Hydrocarbon production apparatus and hydrocarbon production method

Abstract

To provide a hydrocarbon production apparatus and a hydrocarbon production method that can improve hydrocarbon production efficiency.SOLUTION: A hydrocarbon production apparatus 1 comprises: a reverse shift reaction part 2 that uses carbon dioxide and hydrogen to obtain a synthesis gas containing carbon monoxide and hydrogen; a hydrocarbon production part 4 that produces hydrocarbons using the synthesis gas; a gas-liquid separation part 6 that separates a gas component containing hydrogen, carbon dioxide and light hydrocarbons with 4 or less carbon atoms and a liquid component containing the hydrocarbons with 5 or more carbon atoms from an effluent from the hydrocarbon production part 4; a first separation part 10 that separates hydrogen and carbon dioxide and the light hydrocarbons from the gas component; and a catalytic reaction part 8 that generates hydrogen and carbon monoxide using the light hydrocarbons separated by the first separation part 10. The reverse shift reaction part 2 also uses the hydrogen and carbon dioxide separated by the first separation part 10 to generate synthesis gas. The hydrocarbon production part 4 also uses hydrogen and carbon monoxide produced by the catalytic reaction part 8 to produce the hydrocarbons.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a hydrocarbon production apparatus and a hydrocarbon production method. [Background technology]

[0002] A technology for producing liquid fuels using GTL (Gas to Liquid) is known (see Patent Document 1). One example of this production technology involves a process of obtaining synthesis gas containing hydrogen and carbon monoxide from natural gas, and a process of producing liquid hydrocarbons with high energy density using this synthesis gas as a feedstock through the Fischer-Tropsch reaction (hereinafter referred to as the "FT reaction"). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2008-248179 Summary of the Invention [Problem to be solved by the invention]

[0004] In recent years, reducing carbon dioxide emissions from various economic activities has become a major challenge. Utilizing carbon dioxide contained in exhaust gases and the like to produce the above-mentioned hydrocarbons can greatly contribute to the realization of carbon neutrality. From this perspective, the present inventors have conducted extensive research into hydrocarbon production technologies, and have come up with a technology for improving the efficiency of hydrocarbon production.

[0005] The present invention has been made in view of the above circumstances, and one of its objects is to provide a technique for improving the efficiency of hydrocarbon production. [Means for solving the problem]

[0006] One embodiment of the present invention is a hydrocarbon production apparatus. This apparatus includes: a reverse shift reaction section that uses carbon dioxide and hydrogen as feed gases and reduces carbon dioxide to carbon monoxide through a reverse shift reaction to obtain a synthesis gas containing carbon monoxide and hydrogen; a hydrocarbon production section that produces hydrocarbons using the synthesis gas; a gas-liquid separation section that separates a gas component containing hydrogen, carbon dioxide, and light hydrocarbons having 4 or less carbon atoms and a liquid component containing hydrocarbons having 5 or more carbon atoms from an effluent from the hydrocarbon production section; a first separation section that separates hydrogen, carbon dioxide, and the light hydrocarbons from the gas component; and a catalytic reaction section that receives the light hydrocarbons separated by the first separation section and produces hydrogen and carbon monoxide using the light hydrocarbons. The reverse shift reaction section receives the hydrogen and carbon dioxide separated by the first separation section and uses the hydrogen and carbon dioxide to produce synthesis gas. The hydrocarbon production section receives the hydrogen and carbon monoxide produced by the catalytic reaction section and uses the hydrogen and carbon monoxide to produce hydrocarbons.

[0007] Another aspect of the present invention is a hydrocarbon production method. This method includes: a reverse shift reaction step using carbon dioxide and hydrogen as feed gases to reduce carbon dioxide to carbon monoxide by a reverse shift reaction to obtain a synthesis gas containing carbon monoxide and hydrogen; a hydrocarbon production step using the synthesis gas to produce hydrocarbons; a gas-liquid separation step separating a gas component containing hydrogen, carbon dioxide, and light hydrocarbons having 4 or less carbon atoms and a liquid component containing hydrocarbons having 5 or more carbon atoms from an effluent from the hydrocarbon production step; a first separation step separating hydrogen, carbon dioxide, and the light hydrocarbons from the gas component; and a catalytic reaction step receiving the light hydrocarbons separated in the first separation step and using the light hydrocarbons to produce hydrogen and carbon monoxide. The reverse shift reaction step receives the hydrogen and carbon dioxide separated in the first separation step and uses the hydrogen and carbon dioxide to produce synthesis gas. The hydrocarbon production step receives the hydrogen and carbon monoxide produced in the catalytic reaction step and uses the hydrogen and carbon monoxide to produce hydrocarbons.

[0008] Any combination of the above components, and conversion of the expression of the present disclosure into a method, device, system, etc., are also valid aspects of the present disclosure. [Effects of the Invention]

[0009] According to the present invention, it is possible to improve the efficiency of hydrocarbon production. [Brief explanation of the drawings]

[0010] [Figure 1] 1 is a schematic diagram of a hydrocarbon production apparatus according to an embodiment. [Figure 2] FIG. 2 is a schematic diagram of a hydrocarbon production apparatus according to a comparative example. [Figure 3] FIG. 1 is a schematic diagram of a hydrocarbon production apparatus according to Test Example 1. [Figure 4] FIG. 1 is a schematic diagram of a hydrocarbon production apparatus according to Test Example 2. [Figure 5] FIG. 1 is a schematic diagram of a hydrocarbon production apparatus according to Test Example 3. [Figure 6] FIG. 10 is a schematic diagram of a hydrocarbon production apparatus according to Test Example 4. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present invention will be described below with reference to the drawings, based on preferred embodiments. The embodiments are merely illustrative and do not limit the technical scope of the present invention. Not all features or combinations thereof described in the embodiments are necessarily essential to the invention. Therefore, many design modifications, such as changes, additions, or deletions of components, are possible within the scope of the invention as defined in the claims. A new embodiment incorporating design modifications will combine the effects of the combined embodiments and modifications. In the embodiments, design modifications that are possible are emphasized by using terms such as "in this embodiment" or "in this embodiment." However, design modifications are also permitted even in areas without such notation. Any combination of the components described in the embodiments is also valid as an aspect of the present invention. Identical or equivalent components, members, and processes shown in each drawing are designated by the same reference numerals, and redundant descriptions are omitted where appropriate. Furthermore, the scale and shape of each part shown in each drawing are set for convenience and should not be construed as limiting unless otherwise specified. Furthermore, when terms such as "first" and "second" are used in this specification or claims, these terms do not represent any order or importance, but are used to distinguish one configuration from another. Furthermore, in each drawing, some members that are not important for explaining the embodiments are omitted.

[0012] 1 is a schematic diagram of a hydrocarbon production apparatus 1 according to an embodiment. The hydrocarbon production apparatus 1 includes a reverse shift reaction section 2, a hydrocarbon production section 4, a gas-liquid separation section 6, a contact reaction section 8, a first separation section 10, a second separation section 12, a third separation section 14, a fourth separation section 16, and a fifth separation section 18.

[0013] The reverse shift reaction section 2 is arranged upstream of the hydrocarbon production section 4. A fourth separation section 16 is arranged between the reverse shift reaction section 2 and the hydrocarbon production section 4. A gas-liquid separation section 6 is arranged downstream of the hydrocarbon production section 4. A first separation section 10 is arranged between the gas-liquid separation section 6 and the reverse shift reaction section 2 and the catalytic reaction section 8. A second separation section 12 is arranged in parallel to the first separation section 10 between the gas-liquid separation section 6 and the catalytic reaction section 8. A third separation section 14 is arranged between the second separation section 12 and the catalytic reaction section 8. A fifth separation section 18 is arranged between the catalytic reaction section 8 and the hydrocarbon production section 4.

