Hydrocarbon manufacturing method and slurry bed reactor

Abstract

Provided is a method for producing a hydrocarbon by using a Fischer-Tropsch process, said method involving: (a) in a slurry bed reactor comprising a reactor body and a stirring means that is disposed inside of the reactor body and that has a shaft part and a stirring blade connected to the shaft part, bringing a slurry containing a catalyst and an organic solvent into contact with a starting material gas supplied from the side part or bottom part of the reactor body; and (b) stirring the slurry by using the stirring means.

Description

Method for producing hydrocarbons and slurry bed reactor 【0001】 The present invention relates to a method for producing hydrocarbons and a slurry bed reactor. 【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." 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. The catalyst described in Patent Document 1 is used in liquid-phase reactions in a slurry bed and is said to have high stability and a long lifespan. 【0004】 Patent No. 6920952 【0005】 In the production of hydrocarbons by the FT method, assuming the use of a slurry bed reactor, there is room for further improvement in reaction efficiency in conventional technology. 【0006】 In view of the above, the present invention provides a technology to improve reaction efficiency in the production of hydrocarbons by the FT method. 【0007】In other words, the present invention encompasses the following embodiments: [1] A method for producing hydrocarbons by the Fischer-Tropsch process, comprising: (a) bringing a slurry containing a catalyst and an organic solvent into contact with a raw material gas supplied from the side or bottom of the reactor body in a slurry bed reactor comprising a reactor body and a stirring means disposed inside the reactor body and comprising a shaft and a stirring blade connected to the shaft; and (b) stirring the slurry with the stirring means. [2] The method according to [1], wherein the ratio of the specific gravity of the catalyst to the specific gravity of the organic solvent is 1.1 or more and 15 or less as the specific gravity of the catalyst / specific gravity of the organic solvent. [3] The method according to [1] or [2], wherein at least one of (a) and (b) is controlled to control the pressure inside the slurry bed reactor to more than 0 MPa and less than 2.0 MPa. [4] The method according to any one of [1] to [3], wherein the concentration of the catalyst in the slurry is 2.5% or more and 40% or less as the ratio of the mass of the catalyst to the volume of the slurry. [5] The method according to any one of [1] to [4], wherein the catalyst comprises at least one catalyst metal selected from the group consisting of cobalt, nickel, ruthenium and iron, and a carrier supporting the catalyst metal, and the amount of catalyst supported is 5% or more and 30% or less as the mass ratio of the catalyst metal to the catalyst. [6] The method according to [5], wherein the carrier comprises silica. [7] The method according to [5] or [6], wherein the amount of catalyst supported is 10% or more and 25% or less. [8] The method according to any one of [1] to [7], wherein at least one of (a) and (b) is controlled to control the ratio of the liquid level height LH of the slurry to the inner diameter Dc of the slurry bed reactor as LH / Dc to 1.5 to 300. [9] The method according to any one of [1] to [8], wherein (b) is controlled to control the stirring speed of the stirring means to 5 rpm or more and 8000 rpm or less.

[10] The method according to any one of [1] to [9], wherein at least one of (a) and (b) is controlled to control the temperature in the slurry bed reactor to 100°C or more and 300°C or less.

[11] The method according to any one of [1] to

[10] , wherein (a) and (b) are performed simultaneously.

[12] A slurry bed reactor for producing hydrocarbons by the Fischer-Tropsch process, comprising: a reactor body; a gas supply unit configured to bring a slurry containing a catalyst and an organic solvent into contact with the raw material gas by supplying a raw material gas from the side or bottom of the reactor body; and a stirring means disposed inside the reactor body and comprising a shaft and a stirring blade connected to the shaft.

