Method, device, and program for producing hydrocarbon

Abstract

A method for producing a hydrocarbon by a Fischer-Tropsch method, said production method including: (a) a step for reacting a starting material gas in the presence of a catalyst so as to obtain a product gas; (b) a step for subjecting the product gas to analysis so as to obtain first information on a quantification result of at least one light hydrocarbon selected from the group consisting of ethane and ethylene, propane and propylene, and butane and butene in the product gas; (c) a step for calculating at least one ratio selected from the group consisting of an ethylene / ethane ratio, a propylene / propane ratio, and a butene / butane ratio on the basis of the first information so as to obtain second information relating to the calculated value of the ratio; and (d) a step for obtaining third information relating to the selectivity of a hydrocarbon having 5 or more carbon atoms on the basis of the second information.

Description

Hydrocarbon production method, apparatus, and program

[0001] This invention relates to a method, apparatus, and program for producing hydrocarbons.

[0002] Hydrocarbons can be produced, for example, by the Fischer-Tropsch process (hereinafter also referred to as the "FT process"). In the FT process, hydrocarbons are synthesized in a gas-solid catalytic reaction by contacting a raw material gas with a solid catalyst in a reactor. Hereinafter, the hydrocarbon synthesis reaction by the FT process will also be referred to as the "FT reaction." From the liquid hydrocarbons produced by the FT reaction, liquid fuels such as kerosene, jet fuel including SAF (Sustainable Aviation Fuel), and diesel fuel can be obtained. Various types of reactors can be used in the FT process, including fixed-bed reactors, slurry-bed reactors, and fluidized-bed reactors.

[0003] Patent Document 1 describes a method for producing hydrocarbons by the FT method and a catalyst that can be used in said production method. According to Patent Document 1, by applying a predetermined catalyst to a slurry bed reactor, the selectivity for liquid hydrocarbons (hydrocarbons with 5 or more carbon atoms) is increased.

[0004] Japanese Patent Publication No. 2002-161279

[0005] In the production of hydrocarbons by the FT method, the selectivity of liquid hydrocarbons (hereinafter referred to as "C") ５＋ Also called "selectivity," the C20% can fluctuate over time. For example, using the catalyst described in Patent Document 1, the C20% can temporarily be high. ５＋ Even if the selectivity is achieved, C may be affected due to the deterioration of the catalyst, etc. ５＋ The selection rate may eventually decrease. Here, C ５＋It is usually difficult to grasp the selectivity level in real time. For example, one could consider subjecting the liquid hydrocarbons discharged from the reactor to compositional analysis to determine the hydrocarbon distribution from C1 to C20, and then calculating the proportion of hydrocarbons with 5 or more carbon atoms in the total. In this case, the determination of methane (C1), hydrocarbons with 2 to 4 carbon atoms, and hydrocarbons with 5 to 20 carbon atoms would be performed. In particular, hydrocarbons with 5 to 20 carbon atoms are fractions with large molecular weights. Therefore, the time required for the determination of hydrocarbons with 5 to 20 carbon atoms is relatively long, usually requiring about 1 to 1.5 hours. Thus, the method for determining the hydrocarbon distribution from C1 to C20 is C ５＋ This method is not ideal for monitoring selectivity in real time. Furthermore, hydrocarbons tend to solidify more easily as the number of carbon atoms increases. For example, hydrocarbons with around 20 carbon atoms can solidify at temperatures below 37°C, requiring measures such as temperature control during analysis, which can complicate the analytical procedure.

[0006] In view of the above, the present invention provides a technology that can simplify the evaluation process for the selectivity of liquid hydrocarbons in the production of hydrocarbons by the FT method.

[0007] In other words, the present invention encompasses the following aspects: [1] A method for producing hydrocarbons by the Fischer-Tropsch process, comprising: (a) reacting a raw material gas in the presence of a catalyst to obtain a product gas; (b) subjecting the product gas to analysis to obtain first information regarding the quantitative determination of at least one light hydrocarbon selected from the group consisting of ethane and ethylene, propane and propylene, and butane and butene in the product gas; (c) calculating at least one ratio selected from the group consisting of ethylene / ethane ratio, propylene / propane ratio and butene / butane ratio based on the first information to obtain second information regarding the calculated value of said ratio; and (d) obtaining third information regarding the selectivity of hydrocarbons having 5 or more carbon atoms based on the second information. [2] The method according to [1], wherein the reaction conditions in (a) are controlled based on the third information. [3] The method according to [2], wherein the reaction conditions controlled based on the third information include at least one condition selected from the group consisting of reaction temperature, reaction pressure, supply amount of raw material gas and amount of catalyst. [4] The method according to any one of [1] to [3], further comprising (e) notifying the user of the third information. [5] The method according to [4], wherein the third information notified in (e) includes the result of comparing a preset threshold of the ratio with the calculated value. [6] The method according to [4] or [5], wherein the third information notified in (e) includes an estimate of the selectivity, the estimate is calculated based on the calculated value and preset information relating the ratio and the selectivity. [7] The method according to any one of [1] to [6], wherein (a), (b), (c) and (d) are repeated.[8] An apparatus for producing hydrocarbons by the Fischer-Tropsch process, comprising: a reactor; a gas supply unit for supplying raw material gas to the reactor; an analytical means for analyzing the product gas discharged from the reactor; and a control unit, wherein the control unit is configured to perform control including: (a) reacting raw material gas in the presence of a catalyst to obtain a product gas; (b) subjecting the product gas to analysis to obtain first information regarding the quantitative results of at least one light hydrocarbon selected from the group consisting of ethane and ethylene, propane and propylene, and butane and butene in the product gas; (c) calculating at least one ratio selected from the group consisting of ethylene / ethane ratio, propylene / propane ratio and butene / butane ratio based on the first information to obtain second information regarding the calculated value of the ratio; and (d) obtaining third information regarding the selectivity of hydrocarbons having 5 or more carbon atoms based on the second information. [9] The apparatus according to [8], wherein the control unit further comprises a notification unit for notifying the third information.

[10] A program that causes the computer of an apparatus for producing hydrocarbons by the Fischer-Tropsch process to perform: (a) reacting a raw material gas in the presence of a catalyst to obtain a product gas; (b) subjecting the product gas to analysis to obtain first information regarding the quantitative results of at least one light hydrocarbon selected from the group consisting of ethane and ethylene, propane and propylene, and butane and butene in the product gas; (c) calculating at least one ratio selected from the group consisting of ethylene / ethane ratio, propylene / propane ratio and butene / butane ratio based on the first information to obtain second information regarding the calculated value of said ratio; and (d) obtaining third information regarding the selectivity of hydrocarbons having 5 or more carbon atoms based on the second information.

[0008] According to the present invention, a technology is available that can simplify the evaluation process for the selectivity of liquid hydrocarbons in the production of hydrocarbons by the FT method.

[0009] Figure 1 is a schematic diagram illustrating an example of the configuration of the apparatus according to this embodiment. Figure 2 is a diagram showing an example of the physical configuration of the control unit in the apparatus according to this embodiment. Figure 3 is a flowchart showing an example of the method according to this embodiment. Figure 4 is a flowchart showing another example of the method according to this embodiment. Figure 5 is a diagram showing an example of the display screen of the apparatus according to this embodiment. Figure 6 is a diagram showing another example of the display screen of the apparatus according to this embodiment. Figure 7 is a diagram showing yet another example of the display screen of the apparatus according to this embodiment. Figure 8 shows the ethylene / ethane ratio and C obtained in the embodiment. ５＋ This graph shows the relationship with selectivity. Figure 9 shows the propylene / propane ratio and C obtained in the example. ５＋ This graph shows the relationship with selectivity. Figure 10 shows the butene / butane ratio and C obtained in the example. ５＋ This graph shows the relationship with the selection rate.

