Catalyst for manufacturing bio-jet fuel and method for manufacturing bio-jet fuel using catalyst for manufacturing bio-jet fuel

Abstract

The purpose of the present invention is to provide a catalyst for producing a bio-jet fuel, the catalyst being used in a method for producing a bio-jet fuel, the method being capable of easily producing a high-quality bio-jet fuel having high energy-saving properties. A catalyst for producing a bio-jet fuel, which is used in a method for producing a bio-jet fuel by modifying a biomass-derived oil containing triacylglycerol, is characterized in that: a solid base catalyst is supported on a solid acid catalyst, and zeolite is used as the solid acid catalyst; an oxide of a Group 2 metal is used as a solid base catalyst, and a noble metal is supported on the solid base catalyst.

Description

Technical Field

[0001] The present invention relates to a catalyst for producing biojet fuel for modifying bio-oil derived from biomass to obtain biojet fuel, and a method for producing biojet fuel using the catalyst for producing biojet fuel. Background Art

[0002] In recent years, global warming caused by carbon dioxide has become an international environmental problem. In response to this problem, according to the United Nations Framework Convention on Climate Change, the Kyoto Protocol, etc., each country is required to reduce greenhouse gas emissions. Japan's carbon dioxide emissions in 2018 were 1.138 billion tons, accounting for 3.4% of the global carbon dioxide emissions. It is difficult to say that sufficient reduction of greenhouse gases required by the convention can be achieved. Among these carbon dioxide emissions, the proportion of carbon dioxide emitted during energy conversion has risen to 40.1%. Therefore, in order to achieve a sustainable society, there is a need to develop a technology that can produce clean and renewable resources from the production of energy / chemical products mainly based on fossil resources so far.

[0003] In this context, from the perspective of suppressing carbon dioxide emissions, biofuels have attracted much attention as alternative products to fossil fuels that can achieve carbon neutrality. Regarding biofuels, the carbon dioxide generated by their combustion comes from the carbon dioxide absorbed from the atmosphere during the growth of biomass. Therefore, even if biofuels are used, carbon neutrality can be achieved, which is a concept that the amount of carbon dioxide emitted during production and biological activities is the same as the amount of carbon dioxide absorbed.

[0004] As biofuels that achieve such carbon neutrality, in addition to bioethanol fuel and biodiesel fuel that have been widely popularized in recent years, there is also biojet fuel. The popularization of biojet fuel is slower compared to bioethanol fuel and biodiesel fuel due to strict product standards and the like. However, the global aviation industry consumes approximately 1.5 billion to 1.7 billion barrels (equivalent to 238 to 270 Mm 3 ) of ordinary jet fuel per year, and there is a need to quickly develop high-quality biojet fuel to replace ordinary jet fuel.

[0005] Conventionally, as a method for producing biojet fuel from biomass resources, hydrocarbon is generated by subjecting raw material oil derived from biomass to hydrodeoxygenation treatment, and the hydrocarbon is isomerized and decomposed to generate isomerized hydrocarbon of C 7-16 that becomes biojet fuel.

[0006] As a method for producing such a biogenic jet fuel, for example, Patent Document 1 discloses a method for producing a diesel fuel boiling point range product and an aviation fuel boiling point range product from renewable feedstocks, which includes: a) in a first reaction zone, in the presence of hydrogen under reaction conditions, using a catalyst, hydrogenating and deoxygenating the renewable feedstock, thereby performing treatment to obtain a product stream of the first reaction zone, the product stream of the first reaction zone containing hydrogen, water, carbon monoxide, carbon dioxide, and a hydrocarbon fraction containing paraffins in the diesel fuel boiling point range and paraffins in the aviation fuel boiling point range; b) in a high-temperature and high-pressure hydrogen stripping column, selectively separating a gas stream containing at least a part of hydrogen, water, carbon monoxide, and carbon dioxide from the remaining fluid containing at least paraffins from the product stream of the first reaction zone; c) introducing the remaining fluid into a second reaction zone in a manner of contacting with an isomerization / selective cracking catalyst under isomerization / selective cracking conditions, selectively hydrocracking at least a part of the paraffins, and isomerizing at least a part of the paraffins to generate a fluid with a high content of branched paraffins; d) cooling the fluid with a high content of branched paraffins and the gas stream, separating the gas components containing at least hydrogen and carbon dioxide from the liquid hydrocarbon components and water components; and e) separating the liquid hydrocarbon components into a top distillate stream, a diesel fuel boiling point range product, and an aviation fuel boiling point range product.

