Carbon monoxide conversion rate calculation method, carbon monoxide conversion rate calculation device, and hydrocarbon production device

Abstract

One problem to be addressed by the present invention is to provide a technology relating to: a carbon monoxide conversion rate calculation method that enables easier and quicker determination of the carbon monoxide conversion rate in a catalytic reaction using carbon monoxide and hydrogen as raw materials; and a calculation device therefor.　For solving said problem, provided are: a carbon monoxide conversion rate calculation method including a catalytic reaction step for performing a catalytic reaction using carbon monoxide and hydrogen as raw materials and a calculation step for calculating the carbon monoxide conversion rate on the basis of the proportion of α-olefins in olefins generated in the catalytic reaction step or the cis / trans ratio in the olefins; and a calculation device for implementing said calculation method.　The present invention replaces, in CO conversion rate calculation, measurement of the amount of moles of CO in gases (raw material gas and outlet gas) per unit time with measurement relating to the ratio of components in a generated hydrocarbon mixture. As a result, the CO conversion rate can be easily and quickly calculated.

Description

Carbon monoxide conversion rate calculation method, carbon monoxide conversion rate calculation device, and hydrocarbon production device

[0001] The present invention relates to a carbon monoxide conversion calculation method and device, and a hydrocarbon production apparatus. More specifically, the present invention relates to a carbon monoxide conversion calculation method and device that simply and quickly determine the carbon monoxide conversion involved in a catalytic reaction using carbon monoxide and hydrogen as raw materials. The present invention also relates to a hydrocarbon production apparatus equipped with this carbon monoxide conversion calculation device.

[0002] In the production and manufacture of various carbon-containing compounds (particularly hydrocarbons), a catalytic reaction is known in which a mixed gas of carbon monoxide and hydrogen is reacted in the presence of a catalyst. One specific example of this catalytic reaction is the Fischer-Tropsch synthesis reaction (hereinafter also referred to as the "FT synthesis reaction" or "FT reaction"). The FT synthesis reaction is a reaction in which a mixed gas of carbon monoxide and hydrogen is reacted in the presence of a catalyst to produce a hydrocarbon mixture (olefins).

[0003] In catalytic reactions using carbon monoxide as a feedstock, such as the FT synthesis reaction, carbon monoxide conversion (hereinafter also referred to as "CO conversion") is used as one of the parameters for obtaining information related to the progress and efficiency of the reaction and the activity of the catalyst used. For example, Patent Document 1 describes that in a method for producing hydrocarbons by the FT synthesis reaction, the CO conversion is determined from the number of moles of CO in the feedstock gas per unit time and the number of moles of CO in the outlet gas per unit time.

[0004] Japanese Patent Application Laid-Open No. 2002-069007

[0005]

[0005] Here, as described in Patent Document 1, in order to calculate the CO conversion rate, it is necessary to measure the number of moles of CO in the feed gas per unit time and the number of moles of CO in the outlet gas per unit time. However, the operations related to each measurement are complicated in practice. In particular, when determining the number of moles of CO in the outlet gas per unit time, not only are there many steps related to the operation, but the time required for sampling and the time required for analysis are long, and this may exceed the time interval between samplings for monitoring. For this reason, there is a problem in that it is difficult to use information related to the calculated CO conversion rate as a parameter for understanding the status of the catalytic reaction (FT synthesis reaction) in real time.

[0006] Furthermore, among the hydrocarbons obtained by the FT synthesis reaction, saturated hydrocarbons with a carbon number of approximately 8 to 16 have traditionally been used as kerosene and diesel. In recent years, however, attention has been focused on their use as jet fuel known as SAF (Sustainable Aviation Fuel) from the perspective of reducing carbon dioxide emissions. Thus, SAF has become an important middle distillate alongside kerosene and diesel. Under these circumstances, in order to advance technological development related to SAF, which is expected to contribute to the realization of a carbon-neutral society, it is necessary to perform fuel synthesis adjacent to facilities for supplying the raw materials, carbon monoxide (including carbon dioxide) and hydrogen (e.g., carbon dioxide capture facilities, hydrogen electrolysis equipment, etc.), and there is an urgent need to develop new technologies that can eliminate or simplify the associated equipment. In other words, in order to produce SAF on-site, there is a demand for a technology that reduces the facilities and equipment that make up the plant and allows SAF to be obtained more easily, as well as a technology that allows for the rapid acquisition of CO conversion, which is information related to the catalytic reaction.

[0007] An object of the present invention is to provide a technology relating to a carbon monoxide conversion calculation method and a calculation device therefor, which can more simply and quickly determine the carbon monoxide conversion in a catalytic reaction using carbon monoxide and hydrogen as raw materials.In addition, an object of the present invention is to provide a technology relating to a hydrocarbon production apparatus, which uses the carbon monoxide conversion calculation device to reduce the facilities and equipment that make up a plant and can quickly obtain information related to the efficiency of hydrocarbon production (carbon monoxide conversion).

[0008] As a result of intensive research into the above-mentioned problems, the present inventors have found that the ratio of specific components in a product (hydrocarbon mixture) produced in a catalytic reaction using carbon monoxide and hydrogen as raw materials correlates with the CO conversion rate. They have also found that the CO conversion rate can be easily and quickly determined by using this correlation, and have completed the present invention.

[0009] The carbon monoxide conversion calculation method of the present invention, which solves the above-mentioned problems, is characterized by comprising: a catalytic reaction step of performing a catalytic reaction using carbon monoxide and hydrogen as feedstocks; and a calculation step of calculating the carbon monoxide conversion based on the proportion of α-olefins in the olefins produced in the catalytic reaction step or the cis / trans ratio in the olefins. As a result of extensive research, the present inventors have discovered that, in a catalytic reaction using carbon monoxide and hydrogen as feedstocks, a correlation exists between the proportion of α-olefins in the olefins produced and the CO conversion, and that, among the olefins produced, particularly for olefins having geometric isomers, a correlation exists between the cis / trans ratio in the olefins and the CO conversion. The carbon monoxide conversion calculation method of the present invention is based on the above-mentioned findings obtained by the present inventors, and enables the CO conversion to be calculated by measuring the component ratio in the hydrocarbon mixture produced, instead of measuring the number of moles of CO in the feed gas per unit time and the number of moles of CO in the outlet gas per unit time as in the conventional method. Measurement of the component ratio of a hydrocarbon mixture requires fewer steps (operations) and can be completed in a shorter time than the step of measuring the number of moles of CO in a gas, making it possible to more easily and quickly grasp the CO conversion rate involved in the catalytic reaction.Furthermore, since monitoring can be performed more frequently, it becomes easier to appropriately evaluate changes in catalytic activity.