[0010] Hereinafter, embodiments for carrying out the present invention (hereinafter also referred to as "this embodiment") will be described in detail with reference to the drawings as appropriate. The following embodiments are illustrative examples for explaining the present invention and are not intended to limit the present invention to the following content. The present invention can be carried out by modifying it as appropriate within the scope of its gist. In addition, although the explanation may be given with reference to the drawings, the same or equivalent elements in each drawing will be denoted by the same reference numeral, and redundant explanations will be omitted. Unless otherwise specified, the positional relationships such as up, down, left, and right in the drawings are based on the positional relationships shown in the drawings. Furthermore, the dimensional ratios of each component explained in the drawings are not limited to the ratios shown.

[0011] <Apparatus> The apparatus according to this embodiment (hereinafter also referred to as "this apparatus") is an apparatus for producing hydrocarbons by the FT method, comprising a reactor, a gas supply unit for supplying raw material gas to the reactor, analytical means for analyzing the product gas discharged from the reactor, and a control unit, wherein the control unit is configured to perform control including: (a) reacting the raw material gas in the presence of a catalyst to obtain a product gas; (b) subjecting the product gas to analysis to obtain first information regarding the quantitative results of at least one light hydrocarbon selected from the group consisting of ethane and ethylene, propane and propylene, and butane and butene in the product gas; (c) calculating at least one ratio selected from the group consisting of ethylene / ethane ratio, propylene / propane ratio and butene / butane ratio based on the first information to obtain second information regarding the calculated value of said ratio; and (d) obtaining third information regarding the selectivity of hydrocarbons having 5 or more carbon atoms based on the second information. Because this apparatus is configured as described above, the evaluation process for the selectivity of liquid hydrocarbons can be simplified.

[0012] Figure 1 is a schematic diagram illustrating an example of the configuration of this apparatus. In the example shown in Figure 1, the apparatus 100 comprises a reactor 10, a gas supply unit 20, an analysis means 30, and a control unit 40. The following describes examples of each of these configurations.

[0013] (Reactor) The reactor 10 can be appropriately designed to serve as the reaction field for the FT reaction. For example, the reactor 10 can be a heat-resistant and pressure-resistant vessel configured to withstand the reaction conditions of the FT reaction. The capacity of the reactor 10 is not particularly limited, but may be, for example, 1000 L or less.

[0014] The FT reaction that can proceed in reactor 10 is a gas-liquid catalytic reaction. In this embodiment, the specific gravity of the raw material gas SG tends to be lower than that of the slurry SL. When there is such a difference in specific gravity, if the raw material gas SG is blown into the slurry SL from the bottom of reactor 10, it moves upward within the slurry SL. In this way, as the raw material gas SG passes through the slurry SL in reactor 10, the raw material gas SG comes into contact with the catalyst CT in the slurry SL, and the FT reaction proceeds. The reaction raw materials and reaction products used in such an FT reaction may include liquids and gases. Therefore, reactor 10 can be configured to allow liquids and gases to be introduced from the outside into the inside and to be discharged from the inside into the outside. The gas-liquid catalytic reaction described above is also called a slurry bed reaction. Slurry bed FT reactions tend to have superior temperature controllability compared to fixed bed FT reactions, etc.

[0015] The reactor 10 may be configured to allow the introduction of slurry SL from the outside. The reactor 10 may also be configured to allow the discharge of slurry SL from the inside to the outside. The introduction of slurry SL into the reactor 10 and the discharge of slurry SL from the reactor 10 may be carried out via piping (not shown). The piping for introducing slurry SL into the reactor 10 may be formed, for example, at the top, side, or bottom of the reactor 10. The slurry supply pipe may be connected to a slurry supply source. The slurry supply pipe may also be connected to a catalyst source and an organic solvent source, so that the catalyst CT and the organic solvent SV are mixed inside the reactor 10 to prepare slurry SL.

[0016] In the slurry SL, a product liquid may be generated over time as the FT reaction progresses. The product liquid may be discharged to the outside of the reactor 10 through a product liquid outlet pipe 10a. The product liquid discharged to the outside of the reactor 10 may be purified by a purification method (not shown). As illustrated in Figure 1, the product liquid outlet pipe 10a may be formed on the side of the reactor 10, and its height may be determined based on a predetermined slurry liquid level. The slurry SL near the product liquid outlet pipe 10a may be discharged to the outside of the reactor 10 together with the product liquid via the product liquid outlet pipe 10a. The slurry SL discharged to the outside of the reactor 10 can be separated from the product liquid by the purification method described above and reused in the FT reaction as appropriate.

[0017] In the FT reaction, in addition to the product liquid, a product gas may also be produced. As shown in Figure 1, the product gas may be discharged to the outside of the reactor 10 through a product gas outlet pipe 10b formed at the top of the reactor 10. The product gas discharged to the outside of the reactor 10 may be purified by a purification means (not shown). The raw material gas SG supplied from the side or bottom of the reactor 10 may, for example, rise through the slurry SL inside the reactor 10 and move to the gas phase portion inside the reactor 10. The raw material gas SG that has moved to the gas phase portion may be discharged to the outside of the reactor 10 together with the product gas via the product gas outlet pipe 10b. The raw material gas SG discharged to the outside of the reactor 10 can be separated from the product gas by the purification means described above and reused in the FT reaction as appropriate.

[0018] In the FT reaction, the raw material gas SG, which is the raw material for synthesis, can be supplied from the side or bottom of the reactor 10 by the gas supply unit 20, which will be described later. In this embodiment, the raw material gas SG used usually moves upward in the slurry SL due to the difference in specific gravity between it and the slurry SL. Therefore, when the raw material gas SG is supplied from the side or bottom of the reactor 10, it tends to be possible to ensure a sufficient distance for the raw material gas SG to move within the slurry SL. As a result, the catalyst CT and the raw material gas SG tend to come into efficient contact. However, when the raw material gas SG is supplied from the side of the reactor 10, due to the difference in specific gravity between the raw material gas SG and the slurry SL, a dead space tends to be created near the inner wall of the reactor on the opposite side where the raw material gas SG is difficult to reach. Taking this dead space into consideration, and from the viewpoint of further increasing the distance for the raw material gas SG to move within the slurry SL, the reactor 10 may be configured so that the raw material gas SG is supplied from the bottom of the reactor 10. As an example, as shown in Figure 1, the raw material gas supply pipe 10c may be formed at the bottom of the reactor 10.

[0019] When the raw material gas SG is supplied from the side of the reactor 10, the raw material gas supply pipe 10c may be formed on the side of the reactor 10, and its height may be determined based on a predetermined slurry liquid level.

[0020] (Gas supply unit) The gas supply unit 20 supplies the raw material gas SG to the reactor 10. The gas supply unit 20 may be configured to store the raw material gas SG when the FT reaction is not being carried out and to supply the raw material gas SG to the reactor 10 when the FT reaction is being carried out. As shown in Figure 1, the gas supply unit 20 may be connected to the reactor 10 via the raw material gas supply pipe 10c. The gas supply unit 20 may be equipped with flow control means (not shown), such as a flow meter to monitor the flow rate of the raw material gas SG and a valve to control the flow rate.

[0021] (Analysis means) The analysis means 30 analyzes the product gas discharged from the reactor 10. As shown in Figure 1, the analysis means 30 may be connected to the product gas discharge pipe 10b and may be configured to sample at least a portion of the product gas passing through the product gas discharge pipe 10b. For example, a portion of the product gas GG may be introduced into the analysis means 30 via a pipe 10b' connecting the product gas discharge pipe 10b and the analysis means 30. The analysis means 30 may be a means capable of qualitatively and quantitatively analyzing multiple types of hydrocarbons contained in the product gas, and as an example, it may be a gas chromatography (GC) analyzer. The detector used for GC analysis may be a flame ionization detector (FID). In this embodiment, various known GC analyzers may be used as the analysis means 30, for example, the apparatus described in the embodiments described later may be used. In addition to GC, mass spectrometry (MS) can be used, and the analysis means 30 may be an MS measuring device. In MS, analysis including fragments is usually performed using an ionization voltage of 50 eV or higher, but it is preferable to obtain molecular ion peaks (also called parent ion peaks). Specifically, the optimal ionization voltage for each component is determined in advance by preliminary measurements, and a mass spectrum is obtained using the optimal ionization voltage for each component. To obtain a good mass spectrum, it is preferable to control the vacuum level of the apparatus. Furthermore, it is preferable to optimize the ionization voltage to suppress fragmentation and obtain good molecular ion peaks.

