WO2023085337A1 - バイオジェット燃料製造方法及び該方法に用いるバイオジェット燃料製造用触媒 - Google Patents

バイオジェット燃料製造方法及び該方法に用いるバイオジェット燃料製造用触媒 Download PDF

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WO2023085337A1
WO2023085337A1 PCT/JP2022/041796 JP2022041796W WO2023085337A1 WO 2023085337 A1 WO2023085337 A1 WO 2023085337A1 JP 2022041796 W JP2022041796 W JP 2022041796W WO 2023085337 A1 WO2023085337 A1 WO 2023085337A1
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catalyst
bio
jet fuel
oil
biomass
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French (fr)
Japanese (ja)
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衛華 銭
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Green Power Development Corp Of Japan
Tokyo University of Agriculture and Technology NUC
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Green Power Development Corp Of Japan
Tokyo University of Agriculture and Technology NUC
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Priority to EP22892835.4A priority patent/EP4431584A4/en
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    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/45—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/47—Catalytic treatment characterised by the catalyst used containing platinum group metals or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
    • C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
    • 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
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/12—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C10G2300/1014—Biomass of vegetal origin
    • 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
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • the present invention relates to a bio-jet fuel production method and a bio-jet fuel production catalyst for reforming biomass-derived bio-oil to obtain bio-jet fuel.
  • biofuels are attracting attention as a carbon-neutral alternative to fossil fuels. Since the carbon dioxide generated by burning biofuels is the carbon dioxide absorbed from the atmosphere during the growth process of biomass, the use of biofuels does not increase the amount of carbon dioxide in the atmosphere. Carbon neutrality can be achieved, the concept that the amount of carbon dioxide emitted is the same as the amount of carbon dioxide absorbed when done.
  • Biofuels that achieve such carbon neutrality include bioethanol fuels and biodiesel fuels, which have been widely used in recent years, as well as biojet fuels.
  • the spread of bio-jet fuel has lagged compared to bio-ethanol fuel and bio-diesel fuel due to strict product standards, etc.
  • the global aviation industry consumes about 1.5 billion to 1.5 billion dollars a year of regular jet fuel. Since 1.7 billion barrels (equivalent to 238-270 Mm 3 ) are being consumed, urgent development of high-quality bio-jet fuel is required.
  • biomass-derived raw material oil is decarbonated or deoxygenated, hydrotreated to produce hydrocarbons, and the hydrocarbons are isomerized and cracked. This is done by producing C 7-14 isomerized hydrocarbons, which are then bio-jet fuels.
  • Patent Document 1 describes: a) hydrogenation of a renewable feedstock in a first reaction zone using a catalyst under reaction conditions in which hydrogen is present; Treated by deoxygenation to obtain a first reaction zone product stream comprising hydrogen, water, carbon dioxide, and a hydrocarbon fraction comprising diesel fuel boiling range paraffins and aviation fuel boiling range paraffins.
  • Patent Document 2 in a first step, biological oil and hydrogen gas are subjected to conditions sufficient to hydrodeoxygenate in the presence of a hydrodeoxygenation catalyst to produce n-paraffins, In a second stage, the n-paraffins and hydrogen gas are subjected to conditions sufficient to effect isomerization in the presence of an isomerization catalyst to produce isoparaffins and a separate fraction, obtained from the second stage through re-isomerization
  • a process for producing hydrocarbons comprising recycling fractions boiling above 200° C. under atmospheric pressure and isomerizing in the presence of an isomerization catalyst.
  • US Pat. No. 5,300,003 discloses a method for converting triacylglyceride-containing oils into crude precursors and/or distillate hydrocarbon fuels comprising heating a mixture of triacylglyceride-containing oils, water, and diatomic hydrogen to about 250° C. to about reacting at a temperature in the range of 560° C. and a pressure greater than about 75 bar to convert at least a portion of the triacylglycerides, water and one or more of isoolefins, isoparaffins, cycloolefins, cycloparaffins, aromatics; and hydrotreating the reaction effluent to form a hydrotreated effluent.
  • Patent Documents 1 and 2 are performed in two steps of a hydrodeoxygenation process and an isomerization cracking process, and consume a large amount of energy, and are highly suitable for producing bio jet fuel. There is a problem that cost is required.
