TEST DEVICE AND TEST PROCEDURE

Abstract

A technology is provided for automatically conducting a reaction rate test under the same flow conditions while varying the residence time in catalyst beds. In this test device for conducting a reaction rate test for a chemical reaction proceeding in the presence of a catalyst, sample supply units 31 and 411 supply a sample to be supplied to catalyst at a preset flow rate, and a plurality of reaction vessels 2a to 2f each contain a catalyst bed filled with the catalyst. Supply-side switching valves 61, 62 connect supply flow paths through which the sample is supplied to the reaction vessel 2e, which is a supply destination, and an outflow-side switching valve 63 connects a sample flow path 701 for collecting the sample for analysis to the reaction vessel 2e, which is an outflow point where the sample drains from the catalyst bed.A control unit 11 performs switching control on the reaction vessels 2a to 2f, which are supply and discharge points, by means of the supply-side switching valves 61, 62 and the outlet-side switching valve 63 so that the reaction rate test is carried out under at least three sets of conditions with different residence times in the catalyst beds.

Description

Technical field

[0001] The present invention relates to a method for carrying out a test to determine the reaction rate of a chemical reaction that takes place in the presence of a catalyst. State of the art

[0002] When designing a reactor that feeds a raw material into a catalyst layer filled with a solid catalyst and yields a desired end product, it is necessary to determine the reaction rate (catalytic reaction) using this catalyst. However, to determine an accurate reaction rate while avoiding changes in the fluidized state of the catalyst layer, it is required to repeatedly perform the reaction rate test while exchanging a variety of reaction vessels with different volumes of catalyst layer. Measuring the reaction rate of the catalytic reaction while exchanging reaction vessels is very labor-intensive for the experimenter.

[0003] Patent 1 describes a technique in which the same quantity of sample liquid is added per unit time to a vessel containing a catalyst during a screening process in which a reactant is reacted in the presence of a catalyst using a combinatorial library approach. Furthermore, patent 2 describes a reaction analysis device that detects the temperature distribution of a reaction fluid along a flow direction of the reaction fluid flowing through a flow reactor immediately after the start of a reaction and indicates the reaction state of the reaction fluid. However, neither patent 1 nor patent 2 discloses a method for measuring the reaction rate using multiple reaction vessels with different volumes of catalyst layer. Bibliography Patent literature

[0004] Patent specification 1: US 2002 / 0141900 A Patent specification 2: JP 2021-159910 A Brief description of the technical problem

[0005] The present invention was made against such a background and provides a method for automatically carrying out a reaction test while simultaneously changing the residence time in a catalyst layer under conditions with the same fluidized state. Solution to the problem

[0006] The present invention provides a test apparatus that performs a reaction rate test of a chemical reaction that takes place in the presence of a catalyst, wherein the test apparatus comprises: a sample feeder that supplies a sample to be fed to the catalyst at a preset flow rate; a plurality of reaction vessels, each containing a catalyst layer filled with the catalyst; a temperature control mechanism that regulates the temperature of the reaction vessels; a feed-side switching valve that connects a feed flow path, through which the sample is fed from the sample feeder, with a feed target reaction vessel selected from the multitude of reaction vessels; a drain-side switching valve connecting a sample flow path, designed to collect the sample for analysis that has passed through the catalyst layer, to a drain-source reaction vessel from which the sample flows out of the catalyst layer; and a control unit which, together with the feed-side switching valve and the drain-side switching valve, performs a switching control of the feed target and drain source reaction vessels, so that the reaction rate test is carried out under at least three conditions with different residence times in the catalyst layer.