[0022] (Control Unit) The control unit 40 may be configured to control each component of the apparatus 100 to execute the FT reaction. As illustrated in Figure 1, the control unit 40 may include a reaction processing unit 42, a first information acquisition unit 43, a second information acquisition unit 44, a third information acquisition unit 45, a notification unit 46, and a storage unit 47. The reaction processing unit 42 may be configured to process gas supply and reaction conditions. The first information acquisition unit 43 may be configured to acquire first information, which will be described later. The second information acquisition unit 44 may be configured to acquire second information, which will be described later. The third information acquisition unit 45 may be configured to acquire third information, which will be described later. The notification unit 46 may be configured to perform notification control to the user, display of third information, etc. The storage unit 47 may be configured to store information set in advance for reference, etc., and acquired information (for example, first information, second information, third information, and information such as predetermined relational expressions, which will be described later). The control unit 40 may be configured to control, for example, the reactor 10, the gas supply unit 20, and the analysis means 30. As shown in Figure 1, the control unit 40 may be configured separately from the reactor 10, the gas supply unit 20, and the analysis means 30, or it may be incorporated into at least one of the reactor 10, the gas supply unit 20, and the analysis means 30. The control by the control unit 40 may include adjusting the reaction temperature, reaction pressure, the amount of raw material gas SG supplied, and the amount of catalyst CT, etc.

[0023] The control unit 40 may be a computer physically comprising a CPU (Central Processing Unit), RAM (Random Access Memory), ROM (Read Only Memory), a communication unit, an input unit, and an output unit. Each of these components may be connected to each other via a bus to enable data transmission and reception.

[0024] The following explanation will use the case where the control unit 40 is composed of a single computer as an example, but the control unit 40 may be implemented by combining multiple computers. The computer in this embodiment may be configured as a tablet terminal. Furthermore, a part of the configuration of the control unit 40 may be located in a remote location, as long as it is connected to enable data transmission and reception. In this case, the control unit 40 may be configured to acquire control signals generated in each of the remotely located components via a network.

[0025] As shown in the example in Figure 2, the control unit 40 may include a CPU 41a, RAM 41b, ROM 41c, communication unit 41d, input unit 41e, and output unit 41f.

[0026] The CPU 41a may function as an arithmetic unit that controls the execution of programs stored in the RAM 41b or ROM 41c, and performs calculations and processing of data. The CPU 41a may be an arithmetic unit that executes a program (monitoring program) that displays graphs and explanatory text related to the process data of this device. The CPU 41a receives various data from the input unit 41e and the communication unit 41d, and outputs the calculation results of the data to the notification unit 46 or stores them in the RAM 41b.

[0027] RAM 41b is a data-rewritable memory unit and may be composed of semiconductor memory elements such as DRAM or SRAM. RAM 41b may store data such as the program executed by CPU 41a and process data of this device. These are examples, and RAM 41b may store other data, or some of this data may not be stored.

[0028] ROM 41c is a data readable memory unit and may be composed of, for example, a semiconductor memory element such as flash memory or an HDD. ROM 41c may store, for example, a computer program for executing various processes in this embodiment, and data that is not rewritten. The data that is not rewritten includes, for example, information regarding the specifications of this device and its components. Furthermore, ROM 41c may store, for example, process data of this device, indicators related to the operation of this device (such as operating rate and efficiency), and data such as planned downtime.

[0029] The communication unit 41d may be, for example, an interface connecting the various components that make up this device. The communication unit 41d may be connected to a communication network such as the Internet.

[0030] The input unit 41e accepts data input in response to user operations and may include, for example, a keyboard and a touch panel.

[0031] The output unit 41f may, for example, output the calculation results from the CPU 41a to the notification means 50. For example, the notification means 50 may be configured to display a graph of process data or an explanatory text via the output unit 41f.

[0032] The computer program for executing the various processes in this embodiment may be stored and provided on a computer-readable storage medium such as a ROM 41c, or it may be provided via a communication network connected by the communication unit 41d. In the control unit 40, various operations included in this embodiment may be realized by the CPU 41a executing the program. For example, the program in this embodiment may be a program that causes the computer of an apparatus for producing hydrocarbons by the Fischer-Tropsch process to execute: (a) reacting a raw material gas in the presence of a catalyst to obtain a product gas; (b) subjecting the product gas to analysis to obtain first information regarding the quantitative results of at least one light hydrocarbon selected from the group consisting of ethane and ethylene, propane and propylene, and butane and butene in the product gas; (c) calculating at least one ratio selected from the group consisting of ethylene / ethane ratio, propylene / propane ratio and butene / butane ratio based on the first information to obtain second information regarding the calculated value of the ratio; and (d) obtaining third information regarding the selectivity of hydrocarbons having 5 or more carbon atoms based on the second information. The program can be stored in a storage medium. The storage medium storing the program may be a computer-readable non-temporary storage medium. Note that these physical configurations are illustrative and do not necessarily have to be independent. For example, the control unit 40 may include an LSI (Large Scale Integration) that integrates the CPU 41a and RAM 41b or ROM 41c.

[0033] The notification unit 46 may be configured to notify the user of at least one piece of information selected from the group consisting of first information, second information, and third information. The notification unit 46 may be configured to generate a screen containing at least one piece of information selected from the group consisting of first information, second information, and third information, and to output the screen. For example, the notification unit 46 may be configured to generate a screen containing third information and output it to a monitor or the like. The notification unit 46 may also be configured to generate audio containing at least one piece of information selected from the group consisting of first information, second information, and third information, and to output the audio to the operator (user) of the device. For example, the notification unit 46 may be configured to generate audio containing third information and output it to a speaker or the like. Thus, the notification unit 46 may be a display unit or a notification unit.

[0034] (Other configurations) The apparatus may further include stirring means (not shown) configured to stir the slurry SL and raw material gas SG supplied into the reactor 10. The stirring means may be located inside the reactor 10. When the slurry SL and raw material gas SG supplied into the reactor 10 are stirred by the stirring means, the opportunity for contact between the slurry SL and the raw material gas SG increases, which can improve the reaction efficiency.

[0035] The apparatus may be equipped with heat exchange means (not shown) for maintaining the temperature inside the reactor 10 within a predetermined range. Since the FT reaction is an exothermic reaction, the heat exchange means may be configured to suppress an excessive temperature rise inside the reactor 10. For example, the heat exchange means may include a cooling medium introduction pipe for introducing a cooling medium into the heat exchange means and a heated steam outlet pipe for discharging heated steam from the heat exchange means.

[0036] This apparatus may be equipped with a gas dispersion means (not shown). The raw material gas SG that has passed through the gas dispersion means tends to become minute bubbles in the slurry SL and disperse more uniformly within the reactor 10. The more uniformly the raw material gas SG is dispersed within the reactor 10, the more opportunities there are for contact between the raw material gas SG and the catalyst CT, which can improve the reaction efficiency.

[0037] As an example of this apparatus, an apparatus 100 comprising one reactor 10, one gas supply unit 20, one analysis means 30, one control unit 40, and one notification means 50 has been described, but the apparatus is not limited to this, and each component may be provided in one or two or more parts. This apparatus may, for example, comprise two or more reactors 10, and the control unit 40 may be configured to control each reactor in parallel. This apparatus may, for example, comprise two or more reactors 10, and may also comprise a number of analysis means 30, control units 40, and notification means 50 corresponding to the number of reactors.

