Apparatus and method for producing synthetic fuel

Abstract

Provided are an apparatus and a method for producing a synthetic fuel with which it is possible to obtain a hydrocarbon having a high selectivity of jet fuel components and to produce a jet fuel at a high yield. A synthetic fuel production device (1) for producing a predetermined synthetic fuel by a direct FT synthesis reaction using a raw material gas containing hydrogen gas and carbon dioxide, the synthetic fuel production device (1) being provided with: a reactor (9) having a cylindrical reactor main body section (9a) filled with a predetermined FT catalyst (20) for generating a direct FT synthesis reaction; a raw material gas flow rate adjustment unit (7) and / or composition adjustment units (5a, 5b) for adjusting the flow rate of the raw material gas supplied to the reactor (9); and a control device (3) that controls the linear velocity, which is the flow rate of the raw material gas per unit cross-sectional area of the reactor main body section (9a), by controlling the raw material gas flow rate adjustment section (7) and / or the composition adjustment sections (5a, 5b), and that controls the linear velocity to 0.2 m / sec to 4.0 m / sec when a given synthetic fuel is a jet fuel.

Description

Technical Field

[0001] The present invention relates to a manufacturing apparatus and a manufacturing method for producing a given synthetic fuel, particularly jet fuel, using a feedstock gas containing hydrogen and carbon dioxide via a direct FT synthesis reaction. Background Technology

[0002] Conventionally, a method for manufacturing jet fuel using a Fischer-Tropsch (FT) synthesis reaction, comprising a synthesis gas containing hydrogen and carbon monoxide, is known, for example, as disclosed in Patent Document 1. In this jet fuel manufacturing method, an FT crude oil containing various hydrocarbons is generated by a chemical reaction in which alkanes are synthesized from the synthesis gas within a reactor filled with an FT catalyst for the FT synthesis reaction. Furthermore, by combining this FT crude oil with various hydrogenation, alkylation, and aromatication treatments, a high yield of synthetic fuel suitable for jet fuel is achieved.

[0003] In addition, in recent years, research has been conducted on direct FT synthesis methods that use carbon dioxide instead of carbon monoxide in the synthesis gas to achieve carbon neutrality. In Japanese Patent Application No. 2022-052774, filed by the applicant, an FT catalyst was proposed for producing hydrocarbons with 5 or more carbon atoms in high yield using a mixture of hydrogen and carbon dioxide as feed gas. This FT catalyst is constructed by including Fe (iron) and Zr (zirconium), and also including Ga (gallium), or further including Na (sodium) as catalyst metals.

[0004] Existing technical documents Patent documents Patent Document 1: Japanese Patent No. 5826488 Summary of the Invention

[0005] The problem that the invention aims to solve However, in the aforementioned FT catalysts, the selectivity of synthetic fuels suitable for jet fuels, specifically synthetic fuels containing hydrocarbons with 8 to 16 carbon atoms, is insufficient. Through repeated and in-depth research, the inventors discovered that by considering the relationship between the flow rate and velocity of the FT catalyst packed in the reactor and the feed gas supplied to the reactor, the selectivity of hydrocarbons with the desired number of carbon atoms can be improved, thus completing this invention.

[0006] The present invention was made to solve the above-mentioned problems, and its object is to provide an apparatus and method for manufacturing synthetic fuels, which can obtain hydrocarbons with high selectivity of given synthetic fuel components, particularly jet fuels, and can manufacture jet fuels in high yield.

[0007] Technical solutions for solving the problem To achieve the above objectives, the invention involved in technical solution 1 is a synthetic fuel manufacturing apparatus (synthetic fuel manufacturing apparatus 1 in this embodiment (hereinafter, the same as in this item)), characterized in that it is used to manufacture a given synthetic fuel using a feedstock gas containing hydrogen and carbon dioxide through a direct FT synthesis reaction. The synthetic fuel manufacturing apparatus comprises: a reactor 9 having a cylindrical reactor body 9a, in which a given FT catalyst 20 for conducting a direct FT synthesis reaction is filled; an adjustment unit (feedstock gas flow rate adjustment unit 7 and / or composition adjustment unit 5a, composition adjustment unit 5b) for adjusting the flow rate of the feedstock gas supplied to the reactor; and a control unit (control device 3) for controlling the flow rate, i.e., the linear velocity, of the feedstock gas per unit cross-sectional area of ​​the reactor body by controlling the adjustment unit. When the given synthetic fuel is jet fuel, the control unit controls the linear velocity to be 0.2 m / sec to 4.0 m / sec.