[0007] Patent Document 2 discloses a method for hydrocarbon production, which includes: in a first stage, setting conditions sufficient for hydrodeoxygenation of a bio-derived oil and hydrogen in the presence of a hydrodeoxygenation catalyst to produce n-paraffins, and in a second stage, setting conditions sufficient for isomerization of n-paraffins and hydrogen in the presence of an isomerization catalyst to produce iso-paraffins and a separated fraction, recycling the fraction that boils at 200 °C or higher under the atmospheric pressure obtained from the second stage to the isomerization stage where isomerization is carried out in the presence of an isomerization catalyst.

[0008] Patent Document 3 discloses a method for converting an oil containing triacylglycerides into a crude oil precursor and / or a distillate hydrocarbon fuel, which includes: reacting a mixture of an oil containing triacylglycerides, water, and diatomic hydrogen at a temperature in the range of about 250 °C to about 560 °C and a pressure of about more than 75 bar to convert at least a part of the triacylglycerides, and recovering a reaction effluent containing water and one or more selected from iso-olefins, iso-paraffins, cyclo-olefins, cyclo-paraffins, and aromatics; and subjecting the reaction effluent to hydrotreatment to form a hydrotreated effluent.

[0009] Prior art documents

[0010] Patent documents

[0011] Patent Document 1: Japanese Patent Application Laid-Open No. 2011-515539

[0012] Patent Document 2: Japanese Patent Application Laid-Open No. 2011-526640

[0013] Patent Document 3: Japanese Patent Application Laid-Open No. 2015-531430 Summary of the Invention

[0014] Problems to be Solved by the Invention

[0015] The methods described in Patent Documents 1 and 2 are carried out through two-stage processes of a hydrodeoxygenation treatment process and an isomerization cracking process, and there are problems of high energy consumption and high cost in the production of biojet fuel.

[0016] In the method of Patent Document 3, the hydrothermal treatment of fats and oils is carried out under a high pressure of about more than 75 bar, and then a hydrogenation reaction is carried out. Therefore, facilities resistant to high pressure and a large amount of hydrogen are required, and thus there are problems of high energy consumption and high cost in the production of biojet fuel.

[0017] In addition, in the hydrodeoxygenation reaction of Patent Documents 1 and 2, by-products of carbon monoxide and short-chain hydrocarbons are produced, and these by-products of carbon monoxide and short-chain hydrocarbons react with hydrogen, so the hydrogen consumption increases, and thus the cost becomes high.

[0018] The inventors of the present application focused on a multifunctional catalyst to solve the above problems and achieved the present invention. The present invention is a catalyst capable of carrying out a hydrodeoxygenation reaction, hydroisomerization, and hydrocracking in one stage, and a method for producing a biojet fuel with low hydrogen consumption under low-pressure hydrogen, and a method for producing a biojet fuel using the catalyst.

[0019] The present invention provides a catalyst for producing a biojet fuel used in a method for producing a biojet fuel capable of easily producing a biojet fuel with high energy efficiency and high quality, and a method for producing a biojet fuel using the catalyst.

[0020] Means for Solving the Problems

[0021] In order to solve the above problems, the present invention is characterized in that it is a catalyst for producing a biojet fuel used in a method for producing a biojet fuel by modifying a biomass-derived oil containing triacylglycerol, which is formed by supporting a solid base catalyst on a solid acid catalyst, using zeolite as the solid acid catalyst, using an oxide of a Group II metal as the solid base catalyst, and further supporting a noble metal thereon.

[0022] The catalyst for producing bio-jet fuel of the present invention may further carry tin.

[0023] As the noble metal carried by the catalyst for producing bio-jet fuel of the present invention, platinum can be used.

[0024] The zeolite as the solid acid catalyst in the catalyst for producing bio-jet fuel of the present invention may be ZSM-5 type zeolite or SAPO-11 type zeolite.

[0025] The oxide of the Group II metal used in the catalyst for producing bio-jet fuel of the present invention may be one or more selected from magnesium oxide, calcium oxide, and barium oxide.