[0038] Although this apparatus has been described based on an example where reactor 10 is a slurry bed reactor, it is not limited to this and may include other reactors. For example, in addition to reactor 10, or in place of reactor 10, this apparatus may include other reactors capable of producing hydrocarbons by the FT method, such as a fixed bed reactor or a fluidized bed reactor.

[0039] <Method> The method of this embodiment (hereinafter also referred to as "this method") is a method for producing hydrocarbons by the FT method, and includes: (a) a step of reacting a raw material gas in the presence of a catalyst to obtain a product gas; (b) a step of subjecting the product gas to analysis to obtain first information regarding the quantitative results of at least one light hydrocarbon selected from the group consisting of ethane and ethylene, propane and propylene, and butane and butene in the product gas; (c) a step of calculating at least one ratio selected from the group consisting of ethylene / ethane ratio, propylene / propane ratio and butene / butane ratio based on the first information to obtain second information regarding the calculated value of said ratio; and (d) a step of obtaining third information regarding the selectivity of hydrocarbons having 5 or more carbon atoms based on the second information. Because this method is configured as described above, the evaluation process for the selectivity of liquid hydrocarbons can be simplified.

[0040] Figure 3 is a flowchart illustrating an example of this method. As illustrated in Figure 3, this method may include a step S1 for producing hydrocarbons, a step S2 for acquiring first information, a step S3 for acquiring second information, and a step S4 for acquiring third information. Step (a) above may include step S1. Step (b) above may include step S2. Step (c) above may include step 3. Step (d) above may include step S4. Steps S1, S2, S3, and S4 may be executed in this order, and at least two of these steps may be executed simultaneously. Furthermore, at least one of steps S1, S2, S3, and S4 may be executed repeatedly. For example, steps S1, S2, S3, and S4 can be executed repeatedly.

[0041] This method may be carried out using the apparatus 100 illustrated in Figure 1, or it may be carried out using other apparatus. In the following, the case in which this method is carried out using apparatus 100 will be described as an example. That is, the control unit 40 in apparatus 100 controls the reactor 10, gas supply unit 20, analysis means 30 and notification means 50 to carry out this method.

[0042] (Step S1) In Step S1, hydrocarbons are produced by the FT reaction. That is, in Step S1, the raw material gas is reacted in the presence of a catalyst to obtain gaseous hydrocarbons (product gases) and liquid hydrocarbons.

[0043] In step S1, as shown in Figure 1, slurry SL is supplied to the apparatus 100. In this embodiment, slurry SL can be supplied into the reactor 10 from a slurry supply pipe (not shown). As shown in Figure 1, slurry SL may contain an organic solvent SV and a catalyst CT.

[0044] The organic solvent SV serves as a medium for suspending the catalyst CT and introducing it into the reactor for gas-liquid catalytic reactions. The organic solvent SV may be, for example, a liquid hydrocarbon. The liquid hydrocarbon may be, for example, a saturated hydrocarbon having 10 to 20 carbon atoms. The organic solvent SV may, as an example, be hexadecane.

[0045] Catalyst CT may contain a catalyst metal MT. The catalyst CT may include, for example, a catalyst metal MT and a carrier SP that supports the catalyst metal MT. The catalyst metal MT may include at least one selected from the group consisting of cobalt, nickel, ruthenium, and iron. From the perspective of obtaining middle distillates such as gas oil, jet fuel, and kerosene, the catalyst metal MT may include cobalt. The carrier SP may include at least one selected from the group consisting of silica (SiO ２ ), alumina (Al ２ O ３ ), and zeolite (aluminosilicate). From the perspective of exerting the performance derived from the catalyst metal MT and the contact efficiency with the raw material gas, the carrier SP may include silica. The catalyst CT may further include at least one selected from the group consisting of yttrium, cerium, lanthanum, praseodymium, neodymium, and holmium, which are rare earth elements, at least one selected from the group consisting of sodium, potassium, rubidium, and cesium, which are alkali metals, at least one selected from the group consisting of beryllium, magnesium, calcium, strontium, and barium, which are alkaline earth metals, and may also include copper or the like.

[0046] The loading amount in the catalyst CT is expressed as the mass ratio of the catalyst metal to the catalyst and may be adjusted as appropriate. In the present embodiment, the above loading amount may be 5% or more and 30% or less. When the above loading amount is 5% or more, the conversion rate of carbon monoxide tends to improve. When the above loading amount is 30% or less, the chain growth rate tends to improve. From the above perspective, the above loading amount may be 10% or more and 25% or less.

[0047] The shape of the catalyst CT is not particularly limited and may be, for example, powdery. The size of the catalyst CT is also not particularly limited and may be, for example, 0.07 mm or more and 0.2 mm or less as the measurement value by the laser diffraction method.

[0048] The ratio of the specific gravity of the catalyst CT (in this specification, it means the true specific gravity. The same shall apply hereinafter.) to the specific gravity of the organic solvent SV (specific gravity at a temperature of 20°C) is expressed as the specific gravity of the catalyst / specific gravity of the organic solvent and may be adjusted as appropriate. In the present embodiment, the above specific gravity may be 1.15 or more and 5.13 or less.

[0049] The concentration of catalyst CT in the slurry SL is expressed as the ratio of the mass of the catalyst to the volume of the slurry and may be adjusted as appropriate. In this embodiment, the above ratio may be 2.5% or more and 40% or less. When the above ratio is 2.5% or more, the carbon monoxide conversion rate and chain growth rate tend to improve. When the above ratio is 40% or less, it is possible to prevent the catalyst CT from precipitating excessively in the slurry SL.

[0050] In step S1, the raw material gas SG is supplied to the apparatus 100. In this embodiment, the raw material gas SG can be supplied into the reactor 10 from the gas supply unit 20. When the raw material gas SG is supplied into the reactor 10, the FT reaction proceeds when the catalyst CT contained in the slurry SL inside the reactor 10 comes into contact with the raw material gas SG.

[0051] The raw material gas SG is hydrogen (H ２ ) may be a mixed gas of carbon dioxide (CO). The raw material gas SG in this embodiment is carbon dioxide (CO ２ ) may further contain. From the viewpoint that the rate of the FT reaction depends on the partial pressure of hydrogen, the partial pressure ratio (molar ratio) of hydrogen to the total amount of carbon monoxide and carbon dioxide in the raw material gas SG may be 0.6 to 2.7, 0.8 to 2.5, or 1 to 2.3. The ratio of carbon monoxide to carbon dioxide in the raw material gas SG may also be adjusted as appropriate. For example, from the viewpoint of carbon recycling, the ratio of carbon dioxide may be increased, and from the viewpoint of increasing the conversion rate to hydrocarbons, the ratio of carbon monoxide may be increased. In this embodiment, the ratio of carbon dioxide to carbon monoxide is the ratio of carbon dioxide to the total amount of carbon monoxide and carbon dioxide, and may be 1 volume% or more, 10 volume% or more, 30 volume% or more, or 40 volume% or more. Other components in the raw material gas SG may include, for example, sulfur, organic nitrogen, phosphorus, etc. The content of the above other components may be 5 vol. ppm or less per 100 volume% of the raw material gas SG.

[0052] When the raw material gas SG comes into contact with the catalyst CT in the slurry SL, the FT reaction proceeds, and a liquid product can be generated. The liquid product is a hydrocarbon with a relatively high boiling point and a high number of carbon atoms among the hydrocarbons produced by the FT reaction, and may be, for example, a heavy naphtha fraction (crude gasoline), kerosene, diesel fuel, or other intermediate distillates.

[0053] When the raw material gas SG comes into contact with the catalyst CT in the slurry SL, the FT reaction proceeds and a product gas may be generated. The product gas is a hydrocarbon with a relatively low boiling point and a low number of carbon atoms among the hydrocarbons produced by the FT reaction, and may be, for example, a hydrocarbon with 1 to 4 carbon atoms. Specific examples of such hydrocarbons include methane, ethane, ethylene, propane, propylene, butane, and butene.