[0007] The test device may have the following features. (a) At least three reaction vessels with different volumes of the catalyst layer are provided, in which the control unit performs the switching control so that the feed target reaction vessel and the effluent source reaction vessel are identical. (b) The temperature control mechanism is configured to control the temperature while the reaction vessels are in a state where they are located in a temperature control chamber, and furthermore, it provides: an upstream temperature control chamber and a downstream temperature control chamber, each accommodating a plurality of reaction vessels with different volumes of the catalyst layer, and an intermediate valve connecting an upstream reaction vessel located in the upstream temperature control chamber, through which the sample flows out of the catalyst layer, and a downstream reaction vessel selected from the plurality of reaction vessels located in the downstream temperature control chamber, to which the sample flowing out of the upstream reaction vessel is fed.wherein, in addition to switching the reaction vessels, the control unit performs a connection control between the upstream reaction vessel and the downstream reaction vessel with the intermediate valve. (c) The temperature control mechanism is configured to control the temperature while a plurality of reaction vessels having different volumes of catalyst layer are in a housed state within a temperature control chamber, and furthermore, the following are provided: a connection target switching valve that connects a reaction vessel through which the sample flows out of the catalyst layer to another reaction vessel selected from the reaction vessels that are not the one reaction vessel from the plurality of reaction vessels;and a selection valve that selects a discharge destination of the sample from one reaction vessel between the sample flow path and the other reaction vessel via the connection destination switching valve, wherein the control unit is configured to perform a control to select the discharge destination from the sample with the selection valve, the switching control with the discharge-side switching valve to ensure that one reaction vessel operates as a discharge source reaction vessel when the connection to the sample flow path is selected by the selection, and the switching control with the discharge-side switching valve to ensure that the other reaction vessel operates as a discharge source reaction vessel when the connection to the other reaction vessel is selected by the selection. (d) The control unit performs the switching control to a next reaction vessel from the feed target reaction vessel and a next reaction vessel from the outflow source vessel after a preset settling period has elapsed since a feed of the sample from the feed flow path to the feed target reaction vessel was started and the sample flowing from the outflow source reaction vessel via the sample flow path has been collected. (e) The control unit performs the switching control to a next reaction vessel of the feed target reaction vessel and a next reaction vessel of the outflow source reaction vessel after the sample flowing from the outflow source reaction vessel via the sample flow path has been collected in each sampling period determined based on a preset rule since a feed of the sample from the feed flow path into the feed target reaction vessel was started and a concentration change index of a focused component contained in the sample, based on a result of the concentration analysis performed on the focused component, has become equal to or less than a preset threshold. (f) The control unit performs the switching control to a next feed target reaction vessel and a next discharge source reaction vessel after the sample feed has been stopped. Advantageous effects of the invention

[0008] The present invention provides a switching control for a feed-side control valve and a discharge-side control valve, enabling a reaction rate test to be performed using a plurality of reaction vessels containing a catalyst layer under at least three conditions with different residence times in the catalyst layer. As a result, the reaction rate test, which is intended to measure the reaction rate of a chemical reaction occurring in the presence of a catalyst, can be performed without manually changing the reaction vessel. Brief description of the drawings Fig. Figure 1 is a schematic diagram showing a reaction of feeding a raw material to a catalyst layer to obtain a product. Fig. Figure 2 is a schematic diagram illustrating how a reaction rate curve changes according to variations in the reaction systems. Fig. Figure 3 is an explanatory diagram of a procedure for determining a reaction rate curve. Fig. Figure 4 is a configuration diagram of a conventional test device. Fig. Figure 5 is a configuration diagram of a test device according to a first embodiment. Fig. Figure 6 is an example of an operating sequence of the test device according to the first embodiment. Fig. Figure 7 is a flowchart relating to a process for verifying the switching of a column. Fig. Figure 8 is a configuration diagram of a test device according to a second embodiment. Fig. Figure 9 is a configuration diagram of a test device according to a third embodiment. Description of the embodiments

[0009] First, the reasons for the need to determine the reaction rate when constructing a reactor containing a catalyst layer filled with a solid catalyst are described, as well as the disadvantages of a conventional test device.

[0010] As in Fig. As shown in Figure 1, in a reaction system using a catalyst layer, a feedstock fluid is passed through the catalyst layer, and the feedstock and catalyst are brought into contact to effect a catalytic reaction, yielding a target component from the products generated by the reaction. Generally, given that the reaction temperature and the concentration of the feedstock in the liquid are fixed, while a longer residence time in the catalyst layer results in more feedstock being consumed by the reaction and a product yield equal to the amount of feedstock consumed.

[0011] At this point, the relationship (reaction rate curve) between the residence time of the raw material in the catalyst layer, i.e., the reaction time (e.g., in "seconds"), and the raw material concentration at the outlet or outflow of the catalyst layer (the percentage value indicating the outlet concentration relative to the inlet concentration in the catalyst layer) can be determined as shown in Fig. Figure 2 illustrates this. In a reaction system with a high reaction rate, the raw material concentration decreases rapidly with a short residence time, as indicated by the dashed-dotted line. Conversely, in a reaction system with a low reaction rate, as indicated by the solid line, the decrease in raw material concentration due to the increase in residence time is moderate compared to the reaction system with a high reaction rate.