[0010] Furthermore, one embodiment of the carbon monoxide conversion calculation method of the present invention is characterized in that the olefin has four or more carbon atoms. As a result of intensive research by the present inventors, it was discovered that, among the products (hydrocarbon mixtures) produced in catalytic reactions using carbon monoxide and hydrogen as raw materials, there is a high correlation (good linear relationship) between the component ratio and the CO conversion, particularly for olefins having four or more carbon atoms and structural isomers. According to the present invention, when calculating the CO conversion in the calculation step, the carbon number of the hydrocarbon (olefin) to be focused on is specified, which further facilitates reducing the number of steps (operations) and time required for measurements to determine the component ratio. In other words, it becomes easier to grasp the CO conversion related to the catalytic reaction more simply and quickly.

[0011] In one embodiment of the carbon monoxide conversion calculation method of the present invention, the olefin is butene. According to the present invention, when calculating the CO conversion in the calculation step, butene, which has the smallest carbon number and has structural isomers, is used as the hydrocarbon (olefin) of interest. This makes it easier to reduce the number of steps (operations) and time required for measurements to determine the component ratio. In other words, it becomes easier to grasp the CO conversion related to the catalytic reaction more simply and quickly.

[0012] The carbon monoxide conversion calculation device of the present invention, which solves the above-mentioned problems, is characterized by comprising an analysis unit that performs component analysis of olefins produced by a catalytic reaction using carbon monoxide and hydrogen as feedstocks, and a calculation unit that calculates the carbon monoxide conversion based on the proportion of α-olefins in the olefins or the cis / trans ratio in the olefins. The carbon monoxide conversion calculation device of the present invention is based on the above-mentioned findings of the inventors. When calculating the CO conversion rate, instead of measuring the number of moles of CO in the feed gas per unit time and the number of moles of CO in the outlet gas per unit time as in the conventional method, the device performs component analysis of the olefins as a measurement of the component ratios in the produced hydrocarbon mixture, and then performs calculations based on the component ratios of specific components in the hydrocarbon mixture. Measuring the component ratios of the hydrocarbon mixture requires fewer steps (operations) and can be performed in a shorter time than the step of measuring the number of moles of CO in the gas, making it possible to more simply and quickly determine the CO conversion rate associated with the catalytic reaction. Furthermore, since monitoring can be performed frequently, it becomes easier to appropriately evaluate changes in catalytic activity.

[0013] Furthermore, the hydrocarbon production apparatus of the present invention for solving the above-mentioned problems is characterized by comprising a catalytic reaction section that performs a catalytic reaction using carbon monoxide and hydrogen as raw materials, and the carbon monoxide conversion calculation device. According to the hydrocarbon production apparatus of the present invention, when hydrocarbons are produced by a catalytic reaction using carbon monoxide and hydrogen as raw materials, the carbon monoxide conversion in the catalytic reaction can be calculated simply and quickly. This makes it possible to quickly obtain information related to the efficiency of hydrocarbon production (carbon monoxide conversion) in hydrocarbon production by a catalytic reaction, and also to simplify the equipment for determining the carbon monoxide conversion. Therefore, it is also possible to reduce or eliminate the facilities and equipment that make up a hydrocarbon production plant.

[0014] The present invention can provide a technology relating to a carbon monoxide conversion calculation method and a calculation device therefor, which can more simply and quickly determine the carbon monoxide conversion in a catalytic reaction using carbon monoxide and hydrogen as raw materials. In addition, the present invention can provide a technology relating to a hydrocarbon production apparatus that uses the carbon monoxide conversion calculation device to reduce the facilities and equipment that make up a plant and can quickly obtain information related to the efficiency of hydrocarbon production (carbon monoxide conversion).

[0015] 1 is a schematic diagram illustrating a catalyst surface reaction in an FT synthesis reaction. FIG. 2 is a schematic explanatory diagram illustrating an example of an apparatus configuration (comparative example) equipped with a means for determining CO conversion based on a conventional method in an apparatus (hydrocarbon production apparatus) for performing a catalytic reaction using carbon monoxide and hydrogen as feedstocks. FIG. 3 is a flow chart of a carbon monoxide conversion calculation method according to an embodiment of the present invention. FIG. 4 is a graph showing the correlation between the proportion of α-olefins in olefins produced by a catalytic reaction and the CO conversion at that time. FIG. 5 is a graph showing the correlation between the cis / trans ratio in olefins produced by a catalytic reaction and the CO conversion at that time. FIG. 6 is a schematic explanatory diagram of a carbon monoxide conversion calculation apparatus and a hydrocarbon production apparatus in this embodiment.

[0016] Hereinafter, embodiments of the carbon monoxide conversion calculation method and carbon monoxide conversion calculation device, and hydrocarbon production apparatus according to the present invention will be described in detail with reference to the drawings. Note that the carbon monoxide conversion calculation method and carbon monoxide conversion calculation device, and hydrocarbon production apparatus described as embodiments are merely examples used to explain the carbon monoxide conversion calculation method and carbon monoxide conversion calculation device, and hydrocarbon production apparatus according to the present invention, and are not limited thereto.

[0017] The "catalytic reaction" in the present invention may be any catalytic reaction using carbon monoxide and hydrogen as raw materials and containing olefins as products. Specific examples include the FT synthesis reaction that produces hydrocarbons, and alcohol synthesis reactions and aldehyde synthesis reactions based on hydroformylation reactions. Hereinafter, in this embodiment, the FT synthesis reaction will be mainly described as the catalytic reaction, but the present invention is not limited to this.

[0018] First, an outline of the FT synthesis reaction will be explained with reference to FIG. 1. The FT synthesis reaction is a process in which synthesis gas (carbon monoxide (CO) and hydrogen (H ２ ) as a raw material gas is contacted with the catalyst, and methylene groups (-CH ２ -) and methane (C １ ) ~ Wax (C ３０＋ ) to produce hydrocarbons with a wide range of carbon numbers.