[13] The slurry bed reactor according to

[12] , further comprising a control unit for controlling the gas supply unit and the stirring means, wherein the control unit is configured to perform control including: (a) bringing the slurry into contact with the raw material gas supplied from the side or bottom within the slurry bed reactor; and (b) stirring the slurry with the stirring means. 【0008】 According to the present invention, a technique for improving reaction efficiency in the production of hydrocarbons by the FT method can be provided. 【0009】 Figure 1 is a schematic diagram illustrating an example of the configuration of a slurry bed reactor. Figure 2 is a flowchart showing an example of a hydrocarbon production method that can be carried out in a slurry bed reactor. 【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】<Slurry Bed Reactor> The slurry bed reactor of this embodiment is a slurry bed reactor for producing hydrocarbons by the Fischer-Tropsch process, and comprises a reactor body, a gas supply unit configured to bring a slurry containing a catalyst and an organic solvent into contact with the raw material gas by supplying the raw material gas from the side or bottom of the reactor body, and a stirring means disposed inside the reactor body and comprising a shaft and a stirring blade connected to the shaft. Because the slurry bed reactor of this embodiment is configured as described above, the reaction efficiency can be improved in the production of hydrocarbons by the FT process. 【0012】 Figure 1 is a schematic diagram illustrating an example of the configuration of a slurry bed reactor. In the example in Figure 1, the slurry bed reactor 100 comprises a reactor body 10, a stirring means 20, a gas supply unit 30, and a control unit 40. The following describes examples of each of these configurations. 【0013】 (Reactor body) The reactor body 10 can be appropriately designed to serve as the reaction field for the FT reaction. For example, the reactor body 10 can be a heat-resistant and pressure-resistant container configured to withstand the reaction conditions of the FT reaction. The capacity of the reactor body 10 is not particularly limited, but may be, for example, 1000 L or less. 【0014】 The FT reaction that can proceed within the reactor body 10 is a gas-liquid catalytic reaction. In this embodiment, the raw material gas SG usually has a lower specific gravity than the slurry SL, and when blown into the slurry SL, it moves upward within the slurry SL. In this way, as the raw material gas SG passes through the slurry SL in the reactor body 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, the reactor body 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】Figure 1 shows an example in which slurry SL is introduced into the reactor body 10 up to the slurry liquid level height LH. In this embodiment, "slurry liquid level height LH" corresponds to a value that serves as a guideline for the liquid level height of slurry SL during the operation of the slurry bed reactor 100 (during the FT reaction). In particular, during the operation of the slurry bed reactor 100, the liquid level height of slurry SL may fluctuate over time. Therefore, the actual liquid level height of slurry SL does not necessarily coincide with the slurry liquid level height LH, and may be higher or lower than the slurry liquid level height LH. The slurry liquid level height LH may be input in advance to the control unit 40, which will be described later, and managed as a reference value for the liquid level height of slurry SL during the operation of the slurry bed reactor 100 (during the FT reaction). 【0016】 The reactor body 10 may be configured to allow slurry SL to be introduced into it from the outside. The reactor body 10 may also be configured to allow slurry SL inside to be discharged to the outside. The introduction of slurry SL into the reactor body 10 and the discharge of slurry SL from the reactor body 10 may be carried out via piping (not shown). The piping for introducing slurry SL into the reactor body 10 may be formed, for example, in the top, side, or bottom of the reactor body 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 organic solvent SV are mixed inside the reactor body 10 to prepare slurry SL. 【0017】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 body 10 through the product liquid outlet pipe 10a. The product liquid discharged to the outside of the reactor body 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 body 10, and its height may be determined based on the slurry liquid level height LH. The product liquid outlet pipe 10a may be formed, for example, on the side of the reactor body 10 at a position between "slurry liquid level height LH × 1 / 2" and "slurry liquid level height LH". The slurry SL near the product liquid outlet pipe 10a may be discharged to the outside of the reactor body 10 together with the product liquid via the product liquid outlet pipe 10a. The slurry SL discharged outside the reactor body 10 can be separated from the product liquid by the purification means described above and reused in the FT reaction as appropriate. 