[0014] The reverse shift reaction section 2 receives carbon dioxide and hydrogen as raw material gases and reduces the carbon dioxide to carbon monoxide through a reverse shift reaction using the carbon dioxide and hydrogen to obtain a synthesis gas containing carbon monoxide and unreacted hydrogen.

[0015] The reverse shift reaction unit 2 of this embodiment receives a supply of hydrogen from, for example, a water electrolysis module 20. Although the water electrolysis module 20 is illustrated in FIG. 1 as an external device to the hydrocarbon production apparatus 1, the water electrolysis module 20 may be incorporated inside the hydrocarbon production apparatus 1.

[0016] The water electrolysis module 20 is an electrolytic cell that generates hydrogen and oxygen by electrolysis of water. As an example, the water electrolysis module 20 has a structure in which an oxygen generating electrode having a catalyst such as iridium or platinum and a hydrogen generating electrode having a catalyst such as platinum are separated by a proton-conductive diaphragm. In other words, the water electrolysis module 20 is a solid polymer water electrolysis module. Other examples of the water electrolysis module 20 include an alkaline water electrolysis module and a solid oxide water electrolysis module. The reactions during water electrolysis in the solid polymer water electrolysis module are represented by the following formulas (1) and (2). Reaction occurring at the oxygen generating electrode: 2H2O → O2 + 4H + +4e - (1) Reaction occurring at the hydrogen evolution electrode: 4H + +4e -→2H2(2)

[0017] The water electrolysis module 20 receives the power required for water electrolysis from a power supply device (not shown). Examples of the power supply device include a power generation device that generates electricity using renewable energy, such as a wind power generation device or a solar power generation device. This reduces carbon dioxide emissions associated with the production of hydrogen and, ultimately, the target hydrocarbons with five or more carbon atoms (hereinafter referred to as "C5+ components"). The power supply device is not limited to a power generation device that uses renewable energy, but may also be a grid power source, a renewable energy power generation device, or a power storage device that stores power from a grid power source. It may also be a combination of two or more of these. However, in order to contribute to the realization of carbon neutrality, the power supply device is preferably a power generation device that uses renewable energy. Furthermore, when a grid power source or a power storage device is used as the power supply device, it is preferable that the carbon dioxide emissions associated with the power generation and storage thereof are equal to or less than those of a power generation device that uses renewable energy.

[0018] Furthermore, the reverse shift reaction section 2 of this embodiment receives a supply of carbon dioxide from a carbon dioxide recovery section 22, for example. In Fig. 1, the carbon dioxide recovery section 22 is illustrated as an external device relative to the hydrocarbon production apparatus 1, but the carbon dioxide recovery section 22 may be incorporated inside the hydrocarbon production apparatus 1. Note that this does not mean that the hydrocarbon production apparatus 1 as a whole is a single reactor.

[0019] The carbon dioxide capture unit 22 can capture carbon dioxide from the atmosphere by, for example, direct air capture (DAC) or the like. The carbon dioxide capture unit 22 can also separate and capture carbon dioxide from exhaust gases emitted from thermal power plants, chemical plants, and the like by a chemical adsorption method or the like. Receiving carbon dioxide from the carbon dioxide capture unit 22 to the reverse shift reaction unit 2 is expected to reduce the amount of carbon dioxide in the atmosphere and exhaust gases. Furthermore, the consumption of fossil fuels involved in the production of C5+ components can be reduced.

[0020] In the reverse shift reaction section 2, the reverse shift reaction shown in the following formula (3) occurs, and carbon dioxide is reduced to carbon monoxide. As a result, a synthesis gas containing at least carbon monoxide and unreacted hydrogen is obtained. The synthesis gas also contains water produced in the reverse shift reaction. The synthesis gas may also contain unreacted carbon dioxide. H2+CO2→CO+H2O (3)

[0021] The reaction temperature in the reverse shift reaction section 2 is, for example, 290°C to 1100°C, preferably 700°C to 1100°C, and more preferably 700°C to 950°C. The reverse reaction of formula (3) is called the water-gas shift reaction. A catalyst for the water-gas shift reaction may be used as a catalyst for the reverse shift reaction. However, a reaction temperature of 700°C or higher is much higher than the temperature in a typical water-gas shift reaction. Therefore, when the reaction temperature is set to a high temperature of 700°C or higher, a typical water-gas shift catalyst is not suitable for use.

[0022] In contrast, the reverse shift reaction section 2 of this embodiment includes a composite oxide having a perovskite structure ABO3 as a reverse shift catalyst. In the perovskite structure ABO3, A is an alkaline earth metal selected from the group consisting of calcium (Ca), strontium (Sr), and barium (Ba), preferably barium. B is a metal selected from the group consisting of titanium (Ti), aluminum (Al), zirconium (Zr), iron (Fe), tungsten (W), and molybdenum (Mo), preferably zirconium. When B is titanium or zirconium, it may be partially substituted with manganese (Mn), iron (Fe), or cobalt (Co), preferably manganese. In addition, the reverse shift catalyst preferably does not have acid sites that cleave bonds between carbon atoms in hydrocarbons and does not have hydrogen dissociation ability that cleaves bonds between hydrogen atoms. A reverse shift catalyst with this characteristic can be screened by confirming that a catalytic reaction using a mixed gas of isobutene and hydrogen does not produce hydrocarbons with eight carbon atoms through a dimerization reaction or isobutane through a hydrogenation reaction. By using such a reverse shift catalyst, the reverse shift reaction can be realized while suppressing side reactions such as methanation at high temperatures of 700°C or higher.

[0023] It is preferable to measure whether or not the raw material gas for the reverse shift reaction contains metal components using an atomic absorption spectrophotometer, a Fourier transform infrared spectrophotometer, or the like. Furthermore, it is preferable to install a filter capable of removing fine metal carbide powder generated by carburization and an adsorbent capable of removing metal carbonyls on the recycle line through which carbon monoxide flows. The filter is preferably made of ceramic, and the adsorbent is preferably Y-type zeolite.

[0024] When the synthesis gas obtained by the reverse shift reaction is used to produce hydrocarbons, a carbon dioxide remover may be installed between the reverse shift reaction section 2 and the hydrocarbon production section 4 to reduce the carbon dioxide concentration in the synthesis gas. Using the reverse shift catalyst described above to perform a high-temperature reverse shift reaction can improve the CO / (CO + CO2) ratio at the outlet of the reverse shift reaction section 2. The CO / (CO + CO2) ratio is calculated from the carbon monoxide and carbon dioxide concentrations at the outlet of the reverse shift reaction section 2. In other words, it is the proportion of carbon dioxide in the feedstock that is converted (reduced) to carbon monoxide. This reduces the carbon dioxide concentration at the outlet of the reverse shift reaction section 2. This increases the partial pressure of the synthesis gas, consisting of carbon monoxide and hydrogen, in the hydrocarbon production section 4, improving the carbon monoxide conversion rate and the selectivity for C5+ components. Furthermore, the thermal energy required for the carbon dioxide remover can be supplied from the hydrocarbon production section 4, which uses the exothermic FT reaction. This reduces the energy required for hydrocarbon production and improves the production efficiency of the target C5+ components.

