Test apparatus and test methods

Abstract

A testing apparatus and method are provided for automatically performing reaction rate tests while varying the residence time in a catalyst bed under the same flow conditions. In the testing apparatus for testing the reaction rate of a chemical reaction proceeding in the presence of a catalyst, a sample supply unit supplies a sample to the catalyst at a preset flow rate, and multiple reaction vessels each include a catalyst bed filled with the catalyst. A supply-side switching valve is connected to a supply flow path for the sample to be supplied to the reaction vessel that is the target of the supply, and an outflow-side switching valve is connected to a sample flow path for collecting samples for analysis to the reaction vessel that is the source of the outflow from the catalyst bed. A control unit controls the switching between the target and source reaction vessels via the supply-side and outflow-side switching valves, enabling reaction rate tests to be performed under at least three conditions with different residence times in the catalyst bed.

Description

Technical Field

[0001] This invention relates to a technique for conducting tests to determine the reaction rate of a chemical reaction carried out in the presence of a catalyst, and more particularly to a testing apparatus and a testing method. Background Technology

[0002] When designing a reaction apparatus that supplies feedstock to a catalyst bed filled with solid catalyst to obtain a desired target composition, the reaction rate of the reaction using the catalyst (catalytic reaction) must be determined. However, in order to avoid changes in the flow state within the catalyst bed while accurately determining the reaction rate, it is necessary to repeatedly conduct reaction rate tests while changing multiple reaction vessels with different catalyst bed capacities. Determining the reaction rate of catalytic reactions requiring such vessel changes becomes a heavy workload for the testers.

[0003] Here, Patent Document 1 describes a technique in which, when screening reactants in the presence of a catalyst is performed using a combinatorial library, the same amount of test fluid is supplied per unit time to the container holding the catalyst. Furthermore, Patent Document 2 describes a reaction analysis apparatus that acquires the temperature distribution of the reaction fluid immediately after the reaction begins, along the flow direction of the reaction fluid flowing in a flow reactor, in order to determine the reaction state of the reaction fluid.

[0004] However, neither Patent Document 1 nor Patent Document 2 discloses a technique for measuring reaction rate using multiple reaction vessels with different catalyst layer capacities.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: U.S. Patent Application Publication No. 2002 / 0141900

[0008] Patent Document 2: Japanese Patent Application Publication No. 2021-159910 Summary of the Invention

[0009] The problem that the invention aims to solve

[0010] The present invention was made in this context, providing a technology that automatically performs reaction rate testing while changing the residence time in the catalyst layer under the same flow conditions.

[0011] Technical means to solve the problem

[0012] This invention is a testing device for testing the reaction rate of a chemical reaction advanced in the presence of a catalyst, the testing device comprising:

[0013] The sample supply unit supplies the sample to the catalyst at a preset flow rate;

[0014] Multiple reaction vessels, each including a catalyst layer filled with the catalyst;

[0015] A temperature control mechanism is used to regulate the temperature of the reaction vessel.

[0016] A supply-side switching valve connects to a supply flow path that supplies a sample from the sample supply unit for the reaction vessel selected from the plurality of reaction vessels as the supply target.

[0017] An effluent-side switching valve connects to a sample flow path for the reaction vessel, which serves as the effluent source from the catalyst layer, to collect the sample that has passed through the catalyst layer for analysis; and

[0018] The control unit controls the switching of the reaction vessel, which serves as the supply target and the outflow source, through the supply-side switching valve and the outflow-side switching valve, so as to perform reaction rate tests under at least three conditions with different residence times in the catalyst layer.

[0019] The testing device may also have the following features.

[0020] (a) A reaction vessel having at least three catalyst layers of different capacities, wherein the control unit performs the switching control to make the reaction vessel serving as the supply target consistent with the reaction vessel serving as the outflow source.

[0021] (b) The temperature regulating mechanism is configured to regulate the temperature while the reaction vessel is housed inside the temperature regulating chamber. The testing device includes: an upstream temperature regulating chamber and a downstream temperature regulating chamber, each housing a plurality of reaction vessels with different capacities of the catalyst layer; and an intermediate switching valve connecting the upstream reaction vessel and the downstream reaction vessel. The upstream reaction vessel is housed in the upstream temperature regulating chamber and the sample flows out from the catalyst layer. The downstream reaction vessel is selected from the plurality of reaction vessels housed in the downstream temperature regulating chamber and is supplied with the sample flowing out from the upstream reaction vessel. In addition to controlling the switching of the reaction vessels, the control unit also controls the connection between the upstream and downstream reaction vessels via the intermediate switching valve.

[0022] (c) The temperature control mechanism is configured to perform temperature control while multiple reaction vessels with different capacities of the catalyst layer are housed inside a temperature control chamber. The testing apparatus includes: a target switching valve that connects one reaction vessel from which the sample flows out of the catalyst layer to another reaction vessel selected from the reaction vessels other than the one reaction vessel; and a selection valve that selects an outflow target of the sample from the one reaction vessel between the sample flow path and the other reaction vessel via the target switching valve. The control unit implements control to select the outflow target of the sample via the selection valve. If a connection toward the sample flow path is selected via the selection, switching control is performed via the outflow-side switching valve to make the one reaction vessel the outflow source. If a connection toward the other reaction vessel is selected via the selection, switching control is performed via the outflow-side switching valve to make the other reaction vessel the outflow source.

[0023] (d) After a preset stabilization time elapses from the start of supplying the sample to the reaction vessel that is the supply target from the supply flow path, the control unit collects the sample flowing out of the reaction vessel that is the outflow source via the sample flow path, and then performs the switching control for the next reaction vessel that is both the supply target and the outflow source.

[0024] (e) From the start of supplying the sample to the reaction vessel that is the supply target from the supply flow path, the control unit collects the sample flowing out of the reaction vessel that is the effluent source via the sample flow path at each sampling period determined based on a preset rule. Based on the results of concentration analysis of the component of interest contained in the sample, after the concentration change index of the component of interest falls below a preset threshold, the control unit performs the switching control to the next reaction vessel that is both the supply target and the effluent source.

