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  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
  • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
  • B01J21/04—Alumina
• • 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
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
  • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
  • B01J29/44—Noble metals
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  • 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
  • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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  • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/19—Catalysts containing parts with different compositions
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  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
  • B01J35/31—Density
  • B01J35/32—Bulk density
• • 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
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
• • 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
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
  • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
• • 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
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
  • B01J37/0063—Granulating
• • 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
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/16—Reducing
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  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/16—Reducing
  • B01J37/18—Reducing with gases containing free hydrogen
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/28—Phosphorising
• • 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
  • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
  • C07C1/0425—Catalysts; their physical properties
  • C07C1/043—Catalysts; their physical properties characterised by the composition
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
  • C10L3/12—Liquefied petroleum gas
• • 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
  • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
  • B01J2229/10—After treatment, characterised by the effect to be obtained
  • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
  • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
• • 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
  • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
  • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
  • C07C2521/04—Alumina
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
  • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
  • C07C2523/72—Copper
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
  • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
  • C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
  • C07C2523/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with zinc, cadmium or mercury
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2529/00—Catalysts comprising molecular sieves
  • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
  • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
  • C07C2529/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing iron group metals, noble metals or copper
  • C07C2529/44—Noble metals

Definitions

• the present disclosure relates to a catalyst for synthesizing liquefied petroleum gas and a method for producing liquefied petroleum gas.
• LPG Liquefied petroleum gas
• propane and butane exists inside oil and natural gas fields mixed with impurity gases such as methane and ethane. After such gas is transferred to an aboveground facility, propane and butane are separated and recovered from the gas, and impurities such as sulfur and mercury are removed to obtain liquefied petroleum gas.
• liquefied petroleum gas is also contained in crude oil. Therefore, propane and butane can also be separated and extracted to obtain liquefied petroleum gas in the refinery refining process.
• Patent Documents 1 to 4 describe methods for producing liquefied petroleum gas whose main component is butane.
• Non-Patent Documents 1 and 2 disclose a method for producing hydrocarbons whose main component is isobutane from synthesis gas of carbon monoxide and hydrogen.
• liquefied petroleum gas and gasoline are mainly produced using a mixed catalyst of a methanol synthesis catalyst and a palladium-supporting zeolite.
• the yield of liquefied petroleum gas such as propane is reduced when liquefied petroleum gas is synthesized at low temperature using the conventional mixed catalyst such as the above-mentioned patent document. is very low.
• propane is easily vaporized and can be used as a fuel even in cold regions, it is desirable that the yield of propane is particularly high among liquefied petroleum gases.
• An object of the present disclosure is to provide a catalyst for synthesizing liquefied petroleum gas and a method for producing liquefied petroleum gas, which can produce propane at a high yield even if the synthesis temperature of liquefied petroleum gas is low.
• a ratio of the number of moles of SiO 2 to the number of moles of Al 2 O 3 contained in the MFI-type zeolite catalyst material containing a Cu—Zn-based catalyst material and a Pt-supporting MFI-type zeolite catalyst material ( A catalyst for synthesizing liquefied petroleum gas, wherein the number of moles of SiO2 /the number of moles of Al2O3 ) is 20 or more and 60 or less.
• [3] The catalyst for synthesizing liquefied petroleum gas according to [1] above, wherein the MFI-type zeolite catalyst material further supports Pd.
• [4] The ratio of the mass of Pd (M Pd ) to the total mass (M Pt +M Pd ) of the mass of Pt (M Pt ) and the mass of Pd (M Pd ) supported on the MFI-type zeolite catalyst material (M Pd).
• M Pd The catalyst for synthesizing liquefied petroleum gas according to [3] above, wherein /(M Pt +M Pd )) is 0.70 or less.
• the ratio (M1/( The catalyst for synthesizing liquefied petroleum gas according to any one of [1] to [4] above, wherein M1+M2)) is 0.30 or more and 0.95 or less.
• the ratio (M1/( The catalyst for synthesizing liquefied petroleum gas according to any one of [1] to [5] above, wherein M1+M2)) is 0.30 or more and less than 0.70.
• the ratio (M1/( The catalyst for synthesizing liquefied petroleum gas according to any one of [1] to [5] above, wherein M1+M2)) is 0.50 or more and 0.95 or less.
