalyst elements may be formed. At least a portion of the co-catalyst elements may be contained in the carrier as oxides.

[0017] The amount of co-catalyst elements in the catalyst may be 0.5% by mass or more and 70% by mass or less, relative to the mass of the catalyst. The amount of co-catalyst elements in the catalyst may be 1% by mass or more, or 2% by mass or more, or 60% by mass or less, or 50% by mass or less.

[0018] The catalyst according to this disclosure can be easily produced, for example, by a sol-gel method involving a sol-like dispersion containing aluminum, silicon, copper, and a solvent. According to the sol-gel method, a catalyst in which copper is uniformly dispersed throughout individual supports containing a complex oxide can be easily formed. The supports of catalysts formed by the sol-gel method are usually amorphous.

[0019] In one example of the sol-gel method, a sol-like dispersion is prepared by a method comprising forming a mixture containing an aluminum compound containing an aluminum element, a silicon compound containing a silicon element, and a solvent, wherein at least one of the aluminum compound or silicon compound is a hydrolyzable compound; forming a sol-like dispersion from the mixture by hydrolysis of the hydrolyzable compound; and adding copper element to the dispersion. Either the aluminum compound or the silicon compound may be a hydrolyzable compound. When only one of the aluminum compound or the silicon compound is a hydrolyzable compound, the resulting catalyst tends to produce DME more efficiently compared to when both the aluminum compound and the silicon compound are hydrolyzable compounds.

[0020] The silicon compound may be a hydrolyzable compound, and examples of such compounds include various silicon alkoxides. Examples of silicon alkoxides include tetraethoxysilane (tetraethyl orthosilicate), tetramethoxysilane, tetrapropoxysilane, and tetrabutoxylan.

[0021] The aluminum compound may be a hydrolyzable compound, and examples of such compounds include various aluminum alkoxides. Examples of aluminum alkoxides include aluminum isopropoxide, aluminum ethoxide, and aluminum butoxide.

[0022] The aluminum compound may be an aluminum salt, and the silicon compound may be a hydrolyzable compound. Examples of aluminum salts include aluminum nitrate, aluminum acetate, aluminum lactate, aluminum hydrochloride, aluminum sulfate, and aluminum hydroxide.

[0023] The solvent contained in the sol-like dispersion and the mixture used to form it may include water, a hydrophilic solvent, or both. The hydrophilic solvent may be, for example, an alcohol (methanol, ethanol, etc.) or N,N-dimethylformamide.

[0024] The sol-like dispersion and the mixture used to form it may contain a template agent for forming pores in the carrier. The template agent may be, for example, ethylene glycol.

[0025] By adding an acid or base to a mixture containing an aluminum compound, a silicon compound, and a solvent, the hydrolysis of the hydrolyzable compound (aluminum compound and / or silicon compound) can be promoted. As hydrolysis progresses, a sol-like dispersion containing particulate hydrolysates is formed. For example, an acid may be added so that the pH of the mixture (dispersion) is 3 or less, or 2 or less. As the acid, inorganic acids such as nitric acid, hydrochloric acid, and sulfuric acid may be used. A base may also be added so that the pH of the mixture (dispersion) is 9 or more. As the base, inorganic bases such as ammonia, sodium carbonate, and sodium hydroxide may be used. The mixture may be heated while adding the acid or base. The heating temperature may be, for example, 40°C to 80°C.

[0026] Copper is introduced into a sol-like dispersion by adding, for example, an aqueous solution or alcohol solution of a copper compound containing copper. The copper compound can be, for example, a nitrate, carbonate, acetate, chloride, sulfate, alkoxide compound, or carbonyl compound. An aqueous solution or alcohol solution containing the copper compound and a metal compound containing a co-catalyst element may be added to the dispersion. Separately from the copper compound solution, an aqueous solution or alcohol solution containing a metal compound containing a co-catalyst element may be added to the dispersion. The metal compound containing a co-catalyst element can be, for example, a nitrate, carbonate, acetate, chloride, sulfate, alkoxide compound, carbonyl compound, or oxide.