[0012] Such variations in reaction rate affect the design of a reactor intended to extract a target component from the raw material. For example, in a reaction system (high reaction rate) where a predetermined quantity of raw material can be converted into a product in a short reaction time (residence time), the volume of the catalyst layer can be reduced, meaning the capacity of the reaction tower can be smaller. Conversely, in a reaction system (low reaction rate) where a longer reaction time (residence time) is required to convert a predetermined quantity of raw material into a product, the capacity of the reaction tower, i.e., the volume of the catalyst layer, must be increased.

[0013] In this way, the reaction rate of the catalytic reaction is one of the most important catalyst properties that should be determined in advance during reactor design. To determine the reaction rate of a specific reaction system, a reaction test is performed in which the concentration of the feedstock at the outlet of the catalyst layer is measured while the residence time during which the feedstock passes through the catalyst layer is varied. Then, as in Fig. Figure 3 shows the reaction rate curve found by fitting a curve to the result of plotting a large number of points of the correspondence relationship of the raw material concentration at the outlet of the catalyst layer as a function of residence time.

[0014] One method for changing the residence time of the raw material in the catalyst layer is to sequentially vary the feed rate of the raw material to the catalyst layer, which is filled with a predetermined amount of catalyst. However, with such a method, the fluidized state of the raw material flowing through the catalyst layer can sometimes differ significantly depending on the change in the feed rate. Consequently, it is difficult to perform the reaction test while conditions other than residence time are in a controlled state, and it is unlikely that an accurate reaction curve will be obtained.

[0015] Conventionally, a reaction rate test was therefore performed using a test device 100, which included the Fig. The configuration shown in section 4 is used to determine a reaction rate curve. The configuration shown in Fig. 4 The test apparatus 100 shown is configured as a device that performs a reaction experiment to obtain a reaction rate curve of a hydrogenation reaction for the hydrogenation of a raw material contained, for example, in a raw material fluid.

[0016] To briefly describe the setup of the test device 100, a raw material fluid (e.g., a liquid) containing a raw material is collected in a raw material feeder 31. This raw material fluid is fed via a raw material feeder line 301 at a preset flow rate by a pump 32, which is based on a flow meter 33. The raw material feeder line 301 is equipped with a pressure gauge 34 and a thermometer 35 and can measure the feeder pressure and feeder temperature of the raw material fluid. The raw material feeder 31, the pump 32, and the flow meter 33 form a sample feeder, which supplies a raw material fluid as a sample at a preset flow rate, and the raw material feeder line 301 forms a sample feeder path.

[0017] Meanwhile, hydrogen gas is stored in a hydrogen gas supply 411 for use in the hydrogenation reaction. The hydrogen gas is supplied at a preset flow rate, which is adjusted by a flow control valve 412 based on a flow meter reading 413. Additionally, nitrogen gas is stored in a nitrogen gas supply 421 for use in adjusting the hydrogen gas concentration. The nitrogen gas is supplied at a preset flow rate, which is adjusted by a flow control valve 422 based on a flow meter reading 423.

[0018] These hydrogen and nitrogen gases are combined and then fed as a mixed gas (hereinafter also referred to as "reaction gas") via a reaction gas supply line 401. A downstream section of the reaction gas supply line 401 leads into the raw material supply line 301, which supplies the raw material fluid. The hydrogen gas supply 411, the flow control valve 412, and the flow meter 413, as well as the nitrogen gas supply 421, the flow control valve 422, and the flow meter 423, form a sample supply that feeds the hydrogen gas or nitrogen gas as a sample at a preset flow rate, and the reaction gas supply line 401 forms a sample supply path.

[0019] The catalyst used in the hydrogenation reaction of the raw material is placed in each of a series of catalyst columns 2a to 2f, which are reaction vessels. These catalyst columns 2a to 2f consist, for example, of cylindrical stainless steel vessels with a diameter of 5 mm. The cylindrical vessels comprising the catalyst columns 2a to 2f are configured so that their lengths differ from one another within a range of, for example, 50 to 300 mm and are filled with different volumes of catalyst corresponding to their respective lengths. In this example, a catalyst layer filled with a larger volume of catalyst is provided for a catalyst column with a greater length below the catalyst columns 2a to 2f.It should be noted that the components and dimensions described above, as well as the number of catalyst columns 2a to 2f to be used, are examples and can be modified as appropriate.