• the total mass (M Pt +M Pd ) of the mass of Pt (M Pt ) and the mass of Pd (M Pd ) in the MFI-type zeolite catalyst material is the mass (M2) of the MFI-type zeolite catalyst material
• the mass of P (M P ) in the MFI-type zeolite catalyst material is more than 0% by mass and less than 5.0% by mass with respect to the mass (M2) of the MFI-type zeolite catalyst material, above [9]
• the Cu—Zn-based catalyst material and the MFI-type zeolite catalyst material exist independently of each other, and the Cu--Zn-based catalyst material and the MFI-type zeolite catalyst material are both granules or compacts.
• the catalyst for synthesizing liquefied petroleum gas according to any one of [1] to [10] above.
• a method for producing liquefied petroleum gas. [13] The method for producing liquefied petroleum gas according to [12] above, wherein in the supply step, a gas hourly space velocity (GHSV) for supplying carbon monoxide and hydrogen is 500/h or more and 20000/h or less.
• GHSV gas hourly space velocity
• a catalyst for synthesizing liquefied petroleum gas and a method for producing liquefied petroleum gas which can produce propane at a high yield even when the synthesis temperature of liquefied petroleum gas is low.
• the present inventors have focused on a zeolite catalyst material in a catalyst for synthesizing liquefied petroleum gas containing a Cu—Zn-based catalyst material and a zeolite catalyst material.
• the present inventors have found that propane can be produced at a high yield even if the synthesis temperature of liquefied petroleum gas is low by controlling the substance supported in the liquefied petroleum gas, and have completed the present disclosure based on this finding.
• a catalyst for synthesizing liquefied petroleum gas of an embodiment includes a Cu—Zn-based catalyst material and an MFI-type zeolite catalyst material supporting Pt (hereinafter also simply referred to as a zeolite catalyst material), and is included in the MFI-type zeolite catalyst material.
• the ratio of the number of moles of SiO 2 to the number of moles of Al 2 O 3 contained is 20 or more and 60 or less.
• the catalyst for synthesizing liquefied petroleum gas of the embodiment includes a Cu—Zn-based catalyst material and an MFI-type zeolite catalyst material.
• the liquefied petroleum gas synthesis catalyst can synthesize liquefied petroleum gas from carbon monoxide and hydrogen.
• the liquefied petroleum gas synthesized by the catalyst for synthesizing liquefied petroleum gas of the present embodiment contains propane and butane as main components, and contains more propane than butane.
• the total ratio of propane and butane to the liquefied petroleum gas is, for example, 20 Cmol% or more.
• the ratio of propane to the total of propane and butane is, for example, 55 mol % or more.
• the Cu-Zn-based catalyst material that constitutes the liquefied petroleum gas synthesis catalyst functions as a liquefied petroleum gas precursor synthesis catalyst that synthesizes liquefied petroleum gas precursors such as methanol and dimethyl ether from carbon monoxide and hydrogen.
• the ratio (M1/(M1+M2 )) (hereinafter simply referred to as the mass ratio of the Cu—Zn-based catalyst material), the lower limit is preferably 0.30 or more, more preferably 0.35 or more, and still more preferably 0.40 or more, and the upper limit The value is preferably 0.95 or less, more preferably 0.70 or less, even more preferably 0.65 or less, and particularly preferably 0.60 or less.
• the mass ratio of the Cu—Zn-based catalyst material is 0.30 or more and 0.95 or less, liquefied petroleum gas can be efficiently synthesized from carbon monoxide and hydrogen.
• the ratio (M1/(M1+M2)) is 0.30 or more and less than 0.70, the initial catalytic activity of the catalyst for synthesizing liquefied petroleum gas is high.
• the lower limit is more preferably 0.35 or more, more preferably 0.40 or more, and the upper limit is more preferably 0.65 or less, still more preferably 0.60 or less.
• the catalyst for synthesizing liquefied petroleum gas exhibits excellent long-term stability of catalytic activity.
• the lower limit is preferably 0.50 or more, more preferably 0.60 or more, and still more preferably 0.70 or more
• the upper limit is preferably 0.95 or less, more preferably 0.90. 0.85 or less, more preferably 0.85 or less.