[0025] Furthermore, by performing the reverse shift reaction at a high temperature of 700°C or higher, it is possible to suppress the generation of oxygen-containing hydrocarbons, etc., thereby suppressing the inclusion of oxygen-containing impurities in the by-product water. This makes it possible to recycle the water separated in the fourth separation section 16 located downstream of the reverse shift reaction section 2 to the water electrolysis module 20 without subjecting it to a purification treatment (removal of oxygen-containing impurities). Note that when the high-temperature reverse shift reaction is not performed, the water separated in the fourth separation section 16 can be supplied to the third separation section 14, which will be described later, to undergo a water purification treatment.

[0026] Furthermore, by employing the reverse shift catalyst described above, it is possible to more easily suppress the methanation reaction in which methane is produced from carbon dioxide than with conventional Ni catalysts, etc. This also makes it possible to improve the CO / (CO+CO2) ratio. By improving the CO / (CO+CO2) ratio, it is possible to increase the yield of liquid components in the hydrocarbon production section 4.

[0027] In this embodiment, as will be described later, the production efficiency of C5+ components is improved by recycling the off-gas from the hydrocarbon production section 4, but this recycling also requires energy. By increasing the CO / (CO + CO2) ratio, the yield of liquid components increases, making it possible to reduce the amount of off-gas recycled. This reduces the auxiliary power required for recycling, the energy required for off-gas separation, and the heat required for catalytic reactions at the recycling destination. This is expected to improve the production efficiency of the entire C5+ component production process.

[0028] The synthesis gas flowing out from the reverse shift reaction unit 2 is sent to the fourth separation unit 16. The fourth separation unit 16 can be configured with a known gas-liquid separator and separates water from the synthesis gas. The water separated in the fourth separation unit 16 is supplied to the water electrolysis module 20 and used to generate hydrogen. The water separated in the fourth separation unit 16 is also supplied to the contact reaction unit 8 and used in the contact reaction in the contact reaction unit 8. This improves the production efficiency of C5+ components. The water separated from the synthesis gas may be recycled to either the water electrolysis module 20 or the contact reaction unit 8, or not to both.

[0029] The synthesis gas from which water has been separated in the fourth separation section 16 is sent to the hydrocarbon production section 4. The hydrocarbon production section 4 uses the supplied synthesis gas to produce the target C5+ components. The C5+ components are, for example, normal paraffins. The hydrocarbon production section 4 in this embodiment is configured with a known FT reactor. As the FT reactor, a tubular fixed-bed reactor, a slurry-bed reactor, or the like can be used. In the hydrocarbon production section 4, the FT reaction shown in formula (4) below occurs, and the C5+ components are produced by carbon-carbon chain growth. As the catalyst for the FT reaction, a cobalt catalyst, a precipitated iron catalyst, a ruthenium catalyst, or the like can be used.

[0030] The rate at which a reaction intermediate with carbon number n grows into a heavy reaction intermediate with carbon number n+1 through carbon-carbon chain growth is represented by the chain growth probability α. α varies depending on the type of catalyst and reaction conditions, but is preferably 0.75 to 0.95, and more preferably 0.85 to 0.95. In formula (4), for example, when α is 0.95, n of the C5+ components contained at 0.1 mol% or more is an integer from 5 to 60. Furthermore, the hydrocarbon production unit 4 also by-produces light hydrocarbons with carbon numbers of 4 or less that are gaseous at room temperature and normal pressure, such as methane, ethane, propane, and butane (hereinafter referred to as "C4-components" where appropriate). nCO+(2n+1)H2→C n H 2n+2 +nH2O (4)

[0031] The effluent from the hydrocarbon production section 4 is sent to the gas-liquid separation section 6. This effluent contains not only C5+ components and C4- components, but also other by-products such as water and oxygenated hydrocarbons (C n H m The resulting effluent may contain unreacted hydrocarbons (e.g., HCl, O, etc.), as well as unreacted hydrogen, carbon monoxide, and carbon dioxide. Oxygenated hydrocarbons are hydrocarbon compounds containing oxygen, are hydrophilic, and readily dissolve in water. Examples of oxygenated hydrocarbons include alcohols, carboxylic acids, esters, ethers, and ketones. The gas-liquid separation section 6 can be configured with a known gas-liquid separator and separates the liquid and gas components from the effluent. Gas-liquid separation is preferably performed in two stages, one at high temperature and one at low temperature. This prevents clogging of the gas-liquid separation section 6 with heavy hydrocarbons. For example, high-temperature gas-liquid separation can be performed at 80°C, and low-temperature gas-liquid separation can be performed at 40°C. If the gas-liquid separation section is operated at high pressure, the temperature during gas-liquid separation may be increased to a temperature 20°C lower than the boiling point of water at that water partial pressure. The liquid component includes an oily component containing C5+ components and an aqueous component containing water and oxygenated hydrocarbons. The gas component includes hydrogen, carbon monoxide, carbon dioxide, and C4- components.

[0032] (Gas separation and recycling process) The gas components separated in the gas-liquid separation section 6 are sent to the first separation section 10. The first separation section 10 separates hydrogen, carbon dioxide, and C4 components from the gas components (first separation step). Carbon monoxide is contained in the C4 components. Note that carbon monoxide may also be contained in the hydrogen and carbon dioxide components. As an example, the first separation section 10 performs separation using at least one of pressure swing adsorption (PSA) and membrane separation. When the first separation section 10 uses membrane separation, as an example, the first separation section 10 has at least one of a polyimide membrane, a carbon membrane obtained by carbonizing a polyimide membrane, and a metal membrane containing Pd.

[0033] The hydrogen and carbon dioxide separated in the first separation unit 10 are sent to the reverse shift reaction unit 2. The reverse shift reaction unit 2 receives the hydrogen and carbon dioxide separated in the first separation unit 10 and uses them to generate synthesis gas. This increases the utilization rate of the hydrogen and carbon dioxide supplied as raw materials, thereby improving the production efficiency of C5+ components. Furthermore, if the recycled gas supplied to the reverse shift reaction unit 2 contains a large amount of compounds other than hydrogen and carbon dioxide, which are the reactants in the reverse shift reaction unit 2, a reverse reaction occurs in the reverse shift reaction unit 2 toward an equilibrium composition, which can reduce the amount of carbon monoxide produced. In contrast, by sending the hydrogen and carbon dioxide separated in the first separation unit 10 to the reverse shift reaction unit 2, the reverse reaction can be suppressed, thereby further improving the production efficiency of C5+ components.

[0034] The C4 − components and carbon monoxide separated in the first separation section 10 are sent to the catalytic reaction section 8. The catalytic reaction section 8 receives the C4 − components separated in the first separation section 10 and uses the C4 − components to produce hydrogen and carbon monoxide. If the C4 − components were sent to the reverse shift reaction section 2 without the first separation section 10, the C4 − components would accumulate in the system because they would be less likely to react in the reverse shift reaction section 2. This would result in a decrease in the partial pressure of the synthesis gas in the system, potentially inhibiting the reaction in the hydrocarbon production section 4. In contrast, in this embodiment, the C4 − components separated in the first separation section 10 are sent to the catalytic reaction section 8 and used to produce hydrogen and carbon monoxide. This further improves the production efficiency of the C5+ components. Carbon monoxide is also used in the reaction in the catalytic reaction section 8.