[0019] It is also known that, depending on the conditions of the FT synthesis reaction (such as the type of catalyst), in addition to the FT synthesis reaction using carbon monoxide as a starting material as shown in Equation 1 above, an FT synthesis reaction using carbon dioxide as a starting material (Equation 2) also proceeds in parallel.

[0020] The reaction formula shown in formula 2 is a general chemical reaction formula, and includes the case where the FT synthesis reaction of formula 1 and the reverse water gas shift reaction shown in formula 3 below occur in parallel. In other words, Equation 2 is also a chemical reaction equation combining Equations 1 and 3.

[0021] More specifically, as shown in FIG. 1, the FT synthesis reaction involves the production of carbon monoxide (CO) and hydrogen (H ２ ) contacts the catalyst surface, methylene species (=CH ２ ) is formed, and this gradually increases the carbon chain, leading to chain growth. The rate of chain growth at this time is expressed as the chain growth rate (kp). Meanwhile, some of the hydrocarbons formed on the catalyst surface are hydrogenated to form paraffins (C ｎ H ２ｎ＋２ ) or olefin (C ｎ H ２ｎ The desorption rate at this time is expressed as the hydrodesorption rate (kh, kd), and in FIG. 1, the rate at which paraffins are desorbed is kh, and the rate at which olefins are desorbed is kd.

[0022] In catalytic reactions using carbon monoxide as a raw material, such as the FT synthesis reaction, the CO conversion rate is used as one of the parameters for obtaining information related to the progress and efficiency of the reaction and the activity of the catalyst used.

[0023] The CO conversion rate is defined by the following equation 4.

[0024] The conventional method of calculating the CO conversion rate based on Equation 4 requires a step of calculating the number of moles of CO in the feed gas per unit time and a step of calculating the number of moles of CO in the outlet gas per unit time. Hereinafter, an example of operations required at a practical level in the conventional method will be described with respect to (1) the step of calculating the number of moles of CO in the feed gas per unit time and (2) the step of calculating the number of moles of CO in the outlet gas per unit time.

[0025] Fig. 2 is a schematic explanatory diagram of an apparatus (hydrocarbon production apparatus) for carrying out a catalytic reaction using carbon monoxide and hydrogen as feedstocks, and shows an example of an apparatus configuration equipped with means for determining CO conversion based on a conventional method. Note that the apparatus (hydrocarbon production apparatus) shown in Fig. 2 corresponds to a comparative example for the carbon monoxide conversion calculation apparatus and hydrocarbon production apparatus in this embodiment, which will be described later.

[0026] In the apparatus 300 shown in FIG. 2, when the catalytic reaction (FT synthesis reaction) is carried out, a raw material gas 1 (CO gas and H ) is introduced via a line L1 and a flow rate control mechanism 11 (a valve 12 and a mass flow controller (MFC) 13). ２The outlet gas) is introduced into the catalytic reaction section 2 where the catalytic reaction takes place via line L2 connected to line L1 by a flow path switching mechanism V1, and the gas after the catalytic reaction (outlet gas) is discharged to the outside of the catalytic reaction section 2 via line L3. Then, in order to determine the CO conversion rate, the flow path switching mechanism V2 switches between introducing the outlet gas into a means for measuring the gas flow rate via line L4 (on the wet integrating flow meter 3 side) and introducing the outlet gas into a means for analyzing the gas components via line L5 (on the gas sampling section 4 side), and the number of moles of CO in the outlet gas per unit time is determined from the measurement results. Meanwhile, in determining the number of moles of CO in the raw material gas 1 required for calculating the CO conversion rate, the raw material gas 1 (CO gas and H ２ The outlet gas (gas) is introduced into line L6 connected to line L1 by flow path switching mechanism V1, bypassing catalytic reaction section 2, and is introduced as raw material gas 1 as is through line L3 to flow path switching mechanism V2 without undergoing catalytic reaction (FT synthesis reaction). The outlet gas is then introduced into a means for measuring the gas flow rate (wet integrating flow meter 3 side) through line L4, and into a means for analyzing the gas components (gas sampling section 4 side) through line L5, while switching between these modes as appropriate. The number of moles of CO in the raw material gas per unit time is determined from the measurement results. The steps involved in calculating the CO conversion rate in the conventional method will be described in more detail below with reference to FIG. 2 .

[0027] (1) Step for determining the number of moles of CO in the raw material gas per unit time Step 1-1: For raw material gas 1 that has been introduced into line L6 by flow path switching mechanism V1 and bypasses catalytic reaction section 2 and has not undergone catalytic reaction, the amount of gas passed through for a certain period of time (approximately 30 minutes to 1 hour) is measured using a calibrated wet integrating flow meter 3. The number of moles of CO in the raw material gas per unit time can be determined from the gas amount measured in step 1-1 and the CO proportion (CO concentration) of raw material gas 1.

[0028] In practice, it becomes necessary to periodically correct the flow control mechanism 11 (mainly the mass flow controller (MFC) 13). The steps involved in this correction are as follows: Step 1-2: Using an atmospheric pressure gauge (not shown), measure the atmospheric pressure inside the room. (Pressure correction) Step 1-3: Measure the temperature of the gas passing through the wet integrating flow meter 3 using the circulating gas thermometer 31. (Temperature correction) Step 1-4: Measure the temperature of the water inside the wet integrating flow meter 3 using the chamber water thermometer 32. (Water vapor pressure correction) Step 1-5: After the corrections in steps 1-2 to 1-4, the gas flow rate adjusted by the flow control mechanism 11 is converted to 0°C and 1 atmosphere and corrected.