• the Cu—Zn-based catalyst material constituting the catalyst for synthesizing liquefied petroleum gas is a catalyst containing copper oxide and zinc oxide, and among the catalysts for synthesizing liquefied petroleum gas precursors, it has the ability to synthesize liquefied petroleum gas precursors.
• the Cu—Zn-based catalyst material may further contain aluminum oxide, gallium oxide, zirconium oxide, indium oxide, and the like. By containing aluminum oxide, gallium oxide, zirconium oxide, indium oxide, etc., the dispersibility of copper oxide and zinc oxide can be improved. From the viewpoint of efficiently forming the number of interfaces between copper and zinc, which are presumed to be active sites, the Cu—Zn-based catalyst material is a ternary oxide of copper oxide, zinc oxide, and aluminum oxide. preferable.
• the zeolite catalyst material that constitutes the catalyst for synthesizing liquefied petroleum gas synthesizes liquefied petroleum gas from the liquefied petroleum gas precursor generated by the Cu-Zn-based catalyst material.
• the synthesized liquefied petroleum gas contains propane and butane as main components, with more propane than butane.
• the type of zeolite is MFI type. Since the MFI-type zeolite catalyst material has a smaller pore size than beta-type zeolite, propane can be synthesized more efficiently than butane, etc., among the components constituting liquefied petroleum gas, and the yield of propane is increased. presumed to be possible.
• the MFI-type zeolite catalyst material supports Pt (platinum).
• Pt platinum
• the MFI-type zeolite catalytic material supports only Pt. It is speculated that the Pt-supported MFI-type zeolite catalyst material can efficiently react liquefied petroleum gas precursors, and thus can increase the yield of propane.
• the yield of liquefied petroleum gas such as propane can be increased.
• a Cu—Zn-based catalyst which has excellent performance in synthesizing a liquefied petroleum gas precursor, is used, it aggregates at high temperatures, so the Cu—Zn-based catalyst significantly deteriorates over time, and liquefied petroleum gas can be produced over a long period of time. Stable and difficult to synthesize.
• the synthesis temperature is lowered (for example, 330 ° C. or lower) in order to suppress the deterioration of the Cu-Zn-based catalyst due to such high temperature, the deterioration of the Cu-Zn-based catalyst can be suppressed, but liquefied petroleum gas such as propane yield is low.
• propane can be produced at a high yield even if the synthesis temperature of liquefied petroleum gas is low (for example, 330°C or lower).
• the catalyst for synthesizing liquefied petroleum gas of the present embodiment and synthesizing at a low temperature (for example, 330° C. or lower), propane can be produced at a high yield, and deterioration of the catalyst due to high temperatures can be suppressed.
• the synthesis temperature is the temperature of the liquefied petroleum gas synthesis catalyst.
• the propane yield of the liquefied petroleum gas produced in the present embodiment is, for example, 10 Cmol% or more, even if the synthesis temperature is low (e.g., 330 ° C. or less), and may be 15 Cmol% or more, or even 17 Cmol% or more. can.
• the yield of butane can be increased by using the catalyst for synthesizing liquefied petroleum gas of the present embodiment.
• the yield of butane is, for example, 8 Cmol % or more even at a low synthesis temperature (eg, 330° C. or lower), and can be 10 Cmol % or more, or even 12 Cmol % or more.
• the yield of propane and butane (the sum of the yield of propane and the yield of butane) produced in the present embodiment is, for example, 25 Cmol % or more, preferably 30 Cmol % or more.
• the ratio of propane to the total of propane and butane can be increased.
• the ratio of propane to the total of propane and butane in the liquefied petroleum gas produced in the present embodiment is, for example, 0.55 or more. , preferably 0.60 or more, more preferably 0.65 or more.
• the zeolite catalyst material may further support platinum group elements such as Pd (palladium), rhodium (Rh), and ruthenium (Ru). 1 type or 2 types or more may be sufficient as a noble metal. When two or more kinds of noble metals are used, the state of the noble metals supported on the zeolite catalyst material is not particularly limited. A simple substance and an alloy may be mixed.
• the zeolite catalyst material preferably supports Pd in addition to Pt.
• Pd in addition to Pt
• the butane yield can be increased while maintaining the high propane yield of loading Pt alone.