[0035] Furthermore, carbon dioxide does not participate in the reaction in the catalytic reaction unit 8. Furthermore, carbon dioxide is generally a non-flammable substance. Therefore, even when the catalytic reaction unit 8 performs a partial oxidation reaction or an autothermal reforming reaction, described below, carbon dioxide is not used for combustion. Therefore, if carbon dioxide is sent to the catalytic reaction unit 8 without providing the first separation unit 10, the carbon dioxide will also be heated when raising the temperature of the catalytic reaction unit 8 to the reaction temperature of the catalytic reaction, which may increase the energy required. In contrast, in this embodiment, the carbon dioxide separated in the first separation unit 10 is sent to the reverse shift reaction unit 2 and used to generate synthesis gas. This makes it possible to suppress an increase in the energy required in the catalytic reaction unit 8 and further improve the production efficiency of C5+ components.

[0036] For example, the catalytic reaction unit 8 produces hydrogen and carbon monoxide from the C4-components through one of a steam reforming reaction, a partial oxidation reaction, and an autothermal reforming reaction. Preferably, the catalytic reaction unit 8 produces hydrogen and carbon monoxide from the C4-components through a reforming reaction (at least one of a steam reforming reaction and an autothermal reforming reaction). If oxygen is required for the reaction carried out in the catalytic reaction unit 8, this oxygen is supplied from, for example, the water electrolysis module 20.

[0037] When the catalytic reaction unit 8 produces hydrogen and carbon monoxide from C4-components through a steam reforming reaction, the catalytic reaction unit 8 can be configured as a known steam reformer. In this case, as an example, the catalytic reaction unit 8 produces methane from C4-components through a first-stage reaction in which a steam reforming reaction is carried out at a first temperature, and produces carbon monoxide and hydrogen from methane through a second-stage reaction in which a steam reforming reaction is carried out at a second temperature higher than the first temperature. The catalytic reaction unit 8 may include a reactor for the first-stage reaction and a reactor for the second-stage reaction, or the temperature may be changed from the first temperature to the second temperature within a single reactor. The first temperature is, for example, 450 to 600°C, preferably 450 to 500°C. The second temperature is, for example, 750°C or higher. The difference in reaction temperature between the first and second stages is preferably 150°C or higher, more preferably 250°C or higher.

[0038] If C4-components (with two or more carbon atoms) are directly subjected to the reforming reaction at the second temperature, adjacent carbon atoms are converted to carbon monoxide, and disproportionation reactions occur between adjacent carbon monoxide atoms, resulting in the deposition of coke (carbon). Furthermore, C4-components (with two or more carbon atoms) are likely to undergo dehydrogenation reactions to produce olefins and their polymerization to deposit coke (heavy hydrocarbons) at temperatures below 850°C. Coke deposition can lead to catalyst degradation and reactor blockage. By converting C4-components primarily to methane in the primary reaction and then subjecting them to the secondary reaction, hydrogen and carbon monoxide can be produced while suppressing catalyst degradation due to coke deposition. This extends the service life of the catalytic reaction section 8 and improves the production efficiency of C5+ components.

[0039] Another method for suppressing coke deposition is to increase the steam-to-carbon ratio (S / C) by supplying an amount of water that causes adjacent carbon monoxide particles to compete for active sites. The S / C ratio is the ratio of the number of moles of oxygen atoms (S) to the number of moles of carbon atoms (C) supplied to the catalytic reaction section 8. However, this increases the amount of heat required to heat the water, reducing the energy efficiency required for producing the C5+ component. In contrast, the use of the two-stage reforming reaction described above can prevent an increase in the amount of water supplied in order to suppress coke deposition. This reduces the energy required for producing the C5+ component and improves its production efficiency.

[0040] When steam reforming is performed in two stages at the first and second temperatures, the equilibrium reactions shown in the following formulas (5) to (8) are thought to occur in the contact reaction section 8. Therefore, the first temperature is set so that the preliminary reforming reaction shown in the following formulas (5) to (7) occurs as the first-stage reaction, producing mainly methane. In this case, the S / C ratio is preferably 2.5 to 3.0. The reaction shown in formula (7) is an exothermic reaction. Therefore, for the same composition and pressure, the lower the temperature, the higher the methane yield. The second temperature is set so that the reaction shown in formula (8) occurs as the second-stage reaction, producing a synthesis gas containing carbon monoxide and hydrogen. The reaction shown in formula (8) is the reverse reaction of formula (7) and is also an endothermic reaction. Therefore, for the same composition and pressure, the higher the temperature, the higher the carbon monoxide and hydrogen yields. For example, the S / C ratio at the second temperature is 1.0 to 2.5. It is preferable to adjust the S / C ratio by not adding water consumed in the first-stage reaction. In formula (5), the C4-component is C n H m where n is an integer of 1 to 4 and m is an integer of 4 to 10. In the following reaction formulas, C4-components will be expressed in the same way. C n H m +nH2O→nCO+(n+m / 2)H2(5) CO+H2O→CO2+H2(6) CO+3H2→CH4+H2O (7) CH4 + H2O → CO + 3H2(8)

[0041] Furthermore, when the catalytic reaction unit 8 produces hydrogen and carbon monoxide from C4-components through an autothermal reforming reaction, the catalytic reaction unit 8 can be configured as a known autothermal reformer. In this case, the reaction shown in the following formula (9) first occurs in the catalytic reaction unit 8, followed by the reaction shown in the following formula (10). The reaction shown in formula (9) is an exothermic reaction. On the other hand, the reaction shown in formula (10) is an endothermic reaction. The heat required for the reaction shown in formula (10) is supplied by the heat generated in the reaction shown in formula (9). The reaction shown in formula (9) can utilize by-product oxygen produced in the water electrolysis module 20. C n H m +(n / 2)O2 → nCO +(m / 2)H2(9) C n H m +nH2O→nCO+(n+m / 2)H2(10)

[0042] Furthermore, when the catalytic reaction unit 8 produces hydrogen and carbon monoxide from C4-components through a partial oxidation reaction, the catalytic reaction unit 8 can be configured as a known partial oxidation reactor. In this case, the reaction shown in the following formula (11) occurs in the catalytic reaction unit 8. In the reaction shown in formula (11), by-product oxygen generated in the water electrolysis module 20 can be used. C n H m +(n / 2)O2 → nCO +(m / 2)H2 (11)

[0043] If the catalytic reaction section 8 is configured as an autothermal reformer, a pre-reformer (not shown) for carrying out the above-mentioned pre-reforming reaction may be provided between the first separation section 10 and the catalytic reaction section 8. This pre-reforming reaction is carried out at the above-mentioned first temperature. As a result, the reactions shown in the above-mentioned formulas (5) to (7) occur, and the C4 − components sent from the first separation section 10 are reformed into methane in the pre-reformer, which can then be subjected to the autothermal reforming reaction. As a result, hydrogen and carbon monoxide can be produced while suppressing catalyst deterioration due to coke deposition and an increase in the S / C ratio, as described above. This further improves the production efficiency of the C5+ components.

[0044] The effluent from the contact reaction unit 8 is sent to the fifth separation unit 18. This effluent may contain not only hydrogen and carbon monoxide but also unreacted water. The fifth separation unit 18 can be configured with a known gas-liquid separator and separates the hydrogen and carbon monoxide from the effluent and water. The water separated in the fifth separation unit 18 is sent to the contact reaction unit 8 and reused for the reaction in the contact reaction unit 8. Note that if the contact reaction unit 8 only performs a partial oxidation reaction, the supply of water from the fifth separation unit 18 to the contact reaction unit 8 is omitted. Similarly, if the contact reaction unit 8 only performs a partial oxidation reaction, the supply of water from the fourth separation unit 16 described above and the supply of the aqueous component from the third separation unit 14 described below are also omitted.