[0020] In test apparatus 100 of this example, the plurality of catalyst columns 2a to 2f with different volumes of the catalyst layer are prepared in advance, and one (the catalyst column 2a in the in Fig. The catalyst column 2a to 2f (as shown in the example 4) is selected from these catalyst columns and is placed in an oven 5. The oven 5 heats the internal temperature to a preset temperature (e.g., 100 °C).

[0021] Oven 5 can also vary the set temperature within a range of, for example, 40 to 150°C. The temperature dependence of the reaction rate can also be evaluated by performing the reaction rate test under each of the different conditions at the set temperature.

[0022] From this point of view, furnace 5 plays the role of a temperature control mechanism (temperature control chamber) that controls the temperature of the catalyst columns 2a to 2f, i.e. the catalyst layer housed in furnace 5.

[0023] A downstream section of the raw material supply line 301 is connected to an inlet side of the catalyst column 2a, which is located inside the furnace 5. This downstream section is located on the downstream side of the connection point with the reaction gas supply line 401 described above. Meanwhile, a sampling line (sample flow path) 701, for collecting a sample for analysis that has passed through the catalyst layer inside the catalyst column 2a, is connected to an outlet side of the catalyst column 2a.

[0024] A downstream end of the sampling line 701 is connected to an analyzer 7 located outside the test apparatus 100. In a case where the sample flowing from the sampling line 701 is a liquid, a liquid chromatography (LC) analyzer 7 can be used to perform compositional and quantitative analysis of the sample. In this case, when the sample is supplied as a liquid, a sample collection mechanism, such as a syringe, may be provided within the analyzer 7. If the sample contains bubbles or dissolved gas, the sample collection mechanism may encounter difficulties. Therefore, a gas-liquid separator or degasser can be installed between the downstream end of the sampling line 701 and the analyzer 7, as needed.After the product has been analyzed by the analyzer 7, the sample is disposed of via a drain line 702.

[0025] It should be noted that the analyzer 7 connected to the sampling line 701 is not limited to LC and gas chromatography (GC) can also be used if the sample is a gas. Furthermore, depending on the nature of the analysis, another analyzer that also provides mass spectrometry (MS), LC-MS, or GC-MS can be used. If the sample is a liquid, a fraction collector can also be provided at one inlet side of the analyzer 7, and the sampling line 701 can be connected to the fraction collector.

[0026] In the test apparatus 100 with the configuration described above, the catalyst column 2a to be used in the current reaction test is selected from the multitude of prepared catalyst columns 2a to 2f and positioned inside the furnace 5. The raw material supply line 301 and the sampling line 701 are connected to the catalyst column 2a. The temperature inside the furnace 5 is then increased, and once the temperature has stabilized at the set temperature, the supply of samples such as the raw material fluid and the reaction gas begins.

[0027] Since the settling of the reaction takes approximately one hour, for example, the sampling and analysis of the sample is carried out by the analyzer 7 after the settling time has elapsed since the start of the sample supply. In a case where the temperature dependence of the reaction rate is also being evaluated, the sample supply is stopped and the setpoint temperature of oven 5 is changed. Once the temperature inside oven 5 has stabilized at the new setpoint temperature, the process described above – "sample supply → waiting for settling → sampling and analysis of the samples" – is repeated. It should be noted that the sample supply is not necessarily interrupted when the setpoint temperature of oven 5 is changed.For example, the supply of raw material and hydrogen gas can be stopped and only the supply of nitrogen gas can be continued, or if a sufficient quantity of raw material and hydrogen gas is available, the supply of raw material and hydrogen gas can be continued.

[0028] Once the procedure described above has been completed for all set temperatures required to evaluate the temperature dependence, the supply of samples (the raw material liquid and the reaction gas) and the heating of furnace 5 are stopped. Then, when the temperature inside furnace 5 has dropped to a level at which the work can be carried out, catalyst column 2a is removed, the next catalyst column 2b is installed, and the reaction rate test is repeated as described above.

[0029] As in Fig. As shown in Figure 2, it is necessary to perform a reaction rate test with at least three residence times (reaction times) that differ from each other in order to obtain a reaction rate curve. To obtain a more accurate reaction rate curve, it may sometimes be necessary to perform a reaction rate test with four or more different residence times.

[0030] Therefore, it is in the test device 100 with the in Fig. The conventional configuration shown in Figure 4 requires the above-described reaction rate test and exchange work on catalyst columns 2a to 2f to be carried out for three or more residence times. However, the waiting time is frequently required, and the exchange work for catalyst columns 2a to 2f, which occurs repeatedly, places a significant burden on the experimenter.