[0054] In step S1, the temperature inside the reactor 10 may be controlled to be between 200°C and 270°C. In this embodiment, the temperature inside the reactor 10 may also be controlled to be between 200°C and 270°C in at least one of steps S2, S3, and S4.

[0055] In step S1, the pressure inside the reactor 10 (meaning gauge pressure; the same applies to reaction pressure hereinafter) may be controlled to be between 0.1 MPa, G and 3.0 MPa, G. In this embodiment, in at least one of steps S2, S3, and S4, the pressure inside the reactor 10 may also be controlled to be between 0.1 MPa, G and 3.0 MPa, G.

[0056] (Step S2) In step S2, first information is obtained. The first information concerns the quantitative results of at least one light hydrocarbon selected from the group consisting of ethane and ethylene, propane and propylene, and butane and butene in the product gas. Such quantitative results are obtained by subjecting the product gas to analysis.

[0057] The product gas GG, which is the target of analysis in step S2, is discharged from the reactor 10 through the product gas outlet pipe 10b. For example, a portion of the product gas GG may be introduced into the analysis means 30 via piping 10b' connecting the product gas outlet pipe 10b and the analysis means 30.

[0058] In step S2, the amount of at least one light hydrocarbon selected from the group consisting of ethane and ethylene, propane and propylene, and butane and butene is measured. Therefore, from the viewpoint of speed of measurement, the analytical means 30 may be a GC analyzer. Also, from the viewpoint of speed of measurement and process simplification in GC analysis, the quantitative result of light hydrocarbons obtained in step S2 may be the quantitative result of ethane and ethylene. For example, the first information may be the quantitative result of ethane and ethylene. Furthermore, from the viewpoint of improving the accuracy of the third information described later, the quantitative result of light hydrocarbons obtained in step S2 may be the quantitative result of ethane and ethylene, propane and propylene, and butane and butene. For example, the first information may be the quantitative result of ethane and ethylene, propane and propylene, and butane and butene.

[0059] The quantitative results of the light hydrocarbons obtained in step S2 are acquired as first information by, for example, the first information acquisition unit 43 in the control unit 40. The first information acquired by the first information acquisition unit 43 is stored in, for example, the storage unit 47 and can be appropriately used as primary information in step S3.

[0060] During the execution of process S2, at least one selected from the group consisting of process S1 and processes S3 and S4 described later may be in operation or stopped.

[0061] (Step S3) In step S3, second information is obtained. The second information concerns a calculated value of at least one ratio selected from the group consisting of ethylene / ethane ratio, propylene / propane ratio, and butene / butane ratio. This calculated value is calculated based on the first information.

[0062] In step S3, the second information is acquired, for example, by the second information acquisition unit 44 in the control unit 40. The second information acquisition unit 44 may be configured to calculate each ratio based on the first information stored in the storage unit 47. The ethylene / ethane ratio can be calculated from the measured amounts of ethane and ethylene included in the first information. The propylene / propane ratio can be calculated from the measured amounts of propane and propylene included in the first information. The butene / butane ratio can be calculated from the measured amounts of butene and butene included in the first information.

[0063] The calculated value obtained in step S2 can be stored as second information in the storage unit 47, for example, and used as primary information in step S3.

[0064] During the execution of process S2, at least one selected from the group consisting of process S1, process S2, and process S4 (described later) may be running or stopped.

[0065] (Step S4) In step S4, third information is obtained. The third information is the selectivity of hydrocarbons with 5 or more carbon atoms (C ５＋ This concerns the selection rate. C ５＋ The selection rate is obtained based on the second piece of information.

[0066] In step S4, the third information is acquired, for example, by the third information acquisition unit 45 in the control unit 40. Based on the second information stored in the storage unit 47, the third information acquisition unit 45 performs C ５＋ It may be configured to obtain information regarding the selection rate.

[0067] In this embodiment, the reason why the third information is obtained based on the second information can be explained as follows: As the reaction mechanism of the FT reaction, a carbene species (metal carbene: M=CH) is generated from carbon monoxide and hydrogen near the catalyst surface. ２ After ) is generated, =CH ２It is thought that carbon atoms are inserted sequentially, extending the hydrocarbon chain one by one. Hydrocarbons with five or more carbon atoms become liquid hydrocarbons at room temperature and atmospheric pressure. For example, in jet fuel (SAF), hydrocarbons with around 10 carbon atoms are used, and in diesel fuel, hydrocarbons with around 16 carbon atoms are used. Considering such applications, increasing the hydrocarbon chain, i.e., =CH ２ To increase this, it is preferable that the carbene species concentration is high when olefins are chemically adsorbed on the catalyst surface (i.e., the catalyst surface becomes olefin-rich). In the process of such investigations, the inventors concluded that in situations where the catalyst surface tends to become olefin-rich, the gas phase tends to be olefin-poor. To verify this point, the inventors conducted several verification experiments. As a result, they found that when the olefin content in light hydrocarbons (gaseous hydrocarbons) with 2 to 4 carbon atoms, such as ethylene / ethane ratio, propylene / propane ratio, and butene / butane ratio, is low (the gas phase is olefin-poor), C ５＋ This suggested a high selectivity. Furthermore, as a result of further verification by the inventors, the olefin / paraffin ratio and C ５＋ Based on the correlation with the selection rate, C ５＋ We found that selectivity can be predicted with high accuracy (see the example described later). That is, instead of directly analyzing liquid hydrocarbons, by analyzing the above light hydrocarbons, C ５＋ We found that the selectivity can be determined from the olefin / paraffin ratio of olefins with 5 or more carbon atoms. ５＋ While selectivity can be evaluated, analysis time tends to increase as the molecular weight of the analyte increases. Furthermore, the number of olefin isomers increases, and accurately analyzing these isomers tends to require longer analysis times than those associated with molecular weight alone. When there are many isomers, calculating the olefin / paraffin ratio becomes more complicated, requiring additional analysis of olefins by mass spectrometry in addition to gas chromatography. Therefore, based on the olefin / paraffin ratio in light hydrocarbons (gaseous hydrocarbons) with 2 to 4 carbon atoms, C2 / paraffin ratio is used. ５＋ Evaluating selectivity can simplify the process of evaluating the selectivity of liquid hydrocarbons.

[0068] As described above, based on at least one ratio selected from the group consisting of ethylene / ethane ratio, propylene / propane ratio and butene / butane ratio, C ５＋ It is possible to understand the level of selection rate. C ５＋ Whether or not the selectivity can be evaluated as sufficiently high can also be used to determine whether or not to maintain the reaction conditions of step S1 before or during the execution of step S4. For example, if a threshold for the above ratio is set in advance, by checking the relationship between the threshold and the calculated value of the above ratio, C ５＋ It is possible to determine whether the selection rate is at the target level. For example, the threshold value of the above ratio may be stored in advance in the storage unit 47 of the control unit 40, and the third information acquisition unit 45 may be made to read the threshold value. Furthermore, the relationship between the threshold value and the calculated value of the above ratio may be determined by the third information acquisition unit 45. More specifically, if the calculated value of the above ratio is lower than the threshold value, C ５＋ It can be determined that the selection rate is at the target level. Also, if the calculated value of the above ratio is higher than the above threshold, C ５＋ It can be determined that the selection rate is not at the target level. ５＋ If the selectivity is not at the target level, the reaction conditions of step S1 before or during step S4 should be reviewed, etc., to adjust the subsequent C in the FT reaction. ５＋ This could improve the selection rate.