[0029] (2) Steps for determining the number of moles of CO in the outlet gas per unit time Step 2-1: Feed gas 1 is introduced into line L2 via flow path switching mechanism V1, and the amount of gas (outlet gas) that has undergone catalytic reaction in catalytic reaction section 2 is measured using a calibrated wet integrating flow meter 3 for a fixed period of time (approximately 30 minutes to 1 hour). (Step 2-1 is performed for each sampling.) Step 2-2: The atmospheric pressure in the room is measured using an atmospheric pressure gauge (not shown). (Pressure correction) Step 2-3: The temperature of the gas ventilating inside the wet integrating flow meter 3 is measured using a circulating gas thermometer 31. (Temperature correction) Step 2-4: The water temperature inside the wet integrating flow meter 3 is measured using a chamber water thermometer 32. (Water vapor pressure correction) Step 2-5: Through the measurements and corrections in steps 2-1 to 2-4, the outlet gas amount is accurately determined. Step 2-6: The outlet gas is introduced into the gas sampling unit 4 (which can store the sampled gas, for example, a known sampling bag) via the line L5 by the flow path switching mechanism V2, and the outlet gas is sampled. Step 2-7: The sampled outlet gas is subjected to a component analysis. Specifically, the component analysis can be performed using a gas chromatograph. Here, a gas chromatograph is widely used for the component analysis in step 2-7, but in order to obtain accurate information on CO in the outlet gas, it is necessary to analyze components other than hydrocarbons (H ２ , CO, CO ２Measurements of inorganic substances (mainly inorganic matter) and low molecular weight hydrocarbons (e.g., methane and ethane, which are paraffins with carbon numbers 1 and 2) must be carried out separately from measurements of hydrocarbons (paraffins with a carbon number of 1 or more) (measurements of organic matter).

[0030] As described above, conventional methods require cumbersome operations to determine the CO conversion rate. Among the steps shown in (1), the operations relating to steps 1-2 to 1-5 in particular may be performed every few months. Although the operations are highly cumbersome, they are not frequently performed. On the other hand, the operations relating to steps 2-1 to 2-7 shown in (2) are required each time sampling is performed, and in addition to being highly cumbersome, they are also frequently performed. Since a considerable amount of time is required to complete the series of operations relating to steps 2-1 to 2-7, it is possible that the time required to calculate the CO conversion rate will exceed the time interval between sampling. The CO conversion rate is also an index for evaluating the activity state of the catalyst, but in this case, it becomes difficult to appropriately evaluate the activity state of the catalyst in the catalytic reaction section 2.

[0031] As a result of extensive research, the present inventors have found that, in a catalytic reaction using carbon monoxide and hydrogen as raw materials, a correlation exists between the proportion of α-olefins in the olefins produced in the product (hydrocarbon mixture) and the CO conversion, and that, among the olefins produced, particularly for olefins having geometric isomers, a correlation exists between the cis / trans ratio in the olefins and the CO conversion.

[0032] The carbon monoxide conversion calculation method, carbon monoxide conversion calculation device, and hydrocarbon production apparatus of the present invention are based on the findings of the present inventors, and when determining the CO conversion rate, instead of measuring the number of moles of CO in the feed gas per unit time and the number of moles of CO in the outlet gas per unit time as in the conventional method, they are replaced by measuring the component ratios in the hydrocarbon mixture produced. Hereinafter, the carbon monoxide conversion calculation method, carbon monoxide conversion calculation device, and hydrocarbon production apparatus as one embodiment of the present invention will be described.

[0033] [Method for Calculating Carbon Monoxide Conversion Rate] First, an embodiment of the method for calculating carbon monoxide conversion rate according to the present invention will be described. Fig. 3 is a flow chart showing each operation (step) involved in the method for calculating carbon monoxide conversion rate according to the embodiment of the present invention. In Fig. 3, solid arrows indicate the movement (introduction) of raw materials and products, and dashed arrows indicate the input and output of information (data).

[0034] As shown in FIG. 3 , the carbon monoxide conversion calculation method according to this embodiment includes a catalytic reaction step of performing a catalytic reaction using carbon monoxide and hydrogen as raw materials, and a calculation step of calculating the carbon monoxide conversion based on the proportion of α-olefins in the olefins produced in the catalytic reaction step or the cis / trans ratio in the olefins.

[0035] The catalytic reaction step may be any step in which a catalytic reaction proceeds using carbon monoxide and hydrogen as raw materials to produce at least olefins. The raw material (raw material gas) for the catalytic reaction in this embodiment may contain components that can be used as raw materials for the catalytic reaction in addition to carbon monoxide and hydrogen, and specifically, carbon dioxide (CO ２ In addition, other components may be mixed into the raw material (raw material gas) as long as they do not interfere with the catalytic reaction.

[0036] The catalyst in the catalytic reaction step may be any catalyst that uses carbon monoxide and hydrogen as raw materials and that can promote a predetermined catalytic reaction (at least a catalytic reaction that produces olefins), and there are no particular limitations on its composition or shape. For example, when an FT synthesis reaction is promoted as the catalytic reaction in this embodiment, a catalyst having a known composition and shape for an FT synthesis reaction can be used. Specific examples of catalysts will be given in the description of the carbon monoxide conversion calculation device and hydrocarbon production device (carbon monoxide conversion calculation device and hydrocarbon production device of this embodiment) that calculate carbon monoxide conversion based on the carbon monoxide conversion calculation method of this embodiment.

[0037] Next, in the calculation step, attention is focused on olefins among the products (outlet gas) produced in the catalytic reaction step, and information related to the proportion of α-olefins in the olefins or the cis / trans ratio in the olefins is obtained, and the carbon monoxide conversion rate is calculated based on this information. Here, with regard to obtaining information related to the proportion of α-olefins in the olefins or the cis / trans ratio in the olefins, as shown in FIG. 3, component analysis of the outlet gas can be performed. In this component analysis of the outlet gas, after obtaining the correlation between the proportion of α-olefins in the olefins and the CO conversion rate, or the correlation between the cis / trans ratio in the olefins and the CO conversion rate, as described below, it is sufficient to be able to obtain information related to the olefin of interest. Unlike calculation of CO conversion rate by conventional methods, it is not necessary to obtain information related to the proportion of CO in the outlet gas (number of moles of CO).

[0038] As one of the calculation steps, a calculation means for calculating the carbon monoxide conversion rate based on information relating to the proportion of α-olefins in the olefins or the cis / trans ratio in the olefins will be described below together with findings obtained by the present inventors.

[0039] As described above, hydrocarbons are produced in the catalytic reaction (FT synthesis reaction in this embodiment) using carbon monoxide and hydrogen as raw materials, and paraffins (C ｎ H ２ｎ＋２ ) or olefin (C ｎ H ２ｎ The present inventors focused on the olefins produced in this process. More specifically, they focused on the component ratio of structural isomers of the olefins produced (isomers with different double bond positions and geometric isomers (cis-trans isomers)), and found that this component ratio varies depending on the catalytic activity (hydrogenation activity), i.e., that it correlates with the carbon monoxide conversion rate.