[0008] According to this structure, the reactor has a cylindrical reactor body, which is filled with a given FT catalyst for direct FT synthesis. Furthermore, a control unit controls the flow rate of the feed gas supplied to the reactor. When the given synthetic fuel to be produced is jet fuel, the flow rate, i.e., the linear velocity, of the feed gas per unit cross-sectional area of ​​the reactor body is controlled to be 0.2 m / sec to 4.0 m / sec. By supplying the feed gas to the reactor at a linear velocity within the aforementioned range, hydrocarbons with high selectivity for the given synthetic fuel, particularly jet fuel components, can be obtained, enabling the production of jet fuel in high yield.

[0009] The invention involved in technical solution 2 is characterized in that, in the synthetic fuel manufacturing apparatus described in technical solution 1, the control unit controls the linear velocity to be 2.7 m / sec to 3.0 m / sec.

[0010] According to this structure, by using a control unit to control the linear velocity to 2.7 m / sec to 3.0 m / sec, it is possible to obtain hydrocarbon components of jet fuel with a higher selectivity.

[0011] The invention involved in technical solution 3 is a method for manufacturing synthetic fuel, characterized in that it is used to manufacture a given synthetic fuel by using a feedstock gas containing hydrogen and carbon dioxide and through a direct FT synthesis reaction. The method for manufacturing synthetic fuel includes: a reactor preparation step, in which a reactor 9 is prepared by filling a cylindrical reactor body 9a with an FT catalyst for the direct FT synthesis reaction; and a feedstock gas supply step, in which, when the given synthetic fuel is jet fuel, the feedstock gas is supplied to the reactor in such a way that the flow rate, i.e., the linear velocity, of the feedstock gas per unit cross-sectional area of ​​the reactor body is 0.2 m / sec to 4.0 m / sec.

[0012] According to this structure, when producing a given synthetic fuel using feedstock gases containing hydrogen and carbon dioxide via a direct FT synthesis reaction, firstly, a reactor is prepared by filling the cylindrical reactor body with a given FT catalyst (reactor preparation step). Next, when the given synthetic fuel to be produced is jet fuel, the feedstock gas is supplied to the reactor at a flow rate (linear velocity) of 0.2 m / sec to 4.0 m / sec per unit cross-sectional area of ​​the reactor body (feedstock gas supply step). By supplying the feedstock gas to the reactor at a linear velocity within the aforementioned range, the given synthetic fuel, particularly a synthetic fuel containing hydrocarbons with high selectivity for jet fuel components, can be produced. Attached Figure Description

[0013] Figure 1 This is a schematic diagram of a synthetic fuel manufacturing apparatus that applies a synthetic fuel manufacturing apparatus and manufacturing method based on one embodiment of the present invention.

[0014] Figure 2 (a) is a diagram showing a reactor filled with FT catalyst. Figure 2 (b) is a graph used to illustrate the linear velocity of the feed gas supplied to the reactor.

[0015] Figure 3 It is a graph showing the distillation properties of synthetic fuels obtained when feedstock gases are supplied to the reactor at high and low linear velocities.

[0016] Figure 4 It is a graph showing the distribution of hydrocarbons, representing the relationship between the number of carbon atoms and the weight of hydrocarbons contained in synthetic fuels. Figure 4 (a) shows the jet fuel for the Jet-A1 standard. Figure 4 (b) shows the synthetic fuel obtained at a low linear velocity. Figure 4 (c) shows the hydrocarbon distribution of the synthetic fuel obtained at a high linear velocity.

[0017] Figure 5It is a graph showing the relationship between the linear velocity of the feed gas and the Jet fuel selectivity based on experimental results.

[0018] Figure 6 This is about two FT catalysts, showing graphs of pore distribution representing the relationship between pore size and pore volume. Detailed Implementation

[0019] Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. Figure 1 The diagram schematically illustrates a synthetic fuel manufacturing apparatus and manufacturing method based on an embodiment of the present invention. As shown in the figure, the synthetic fuel manufacturing apparatus 1 includes a raw material gas supply unit, a composition adjustment unit, a compression unit, a flow rate adjustment unit, a preheating unit, a catalyst reaction unit, a cooling unit, a gas-liquid separation unit, and a collection unit, which are connected via piping 2 and controlled by a control device 3 (control unit).

