Test device and test method

Abstract

Provided is a technique for automatically performing a reaction speed test while changing the residence time in a catalyst layer under the same flow condition. In a test device for testing the reaction speed of a chemical reaction propelled in the presence of a catalyst, a sample supply unit 31, 411 supplies a sample supplied to the catalyst at a preset flow rate, and each of a plurality of reaction containers 2a-2f includes a catalyst layer filled with the catalyst. The supply-side switching valves (61, 62) connect a supply flow path for supplying a sample to the reaction vessel (2e) as a supply target, and the outflow-side switching valve (63) connects a sample flow path (701) for collecting the sample for analysis to the reaction vessel (2e) as an outflow source from which the sample flows out of the catalyst layer. The control unit (11) performs switching control of the reaction vessels (2a-2f), which are supply targets and outflow sources, by means of the supply-side switching valves (61, 62) and the outflow-side switching valve (63) so that the reaction speed test is performed under at least three conditions in which the residence times in the catalyst layer differ.

Description

Technical Field

[0001] The present invention relates to a technique for performing tests for determining the reaction rate of a chemical reaction driven in the presence of a catalyst. Background Art

[0002] When designing a reaction device for supplying raw materials to a catalyst layer filled with a solid catalyst to obtain a desired target component, the reaction rate of the reaction (catalytic reaction) using the catalyst must be determined. However, in order to avoid the change of the flow state in the catalyst layer and determine the accurate reaction rate, it is necessary to replace multiple reaction vessels with different capacities of the catalyst layer while repeatedly implementing the reaction rate test. The determination of the reaction rate of the catalyst reaction that requires such a reaction vessel to be replaced becomes a burdensome operation for the implementer of the test.

[0003] Here, Patent Document 1 describes a technique in which, when screening is performed by combinatorial library to make reactants react in the presence of a catalyst, the same amount of test fluid is supplied per unit time to a container containing the catalyst. Furthermore, Patent Document 2 describes a reaction analysis device in which the temperature distribution of the reaction fluid immediately after the reaction starts is obtained along the flow direction of the reaction fluid flowing in a flow reactor to determine the reaction state of the reaction fluid.

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

[0005] Prior art literature

[0006] Patent Literature

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

[0008] Patent document 2: Japanese Patent Laid-Open No. 2021-159910 Summary of the invention

[0009] Problems to be solved by the invention

[0010] The present invention was made under such background, and provides a technique for automatically performing a reaction rate test while changing the residence time in a catalyst layer under the same flow state.

[0011] Technical means of solving problems

[0012] The present invention is a testing device for testing the reaction rate of a chemical reaction promoted in the presence of a catalyst, wherein the testing device is characterized by comprising:

[0013] a sample supply unit for supplying the sample to the catalyst at a preset flow rate;

[0014] a plurality of reaction containers, each comprising a catalyst layer filled with the catalyst;

[0015] A temperature regulating mechanism for regulating the temperature of the reaction container;

[0016] a supply-side switching valve that connects a supply flow path for supplying a sample from the sample supply unit to a reaction container selected as a supply target from among the plurality of reaction containers;

[0017] an outflow-side switching valve for connecting a sample flow path to a reaction container as an outflow source of the sample flowing out of the catalyst layer, the sample flow path being used to collect the sample passing through the catalyst layer for analysis; and

[0018] The control unit controls switching of the reaction container serving as the supply target and the outflow source through the supply-side switching valve and the outflow-side switching valve so as to perform a reaction rate test 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) The control unit performs the switching control so that the reaction container serving as the supply destination and the reaction container serving as the outflow source are matched with each other, wherein the reaction container has at least three catalyst layers with different capacities.

[0021] (b) The temperature regulating mechanism is configured to perform temperature regulation in a state where the reaction container is accommodated in a temperature regulating box, and the testing device includes: a temperature regulating box on an upstream side and a temperature regulating box on a downstream side, each of which accommodates a plurality of the reaction containers having different capacities of the catalyst layer; and an intermediate switching valve connecting the reaction container on the upstream side with the reaction container on the downstream side, the reaction container on the upstream side being accommodated in the temperature regulating box on the upstream side, and the sample flowing out of the catalyst layer, the reaction container on the downstream side being selected from the plurality of reaction containers accommodated in the temperature regulating box on the downstream side, and being supplied with the sample flowing out of the reaction container on the upstream side, and the control unit, in addition to controlling the switching of the reaction containers, also controls the connection between the reaction container on the upstream side and the reaction container on the downstream side by means of the intermediate switching valve.

[0022] (c) The temperature regulating mechanism is configured to perform temperature regulation in a state where a plurality of reaction containers having different capacities of the catalyst layer are housed in a temperature regulating box, and the testing device includes: a connection target switching valve for connecting, for the plurality of reaction containers, a reaction container from which the sample flows out of the catalyst layer with another reaction container selected from reaction containers other than the one reaction container; and a selection valve for selecting an outflow target of the sample from the one reaction container between the sample flow path and the other reaction container via the connection target switching valve, the control unit implements control of selecting the outflow target of the sample through the selection valve, and when the connection toward the sample flow path is selected through the selection, switching control is performed by means of the outflow side switching valve so that the one reaction container becomes the reaction container serving as the outflow source, and when the connection toward the other reaction container is selected through the selection, switching control is performed by means of the outflow side switching valve so that the other reaction container becomes the reaction container serving as the outflow source.