[0045] From the viewpoint of simplifying the structure of the hydrocarbon production apparatus 1, it is conceivable to omit the fifth separation section 18 and send the effluent from the contact reaction section 8 to the fourth separation section 16. However, the effluent from the contact reaction section 8 may contain oxygen-containing hydrocarbons. For this reason, it is desirable to provide the fifth separation section 18 separately from the fourth separation section 16 and loop water between the contact reaction section 8 and the fifth separation section 18.

[0046] The hydrogen and carbon monoxide separated in the fifth separation section 18 are sent to the hydrocarbon production section 4. The hydrocarbon production section 4 receives the hydrogen and carbon monoxide produced in the contact reaction section 8 and uses the hydrogen and carbon monoxide in the production of C5+ components. This improves the utilization rate of the hydrogen and carbon dioxide supplied as raw materials, and improves the production efficiency of C5+ components.

[0047] (Aqueous component recycling treatment) The liquid component separated in the gas-liquid separation section 6 is sent to the second separation section 12. The second separation section 12 can be configured as a known oil-water separator and separates the oil component and aqueous component from the liquid component (second separation step). The C5+ components contained in the oil component separated in the second separation section 12 are optionally upgraded using catalytic reforming, hydrocracking, hydrotreating, alkylation, isomerization, or other processes, and then used as a substitute for, for example, jet fuel, gasoline, or kerosene. If crude oil-derived oil components containing heteroatoms such as sulfur and nitrogen are not processed in the upgrader, and therefore crude oil-derived gas components are not included in the effluent from the upgrader, the C4- components by-produced in the upgrader may be returned to the first separation section 10. This can improve the production efficiency of substitutes for jet fuel, etc.

[0048] A portion of the aqueous component separated by the second separation unit 12 is sent to the contact reaction unit 8. The contact reaction unit 8 receives the aqueous component separated by the second separation unit 12 and uses the aqueous component to produce hydrogen and carbon monoxide. This allows the water in the aqueous component to be converted to hydrogen in the contact reaction unit 8. This reduces the amount of hydrogen supplied as a raw material, thereby improving the production efficiency of the C5+ component. Furthermore, the contact reaction unit 8 converts oxygenated hydrocarbons in the aqueous component to carbon monoxide. This also improves the production efficiency of the C5+ component. Furthermore, a portion of the aqueous component separated by the second separation unit 12 is sent to the water electrolysis module 20. The water electrolysis module 20 receives the aqueous component separated by the second separation unit 12 and uses the aqueous component to produce hydrogen.

[0049] In this embodiment, the aqueous component separated in the second separation section 12 is sent to the contact reaction section 8 and the water electrolysis module 20 via the third separation section 14. The third separation section 14 separates at least a portion of the water from the aqueous component. The third separation section 14 obtains water that is substantially free of oxygenated hydrocarbons and water enriched in oxygenated hydrocarbons. In other words, the water is purified. As an example, the third separation section 14 performs separation using at least one of pressure swing adsorption (PSA), precision distillation, and membrane separation. When the third separation section 14 uses membrane separation, as an example, the third separation section 14 has at least one of a reverse osmosis membrane, a zeolite membrane, and a carbon membrane.

[0050] The water separated in the third separation unit 14, i.e., the water from which oxygen-containing hydrocarbons have been removed, in other words, the purified water, is supplied to the water electrolysis module 20. The water electrolysis module 20 receives the water separated by the third separation unit 14 and uses the water to produce hydrogen. Supplying the water from which oxygen-containing hydrocarbons have been removed to the water electrolysis module 20 can suppress catalyst deterioration in the water electrolysis module 20. This can extend the service life of the water electrolysis module 20 and improve the production efficiency of C5+ components.

[0051] Furthermore, the aqueous component from which water has been separated in the third separation section 14, in other words, the water in which oxygen-containing hydrocarbons are concentrated, is supplied to the contact reaction section 8. The contact reaction section 8 receives the aqueous component from which water has been separated by the third separation section 14 and uses the aqueous component to produce hydrogen and carbon monoxide. The contact reaction section 8 produces hydrogen and carbon monoxide from the oxygen-containing hydrocarbons through a reforming reaction.

[0052] When the contact reaction unit 8 produces hydrogen and carbon monoxide from oxygenated hydrocarbons through a steam reforming reaction, the contact reaction unit 8 can be configured as a known steam reformer. In this case, as an example, the contact reaction unit 8 produces methane from oxygenated hydrocarbons through a first-stage reaction in which a steam reforming reaction is carried out at a first temperature, and produces carbon monoxide and hydrogen from methane through a second-stage reaction in which a steam reforming reaction is carried out at a second temperature higher than the first temperature. The first temperature is, for example, 450 to 600°C, preferably 450 to 500°C. The second temperature is, for example, 750°C or higher. The difference in reaction temperature between the first and second stages is preferably 150°C or higher, more preferably 250°C or higher.

[0053] By converting oxygenated hydrocarbons primarily to methane in the first-stage reaction and then subjecting them to the second-stage reaction, hydrogen and carbon monoxide can be produced while suppressing catalyst deterioration due to coke deposition and an increase in the S / C ratio, as in the case of C4- components. This improves the production efficiency of C5+ components. Furthermore, when oxygenated hydrocarbons are converted to carbon monoxide and hydrogen in a two-stage reaction, the reaction temperature in the first stage can be lower than that in the second stage. Furthermore, the reaction temperature in the first stage can be further lowered than in the case of C4- components. This reduces the energy required to produce C5+ components, further improving the production efficiency of C5+ components.

[0054] When steam reforming is performed in two stages at the first and second temperatures, the equilibrium reactions shown in the following formulas (12) to (15) are thought to occur in the contact reaction section 8. Therefore, the first temperature is set so that the preliminary reforming reaction shown in the following formulas (12) to (14) occurs as the first-stage reaction, producing mainly methane. In this case, the S / C ratio is preferably 2.5 to 3.0. The reaction shown in formula (14) is an exothermic reaction. Therefore, for the same composition and pressure, the lower the temperature, the higher the methane yield. The second temperature is set so that the reaction shown in formula (15) occurs as the second-stage reaction, producing a synthesis gas containing carbon monoxide and hydrogen. The reaction shown in formula (15) is the reverse reaction of formula (14) and is also an endothermic reaction. Therefore, for the same composition and pressure, the higher the temperature, the higher the carbon monoxide and hydrogen yields. For example, the S / C ratio at the second temperature is 1.0 to 2.5. It is preferable to adjust the S / C ratio by not adding water consumed in the first-stage reaction. In formula (12), n is, for example, an integer of 1 to 7, and m is, for example, an integer of 4 to 16. In the subsequent reaction formulae, the values ​​of n and m in the oxygen-containing hydrocarbon are similar. C n H m O+(n-1)H2O=nCO+(n-1+m / 2)H2(12) CO + H2O → CO2 + H2(13) CO+3H2→CH4+H2O (14) CH4 + H2O → CO + 3H2 (15)

[0055] Furthermore, when the catalytic reaction unit 8 produces hydrogen and carbon monoxide from oxygen-containing hydrocarbons through an autothermal reforming reaction, the catalytic reaction unit 8 can be configured as a known autothermal reformer. In this case, the reaction shown in the following formula (16) first occurs in the catalytic reaction unit 8, followed by the reaction shown in the following formula (17). The reaction shown in formula (16) is an exothermic reaction. On the other hand, the reaction shown in formula (17) is an endothermic reaction. The heat required for the reaction shown in formula (17) is supplied by the heat generated in the reaction shown in formula (16). The reaction shown in formula (16) can utilize by-product oxygen produced in the water electrolysis module 20. C n H mO+{(n-1) / 2}O2→nCO+(m / 2)H2(16) C n H m O+(n-1)H2O=nCO+(n-1+m / 2)H2(17)

[0056] If the catalytic reaction section 8 is configured as an autothermal reformer, a pre-reformer (not shown) for carrying out the above-mentioned pre-reforming reaction may be provided between the third separation section 14 and the catalytic reaction section 8. This pre-reforming reaction is carried out at the first temperature. As a result, the reactions shown in the above-mentioned formulas (12) to (14) occur, and the oxygen-containing hydrocarbons sent from the third separation section 14 are reformed into methane in the steam reformer, and this methane can be subjected to the autothermal reforming reaction. As a result, hydrogen and carbon monoxide can be produced while suppressing catalyst deterioration due to coke deposition and an increase in the S / C ratio, as described above. This further improves the production efficiency of C5+ components.