[0069] In this embodiment, the third information is C ５＋ It may include an estimate of the selectivity. This estimate is a ratio selected from the group consisting of ethylene / ethane ratio, propylene / propane ratio and butene / butane ratio and C ５＋ It can be calculated by knowing in advance the relationship with the selection rate. For example, the above ratio and C ５＋ The relationship formula for the selectivity rate (see the modified example described later and Figures 6-7) may be stored in advance in the storage unit 47 of the control unit 40, and the relationship formula may be read into the third information acquisition unit 45. Furthermore, C ５＋ The estimated selection rate may be calculated by the third information acquisition unit 45 based on the calculated value of the ratio and the relational expression. In this embodiment, C ５＋ A threshold for the selectivity rate may be set in advance. For example, C５＋ The selectivity threshold may be pre-stored in the storage unit 47 of the control unit 40, and the third information acquisition unit 45 may be made to read the threshold. Furthermore, C ５＋ Selection threshold and C ５＋ The relationship between the estimated selection rate and the third information acquisition unit 45 may be determined. More specifically, C ５＋ The estimated selection rate is C ５＋ If it is higher than the selectivity threshold, C ５＋ The selection rate can be judged to be at the target level. Also, C ５＋ The estimated selection rate is C ５＋ If the selectivity is lower than the threshold, C ５＋ It can be determined that the selection rate is not at the target level. ５＋ If the selectivity is not at the target level, the reaction conditions of step S1 before or during step S4 should be reviewed, etc., to adjust the subsequent C in the FT reaction. ５＋ This could improve the selection rate.

[0070] <Modification> As described above, in this method, information regarding predetermined magnitude relationships and estimated values ​​that can be obtained in step S3 is stored as third information in the memory unit 47, for example, and used as appropriate in step S1, etc. As one modification of this method, a specific example of how to utilize the third information is described below.

[0071] Figure 4 is a flowchart of another example of the present method (hereinafter also referred to as the "modified method"). As shown in Figure 4, the modified method includes a step S21 of producing hydrocarbons under first reaction conditions, a step S22 of acquiring first information, a step S23 of acquiring second information, a step S24 of acquiring third information, a step S25 of notifying the user of the third information, and a step S26 of producing hydrocarbons under first reaction conditions. Step (a) above may include steps S21 and S26. Step (b) above may include step S22. Step (c) above may include step 23. Step (d) above may include steps S24 and S25. Steps S21, S22, S23, S24, S25 and S26 may be executed in this order, and at least two of these steps may be executed simultaneously. Furthermore, at least one of steps S21, S22, S23, S24, S25, and S26 may be performed repeatedly. For example, steps S21, S22, S23, S24, S25, and S26 can be performed repeatedly.

[0072] Steps S21 and S26 in the modified method can be carried out in the same way as step S1 described in relation to the present method. The processing conditions (first reaction conditions) in step S21 and the processing conditions (second reaction conditions) in step S26 may be the same or different. Steps S22, S23, and S24 in the modified method can be carried out in the same way as steps S2, S3, and S4 described in relation to the present method, respectively.

[0073] In step S25, the third information acquired in step S24 is notified to the user. For example, the third information acquired by the third information acquisition unit 45 in the control unit 40 may be notified to the user by the notification unit 46. In step S25, for example, at least one piece of information selected from the group consisting of first information, second information, and third information may be notified to the user by the notification unit 46. As an example, the notification unit 46 functions as a notification means such as a monitor, and the third information may be displayed on the screen of the notification unit 46. As another example, the notification unit 46 functions as a notification means such as a speaker, and the third information may be output as sound from the notification unit 46. In this embodiment, the third information notified in step S25 may include the result (i) of comparing a preset ratio threshold with the calculated value. In this embodiment, the third information notified in step S25 is C ５＋ An estimated value of the selectivity rate, which may include an estimated value (ii) calculated based on the calculated value and a preset information relating the ratio and the selectivity rate. In this embodiment, the third information notified in step S25 may include both the result (i) and the estimated value (ii).

[0074] Figure 5 is a flowchart showing an example of a screen output by a notification means that may be included in this device. In the example in Figure 5, screen DP1 displays the third information and other reference information together. Specifically, screen DP1 displays information regarding the reaction conditions, analytical values ​​(first information), calculated values ​​(second information), and selectivity evaluation (third information). The reaction conditions displayed on screen DP1 correspond to the first reaction conditions, and in the example in Figure 5, these include reactor temperature, reactor pressure, catalyst concentration in slurry, CO supply amount (volume ratio), and CO ２ Supply amount (by volume) and H ２ Supply amount (CO and CO ２The partial pressure ratio (total of the total) is displayed. The analysis values ​​displayed on screen DP1 correspond to the first information, and in the example in Figure 5, the amounts of ethane, ethylene, propane, propylene, butane, and butene are displayed. The calculated values ​​displayed on screen DP1 correspond to the second information, and in the example in Figure 5, the ethylene / ethane ratio R1, the propylene / propane ratio R2, and the butene / butane ratio R3 are displayed. The selectivity evaluation displayed on screen DP1 corresponds to the third information, and in the example in Figure 5, the threshold T1 for the ethylene / ethane ratio, the comparison result between R1 and T1, the threshold T2 for the propylene / propane ratio, the comparison result between R2 and T2, and the threshold T2 for the butene / butane ratio, the comparison result between R3 and T3 are displayed. In this example, thresholds T1, T2, and T3 are all preset values. In the example in Figure 5, the relationship between the calculated ratio and the threshold is R1 < T1, R2 < T2, and R3 < T3, therefore C ５＋ The selection rate can be considered sufficiently high.

[0075] In step S26, hydrocarbons are produced by an FT reaction under second reaction conditions. The second reaction conditions can be determined based on the third information obtained in step S24. As described above regarding this method, from the third information, C ５＋ The level of selectivity can be determined. For example, in processes S24 and S25, C ５＋ If the selectivity can be evaluated as sufficiently high (see, for example, Figure 5), the second reaction conditions may be the same as the first reaction conditions. Also, for example, in steps S24 and S25, C ５＋ If the selectivity cannot be evaluated as sufficiently high, the first reaction conditions may be reviewed as necessary, and a second reaction condition different from the first reaction condition may be adopted.

[0076] Figure 6 shows another example of a screen output by a notification means that may be included in this device. More specifically, Figure 6 shows an example of a screen that may be generated as a result of performing steps S21, S22, S23, S24 and S25 in the modified method. In the example in Figure 6, the upper part of screen DP2 shows the calculated value of the ethylene / ethane ratio and C ５＋A graph showing the relationship with the estimated selectivity is displayed. The lower part of screen DP2 displays information regarding the analyzed value (first information), the calculated value (second information), and the selectivity evaluation (third information). In the graph of Figure 6, the pre-set relationship equation y = ax + b is displayed. This relationship equation (i.e., the numerical values ​​of a and b) is used, for example, when hydrocarbon production is carried out by the FT method under multiple conditions, and the measured value of the ethylene / ethane ratio and C ５＋ The measured selectivity value and the resulting plot can be obtained by linear approximation. The measured ethylene / ethane ratio and C ５＋ The measured selectivity can be obtained by the GC analysis described above. The measured ethylene / ethane ratio can be obtained, for example, based on GC analysis 1 described in the example below. Also, C ５＋ The measured selectivity can be obtained, for example, based on GC analysis 2 described in the example below. In the example in Figure 6, the preset C ５＋ The estimated threshold value y2 for selectivity and the corresponding ethylene / ethane ratio x2 are shown in the graph. The analysis values ​​(first information) displayed on screen DP2 show the amount of ethane and ethylene. Based on these values, the ethylene / ethane ratio is calculated as the calculated value (second information). Based on the calculated ethylene / ethane ratio and the above relationship, the selectivity evaluation (third information) is C ５＋ An estimated selection rate is calculated. In the graph in Figure 6, C ５＋ The C obtained from the estimated selectivity threshold y2 and the measured ethylene / ethane ratio x1 based on the above relational expression is ５＋ The estimated selection rate y1 is also shown. In the example in Figure 6, since y1 < y2, C ５＋ The selection rate cannot be considered sufficiently high. Based on these display results, the first reaction conditions may be reviewed as needed, and a second reaction condition different from the first may be adopted. The process from reviewing the first reaction conditions to determining the second reaction conditions may be executed mechanically using artificial intelligence technology, or the user who has been notified of the third information may manually change the conditions.