[0023] (d) The control unit collects the sample flowing out from the reaction container serving as the outflow source via the sample flow path after a predetermined stabilization time has elapsed since the supply of the sample from the supply flow path to the reaction container serving as the supply target, and then performs the switching control to the next reaction container serving as the supply target and the outflow source.

[0024] (e) The control unit collects the sample flowing out from the reaction container serving as the outflow source via the sample flow path at each sampling period determined based on a preset rule from the start of supplying the sample from the supply flow path to the reaction container serving as the supply target, and based on a result of a concentration analysis of a component of interest contained in the sample, performs the switching control to the next reaction container serving as the supply target and the outflow source after a concentration change index of the component of interest becomes below a preset threshold value.

[0025] (f) The control unit performs the switching control to the next reaction container serving as the supply destination and the outflow source after the supply of the sample from the sample supply unit is stopped.

[0026] Effects of the Invention

[0027] The present invention uses a plurality of reaction vessels including a catalyst layer, and performs switching control of a supply-side switching valve and an outflow-side switching valve, so that a reaction rate test is performed under at least three conditions with different residence times in the catalyst layer. As a result, a reaction rate test for measuring the reaction rate of a chemical reaction promoted in the presence of a catalyst can be performed without manually replacing the reaction vessels. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] [ Figure 1 ] is a schematic diagram showing a reaction in which a raw material is supplied to a catalyst layer to obtain a product.

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

[0030] [ Figure 3 ] is an explanatory diagram of the method of obtaining the reaction rate curve.

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

[0032] [ Figure 5 ] is a structural diagram of the testing device of the first embodiment.

[0033] [ Figure 6 ] is an example of the action flow of the testing device of the first embodiment.

[0034] [ Figure 7 ] is a flowchart related to the action of performing column switching judgment.

[0035] [ Figure 8 ] is a structural diagram of the testing device of the second embodiment.

[0036] [ Fig. 9 ] is a structural diagram of the test device of the third embodiment. DETAILED DESCRIPTION

[0037] First, the reasons why it is necessary to determine the reaction rate when designing a reaction apparatus including a catalyst layer filled with a solid catalyst and the problems of conventional testing apparatuses are described.

[0038] like Figure 1 As shown, in a reaction system using a catalyst layer, a fluid as a raw material is circulated in the catalyst layer so that the raw material contacts the catalyst, thereby promoting the catalyst reaction and obtaining a target component from the product generated by the reaction. Generally speaking, under the condition that the reaction temperature and the raw material concentration in the fluid are fixed, the longer the residence time in the catalyst layer is, the more raw material will be consumed by the reaction, thereby obtaining a product in an amount corresponding to the consumption of the raw material.

[0039] At this time, the relationship between the residence time of the raw material in the catalyst layer, i.e., the reaction time (e.g., "seconds") and the raw material concentration at the outlet of the catalyst layer (the percentage display value of the outlet concentration relative to the inlet concentration toward the catalyst layer) (reaction rate curve) can be shown as Figure 2In a reaction system with a high reaction rate, as shown by a dotted line, the raw material concentration drops sharply in a short residence time. On the other hand, in a reaction system with a low reaction rate, as shown by a solid line, the raw material concentration drops more slowly as the residence time increases compared to a reaction system with a high reaction rate.

[0040] Such a difference in reaction rate affects the design of the reaction device for obtaining the target component from the raw material. For example, in a reaction system (reaction rate: large) that can convert a specified amount of raw materials into a product in a short reaction time (retention time), the capacity of the catalyst layer can be reduced, that is, the volume of the reaction tower can be reduced. On the other hand, in a reaction system (reaction rate: small) that requires a longer reaction time (retention time) to convert a specified amount of raw materials into a product, the volume of the reaction tower, that is, the capacity of the catalyst layer, has to be made larger.

[0041] Thus, the reaction rate of the catalytic reaction is one of the important catalyst characteristics that should be mastered in advance when designing a reaction device. Therefore, when determining the reaction rate of a certain reaction system, the following reaction rate test should be carried out, that is, while changing the residence time of the raw material passing through the catalyst layer, the raw material concentration at the outlet of the catalyst layer should be measured. Figure 3 As shown in FIG. 1 , the reaction rate curve is obtained by plotting the relationship between the raw material concentration at the catalyst layer outlet and the residence time at multiple points and fitting the curve.

[0042] Here, as a method for changing the residence time of the raw material in the catalyst layer, it is also considered to change the supply flow rate of the raw material in sequence for the catalyst layer filled with a predetermined amount of catalyst. However, in this method, the flow state of the raw material flowing in the catalyst layer may be greatly different depending on the change in the supply flow rate. As a result, it is difficult to perform the reaction rate test under the condition that the conditions other than the residence time are consistent, and it is possible that an accurate reaction rate curve cannot be obtained.

[0043] Therefore, the previous use Figure 4 The reaction speed test is carried out using the test device 100 having the structure illustrated in the figure to obtain a reaction speed curve. Figure 4 The test device 100 shown is configured as a device for performing a reaction experiment for obtaining a reaction rate curve of a hydrogenation reaction in which a raw material contained in a raw material fluid is hydrogenated, for example.