[0025] (f) The control unit performs the switching control to the next reaction vessel that serves as both the supply target and the effluent source after it stops supplying the sample from the sample supply unit.

[0026] The effects of the invention

[0027] This invention utilizes multiple reaction vessels, each including a catalyst layer, and employs switching control of supply-side and outflow-side switching valves to enable reaction rate testing under at least three conditions with varying residence times in the catalyst layer. As a result, reaction rate testing can be performed without the need for manual vessel swapping; this reaction rate testing is used to determine the rate of a chemical reaction proceeding in the presence of a catalyst. Attached Figure Description

[0028] Figure 1 This is a schematic diagram illustrating the reaction in which raw materials are supplied to the catalyst layer to obtain the product.

[0029] Figure 2 This is a schematic diagram showing how the reaction rate curve changes depending on the reaction system.

[0030] Figure 3 This is an explanatory diagram illustrating the method for determining the reaction rate curve.

[0031] Figure 4 This is a structural diagram of a previous testing device.

[0032] Figure 5 This is a structural diagram of the test apparatus according to the first embodiment.

[0033] Figure 6 This is an example of the operation flow of the test device in the first embodiment.

[0034] Figure 7 This is a flowchart related to the action of making a switch decision on the tubing.

[0035] Figure 8 This is a structural diagram of the test apparatus according to the second embodiment.

[0036] Figure 9 This is a structural diagram of the test apparatus according to the third embodiment.

[0037] Explanation of symbols

[0038] 1, 1a, 1b, 100: Testing apparatus

[0039] 11: Control Department

[0040] 2a~2f: Catalyst column

[0041] 301: Raw material supply pipeline

[0042] 31: Raw Material Supply Department

[0043] 32: Pump

[0044] 33: Flow meter

[0045] 34: Pressure gauge

[0046] 35: Thermometer

[0047] 401: Reaction gas supply line

[0048] 411: Hydrogen Supply Department

[0049] 412: Flow regulating valve

[0050] 413: Flow meter

[0051] 421: Nitrogen Supply Department

[0052] 422: Flow regulating valve

[0053] 423: Flow meter

[0054] 5: Oven

[0055] 5a: Upstream side drying oven

[0056] 5b: Downstream side oven

[0057] 61: Supply-side switching valve

[0058] 62: Supply-side switching valve

[0059] 63: Outflow side switching valve

[0060] 64: Selector Valve

[0061] 65: Intermediate switching valve

[0062] 66: Outflow side switching valve

[0063] 67: Connect the target switching valve

[0064] 701, 701a, 701b: Sampling pipelines

[0065] 702: Discharge pipeline

[0066] 7: Analyzer Detailed Implementation

[0067] First, the reasons why the reaction rate must be determined when designing a reaction apparatus that includes a catalyst layer filled with a solid catalyst, and the problems with previous test apparatuses, will be explained.

[0068] like Figure 1 As shown, in a reaction system using a catalyst bed, a fluid serving as the raw material flows through the catalyst bed, bringing the raw material into contact with the catalyst to drive the catalytic reaction. The target component is obtained from the products generated through the reaction. Generally, under the condition that the reaction temperature and the concentration of the raw material in the fluid are set constant, the longer the residence time in the catalyst bed, the more raw material will be consumed by the reaction, thereby obtaining a product in an amount corresponding to the amount of raw material consumed.

[0069] At this point, the relationship between the residence time of the feedstock in the catalyst bed, i.e., the reaction time (e.g., in "seconds"), and the feedstock concentration at the catalyst bed outlet (a percentage of the outlet concentration relative to the inlet concentration towards the catalyst bed) (reaction rate curve) can be expressed as follows: Figure 2As shown in the diagram, in a reaction system with a high reaction rate, as indicated by the dotted chain line, the feed concentration decreases sharply within a short residence time. On the other hand, in a reaction system with a low reaction rate, as indicated by the solid line, the decrease in feed concentration with increasing residence time becomes slower compared to a reaction system with a high reaction rate.

[0070] This difference in reaction rate affects the design of the reaction apparatus used to obtain the target component from the raw materials. For example, in a reaction system that can convert a specified amount of raw materials into products in a short reaction time (residence time) (reaction rate: high), the capacity of the catalyst bed can be reduced, that is, the volume of the reaction tower can be reduced. On the other hand, in a reaction system that requires a longer reaction time (residence time) to convert a specified amount of raw materials into products (reaction rate: low), the volume of the reaction tower, i.e., the capacity of the catalyst bed, must be increased.

[0071] Thus, the reaction rate of a catalytic reaction is one of the important catalyst characteristics that must be understood in advance when designing a reaction apparatus. Therefore, when determining the reaction rate of a certain reaction system, the following reaction rate test should be performed: while varying the residence time of the feedstock through the catalyst bed, the feedstock concentration at the catalyst bed outlet should be measured. Furthermore, as... Figure 3 As shown, the reaction rate curve is obtained by fitting the curves based on the results of plotting the relationship between the feed concentration and residence time at multiple catalyst layer outlets.

[0072] Here, as a method to vary the residence time of the feedstock in the catalyst bed, it is also considered to vary the feedstock flow rate sequentially for a catalyst bed filled with a predetermined amount of catalyst. However, in this method, the flow state of the feedstock flowing in the catalyst bed can sometimes be quite different depending on the change in the supply flow rate. As a result, it is difficult to conduct reaction rate tests under conditions that are consistent except for the residence time, and an accurate reaction rate curve may not be obtained.

[0073] Therefore, in the past, the use Figure 4 The test apparatus 100, as illustrated in the example, is used to perform reaction rate tests and obtain the reaction rate curve. Figure 4 The test apparatus 100 shown is configured, for example, as an apparatus for conducting a reaction experiment to obtain a reaction rate curve for a hydrogenation reaction, wherein the hydrogenation reaction is a reaction in which a raw material contained in a raw material fluid is hydrogenated.