[0027] Instead of introducing copper elements into a sol-like dispersion, a copper compound containing copper elements may be added to a mixture for forming a sol-like dispersion, and then hydrolysis of a hydrolyzable compound (aluminum compound and / or silicon compound) may be carried out to form particulate hydrolysates and a sol-like dispersion containing copper elements. The mixture may further contain co-catalyst elements. Examples of the raw materials that can be used in this case are the same as described above.

[0028] A catalyst is formed by a method that includes removing the solvent from the formed sol-like dispersion to form a gel, and then forming a catalyst containing copper elements by calcining the gel.

[0029] If copper is added after a sol-like dispersion has been formed, the dispersion containing copper may be aged, and then the solvent may be removed. The dispersion may be heated during aging. The heating temperature for aging may be, for example, between 40°C and 80°C. The solvent is removed under reduced pressure if necessary. Removal of the solvent yields a non-flowing gel.

[0030] By firing the gel, a composite oxide containing aluminum and silicon elements is formed, thereby creating a catalyst body containing a support containing the composite oxide and copper elements dispersed in the support. The gel may be fired in air. The heating temperature for firing may be, for example, 250°C to 800°C. The heating time for firing may be, for example, 1 hour to 30 hours.

[0031] The catalyst after calcination can be crushed as needed to obtain a granular catalyst. The catalyst may also be molded into any shape (granular, spherical, cylindrical, or otherwise).

[0032] The catalyst and support may be porous. From the viewpoint of efficient DME production, the specific surface area of ​​the catalyst may be, for example, 10 m². ２ / g or more 500m ２ It may be less than / g. From a similar viewpoint, the specific surface area of ​​the catalyst is 100 m². ２ / g or more, 150m ２ / g or more, 200m ２ / g or more, 250m ２ / g or more, or 300m ２ The amount may be greater than or equal to / g. The specific surface area of ​​the catalyst can be measured, for example, by the BET method or the Langmuir method.

[0033] The catalyst may be supported on a substrate. In other words, a structure having a substrate and a catalyst layer containing the catalyst may be used for DME production, etc. The substrate may be a heat-conducting substrate. Examples of materials constituting the substrate include metals such as iron, copper, aluminum, nickel, and titanium; metal carbides such as iron carbide, aluminum carbide, nickel carbide, and titanium carbide; metal nitrides such as iron nitride, aluminum nitride, nickel nitride, and titanium nitride; and metal oxides such as alumina, silica, zeolite, zirconia, and titania. The substrate may have, for example, a plate-like, spherical, mesh-like, or honeycomb-like shape.

[0034] A structure having a catalyst layer can be obtained, for example, by a method that includes attaching a sol-like dispersion for forming a catalyst to a substrate, removing the solvent from the dispersion attached to the substrate to form a gel, and forming a catalyst by calcining the gel.

[0035] The catalyst may be subjected to a reduction treatment before being used for the production of fuels containing DME. The reduction treatment is carried out, for example, by heating the catalyst in a reducing atmosphere. The heating temperature for the reduction treatment may be, for example, 200°C to 800°C. The heating time for the reduction treatment may be, for example, 1 hour or more, 3 hours or more, or 10 hours or less.

[0036] The catalysts exemplified above can be used as fuel-producing catalysts for manufacturing fuels containing DME by the reaction of carbon oxides and hydrogen. For DME production, the catalyst is usually placed in any reactor. The reactor may be, for example, a fixed-bed reactor, a fluidized-bed reactor, a moving-bed reactor, or a slurry reactor.