[0044] If the structure of the test device 100 is briefly described, a raw material fluid (e.g., liquid) containing a raw material is stored in the raw material supply unit 31. The raw material fluid is supplied at a preset flow rate through the raw material supply pipeline 301 by the pump 32 based on the flow measurement result obtained by the flow meter 33. A pressure gauge 34 or a thermometer 35 is provided in the raw material supply pipeline 301, which can measure the supply pressure or supply temperature of the raw material fluid. The raw material supply unit 31, the pump 32, and the flow meter 33 constitute a sample supply unit that supplies the raw material fluid as a sample at a preset flow rate, and the raw material supply pipeline 301 constitutes a sample supply path.

[0045] On the other hand, hydrogen gas for hydrogenation reaction is stored in the hydrogen supply unit 411. Hydrogen gas is supplied at a preset flow rate while flow rate adjustment is performed by the flow control valve 412 based on the flow measurement result obtained by the flow meter 413. Furthermore, nitrogen gas for hydrogen concentration adjustment is stored in the nitrogen supply unit 421. Nitrogen gas is supplied at a preset flow rate while flow rate adjustment is performed by the flow control valve 422 based on the flow measurement result obtained by the flow meter 423.

[0046] After these hydrogen and nitrogen gases converge, they are supplied as a mixed gas (hereinafter also referred to as "reaction gas") through the reaction gas supply line 401. The downstream end of the reaction gas supply line 401 converges to the raw material supply line 301 for supplying the raw material fluid. The hydrogen supply unit 411, the flow rate control valve 412, the flow meter 413 and the nitrogen supply unit 421, the flow rate control valve 422, the flow meter 423 constitute a sample supply unit for supplying hydrogen or nitrogen as a sample at a preset flow rate, and the reaction gas supply line 401 constitutes a sample supply path.

[0047] The catalyst used for the hydrogenation reaction of the raw material is respectively filled in a plurality of catalyst columns 2a to 2f as reaction containers. These catalyst columns 2a to 2f include, for example, cylindrical containers made of stainless steel with a diameter of 5 mm. The cylindrical containers constituting the catalyst columns 2a to 2f are, for example, constructed so that the length dimensions are different from each other within the range of 50 mm to 300 mm, and are filled with catalysts of different capacities corresponding to their respective length dimensions. In this example, for the catalyst columns 2a to 2f with larger length dimensions, a catalyst layer filled with a larger capacity of catalyst is provided. In addition, the constituent materials or dimensions, and the number of catalyst columns 2a to 2f used are exemplified and may be appropriately changed.

[0048] In the test apparatus 100 of this example, a plurality of catalyst columns 2a to 2f having different catalyst layer capacities are prepared in advance, and one of the catalyst columns ( Figure 4In the example shown, the catalyst column 2a) is arranged in an oven 5. The oven 5 is heated to a preset temperature (eg, 100°C).

[0049] Moreover, the setting temperature of the oven 5 can be changed within the range of 40°C to 150°C, for example. By carrying out reaction rate tests under different setting temperatures, the temperature dependence of the reaction rate can also be evaluated. In this regard, the oven 5 serves as a temperature control mechanism (temperature control box) for controlling the temperature of the catalyst columns 2a to 2f, i.e., the catalyst layer, housed therein.

[0050] The downstream end of the raw material supply line 301 is connected to the inlet side of the catalyst column 2a housed in the oven 5. The downstream end is located on the downstream side of the confluence position with the reaction gas supply line 401. On the other hand, the sampling line (sample flow path) 701 is connected to the outlet side of the catalyst column 2a, and the sampling line (sample flow path) 701 is used to collect the sample passing through the catalyst layer in the catalyst column 2a for analysis.

[0051] The downstream end of the sampling line 701 is connected to the analyzer 7 provided outside the test device 100. In the case where the sample flowing out of the sampling line 701 is a liquid, a case where a liquid chromatograph (LC) is used as the analyzer 7 for performing component analysis / quantitative analysis of the sample can be exemplified. Here, when a sample as a liquid is supplied, a sample collection mechanism using, for example, a syringe is sometimes provided in the analyzer 7. At this time, if bubbles or dissolved gas are contained in the sample, a malfunction may occur when the sample is collected by the sample collection mechanism. Therefore, a gas-liquid separator or a degasser may be provided between the downstream end of the sampling line 701 and the analyzer 7 as required.

[0052] The sample after the product is analyzed by the analyzer 7 is discharged through the discharge line 702 .

[0053] In addition, the analyzer 7 connected to the sampling line 701 is not limited to LC. When the sample is a gas, a gas chromatograph (GC) may be used. Furthermore, an LC or GC-MS or other analyzers provided with a mass analyzer (mass spectrometer (MS)) may be used according to the content of the analysis. Moreover, when the sample is a liquid, a fraction collector may be provided at the inlet side of the analyzer 7, and the sampling line 701 may be connected to the fraction collector.

[0054] In the test device 100 having the above structure, the catalyst column 2a to be used in the current reaction rate test is selected from a plurality of catalyst columns 2a to 2f prepared in advance, and is placed in the oven 5, and the raw material supply line 301 or the sampling line 701 is installed. Then, the temperature in the oven 5 is raised, and once it stabilizes at the set temperature, the supply of samples such as raw material fluid or reaction gas is started.