【0018】 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 body 10 through a product gas outlet pipe 10b formed at the top of the reactor body 10. The product gas discharged to the outside of the reactor body 10 may be purified by a purification means (not shown). The raw material gas SG supplied from the side or bottom of the reactor body 10 may, for example, rise through the slurry SL inside the reactor body 10 and move to the gas phase portion inside the reactor body 10. The raw material gas SG that has moved to the gas phase portion may be discharged to the outside of the reactor body 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 body 10 can be separated from the product gas by the purification means described above and reused in the FT reaction as appropriate. 【0019】In the FT reaction, the raw material gas SG, which is the raw material for synthesis, is supplied from the side or bottom of the reactor body 10 by the gas supply unit 30, 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 body 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 contact efficiently. However, when the raw material gas SG is supplied from the side of the reactor body 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. Considering this dead space, and from the viewpoint of further increasing the distance for the raw material gas SG to move within the slurry SL, it is preferable that the reactor body 10 is configured so that the raw material gas SG is supplied from the bottom of the reactor body 10. As an example, as shown in Figure 1, it is preferable that the raw material gas supply pipe 10c is formed at the bottom of the reactor body 10. 【0020】 When the raw material gas SG is supplied from the side of the reactor body 10, the raw material gas supply pipe 10c may be formed on the side of the reactor body 10, and its height may be determined based on the slurry liquid level height LH. For example, the raw material gas supply pipe 10c may be formed on the side of the reactor body 10 at a position between "slurry liquid level height LH × 1 / 2" and "slurry liquid level height LH". 【0021】(Agitation means) The agitation means 20 is located inside the reactor body 10. The agitation means 20 is configured to agitate the slurry SL and raw material gas SG supplied into the reactor body 10. The agitation means 20 comprises a shaft portion 20a and a stirring blade 20b connected to the shaft portion 20a. When the slurry SL and raw material gas SG supplied into the reactor body 10 are agitated by the agitation means 20, the opportunity for contact between the slurry SL and the raw material gas SG increases, which can improve the reaction efficiency. The shaft portion 20a may be connected to a motor (not shown) and may be configured to rotate when driven by the motor. The stirring blade 20b may be configured to agitate the slurry SL and raw material gas SG by rotating in conjunction with the rotation of the shaft portion 20a. As a slurry agitation means in the FT reaction, for example, the use of a magnetic stirrer may be considered, but in this case, not only is the agitation position limited to one place, but sufficient agitation power may not be obtained, and as a result, catalyst precipitation is likely to occur in the slurry. When catalyst precipitation occurs, the opportunity for contact between the catalyst and the raw material gas decreases, and the reaction efficiency tends to decline. In contrast, the stirring means 20, having the above-described configuration, makes it easy to adjust the position (stirring position) of the stirring blades 20b within the reactor body 10 and also makes it easy to secure stirring power. Therefore, the stirring means 20 can suppress the precipitation of catalyst CT in the slurry SL. As a result of suppressing the precipitation of catalyst CT, sufficient opportunity for contact between catalyst CT and raw material gas SG can be secured, and the reaction efficiency tends to improve. The stirring position of the slurry SL by the stirring blades 20b is not particularly limited and can be adjusted to any part below the slurry liquid level LH ​​within the reactor body 10. The stirring position can be adjusted, for example, by moving the stirring blades 20b in the vertical direction of the paper by driving the shaft portion 20a. The position (stirring position) of the stirring blades 20b may be changed as appropriate during the operation of the slurry bed reactor 100 (while the FT reaction is in progress), or it may be fixed in one place. Furthermore, the position of the stirring blade, as a height from the bottom of the reactor body 10, is preferably set at a height of 0.1 to 4.5 times the diameter or lateral length of the stirring blade, and more preferably at 0.5 to 2.5 times. In Figure 1, an example of a paddle blade is shown as the stirring blade 20b, but the type of stirring blade is not limited to this.Examples of types of stirring blades include propeller blades, turbine blades, paddle blades, anchor blades, and ribbon blades. The shape and number of blades of the stirring blades can be appropriately selected depending on the type and purpose of the slurry liquid used. Furthermore, multiple stages of stirring blades may be installed on a single shaft 20a, and the number of stages and the position of each stage can be set as appropriate. 