[0037] Figure 1 is a schematic diagram showing an example of a gas-phase reactor equipped with a catalyst according to the present disclosure. The gas-phase reactor 10 shown in Figure 1 comprises a fixed-bed reactor 1 forming a gas flow path and a catalyst 3 provided inside the reactor 1. The reactor 1 can be a tubular body having a gas inlet and a gas outlet, and a gas flow path is formed from the gas inlet to the gas outlet. The catalyst 3 forms a catalyst layer inside the reactor 1. Gas-permeable members (e.g., quartz wool) may be placed upstream and downstream of the catalyst layer containing the catalyst 3 as partitions for the area where the catalyst 3 is provided. A raw material gas G containing carbon oxides and hydrogen is supplied from the gas inlet on the upstream side of the gas flow path. ０ The product gas G containing DME is introduced into reactor 1. １ The generated gas G is discharged from reactor 1. １ This may also contain DME and methanol. Raw material gas G ０ The catalyst 3 may be subjected to a reduction treatment before it is introduced into the reactor 1.

[0038] Raw material gas G ０ This may include a carbon oxide, hydrogen, and an inert gas. The carbon oxide may be carbon monoxide, carbon dioxide, or both. The inert gas may be, for example, nitrogen, argon, or helium.

[0039] Raw material gas G ０ While the mixture is flowing through reactor 1, the catalyst 3 is heated as needed. The heating temperature may be, for example, 150°C to 350°C. The pressure inside reactor 1 may be 0.1 MPa to 10 MPa.

[0040] Figure 2 is a schematic diagram showing another example of a gas-phase reactor. The gas-phase reactor 11 shown in Figure 2 differs from the gas-phase reactor 10 in Figure 1 in that it includes an FT catalyst 5 located downstream of the catalyst 3 in the gas flow path. The FT catalyst 5 is a catalyst that promotes the Fischer-Tropsch reaction of the following formula. By providing the FT catalyst 5, carbon monoxide that remains in the gas without being converted to methanol can be converted into hydrocarbons that can be used as fuel together with DME and undehydrated methanol. As a result, the product gas G containing DME and hydrocarbons is produced. １(2n+1)H can be obtained efficiently. ２ +nCO→C ｎ H ２ｎ＋２ +nH ２ O

[0041] The present invention is not limited to the following examples. Test 1 1-1. Preparation of catalyst Catalyst (Al ２ O ３ -SiO ２ (=10-50) Tetraethoxysilane (27.4 g), ethanol (46.9 mL), and ethylene glycol (14.8 mL) were added to water (500 mL) to form a mixture. This mixture was heated to approximately 70°C and stirred for approximately 1 hour. An aqueous solution containing aluminum nitrate nonahydrate (11.3 g) was then slowly added little by little, while monitoring the pH change, until the pH decreased by approximately 0.25 in 15 minutes and the pH became 2 or less. During this time, heating at approximately 70°C and stirring were continued. If the pH did not become 2 or less after adding all of the aluminum nitrate aqueous solution, dilute nitric acid aqueous solution was added little by little while continuing heating at approximately 70°C and stirring, until the pH was finally reduced to 1.0-1.5. The mixture with a pH of 2 or less was heated and stirred for more than 30 minutes. The entire process up to this stage took approximately 6 hours. At this stage, a sol-like dispersion was formed from the mixture.

[0042] To a sol-like dispersion, an aqueous copper nitrate solution obtained by dissolving copper(II) nitrate trihydrate (22.9 g) in pure water was added. The dispersion was then heated to approximately 70°C and stirred overnight. After that, water was removed from the dispersion under reduced pressure to obtain a gel. The gel was crushed to obtain granular gel. The granular gel was calcined in an air atmosphere by heating at 500°C for 5 hours to obtain approximately 15 g of calcined material (catalyst). The obtained calcined material was subjected to a reduction treatment in a hydrogen atmosphere at 450°C for 10 hours to obtain a granular catalyst body (Al) containing aluminum silicate and copper elements. ２ O ３ -SiO ２ A value of 10⁻⁵⁰ was obtained. The copper content was 40% by mass relative to the mass of the catalyst.