[0055] The stabilization of the reaction takes about one hour, for example, so after the stabilization time has passed since the start of the sample supply, the sample is sampled and analyzed using the analyzer 7. When the temperature dependence of the reaction rate is also evaluated, the sample supply is stopped and the set temperature of the oven 5 is changed. And once the temperature in the oven 5 stabilizes at the new set temperature, the above-mentioned operation of "supply of sample → waiting for stabilization → sampling and analysis of sample" is repeated. In addition, the sample supply may not necessarily be stopped when the set temperature of the oven 5 is changed. For example, the supply of raw materials and hydrogen may be stopped and only the supply of nitrogen may be continued, or the supply of raw materials or hydrogen may be continued when there is a sufficient amount of raw materials or hydrogen.

[0056] In this way, once the above operation is completed for all the set temperatures required for the evaluation of temperature dependence, the supply of the sample (raw material fluid, reaction gas) or the heating of the oven 5 is stopped. Then, once the temperature in the oven 5 drops to a temperature at which the operation can be performed, the catalyst column 2a is removed, and after the next catalyst column 2b is installed, the reaction rate test is repeated according to the above procedure.

[0057] Here, in order to obtain Figure 2 The reaction rate curve shown as a curve must be tested at least at three different residence times (reaction times). In order to obtain a more accurate reaction rate curve, the reaction rate test must be performed at four or more different residence times.

[0058] thus, Figure 4 In the test apparatus 100 of the conventional structure shown, the reaction rate test and the replacement operation must be performed on the catalyst columns 2a to 2f corresponding to the residence times at three or more points. However, the waiting time is long and the replacement operation of the catalyst columns 2a to 2f that is repeated is a great burden for the test implementer.

[0059] Therefore, the test device 1 of the present embodiment is configured to automatically perform a reaction rate test for obtaining a reaction rate curve without replacing the catalyst columns 2a to 2f. Figure 5 to Figure 7 , while explaining the structure and function of the test device 1 of this embodiment.

[0060] In addition, Figure 5 , Figure 8 , Fig. 9 In each of the test devices 1, 1a, 1b shown, for use with Figure 1 The components common to the test apparatus 100 are labeled Figure 1 The symbols used in the common symbols.

[0061] Figure 5 In the test apparatus 1 shown, at least three (six in the example of the figure) catalyst columns 2a to 2f having different catalyst layer capacities are pre-installed in a common oven 5. Thus, the test apparatus 1 of the present embodiment has a structure that does not require replacement work of the catalyst columns 2a to 2f.

[0062] On the other hand, when a plurality of catalyst columns 2a to 2f are housed in the oven 5, it is necessary to select the catalyst column 2a to 2f which is the supply target of the sample from the raw material supply line 301 and the reaction gas supply line 401 or the outflow source of the sample toward the sampling line 701.

[0063] In view of this, the test device 1 of the present 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 valve 61 and the supply-side switching valve 62 play the role of connecting the raw material supply line 301 of the raw material fluid as the sample and the reaction gas supply line 401 of the reaction gas to the supply target selected from the plurality of catalyst columns 2a to 2f, respectively. Furthermore, the outflow-side switching valve 63 plays the role of connecting the sample flow path to the catalyst columns 2a to 2f as the outflow sources of the sample flowing out of the catalyst layer.

[0064] The supply-side switching valves 61, 62 and the outflow-side switching valve 63 are switched by the control unit 11. The control unit 11 uses the supply-side switching valves 61, 62 and the outflow-side switching valve 63 to switch the catalyst columns 2a to 2f as the supply destination and outflow source of the sample. For example, the control unit 11 includes a computer or a control circuit. In particular, in the test device 1 of the present embodiment, the control unit 11 switches the supply-side switching valve 61, the supply-side switching valve 62 and the outflow-side switching valve 63 so that the catalyst columns 2a to 2f as the supply destination and outflow source of the sample are consistent.

[0065] For example, Figure 56 shows the state where the supply-side switching valve 61, the supply-side switching valve 62 and the outflow-side switching valve 63 are switched to connect the catalyst column 2e with the raw material supply line 301, the reaction gas supply line 401 and the sampling line 701. And, by sequentially performing this switching, it is possible to connect at least three ( Figure 5 The reaction speed test was performed under a maximum of six conditions in the example shown.

[0066] Next, in addition to Figure 5 In addition, we also refer to Figure 6 The operation of the test device 1 having the above structure will be described. When the reaction rate test using the test device 1 is performed (start), the catalyst column 2e to be the test object is selected from the catalyst columns 2a to 2f accommodated in the oven 5, and the supply side switching valve 61, the supply side switching valve 62 and the outflow side switching valve 63 are switched (step S101). Next, the raw material fluid and the reaction gas as the sample are supplied to the switched catalyst column 2e (step S102).

[0067] Subsequently, the sample supply is continued until a preset stabilization time has passed (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 passed, the sample is sampled and analyzed via the sampling line 701 (step S104). Then, the supply of the raw material fluid and the reaction gas to the catalyst column 2e is stopped (step S105).

[0068] In addition, here, we also use Figure 4 In the case of evaluating the temperature dependency of the reaction rate 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, in this case, step S102 implements the operation of supplying the raw material fluid and the reaction gas to the catalyst column 2e after the set temperature is changed.