[0040] FIG. 4 is a graph showing the correlation between the proportion of α-olefins in the olefins produced by the catalytic reaction and the CO conversion rate at that time. FIG. 5 is a graph showing the correlation between the cis / trans ratio in the olefins produced by the catalytic reaction and the CO conversion rate at that time. The olefin of interest in FIGS. 4 and 5 is butene, which has four carbon atoms. That is, in FIG. 4, the vertical axis represents the proportion of 1-butene, an α-olefin, in all butenes produced by the catalytic reaction, expressed as a percentage, and the horizontal axis represents the CO conversion rate at that time, calculated in percentage based on a conventional method. In FIG. 5, the vertical axis represents the ratio of cis to trans isomers (cis / trans ratio) in 2-butene, which has geometric isomers, among the butenes produced by the catalytic reaction, and the horizontal axis represents the CO conversion rate at that time, calculated in percentage based on a conventional method.

[0041] The conditions for the catalytic reaction shown in FIGS. 4 and 5 are as follows: Raw material gas: a mixed gas of carbon monoxide and hydrogen (H ２ / CO ratio: 1.96) Catalyst: Co / SiO ２ Reactor: Slurry bed bubble column reactor (SBCR) Reaction temperature: 230 ° C. Pressure: 0.6 MPa, G

[0042] As shown in FIG. 4, it can be seen that there is a strong correlation between the proportion of α-olefins in the olefins produced by the catalytic reaction and the CO conversion rate at that time. Furthermore, the coefficient of determination (R ２ ) was 0.90, indicating that a good linear relationship (proportional relationship) was established. Also, as shown in Figure 5, it can be seen that there is a strong correlation between the cis / trans ratio in the olefins produced by the catalytic reaction and the CO conversion rate at that time. Furthermore, the coefficient of determination (R ２ ) was 0.89, which also showed that a good linear relationship (proportional relationship) was established.

[0043] The results of Figures 4 and 5 show that the CO conversion in a catalytic reaction is strongly correlated with the component ratio (the proportion of α-olefins in the olefins or the cis / trans ratio in the olefins) of structural isomers of olefins produced in the catalytic reaction. Therefore, as shown in Figure 3, the CO conversion can be calculated by using information previously acquired regarding this correlation and the component analysis results of the olefins in the outlet gas produced by the catalytic reaction. That is, of the steps related to the CO conversion calculation based on the conventional method described above, the CO conversion can be calculated by performing two steps, Step 2-6 and Step 2-7 (only the component analysis related to the olefin of interest). This significantly reduces the number of steps related to the CO conversion calculation and allows it to be completed in a short time, making it possible to more simply and quickly grasp the CO conversion related to the catalytic reaction. Furthermore, the carbon monoxide conversion calculation method in this embodiment enables monitoring of the CO conversion rate at high frequency, making it easy to appropriately evaluate changes in catalytic activity. In other words, the carbon monoxide conversion calculation method in this embodiment can also be used as a method for evaluating catalytic activity.

[0044] The olefin of interest in the carbon monoxide conversion calculation method of this embodiment may be any olefin as long as it has structural isomers, and specifically, it is an olefin having 4 or more carbon atoms, preferably 4 to 6 carbon atoms, and more preferably 4 carbon atoms (butene). Specifying the carbon number of the olefin of interest makes it easy to reduce the number of steps and the time required for component analysis, and enables the calculation of CO conversion to be performed more simply and quickly.

[0045] [Carbon monoxide conversion calculation device and hydrocarbon production apparatus] Next, an example of a carbon monoxide conversion calculation device for carrying out the carbon monoxide conversion calculation method of this embodiment will be described. In addition, a hydrocarbon production apparatus equipped with the carbon monoxide conversion calculation device of this embodiment will also be described. Figure 6 is a schematic explanatory diagram showing the carbon monoxide conversion calculation device and hydrocarbon production apparatus of this embodiment. In Figure 6, solid arrows indicate the movement (introduction) of raw materials and products, and dashed arrows indicate the input and output of information (data).

[0046] As shown in Fig. 6, the carbon monoxide conversion calculation device 100 in this embodiment includes an analysis unit 110 that performs component analysis of olefins produced by a catalytic reaction using carbon monoxide and hydrogen as raw materials, and a calculation unit 120 that calculates the carbon monoxide conversion based on the proportion of α-olefins in the olefins or the cis / trans ratio in the olefins. Furthermore, the hydrocarbon production apparatus 200 in this embodiment includes, in addition to the configuration of the carbon monoxide conversion calculation device 100, a catalytic reaction unit 210 that performs a catalytic reaction using carbon monoxide and hydrogen as raw materials. Note that the same components as those in the apparatus (hydrocarbon production apparatus) shown in Fig. 2 are designated by the same reference numerals, and some descriptions will be omitted.

[0047] (Carbon Monoxide Conversion Ratio Calculation Device) First, each component of the carbon monoxide conversion ratio calculation device 100 will be described. The carbon monoxide conversion ratio calculation device 100 in this embodiment has a device configuration for performing operations particularly related to the calculation step among the steps related to the carbon monoxide conversion ratio calculation method described above, and may be incorporated as part of the hydrocarbon production apparatus 200 in this embodiment, or may be applied to an existing hydrocarbon production apparatus (for example, the apparatus shown in FIG. 2 ). That is, the carbon monoxide conversion ratio calculation device 100 in this embodiment may be any device that receives the product (outlet gas) produced in the catalytic reaction step described above, and there are no limitations on the means for performing the catalytic reaction. Note that FIG. 6 illustrates an example in which the product (outlet gas) produced in the catalytic reaction section 2 in the hydrocarbon production apparatus 200, which will be described later, is introduced into the carbon monoxide conversion ratio calculation device 100 (analysis section 110) in this embodiment via line L3 and line L5.

[0048] The analysis unit 110 focuses on the olefins contained in the product (outlet gas) produced by the above-mentioned catalytic reaction step, and acquires information related to the proportion of α-olefins in the olefins or the cis / trans ratio in the olefins, and specifically, performs component analysis on the outlet gas.