[0057] Furthermore, in the contact reaction section 8, the dehydration reaction shown in the following formula (18) and the dehydration condensation reaction shown in formula (19) occur as side reactions, and water can be produced from the hydrogen-containing hydrocarbon. In formulas (18) and (19), the numerical range of a is the same as that of n, and the numerical range of b is the same as that of m. C n H m O=C n H m-2 +H2O (18) C n H m O+C a H b O=C n H m-1 O.C. a H b-1 +H2O (19)

[0058] In the catalytic reaction section 8, coke deposition tends to occur due to the disproportionation reaction of carbon monoxide. As mentioned above, water is required to suppress coke deposition. In general, the amount of water supplied is increased to ensure the water required to suppress coke deposition. Increasing the amount of water supplied increases the S / C ratio in the catalytic reaction section 8, making it greater than the stoichiometric ratio.

[0059] In contrast, in the present embodiment, at least a portion of the water is separated in the third separation section 14, thereby reducing the amount of water supplied to the contact reaction section 8. This reduces the S / C ratio in the contact reaction section 8. Furthermore, by supplying oxygenated hydrocarbons to the contact reaction section 8 and generating by-product water from the oxygenated hydrocarbons in the contact reaction section 8, this by-product water can be used to suppress coke deposition. Therefore, while reducing the amount of water supplied to the contact reaction section 8 and reducing the S / C ratio, it is possible to suppress coke deposition and thereby reduce catalyst deterioration in the contact reaction section 8. As a result, the service life of the contact reaction section 8 can be extended, and the production efficiency of C5+ components can be improved.

[0060] In addition, the energy efficiency required for producing C5+ components can be expressed by the following equation (20): Energy efficiency = calorific value of the C5+ component obtained / (calorific value of the hydrogen used + heat required for production assuming heat recovery + electricity required to produce the hydrogen used + heat and electricity required to recover the carbon dioxide used) (20) In equation (20), the "required heat amount for production assuming heat recovery" means the amount of heat added from outside the system, assuming that the heat corresponding to the temperature difference between the inlet gas and the outlet gas in each reaction section is recovered and the recovered heat is reused in the reaction.

[0061] Specifically, for example, the raw material supplied to the reverse shift reaction unit 2 needs to be heated to the reaction temperature (e.g., 800°C) in the reverse shift reaction unit 2. In addition, since the reverse shift reaction is an endothermic reaction, heat needs to be added. On the other hand, in order to subject the synthesis gas obtained in the reverse shift reaction unit 2 to gas-liquid separation treatment in the fourth separation unit 16, the synthesis gas needs to be cooled. Therefore, the heat of the synthesis gas (outlet gas) discharged from the reverse shift reaction unit 2 is recovered by a heat exchanger, and the recovered heat is transferred to the raw material (inlet gas). This makes it possible to reduce the fuel for the heating furnace used to heat the raw material and the electricity for the chiller used to cool the synthesis gas.

[0062] In addition, for example, when the carbon dioxide capture unit 22 separates and captures carbon dioxide by a chemical adsorption method or the like, heat is required to dissipate the adsorbed carbon dioxide. On the other hand, the FT reaction that occurs in the hydrocarbon production unit 4 is an exothermic reaction. For this reason, the heat generated in the hydrocarbon production unit 4 can be recovered by a heat exchanger, and the recovered heat can be used to dissipate carbon dioxide in the carbon dioxide capture unit 22.

[0063] Even if as much heat as possible is recovered in this way, the remaining heat must be generated in a heating furnace. The heat generated in this heating furnace corresponds to the "heat amount required for production assuming heat recovery." Note that when the contact reaction unit 8 is configured as an autothermal reformer, the required heat amount can be made smaller than when it is configured as a steam reformer.

[0064] As the amount of water supplied to the catalytic reaction unit 8 increases, i.e., as the S / C ratio increases, the amount of heat required to heat the water increases. This increases the "heat required for production assuming heat recovery" in equation (20), reducing the energy efficiency of C5+ component production. In contrast, if oxygenated hydrocarbons are supplied to the catalytic reaction unit 8 instead of water, the C5+ component is produced from carbon monoxide derived from the oxygenated hydrocarbons, thereby increasing the "calorific value of the resulting C5+ component" in equation (20). This improves the energy efficiency of C5+ component production. Therefore, reducing the amount of water supplied to the catalytic reaction unit 8 and supplying oxygenated hydrocarbons instead can further improve the production efficiency of C5+ component production.

[0065] When the catalytic reaction unit 8 is configured as an autothermal reformer, if the first separation unit 10 is not provided and hydrogen and carbon dioxide are also supplied to the catalytic reaction unit 8, heat is required to warm the carbon dioxide, making it difficult to provide the reaction heat required for the reforming reaction through the partial oxidation of C4-components. The insufficient reaction heat is provided by burning the hydrogen sent to the catalytic reaction unit 8 together with the carbon dioxide.

[0066] When hydrogen is combusted, water is produced as a by-product. This water is then used in the reforming reaction in the contact reaction section 8. As a result, consumption of the water recycled from the effluent of the hydrocarbon production section 4 to the contact reaction section 8 is stagnated. If the recycled water is not consumed, the amount of by-product water that requires wastewater treatment increases. In other words, if the by-product water is not recycled and converted into hydrogen to be used in the hydrocarbon production section 4, the amount of hydrogen that needs to be added as a feedstock from outside the hydrocarbon production apparatus 1 increases. As a result, the H2 / CO2 ratio (molar ratio) of the feedstock (so-called fresh feed) supplied from outside the hydrocarbon production apparatus 1 increases.

[0067] On the other hand, when the contact reaction unit 8 is configured as a steam reformer, hydrogen combustion does not occur in the contact reaction unit 8, and by-product water is not produced. Therefore, even if hydrogen is supplied to the contact reaction unit 8, water recycled from the hydrocarbon production unit 4 is used for the reforming reaction in the contact reaction unit 8. This makes it possible to reduce the H2 / CO2 ratio of the fresh feed compared to when the contact reaction unit 8 is configured as an autothermal reformer. Reducing the H2 / CO2 ratio of the fresh feed makes it possible to reduce the amount of electricity required to produce hydrogen. Therefore, the decrease in energy efficiency shown in equation (20) can be suppressed.

[0068] Therefore, when the catalytic reaction unit 8 is configured as a steam reformer, the effect of improving the production efficiency of the C5+ component by recycling the aqueous component can be more pronounced. Also, when the catalytic reaction unit 8 is configured as an autothermal reformer, combining it with the first separation unit 10 can make it easier to achieve this improvement.