[0069] After the sample supply stop operation in step S105, it is confirmed whether the catalyst column 2a to catalyst column 2d and catalyst column 2f are set to be subjected to the reaction rate test next (step S106). For example, when the reaction rate test of catalyst column 2e is completed, it is considered that the reaction rate test of catalyst column 2a to catalyst column 2d has been completed, and the reaction rate test of the remaining catalyst column 2f is to be subjected to (step S106: yes). At this time, the catalyst column 2f is switched in step S101, and the operations of steps S102 to S106 are repeated.

[0070] If there is no catalyst column 2a to 2f to be switched to for the next reaction rate test (step S106: No), the reaction rate test is terminated. Then, for example, a curve is fitted in an external computer that obtains the test results from the analyzer 7, and a reaction rate curve is automatically prepared to terminate the operation (end).

[0071] According to the test device 1 of the present embodiment, the following effects are achieved. Using a plurality of catalyst columns 2a to 2f including a catalyst layer, the supply-side switching valve 61, the supply-side switching valve 62, and the outflow-side switching valve 63 are switched and controlled so that a reaction rate test is performed under at least three conditions with different residence times in the catalyst layer. As a result, a reaction rate test for determining the reaction rate of a chemical reaction that is advanced in the presence of a catalyst can be performed without manually replacing the catalyst columns 2a to 2f.

[0072] Here, for the use Figure 6 In the step S103 described above, instead of waiting for the elapse of the preset stabilization time, the actual elapse of the stabilization time may be confirmed. Figure 7 An example of an operation to be performed in place of step S103 at this time is shown.

[0073] At the beginning Figure 6 After the sample is supplied in step S102, the control unit 11 starts counting the number of sampling times (n=1) (step S201). Then, after a sampling interval determined based on a pre-programmed sampling rule, the first sampling of the sample that has passed through the catalyst layer is performed and analyzed by the analyzer 7 (step S202).

[0074] Here, regarding the sampling rule, it is conceivable that various rules can be freely set for the control unit 11. However, in order to efficiently grasp the actual passage of stable time, it is preferable to use " Figure 6 The sampling period is set in the manner of "stabilization time (e.g., one hour)>sampling period" in step S103.

[0075] As a specific example, the following rule may be set: the sampling cycle after the counting of the number of sampling executions in step S201 is started is set to 30 minutes, and the subsequent sampling cycle is set to every 10 minutes.

[0076] Furthermore, the following rule may be set: the first sampling cycle is set to 0 minutes, sampling is performed immediately after the counting of the number of sampling executions begins, and the subsequent sampling cycles are set to every 5 minutes.

[0077] In addition, the first sampling period is set to 0 minutes. And, for the subsequent sampling periods, a table is prepared that associates the concentration change of the component of interest obtained from the analysis result of the analyzer 7 with the sampling period, and the sampling period is changed based on the table. The following example can be given: in the table, the greater the concentration change of the component of interest that is judged to be stable, the longer the sampling period is set, and the smaller the concentration change of the component of interest becomes and the closer it is to stability, the shorter the sampling period is set.

[0078] Once the first sampling and analysis is performed in this way, the number of samplings 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.

[0079] If the incremented value exceeds 2 (step S204: No), at least two sampling and analysis have been performed, so the previous analysis result and the current analysis result can be compared. Therefore, based on the previous and current concentration analysis results of the component of interest, which are used to determine whether the reaction system has stabilized, it is determined whether the concentration change index of the component of interest has become below a preset threshold (step S205).

[0080] For example, when the concentration of the target component in the product contained in the sample has stabilized and it is judged that the actual stabilization time has passed, the target component is selected as the component of interest. Also, when the concentration of the byproduct in the product has stabilized in a sufficiently reduced state and it is judged that the stabilization time has passed, the byproduct is selected as the component of interest.

[0081] Furthermore, the concentration change index may be the absolute value of the concentration difference between the previous and current components of interest, or the ratio of the current concentration to the concentration at the time of the previous analysis. Furthermore, the ratio of the absolute value of the concentration difference between the previous and current components of interest to the concentration at the time of the previous analysis may be expressed as the rate of change.

[0082] If the concentration change index of the component of interest is not below the preset threshold (step S205: No), the actions of steps S202 to S204 are repeated. On the other hand, if the concentration change index is below the threshold (step S205: Yes), it is determined that the actual stabilization time has passed, and the analysis result of the last sampling is adopted as the analysis result of the reaction speed test (step S206). Then, return to Figure 6 In step S105, the supply of the raw material fluid and the reaction gas is stopped, and the necessity of switching the catalyst columns 2a to 2f is determined (step S106).

[0083] According to the use Figure 7 The described operation can proactively grasp the actual passage of stabilization time and reduce unnecessary waiting time.

[0084] Next, refer to Figure 8 , while explaining a structural example of a test device 1a of the second embodiment. The test device 1a of the second embodiment is a structure in which a plurality of, for example, two ovens 5 (an upstream oven 5a and a downstream oven 5b) are connected in series. The upstream oven 5a houses a plurality of catalyst columns 2a to 2f having different catalyst layer capacities, and the downstream oven 5b houses a plurality of catalyst columns 2g to 2l in the same manner.