[0074] To briefly describe the structure of the testing apparatus 100, a raw material fluid (e.g., liquid) containing raw materials is stored in the raw material supply section 31. This raw material fluid is supplied via the raw material supply line 301 at a preset flow rate by a pump 32, based on the flow rate measurement result obtained from the flow meter 33. A pressure gauge 34 or a thermometer 35 is provided in the raw material supply line 301 to measure the supply pressure or temperature of the raw material fluid. The raw material supply section 31, the pump 32, and the flow meter 33 constitute a sample supply section that supplies the raw material fluid used as a sample at a preset flow rate, and the raw material supply line 301 constitutes a sample supply path.

[0075] On the other hand, hydrogen for the hydrogenation reaction is stored in the hydrogen supply unit 411. Hydrogen is supplied at a preset flow rate by adjusting the flow rate via the flow regulating valve 412 based on the flow rate measurement result obtained from the flow meter 413. Furthermore, nitrogen for hydrogen concentration adjustment is stored in the nitrogen supply unit 421. Nitrogen is supplied at a preset flow rate by adjusting the flow rate via the flow regulating valve 422 based on the flow rate measurement result obtained from the flow meter 423.

[0076] The hydrogen and nitrogen gases, after converging, are supplied as a mixed gas (hereinafter also referred to as "reaction gas") via reaction gas supply line 401. The downstream end of reaction gas supply line 401 merges into raw material supply line 301, which supplies the raw material fluid. Hydrogen supply unit 411, flow regulating valve 412, flow meter 413 and nitrogen supply unit 421, flow regulating valve 422, flow meter 423 constitute a sample supply unit that supplies hydrogen or nitrogen as a sample at a preset flow rate, and reaction gas supply line 401 constitutes a sample supply path.

[0077] The catalyst used for the hydrogenation reaction of the raw materials is respectively filled into multiple catalyst columns 2a to 2f, which serve as reaction vessels. These catalyst columns 2a to 2f, for example, comprise stainless steel cylindrical containers with a diameter of 5 mm. The cylindrical containers constituting the catalyst columns 2a to 2f are configured, for example, to have different lengths ranging from 50 mm to 300 mm, and are filled with different capacities of catalyst corresponding to their respective lengths. In this example, for the catalyst columns 2a to 2f with larger lengths, a catalyst layer filled with a larger capacity of catalyst is provided. Furthermore, the constituent materials or dimensions, and the number of catalyst columns 2a to 2f used, are exemplified but can be appropriately varied.

[0078] In the test apparatus 100 of this example, multiple catalyst columns 2a to 2f with different catalyst layer capacities are prepared in advance, and one of these catalyst columns will be selected ( Figure 4In the example shown, the catalyst column 2a) is arranged inside the oven 5. The oven 5 heats the internal temperature to a preset temperature (e.g., 100°C).

[0079] Furthermore, the oven 5 can have its set temperature varied within a range of 40°C to 150°C. By conducting reaction rate tests under different set temperatures, the temperature dependence of the reaction rate can also be evaluated. In this respect, the oven 5 functions as a temperature control mechanism (temperature control chamber) to regulate the temperature of the catalyst columns 2a to 2f, i.e., the catalyst layer, housed within it.

[0080] On the inlet side of the catalyst column 2a housed within the oven 5, a downstream end of a raw material supply line 301 is connected. This downstream end is located further downstream than the confluence point with the previously described reaction gas supply line 401. On the outlet side of the catalyst column 2a, a sampling line (sample flow path) 701 is connected. This sampling line (sample flow path) 701 is used to collect samples that have passed through the catalyst layer within the catalyst column 2a for analysis.

[0081] The downstream end of sampling line 701 is connected to analyzer 7, which is located outside the testing apparatus 100. When the sample flowing from sampling line 701 is liquid, a liquid chromatograph (LC) can be used as analyzer 7 for component / quantitative analysis of the sample. Here, when the sample is liquid, a sample collection mechanism, such as a syringe, may be provided within analyzer 7. In this case, if the sample contains air bubbles or dissolved gases, malfunctions may occur during sample collection using the sample collection mechanism. Therefore, a gas-liquid separator or degasser may be provided between the downstream end of sampling line 701 and analyzer 7 as needed.

[0082] The sample after analysis of the product using analyzer 7 is discharged via discharge line 702.

[0083] Furthermore, the analyzer 7 connected to the sampling line 701 is not limited to an LC; when the sample is a gas, a gas chromatograph (GC) can also be used. Moreover, depending on the analysis, an LC-MS or GC-MS equipped with a mass spectrometer (MS), or other analyzers, can be used. Furthermore, when the sample is a liquid, a fraction collector can be installed at the inlet side of the analyzer 7, and the sampling line 701 can be connected to the fraction collector.

[0084] In the test apparatus 100 including the aforementioned structure, the catalyst column 2a to be used in this reaction rate test is selected from a plurality of pre-prepared catalyst columns 2a to 2f, and placed inside the oven 5. The raw material supply line 301 or sampling line 701 is then installed. The oven 5 is then heated, and once the temperature stabilizes at the set point, the supply of the sample, such as the raw material fluid or reaction gas, begins.

[0085] The reaction stabilizes, for example, in about an hour. Therefore, after the stabilization time has elapsed since the initial sample supply, the sample is sampled and analyzed using analyzer 7. While also assessing the temperature dependence of the reaction rate, the sample supply is stopped, and the set temperature of oven 5 is changed. Once the temperature inside oven 5 stabilizes at the new set temperature, the previously described process of "sample supply → waiting for stabilization → sample sampling and analysis" is repeated. Furthermore, stopping the sample supply when the set temperature of oven 5 is changed may not be necessary. For example, the supply of raw materials and hydrogen may be stopped while only the supply of nitrogen continues, or the supply of raw materials or hydrogen may continue if a sufficient amount of raw materials or hydrogen is available.