【0022】 (Gas supply unit) The gas supply unit 30 supplies the raw material gas SG to the reactor body 10. The gas supply unit 30 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 body 10 when the FT reaction is being carried out. As shown in Figure 1, the gas supply unit 30 may be connected to the reactor body 10 via the raw material gas supply pipe 10c. The gas supply unit 30 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. 【0023】 (Control Unit) The control unit 40 may be configured to control each component of the slurry bed reactor 100 to carry out the FT reaction. The control unit 40 may, for example, control the reactor body 10, the stirring means 20, and the gas supply unit 30. As shown in Figure 1, the control unit 40 may be configured separately from the reactor body 10, the stirring means 20, and the gas supply unit 30, or it may be incorporated into at least one of the reactor body 10, the stirring means 20, and the gas supply unit 30. Control by the control unit 40 may include adjusting the stirring speed of the stirring means 20, the position of the stirring blades 20b, the temperature inside the reactor body, the pressure, the amount of slurry liquid (slurry liquid level), the catalyst concentration in the slurry, and / or the amount of raw material gas SG supplied. 【0024】 (Other configurations) The slurry bed reactor 100 may be equipped with heat exchange means (not shown) for maintaining the temperature inside the reactor body 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 body 10. As an 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. 【0025】The slurry bed reactor 100 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 tiny bubbles in the slurry SL and disperse more uniformly within the reactor body 10. The more uniformly the raw material gas SG is dispersed within the reactor body 10, the more opportunities there are for contact between the raw material gas SG and the catalyst CT, which can improve the reaction efficiency. 【0026】 <Method for Producing Hydrocarbons> The method for producing hydrocarbons according to this embodiment (hereinafter also referred to as "the method of this embodiment") is a method for producing hydrocarbons by the Fischer-Tropsch process, and includes (a) bringing a slurry containing a catalyst and an organic solvent into contact with the raw material gas supplied from the side or bottom of the reactor body in a slurry bed reactor comprising a reactor body and a stirring means disposed inside the reactor body and comprising a shaft and a stirring blade connected to the shaft, and (b) stirring the slurry with the stirring means. Because the method of this embodiment is configured as described above, the reaction efficiency can be improved in the production of hydrocarbons by the FT method. 【0027】 Figure 2 is a flowchart showing an example of the method according to this embodiment. As shown in Figure 2, the method includes steps S1 of supplying slurry to a reactor, step S2 of supplying raw material gas to the reactor, and step S3 of stirring the slurry with a stirring means. Step (a) above may include steps S1 and S2. Step (b) above may include step S3. Steps S1, S2 and S3 may be performed in this order, and at least two of these steps may be performed simultaneously. Steps S1, S2 and S3 may also be performed repeatedly. For example, when starting up a slurry bed reactor, steps S1, S2 and S3 may be performed in this order, and when each step is then repeated, steps S1, S2 and S3 are not limited to this order and may be repeated in any order, and at least two of these steps may be performed simultaneously. 【0028】The method of this embodiment may be carried out using the slurry bed reactor 100 illustrated in Figure 1, or it may be carried out using other equipment. In the following, the case in which the method of this embodiment is carried out using the slurry bed reactor 100 will be described as an example. That is, the control unit 40 in the slurry bed reactor 100 controls the reactor body 10, the stirring means 20, and the gas supply unit 30 to carry out the method of this embodiment. 【0029】 (Step S1) In step S1, slurry SL is supplied to the slurry bed reactor 100. In this embodiment, slurry SL can be supplied into the reactor body 10 from a slurry supply pipe (not shown). As shown in Figure 1, slurry SL contains an organic solvent SV and a catalyst CT. 【0030】 The organic solvent SV serves as a medium for suspending the catalyst CT and introducing it into the reactor body for the gas-liquid catalytic reaction. 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. Among these, liquid hydrocarbons having 15 or more carbon atoms with a volatilization temperature of 200°C or higher are preferred, and pentadecane, hexadecane, heptadecane, and octadecane are more preferred. 【0031】 The catalyst CT comprises a catalyst metal MT and a carrier SP supporting the catalyst metal MT. The catalyst metal MT may contain at least one selected from the group consisting of cobalt, nickel, ruthenium, and iron. From the viewpoint of obtaining middle distillates such as diesel fuel, jet fuel, and kerosene, it is preferable that the catalyst metal MT contains cobalt. The carrier SP is silica (SiO ２ ), alumina (Al ２ O ３The catalyst may further contain at least one selected from the group consisting of ) and zeolite (aluminosilicate). From the viewpoint of exhibiting performance derived from the catalyst metal MT and from the viewpoint of contact efficiency with the raw material gas, the carrier SP preferably contains silica. The catalyst CT may further contain at least one selected from the group consisting of rare earth elements yttrium, cerium, lanthanum, praseodymium, neodymium and holmium, at least one selected from the group consisting of alkali metals sodium, potassium, rubidium and cesium, at least one selected from the group consisting of alkaline earth metals beryllium, magnesium, calcium, strontium and barium, and copper, etc. 