• Pt as an elemental metal and Pd as an elemental metal may be mixed, Pt and Pd may be alloyed, or at least one of Pt and Pd may be mixed. A single metal and an alloy of Pt and Pd may be mixed.
• the mass of Pd (M Pd ) ratio (M Pd /(M Pt +M Pd )) (hereinafter also referred to as mass ratio (M Pd /(M Pt +M Pd ))
• the upper limit is preferably 0.70 or less, more preferably 0 0.60 or less, more preferably 0.50 or less.
• the lower limit of the mass ratio (M Pd /(M Pt +M Pd )) is, for example, 0.01 or more, preferably 0.15 or more, more preferably 0.20 or more, and still more preferably 0.25. That's it.
• the mass ratio (M Pd /(M Pt +M Pd )) is 0.70 or less, the yield of butane can be further increased.
• the total mass (M Pt +M Pd ) of the mass of Pt (M Pt ) and the mass of Pd (M Pd ) in the zeolite catalyst material has a lower limit with respect to the mass (M2) of the zeolite catalyst material, preferably It is 0.1% by mass or more, more preferably 0.2% by mass or more, and still more preferably 0.3% by mass or more, and the upper limit is preferably 1.0% by mass or less, more preferably 0.8% by mass. 0.7% by mass or less, and more preferably 0.7% by mass or less.
• the mass of Pd (M Pd ) in the total mass is 0 (zero), ie the total mass is the mass of Pt.
• the mass ratio (M Pd /(M Pt +M Pd )), the mass of Pt (M Pt ) and the mass of Pd (M Pd ) total mass (M Pt +M Pd ) can be measured by ICP-OES (Inductively Coupled Plasma Optical Emission Spectroscopy).
• the ratio of the number of moles of SiO2 to the number of moles of Al2O3 contained in the zeolite catalyst material (the number of moles of SiO2 /the number of moles of Al2O3 ) ( hereinafter simply referred to as the molar ratio ( SiO2 / Al2 O 3 )) is 20 or more and 60 or less.
• Zeolite catalytic materials are aluminosilicates. By replacing some of the silicon atoms in the silicate constituting the zeolite skeleton of the zeolite catalyst material with aluminum atoms, the aluminum atoms become acid sites, so that the zeolite catalyst material exhibits a function as a solid acid.
• the acid sites of the zeolite catalyst material increase, so that the amount of liquefied petroleum gas produced can be increased, and propane can be efficiently synthesized to liquefy
• the amount of propane contained in oil gas can be increased.
• the molar ratio (SiO 2 /Al 2 O 3 ) is 20 or more, a zeolite catalyst material supporting Pt can be easily produced while maintaining a high ability to generate liquefied petroleum gas and a high ability to synthesize propane. can.
• the molar ratio (SiO 2 /Al 2 O 3 ) is 20 or more, preferably 25 or more, more preferably 30 or more. From the viewpoint of high catalytic performance, the molar ratio (SiO 2 /Al 2 O 3 ) is 60 or less, preferably 50 or less, more preferably 40 or less.
• the molar ratio (SiO 2 /Al 2 O 3 ) can be measured by ICP-OES (inductively coupled plasma optical emission spectroscopy).
• the solid acid content of the zeolite catalyst material is, for example, 0.6 mmol/g or more, preferably 0.8 mmol/g or more.
• the amount of solid acid is 0.6 mmol/g or more, a zeolite catalyst material supporting a noble metal can be easily produced while maintaining high liquefied petroleum gas generating ability and high propane synthesizing ability.
• the amount of solid acid can be measured by NH 3 -TPD (ammonia temperature programmed desorption method).
• the Cu—Zn based catalyst material and the MFI type zeolite catalyst material exist independently of each other, and both the Cu—Zn based catalyst material and the MFI type zeolite catalyst material are preferably granules or compacts. In the catalyst for synthesizing liquefied petroleum gas, it is preferable that the Cu—Zn-based catalyst material and the MFI-type zeolite catalyst material are not integrated (mixedly integrated).
• the state of the Cu--Zn-based catalyst material and the zeolite catalyst material may be a granular material (powder, for example, a particle size of 10 ⁇ 9 to 10 ⁇ 4 m), or a granule having a larger particle size than the granular material.