[0069] In one example of a hydrocarbon production apparatus 1, the molar ratio of carbon monoxide to hydrogen (CO / H2 ratio) supplied to the hydrocarbon production section 4 is preferably 1.5 or more and 4.0 or less, more preferably 2.0 or more and 3.5 or less, and even more preferably 2.2 or more and 3.0 or less. In order to suppress coke deposition in the contact reaction section 8 and satisfy the above-mentioned CO / H2 ratio, the S / C ratio in the first-stage reaction is preferably 3.0 or more and 6.0 or less, and the S / C ratio in the second-stage reaction is preferably 0.5 or more and 3.0 or less, and more preferably 1.0 or more and 2.5 or less.

[0070] The operation of the hydrocarbon production apparatus 1 according to this embodiment will be verified below. FIG. 2 is a schematic diagram of a hydrocarbon production apparatus according to a comparative example. FIG. 3 is a schematic diagram of a hydrocarbon production apparatus according to Test Example 1. FIG. 4 is a schematic diagram of a hydrocarbon production apparatus according to Test Example 2. FIG. 5 is a schematic diagram of a hydrocarbon production apparatus according to Test Example 3. FIG. 6 is a schematic diagram of a hydrocarbon production apparatus according to Test Example 4.

[0071] 2, the hydrocarbon production apparatus according to the comparative example does not include a contact reaction section 8 or a first separation section 10, and the gas components separated in the gas-liquid separation section 6 are recycled directly to the reverse shift reaction section 2. In addition, the apparatus does not include a third separation section 14, and separation of water from the aqueous components separated in the second separation section 12, i.e., concentration treatment of oxygen-containing hydrocarbons, is not performed.

[0072] As shown in FIG. 3, the hydrocarbon production apparatus according to Test Example 1 does not include a first separation section 10, and the gas components separated in the gas-liquid separation section 6 are recycled directly to the contact reaction section 8. The contact reaction section 8 is composed of an autothermal reformer (ATR). The hydrogen, carbon monoxide, and carbon dioxide separated in the fifth separation section 18 are recycled to the reverse shift reaction section 2. The apparatus is also equipped with a third separation section 14, and the aqueous component separated in the second separation section 12 is subjected to a treatment for concentrating oxygen-containing hydrocarbons. The water in which oxygen-containing hydrocarbons have been concentrated is then recycled to the contact reaction section 8.

[0073] As shown in FIG. 4, the hydrocarbon production apparatus according to Test Example 2 includes a first separation section 10, in which the C4-components and carbon monoxide separated in the first separation section 10 are recycled to the catalytic reaction section 8, and the hydrogen and carbon dioxide separated in the first separation section 10 are recycled to the reverse shift reaction section 2. The catalytic reaction section 8 is configured as an autothermal reformer. The hydrogen and carbon monoxide separated in the fifth separation section 18 are recycled to the hydrocarbon production section 4. The apparatus also includes a third separation section 14, in which the aqueous component separated in the second separation section 12 is subjected to a treatment to concentrate oxygenated hydrocarbons. The water in which the oxygenated hydrocarbons have been concentrated is then recycled to the catalytic reaction section 8.

[0074] As shown in FIG. 5, the hydrocarbon production apparatus according to Test Example 3 does not include a first separation section 10, and the gas components separated in the gas-liquid separation section 6 are recycled directly to the contact reaction section 8. The contact reaction section 8 is composed of a steam reformer (SR). The hydrogen, carbon monoxide, and carbon dioxide separated in the fifth separation section 18 are recycled to the reverse shift reaction section 2. The apparatus is also equipped with a third separation section 14, and the aqueous component separated in the second separation section 12 is subjected to a treatment to concentrate oxygenated hydrocarbons. The water in which oxygenated hydrocarbons have been concentrated is then recycled to the contact reaction section 8.

[0075] As shown in FIG. 6, the hydrocarbon production apparatus according to Test Example 4 includes a first separation section 10, in which the C4-components and carbon monoxide separated in the first separation section 10 are recycled to the catalytic reaction section 8, and the hydrogen and carbon dioxide separated in the first separation section 10 are recycled to the reverse shift reaction section 2. The catalytic reaction section 8 is configured as a steam reformer. The hydrogen and carbon monoxide separated in the fifth separation section 18 are recycled to the hydrocarbon production section 4. The apparatus also includes a third separation section 14, in which the aqueous component separated in the second separation section 12 is subjected to a treatment for concentrating oxygenated hydrocarbons. The water in which the oxygenated hydrocarbons have been concentrated is then recycled to the catalytic reaction section 8.

[0076] Using the hydrocarbon production apparatuses of the comparative example and each test example, C5+ components were produced under specified conditions. The energy efficiency (see formula (20)) during the production was calculated. The reaction conditions used to calculate the energy efficiency were as follows. In addition to the reaction conditions below, the H2 / CO2 ratio of the fresh feed was adjusted so that the H2 / CO2 ratio (molar ratio) supplied to the reverse shift reaction section was maintained at 3. Reaction temperature in the reverse shift reaction section: 800°C Hydrocarbon production section reaction temperature: 200℃ Autothermal reformer or steam reformer reaction temperature: 880°C Reaction pressure (constant within the system): 4 MPa

[0077] The energy efficiency of each test example (energy efficiency of test example / energy efficiency of comparative example) was compared between cases where the aqueous component separated in the second separation section 12 or the water separated in the third separation section 14 was recycled to the water electrolysis module 20 and cases where it was not, assuming that the energy efficiency of the comparative example was 1. The results were as follows:

[0078] If the aqueous component is not recycled Comparative example: 1.00 Test Example 1: 1.05 Test Example 2: 1.17 Test Example 3: 0.99 Test Example 4: 1.19 When the aqueous component is recycled Comparative example: 1.00 Test Example 1: 1.03 Test Example 2: 1.13 Test Example 3: 1.12 Test Example 4: 1.34

[0079] Comparisons between Test Examples 1 and 2, and between Test Examples 3 and 4, respectively, confirmed that separating hydrogen and carbon dioxide from the C4-components in the first separation section 10 and recycling the hydrogen and carbon dioxide to the reverse shift reaction section 2 and the C4-components to the catalytic reaction section 8 can improve the energy efficiency required to produce the C5+components, and therefore the production efficiency of the C5+components. The inventors also confirmed that changing the catalytic reaction section 8 from an autothermal reformer to a steam reformer can reduce the H2 / CO2 ratio of the fresh feed from approximately 3 to approximately 2.