【0032】 The amount of material supported in the catalyst CT is expressed as the mass ratio of the catalyst metal to the catalyst and may be adjusted as appropriate. In this embodiment, the amount of material supported may be 5% or more and 30% or less. When the amount of material supported is 5% or more, the carbon monoxide conversion rate tends to improve. When the amount of material supported is 30% or less, the chain growth rate tends to improve. From the above viewpoint, the amount of material supported may be 10% or more and 25% or less. 【0033】 The shape of the catalyst CT is not particularly limited and may be, for example, in powder form. 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 measured by laser diffraction. 【0034】 The ratio of the specific gravity of the catalyst CT to the specific gravity of the organic solvent SV is expressed as the specific gravity of the catalyst / the specific gravity of the organic solvent, and may be adjusted as appropriate. In this embodiment, the specific gravity may be between 1.1 and 15. When the specific gravity is 1.1 or higher, the catalyst CT tends to precipitate more easily in the slurry SL, and as a result, the effect of stirring by the stirring means 20 tends to become more apparent. When the specific gravity is 15 or lower, it is possible to prevent the catalyst CT from precipitation excessively in the slurry SL, and as a result, the control load caused by stirring by the stirring means 20 tends to be reduced. 【0035】The concentration of the 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 the present embodiment, the ratio may be 2.5% or more and 40% or less. When the ratio is 2.5% or more, the conversion rate of carbon monoxide and the chain growth rate tend to improve. When the ratio is 40% or less, it is possible to prevent the catalyst CT from being overly likely to precipitate in the slurry SL, and as a result, the control load due to the agitation of the agitation means 20 tends to be reduced. 【0036】 (Step S2) In step S2, the raw material gas SG is supplied to the slurry bed reactor 100. In the present embodiment, the raw material gas SG can be supplied into the reactor main body 10 from the gas supply unit 30. When the raw material gas SG is supplied into the reactor main body 10, the FT reaction proceeds by the contact of the catalyst CT contained in the slurry SL in the reactor main body 10 and the raw material gas SG. 【0037】 The raw material gas SG may be a mixed gas of hydrogen (H ２ ) and carbon monoxide (CO). The raw material gas SG in the present embodiment may further contain carbon dioxide (CO ２ ). From the viewpoint that the rate of the FT reaction depends on the hydrogen partial pressure, the partial pressure ratio (molar ratio) of hydrogen to the total of carbon monoxide and carbon dioxide in the raw material gas SG may be 0.6 to 2.7, may be 0.8 to 2.5, and may be 1 to 2.3. The ratio of carbon monoxide and carbon dioxide in the raw material gas SG may also be adjusted as appropriate. For example, from the viewpoint of carbon recycling, it is preferable to increase the ratio of carbon dioxide, and from the viewpoint of increasing the conversion rate to hydrocarbons, it is preferable to increase the ratio of carbon monoxide. In the present embodiment, the ratio of carbon dioxide to carbon monoxide may be 1 volume% or more, may be 10 volume% or more, may be 30 volume% or more, and may be 40 volume% or more as the proportion of carbon dioxide to the total amount of carbon monoxide and carbon dioxide. As other components in the raw material gas SG, for example, sulfur content, organic nitrogen content, phosphorus content, etc. may be contained. The content of the above other components may be 20 volume% or less with respect to 100 volume% of the raw material gas SG. 【0038】The feed gas SG may contact the catalyst CT in the slurry SL, and as the FT reaction proceeds, a product liquid may be produced. The product liquid is a hydrocarbon having a relatively high boiling point and a relatively large number of carbon atoms among the hydrocarbons produced by the FT reaction, and may be, for example, an intermediate fraction such as a heavy naphtha fraction (crude gasoline), kerosene, or gas oil. 【0039】 The feed gas SG may contact the catalyst CT in the slurry SL, and as the FT reaction proceeds, a product gas may be produced. The product gas is a hydrocarbon having a relatively low boiling point and a relatively small number of carbon atoms among the hydrocarbons produced by the FT reaction, and may be, for example, a hydrocarbon having 1 to 4 carbon atoms. Specific examples of such hydrocarbons include methane, ethane, ethylene, propane, propylene, butane, butene, and the like. 【0040】 (Step S3) In step S3, the slurry SL is stirred by the stirring means 20. Stirring of the slurry SL by the stirring means 20 may include stirring only the slurry SL, or may include stirring a gas-liquid mixing system of the slurry SL and the feed gas SG. 