[0043] In the resulting catalyst, Al ２ O ３ and SiO ２The mass ratio was 10:50. This mass ratio is equal to the amount of aluminum element calculated from the amount of aluminum nitrate nonahydrate used. ２ O ３ The amount of SiO2 is the same as the amount of silicon element calculated from the mass of tetraethoxysilane and the amount of tetraethoxysilane used. ２ This is the ratio to the mass of. The amount of copper nitrate aqueous solution added to the sol-like dispersion is Al ２ O ３ SiO ２ The amount of copper element was adjusted so that its ratio to the total amount of copper element was 40% by mass.

[0044] Catalyst (Al ２ O ３ -SiO ２ (=60-0, 30-30, 24-36, 15-45, 5-55 or 0-60) Amount of aluminum nitrate xahydrate and tetraethoxysilane Al ２ O ３ and SiO ２ Other than changing the mass ratio to 60:0, 30:30, 24:36, 15:45, 5:55, or 0:60, the catalyst (Al ２ O ３ -SiO ２ Using the same procedure as in (=10-50), the catalyst (Al ２ O ３ -SiO ２ =60-0), catalyst body (Al ２ O ３ -SiO ２ =30-30), catalyst body (Al ２ O ３ -SiO ２ =24-36), catalyst body (Al ２ O ３ -SiO ２ =15-45), catalyst body (Al ２ O ３ -SiO ２ = 5-55), and catalyst (Al ２ O ３ -SiO ２ We obtained (= 0 - 60).

[0045] Catalyst (Cu-Zn-Al ２ O ３ -SiO２ = 30 - 10 - 10 - 50) Instead of the copper nitrate aqueous solution, copper(II) nitrate trihydrate (17.2 g) corresponding to 30% by mass of copper element and zinc(II) nitrate hexahydrate (6.89 g) corresponding to 10% by mass of zinc element were dissolved in pure water to obtain a mixed aqueous solution of copper nitrate and zinc nitrate. This mixed aqueous solution was added to the sol-like dispersion instead of the copper nitrate aqueous solution, and other than this, the catalyst support (Al ２ O ３ -SiO ２ = 10 - 50) was obtained in the same procedure as the catalyst support (Cu - Zn - Al ２ O ３ -SiO ２ = 30 - 10 - 10 - 50). The content of copper element was 30% by mass based on the mass of the catalyst support, and the content of zinc element was 10% by mass based on the mass of the catalyst support. The mass ratio of Al ２ O ３ to SiO ２ was 10:50.

[0046] 1 - 2. Synthesis test of DME and methanol Comparison for each mass ratio of Al ２ O ３ to SiO ２ For each catalyst support (0.500 g) with a mass ratio of Al ２ O ３ -SiO ２ = 60 - 0, 30 - 30, 24 - 36, 15 - 45, 10 - 50, 5 - 55 or 0 - 60, they were placed in the reaction tube of a fixed-bed reactor to form a catalyst layer. The reaction tube was heated by an electric furnace, and the reaction temperature was measured by a thermocouple connected to the downstream side of the catalyst layer. The heating temperature by the electric furnace was adjusted so that the reaction temperature became 240 °C. A mixed gas of carbon dioxide - hydrogen (CO ２ / H ２ = 1 / 3) - argon was introduced at a supply rate of 22.0 mL / min. The ratio of each gas in the mixed gas was CO ２ / H ２The ratio of Ar was 22.40 / 68.17 / 9.43 (volume %). The atmospheric pressure inside the reaction tube was approximately 0.90 MPa gauge pressure (absolute pressure 1.0 MPa). The amount of dimethyl ether (DME) and methanol produced was measured by analyzing the gas discharged from the reaction tube using gas chromatography. From the measurement results and the amount of catalyst, the production rate of DME and methanol per 1.00 g of catalyst (μmolg) was calculated. ｃａｔ －１ h －１ Figure 3 is a graph showing the production rates of DME, methanol, and their sum. A catalyst (Al) was obtained using a catalyst having a support containing a composite oxide containing aluminum and silicon elements. ２ O ３ -SiO ２ It was confirmed that DME and methanol were produced at a much higher rate compared to (60-0).