[0086] Thus, once all the set temperatures required for the temperature dependence assessment have been achieved, the supply of the sample (raw material fluid, reaction gas) or the heating of the oven 5 is stopped. Then, once the temperature inside the oven 5 has dropped to a temperature suitable for operation, the catalyst column 2a is disassembled, and the next catalyst column 2b is installed, and the reaction rate test is repeated according to the above procedure.

[0087] Here, in order to obtain such Figure 2 The reaction rate curve shown must be tested using at least three different residence times (reaction times). Furthermore, to obtain a more accurate reaction rate curve, it is sometimes necessary to test the reaction rate using four or more different residence times.

[0088] thus, Figure 4 In the conventional test apparatus 100 shown, the reaction rate test and replacement operation must be performed on catalyst columns 2a to 2f corresponding to residence times of three or more points. However, the long waiting time and the repetitive replacement operation of catalyst columns 2a to 2f pose a significant burden to the tester.

[0089] Therefore, the test apparatus 1 of this embodiment eliminates the need for changing the catalyst columns 2a to 2f, and can automatically perform reaction rate tests to obtain reaction rate curves. Hereinafter, with reference to... Figures 5-7 The structure and function of the test device 1 in this embodiment will be explained.

[0090] In addition, Figure 5 , Figure 8 , Figure 9 Among the test devices 1, 1a, and 1b shown, for those used... Figure 1 The common components of the test apparatus 100 described are labeled as follows: Figure 1 The symbols used are common symbols.

[0091] Figure 5 In the test apparatus 1 shown, at least three (six in the example shown) catalyst columns 2a to 2f with different catalyst layer capacities are pre-installed in a common oven 5. Thus, the test apparatus 1 of this embodiment has a structure that eliminates the need for replacing catalyst columns 2a to 2f.

[0092] On the other hand, when multiple catalyst columns 2a to 2f are housed in the oven 5, it is necessary to select catalyst columns 2a to 2f that are either the target of the sample supply from the raw material supply line 301 or the reaction gas supply line 401, or the outflow source of the sample toward the sampling line 701.

[0093] In this respect, the test apparatus 1 of this embodiment is provided with a supply-side switching valve 61, a supply-side switching valve 62, and an outflow-side switching valve 63. The supply-side switching valves 61 and 62 function as follows: for a supply target selected from multiple catalyst columns 2a to 2f, they are respectively connected to the raw material supply line 301 (the raw material fluid used as the sample) and the reaction gas supply line 401 (the reaction gas). Furthermore, the outflow-side switching valve 63 functions as follows: for the catalyst columns 2a to 2f (the outflow source) from which the sample flows out of the catalyst layer, it connects to the sample flow path.

[0094] These supply-side switching valves 61, 62 and outflow-side switching valves 63 are switched via a control unit 11. The control unit 11 uses these supply-side switching valves 61, 62 and outflow-side switching valves 63 to switch the catalyst columns 2a to 2f, which serve as the sample supply target and outflow source. For example, the control unit 11 may include a computer or control circuitry. In particular, in the test apparatus 1 of this embodiment, the control unit 11 controls the switching of the supply-side switching valves 61, 62 and 63 to ensure that the catalyst columns 2a to 2f, which serve as the sample supply target and outflow source, are aligned.

[0095] For example, Figure 5The diagram illustrates the switching of supply-side switching valve 61, supply-side switching valve 62, and outflow-side switching valve 63 to connect the catalyst column 2e to the raw material supply line 301, the reactant gas supply line 401, and the sampling line 701. Furthermore, by sequentially implementing this switching, it is possible to switch at least three different residence times. Figure 5 The reaction rate test was conducted under conditions with a maximum of six conditions as shown in the example.

[0096] Next, besides Figure 5 In addition, while referring to Figure 6 The operation of the test apparatus 1, including the aforementioned structure, will be explained. When a reaction rate test using the test apparatus 1 is performed (start), catalyst column 2e, selected as the test target, is chosen from catalyst columns 2a to 2f housed in the oven 5. The supply-side switching valve 61, supply-side switching valve 62, and outflow-side switching valve 63 are switched (step S101). Next, the raw material fluid and reaction gas used as the sample are supplied to the switched catalyst column 2e (step S102).

[0097] Subsequently, the sample supply continues until a predetermined stabilization time has elapsed (step S103). During this period, the sample may also be discharged from the discharge line 702 via the sampling line 701. After the stabilization time has elapsed, the sample is sampled and analyzed via the sampling line 701 (step S104). Then, the supply of raw material fluid and reaction gas to the catalyst column 2e is stopped (step S105).

[0098] Additionally, it is also used here. Figure 4 In the case of evaluating the temperature dependence of the reaction rate as described in the conventional test apparatus 100, after changing the set temperature of the oven 5, the operations of steps S102 to S104 are repeated. However, at this time, step S102 will perform the operation of supplying raw material fluid and reaction gas to the catalyst column 2e after the set temperature is changed.

[0099] After the sample supply is stopped in step S105, it is confirmed whether catalyst columns 2a to 2d and catalyst column 2f are set up for the next reaction rate test (step S106). For example, when the reaction rate test of catalyst column 2e is completed, it is considered that the reaction rate test for catalyst columns 2a to 2d has been completed, and the reaction rate test will be performed on the remaining catalyst column 2f (step S106: Yes). At this time, the switching of catalyst column 2f is performed in step S101, and the actions of steps S102 to S106 are repeated.

[0100] Then, if there are no catalyst columns 2a to 2f to be switched to perform reaction rate testing next (step S106: No), the reaction rate test ends. Furthermore, for example, curve fitting is performed on an external computer that obtains the test results from the analyzer 7, and the reaction rate curve is automatically generated, thus ending the operation (end).

[0101] The test apparatus 1 according to this embodiment has the following advantages. By using multiple catalyst columns 2a to 2f, each including a catalyst layer, and switching control of the supply-side switching valve 61, supply-side switching valve 62, and outflow-side switching valve 63, reaction rate tests can be performed under at least three conditions with different residence times in the catalyst layer. As a result, reaction rate tests can be conducted without the need for manual replacement of the catalyst columns 2a to 2f, and these reaction rate tests are used to determine the reaction rate of a chemical reaction proceeding in the presence of a catalyst.