[0031] A test device 1 of the present embodiment thus has a configuration that makes it possible to automatically perform a reaction rate test in order to obtain a reaction rate curve by completing the exchange operations for the catalyst columns 2a to 2f described above. The following describes the setup and operation of the test device 1 according to the present embodiment with reference to the Fig. 5 to 7 described. Note that in each of the Fig. 5, Fig. 8 and Fig. The test devices 1, 1a and 1b shown in Figure 9 have the same components as in the one relating to Fig. 1 described test device 100 with the same reference numerals as in Fig. 1.

[0032] In the Fig. In the test apparatus 1 shown in Figure 5, at least three (six in the example of the drawing) catalyst columns 2a to 2f, which have different volumes of the catalyst layer, are pre-installed in a common oven 5. In this way, the test apparatus 1 of the present embodiment has a configuration in which the exchange work for catalyst columns 2a to 2f does not occur.

[0033] When the plurality of catalyst columns 2a to 2f are housed inside the furnace 5, it is necessary to select the catalyst columns 2a to 2f as the feed destinations for the samples from a raw material feed line 301 and a reaction gas feed line 401, and the catalyst columns 2a to 2f as the outlet sources for the samples to a sampling line 701. For this purpose, the test apparatus 1 of the present embodiment is provided with feed-side switching valves 61 and 62 and an outlet-side switching valve 63. The feed-side switching valves 61 and 62 play a role in connecting each of the raw material feed line 301 for the raw material fluid and the reaction gas feed line 401 for the reaction gas, which are the samples, to the feed destination selected from the plurality of catalyst columns 2a to 2f.Furthermore, the outflow-side switching valve 63 plays a role in connecting the sample flow path to the outflow-side catalyst columns 2a to 2f, through which the sample flows from the catalyst layer.

[0034] These feed-side switching valves 61 and 62 and the outlet-side switching valve 63 are subject to switching control by a control unit 11. The control unit 11 switches the catalyst columns 2a to 2f as the feed destination and outlet source of the samples using these feed-side switching valves 61 and 62 and the outlet-side switching valve 63. The control unit 11 is, for example, a computer, a control circuit, or the like. In particular, in the test device 1 of the present embodiment, the control unit 11 performs switching control of the feed-side switching valves 61 and 62 and the outlet-side switching valve 63, so that the feed destination and outlet source of the samples between the catalyst columns 2a to 2f coincide.

[0035] In Fig. Figure 5, for example, shows a state in which the feed-side switching valves 61 and 62 and the outlet-side switching valve 63 are switched such that the raw material feed line 301, the reaction gas feed line 401, and the sampling line 701 are connected to the catalyst column 2e. By performing this switching sequentially, the reaction rate test can be carried out under at least three (up to six in the Fig. The 5 examples shown are performed under conditions with different dwell times.

[0036] The following describes the operation of test device 1 with the configuration described above, also with reference to Fig. 6 in addition to Fig. 5 described. When performing the reaction rate test with the test device 1 (start), the catalyst column 2e to be tested is selected from the catalyst columns 2a to 2f housed in the furnace 5, and the feed-side switching valves 61 and 62 as well as the outlet-side switching valve 63 are switched (step S101). Subsequently, the raw material liquid and the reaction gas are fed as samples into the switched catalyst column 2e (step S102).

[0037] The sample feed continues until a preset settling time has elapsed (step S103). During this time, the samples can be discharged via a drain line 702 and the sampling line 701. After the settling time has elapsed, the samples are sampled and analyzed via the sampling line 701 (step S104). The feed of the raw material fluid and the reaction gas to the catalyst column 2e is then stopped (step S105).

[0038] Note that in a case where the temperature dependence of the reaction rate, which is determined using the conventional test apparatus 100 in Fig. As described in section 4, and also evaluated here, the processes in steps S102 to S104 are repeated after the set temperature of the furnace 5 has been changed. In this case, however, in step S102, the process of supplying the raw material fluid and the reaction gas to the catalyst column 2e is carried out after the set temperature has been changed.

[0039] After stopping the sample feed in step S105, it is confirmed whether one of the catalyst columns 2a to 2d and 2f, on which the reaction rate test is to be performed next, is set up (step S106). For example, it is assumed that the reaction rate test for catalyst columns 2a to 2d is already complete when the reaction rate test for catalyst column 2e is finished, and the reaction rate test is to be performed on the remaining catalyst column 2f (step S106: YES). In this case, the system switches to catalyst column 2f in step S101, and the operations in steps S102 to S106 are repeated.