  • the inventors of the present application have developed bio-oil obtained by pyrolyzing biomass resources using superheated steam and a bifunctional catalyst in which a solid base catalyst is supported on a solid acid catalyst. Focusing attention, the present inventors have invented the method for producing bio-jet fuel and the catalyst for bio-jet fuel production of the present application.
  • An object of the present invention is to provide a method for producing bio-jet fuel that is highly energy-saving and capable of easily producing high-quality bio-jet fuel, and a catalyst for producing bio-jet fuel used in this method.
  • the invention of claim 1 uses a catalyst obtained by supporting a solid base catalyst on a solid acid catalyst with a biomass-derived oil containing free fatty acids, hydrocarbons and triacylglycerols, It is characterized by having a reforming treatment step in which decarbonation, hydrogenation, isomerization and decomposition are performed under conditions of a reaction temperature of 200°C to 450°C.
  • the invention of claim 2 is characterized in that the biomass-derived oil of claim 1 is bio-oil obtained by heating a biomass resource and cooling the generated pyrolysis gas.
  • the invention of claim 3 is characterized in that the bio-oil of claim 2 is obtained by cooling the pyrolysis gas generated by heating the biomass resource at 200-450°C.
  • the bio-oil of claim 2 or 3 is obtained by cooling pyrolysis gas generated by heating using a heating means including injection of superheated steam to the biomass resource. It is characterized by being
  • the bio-oil according to any one of claims 2 to 4 is obtained by cooling pyrolysis gas generated by heating coconut palm fruits as the biomass resource. It is characterized by
  • the invention of claim 6 is characterized in that the amount of the catalyst used in any one of claims 1 to 5 is 5 to 15 wt% of the biomass-derived oil.
  • the invention of claim 7 is characterized in that the reforming treatment step of any one of claims 1 to 6 is performed in a reactor filled with hydrogen gas at a pressure of 0 to 2 MPa.
  • the invention of claim 9 is characterized in that the solid acid catalyst of the catalyst of any one of claims 1 to 8 is zeolite.
  • the invention of claim 10 is characterized in that the zeolite, which is the solid acid catalyst, of the catalyst of claim 9 is ZSM-5 type zeolite.
  • the invention of claim 11 is characterized in that the solid base catalyst of the catalyst of any one of claims 1 to 10 contains a group 2 metal oxide.
  • the oxide of the Group 2 metal which is the solid base catalyst of the catalyst of claim 11, is one or more selected from magnesium oxide, calcium oxide and barium oxide. characterized by being
  • the invention of claim 13 is the solid acid catalyst of the catalyst of any one of claims 1 to 12, wherein one or more metals selected from groups 8, 9, and 10 are supported. It is characterized by being
  • the invention of claim 14 is characterized in that one or more metals selected from groups 8, 9, and 10 supported on the solid acid catalyst of the catalyst of claim 13 are platinum. Characterized by
  • the invention of claim 16 is characterized in that the solid acid catalyst of claim 15 is zeolite.
  • the invention of claim 17 is characterized in that the zeolite of claim 16 is ZSM-5 type zeolite.
  • the invention of claim 19 is characterized in that the Group 2 metal oxide of claim 18 is one or more selected from magnesium oxide, calcium oxide and barium oxide.
  • the solid acid catalyst of any one of claims 15 to 19 supports one or more metals selected from groups 8, 9 and 10. It is characterized by
  • the invention of claim 21 is characterized in that the one or more metals selected from groups 8, 9, and 10 supported on the solid acid catalyst of claim 20 are platinum.
  • a biomass-derived oil containing free fatty acids, hydrocarbons and triacylglycerol is reacted at a reaction temperature of 200 ° C. to 450 ° C. using a catalyst in which a solid base catalyst is supported on a solid acid catalyst.
  • C 7-14 isomerized hydrocarbons suitable for use as bio-jet fuel can be obtained because the reforming process includes decarbonation gas, hydrogenation, isomerization and cracking.
  • the bio-oil obtained by heating the biomass resource and cooling the generated pyrolysis gas used in the present invention has little high-molecular fraction such as tar, so the amount of coke deposition on the catalyst surface is small. Reforming to biofuel can be efficiently performed with a small amount.