[0102] Here, for use Figure 6 The described step S103 can also replace the method of waiting for a preset stabilization time to elapse, and confirm the actual stabilization time elapsed. Figure 7 This illustrates an example of the action performed at this point instead of step S103.

[0103] It started Figure 6 After the sample is supplied in step S102, the control unit 11 starts counting the number of sampling operations (n=1) (step S201). Then, after a sampling interval determined based on a pre-planned sampling rule, the first sampling of the sample that has passed through the catalyst layer is performed, and analysis is performed using the analyzer 7 (step S202).

[0104] Regarding the sampling rules, it is conceivable that various rules can be freely set for the control unit 11. However, in order to efficiently grasp the actual elapsed settling time, it is preferable to use " Figure 6 The sampling period is set in the manner of “the stabilization time (e.g., one hour) > the sampling period” in step S103.

[0105] As a specific example, the following rule can also be set: the sampling period after the counting of the number of samplings in step S201 begins is set to 30 minutes, and the subsequent sampling period is set to every 10 minutes.

[0106] Furthermore, the following rules can be set: the first sampling period is set to 0 minutes, sampling is performed immediately after the counting of sampling begins, and subsequent sampling periods are set to every 5 minutes.

[0107] In addition, the first sampling period is set to 0 minutes. Furthermore, for subsequent sampling periods, a table is created that correlates the concentration changes of the component of interest obtained from the analysis results of analyzer 7 with the sampling period, and the sampling period is adjusted based on this table. For example, in the table, the larger the concentration change of the component of interest used to determine whether it has stabilized, the longer the sampling period is set; conversely, the smaller the concentration change of the component of interest and the closer it is to stabilization, the shorter the sampling period is set.

[0108] Once the first sampling and analysis has been performed, the number of sampling operations is incremented (step S203), and it is confirmed whether the incremented value exceeds 2 (step S204). If it does not exceed 2 (step S204: No), the actions of steps S202 to S203 are repeated to perform the second sampling and analysis.

[0109] If the incremented value exceeds 2 (step S204: No), then at least two sampling and analysis operations have been performed, thus enabling a comparison between the previous analysis results and the current analysis results. Therefore, based on the previous and current concentration analysis results of the component of interest, used to determine whether the reaction system has stabilized, a determination is made as to whether the concentration change index of the component of interest has fallen below a pre-set threshold (step S205).

[0110] For example, if the concentration of the target component in the product contained in the sample has stabilized and it is determined that the actual stabilization time has passed, the target component is selected as the component of interest. Furthermore, if the concentration of the byproduct in the product has sufficiently decreased and stabilized, and it is determined that the stabilization time has passed, the byproduct is selected as the component of interest.

[0111] Furthermore, the concentration change index can be either the absolute value of the concentration difference between the previous and current analyses of the component of interest, or the ratio of the current concentration to the concentration at the time of the previous analysis. Alternatively, it can be the rate of change of the ratio of the absolute value of the concentration difference between the previous and current analyses of the component of interest to the current concentration, based on the concentration at the time of the previous analysis.

[0112] If the concentration change index of the component of interest does not fall below the preset threshold (step S205: No), then repeat steps S202 to S204. On the other hand, if the concentration change index has fallen below the threshold (step S205: Yes), then it is determined that the actual stabilization time has passed, and the analysis result of the final sampling is used as the analysis result of the reaction rate test (step S206). Then, return to... Figure 6 In step S105, the supply of raw material fluid and reaction gas is stopped, and a decision is made on whether to switch catalyst column 2a to catalyst column 2f (step S106).

[0113] According to usage Figure 7 The actions described enable you to proactively control the actual time elapsed and reduce futile waiting time.

[0114] Next, while referring to Figure 8 The following describes a structural example of the test apparatus 1a according to the second embodiment. The test apparatus 1a of the second embodiment is a structure in which multiple, for example two, ovens 5 (upstream oven 5a and downstream oven 5b) are connected in series. In the upstream oven 5a, multiple catalyst columns 2a to 2f with different catalyst layers are housed, and in the downstream oven 5b, multiple catalyst columns 2g to 2l are similarly housed.

[0115] Furthermore, an intermediate switching valve 65 is provided in the flow path connecting the upstream oven 5a and the downstream oven 5b. The intermediate switching valve 65 connects the upstream catalyst columns 2a to 2f and the downstream catalyst columns 2g to 2l. The upstream catalyst columns 2a to 2f are housed in the upstream oven 5a, from which the sample flows out, while the downstream catalyst columns 2g to 2l are housed in the downstream oven 5b. In addition, the control unit 11, besides using… Figure 5 In addition to the switching control of catalyst columns 2a to 2f via supply-side switching valve 61, supply-side switching valve 62 and outflow-side switching valve 63, the connection control of catalyst columns 2a to 2f on the upstream side and catalyst columns 2g to 2l on the downstream side via intermediate switching valve 65 is also performed.

[0116] Additionally, the selector valve 64 located upstream of the intermediate switching valve 65 functions to switch between using the upstream oven 5a alone and using the upstream oven 5a and the downstream oven 5b in series. When using the upstream oven 5a alone, it becomes a switch between using... Figure 5 The same structure is used in the example, and the reaction rate test is carried out using any one of the catalyst columns 2a to 2f alone. The sample flowing out of the catalyst layer is sent to the analyzer 7 via the sampling line 701a.

[0117] On the other hand, when the upstream oven 5a and the downstream oven 5b are connected in series, the total capacity of the catalyst layer becomes the sum of the capacity of the catalyst layer housed in the upstream oven 5a and any one of the catalyst columns 2a to 2f, and the capacity of the catalyst layer housed in the downstream oven 5b and any one of the catalyst columns 2g to 2l. As a result, in Figure 8In the example shown, six catalyst columns 2a-2f and six catalyst columns 2g-2l can be combined to set thirty-six different residence times for reaction rate testing. The outlet side of catalyst columns 2g-2l is connected to sampling line 701b via outflow-side switching valve 66, and the sample flowing out of the catalyst layer is sent to analyzer 7 through sampling line 701b.