[0049] As described above, the content of the component analysis in this case is such that, after the correlation between the proportion of α-olefins in the olefins and the CO conversion rate, or the correlation between the cis / trans ratio in the olefins and the CO conversion rate, is obtained, it is sufficient to be able to acquire information about the olefin of interest, and unlike the calculation of the CO conversion rate by the conventional method, it is not necessary to acquire information about the proportion of CO in the outlet gas (number of moles of CO).

[0050] In this embodiment, the analysis unit 110 can be a known analytical instrument that can easily and quickly analyze and detect the olefin of interest, in addition to measuring organic matter using a gas chromatograph. Specific examples of such analytical instruments include gas sensors, mass spectrometers, １ Examples of spectrometers that can be used include a H-NMR and an infrared spectrophotometer. Furthermore, the analysis unit 110 in this embodiment may be configured to directly introduce the outlet gas from the catalytic reaction step into the analysis unit 110 and simultaneously perform sampling and component analysis (in-line analysis), without performing sampling that involves primary gas storage, as in the gas sampling unit 4 in the conventional method shown in Figure 2. This significantly reduces the time required to calculate the CO conversion rate, and also makes it possible to evaluate the catalytic activity in the catalytic reaction in real time.

[0051] The calculation unit 120 calculates the CO conversion rate from the component analysis results of the olefins in the outlet gas obtained by the analysis unit 110 and the above-mentioned correlation between the proportion of α-olefins in the olefins and the CO conversion rate, or information (previously acquired) relating to the correlation between the cis / trans ratio in the olefins and the CO conversion rate.

[0052] As described above, the CO conversion rate in a catalytic reaction is strongly correlated with the component ratio of structural isomers of olefins produced in the catalytic reaction (the proportion of α-olefins in the olefins or the cis / trans ratio in the olefins). This correlation is strongly influenced by changes in catalytic activity, and the correlation is maintained as long as other conditions related to the catalytic reaction (such as the reactor structure, reaction conditions, and the composition of the feed gas) remain the same. In other words, by obtaining information related to the correlation as shown in FIG. 4 or FIG. 5 once, the information can be continuously utilized in catalytic reactions in the same reaction system (within the same apparatus).

[0053] The calculation unit 120 is, based on the results from the analysis unit 110, a step (step I) of determining the proportion of α-olefins in the olefins or the cis / trans ratio in the olefins, and a step (step II) of calculating the CO conversion rate from the results of step I based on the correlation between the proportion of α-olefins in the olefins and the CO conversion rate, or the correlation between the cis / trans ratio in the olefins and the CO conversion rate. It is sufficient if it can perform this step, and it may include manual calculations by an operator, but it is preferable to use a calculation device that has a data input / output function for acquiring information, creates a program for performing calculations (calculations) related to each step (steps I and II), and executes it using a processor such as a CPU. This makes it easy to perform operations related to CO conversion rate calculation accurately and quickly.

[0054] Furthermore, the calculation unit 120 may be provided with a data storage unit that can store (accommodate) information acquired in advance (the correlation between the proportion of α-olefins in the olefins and the CO conversion rate, or the correlation between the cis / trans ratio in the olefins and the CO conversion rate) and input the information to the calculation unit 120 as needed. This allows the operation related to Step II to proceed smoothly.

[0055] 6 also shows a wet integrating flow meter 3, which is a means for measuring the flow rate of the outlet gas, as well as a flow gas thermometer 31 and a chamber water thermometer 32 provided within the wet integrating flow meter 3. On the other hand, the carbon monoxide conversion calculation device 100 in this embodiment does not perform calculations using the flow rate of the outlet gas as a parameter, other than obtaining information related to the correlation between the proportion of α-olefins in olefins and the CO conversion rate, or the correlation between the cis / trans ratio in olefins and the CO conversion rate. Therefore, the carbon monoxide conversion calculation device 100 in this embodiment may omit the wet integrating flow meter 3, the flow gas thermometer 31, and the chamber water thermometer 32. However, because information related to the outlet gas flow rate can be an important parameter in technologies related to the production of hydrocarbons, it is preferable to incorporate means for measuring the outlet gas flow rate (such as the wet integrating flow meter 3) into the hydrocarbon production apparatus 200.

[0056] In calculating the CO conversion rate, the carbon monoxide conversion calculation device 100 of this embodiment does not measure the number of moles of CO in the feed gas per unit time and the number of moles of CO in the outlet gas per unit time as in the conventional method, but instead performs olefin component analysis as a measurement of the component ratio in the produced hydrocarbon mixture, and then performs calculations based on the correlation between the proportion of α-olefins in the olefins and the CO conversion rate, or the correlation between the cis / trans ratio in the olefins and the CO conversion rate. Measurement of the component ratio of a hydrocarbon mixture (olefin component analysis) requires fewer steps (operations) and can be completed in a shorter time than the step of measuring the number of moles of CO in the gas. Therefore, the carbon monoxide conversion calculation device 100 of this embodiment can more simply and quickly determine the CO conversion rate associated with the catalytic reaction. Furthermore, because the carbon monoxide conversion calculation device 100 of this embodiment can monitor the CO conversion rate frequently, it can also be used as a catalytic activity evaluation device that can appropriately evaluate changes in catalytic activity.

[0057] (Hydrocarbon Production Apparatus) Next, a description will be given of each component of the hydrocarbon production apparatus 200. The hydrocarbon production apparatus 200 in this embodiment is for producing hydrocarbons using carbon monoxide and hydrogen as raw materials, and is equipped with an apparatus configuration for carrying out operations related to the catalyst activation step and calculation step among the steps related to the carbon monoxide conversion calculation method described above.

[0058] The catalytic reaction section 210 is for carrying out the catalytic reaction step according to the carbon monoxide conversion rate calculation method of this embodiment, and for carrying out a catalytic reaction using carbon monoxide and hydrogen as raw materials.

[0059] As described above, the FT synthesis reaction is one example of the catalytic reactions that are allowed to proceed in the catalytic reaction section 210. The catalytic reaction section 210 in this embodiment may be any one that allows the FT synthesis reactions based on the above-described formulas 1 to 3 to proceed, and known FT reactors and catalysts can be used.