  • bio-oil since bio-oil is in an emulsion state with water generated by thermal decomposition of biomass resources, it can be removed without supplying water or hydrogen in the reforming process, or with a small amount of water or hydrogen. Carbon dioxide gas, hydrogenation, isomerization, and decomposition can be performed, and low-cost production of bio-jet fuel can be realized.
  • the bio-oil is preferably produced by cooling pyrolysis gas obtained by heating in the range of 200-450°C. Since such bio-oils contain large amounts of C 6-19 hydrocarbons and free fatty acids, bio-jet fuels composed of C 7-14 isomerized hydrocarbons can be efficiently produced.
  • a catalyst consisting of a solid acid catalyst supported by a solid base catalyst is used. Since reforming is possible under pressure, it is possible to save energy and to produce bio-jet fuel at low cost.
  • the solid base catalyst of the catalyst preferably one or more selected from group 2 metal oxides, more preferably magnesium oxide, calcium oxide and barium oxide, of free fatty acids and triacylglycerols can be suitably decarboxylated and hydrogenated.
  • group 2 metal oxides more preferably magnesium oxide, calcium oxide and barium oxide, of free fatty acids and triacylglycerols can be suitably decarboxylated and hydrogenated.
  • bio-oil by reforming bio-oil under conditions of a reaction temperature of 200°C to 450°C, bio-oil can be reliably reformed.
  • bio-jet fuel production catalyst used in this method.
  • FIG. 4 is an explanatory diagram showing a fixed-bed flow reactor used in Test 5.
  • the present invention is a method for producing bio-jet fuel by reforming biomass-derived oil containing free fatty acids, hydrocarbons and triacylglycerols.
  • biomass-derived oil containing free fatty acids, hydrocarbons and triacylglycerol is not particularly limited, but bio-oil obtained by heating biomass resources and cooling the generated pyrolysis gas is suitable.
  • Biomass resources are not particularly limited as long as they are derived from animals and plants, with the exception of fossil fuels.
  • Oil-rich plant seeds are preferably used for stable supply and easy production of bio-oil.
  • bintaro, bengowan, poron, jatropha, coconut palm fruit, palm fruit, date palm fruit and the like are suitable.
  • coconut palm fruit is more preferably used because its endosperm contains a large amount of oil.
  • the bio-oil used in the present invention is obtained by heating biomass resources and cooling the generated pyrolysis gas. In this way, since bio-oil contains a small amount of high-molecular fractions such as tar, the amount of coke deposited on the surface of the catalyst is small, and reforming into bio-fuel can be efficiently performed.
  • superheated steam it is suitable to use superheated steam to heat biomass resources. It is not necessary to heat the biomass resource with superheated steam alone, and the biomass resource may be heated in combination with other heating means.
  • the superheated steam used to heat the biomass oil is mixed with the bio-oil pyrolysis gas. Also, by using superheated steam, the proportion of hydrocarbons in the bio-oil can be increased. It is considered that the pyrolysis gas generated from the biomass resource is thermally decomposed and steam reformed by contacting the superheated steam at a high temperature.
  • the temperature for heating the biomass resource is preferably 200 to 450°C.
  • Bio-oil obtained by heating biomass resources in this temperature range contains a large amount of hydrocarbons in the range of C6-19 and free fatty acids. can be manufactured to
  • the time for heating the biomass resources is appropriately selected depending on the amount of biomass resources, the heating temperature, etc., and is not particularly limited.
  • a catalyst made by supporting a solid base catalyst on a solid acid catalyst is used.
  • Silica alumina, activated alumina, activated clay, and zeolite can be used as solid acid catalysts. Of these, zeolite is preferred because it is readily available and exhibits high acidity. As the zeolite, mordenite, ⁇ zeolite, ZSM zeolite, A-type zeolite, X-type zeolite, Y-type zeolite, etc. can be used, among which ZSM-5-type zeolite is preferably selected.
  • the solid acid catalyst can support one or more metals selected from Groups 8, 9 and 10. Of the group 9 and/or group 10 metals, platinum is most preferably used.
  • the catalyst is produced by dissolving the solid base catalyst precursor in distilled water, impregnating the solid acid catalyst with this, drying it, forming it into pellets, and then calcining it to obtain the catalyst.