• the yield of propane and butane can be further increased if the Cu--Zn-based catalyst material is a molded body containing a Cu--Zn-based catalyst material and the zeolite catalyst material is a molded body containing a zeolite catalyst material.
• the catalyst for synthesizing liquefied petroleum gas is preferably a mixture of a molded body containing a Cu--Zn catalyst material and a molded body containing a zeolite catalyst material.
• the content of the Cu--Zn-based catalyst material contained in the molded body is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more. is.
• a liquefied petroleum gas precursor can be efficiently synthesized from carbon monoxide and hydrogen.
• the content of the Cu--Zn-based catalyst material contained in the compact may be 100% by mass.
• the above content is preferably 98% by mass or less, more preferably 96% by mass or less, and even more preferably 94% by mass or less. When the content is 98% by mass or less, it is possible to improve the moldability and mechanical strength of the molded product while maintaining efficient synthesis of the liquefied petroleum gas precursor.
• a molded body containing a Cu--Zn-based catalyst material may contain, in addition to the Cu--Zn-based catalyst material, various additives that improve moldability and mechanical strength.
• various additives include molding binders such as graphite and carbon black.
• the content of the zeolite catalyst material in the molded body containing the zeolite catalyst material is preferably 70% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more.
• the content of the zeolite catalyst material contained in the compact may be 100% by mass.
• the above content is preferably 98% by mass or less, more preferably 96% by mass or less, and even more preferably 94% by mass or less. When the content is 98% by mass or less, it is possible to improve the moldability and mechanical strength of the compact while maintaining efficient synthesis of liquefied petroleum gas.
• the molded body containing the zeolite catalyst material may contain various additives that improve moldability and mechanical strength in addition to the zeolite catalyst material.
• various additives include molding binders such as various clay binders, alumina-based binders, and silica-based binders.
• various clay binders include kaolin-based, bentonite-based, talc-based, pyrophyllite-based, molysite-based, verculolite-based, montmorillonite-based, chlorite-based, and halloysite-based binders.
• the molding binder is preferably a silica-based binder.
• the shape of the Cu--Zn-based catalyst material and zeolite catalyst material is not particularly limited.
• a desired shape such as columnar, clover-shaped, ring-shaped, spherical, or multi-hole-shaped can be selected.
• a columnar or clover-shaped molded article it is preferably an extruded article.
• the lower limit is preferably 200 ⁇ m or more, more preferably 300 ⁇ m or more
• the upper limit is preferably 10 mm or less, more preferably 10 mm or less. It is preferably 5 mm or less, more preferably 3 mm or less.
• the particle diameter is 200 ⁇ m or more, pressure loss in the reactor can be prevented.
• the particle size is 10 mm or less, the contact efficiency between the reactant and the catalyst can be increased in the reactor.
• Particle size can be determined by the dry sieving test method.
• the lower limit is preferably 0.5 g/cm 3 or more, and the upper limit is preferably 1.5 g. /cm 3 or less, more preferably 1.0 g/cm 3 or less.
• the bulk density can be determined by a sock-filled bulk density measurement method using a graduated cylinder.
• the zeolite catalyst material preferably further contains P (phosphorus).
• P phosphorus
• the acid sites (solid acid sites) of the zeolite catalyst material increase and simultaneously change to weak acid sites, so that the ratio of propane to the total of propane and butane can be increased.
• P binds to O (oxygen) that binds to Si and O that binds to Al, which are present on the surface of the zeolite catalyst material, as shown in the following formula (1). It is estimated that
• the lower limit of the mass of P (M P ) in the zeolite catalyst material is preferably more than 0% by mass, more preferably 0.5% by mass or more, and still more preferably 1 with respect to the mass (M2) of the zeolite catalyst material.
• 0% by mass or more, and the upper limit is preferably less than 5.0% by mass, more preferably 4.0% by mass or less, and even more preferably 3.0% by mass or less.
• the ratio of propane to the total of propane and butane can be increased. Further, when the mass of P (M P ) is less than 5.0% by mass with respect to the mass (M2) of the zeolite catalyst material, the ratio of propane to the total of propane and butane due to the excessive P content ratio It is possible to suppress the decrease in the yield of propane and butane.