[0060] For example, examples of FT reactors that can be used as the catalytic reaction section 210 in this embodiment include a slurry fluidized bed reactor based on a gas-liquid catalytic reaction and a fixed bed reactor based on a gas-solid catalytic reaction. One of the most preferred types of FT reactors in this embodiment is a slurry bubble column reactor (SBCR). However, in addition to the SBCR, FT reactors based on known reaction types such as a circulating fluidized bed (CFB) reactor, a fluidized bed reactor, and a fixed bed reactor can also be used.

[0061] The catalyst (FT synthesis catalyst) used in the catalytic reaction section 210 in this embodiment functions as a catalyst in the FT synthesis reaction, and includes an active metal (hereinafter also referred to as the "main catalyst") that is the main component of the catalyst, a carrier (catalyst carrier) that supports the active metal, and an auxiliary catalyst. The FT synthesis catalyst to be used can have a suitable composition and shape selected depending on the catalytic reaction section 210 (type of FT reactor, etc.). Below, FT synthesis catalysts suitable for a slurry bed bubble column reactor (SBCR), which is an FT reactor, are exemplified, but are not limited to these.

[0062] <Active Metal (Main Catalyst)> As the active metal (main catalyst) of the FT synthesis catalyst in this embodiment, a metal catalyst selected from cobalt, ruthenium, and iron is used. Iron is inexpensive but has relatively low catalytic activity, while ruthenium has high catalytic activity but is an extremely expensive noble metal. Furthermore, the product of the FT synthesis reaction using an iron-based catalyst is characterized by a high naphtha content and also contains oxygen-containing compounds. For this reason, cobalt is most preferably used to obtain hydrocarbon fractions (so-called middle distillates) such as jet fuel, kerosene, and diesel, from the viewpoint of achieving both catalytic activity and cost.

[0063] Furthermore, the amount of active metal (main catalyst) is preferably 5% by weight or more and 25% by weight or less, expressed as the weight-based amount of active metal supported in the FT synthesis catalyst. It is more preferably 7.5% by weight or more and 20% by weight or less, and even more preferably 8% by weight or more and 15% by weight or less. An amount below this range tends to result in insufficient catalytic activity for the FT synthesis reaction, while an amount exceeding this range saturates the catalytic activity for the FT synthesis reaction, making the catalyst less technically significant, particularly in terms of cost.

[0064] <Carrier (catalyst carrier)> In this embodiment, a carrier containing silicon or aluminum is used as the carrier (catalyst carrier) of the FT synthesis catalyst. More specifically, silica (SiO ２ ), alumina (Al ２ O ３ ), zeolites (crystalline aluminosilicates), amorphous silica-alumina (SiO ２ -Al ２ O３ ) is preferably used. Among these, it is particularly preferable to use a carrier containing silica. Silica is chemically stable and therefore does not affect the main catalyst or auxiliary catalyst. This allows the chemical properties of the main catalyst and auxiliary catalyst to be fully exhibited. Furthermore, because of its large specific surface area, it has high contact efficiency with the raw material gas (substrate), allowing the FT synthesis reaction to proceed efficiently. Furthermore, the true density (true specific gravity) of the carrier increases in the order of alumina > zeolite > silica. For example, in the production of hydrocarbons by the FT synthesis reaction, when a bubble column such as an SBCR is used as the catalytic reaction section 210, the smaller the true density (true specific gravity) of the carrier, the easier it is for catalyst particles to be dispersed by bubbles, and therefore silica is considered to be the carrier with the best operability.

[0065] <Auxiliary Catalyst> The FT synthesis catalyst in this embodiment may contain an auxiliary catalyst in addition to the main catalyst. Examples of the auxiliary catalyst include at least one selected from the group consisting of rare earth elements such as yttrium, cerium, lanthanum, praseodymium, neodymium, and holmium, at least one selected from the group consisting of alkali metals such as sodium, potassium, rubidium, and cesium, at least one selected from the group consisting of alkaline earth metals such as beryllium, magnesium, calcium, strontium, and barium, and at least one selected from the group consisting of copper, silver, molybdenum, and tungsten.

[0066] It is believed that the addition of an auxiliary catalyst to the FT synthesis catalyst in this embodiment increases the amount of carbon monoxide and carbon dioxide adsorbed on the catalyst surface and also increases the number of reaction active sites. In particular, when one selected from the group consisting of copper, silver, molybdenum, and tungsten is used, charge transfer occurs between the active metal (main catalyst) and the oxidation number of the main catalyst slightly decreases (δ-), and CO and CO ２This is expected to have an effect of improving the reaction frequency (TOF (turnover frequency)) at the active site of the FT synthesis reaction, which is a type of hydrogenation reaction of the above. Furthermore, when one member is selected from the group consisting of copper, silver, molybdenum, and tungsten as the auxiliary catalyst, it is particularly preferable to select copper from the viewpoints of cost and the effect of improving the reaction frequency.

[0067] The amount of the auxiliary catalyst is preferably 1 / 30 to 1 / 3 of the weight-based amount of the active metal (main catalyst), and more preferably 1 / 20 to 1 / 5.

[0068] <Catalyst Shape> The FT synthesis catalyst in this embodiment is preferably in the form of a fine powder from the viewpoint of the processing efficiency of catalyst preparation and the reaction efficiency of the FT synthesis reaction. In this case, the particle shape is preferably crushed, ellipsoidal, spherical, cylindrical, or the like, and it is also preferable to use a combination of these shapes. Furthermore, the size of the FT synthesis catalyst (the longest part of the across length) is preferably 0.07 mm or more and 1 mm or less, more preferably 0.07 mm or more and 0.7 mm or less, and even more preferably 0.08 mm or more and 0.17 mm or less.

[0069] <Specific surface area of ​​catalyst> The specific surface area (SA) of the FT synthesis catalyst is 100 m ２ / g or more is preferable, and 200m ２ / g or more is more preferable, ２ The upper limit of the specific surface area of ​​the FT synthesis catalyst is not particularly limited, but the practical upper limit is 500 m ２ If the amount is less than the lower limit of the range, the active metals related to the main catalyst and the like cannot be sufficiently supported as an FT synthesis catalyst.