[0020] The feed gas supply section includes an H2 supply section 4a and a CO2 supply section 4b, which supply hydrogen and carbon dioxide, respectively. Furthermore, downstream of the H2 supply section 4a and the CO2 supply section 4b, respectively, are H2 composition adjustment sections 5a and CO2 composition adjustment sections 5b. By controlling these sections, the composition and mixing ratio of the H2 and CO2 mixture supplied as feed gas to the reactor 9 (described later) in the catalyst reaction section are adjusted. Moreover, these H2 composition adjustment sections 5a and CO2 composition adjustment sections 5b are controlled by the control device 3, allowing the feed gas flow rate to be adjusted individually or in cooperation with the feed gas flow rate adjustment section 7 (described later).

[0021] The compression unit has a compressor 6, which, controlled by a control device 3, pressurizes the raw material gas to a given pressure (e.g., 3 MPa). Additionally, the flow adjustment unit has a raw material gas flow adjustment unit 7, which, controlled by the control device 3, adjusts the flow rate of the raw material gas compressed by the compressor 6.

[0022] The preheating section has a preheating pipe 8a and a preheating heater 8b. The preheating heater 8b is controlled by the control device 3, thereby heating the raw material gas in the preheating pipe 8a connected to the piping 2 to a given temperature.

[0023] The catalyst reaction section includes a reactor 9 and a temperature control section 10. For example... Figure 2As shown in (a), the reactor 9 has a cylindrical reactor body 9a with a given inner diameter, and the reactor body 9a is filled with FT catalyst 20. Furthermore, the preparation of the reactor 9 by filling the reactor body 9a with FT catalyst 20 is equivalent to the reactor preparation step in the synthetic fuel manufacturing method of the present invention, but the reactor preparation step may also include a step of heating the reactor 9 to a given temperature (reaction temperature, etc.) using an inactive gas or the like.

[0024] The aforementioned FT catalyst 20 is used to generate various hydrocarbons with different numbers of carbon atoms by causing the feed gas supplied to reactor 9 to undergo a direct FT synthesis reaction. Furthermore, the FT catalyst 20 is similar to the FT catalyst disclosed in Japanese Patent Application No. 2022-052774, specifically, as a metal catalyst, it comprises Fe, Zr, Ga, and Na. Additionally, this FT catalyst 20 is composed of multiple particulate materials each having a given size and shape, configured to have multiple micropores. The specific surface area of ​​these micropores is approximately 30 m². 2 / g, with an average pore size of 10nm~100nm.

[0025] In addition, the temperature adjustment unit 10 in the catalyst reaction section is controlled by the control device 3, which adjusts the direct FT synthesis reaction generated in the reactor 9 to a given temperature (e.g., 380°C).

[0026] like Figure 1 As shown by the double-dotted line, in the synthetic fuel manufacturing apparatus 1, the feed gas is maintained at high pressure from the compression section to the catalyst reaction section, and furthermore, as... Figure 1 As shown by the dashed line, the feed gas is heated from the preheating section to the catalyst reaction section.

[0027] The cooling section has a cooler 11, which is controlled by a control device 3 to cool the products removed from the reactor 9.

[0028] The gas-liquid separation unit includes a gas-liquid separator 12, which separates the liquefied products cooled by the cooler 11 from the unreacted or unliquefied gaseous post-reaction gases. Furthermore, although the aforementioned post-reaction gases are discharged outside the synthetic fuel manufacturing apparatus 1, they are effectively reused as raw material gases for other refining processes and chemical reactions.

[0029] The collection section has a collection tank 13, through which the liquid products separated by the gas-liquid separator 12 are collected.

[0030] In the synthetic fuel manufacturing apparatus 1 configured as described above, as shown below, by controlling the linear velocity of the feed gas supplied to the reactor 9 within a given range while conducting a direct FT synthesis reaction, it is possible to obtain synthetic fuel containing hydrocarbons with high selectivity of jet fuel components, and jet fuel can be manufactured in high yield.

[0031] like Figure 2 As shown in (b), the aforementioned linear velocity is the flow rate of the raw material gas per unit cross-sectional area inside the cylindrical reactor body 9a of reactor 9, defined by the following formula.