• the presence or absence of P content in the zeolite catalyst material and the content ratio of P can be measured by ICP-OES (Inductively Coupled Plasma Emission Spectroscopy).
• the method for producing liquefied petroleum gas of the embodiment has a reduction treatment process, a supply process, and a synthesis process.
• the catalyst for synthesizing liquefied petroleum gas is reduced.
• the liquefied petroleum gas synthesis catalyst is reduced with hydrogen.
• carbon monoxide and hydrogen are supplied to the liquefied petroleum gas synthesis catalyst reduced in the reduction treatment step.
• Carbon monoxide and hydrogen are gases.
• carbon monoxide and hydrogen may be supplied separately, or a mixed gas containing carbon monoxide and hydrogen, such as synthesis gas, may be supplied.
• the carbon monoxide and hydrogen supplied in the supply process are reacted with the reduced liquefied petroleum gas synthesis catalyst to synthesize liquefied petroleum gas.
• the catalyst for synthesizing liquefied petroleum gas of the present embodiment is resistant to deterioration and has excellent long-term stability, and can exhibit good catalytic performance for a long period of time (for example, 70 hours or longer when the synthesis temperature is 330° C. or lower).
• the lower limit of the gas hourly space velocity (GHSV) for supplying carbon monoxide and hydrogen is preferably 500/h or more, more preferably 1000/h or more, and still more preferably 1500/h or more.
• the upper limit is preferably 20000/h or less, more preferably 10000/h or less, and even more preferably 5000/h or less.
• gas hourly space velocity 500/h or more
• liquefied petroleum gas can be efficiently produced from carbon monoxide and hydrogen.
• gas hourly space velocity 20000/h or less, it is possible to suppress an increase in the content of unreacted substances such as carbon monoxide and hydrogen in the gas containing liquefied petroleum gas obtained after synthesis.
• the lower limit is preferably 260° C. or higher, more preferably 270° C. or higher, and still more preferably 280° C. or higher, and the upper limit is preferably 330° C. or lower. It is preferably 325° C. or lower, more preferably 320° C. or lower.
• liquefied petroleum gas can be efficiently produced from carbon monoxide and hydrogen. Further, in the synthesis step, if carbon monoxide and hydrogen are reacted at a temperature of 330° C. or lower, the deterioration of catalytic performance of the catalyst for synthesizing liquefied petroleum gas due to temperature can be suppressed. In addition, in the synthesis process, if carbon monoxide and hydrogen are reacted at a temperature of 330 ° C. or less, the resulting liquefied petroleum gas will be excessively cracked (decomposition from propane to ethane, decomposition from ethane to methane). Decrease can be suppressed.
• the lower limit is preferably 2.0 MPa or more, more preferably 3.0 MPa or more, still more preferably 3.5 MPa or more, and the upper limit is preferably 6.0 MPa or less, more preferably Carbon monoxide and hydrogen are reacted at 5.5 MPa or less, more preferably 5.0 MPa or less.
• a catalyst for synthesizing liquefied petroleum gas can be produced, for example, by mixing a Cu--Zn-based catalyst material and a zeolite catalyst material.
• the composition, ratio, state, etc. of the Cu—Zn-based catalyst material and the zeolite catalyst material are appropriately set according to the desired liquefied petroleum gas.
• the molar ratio (SiO 2 /Al 2 O 3 ) of the zeolite catalyst material can be controlled, for example, by adjusting the amount of aluminum source added during synthesis of the zeolite catalyst material.
• the amount of solid acid in the zeolite catalyst material can be controlled, for example, by the synthesis conditions (such as pH) during synthesis of the zeolite catalyst material.
• the method of supporting precious metals such as platinum and palladium on the zeolite catalyst material is not particularly limited, but examples include an impregnation method, an immersion method, and an ion exchange method.
• platinum and palladium are loaded simultaneously using an impregnation or immersion fluid containing platinum and palladium. is preferred.
• Starting materials for platinum and palladium supported on zeolite catalyst materials include compounds containing platinum and palladium.
• platinum chloroplatinic acid hexahydrate, dinitrodiammineplatinum, dichlorotetraammineplatinum, platinum oxide, platinum chloride, and the like can be used.
