WO2021002224A1 - 触媒、反応装置、及び、炭化水素を製造する方法 - Google Patents

触媒、反応装置、及び、炭化水素を製造する方法 Download PDF

Info

Publication number
WO2021002224A1
WO2021002224A1 PCT/JP2020/024203 JP2020024203W WO2021002224A1 WO 2021002224 A1 WO2021002224 A1 WO 2021002224A1 JP 2020024203 W JP2020024203 W JP 2020024203W WO 2021002224 A1 WO2021002224 A1 WO 2021002224A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
iron
copper
based catalyst
powder
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2020/024203
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
康嗣 橋本
一則 宮沢
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eneos Corp
Original Assignee
JXTG Nippon Oil and Energy Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by JXTG Nippon Oil and Energy Corp filed Critical JXTG Nippon Oil and Energy Corp
Publication of WO2021002224A1 publication Critical patent/WO2021002224A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C9/00—Aliphatic saturated hydrocarbons
    • C07C9/14—Aliphatic saturated hydrocarbons with five to fifteen carbon atoms
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to a catalyst, a reactor, and a method for producing a hydrocarbon.
  • Patent Document 1 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).
  • FT Fischer-Tropsch
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 ⁇ m or more and less than 1000 ⁇ m.
  • 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.
  • ZnO zinc oxide
  • 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.
  • a carrier that supports a copper component.
  • zinc oxide is also usually supported on the carrier.
  • the carrier is preferably alumina such as ⁇ -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.
  • 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.
  • the additive metal may contain at least one selected from the group consisting of sodium, potassium and cesium.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • a single catalyst layer 10 including a copper-based catalyst and an iron-based catalyst is provided in the catalyst layer 10.
  • 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.
  • the amount of the iron-based catalyst may be larger than the amount of the copper-based catalyst.
  • 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.
  • 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.
  • 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.
  • Example 1 Preparation of catalyst Preparation of copper-based catalyst 5.0 g of ⁇ -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.
  • ⁇ -alumina BK-105, manufactured by Sumitomo Chemical Co., Ltd.
  • 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.
  • 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.
  • 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).
  • 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.
  • 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.
  • a distribution gas hydrogen gas
  • 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.
  • an aqueous solution containing 0.64 g of potassium hydroxide manufactured by Wako Pure Chemical Industries, Ltd.
  • 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.
  • an aqueous solution containing 1.28 g of potassium hydroxide manufactured by Wako Pure Chemical Industries, Ltd.
  • 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.
  • an aqueous solution containing 0.45 g of cesium hydroxide manufactured by Wako Pure Chemical Industries, Ltd.
  • 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.
  • an aqueous solution containing 0.90 g of cesium hydroxide manufactured by Wako Pure Chemical Industries, Ltd.
  • 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.
  • an aqueous solution containing 1.35 g of cesium hydroxide manufactured by Wako Pure Chemical Industries, Ltd.
  • 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.
  • an aqueous solution containing 1.80 g of cesium hydroxide manufactured by Wako Pure Chemical Industries, Ltd.
  • 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.
  • 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.
  • 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.
  • 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.
  • Reaction device 3 ... Reaction vessel, 3A ... Gas inlet, 3B ... Gas outlet, 10 ... Catalyst layer, 11 ... First catalyst layer, 12 ... Second catalyst layer.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
PCT/JP2020/024203 2019-07-03 2020-06-19 触媒、反応装置、及び、炭化水素を製造する方法 Ceased WO2021002224A1 (ja)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2019-124449 2019-07-03
JP2019124449A JP7181161B2 (ja) 2019-07-03 2019-07-03 触媒、反応装置、及び、炭化水素を製造する方法

Publications (1)

Publication Number Publication Date
WO2021002224A1 true WO2021002224A1 (ja) 2021-01-07

Family

ID=74100261

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2020/024203 Ceased WO2021002224A1 (ja) 2019-07-03 2020-06-19 触媒、反応装置、及び、炭化水素を製造する方法

Country Status (2)