[0085] In addition, 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 serves to connect the upstream catalyst column 2a to the upstream catalyst column 2f and the downstream catalyst column 2g to the downstream catalyst column 2l. The upstream catalyst column 2a to the upstream catalyst column 2f are accommodated in the upstream oven 5a and the sample flows out from the catalyst layer, and the downstream catalyst column 2g to the downstream catalyst column 2l are accommodated in the downstream oven 5b. In addition, the control unit 11 uses Figure 5 In addition to the switching control of the catalyst columns 2a to 2f by means of the supply-side switching valve 61, the supply-side switching valve 62 and the outflow-side switching valve 63 as described above, connection control of the upstream catalyst column 2a to the upstream catalyst column 2f and the downstream catalyst column 2g to the downstream catalyst column 2l is also performed by means of the intermediate switching valve 65.

[0086] The selector valve 64 provided on the upstream side of the intermediate switching valve 65 plays the role of switching between the case where the upstream oven 5a is used alone and the case where the upstream oven 5a and the downstream oven 5b are connected in series. Figure 5 In the same structure as in the example of FIG. 7 , a reaction rate test is performed using any one of the catalyst columns 2 a to 2 f alone, and the sample flowing out of the catalyst layer is sent to the analyzer 7 through the sampling line 701 a .

[0087] 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 of any one of the catalyst columns 2a to 2f housed in the upstream oven 5a and the capacity of the catalyst layer of any one of the catalyst columns 2g to 2l housed in the downstream oven 5b. Figure 8In the example shown, six catalyst columns 2a to 2f and six catalyst columns 2g to 2l can be combined to set thirty-six different retention times to perform a reaction rate test. The outlet side of the catalyst column 2g to the catalyst column 2l is connected to the sampling line 701b through the outflow side switching valve 66, and the sample flowing out of the catalyst layer is sent to the analyzer 7 through the sampling line 701b.

[0088] If we summarize the above usage, then Figure 8 In the test device 1a shown as a whole, 42 different residence times can be set in combination with the case where the upstream oven 5a is used alone. In addition, it is not necessary to set the selection valve 64 and the sampling line 701a, and the upstream oven 5a and the downstream oven 5b can also be used in a state of being always connected in series. In this case, as long as at least two catalyst columns 2a, 2b and catalyst columns 2g, 2h are respectively provided in the upstream oven 5a and the downstream oven 5b, four different residence times can be set to perform the reaction rate test. This satisfies at least three conditions of different residence times, so that the reaction rate curve can be determined.

[0089] Furthermore, the number of ovens 5 connected in series is not limited to two, and may be three or more. At this time, the upstream oven 5a and the downstream oven 5b are determined by focusing on the two ovens 5 connected to each other via the intermediate switching valve 65. Moreover, as long as the selection valve 64 and the sampling line 701a are provided on the upstream side of each intermediate switching valve 65, a reaction rate test can be performed by providing a catalyst column 2a in each of the minimum three ovens 5 and setting at least three conditions with different residence times. At this time, the three catalyst columns 2a do not need to have different catalyst layer capacities, and the catalyst layer capacities may be the same as each other.

[0090] Next, refer to Fig. 9 The configuration example of the test apparatus 1b of the third embodiment will be described. The test apparatus 1b of the third embodiment has a plurality of catalyst columns 2a to 2f having different catalyst layer capacities in a common oven 5, and two selected ones of the catalyst columns 2a to 2f can be connected in series.

[0091] In this regard, the test device 1b becomes a Figure 5 The structure of the test device 1 described above is additionally provided with a selector valve 64 and a connection destination switching valve 67. The connection destination switching valve 67 serves to connect one of the catalyst columns 2a to 2f ( Fig. 9 In the example, the catalyst column 2e) and another catalyst column 2b to 2f, 2a (selected from the catalyst column 2e) Fig. 9The selector valve 64 plays a role of selecting the outflow destination of the sample from one catalyst column 2a to 2f between the sampling line 701a and the other catalyst columns 2b to 2f, 2a connected via the connection destination switching valve 67.

[0092] Furthermore, the test device 1b includes: a first-stage outflow-side switching valve 63, which is provided on the upstream side of the selection valve 64; and a second-stage outflow-side switching valve 66, which is provided on the most downstream side of one catalyst column 2a to 2f and the other catalyst columns 2b to 2f, 2a connected to each other. The second-stage outflow-side switching valve 66 serves to connect the other catalyst columns 2b to 2f, 2a to the sampling line 701b.

[0093] In the test device 1b having the above-mentioned structure, the control unit 11 implements control to select the outflow destination of the sample through the selection valve 64. When the connection to the sampling line 701a is selected through the selection, the switching control to the sampling line 701a is performed through the outflow side switching valve 63 so that one of the catalyst columns 2a to 2f becomes the outflow source. Moreover, when the connection to the other 2a to 2f, 2a is selected through the selection valve 64, the switching control to the sampling line 701b is performed through the outflow side switching valve 66 so that the other 2a to 2f, 2a becomes the outflow source.

[0094] Fig. 9 In the test device 1b shown, as long as at least two catalyst columns 2a and 2b are provided in the oven 5, it is possible to implement a reaction rate test by setting at least three conditions with different residence times, namely, when each catalyst column 2a and 2b is used alone and when the catalyst columns 2a and 2b are connected in series.