  • the method for producing the catalyst is not limited to this method, and other methods may be used.
  • a batch-type reforming process will be described first.
  • the bio-oil and the catalyst are placed in the reactor of the above-described reforming apparatus and heated at a reaction temperature of 200° C. to 450° C. to reform the bio-oil.
  • a gas injection means may be used to fill the reactor with hydrogen at a pressure of 1-5 MPa.
  • the amount of catalyst contained is 1-20 wt% of the bio-oil, preferably 5-15 wt%.
  • the continuous reforming process will be described.
  • the continuous reforming process is preferably carried out using the above-mentioned flow reactor at a reaction temperature of 200° C. to 450° C.
  • the hydrogen pressure should be about 0.5 to 3 MPa, and the volume ratio of hydrogen to biomass-derived oil should be about 100:1 to 1200:1. is preferred.
  • the time for which the modification treatment is performed is not particularly limited, but it is preferable to perform it for 1 to 6 hours.
  • a catalyst was produced by using ZSM-5 type zeolite as a solid acid catalyst and supporting 5% by mass of magnesium oxide as a solid base catalyst.
  • Example 2 Using the above-described method for producing a catalyst, ZSM-5 type zeolite was used as a solid acid catalyst, and a catalyst supporting 5% by mass of calcium oxide was produced as a solid base catalyst.
  • a catalyst was produced by using ZSM-5 type zeolite as a solid acid catalyst and supporting 5% by mass of barium oxide as a solid base catalyst.
  • the amount of base was measured by the CO 2 -TPD method using ChemBET Pulser (manufactured by Quantachrome). The analysis results are shown in FIG. 2 and Table 1.
  • ⁇ Test 2 Reforming test using the catalyst of Example 1> Next, liquid products obtained by reforming bio-oil using the catalyst of Example 1 of Test 1 were analyzed. In this test, bio-oil obtained by heating copra, which is the endosperm of coconut, using superheated steam and cooling the generated pyrolysis gas was used as bio-oil as a raw material. Table 2 shows the results of CHN elemental analysis of the components of the bio-oil used.
  • the catalyst of Example 1 was crushed to 80-120 mesh and dried at 110°C for 1 hour before use.
  • the amount of bio-oil to be reformed was 10.0 g, the catalyst was 0.5 g, and the reactor was filled with hydrogen gas at a pressure of 1.0 MPa. This was reacted for 3 hours at a reaction temperature of 300° C. and a stirring speed of 400 rpm.
  • the reaction pressure in this specification means the pressure at which hydrogen gas is enclosed in the reactor.
  • Table 3 shows the analysis results of the components of the gaseous product obtained by this operation
  • Table 4 shows the analysis results of the components of the liquid product.
  • M w indicates the molecular weight of each component
  • V i indicates the volume ratio of each component
  • W i yield indicates the weight ratio of each component.
  • the gaseous product contains a large amount of carbon dioxide, and the liquid product contains C 7-14 isohydrocarbons with side chains that can be used as bio-jet fuel. It was found that by using the catalyst of Example 1, the bio-oil was hydrogenated, decarboxylated, cracked and isomerized.
  • Experiment 1 a catalyst employing magnesium oxide as a solid base catalyst was used, the amount of catalyst was 0.5 g, hydrogen gas was charged at a reaction pressure of 1.0 MPa, and the reaction time was 3 hours.
  • Experiment 2 a catalyst employing calcium oxide as a solid base catalyst was used, the amount of catalyst was 0.5 g, hydrogen gas was charged at a reaction pressure of 1.0 MPa, and the reaction was carried out for 3 hours.
  • Experiment 3 a catalyst employing barium oxide as a solid base catalyst was used, the amount of catalyst was 0.5 g, hydrogen gas was charged at a reaction pressure of 1.0 MPa, and the reaction was carried out for 3 hours.
  • Experiment 4 a catalyst employing magnesium oxide as a solid base catalyst was used, the amount of catalyst was 1.0 g, hydrogen gas was charged at a reaction pressure of 1.0 MPa, and the reaction was performed for 3 hours.
  • Experiment 5 a catalyst employing magnesium oxide as a solid base catalyst was used, the amount of catalyst was 1.0 g, hydrogen gas was charged at a reaction pressure of 1.0 MPa, and the reaction was performed for 3 hours.