[0047] Comparison with and without co-catalyst (Zn) Al ２ O ３ -SiO ２ =10-50, or Cu-Zn-Al ２ O ３ -SiO ２ 0.500 g of catalyst = 30-10-10-50 was placed in the reaction tube of a fixed-bed reactor. The only difference was that the reaction temperature was changed to 160°C, 180°C, 200°C, 220°C, 240°C, 260°C, 280°C, or 300°C. ２ O ３ and SiO ２ Under the same conditions as in the "Comparison by Mass Ratio," synthesis tests of DME and methanol were conducted. From the measurement results and the amount of catalyst, the production rate of DME and methanol per 1.00 g of catalyst (μmolg) was determined. ｃａｔ －１ h －１ The following was determined. Figures 4, 5, and 6 are graphs showing the relationship between the production rates of DME, methanol, and the sum of these, and the reaction temperature, respectively. The Cu-Zn-Al shown in these figures ２ O ３ -SiO ２ = 40 - 0 - 10 - 50 is the above Al ２ O３ -SiO ２ = 10⁻⁵⁰. It was confirmed that the introduction of a co-catalyst element leads to even more efficient production of DME and methanol over a wide temperature range.

[0048] Test 2 2-1. Preparation of catalyst Catalyst A (aluminum nitrate / tetraethoxysilane) Catalyst (Cu-Zn-Al) from Test 1, using aluminum nitrate nonahydrate, tetraethoxysilane, copper(II) nitrate trihydrate, and zinc(II) nitrate hexahydrate. ２ O ３ -SiO ２ Catalyst A was obtained using the same procedure as for the preparation method of (30-10-10-50), including the amount of raw materials used.

[0049] Catalyst B (aluminum isopropoxide / tetraethoxysilane) Aluminum isopropoxide, tetraethoxysilane, ethanol, and ethylene glycol were added to water to form a mixture. Dilute nitric acid aqueous solution was added to adjust the pH of the mixture to 2 or less. The mixture was heated to approximately 70°C while stirring to form a sol-like dispersion. The catalyst B was the same as in Test 1 (Cu-Zn-Al), except that a copper nitrate / zinc nitrate mixed aqueous solution was added to the obtained sol-like dispersion. ２ O ３ -SiO ２ Catalyst B was obtained using the same procedure as the preparation method for (30-10-10-50). The amount of each raw material charged was Al ２ O ３ SiO ２ The ratio of copper and zinc elements is the same as that of the catalyst (Cu-Zn-Al) in Test 1. ２ O ３ -SiO ２ It was adjusted to be the same as (=30-10-10-50).

[0050] 2-2. Adsorption isotherms for catalysts A and B were obtained by measuring the amount of nitrogen gas adsorbed using a gas adsorption measuring device, which measures specific surface area, pore volume, and pore diameter. From the obtained adsorption isotherms, the specific surface area, pore volume, and pore diameter were determined by the BET method. The results are shown in Table 1.

[0051] 2-3. Synthesis Tests of DME and Methanol The synthesis tests, using the same procedure as in the synthesis test of Test 1, measured the production rate of DME or methanol by catalyst A or B in the reaction temperature range of 220 to 320°C. Figures 7 and 8 are graphs showing the relationship between the production rate of DME and methanol and the reaction temperature, respectively. This test also confirmed that DME and methanol are efficiently produced over a wide temperature range. Catalyst A tended to show a higher production rate compared to catalyst B, particularly in the high-temperature range.