【0041】 The stirring speed of the stirring means 20 is not particularly limited and can be appropriately adjusted in consideration of the ratio of the specific gravity of the catalyst CT to the specific gravity of the organic solvent SV, the slurry viscosity, and the like. In the present embodiment, step S3 may include controlling the stirring speed of the stirring means 20 to be 5 rpm or more and 8000 rpm or less. When the stirring speed is 5 rpm or more, the dispersibility of the catalyst CT in the slurry SL tends to improve. When the stirring speed is 8000 rpm or less, structural changes of the catalyst due to collisions between the catalyst CTs, collisions between the catalyst CT and the inner wall of the reactor body 10 and the catalyst CT, etc. tend to be suppressed, and a high reaction efficiency can tend to be maintained over a longer period. 【0042】 (Other conditions) At least one of step S1, step S2, and step S3 may include controlling the ratio of the slurry liquid level height LH to the inner diameter Dc of the slurry bed reactor, expressed as LH / Dc, to be 1.5 to 300. 【0043】At least one of steps S1, S2, and S3 may include controlling the temperature inside the slurry bed reactor 100 to 100°C or more and 300°C or less. That is, at least one of steps S1, S2, and S3 may include controlling the temperature inside the reactor body 10 to 100°C or more and 300°C or less. 【0044】 At least one of steps S1, S2, and S3 may include controlling the pressure inside the slurry bed reactor 100 to more than 0 MPa and less than 2.0 MPa. That is, at least one of steps S1, S2, and S3 may include controlling the pressure inside the reactor body 10 to more than 0 MPa and less than 2.0 MPa. In this embodiment, pressure fluctuations may increase due to the fact that the slurry bed reactor 100 is equipped with a stirring means 20 and / or due to the operation of the stirring means 20 inside the reactor body 10. When the above pressure is controlled to less than 2.0 MPa, the effects of pressure fluctuations are suppressed, and it tends to be possible to maintain high reaction efficiency over a long period of time. From the above viewpoint, the above pressure may be more than 0 MPa and less than 1.5 MPa. When the above pressure is controlled to less than 1.5 MPa, the effects of pressure fluctuations are suppressed even more, and it tends to be possible to maintain high reaction efficiency over an even longer period of time. Also, the above pressure may be more than 0 MPa and less than 1.0 MPa. When the above pressure is controlled to less than 1.5 MPa, the effects of pressure fluctuations are further suppressed, and it tends to be possible to maintain high reaction efficiency over a longer period of time. 【0045】 <Examples> The embodiment will be described in more detail below based on examples. This embodiment is not limited to these examples. 【0046】 [Comparative Example 1] (Reactor) Using a reactor having the same configuration as the slurry bed reactor 100 shown in Figure 1, except that it does not have a stirring means 20, hydrocarbons were produced by the FT method as follows. 【0047】(Slurry Preparation) Silica gel (Merck: Silica Gel 60, 70 - 230 mesh) was placed in a magnetic dish and heated at 120°C for 30 minutes using a muffler furnace to dehydrate it. Then, it was calcined at 500°C for 3 hours to obtain a silica support precursor. Next, cobalt nitrate hexahydrate was transferred to a beaker and dissolved in pure water to obtain an active metal impregnation solution. After calcination, the above-mentioned silica gel cooled to room temperature was transferred to an eggplant flask, and the active metal impregnation solution was added to obtain a catalyst slurry. Using a rotary evaporator, while maintaining the pressure at 30 mmHg (4 kPa), the moisture was removed at 50°C for 1 hour to obtain a light pink powder. This was transferred to a quartz furnace core tube and heated at 270°C for 10 minutes while passing air at 100 - 200 mL / min (stp), and then the temperature was raised to 500°C and calcined for 3 hours. The obtained catalyst precursor (Co ３ O ４ / SiO ２ ) was transferred to a sample bottle and stored at room temperature under air. Next, the above-mentioned catalyst precursor (Co ３ O ４ / SiO ２ ) was filled into a slurry bed reactor 100. While passing Ar at a set flow rate of 40 mL / min, the temperature was raised to 150°C, then the feed gas was switched to hydrogen and passed at a set flow rate of 50 mL / min, and the temperature was raised to 450°C and reduced for 1 hour. As described above, a catalyst in which cobalt was supported on a silica support was prepared. In this catalyst, the mass ratio of the silica support (specific gravity 1.8) to cobalt (specific gravity 8.9) was 4:1, and the catalyst loading was 20% by mass. Also, the specific gravity as a catalyst was 3.2. For the measurement of the catalyst metal loading, SEM-EDS was used. As the organic solvent, hexadecane (specific gravity 0.77) was used, and it was mixed with the catalyst so that the catalyst concentration was 20% (catalyst mass / slurry volume) to prepare a slurry. 