  • Experiment 6 a catalyst employing magnesium oxide as a solid base catalyst was used, the amount of catalyst was 1.0 g, 1 MPa of nitrogen was charged without charging hydrogen, and the reaction time was 3 hours.
  • Experiment 7 a catalyst employing magnesium oxide as a solid base catalyst was used, the amount of catalyst was 1.0 g, hydrogen gas was charged at a reaction pressure of 2.0 MPa, and the reaction time was 3 hours.
  • Experiment 8 a catalyst employing magnesium oxide as a solid base catalyst was used, the amount of catalyst was 1.0 g, hydrogen gas was charged at a reaction pressure of 1.0 MPa, and the reaction was performed for 6 hours.
  • Experiment 10 the same catalyst as used in Experiment 9 was subjected to hydrogen reduction treatment at a reaction temperature of 400° C. for a reaction time of 3 hours, and the amount of catalyst was 1.0 g, and hydrogen gas was used as the reaction pressure. The pressure was sealed at 1.0 MPa, and the reaction time was 6 hours.
  • fatty acid conversion rate x FFA
  • S DCO fatty acid decarboxylation rate
  • YJF carbon mole fraction of C 7-14 hydrocarbons
  • the carbon molar fraction of C 7-14 hydrocarbons is the total molar amount of carbon of C 7-14 hydrocarbons, which is the main component of jet fuel in the liquid product, in the raw material (bio-oil). This is to confirm the ratio in the molar amount of carbon in the compound. This evaluation allows identification of suitable catalysts and processes for producing bio-jet fuel.
  • Fatty acid conversion rate (x FFA ) is calculated by Equation 1
  • fatty acid decarboxylation rate (S DCO ) is calculated by Equation 2
  • carbon mole fraction (Y JF ) of C 7-14 hydrocarbons is calculated by Equation 3.
  • the amount of coke on the spent catalyst was measured and each experiment was evaluated. If the amount of coke on the spent catalyst is low, the catalyst has not lost activity and can withstand repeated use. When the amount of coke is large, the catalyst is deactivated early, and not only can it not be used repeatedly, but also there is a possibility that sufficient reforming treatment cannot be performed.
  • the amount of coke was measured by washing the remaining used catalyst with tetrahydrofuran and drying it, followed by TG analysis. In the TG analysis, the amount of coke produced during the reaction can be measured by analyzing the weight loss within the analysis temperature range. Using the numerical values obtained in this manner, the coke production rate (W coke ) was calculated by calculating the amount of coke on the used catalyst by calculating with the following formula 2.
  • Table 5 shows the results of experiments 1 to 10 evaluated using formulas 1 to 4.
  • Experiments 8, 9 and 10 were contrasted to investigate the effect on the reaction with or without supporting one or more metals selected from Groups 8, 9 and 10 in the catalyst.
  • the amount of coke attached to the catalyst was found to be smaller than in Experiment 8 in which platinum was not supported.
  • Experiment 10 in which hydrogen-reduced platinum was supported on the catalyst the amount of coke deposited was significantly reduced compared to Experiment 8. From the above, it is preferable to support one or more metals selected from Groups 8, 9, and 10 in order to enable long-term use of the catalyst. It was confirmed that one or more metals selected from Groups 8, 9 and 10 are more preferably subjected to hydrogen reduction treatment.
  • ⁇ Test 4 Reaction evaluation test by reaction temperature> Next, using the catalyst used in Experiment 10, 10.0 g of bio oil, 1.0 g of catalyst, reaction pressure of 1.0 MPa, stirring speed of 400 rpm, reaction time of 6 hours, reaction temperature of 320 ° C.
  • Experiment 11 A reforming experiment was carried out at a reaction temperature of 340° C., and a suitable reaction temperature was confirmed by evaluating the reaction in comparison with Experiment 10. The same evaluation as in test 3 was used. Table 6 shows the results.
  • the hydrocarbon isomerization rate was calculated by dividing the carbon molar amount of the C7-14 isomerized hydrocarbons in the liquid product by the carbon molar amount of all the hydrocarbons in the liquid product and multiplying by 100.
  • Table 7 shows the results of Test 5 above.

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