[0077] The second reaction conditions may be reaction conditions controlled based on the third information. The reaction conditions controlled based on the third information may include at least one condition selected from the group consisting of reaction temperature, reaction pressure, supply amount of raw material gas, and amount of catalyst. By increasing or decreasing the reaction temperature, reaction pressure, supply amount of raw material gas, and amount of catalyst as needed, C obtained as a result of the second and subsequent steps S21 can be obtained. ５＋ The selectivity can be controlled to exceed the target threshold.

[0078] Figure 7 shows yet another example of a screen output by a notification means that may be included in this device. More specifically, Figure 7 shows an example of a screen that may be generated as a result of executing step S26, and then steps S22, S23, S24, and S25 again, based on the results shown in Figure 6 (after executing steps S21, S22, S23, S24, and S25 in the modified method). In the example in Figure 7, the upper part of screen DP3 shows the calculated value of the ethylene / ethane ratio and C ５＋ A graph showing the relationship with the estimated selectivity is displayed. The lower part of screen DP3 displays information regarding the analysis value (first information), the calculated value (second information), and the selectivity evaluation (third information). The analysis value (first information) displayed on screen DP3 shows the amount of ethane and ethylene. Based on these values, the ethylene / ethane ratio is calculated as the calculated value (second information). Based on the calculated ethylene / ethane ratio and the above relationship formula, the selectivity evaluation (third information) is C ５＋ An estimated selection rate is calculated. In the graph in Figure 7, C ５＋ The C obtained from the estimated selectivity threshold y2 and the measured ethylene / ethane ratio x3 based on the above relational expression is ５＋ The estimated selection rate y3 is also shown. In the example in Figure 7, since y1 > y2, C ５＋ The selectivity can be evaluated as sufficiently high. Based on these display results, step S21 C ５＋ C in process S26 relative to the selectivity ５＋ It can be confirmed that the selection rate has improved.

[0079] <Examples> The embodiment will be described in more detail below based on examples. This embodiment is not limited to these examples.

[0080] [Experimental Example 1] (Apparatus) Using an apparatus having the same configuration as apparatus 100 shown in Figure 1, hydrocarbons were produced by the FT method as follows.

[0081] (Slurry Preparation) As a catalyst, a catalyst was prepared in which cobalt was supported on a silica support. In this catalyst, the amount of active metal (Co) supported was 10% by mass based on the weight of the catalyst. The true specific gravity of this catalyst was determined by the Gay-Lussac gravity bottle method and was 2.25 g / cm³. ３ The following was the result. n-hexadecane (specific gravity 0.77) was used as the organic solvent, and the catalyst was mixed with it to prepare a slurry so that the catalyst concentration was 10% (catalyst mass / slurry volume).

[0082] (Synthesis Reaction) First, the slurry described above was supplied into a reactor (inner diameter = 50 mm (50φ)). The supply rate was adjusted so that the slurry level in the reactor was 70-80 mm. Next, the supply of raw material gas was started, thereby initiating the hydrocarbon synthesis reaction. The raw material gas used was a mixed gas of synthesis gas (syngas) with mole fractions of hydrogen and carbon monoxide of 67% and 33%, and carbon dioxide. The mole fractions of synthesis gas and carbon dioxide were 80% and 20%, respectively. The reaction temperature was 230°C, and the pressure was 0.3 MPa, G. The reaction time was 10 hours, during which the product liquid was withdrawn from the product liquid outlet pipe, and the product gas was withdrawn from the product gas outlet pipe.

[0083] (GC Analysis 1) A portion of the generated gas extracted from the generated gas outlet tube was sampled and subjected to GC analysis without any treatment such as heating. The analysis conditions were as follows: (Analysis Conditions) A separation column made of a stainless steel tube with an outer diameter of 4 mm, an inner diameter of 3 mm, and a length of 2 m, packed with a packing material consisting of porous spherical silica (Unipack-S, 100-150 mesh, manufactured by GL Sciences), was mounted on a gas chromatograph (GC14-B, manufactured by Shimadzu Corporation) equipped with a hydrogenation flame ionization detector (FID). The carrier gas (mobile phase) was argon, and the mobile phase flow rate was 30 mL / min under standard conditions. The initial column temperature was set to 50°C. 1.0 mL of the gas sample was injected from the gas sampler, and simultaneously, the temperature was increased at 4°C / min until it reached 130°C, where it was maintained for component analysis. The time required for analysis of C2 (ethylene and ethane) was 5 minutes, the time required for analysis of C3 (propylene and propane) was 8 minutes, and the time required for analysis of C4 (butane and butene) was 15 minutes. A chromatogram was generated using a self-recording integrator recorder (Shimadzu C-R8A), and numerical data was recorded into memory simultaneously. The carrier gas flow rate was measured using a soap film flow meter. The time required to reset the column temperature after the analysis was approximately 5 minutes.

[0084] The above GC analysis revealed the content of ethane and ethylene, propane and propylene, and butane and butene in the generated gas (acquisition of first information). The analysis of ethane and ethylene took approximately 5 minutes. The analysis of propane and propylene took approximately 8 minutes. The analysis of butane and butene took approximately 15 minutes.

[0085] Based on the above content (first information), the ethylene / ethane ratio, propylene / propane ratio, and butene / butane ratio were calculated (acquisition of second information). The results of comparing the calculated values ​​of each ratio obtained as second information with the pre-set threshold values ​​for the ethylene / ethane ratio, propylene / propane ratio, and butene / butane ratio were recorded as third information.

[0086] (Verification experiment; GC analysis 2) The smaller the ethylene / ethane ratio, propylene / propane ratio, and butene / butane ratio, the higher the C ５＋ To confirm that the selectivity tends to be high, the following verification experiment was conducted as a process separate from the main method. Specifically, the product liquid extracted from the product liquid outlet tube after the synthesis reaction was subjected to GC analysis while being kept warm using a jacket. In other words, hydrocarbons with 5 to 20 carbon atoms were quantified. (Analysis conditions) A separation column consisting of a stainless steel tube with an outer diameter of 4 mm, an inner diameter of 3 mm, and a length of 2 m, packed with a packing material consisting of silicone oil supported on an inorganic oxide carrier (GL Sciences, Silicone SE-30 (2 wt.%) / Uniport-HP, 60-80 mesh), was attached to a gas chromatograph with a hydrogenation flame ionization detector (FID) (Shimadzu Corporation GC8A), and argon was used as the carrier gas (mobile phase), with the mobile phase flow rate being 25 mL / min under standard conditions. The column was initially set to 70°C. A 1 μL liquid sample was injected through an injection port maintained at 210°C, and component analysis was performed while simultaneously increasing the temperature at 8°C / min. After reaching 270°C, the temperature was maintained and analysis continued. The analysis was terminated when a component with 30 carbon atoms was detected (40 minutes after sample injection). A chromatogram was generated using a self-recording integrator recorder (Shimadzu C-R8A), and numerical data was simultaneously recorded in memory. The carrier gas flow rate was measured using a soap film flow meter. Since the liquid sample volume was small (1 μL) and prone to analytical errors, the same sample was analyzed five times and the average was calculated. After each analysis, the column temperature needed to be lowered from 270°C to a constant temperature of 70°C, requiring approximately 20 minutes for temperature stabilization before re-analysis. Therefore, each analysis took approximately 40 minutes, plus approximately 20 minutes for stabilization, for a total of approximately 1 hour.