Country Link
JP (1) JP7181161B2 (https=)
WO (1) WO2021002224A1 (https=)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011045874A (ja) * 2009-07-28 2011-03-10 Nippon Steel Corp Ｆｔ合成用触媒とその製造方法、並びに当該触媒を用いた炭化水素の製造方法
JP2014012267A (ja) * 2012-06-07 2014-01-23 Toyota Central R&D Labs Inc 炭化水素改質用触媒、それを用いた排ガス浄化用装置、及び炭化水素改質用触媒の製造方法
CN103769241A (zh) * 2014-02-18 2014-05-07 神华集团有限责任公司 一种固定床费托催化剂还原活化系统及其工艺
US20160045903A1 (en) * 2013-04-25 2016-02-18 Wuhan Kaidi Engineering Technology Research Institute Co., Ltd. Catalyst for fischer-tropsch synthesis and method for preparing the same, and method for preparing modified molecular sieve carrier
JP2017109169A (ja) * 2015-12-16 2017-06-22 岩谷産業株式会社 炭化水素合成触媒、炭化水素合成触媒の製造方法、炭化水素製造装置、炭化水素製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011045874A (ja) * 2009-07-28 2011-03-10 Nippon Steel Corp Ｆｔ合成用触媒とその製造方法、並びに当該触媒を用いた炭化水素の製造方法
JP2014012267A (ja) * 2012-06-07 2014-01-23 Toyota Central R&D Labs Inc 炭化水素改質用触媒、それを用いた排ガス浄化用装置、及び炭化水素改質用触媒の製造方法
US20160045903A1 (en) * 2013-04-25 2016-02-18 Wuhan Kaidi Engineering Technology Research Institute Co., Ltd. Catalyst for fischer-tropsch synthesis and method for preparing the same, and method for preparing modified molecular sieve carrier
CN103769241A (zh) * 2014-02-18 2014-05-07 神华集团有限责任公司 一种固定床费托催化剂还原活化系统及其工艺
JP2017109169A (ja) * 2015-12-16 2017-06-22 岩谷産業株式会社 炭化水素合成触媒、炭化水素合成触媒の製造方法、炭化水素製造装置、炭化水素製造方法

Also Published As

Publication number Publication date
JP2021010848A (ja) 2021-02-04
JP7181161B2 (ja) 2022-11-30

Similar Documents

Publication Publication Date Title
CN115485233B (zh) 用于氨分解的催化剂组合物
Tsiotsias et al. The role of alkali and alkaline earth metals in the CO2 methanation reaction and the combined capture and methanation of CO2
Suppiah et al. Supported metal oxide catalysts for CO2 Fischer–Tropsch conversion to liquid fuels─ a review
Cesário et al. Catalytic performances of Ni–CaO–mayenite in CO2 sorption enhanced steam methane reforming
Tada et al. Methanol synthesis via CO 2 hydrogenation over CuO–ZrO 2 prepared by two-nozzle flame spray pyrolysis
JP5778309B2 (ja) 水素製造触媒およびそれを用いた水素製造方法
CN108883408B (zh) 铁氧体催化剂，其制备方法和使用其制备丁二烯的方法
Zhang et al. Hollow submicrospherical Ni/Co-promoted CaO/Ca12Al14O33 for H2 production from sorption-enhanced water–gas shift with in situ CO2 conversion via CH4 reforming of CaCO3
JP6883289B2 (ja) 水素の製造方法及び水素製造用触媒
Daneshmand-Jahromi et al. Preparation of aerogel-supported copper oxide for the methane chemical looping combustion (CLC) process
KR101317723B1 (ko) 수화된 금속염의 용융함침을 이용한 금속 또는 산화금속 촉매 담지체의 제조 방법 및 그 금속 또는 산화금속 촉매 담지체
JP5691119B2 (ja) 水素化触媒の製造方法およびそれを使用したメタンガスの製造方法
Li et al. Efficient metal–organic framework-derived Cu–Zr oxygen carriers with an enhanced reduction reaction rate for chemical looping air separation
Utsis et al. Performance of Reverse Water Gas Shift on Coprecipitated and C‐Templated BaFe‐Hexaaluminate: The Effect of Fe Loading, Texture, and Promotion with K
Sayyed et al. Recent insights into the production of syngas and hydrogen using chemical looping-steam reforming (CL-SR)
Tan et al. Compatibility of NiO/CuO in Ca–Cu Chemical Looping for High‐Purity H2 Production with CO2 Capture
KR102177556B1 (ko) 메탄 개질 반응용 니켈 고담지 촉매의 제조방법 및 그 촉매
JP7181161B2 (ja) 触媒、反応装置、及び、炭化水素を製造する方法
Medeiros et al. Performance of hydroxyapatite-supported catalysts for methane production via CO2 hydrogenation on semi-pilot scale
JP7731195B2 (ja) 反応装置
JP2022102701A (ja) 触媒、触媒システムおよび触媒の製造方法
Gerzeliev et al. Partial oxidation of lower alkanes by active lattice oxygen of metal oxide systems: 2. Synthesis of solid contacts and syngas production in a pilot plant with a riser reactor
JP2011224555A (ja) アンモニア分解用触媒及び該触媒の製造方法、並びに該触媒を用いた水素製造方法
JP2017217630A (ja) マグネシア系触媒担体及びその製造方法
JP2022102705A (ja) 触媒システム

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20834474

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20834474

Country of ref document: EP

Kind code of ref document: A1