[0080] The embodiments may be specified by the following items. [Item 1] a reverse shift reaction section (2) that uses carbon dioxide and hydrogen as raw material gases and reduces the carbon dioxide to carbon monoxide by a reverse shift reaction to obtain a synthesis gas containing carbon monoxide and hydrogen; a hydrocarbon production unit (4) for producing hydrocarbons (C5+) using the synthesis gas; a gas-liquid separation section (6) for separating a gas component containing hydrogen, carbon dioxide, and light hydrocarbons (C4-) having a carbon number of 4 or less from a liquid component containing hydrocarbons (C5+) having a carbon number of 5 or more from the effluent from the hydrocarbon production section (4); a first separation section (10) that separates hydrogen and carbon dioxide, and light hydrocarbons (C4-) from the gas components; a catalytic reaction section (8) that receives the light hydrocarbons (C4-) separated by the first separation section (10) and uses the light hydrocarbons (C4-) to produce hydrogen and carbon monoxide, The reverse shift reaction section (2) receives the hydrogen and carbon dioxide separated by the first separation section (10) and uses the hydrogen and carbon dioxide to generate synthesis gas, The hydrocarbon production section (4) receives the hydrogen and carbon monoxide produced in the contact reaction section (8) and uses the hydrogen and carbon monoxide to produce hydrocarbons (C5+). Hydrocarbon production equipment (1). [Item 2] The liquid component includes an oil component containing hydrocarbons having 5 or more carbon atoms (C5+) and an aqueous component containing water, The catalytic reaction section (8) produces hydrogen and carbon monoxide from light hydrocarbons (C4-) through a reforming reaction, The hydrocarbon production apparatus (1) includes a second separation section (12) that separates an aqueous component from a liquid component, the contact reaction section (8) receives the aqueous component separated by the second separation section (12) and uses the aqueous component to produce hydrogen and carbon monoxide; Item 1. The hydrocarbon production apparatus (1) according to item 1. [Item 3] The aqueous component also includes hydrophilic oxygenated hydrocarbons that dissolve in water; The hydrocarbon production apparatus (1) includes a third separation section (14) that separates at least a portion of water from the aqueous component; the contact reaction section (8) receives the aqueous component from which water has been separated by the third separation section (14) and uses the aqueous component to produce hydrogen and carbon monoxide; Item 2. The hydrocarbon production apparatus (1). [Item 4] The catalytic reaction section (8) produces methane from light hydrocarbons (C4-) through a reforming reaction at a first temperature, and produces carbon monoxide and hydrogen from methane through a reforming reaction at a second temperature higher than the first temperature. 4. A hydrocarbon production apparatus (1) according to any one of items 1 to 3. [Item 5] a reverse shift reaction step in which carbon dioxide and hydrogen are used as raw material gases and carbon dioxide is reduced to carbon monoxide by a reverse shift reaction to obtain a synthesis gas containing carbon monoxide and hydrogen; a hydrocarbon production process using synthesis gas to produce hydrocarbons (C5+); a gas-liquid separation step of separating a gas component containing hydrogen, carbon dioxide, and light hydrocarbons having 4 or less carbon atoms (C4-) from an effluent from the hydrocarbon production step, and a liquid component containing hydrocarbons having 5 or more carbon atoms (C5+); a first separation step of separating hydrogen and carbon dioxide and light hydrocarbons (C4-) from the gaseous components; a catalytic reaction step in which the light hydrocarbons (C4-) separated in the first separation step are supplied and hydrogen and carbon monoxide are produced using the light hydrocarbons (C4-), In the reverse shift reaction step, the hydrogen and carbon dioxide separated in the first separation step are supplied and used to generate synthesis gas; In the hydrocarbon production process, the hydrogen and carbon monoxide produced in the catalytic reaction process are supplied and used to produce hydrocarbons (C5+). Hydrocarbon production methods. [Item 6] The liquid component includes an oil component containing hydrocarbons having 5 or more carbon atoms (C5+) and an aqueous component containing water, In the catalytic reaction step, hydrogen and carbon monoxide are produced from light hydrocarbons (C4-) through a reforming reaction, The hydrocarbon production method includes a second separation step of separating an aqueous component from a liquid component; In the contact reaction step, the aqueous component separated in the second separation step is supplied and the aqueous component is also used to produce hydrogen and carbon monoxide. Item 6. A method for producing hydrocarbons according to item 5. [Explanation of symbols]

[0081] 1 Hydrocarbon production apparatus, 2 Reverse shift reaction section, 4 Hydrocarbon production section, 6 Gas-liquid separation section, 8 Contact reaction section, 10 First separation section, 12 Second separation section, 14 Third separation section, 16 Fourth separation section, 18 Fifth separation section, 20 Water electrolysis module, 22 Carbon dioxide recovery section.

Claims

1. a reverse shift reaction section that uses carbon dioxide and hydrogen as raw material gases and reduces the carbon dioxide to carbon monoxide through a reverse shift reaction to obtain a synthesis gas containing carbon monoxide and hydrogen; a hydrocarbon production unit that produces hydrocarbons using the synthesis gas; a gas-liquid separation section that separates a gas component containing hydrogen, carbon dioxide, and light hydrocarbons having 4 or less carbon atoms and a liquid component containing hydrocarbons having 5 or more carbon atoms from the effluent from the hydrocarbon production section; a first separation section that separates hydrogen and carbon dioxide, and light hydrocarbons from the gas components; a catalytic reaction section that receives the light hydrocarbons separated by the first separation section and produces hydrogen and carbon monoxide using the light hydrocarbons, the reverse shift reaction unit receives the hydrogen and carbon dioxide separated by the first separation unit and uses the hydrogen and carbon dioxide to generate the synthesis gas; the hydrocarbon production unit receives the hydrogen and carbon monoxide produced in the catalytic reaction unit and uses the hydrogen and carbon monoxide in the production of the hydrocarbons. Hydrocarbon production equipment.

2. The liquid component includes an oil component containing a hydrocarbon having 5 or more carbon atoms and an aqueous component containing water, the catalytic reaction section produces hydrogen and carbon monoxide from the light hydrocarbons through a reforming reaction; the hydrocarbon production apparatus includes a second separation section that separates an aqueous component from the liquid component, the contact reaction unit receives the aqueous component separated by the second separation unit and uses the aqueous component to generate hydrogen and carbon monoxide. The hydrocarbon production apparatus according to claim 1 .

3. the aqueous component also includes a hydrophilic oxygenated hydrocarbon that is soluble in water; the hydrocarbon production apparatus includes a third separation section that separates at least a portion of water from the aqueous component; the contact reaction section receives the aqueous component from which water has been separated by the third separation section, and uses the aqueous component to produce hydrogen and carbon monoxide. The hydrocarbon production apparatus according to claim 2 .

4. the catalytic reaction section produces methane from the light hydrocarbons through a reforming reaction at a first temperature, and produces carbon monoxide and hydrogen from the methane through a reforming reaction at a second temperature higher than the first temperature; The hydrocarbon production apparatus according to any one of claims 1 to 3.

5. a reverse shift reaction step in which carbon dioxide and hydrogen are used as raw material gases and carbon dioxide is reduced to carbon monoxide by a reverse shift reaction to obtain a synthesis gas containing carbon monoxide and hydrogen; a hydrocarbon production step of producing hydrocarbons using the synthesis gas; a gas-liquid separation step of separating a gas component containing hydrogen, carbon dioxide, and light hydrocarbons having 4 or less carbon atoms and a liquid component containing hydrocarbons having 5 or more carbon atoms from an effluent from the hydrocarbon production step; a first separation step of separating hydrogen and carbon dioxide and light hydrocarbons from the gas components; a catalytic reaction step in which the light hydrocarbons separated in the first separation step are supplied and hydrogen and carbon monoxide are produced using the light hydrocarbons, In the reverse shift reaction step, the hydrogen and carbon dioxide separated in the first separation step are supplied and the hydrogen and carbon dioxide are also used to generate the synthesis gas; In the hydrocarbon production step, the hydrogen and carbon monoxide produced in the catalytic reaction step are supplied and used in the production of the hydrocarbons. Hydrocarbon production methods.

6. The liquid component includes an oil component containing a hydrocarbon having 5 or more carbon atoms and an aqueous component containing water, In the catalytic reaction step, hydrogen and carbon monoxide are produced from the light hydrocarbons by a reforming reaction; The hydrocarbon production method includes a second separation step of separating an aqueous component from the liquid component; In the contact reaction step, the aqueous component separated in the second separation step is supplied and the aqueous component is also used to produce hydrogen and carbon monoxide. The hydrocarbon production method according to claim 5 .

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