[0070] The hydrocarbon production apparatus 200 in this embodiment is a combination of a catalytic reaction section 210 and the above-described carbon monoxide conversion calculation device 100. In order to cause the catalytic reaction (FT synthesis reaction) to proceed, as shown in FIG. 6, a raw material gas 1 (CO gas and H ) introduced via a line L1 and a flow rate control mechanism 11 (a valve 12 and a mass flow controller (MFC) 13) is supplied. ２The gas (outlet gas) is introduced into the catalytic reaction section 210 where the catalytic reaction takes place via line L2, which is connected to line L1 by a flow path switching mechanism V1, and the gas after the catalytic reaction (outlet gas) is discharged to the outside of the catalytic reaction section 2 via line L3. The discharged outlet gas is then introduced via line L5 by the flow path switching mechanism V2 (optional) into a carbon monoxide conversion rate calculation device 100 (analysis section 110), which is a means for analyzing the components of the outlet gas, and the CO conversion rate is calculated.

[0071] The hydrocarbon production apparatus 200 in this embodiment may be provided with a means (apparatus configuration) for calculating the CO conversion rate based on the above-mentioned conventional method in order to obtain in advance the correlation between the proportion of α-olefins in the olefins and the CO conversion rate, or the correlation between the cis / trans ratio in the olefins and the CO conversion rate. That is, as shown in FIG. 6 , in order to obtain the number of moles of CO in the feed gas 1 per unit time required for calculating the CO conversion rate, the feed gas 1 (CO gas and H 2 ) introduced via line L1 and flow rate control mechanism 11 is ２The outlet gas (outlet gas) is introduced into line L6 connected to line L1 by the flow path switching mechanism V1, bypassing the catalytic reaction section 210, and is introduced as source gas 1 as is through line L3 to the flow path switching mechanism V2 without undergoing the catalytic reaction (FT synthesis reaction). The outlet gas is then introduced into a means for measuring the gas flow rate (on the wet integrating flow meter 3 side) through line L4, and into a means for analyzing the gas components (on the analysis section 110 side) through line L5, while switching between these two modes as needed. The number of moles of CO in the source gas per unit time is calculated from the measurement results. Meanwhile, the gas (outlet gas) after the catalytic reaction, discharged to the outside of the catalytic reaction section 210 through line L3, is introduced into a means for measuring the gas flow rate (on the wet integrating flow meter 3 side) through line L4 by the flow path switching mechanism V2, and into a means for analyzing the gas components (on the analysis section 110 side) through line L5, while switching between these modes as needed. The number of moles of CO in the outlet gas per unit time is calculated from the measurement results. As a result, by calculating the CO conversion rate based on Equation 4 and combining it with the results of the olefin component analysis by the analysis unit 110, it becomes possible to obtain information regarding the correlation between the proportion of α-olefins in the olefins and the CO conversion rate, or the correlation between the cis / trans ratio in the olefins and the CO conversion rate.

[0072] It should be noted that the correlation between the proportion of α-olefins in olefins and the CO conversion rate, or the correlation between the cis / trans ratio in olefins and the CO conversion rate, is maintained so long as conditions other than catalyst activity (reactor structure, reaction conditions, etc.) are the same, and therefore information relating to this correlation can be shared among a plurality of hydrocarbon production apparatuses 200. Therefore, it is not essential for the hydrocarbon production apparatus 200 in this embodiment to be provided with a means (apparatus configuration) for calculating the CO conversion rate based on a conventional method.

[0073] The above-described embodiments show examples of a carbon monoxide conversion calculation method, a carbon monoxide conversion calculation device, and a hydrocarbon production device. The carbon monoxide conversion calculation method, a carbon monoxide conversion calculation device, and a hydrocarbon production device according to the present invention are not limited to the above-described embodiments, and the carbon monoxide conversion calculation method, a carbon monoxide conversion calculation device, and a hydrocarbon production device according to the above-described embodiments may be modified within the scope of the gist of the claims.

[0074] The carbon monoxide conversion calculation method and carbon monoxide conversion calculation device of the present invention can be used as a technique for easily and quickly calculating CO conversion in a technique related to a catalytic reaction using carbon monoxide and hydrogen as raw materials. In addition, they can also be suitably used as a technique for appropriately evaluating catalytic activity.

[0075] Furthermore, the hydrocarbon production apparatus of the present invention can be used as a technology relating to a hydrocarbon production apparatus that can reduce the facilities and equipment that make up a plant and quickly obtain information related to the efficiency of hydrocarbon production (carbon monoxide conversion rate). In particular, the hydrocarbon production apparatus of the present invention can be suitably used in a technology for on-site production of hydrocarbons, specifically in a technology for producing carbon-neutral fuels (kerosene, diesel, and SAF).

[0076] 100 Carbon monoxide conversion rate calculation device, 110 Analysis section, 120 Calculation section, 200 Hydrocarbon production apparatus, 210 Catalytic reaction section, 300 Apparatus (hydrocarbon production apparatus) equipped with CO conversion rate calculation means based on conventional method 1 Feed gas, 11 Flow rate control mechanism, 12 Valve, 13 Mass flow controller (MFC), 2 Catalytic reaction section, 3 Wet type integrating flow meter, 31 Flow gas thermometer, 32 Chamber water thermometer, 4 Gas sampling section, L1 to L6 Lines, V1, V2 Flow path switching mechanism

Claims

1. A method for calculating a carbon monoxide conversion rate, comprising: a catalytic reaction step of carrying out a catalytic reaction using carbon monoxide and hydrogen as raw materials; and a calculation step of calculating a carbon monoxide conversion rate based on the proportion of α-olefins in the olefins produced in the catalytic reaction step or the cis / trans ratio in the olefins.

2. The method for calculating carbon monoxide conversion rate according to claim 1, wherein the olefin has four or more carbon atoms.

3. The method for calculating carbon monoxide conversion rate according to claim 2, wherein the olefin is butene.

4. A carbon monoxide conversion calculation device comprising: an analysis unit that performs component analysis of olefins produced by a catalytic reaction using carbon monoxide and hydrogen as raw materials; and a calculation unit that calculates the carbon monoxide conversion based on the proportion of α-olefins in the olefins or the cis / trans ratio in the olefins.

5. A hydrocarbon production system comprising: a catalytic reaction section that performs a catalytic reaction using carbon monoxide and hydrogen as raw materials; and the carbon monoxide conversion calculation device according to claim 4.

Images