【0048】(Synthesis Reaction) First, the slurry described above was supplied into the reactor body (inner diameter Dc = 10 cm). The supply rate was adjusted so that the slurry level LH ​​in the reactor body was 30 cm. Next, the supply of raw material gas was started, thereby initiating the hydrocarbon synthesis reaction. The raw material gas was a mixed gas containing hydrogen gas and carbon monoxide gas in a molar ratio of 2:1, supplied from the bottom of the reactor body 10. The reaction temperature was set to 230°C and the pressure to 0.9 MPa. The reaction time was set to 10 hours, which is the time from reaching the reaction temperature until the temperature was reduced. During this time, the product liquid was withdrawn from the product liquid outlet pipe, and the product gas was withdrawn from the product gas outlet pipe. 【0049】 (Reaction Results) After the reaction was completed, the reaction results were evaluated as follows: H ２ CO, CH ４ and CO ２ For the analysis, a gas chromatograph TCD-GC (GC323, GL Sciences) with a thermal conductivity detector was used. For the analysis of hydrocarbons with 1 to 6 carbon atoms, a gas chromatograph with a flame ionization detector was used. Argon was used as the carrier gas. For hydrocarbons with 6 or more carbon atoms, the supernatant of the standing slurry was collected for analysis. A separation column was attached to measure the distribution of the generated oil. From the above analysis results, the CO conversion rate was calculated using the following formula. 【0050】 【0051】 Specifically, the carbon monoxide conversion rate (CO conversion rate) and chain growth rate α (chain growth probability α) were calculated based on the flow rate of the raw material gas, the flow rates of the generated gas and liquid, and the results of analysis by gas chromatography. The chain growth rate α was calculated using the formula α = Kp / (Kp + Kd). Here, Kp and Kd were the rate constants for the chain termination reaction and the chain growth reaction, respectively. The above calculations can be performed by referring to "Organic Synthesis Chemistry," Vol. 41, No. 6 (1983), pp. 532-566, edited by the Society of Synthetic Organic Chemistry, Japan. The CO conversion rate and chain growth rate of Comparative Example 1 were 12% and 0.21, respectively. 【0052】[Example 1] Using a slurry bed reactor having a configuration similar to the slurry bed reactor shown in Figure 1, hydrocarbons were produced by the FT method as follows. Specifically, a slurry bed reactor equipped with a stirring mechanism inside the reactor body (inner diameter 10 cm) was used. This stirring mechanism had a configuration in which a stirring blade was connected to the shaft, and the size of the stirring blade was 3 cm wide x 1 cm long. The stirring blade was also adjusted to be fixed at a height of 1.5 cm from the bottom of the reactor body. 【0053】 (Slurry Preparation) As a catalyst, a catalyst was prepared in which cobalt was supported on a silica support. In this catalyst, the amount of cobalt supported on the silica support (specific gravity 1.8) and the amount of cobalt (specific gravity 8.9) was 20% by mass. The specific gravity of the catalyst was 3.2. Hexadecane (specific gravity 0.77) was used as the organic solvent, and the catalyst was mixed with it to prepare a slurry at a catalyst concentration of 20% (mass / volume). 【0054】 (Synthesis Reaction) First, the slurry was supplied into the reactor body (inner diameter Dc = 10 cm). The supply amount was adjusted so that the slurry level LH ​​in the reactor body was 30 cm. Next, stirring of the slurry was started by setting the stirring speed of the stirring means to 5 rpm. After that, the supply of raw material gas was started, thereby initiating the synthesis reaction. As raw material gas, a mixed gas containing hydrogen gas and carbon monoxide gas in a molar ratio of 2:1 was supplied from the bottom of the reactor body 10. The reaction temperature was set to 230°C and the pressure to 0.9 MPa. The reaction time was set to 10 hours, during which time the product liquid was withdrawn from the product liquid outlet pipe and the product gas was withdrawn from the product gas outlet pipe. The slurry was stirred until the end of the reaction. 【0055】 (Reaction Results) After the reaction was completed, the reaction results were evaluated in the same manner as in Comparative Example 1. The CO conversion rate and chain growth rate of Example 1 were 35% and 0.43, respectively. 【0056】 [Examples 2-4] As shown in Table 1 below, the synthesis reaction was carried out in the same manner as in Example 1, except that the stirring speed was changed, and the reaction results were evaluated. The results are also shown in Table 1. 【0057】 【0058】 [Examples 5-16] As shown in Table 2 below, the synthesis reaction was carried out in the same manner as in Example 1, except that the amount of catalyst supported, reaction pressure, and / or catalyst concentration were changed, and the reaction performance was evaluated. The results are also shown in Table 2. 【0059】 【0060】 100...Slurry bed reactor, 10...Reactor body, 10a...Product liquid outlet pipe, 10b...Product gas outlet pipe, 10c...Raw material gas supply pipe, LH...Slurry liquid level height, Dc...Inner diameter, SG...Raw material gas, SL...Slurry, SV...Organic solvent, CT...Catalyst, MT...Catalyst metal, SP...Carrier, 20...Agitation means, 20a...Shaft section, 20b...Agitation blade (propeller blade), 30...Gas supply section, 40...Control section