[0118] If we summarize the above usages, then in Figure 8 The test apparatus 1a shown can be combined with the case of using the upstream oven 5a alone to set forty-two different residence times. Furthermore, the selection valve 64 and sampling line 701a are not necessary components; the upstream oven 5a and downstream oven 5b can always be used in series. In this case, by installing at least two catalyst columns 2a, 2b and catalyst columns 2g, 2h in each of the upstream oven 5a and downstream oven 5b, four different residence times can be set to conduct reaction rate tests. This satisfies at least three conditions for different residence times, thereby enabling the determination of reaction rate curves.

[0119] Furthermore, the number of ovens 5 connected in series is not limited to two, but can be three or more. In this case, the upstream oven 5a and the downstream oven 5b are determined by considering the two ovens 5 connected to each other via intermediate switching valves 65. Moreover, by providing a selection valve 64 and a sampling line 701a upstream of each intermediate switching valve 65, reaction rate tests can be performed by setting at least three conditions with different residence times by providing a catalyst column 2a in each of the minimum three ovens 5. In this case, the three catalyst columns 2a do not need to have different catalyst layer capacities; the catalyst layer capacities can also be the same.

[0120] Next, while referring to Figure 9 Here is an example of the structure of the test apparatus 1b according to the third embodiment. The test apparatus 1b of the third embodiment has multiple catalyst columns 2a to 2f with different catalyst layer capacities in a common oven 5, and two selected from them can be connected in series.

[0121] From this perspective, test device 1b becomes the basis for the use of Figure 5 The described test apparatus 1 is additionally equipped with a selection valve 64 and a target switching valve 67. The target switching valve 67 connects to a catalyst column 2a-2f from which the sample flows out of the catalyst layer. Figure 9 In the example, catalyst column 2e) and another catalyst column 2b-2f, 2a selected from a catalyst column other than 2e are used. Figure 9In the example, this is the function of catalyst column 2a). Moreover, the selection valve 64 serves to select the effluent target of the sample from one of the catalyst columns 2a to 2f between the sampling line 701a and another catalyst column 2b to 2f, 2a connected via the target switching valve 67.

[0122] Furthermore, the testing apparatus 1b includes: a first-stage outflow-side switching valve 63, located upstream of the selection valve 64; and a second-stage outflow-side switching valve 66, located downstream of one catalyst column 2a-2f and another catalyst column 2b-2f, 2a, which are connected to each other. The second-stage outflow-side switching valve 66 serves to connect the other catalyst column 2b-2f, 2a to the sampling line 701b.

[0123] In the testing apparatus 1b including the aforementioned structure, the control unit 11 implements control to select the effluent target of the sample via the selection valve 64. When a connection toward the sampling line 701a is selected via the selection valve 64, switching control is performed via the effluent-side switching valve 63 to make one catalyst column 2a-2f an effluent source. Furthermore, when a connection toward another catalyst column 2b-2f, 2a is selected via the selection valve 64, switching control is performed via the effluent-side switching valve 66 to make the other catalyst column 2b-2f, 2a an effluent source.

[0124] Figure 9 In the test apparatus 1b shown, as long as there are at least two catalyst columns 2a and 2b in the oven 5, at least three conditions with different residence times can be set to conduct reaction rate tests, whether each catalyst column 2a and 2b is used individually or when the catalyst columns 2a and 2b are connected in series.

[0125] Furthermore, in the testing apparatus 1b, catalyst columns 2a to 2f can also be configured to be connected in series in three or more stages. In this case, it is sufficient to set multiple stages of the selector valve 64, the target switching valve 67, the outflow-side switching valve 66, and the sampling line 701b. In the configuration where catalyst columns 2a to 2f can be connected in series in three or more stages, the catalyst layer capacity of catalyst columns 2a to 2f can also be the same, allowing for the setting of at least three conditions with different residence times to perform reaction rate testing.

[0126] For the above usage Figure 8 , Figure 9 The test apparatus 1a and test apparatus 1b of the second and third embodiments described herein can also be used. Figure 6 , Figure 7 The described action flow.

[0127] Furthermore, in the test apparatus 1, test apparatus 1a, and test apparatus 1b of the first to third embodiments, the method for changing the capacity of the catalyst layer is not limited to changing the length of the catalyst columns 2a to 2f. For example, the capacity of the catalyst layer can also be changed by changing the diameter of the catalyst columns 2a to 2f.

[0128] Furthermore, the types of reactions carried out using the catalyst are not limited to the hydrogenation reaction example; other reactions such as oxidation, reduction, and pyrolysis can also be used. Also, depending on the nature of the reaction, a single sample supply unit may be provided, or three or more sample supply units may be provided. Moreover, a preheater may be provided in the sample supply unit as needed to supply the preheated sample to catalyst columns 2a to 2f.

[0129] Examples of temperature control chamber structures for housing and regulating the temperature of multiple catalyst columns 2a to 2f are not limited to oven 5, but may also include aluminum block heaters, constant temperature chambers, or test refrigerators. Furthermore, the temperature control mechanism is not limited to temperature control chambers housing multiple catalyst columns 2a to 2f, but also includes structures that use sleeve heaters or belt heaters to cover individual catalyst columns 2a to 2f.

Claims

1. A testing apparatus for testing the reaction rate of a chemical reaction advanced in the presence of a catalyst, the testing apparatus characterized by comprising: The sample supply unit supplies the sample to the catalyst at a preset flow rate; Multiple reaction vessels, each including a catalyst layer filled with the catalyst; A temperature control mechanism is used to regulate the temperature of the reaction vessel. A supply-side switching valve connects to a supply flow path that supplies a sample from the sample supply unit for the reaction vessel selected from the plurality of reaction vessels as the supply target. An effluent-side switching valve connects to a sample flow path for the reaction vessel, which serves as the effluent source from the catalyst layer, to collect the sample that has passed through the catalyst layer for analysis; and The control unit controls the switching of the reaction vessel, which serves as the supply target and the outflow source, via the supply-side switching valve and the outflow-side switching valve, so as to perform reaction rate tests under at least three conditions with different residence times in the catalyst layer. A reaction vessel having at least three catalyst layers of different capacities. The control unit performs the switching control to make the reaction vessel that is the supply target consistent with the reaction vessel that is the outflow source.