[0026] The biomass-derived oil modified with the catalyst for producing bio-jet fuel of the present invention may be coconut oil.

[0027] Advantages of the Invention

[0028] According to the present invention, isomerized hydrocarbons that become bio-jet fuel can be suitably obtained from biomass-derived oil containing free fatty acids and triacylglycerols. 7-16 Description of the Drawings

[0029] Figure 1 It is an explanatory diagram showing a performance test apparatus for the catalyst for producing bio-jet fuel of the present invention. Detailed Description of the Invention

[0030] Hereinafter, an example of an embodiment of the present invention will be described.

[0031] The catalyst for producing bio-jet fuel in this example is a catalyst for producing bio-jet fuel obtained by supporting an oxide of a Group II metal as a solid base catalyst on a zeolite as a solid acid catalyst and further supporting a noble metal thereon.

[0032] In the catalyst for producing bio-jet fuel in this example, tin may further be supported.

[0033] As the supported noble metal, gold, platinum, ruthenium, rhodium, osmium, iridium, palladium, rhenium can be used, and platinum is preferably used.

[0034] As the zeolite used as the solid acid catalyst, for example, mordenite, β-zeolite, ZSM-based zeolite, A-type zeolite, X-type zeolite, Y-type zeolite, etc. can be used, and ZSM-5 type zeolite or SAPO-11 type zeolite is preferably used.

[0035] The oxide of the Group II metal used as the solid base catalyst is not particularly limited, and one or more selected from magnesium oxide, calcium oxide, rubidium oxide, or barium oxide are suitably used.

[0036] In the manufacture of the catalyst, the solid base catalyst precursor is dissolved in distilled water, impregnated into the solid acid catalyst, dried, formed into pellets, and then calcined to obtain the catalyst. In addition, the noble metal salt is dissolved in distilled water, and a tin salt is further added as necessary, impregnated, and dried / calcined to obtain the catalyst. It should be noted that the manufacturing method of the catalyst is not limited to this method and can be manufactured by other methods.

[0037] The biomass-derived oil containing triacylglycerol to be modified by the catalyst for manufacturing biomass jet fuel according to the present invention is not particularly limited. For stable supply and easy production of the oil, plant seeds containing a large amount of oil can be suitably used as the biomass. For example, Cerbera manghas, Pachyrhizus erosus, Polon, Jatropha, coconut, the fruit of palm coconut, the fruit of Chinese jujube, etc. are suitable. Among them, coconut contains a large amount of oil in its endosperm, so it is more suitable to use. The method for manufacturing oil from biomass is not particularly limited and can be manufactured by extraction, heat treatment, etc.

[0038] The modification of the biomass-derived oil is carried out using a modification treatment device having a reactor, a heating unit, and a gas injection unit capable of injecting hydrogen. The modification treatment device preferably uses a continuous manufacturing device capable of continuously supplying the biomass-derived oil as a raw material and taking out products such as the modified oil and gas.

[0039] As an example of the method for manufacturing biojet fuel by modifying the biomass-derived oil, first, a pretreatment of hydrogenation reduction of the catalyst for manufacturing biomass jet fuel is carried out. The hydrogenation reduction method is not particularly limited, and it is suitably carried out at a hydrogen flow rate of 100 ml / min at 400 °C for about 3 hours. After reduction, the biomass-derived oil and the catalyst are placed in the reactor of the modification treatment device, hydrogen is injected at a reaction temperature of 200 °C to 450 °C, and the hydrogenation deoxygenation reaction, hydrogenation isomerization, and hydrocracking are carried out in one stage to carry out the modification treatment of the biomass-derived oil. The hydrogen pressure can be a low pressure, about 0.5 to 3 MPa, and as the hydrogen supply amount, it is carried out under the condition that the volume ratio of hydrogen to the biomass-derived oil is about 100:1 to 1200:1. In addition, in the case of a continuous manufacturing device, the liquid space velocity can be set to 5 h -1 ~0.2 h -1 or so.

[0040] According to the catalyst for bio-jet fuel of this example as described above, the hydrodeoxygenation reaction, hydroisomerization, and hydrocracking can be carried out in one stage. Compared with the conventional bio-jet fuel manufacturing method, a low hydrogen consumption type bio-jet fuel manufacturing method can be used under low-pressure hydrogen.