• palladium chloride, palladium nitrate, dinitrodiammine palladium, palladium sulfate, palladium oxide and the like can be used.
• the concentration of the compound containing platinum or palladium in the solution of the compound containing platinum or palladium may be set according to the amount of platinum or palladium to be supported.
• the concentration of the chloroplatinic acid hexahydrate solution is preferably 0.15% by mass or more and 3.50% by mass or less.
• the concentration of the palladium chloride solution is preferably 0.10% by mass or more and 2.50% by mass or less.
• the impregnation time and immersion time of the solution are preferably 10 minutes or more and 5 hours or less.
• the calcination temperature of the zeolite catalyst material is preferably 300° C. or more and 600° C. or less, and the calcination time of the zeolite catalyst material is preferably 30 minutes or more and 300 minutes or less.
• the amount of Pt and Pd supported can be controlled by the concentration of the above solution.
• the method for supporting phosphorus on the zeolite catalyst material is not particularly limited, but examples thereof include an impregnation method and an immersion method.
• Orthophosphoric acid, phosphate esters, and the like can be used as starting materials for phosphorus when supporting phosphorus on the zeolite catalyst material.
• an aqueous solution of orthophosphoric acid or phosphate ester can be used as the impregnating liquid or immersion liquid.
• the concentration of the phosphoric acid solution is preferably 2% by mass or more and 20% by mass or less.
• the impregnation time and immersion time of the phosphoric acid solution are preferably 10 minutes or more and 5 hours or less.
• the calcination temperature of the zeolite catalyst material is preferably 300°C or higher and 600°C or lower.
• the calcination time of the zeolite catalyst material is preferably 30 minutes or more and 300 minutes or less.
• the content of P can be controlled by the concentration of the phosphoric acid solution and the impregnation or immersion time with the phosphoric acid solution.
• a noble metal such as platinum or palladium
• the impregnated or immersed zeolite catalyst material is calcined, and the calcined zeolite catalyst material contains a noble metal such as platinum or palladium.
• the zeolite catalyst material After being impregnated or immersed in the solution, it is preferable to calcine the zeolite catalyst material impregnated or immersed in the solution containing precious metals such as platinum and palladium.
• the liquefied petroleum gas obtained using the catalyst for synthesizing liquefied petroleum gas contains a large amount of propane as a component, so it is suitable as a fuel that can be used stably even in cold regions.
• the synthesis temperature of the liquefied petroleum gas is Propane can be produced in high yields even at low .
• Example 1 (Cu—Zn-based catalyst material) A ternary oxide of copper oxide, zinc oxide, and aluminum oxide (product name: 45776 Copper based methanol synthesis catalyst, manufactured by Alpha Acer) was used as the Cu—Zn-based catalyst material.
• the Cu—Zn-based catalyst material was pelletized with a tableting machine at a pressure of 5 MPa to form pellets having a diameter of 20 mm and a thickness of about 1 mm, and the pellets were pulverized in a mortar. was sieved using an overlap of As a result, a molded body made of the Cu--Zn catalyst material having a grain size of 300 to 500 ⁇ m and a bulk density of 0.9 g/cm 3 was obtained.
• An aqueous solution of 0.0574 g of 0.0574 g of palladium chloride and 0.419 g of 0.419 g of palladium chloride was added dropwise with a pipette, mixed uniformly with a pestle, and impregnated for about 1 hour. Then, it was dried at 100° C. for 10 hours, heated from room temperature to 500° C.
• this sample was made into pellets with a diameter of 20 mm and a thickness of about 1 mm using a tableting machine, and the pellets were pulverized in a mortar.
• a granular molded body made of MFI-type zeolite catalyst material supporting Pt and Pd and having a bulk density of 0.8 g/cm 3 with a particle size of 300 to 500 ⁇ m was obtained.
• a catalyst for synthesizing liquefied petroleum gas As a catalyst for synthesizing liquefied petroleum gas, a mixture of a molded body composed of the Cu—Zn catalyst material obtained above and a molded body composed of the MFI-type zeolite catalyst material obtained above was used. The ratio (M1/(M1+M2)) of the mass (M1) of the mixed Cu—Zn-based catalyst material to the total mass of the mass (M1) of the mixed Cu—Zn-based catalyst material and the mass (M2) of the MFI-type zeolite catalyst material is , listed in Table 1. Using the catalyst for synthesizing liquefied petroleum gas, liquefied petroleum gas was produced under the following conditions.