[0087] GC analysis 2 identified the content of hydrocarbons with 5 or more carbon atoms in the generated liquid. Based on these content levels and the results of GC analysis 1 (analysis of the generated gas), the quantitative determination of methane (1 carbon atom), hydrocarbons with 2 to 4 carbon atoms, and hydrocarbons with 5 to 20 carbon atoms was completed. It took approximately 5 hours (1 hour x 5 times) to obtain the results of GC analysis 2 (quantification of hydrocarbons with 5 to 20 carbon atoms). Based on the obtained distribution of hydrocarbons with 1 to 20 carbon atoms, C ５＋ The selection rate was calculated.

[0088] [Experimental Examples 2-50] The synthesis reaction was carried out in the same manner as in Experimental Example 1, except that at least one of the following was appropriately changed: the amount of raw material gas, the composition of the raw material gas, and the amount of catalyst. The reaction results were then evaluated.

[0089] Based on the results of Experimental Examples 1 to 50, the C ratio for the ethylene / ethane ratio in each experimental example is as follows: ５＋ Figure 7 shows the plotted selectivity. As the ethylene / ethane ratio decreases, C ５＋ An increasing trend in selectivity was observed. Also, as shown in Figure 7, the ethylene / ethane ratio and C ５＋ It can be seen that the relationship with selectivity can be approximated by a straight line. That is, if the ethylene / ethane ratio is known, then based on the relationship obtained as described above, C ５＋ It can be seen that selectivity can be estimated with high accuracy. In particular, as mentioned above, since the calculation of the ethylene / ethane ratio can be completed in about 5 minutes, it is possible to use the quantitative results of hydrocarbons with 5 to 20 carbon atoms, which can take about 1.5 hours, as a basis for C ５＋ Compared to the operation of calculating the selectivity, C ５＋ It was evaluated as being able to grasp the selectivity. Furthermore, C was obtained solely by GC analysis of the generated gas. ５＋ Since selectivity can be estimated, based on the quantitative results of hydrocarbons with 5 to 20 carbon atoms, which may require heat retention for GC measurement, C ５＋ Compared to the operation of calculating the selectivity, C ５＋ It was evaluated as making it easier to understand the selection rate.

[0090] Based on the results of Experimental Examples 1-50, C for the propylene / propane ratio in each experimental example. ５＋The results of plotting the selectivity are shown in Fig. 8. As the propylene / propane ratio decreases, the C ５＋ selectivity tends to increase. Also, as shown in Fig. 8, it can be seen that the relationship between the propylene / propane ratio and the C ５＋ selectivity can be linearly approximated. That is, as long as the propylene / propane ratio is known, based on the relational expression obtained as described above, it can be seen that the C ５＋ selectivity can be accurately estimated. In particular, as described above, since the calculation of the propylene / propane ratio can be completed in about 15 minutes, compared with the operation of obtaining the C ５＋ selectivity based on the quantitative results of hydrocarbons having 5 to 20 carbon atoms, which may require about one and a half hours, it was evaluated that the C ５＋ selectivity can be grasped quickly. Also, since the selectivity can be estimated only by GC analysis of the product gas, compared with the operation of obtaining the C ５＋ selectivity based on the quantitative results of hydrocarbons having 5 to 20 carbon atoms, for which heat preservation for GC measurement may be required, it was evaluated that the C ５＋ selectivity can be easily grasped. ５＋

[0091] Based on the results of Experimental Examples 1 to 50, the results of plotting the C ５＋ selectivity against the butene / butane ratio of each experimental example are shown in Fig. 9. As the butene / butane ratio decreases, the C ５＋ selectivity tends to increase. Also, as shown in Fig. 7, it can be seen that the relationship between the butene / butane ratio and the C ５＋ selectivity can be linearly approximated. That is, as long as the butene / butane ratio is known, based on the relational expression obtained as described above, it can be seen that the C ５＋ selectivity can be accurately estimated. In particular, as described above, since the calculation of the butene / butane ratio can be completed in about 15 minutes, compared with the operation of obtaining the C ５＋ selectivity based on the quantitative results of hydrocarbons having 5 to 20 carbon atoms, which may require about one and a half hours, it was evaluated that the C ５＋ selectivity can be grasped quickly. Also, since the selectivity can be estimated only by GC analysis of the product gas, compared with the operation of obtaining the C ５＋ selectivity based on the quantitative results of hydrocarbons having 5 to 20 carbon atoms, for which heat preservation for GC measurement may be required, it was evaluated that the C ５＋Compared to the operation of calculating the selectivity, C ５＋ It was evaluated as making it easier to understand the selection rate.

[0092] As described above, this method was evaluated as being able to simplify the evaluation process for the selectivity of liquid hydrocarbons in the production of hydrocarbons by the FT method.

[0093] 100... Apparatus, 10... Reactor, 10a... Product liquid outlet pipe, 10b... Product gas outlet pipe, 10c... Raw material gas supply pipe, SG... Raw material gas, SL... Slurry, SV... Organic solvent, CT... Catalyst, 20... Gas supply unit, 30... Analytical means, 40... Control unit, 46... Notification unit

Claims

1. A method for producing hydrocarbons by the Fischer-Tropsch process, comprising: (a) reacting a raw material gas in the presence of a catalyst to obtain a product gas; (b) subjecting the product gas to analysis to obtain first information regarding the quantitative determination of at least one light hydrocarbon selected from the group consisting of ethane and ethylene, propane and propylene, and butane and butene in the product gas; (c) calculating at least one ratio selected from the group consisting of ethylene / ethane ratio, propylene / propane ratio and butene / butane ratio based on the first information to obtain second information regarding the calculated value of said ratio; and (d) obtaining third information regarding the selectivity of hydrocarbons having 5 or more carbon atoms based on the second information.

2. The method according to claim 1, wherein the reaction conditions in (a) are controlled based on the third information.

3. The method according to claim 2, wherein the reaction conditions controlled based on the third information include at least one condition selected from the group consisting of reaction temperature, reaction pressure, supply amount of raw material gas, and amount of catalyst.

4. (e) The method according to claim 1, further comprising notifying the user of the third information.

5. The method according to claim 4, wherein the third information notified in (e) includes the result of comparing a preset threshold for the ratio with the calculated value.

6. The method according to claim 4, wherein the third information notified in (e) includes an estimated value of the selection rate, and the estimated value is calculated based on the calculated value and a predetermined information relating the ratio and the selection rate.

7. The method according to any one of claims 1 to 6, wherein (a), (b), (c), and (d) are performed repeatedly.

8. An apparatus for producing hydrocarbons by the Fischer-Tropsch process, comprising: a reactor; a gas supply unit for supplying raw material gas to the reactor; analytical means for analyzing the product gas discharged from the reactor; and a control unit, wherein the control unit is configured to perform control including: (a) reacting raw material gas in the presence of a catalyst to obtain a product gas; (b) subjecting the product gas to analysis to obtain first information regarding the quantitative results of at least one light hydrocarbon selected from the group consisting of ethane and ethylene, propane and propylene, and butane and butene in the product gas; (c) calculating at least one ratio selected from the group consisting of ethylene / ethane ratio, propylene / propane ratio and butene / butane ratio based on the first information to obtain second information regarding the calculated value of said ratio; and (d) obtaining third information regarding the selectivity of hydrocarbons having 5 or more carbon atoms based on the second information.

9. The apparatus according to claim 8, wherein the control unit further comprises a notification unit for notifying the third information.

10. A program that causes the computer of an apparatus for producing hydrocarbons by the Fischer-Tropsch process to perform the following: (a) reacting a raw material gas in the presence of a catalyst to obtain a product gas; (b) subjecting the product gas to analysis to obtain first information regarding the quantitative results of at least one light hydrocarbon selected from the group consisting of ethane and ethylene, propane and propylene, and butane and butene in the product gas; (c) calculating at least one ratio selected from the group consisting of ethylene / ethane ratio, propylene / propane ratio and butene / butane ratio based on the first information to obtain second information regarding the calculated value of said ratio; and (d) obtaining third information regarding the selectivity of hydrocarbons having 5 or more carbon atoms based on the second information.

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