[0041] Example

[0042] Hereinafter, examples are given to explain the invention of the present application in more detail.

[0043] <Example 1>

[0044] Using the above-mentioned catalyst manufacturing method, ZSM-5 type zeolite is used as the solid acid catalyst, 1% by mass of magnesium oxide is supported as the solid base catalyst, and further 0.3% by mass of platinum is supported to manufacture the catalyst.

[0045] <Example 2>

[0046] Using the above-mentioned catalyst manufacturing method, ZSM-5 type zeolite is used as the solid acid catalyst, 1% by mass of magnesium oxide is supported as the solid base catalyst, and further 0.3% by mass of platinum and 0.37% by mass of tin are supported to manufacture the catalyst.

[0047] <Example 3>

[0048] Using the above-mentioned catalyst manufacturing method, SAPO-11 type zeolite is used as the solid acid catalyst, 1% by mass of magnesium oxide is supported as the solid base catalyst, and further 0.3% by mass of platinum and 0.37% by mass of tin are supported to manufacture the catalyst.

[0049] <Example 4>

[0050] Using the above-mentioned catalyst manufacturing method, ZSM-5 type zeolite is used as the solid acid catalyst, 5% by mass of magnesium oxide is supported as the solid base catalyst, and further 0.3% by mass of platinum and 0.37% by mass of tin are supported to manufacture the catalyst.

[0051] <Example 5>

[0052] Using the above-mentioned catalyst manufacturing method, SAPO-11 type zeolite is used as the solid acid catalyst, 5% by mass of magnesium oxide is supported as the solid base catalyst, and further 0.3% by mass of platinum and 0.37% by mass of tin are supported to manufacture the catalyst.

[0053] <Test 1>

[0054] In Test 1, the catalysts of Example 1 and Example 2 were used to carry out the modification test of coconut oil. In the test, Figure 1A fixed-bed flow-type reaction device as shown, which continuously supplies coconut oil to a reactor and continuously discharges the modified liquid product and gas product in the reactor. Regarding the catalyst, as a pretreatment, hydrogen reduction is carried out at 400 °C for 3 hours under the condition that the hydrogen flow rate is 100 ml / min. As test conditions, the reaction temperature is gradually changed to 350 °C, 375 °C, and 400 °C, the hydrogen pressure is set to 3 MPa, the hydrogen supply amount is set to 1000 times the volume of the raw material, and the liquid space velocity is set to 2 h -1 .

[0055] Analyze the liquid product obtained through the above test, and calculate the values of raw material conversion rate, yield of hydrocarbons for bio-jet fuel (C7-C 16 ), and hydrocarbon isomerization rate. The raw material conversion rate refers to the ratio of triglycerides in coconut oil as the raw material being converted into hydrocarbons due to modification, and is obtained by Equation 1. In addition, the yield of hydrocarbons for bio-jet fuel (C7-C 16 ) is obtained by Equation 2, and the hydrocarbon isomerization rate is obtained by Equation 3. It should be noted that regarding the hydrocarbon isomerization rate, the total amount of isomerized hydrocarbons in the liquid product is calculated in the form of hydrocarbons obtained by isomerizing hydrocarbons that cannot be identified through analysis.

[0056] [Equation 1]

[0057]

[0058] [Equation 2]

[0059]

[0060] [Equation 3]

[0061]

[0062] The above test results are shown in Table 1.

[0063] [Table 1]

[0064]

[0065] As shown in Table 1, for the liquid products modified using the catalysts of Example 1 and Example 2, sufficient values were observed in terms of raw material conversion rate, yield of hydrocarbons for bio-jet fuel (C7-C 16 ), and hydrocarbon isomerization rate. Therefore, it is shown that by using the catalysts of Example 1 and Example 2, hydrodeoxygenation reaction, hydroisomerization, and hydrocracking can be carried out in one stage, and compared with the conventional bio-jet fuel manufacturing method, a low-hydrogen consumption type bio-jet fuel manufacturing method can be suitably carried out under low-pressure hydrogen.