2. A testing apparatus for testing the reaction rate of a chemical reaction advanced in the presence of a catalyst, the testing apparatus characterized by comprising: The sample supply unit supplies the sample to the catalyst at a preset flow rate; Multiple reaction vessels, each including a catalyst layer filled with the catalyst; A temperature control mechanism is used to regulate the temperature of the reaction vessel. A supply-side switching valve connects to a supply flow path that supplies a sample from the sample supply unit for the reaction vessel selected from the plurality of reaction vessels as the supply target. An effluent-side switching valve connects to a sample flow path for the reaction vessel, which serves as the effluent source from the catalyst layer, to collect the sample that has passed through the catalyst layer for analysis; and The control unit controls the switching of the reaction vessel, which serves as the supply target and the outflow source, via the supply-side switching valve and the outflow-side switching valve, so as to perform reaction rate tests under at least three conditions with different residence times in the catalyst layer. The temperature regulating mechanism is configured to regulate the temperature while the reaction vessel is housed inside a temperature regulating chamber. The testing apparatus includes: The upstream temperature control box and the downstream temperature control box each contain multiple reaction vessels with different capacities of the catalyst layer; as well as An intermediate switching valve connects the upstream reaction vessel and the downstream reaction vessel. The upstream reaction vessel is housed in a temperature-controlled chamber on the upstream side, from which the sample flows out of the catalyst layer. The downstream reaction vessel is selected from among the plurality of reaction vessels housed in the temperature-controlled chamber on the downstream side, and is supplied with the sample flowing out of the upstream reaction vessel. In addition to controlling the switching of the reaction vessels, the control unit also controls the connection between the upstream reaction vessel and the downstream reaction vessel via the intermediate switching valve.

3. A testing apparatus for testing the reaction rate of a chemical reaction advanced in the presence of a catalyst, the testing apparatus characterized by comprising: The sample supply unit supplies the sample to the catalyst at a preset flow rate; Multiple reaction vessels, each including a catalyst layer filled with the catalyst; A temperature control mechanism is used to regulate the temperature of the reaction vessel. A supply-side switching valve connects to a supply flow path that supplies a sample from the sample supply unit for the reaction vessel selected from the plurality of reaction vessels as the supply target. An effluent-side switching valve connects to a sample flow path for the reaction vessel, which serves as the effluent source from the catalyst layer, to collect the sample that has passed through the catalyst layer for analysis; and The control unit controls the switching of the reaction vessel, which serves as the supply target and the outflow source, via the supply-side switching valve and the outflow-side switching valve, so as to perform reaction rate tests under at least three conditions with different residence times in the catalyst layer. The temperature control mechanism is configured to regulate the temperature while multiple reaction vessels with different capacities of the catalyst layer are housed inside a temperature control chamber. The testing apparatus includes: Connect the target switching valve, for the plurality of reaction vessels, connecting one reaction vessel from which the sample flows out of the catalyst layer to another reaction vessel selected from the reaction vessels other than the first one; and The selection valve selects the effluent target of the sample from one of the reaction vessels between the sample flow path and the other reaction vessel via the connection target switching valve. The control unit implements control to select the effluent target of the sample via the selection valve. When a connection toward the sample flow path is selected via the selection, switching control is performed via the effluent-side switching valve to make one reaction vessel the effluent source. When a connection toward the other reaction vessel is selected via the selection, switching control is performed via the effluent-side switching valve to make the other reaction vessel the effluent source.

4. The testing apparatus according to any one of claims 1 to 3, characterized in that, The control unit, after a preset stabilization time elapses from the start of supplying the sample to the reaction vessel serving as the supply target via the supply flow path, collects the sample flowing out of the reaction vessel serving as the effluent source via the sample flow path, and then performs the switching control for the next reaction vessel serving as both the supply target and the effluent source.

5. A testing apparatus for testing the reaction rate of a chemical reaction advanced in the presence of a catalyst, the testing apparatus characterized by comprising: The sample supply unit supplies the sample to the catalyst at a preset flow rate; Multiple reaction vessels, each including a catalyst layer filled with the catalyst; A temperature control mechanism is used to regulate the temperature of the reaction vessel. A supply-side switching valve connects to a supply flow path that supplies a sample from the sample supply unit for the reaction vessel selected from the plurality of reaction vessels as the supply target. An effluent-side switching valve connects to a sample flow path for the reaction vessel, which serves as the effluent source from the catalyst layer, to collect the sample that has passed through the catalyst layer for analysis; and The control unit controls the switching of the reaction vessel, which serves as the supply target and the outflow source, via the supply-side switching valve and the outflow-side switching valve, so as to perform reaction rate tests under at least three conditions with different residence times in the catalyst layer. From the moment the control unit begins supplying the sample to the reaction vessel, which is the supply target, via the supply flow path, it collects samples flowing out of the reaction vessel, which is the effluent source, via the sample flow path at sampling periods determined based on a preset rule. Based on the results of concentration analysis of the component of interest contained in the sample, after the concentration change index of the component of interest falls below a preset threshold, it performs the switching control to the next reaction vessel, which is both the supply target and the effluent source.

6. The testing apparatus according to any one of claims 1 to 3 and 5, characterized in that, The control unit, after stopping the supply of the sample from the sample supply unit, performs the switching control to the next reaction vessel that serves as both the supply target and the effluent source.