[0040] Then, in a case where there are no catalyst columns 2a to 2f to which the system is to switch and on which the reaction rate test is to be performed next (step S106: NO), the reaction rate test is terminated. Then, for example, the curve fitting is performed by an external computer that has received the test result from an analyzer 7, a reaction rate curve is automatically generated, and the process is terminated (End).

[0041] The test device 1 according to the present embodiment has the following effects. Switching control of the feed-side control valves 61 and 62 and the outlet-side control valve 63 is carried out such that a reaction rate test is performed using the plurality of catalyst columns 2a to 2f, including the catalyst layer, under at least three conditions with different residence times in the catalyst layer. This allows the reaction rate test to determine the reaction rate of a chemical reaction that takes place in the presence of a catalyst to be carried out without manual exchange of the catalyst columns 2a to 2f.

[0042] Here, in step S103, which refers to Fig. As described in section 6, the actual drop-off time must be confirmed instead of waiting for the preset drop-off time to expire. Fig. Figure 7 shows an example of the process that is performed in this case instead of step S103.

[0043] After starting the sample supply in step S102 in Fig. Step 6 of the control unit 11 begins counting the number of samples taken (n=1) (step S201). Then, after a sampling interval determined based on a pre-programmed sampling rule has elapsed, an initial sampling of the samples that have passed through the catalyst layer is carried out, and the analysis is performed by the analyzer 7 (step S202).

[0044] Regarding the sampling rule, a case can be expected here in which various rules are freely set on the control unit 11. However, in order to efficiently capture the actual settling time, it is preferable to set the sampling period so that "the settling time (e.g., one hour) in step S103 in Fig. 6 > the sampling period” applies.

[0045] As a specific example, a rule can be defined in which the sampling period after the start of counting the number of samples taken in step S201 is set to 30 minutes and the subsequent sampling period is set to every 10 minutes.

[0046] Additionally, a rule can be set in which the first sampling period is set to zero minutes, the sampling is carried out immediately after the start of counting the number of samples taken, and the subsequent sampling period is set to every five minutes.

[0047] Furthermore, the initial sampling period is set to zero minutes. Then, for subsequent sampling periods, a table can be predefined in which the concentration change of the focused component, obtained from the analysis result of analyzer 7, is linked to the sampling period. The sampling period can then be modified based on this table. The table can illustrate a case where the sampling time is set longer if the focused component, to be checked for settling, exhibits a larger concentration change, and the sampling time is set shorter if the concentration change of the focused component becomes smaller and approaches equilibrium.

[0048] If the first sampling and analysis were carried out in this manner, the number of samples taken is incremented (step S203), and it is confirmed whether the incremented value exceeds two (step S204). If the value is not more than two (step S204: NO), the operations in steps S202 to S203 are repeated to carry out the second sampling and analysis.

[0049] In a case where the incremented value exceeds two (step S204: NO), because sampling and analysis have been performed at least twice, the previous and current analysis results can be compared. Thus, based on the previous and current concentration analysis results of the focused component for which it is to be verified whether the reaction system has settled, it is checked whether the concentration change index of the focused component is equal to or less than a predefined threshold (step S205).

[0050] For example, if it is determined that the actual settling time has elapsed because the concentration of the target component in the product contained in the sample has stabilized, this target component is selected as the focused component. Furthermore, if it is demonstrated that the settling time has elapsed because the concentration of a byproduct in the product is stable in a sufficiently reduced state, the aforementioned byproduct is selected as the focused component.

[0051] Furthermore, the concentration change index can be an absolute value of the concentration difference of the focused component between the previous time point and the current time point, or a ratio of the current concentration to the concentration at the previous analysis. The concentration change index can also be a rate of change, representing the ratio of the absolute value of the concentration difference of the focused component between the previous time point and the current time point to the concentration at the time of the previous analysis, which is assigned as a reference.

[0052] In a case where the concentration change index of the focused component is not equal to or less than the preset threshold (step S205: NO), the procedures of steps S202 to S204 are repeated. However, if the concentration change index is equal to or less than the threshold (step S205: YES), it is checked whether the actual settling time has elapsed, and the analysis result of the last sample is adopted as the analysis result of the reaction rate test (step S206). The procedure then returns to step S105. Fig. Step 6 is returned, the supply of the raw material fluid and the reaction gas is stopped, and the need to switch catalyst columns 2a to 2f is checked (step S106). According to the Fig. The procedures described in 7 allow the actual drop-off time to be actively recorded and unnecessary waiting time to be reduced.