[0052] 2-4. Analysis by X-ray diffraction Catalyst A was analyzed by X-ray diffraction before and after reduction treatment with hydrogen, and after the synthesis test (CO2 hydrogenation). Figure 9 shows the X-ray diffraction pattern of catalyst A. In all X-ray diffraction patterns, Al ２ O ３ Peaks at reference 2θ values ​​±1° of 45.9° and 67.0° originating from the crystal, and SiO ２ No peaks were observed at the reference 2θ values ​​±1° at 22.0°, 25.9°, and 27.8°, which originate from the crystal, nor were any peaks observed at the reference 2θ values ​​±1° at 7.9° and 23.0°, which originate from the zeolite crystal. From this result, it was confirmed that the support constituting the catalyst is amorphous.

[0053] 1...reactor, 3...catalyst, 5...FT catalyst, 10...gas-phase reactor.

Claims

1. A catalyst comprising: an amorphous carrier which is a single entity containing a composite oxide containing aluminum and silicon elements; and copper elements dispersed within the carrier.

2. The catalyst according to claim 1, wherein the catalyst further comprises one or more co-catalyst elements selected from the group consisting of gallium, zirconium, lanthanum, zinc, cerium, yttrium, manganese, and iron, and the co-catalyst elements are dispersed within the carrier.

3. Al ２ O ３ The amount of aluminum element in the catalyst, converted to mass, is W1, and SiO ２ The catalyst according to claim 1, wherein when the amount of silicon element in the catalyst converted to an amount is W2, the ratio of W2 to the sum of W1 and W2 is 25% by mass or more and 98% by mass or less.

4. The catalyst according to any one of claims 1 to 3, which is a fuel production catalyst for producing a fuel containing dimethyl ether by the reaction of carbon oxide and hydrogen.

5. A method for producing a catalyst, comprising: preparing a sol-like dispersion containing an aluminum element, a silicon element, a copper element, and a solvent; removing the solvent from the dispersion to form a gel; and firing the gel to form a catalyst containing a copper element, wherein the preparation of the dispersion comprises: forming a mixture containing an aluminum compound containing an aluminum element, a silicon compound containing a silicon element, and a solvent, wherein one of the aluminum compound or the silicon compound is a hydrolyzable compound; forming a sol-like dispersion from the mixture by hydrolysis of the hydrolyzable compound; and adding a copper element to the dispersion; or forming a mixture containing an aluminum compound containing an aluminum element, a silicon compound containing a silicon element, a copper element, and a solvent, wherein one of the aluminum compound or the silicon compound is a hydrolyzable compound; and forming a sol-like dispersion from the mixture by hydrolysis of the hydrolyzable compound.

6. The method according to claim 5, wherein the dispersion further contains one or more co-catalyst elements selected from the group consisting of gallium, zirconium, lanthanum, zinc, cerium, yttrium, manganese, and iron, and preparation of the dispersion includes forming a mixture containing an aluminum compound containing an aluminum element, a silicon compound containing a silicon element, and a solvent, wherein one of the aluminum compound or the silicon compound is a hydrolyzable compound; forming a sol-like dispersion from the mixture by hydrolysis of the hydrolyzable compound; and adding a copper element and the co-catalyst element to the dispersion; or the method according to claim 5, wherein the mixture contains an aluminum compound containing an aluminum element, a silicon compound containing a silicon element, a copper element, the co-catalyst element, and a solvent, wherein one of the aluminum compound or the silicon compound is a hydrolyzable compound; and forming a dispersion from the mixture by hydrolysis of the hydrolyzable compound.

7. A method for producing a fuel containing dimethyl ether, comprising generating dimethyl ether by a reaction of a carbon oxide and hydrogen in the presence of a catalyst according to any one of claims 1 to 3.

8. A gas-phase reactor comprising a reactor forming a gas flow path and a catalyst according to any one of claims 1 to 3 provided inside the reactor.

9. The gas-phase reactor according to claim 8, wherein the reactor further comprises an FT catalyst that promotes the Fischer-Tropsch reaction, and the FT catalyst is provided downstream of the catalyst in the gas flow path.

Images