[0095] Furthermore, in the test device 1b, the catalyst columns 2a to 2f may also be configured to be connected in series in three or more stages. In this case, the group of the selection valve 64, the connection target switching valve 67, the outflow side switching valve 66, and the sampling pipeline 701b may be configured to be multiple stages. In the configuration in which the catalyst columns 2a to 2f may be connected in series in three or more stages, the capacities of the catalyst layers of the catalyst columns 2a to 2f may also be the same, and at least three conditions with different residence times may be set to implement the reaction rate test.

[0096] For the above use Figure 8 , Fig. 9 The test devices 1a and 1b of the second and third embodiments described above can also be applied to Figure 6 , Figure 7 The described action flow.

[0097] Furthermore, in the test apparatus 1, test apparatus 1a, and test apparatus 1b of the first to third embodiments, the method of changing the capacity of the catalyst layer is not limited to making the lengths of the catalyst columns 2a to 2f different. For example, the capacity of the catalyst layer may be changed by making the diameters of the catalyst columns 2a to 2f different.

[0098] Furthermore, the type of reaction performed using the catalyst is not limited to the example of hydrogenation reaction, and may also be other reactions such as oxidation reaction, reduction reaction, pyrolysis reaction, etc. Furthermore, depending on the content of the reaction, only one system of test supply units may be provided, or three or more systems of test supply units may be provided. Furthermore, a preheater may be provided in the sample supply unit as needed, and the preheated sample may be supplied to the catalyst columns 2a to 2f.

[0099] The structure of the temperature regulating box for accommodating the plurality of catalyst columns 2a to 2f and regulating the temperature is not limited to the oven 5, and may be an aluminum block heater, a thermostatic box, a test refrigerator, etc. Furthermore, the temperature regulating mechanism is not limited to the temperature regulating box of the type for accommodating the plurality of catalyst columns 2a to 2f, and includes a structure in which the individual catalyst columns 2a to 2f are covered with a jacket heater or a belt heater, etc.

[0100] Explanation of symbols

[0101] 1, 1a, 1b, 100: Test device

[0102] 11: Control Department

[0103] 2a~2f:Catalyst column

[0104] 301: Raw material supply pipeline

[0105] 31: Raw material supply department

[0106] 32: Pump

[0107] 33: Flow meter

[0108] 34: Pressure gauge

[0109] 35: Thermometer

[0110] 401: Reaction gas supply line

[0111] 411: Hydrogen supply unit

[0112] 412: Flow control valve

[0113] 413: Flow meter

[0114] 421: Nitrogen supply unit

[0115] 422: Flow control valve

[0116] 423: Flow meter

[0117] 5. Oven

[0118] 5a: Upstream side oven

[0119] 5b: Downstream oven

[0120] 61: Supply side switching valve

[0121] 62: Supply side switching valve

[0122] 63: Outflow side switching valve

[0123] 64: Selector valve

[0124] 65: Intermediate switching valve

[0125] 66: Outflow side switching valve

[0126] 67: Connect the target switching valve

[0127] 701, 701a, 701b: Sampling lines

[0128] 702: Discharge line

[0129] 7: Analyzer

Claims

1. A test device for testing the reaction rate of a chemical reaction promoted in the presence of a catalyst, the test device being characterized by comprising: a sample supply unit for supplying the sample to the catalyst at a preset flow rate; a plurality of reaction containers, each comprising a catalyst layer filled with the catalyst; A temperature regulating mechanism for regulating the temperature of the reaction container; a supply-side switching valve that connects a supply flow path for supplying a sample from the sample supply unit to a reaction container selected as a supply target from among the plurality of reaction containers; an outflow-side switching valve for connecting a sample flow path to a reaction container as an outflow source of the sample flowing out of the catalyst layer, the sample flow path being used to collect the sample passing through the catalyst layer for analysis; and The control unit controls switching of the reaction container serving as the supply target and the outflow source through the supply-side switching valve and the outflow-side switching valve so as to perform a reaction rate test under at least three conditions with different residence times in the catalyst layer.

2. The testing device according to claim 1, characterized in that: A reaction container having at least three catalyst layers having different capacities, The control unit performs the switching control so that the reaction container serving as the supply destination coincides with the reaction container serving as the outflow source.

3. The testing device according to claim 1, characterized in that: The temperature adjustment mechanism is configured to adjust the temperature of the reaction container in a state where the reaction container is accommodated in a temperature adjustment box. The testing device comprises: The temperature regulating box on the upstream side and the temperature regulating box on the downstream side each accommodate a plurality of the reaction containers having different capacities of the catalyst layer; and an intermediate switching valve, connecting an upstream reaction container and a downstream reaction container, wherein the upstream reaction container is accommodated in a temperature regulating box on the upstream side and the sample flows out from the catalyst layer, and the downstream reaction container is selected from the plurality of reaction containers accommodated in the temperature regulating box on the downstream side and is supplied with the sample flowing out from the upstream reaction container, The control unit controls the connection between the upstream reaction container and the downstream reaction container via the intermediate switching valve in addition to the switching control of the reaction container.