[0053] An exemplary configuration of the test device 1a according to a second embodiment is described below with reference to Fig. 8 described. The test apparatus 1a according to the second embodiment has a configuration in which a plurality of furnaces 5, for example two furnaces 5 (an upstream furnace 5a and a downstream furnace 5b), are connected in series. The upstream furnace 5a accommodates a plurality of catalyst columns 2a to 2f having different volumes of catalyst layer, and similarly, the downstream furnace 5b also accommodates a plurality of catalyst columns 2g to 2l.

[0054] Then, an intermediate switching valve 65 is provided in a flow path connecting the upstream furnace 5a and the downstream furnace 5b. The intermediate switching valve 65 plays a role in connecting the upstream catalyst columns 2a to 2f, which are housed in the upstream furnace 5a and through which the sample flows out of the catalyst layer, and the downstream catalyst columns 2g to 2l, which are housed in the downstream furnace 5b. In addition to the switching control of the catalyst columns 2a to 2f by the feed-side switching valves 61 and 62, and the control described in [reference to] Fig. 5 described outflow-side switching valve 63 a control unit 11 the connection control between the upstream catalyst columns 2a to 2f and the downstream catalyst columns 2g to 2l with the intermediate switching valve 65 through.

[0055] It should be noted that a selection valve 64, provided on an upstream side of the intermediate switching valve 65, has the function of switching between a case in which the upstream furnace 5a is used alone and a case in which the upstream furnace 5a and the downstream furnace 5b are connected and used in series. In a case in which the upstream furnace 5a is used alone, the configuration is similar to that in Fig. 5 example used in which a reaction rate test is carried out using one of the catalyst columns 2a to 2f alone and the sample flowing from the catalyst layer is sent via a sampling line 701a to an analyzer 7.

[0056] On the other hand, in a case where the upstream furnace 5a and the downstream furnace 5b are connected in series and in use, the total volume of the catalyst layer is the sum of the volume of the catalyst layer of any one of the catalyst columns 2a to 2f located in the upstream furnace 5a and the volume of the catalyst layer of any one of the catalyst columns 2g to 2l located in the downstream furnace 5b. Consequently, in the Fig. The reaction rate test shown in Figure 8 is performed with 36 different residence time patterns, which are set by combining the six catalyst columns 2a to 2f and the six catalyst columns 2g to 2l. An outlet side of the catalyst columns 2g to 2l is connected to a sampling line 701b via a drain-side switching valve 66, and the sample flowing from the catalyst layer is directed to the analyzer 7 via the sampling line 701b.

[0057] In summary, in the Fig. In the test apparatus 1a shown in Figure 8, 42 different residence time patterns can be set, including the case of using only the upstream furnace 5a. It is essentially unnecessary to provide the selection valve 64 and the sampling line 701a, and the upstream furnace 5a and the downstream furnace 5b can be regularly used in a coupled, series configuration. At this stage, when the upstream furnace 5a and the downstream furnace 5b are provided with at least two catalyst columns 2a and 2b and at least two catalyst columns 2g and 2h, the reaction rate test can be performed by setting four different residence time patterns. This satisfies at least three conditions with different residence times, and a reaction rate curve can be generated.

[0058] Furthermore, the number of furnaces 5 connected in series is not limited to two and can be three or more. In this case, with regard to the two furnaces 5 connected to each other via the intermediate valve 65, the upstream furnace 5a and the downstream furnace 5b are specified. If the selection valve 64 and the sampling line 701a are provided upstream of each intermediate valve 65, at least three conditions with different residence times can be set up and the reaction rate test can be carried out by providing at least one catalyst column 2a in each of the three furnaces 5. At this point, it is not necessary for these three catalyst columns 2a to have different volumes of catalyst layer, and the volumes of catalyst layer can be the same.

[0059] Next, an exemplary configuration of the test device 1b according to a third embodiment is described with reference to Fig. 9 described. In the test apparatus 1b according to the third embodiment, a plurality of catalyst columns 2a to 2f with different volumes of the catalyst layer are provided within a common oven 5, and two catalyst columns selected from catalyst columns 2a to 2f can be connected in series.