• the catalyst for liquefied petroleum gas synthesis was reduced with hydrogen. Subsequently, carbon monoxide and hydrogen were supplied to the liquefied petroleum gas synthesis catalyst at a gas hourly space velocity (GHSV) of 2000/h. Synthesize liquefied petroleum gas from carbon monoxide and hydrogen by controlling the temperature (synthesis temperature) to 320° C. and the pressure to 5.0 MPa while supplying carbon monoxide and hydrogen to the catalyst for synthesizing liquefied petroleum gas. did.
• GHSV gas hourly space velocity
• a reactor made of stainless steel (inner diameter 6.2 mm, total length 60 cm) was used. The center of the reactor was packed with the catalyst sandwiched between glass wool. The reactor was installed in an electric furnace, and the temperature of the electric furnace was measured by a thermocouple inserted in the center of the furnace and controlled by PID. The catalyst temperature was measured with a thermocouple inserted in the center of the catalyst layer in the reactor. Note that the temperature of the catalyst is the synthesis temperature.
• the reduction treatment of the liquefied petroleum gas synthesis catalyst was performed by supplying H 2 to the catalyst in the reactor at a flow rate of 40 ml/min at 380° C. for 2 hours before the reaction.
• Ratio moles of SiO2 /moles of Al2O3
• the ratio (moles of SiO 2 /moles of Al 2 O 3 ) was measured by ICP-OES (Inductively Coupled Plasma Optical Emission Spectroscopy).
• Presence or absence of P and the ratio of the mass of P (M P ) to the mass (M2) of the MFI-type zeolite catalyst material (M P ⁇ 100/M2)
• M P ⁇ 100/M2 The presence or absence of P content in the MFI-type zeolite catalyst material and the ratio (M P ⁇ 100/M2) were measured by ICP-OES (Inductively Coupled Plasma Emission Spectroscopy).
• Conversion rate of CO CO conversion rate (%) [(CO flow rate at inlet ( ⁇ mol/min) - CO flow rate at outlet ( ⁇ mol/min))/CO flow rate at inlet ( ⁇ mol/min)] x 100
• the CO conversion rate indicates the rate at which carbon monoxide (CO) in the raw material gas is converted to hydrocarbons and the like.
• Example 1 An MFI zeolite supporting Pt. Subsequently, this sample was made into pellets with a diameter of 20 mm and a thickness of about 1 mm using a tableting machine, and the pellets were pulverized in a mortar. As a result, a molded body made of the Pt-supporting MFI-type zeolite catalyst material having a grain size of 300 to 500 ⁇ m and a bulk density of 0.8 g/cm 3 was obtained. Other than that, the same operation as in Example 1 was performed.
• Example 6> Instead of an aqueous solution of 0.0419 g of chloroplatinic acid hexahydrate and 0.0574 g of palladium chloride dissolved in 7.5758 g of 10% hydrochloric acid, 0.0667 g of chloroplatinic acid hexahydrate and chloride were dissolved in 7.5758 g of 10% hydrochloric acid. The same operation as in Example 1 was performed except that an aqueous solution in which 0.0419 g of palladium was dissolved was used.
• Example 2 The same procedure as in Example 1 was repeated except that an aqueous solution of 0.0419 g of chloroplatinic acid hexahydrate and 0.0574 g of palladium chloride dissolved in 7.5758 g of 10% hydrochloric acid was added dropwise with a pipette. performed the operation.
• the same operation as in Example 1 was performed except that an aqueous solution of 0.0837 g of palladium chloride dissolved in 7.5758 g of 10% hydrochloric acid was used instead of the aqueous solution of 0.0574 g of palladium chloride.
• a Cu—Zn-based catalyst material and an MFI-type zeolite catalyst material supporting Pt are included, and the ratio of SiO 2 to the number of moles of Al 2 O 3 contained in the MFI-type zeolite catalyst material is In Examples 1 to 9 in which the mole number ratio (moles of SiO 2 /moles of Al 2 O 3 ) was in the range of 20 or more and 60 or less, the synthesis temperature was as low as 320°C. yield was high.

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