4. The testing device according to claim 1, characterized in that: The temperature control mechanism is configured to control the temperature in a state where the plurality of reaction containers having different catalyst layer capacities are housed in a temperature control box. The testing device comprises: a connection target switching valve for connecting, among the plurality of reaction containers, one reaction container out of which the sample flows out of the catalyst layer and another reaction container selected from reaction containers other than the one reaction container; and a selection valve for selecting an outflow destination of the sample from the one reaction container between the sample flow path and the other reaction container via the connection destination switching valve, The control unit implements control to select an outflow destination of the sample through the selection valve, and when connection to the sample flow path is selected through the selection, switching control is performed by the outflow-side switching valve so that the one reaction container becomes the reaction container serving as the outflow source, and when connection to the other reaction container is selected through the selection, switching control is performed by the outflow-side switching valve so that the other reaction container becomes the reaction container serving as the outflow source.

5. The testing device according to claim 1, characterized in that: The control unit collects the sample flowing out from the reaction container serving as the outflow source via the sample flow path after a preset stabilization time has passed since the sample is supplied from the supply flow path to the reaction container serving as the supply target, and then performs the switching control to the next reaction container serving as the supply target and the outflow source.

6. The testing device according to claim 1, characterized in that: The control unit collects the sample flowing out from the reaction container serving as the outflow source via the sample flow path at each sampling period determined based on a preset rule from the start of supplying the sample from the supply flow path to the reaction container serving as the supply target, and based on a result of a concentration analysis of a component of interest contained in the sample, performs the switching control to the next reaction container serving as the supply target and the outflow source after a concentration change index of the component of interest becomes below a preset threshold value.

7. The testing device according to claim 1, characterized in that: The control unit performs the switching control to the next reaction container serving as the supply destination and the outflow source after the supply of the sample from the sample supply unit is stopped.

8. A test method for testing the reaction rate of a chemical reaction promoted in the presence of a catalyst, the test method being characterized by comprising: supplying a sample to the catalyst at a predetermined flow rate; performing temperature adjustment on a plurality of reaction containers, each of the plurality of reaction containers including a catalyst layer filled with the catalyst; connecting a supply channel for supplying the sample to a reaction container selected as a supply target from among the plurality of reaction containers; as well as A sample flow path is connected to a reaction container as an outflow source of the sample flowing out of the catalyst layer, and the sample flow path is used to collect the sample passing through the catalyst layer for analysis. The process of connecting the supply flow path and the process of connecting the sample flow path are: The reaction container serving as the supply destination and the outflow source is switched so that the reaction rate test is performed under at least three conditions having different residence times in the catalyst layer.

9. The testing method according to claim 8, characterized in that: For at least three reaction containers having different catalyst layer capacities, the step of connecting the supply flow path and the step of connecting the sample flow path are switched so that the reaction container as the supply target and the reaction container as the outflow source coincide with each other.

10. The testing method according to claim 8, characterized in that: The step of adjusting the temperature of the reaction container is performed by placing the reaction container in a temperature adjustment box. The testing method comprises the following steps: using a temperature regulating box on the upstream side and a temperature regulating box on the downstream side, each of which contains a plurality of reaction containers with different capacities for containing the catalyst layer, connecting the reaction container on the upstream side and the reaction container on the downstream side, the reaction container on the upstream side being contained in the temperature regulating box on the upstream side, the sample flowing out from the catalyst layer, the reaction container on the downstream side being selected from the plurality of reaction containers contained in the temperature regulating box on the downstream side, and being supplied with the sample flowing out from the reaction container on the upstream side, In addition to switching the reaction container as the supply destination and the outflow source in the step of connecting the supply channel and the step of connecting the sample channel, a step of connecting the upstream reaction container and the downstream reaction container is also performed.

11. The testing method according to claim 8, characterized in that: The step of adjusting the temperature of the reaction container is performed by accommodating a plurality of the reaction containers having different catalyst layer capacities in a temperature adjustment box. The testing method includes the following steps: among the plurality of reaction containers, connecting one reaction container out of which the sample flows out of the catalyst layer to another reaction container selected from reaction containers other than the one reaction container; and selecting an outflow destination of the sample from the one reaction container between the sample flow path and the other reaction container, In the selection process, when the connection toward the sample flow path is selected, the process of connecting the sample flow path is performed so that the one reaction container becomes the reaction container serving as the outflow source, and when the connection toward the other reaction container is selected, the process of connecting the sample flow path is performed so that the other reaction container becomes the reaction container serving as the outflow source.

12. The testing method according to claim 8, characterized in that: By implementing the process of connecting the supply flow path and the process of connecting the sample flow path, the sample flowing out from the reaction container serving as the outflow source via the sample flow path is collected after a preset stabilization time has passed since the supply of the sample to the reaction container serving as the supply target, and then the process of connecting the supply flow path and the process of connecting the sample flow path are implemented for the next reaction container serving as the supply target and the outflow source.

13. The testing method according to claim 8, characterized in that: By implementing the process of connecting the supply flow path and the process of connecting the sample flow path, since the supply of the sample from the supply flow path to the reaction container serving as the supply target begins, the sample flowing out from the reaction container serving as the outflow source via the sample flow path is collected at each sampling period determined based on a preset rule, and based on the result of performing a concentration analysis on the component of interest contained in the sample, after the concentration change index of the component of interest becomes below a preset threshold value, the process of connecting the supply flow path and the process of connecting the sample flow path are implemented for the next reaction container serving as the supply target and the outflow source.

14. The testing method according to claim 8, characterized in that: After the supply of the sample to the previous reaction container as the supply target is stopped, a step of connecting the supply channel and a step of connecting the sample channel to the next reaction container as the supply target and the outflow source are performed.

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