[0032] Linear velocity (m / sec) = feed gas flow rate (m³ / sec) 3 / sec) / Cross-sectional area (m 2 ) Figure 3 This figure shows the results of a distillation test of the synthesized fuel obtained using the aforementioned synthetic fuel manufacturing apparatus 1. The feed gas was supplied to reactor 9 at a relatively low linear velocity (0.123 m / sec) and a relatively high linear velocity (2.88 m / sec). Under given conditions (reactor temperature: 380°C, reactor pressure: 3 MPa), a direct FT synthesis reaction was carried out. The horizontal axis shows the yield (wt%), and the vertical axis shows the distillation temperature (°C). Furthermore, the TH and TL values ​​for the distillation temperature in this figure represent the upper and lower limits of the distillation temperature suitable as a jet fuel component, respectively. Specifically, for example, the upper limit distillation temperature TH is 232°C, and the lower limit distillation temperature TL is 157°C.

[0033] like Figure 3 As shown by the double-dotted line, the selectivity of jet fuel in the synthetic fuel obtained by supplying the feed gas to reactor 9 at a low linear velocity is 20%.

[0034] In contrast, such as Figure 3 As shown by the solid line, in the synthetic fuel obtained by supplying the feed gas to reactor 9 at a high linear velocity, the selectivity of the jet fuel increases significantly to 55% compared to the case of low linear velocity.

[0035] in addition, Figure 4 The diagram shows the hydrocarbon distribution, representing the relationship between the number of carbon atoms and weight of hydrocarbons in synthetic fuels obtained at the aforementioned low and high linear velocities. Solid lines represent straight-chain hydrocarbons, and dashed lines represent aromatic hydrocarbons. Furthermore, Figure 4 (a) shows the hydrocarbon distribution of jet fuel for a given standard (Jet-A1) for reference.

[0036] like Figure 4As shown in (a), it can be seen that in the jet fuel of Jet-A1, the distribution of straight-chain and aromatic hydrocarbons includes hydrocarbons with 7 to 20 carbon atoms, especially hydrocarbons with 8 to 16 carbon atoms that are suitable for jet fuel (hereinafter referred to as the "Jet range").

[0037] In contrast, such as Figure 4 As shown in (b), the synthetic fuel obtained at low linear velocity contains hydrocarbons with 3 to 13 carbon atoms. Compared with the hydrocarbon distribution of Jet-A1 shown in (a) of the same figure, the Jet range of the synthetic fuel obtained at low linear velocity contains fewer hydrocarbons, and therefore, the number of hydrocarbons with the required number of carbon atoms as a jet fuel component is insufficient.

[0038] On the other hand, such as Figure 4 As shown in (c), it can be seen that the synthetic fuel obtained at high linear velocity contains hydrocarbons with 4 to 20 carbon atoms, especially those in the Jet range with 8 to 16 carbon atoms. Therefore, it can be concluded that the synthetic fuel obtained at high linear velocity fully possesses the number of hydrocarbons with the required number of carbon atoms for jet fuel composition.

[0039] Figure 5 This figure shows the relationship between the feed gas linear velocity and the Jet fuel selectivity based on the above experimental results. Furthermore, in the graph shown, the maximum feed gas linear velocity in the above experiments is 3.0 m / sec. The Jet fuel selectivity for feed gas linear velocities between 3.0 m / sec and 4.0 m / sec is represented by a dashed double-dot line. Additionally, if the feed gas linear velocity exceeds 4.0 m / sec, the linear velocity of the feed gas supplied to reactor 9 becomes excessive, potentially causing adverse effects on the direct FT synthesis reaction due to the pulverization (disintegration) of the FT catalyst 20. Therefore, an upper limit of 4.0 m / sec is set for the good linear velocity range where the Jet fuel selectivity is 40% or higher.

[0040] from Figure 5 As shown in the chart, the Jet fuel selectivity is above 40%, and the feed gas linear velocity for obtaining a relatively good Jet fuel selectivity is 0.2 m / sec to 4.0 m / sec (good linear velocity range).

[0041] In addition, it is known that the Jet fuel selectivity is above 50%, and the feed gas linear velocity for obtaining a relatively high Jet fuel selectivity is 2.7 m / sec to 3.0 m / sec (optimal linear velocity range).

[0042] Figure 6For two FT catalysts, C1 and C2, both possessing multiple micropores, the micropore distributions representing the relationship between micropore diameter and micropore volume are shown. As shown in the figure, the average micropore diameter and median micropore diameter of FT catalyst C1 are 31.5 nm and 38.6 nm, respectively, while those of FT catalyst C2 are 25.5 nm and 20.7 nm, respectively. Furthermore, regarding... Figure 6 The pore distribution shown was determined using a nitrogen gas adsorption method.