Claims

1. A method for producing hydrocarbons by the Fischer-Tropsch process, comprising: (a) bringing a slurry containing a catalyst and an organic solvent into contact with a raw material gas supplied from the side or bottom of the reactor body in a slurry bed reactor comprising a reactor body and a stirring means disposed inside the reactor body and comprising a shaft and a stirring blade connected to the shaft; and (b) stirring the slurry with the stirring means.

2. The method according to claim 1, wherein the ratio of the specific gravity of the catalyst to the specific gravity of the organic solvent is 1.1 or more and 15 or less as the specific gravity of the catalyst / specific gravity of the organic solvent.

3. The method according to claim 1, wherein at least one of (a) and (b) includes controlling the pressure in the slurry bed reactor to more than 0 MPa and less than 2.0 MPa.

4. The method according to claim 1, wherein the concentration of the catalyst in the slurry is 2.5% or more and 40% or less as the ratio of the mass of the catalyst to the volume of the slurry.

5. The method according to claim 1, wherein the catalyst comprises at least one catalyst metal selected from the group consisting of cobalt, nickel, ruthenium, and iron, and a carrier supporting the catalyst metal, wherein the amount of catalyst supported is 5% or more and 30% or less as a mass ratio of the catalyst metal to the catalyst.

6. The method according to claim 5, wherein the carrier contains silica.

7. The method according to claim 5, wherein the amount of material carried is 10% or more and 25% or less.

8. The method according to claim 1, wherein at least one of (a) and (b) is controlled to control the ratio of the liquid level height LH of the slurry to the inner diameter Dc of the slurry bed reactor as LH / Dc to 1.5 to 300.

9. The method according to claim 1, wherein (b) comprises controlling the stirring speed of the stirring means to 5 rpm or more and 8000 rpm or less.

10. The method according to claim 1, wherein at least one of (a) and (b) is to control the temperature in the slurry bed reactor to 100°C or more and 300°C or less.

11. The method according to claim 1, wherein (a) and (b) are performed simultaneously.

12. A slurry bed reactor for producing hydrocarbons by the Fischer-Tropsch process, comprising: a reactor body; a gas supply unit configured to bring a slurry containing a catalyst and an organic solvent into contact with the raw material gas by supplying a raw material gas from the side or bottom of the reactor body; and a stirring means disposed inside the reactor body and comprising a shaft and a stirring blade connected to the shaft.

13. The slurry bed reactor according to claim 12, further comprising a control unit for controlling the gas supply unit and the stirring means, wherein the control unit is configured to perform control including: (a) bringing the slurry and the raw material gas supplied from the side or the bottom within the slurry bed reactor; and (b) stirring the slurry with the stirring means.

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