7. A testing method for testing the reaction rate of a chemical reaction advanced in the presence of a catalyst, the testing method being characterized by comprising: The sample supplied to the catalyst is given at a predetermined flow rate; Temperature regulation is performed on multiple reaction vessels, each of which includes a catalyst layer filled with the catalyst; For the reaction vessel selected from the plurality of reaction vessels as the target of supply, a supply flow path for supplying the sample is connected; as well as A sample flow path is connected to the reaction vessel, which serves as the effluent source from the catalyst layer, to collect the sample that has passed through the catalyst layer for analysis. The steps for connecting the supply flow path and the steps for connecting the sample flow path are: The reaction vessel, serving as both the supply target and the effluent source, is switched to allow for reaction rate testing under at least three conditions with varying residence times in the catalyst bed. For at least three reaction vessels with different catalyst layer capacities, the process of connecting the supply flow path and the process of connecting the sample flow path are switched to ensure that the reaction vessel serving as the supply target is consistent with the reaction vessel serving as the outflow source.

8. A testing method for testing the reaction rate of a chemical reaction advanced in the presence of a catalyst, the testing method being characterized by comprising: The sample supplied to the catalyst is given at a predetermined flow rate; Temperature regulation is performed on multiple reaction vessels, each of which includes a catalyst layer filled with the catalyst; For the reaction vessel selected from the plurality of reaction vessels as the target of supply, a supply flow path for supplying the sample is connected; as well as A sample flow path is connected to the reaction vessel, which serves as the effluent source from the catalyst layer, to collect the sample that has passed through the catalyst layer for analysis. The steps for connecting the supply flow path and the steps for connecting the sample flow path are: The reaction vessel, serving as both the supply target and the effluent source, is switched to allow for reaction rate testing under at least three conditions with varying residence times in the catalyst bed. The process of temperature regulation of the reaction vessel is carried out while the reaction vessel is housed inside a temperature regulation chamber. The testing method includes the following steps: using upstream and downstream temperature-controlled chambers of a plurality of reaction vessels, each containing a catalyst layer, with different capacities, connecting the upstream and downstream reaction vessels; the upstream reaction vessels are housed in the upstream temperature-controlled chambers, from which the sample flows out of the catalyst layer; the downstream reaction vessels are selected from the plurality of reaction vessels housed in the downstream temperature-controlled chambers, and are supplied with the sample flowing out of the upstream reaction vessels. In addition to the switching of the reaction vessel serving as the supply target and the outflow source in the process of connecting the supply flow path and the process of connecting the sample flow path, a process of connecting the upstream reaction vessel and the downstream reaction vessel is also performed.

9. A testing method for testing the reaction rate of a chemical reaction advanced in the presence of a catalyst, the testing method being characterized by comprising: The sample supplied to the catalyst is given at a predetermined flow rate; Temperature regulation is performed on multiple reaction vessels, each of which includes a catalyst layer filled with the catalyst; For the reaction vessel selected from the plurality of reaction vessels as the target of supply, a supply flow path for supplying the sample is connected; as well as A sample flow path is connected to the reaction vessel, which serves as the effluent source from the catalyst layer, to collect the sample that has passed through the catalyst layer for analysis. The steps for connecting the supply flow path and the steps for connecting the sample flow path are: The reaction vessel, serving as both the supply target and the effluent source, is switched to allow for reaction rate testing under at least three conditions with varying residence times in the catalyst bed. The process of temperature regulation of the reaction vessel is carried out while multiple reaction vessels with different capacities of catalyst layers are housed inside a temperature regulation chamber. The testing method includes the following steps: for the plurality of reaction vessels, connecting one reaction vessel from which the sample flows out of the catalyst layer to another reaction vessel selected from among the reaction vessels other than the first reaction vessel; and Select the effluent target of the sample from one of the reaction vessels between the sample flow path and the other reaction vessel. In the selected process, if a connection toward the sample flow path is selected, the process of connecting the sample flow path is performed so that the one reaction vessel becomes the reaction vessel serving as the effluent source; if a connection toward the other reaction vessel is selected, the process of connecting the sample flow path is performed so that the other reaction vessel becomes the reaction vessel serving as the effluent source.

10. The test method according to any one of claims 7 to 9, characterized in that, By implementing the process of connecting the supply flow path and the process of connecting the sample flow path, after a predetermined stabilization time has elapsed since the sample is first supplied to the reaction vessel that is the supply target, the sample flowing out of the reaction vessel that is the outflow source is collected via the sample flow path. After that, the process of connecting the supply flow path and the process of connecting the sample flow path are implemented for the next reaction vessel that is both the supply target and the outflow source.

11. A testing method for testing the reaction rate of a chemical reaction advanced in the presence of a catalyst, the testing method being characterized by comprising: The sample supplied to the catalyst is given at a predetermined flow rate; Temperature regulation is performed on multiple reaction vessels, each of which includes a catalyst layer filled with the catalyst; For the reaction vessel selected from the plurality of reaction vessels as the target of supply, a supply flow path for supplying the sample is connected; as well as A sample flow path is connected to the reaction vessel, which serves as the effluent source from the catalyst layer, to collect the sample that has passed through the catalyst layer for analysis. The steps for connecting the supply flow path and the steps for connecting the sample flow path are: The reaction vessel, serving as both the supply target and the effluent source, is switched to allow for reaction rate testing under at least three conditions with varying residence times in the catalyst bed. By implementing the process of connecting the supply flow path and the process of connecting the sample flow path, starting from the beginning of supplying the sample from the supply flow path to the reaction vessel that is the supply target, the sample flowing out of the reaction vessel from the effluent source is collected every time a sampling period determined based on a pre-set rule is performed. Based on the results obtained from the concentration analysis of the component of interest contained in the sample, after the concentration change index of the component of interest falls below a pre-set threshold, the process of connecting the supply flow path and the process of connecting the sample flow path for the next reaction vessel that is the supply target and the effluent source is implemented.

12. The test method according to any one of claims 7 to 9, 11, characterized in that, From the point where the sample is stopped being supplied to the previous reaction vessel that was the supply target, the process of connecting the supply flow path and the sample flow path is performed for the next reaction vessel that is both the supply target and the effluent source.

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