[0043] The two FT catalysts C1 and C2 described above were filled into reactor 9 of the synthetic fuel manufacturing apparatus 1, and the hydrocarbons obtained by supplying the feed gas to reactor 9 at the same feed gas linear velocity were compared. As a result, although detailed data are omitted, it was confirmed that high-boiling-point hydrocarbons, i.e., hydrocarbons with a large number of carbon atoms, can be obtained from FT catalyst C1, which has both a large average pore size and a large median pore size.

[0044] Furthermore, as an FT catalyst 20 having multiple pores, it is preferable that the average diameter (average pore size) of these pores is 10 nm to 100 nm, thereby improving the yield of higher hydrocarbons with 8 or more carbon atoms required for jet fuel. This is believed to be for the following reasons: If the average pore size is less than 10 nm, the feed gas cannot easily reach deep into the pores of the FT catalyst 20, which may prevent sufficient promotion of the direct FT synthesis reaction. On the other hand, if the average pore size exceeds 100 nm, the surface area of ​​the FT catalyst 20 decreases, and consequently, the amount of feed gas in contact with the FT catalyst 20 also decreases, which may prevent further improvement in the yield of higher hydrocarbons with 8 or more carbon atoms required for jet fuel. Therefore, as described above, it is preferable that the average pore size of the FT catalyst 20 is 10 nm to 100 nm.

[0045] As described above, according to this embodiment, when producing jet fuel as a synthetic fuel, by supplying a feedstock gas containing hydrogen and carbon dioxide to a reactor 9 filled with FT catalyst 20 at a linear velocity of 0.2 m / sec to 4.0 m / sec, hydrocarbons with high selectivity of jet fuel components can be obtained, and jet fuel can be produced in high yield. Furthermore, by setting the linear velocity to 2.7 m / sec to 3.0 m / sec, hydrocarbons of jet fuel components can be obtained with even higher selectivity.

[0046] Furthermore, the present invention is not limited to the embodiments described above and can be implemented in various ways. For example, in the embodiments, an FT catalyst comprising Fe, Zr, Ga, and Na was used as the FT catalyst 20 for the direct FT synthesis reaction, but other catalysts can also be used as long as the direct FT synthesis reaction can be carried out on a feed gas containing hydrogen and carbon dioxide.

[0047] Furthermore, the detailed structure of the synthetic fuel manufacturing apparatus 1 shown in the embodiment is merely an example and can be appropriately modified within the scope of the present invention.

[0048] Explanation of reference numerals in the attached figures 1 Synthetic fuel manufacturing unit 2 piping 3. Control device (control unit) 4a H2 Supply Department 4b CO2 Supply Department 5a H2 composition adjustment section 5b CO2 composition adjustment section 6. Compressor 7. Raw material gas flow rate adjustment unit (flow rate adjustment unit) 8a preheating tube 8b Preheater 9. Reactor 9a Reactor body 10 Temperature Control Section 11 Cooling machine 12 Gas-Liquid Separator 13 Collection tanks 20 FT catalyst.

Claims

1. An apparatus for producing synthetic fuel, characterized by comprising: The synthetic fuel manufacturing apparatus is for manufacturing a given synthetic fuel using a raw material gas containing hydrogen and carbon dioxide and by a direct FT synthesis reaction, The synthetic fuel manufacturing apparatus includes: a reactor having a cylindrical reactor main portion in which a given FT catalyst for causing the direct FT synthesis reaction is filled; an adjustment portion for adjusting a flow rate of the raw material gas supplied to the reactor; and a control unit that controls the flow rate of the raw material gas per unit cross-sectional area of the reactor main portion, i.e., a linear velocity, by controlling the adjustment portion, In the case where the given synthetic fuel is jet fuel, the control unit controls the linear velocity to be 0.2 m / sec to 4.0 m / sec.

2. The synthetic fuel manufacturing apparatus according to claim 1, wherein the control unit controls the linear velocity to be 2.7 m / sec to 3.0 m / sec. The synthetic fuel manufacturing method is for manufacturing a given synthetic fuel using a raw material gas containing hydrogen and carbon dioxide and by a direct FT synthesis reaction, 3. A method for producing synthetic fuel, characterized by, The synthetic fuel manufacturing method includes: a reactor preparation step of preparing a reactor in which a given FT catalyst for causing the direct FT synthesis reaction is filled in a cylindrical reactor main portion; and a raw material gas supply step of supplying the raw material gas to the reactor in such a manner that a flow rate of the raw material gas per unit cross-sectional area of the reactor main portion, i.e., a linear velocity, is 0.2 m / sec to 4.0 m / sec in the case where the given synthetic fuel is jet fuel. ​

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