[0066] [Test 2]

[0067] In Test 2, using the catalysts of Examples 2 to 5, the hydrogen pressure was set to 1 MPa, and the other conditions were the same as in Test 1, and the same evaluation as in Test 1 was carried out. The results are shown in Table 2.

[0068] [Table 2]

[0069]

[0070] As shown in Table 2, for the liquid products modified with the catalysts of Examples 2 to 4, sufficient values were observed in terms of raw material conversion rate, yield of hydrocarbons for biojet fuel (C7-C 16 ), and hydrocarbon isomerization rate. Therefore, it is shown that by using the catalysts of Examples 2 to 4, the hydrodeoxygenation reaction, hydroisomerization, and hydrocracking can be carried out in one stage, and compared with the conventional biojet fuel manufacturing method, a low-hydrogen consumption type biojet fuel manufacturing method can be particularly suitably carried out under low-pressure hydrogen. When comparing the liquid products modified with the catalyst of Example 5 with the liquid products modified with the catalysts of Examples 2 to 4, the yield of hydrocarbons for biojet fuel (C7-C 16 ) and the hydrocarbon isomerization rate are slightly lower, but a high value was also observed for the raw material conversion rate as in the cases of Examples 2 to 4, indicating that by using the catalyst of Example 5, the hydrodeoxygenation reaction, hydroisomerization, and hydrocracking can be carried out in one stage, and compared with the conventional biojet fuel manufacturing method, a low-hydrogen consumption type biojet fuel manufacturing method can be extremely suitably carried out under low-pressure hydrogen.

Claims

1. A catalyst for the production of bio-jet fuel, characterized in that, It is a catalyst for manufacturing biojet fuel used in a biojet fuel manufacturing method for modifying an oil containing triacylglycerol and derived from biomass to manufacture biojet fuel. It is formed by supporting a solid base catalyst on a solid acid catalyst. Zeolite is used as the solid acid catalyst, and an oxide of a Group II metal is used as the solid base catalyst, and further, a noble metal is supported thereon.

2. The catalyst for manufacturing bio-jet fuel according to claim 1, characterized in that, It also supports tin.

3. The catalyst for manufacturing bio-jet fuel according to claim 1 or 2, characterized in that, The noble metal is platinum.

4. The catalyst for manufacturing bio-jet fuel according to claim 1 or 2, characterized in that, The zeolite as the solid acid catalyst is ZSM-5 type zeolite or SAPO-11 type zeolite.

5. The catalyst for manufacturing bio-jet fuel according to claim 1 or 2, characterized in that, The oxide of the Group II metal as the solid acid catalyst is one or more selected from magnesium oxide, calcium oxide, and barium oxide.

6. The catalyst for manufacturing bio-jet fuel according to claim 3, characterized in that, The zeolite as the solid acid catalyst is ZSM-5 type zeolite or SAPO-11 type zeolite.

7. The catalyst for manufacturing bio - jet fuel according to claim 4, characterized in that, The oxide of the Group II metal as the solid acid catalyst is one or more selected from magnesium oxide, calcium oxide, and barium oxide.

8. The catalyst for manufacturing bio - jet fuel according to claim 5, characterized in that, The oxide of the Group II metal as the solid acid catalyst is one or more selected from magnesium oxide, calcium oxide, and barium oxide.

9. The catalyst for manufacturing bio-jet fuel according to claim 1 or 2, characterized in that, The oil derived from biomass is coconut oil extracted from coconuts.

10. A method for manufacturing biojet fuel, characterized in that, A reaction device that continuously supplies an oil containing triacylglycerol and derived from biomass to a reaction furnace and continuously discharges the modified liquid product and gas product in the reaction furnace is used. The oil derived from biomass and the catalyst for manufacturing biojet fuel are placed in the reaction furnace, hydrogen is injected while heating at the reaction temperature, and hydrodeoxygenation reaction, hydroisomerization, and hydrocracking are carried out in one stage to manufacture biojet fuel. The catalyst for manufacturing biojet fuel is formed by supporting a solid base catalyst on a solid acid catalyst. Zeolite is used as the solid acid catalyst, and an oxide of a Group II metal is used as the solid base catalyst, and further, a noble metal is supported thereon. The reaction temperature is 200°C to 450°C. The hydrogen pressure for injecting the hydrogen is 0.5 MPa to 3 MPa.

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