[0060] From this perspective, test device 1b has a configuration that, in addition to that referred to in Fig. The configuration of test device 1 described in section 5 comprises a selection valve 64 and a destination switching valve 67. The destination switching valve 67 has the function of selecting one of the catalyst columns 2a to 2f (catalyst column 2e in the example in section 5). Fig. 9), through which the sample flows from the catalyst layer, and another of the catalyst columns 2b to 2f and 2a (catalyst column 2a in the example in Fig. 9), which is selected from among the catalyst columns other than catalyst column 2e. In addition, the selection valve 64 plays a role in selecting a discharge destination for the sample from one of the catalyst columns 2a to 2f, between a sampling line 701a and the other of the catalyst columns 2b to 2f and 2a, connected via the destination switching valve 67.

[0061] The test apparatus 1b also includes a first-stage, outflow-side switching valve 63, provided on an upstream side of the selection valve 64, and a second-stage, outflow-side switching valve 66, provided on a furthest downstream side of one of the catalyst columns 2a to 2f and the other of the interconnected catalyst columns 2b to 2f and 2a. The second-stage, outflow-side switching valve 66 plays a role in connecting the other of the catalyst columns 2b to 2f and 2a to a sampling line 701b.

[0062] In test apparatus 1b with the configuration described above, a control unit 11 performs a control operation to select the sample discharge destination using the selection valve 64. If the connection to sampling line 701a is selected by this selection, the switching control to sampling line 701a is executed via the discharge-side switching valve 63 such that one of the catalyst columns 2a to 2f operates as the discharge source. Furthermore, if the connection to the other column, 2f and 2a, is selected by the selection valve 64, the switching control to sampling line 701b is executed via the discharge-side switching valve 66 such that the other column, 2f and 2a, operates as the discharge source.

[0063] If in the Fig. In the test apparatus 1b shown in Figure 9, at least two catalyst columns 2a and 2b are provided inside the oven 5. The reaction rate test can be carried out by setting at least three conditions with different residence times, between a case in which each of the catalyst columns 2a and 2b is used alone and a case in which the catalyst columns 2a and 2b are connected in series.

[0064] Furthermore, the test apparatus 1b can also have a configuration in which three or more stages of catalyst columns 2a to 2f can be connected in series. In this case, a multiple of the selection valve 64, the destination switching valve 67, the outlet-side switching valve 66, and the sampling line 701b only need to be provided in stages. In the configuration in which the catalyst columns 2a to 2f can be connected in series in three or more stages, the reaction rate test can be performed by setting at least three conditions with different residence times, even if the catalyst columns 2a to 2f have the same volume of catalyst layer.

[0065] As described above, the references to the Fig. 6 and Fig. The procedures described in section 7 also apply to the test devices 1a and 1b according to the second and third embodiments, which are described with reference to the Fig. 8 and Fig. 9 are described and applied.

[0066] Furthermore, the method for changing the volume of the catalyst layer in the test devices 1, 1a and 1b according to the first to third embodiments is not limited to the case where the catalyst columns 2a to 2f have different length dimensions. For example, the volume of the catalyst layer can be changed by making the diameters of the catalyst columns 2a to 2f different.

[0067] Furthermore, the type of reaction carried out with the catalyst is not limited to the example provided for the hydrogenation reaction and can also include other reactions such as an oxidation reaction, a reduction reaction, and a thermal decomposition reaction. Depending on the nature of the reaction, either only one sample feeder system may be provided, or three or more sample feeder systems may be provided. Additionally, a preheater can be installed in the sample feeder if required, and the preheated sample can be fed to catalyst columns 2a to 2f.

[0068] An exemplary configuration of the temperature control chamber, which accommodates and regulates the temperature of multiple catalyst columns 2a to 2f, is not limited to furnace 5 and can be an aluminum block heater, a thermostat box, a test cooling unit, or the like. Furthermore, the temperature control mechanism is not limited to a temperature control chamber of one type that accommodates multiple catalyst columns 2a to 2f and also includes a configuration in which individual catalyst columns 2a to 2f are covered with a jacket heater, a heating band, or the like. Reference symbol list 1, 1a, 1b, 100 test device 11 Control unit 2a to 2f catalyst column 301 Raw material supply line 31 Raw material supply 32 Pump 33 flow meters 34 pressure gauges 35 Thermometer 401 Reaction gas supply line 411 Hydrogen gas supply line 412 Flow rate control valve 413 Flow meter 421 Nitrogen gas supply line 422 Flow rate control valve 423 Flow meter 5 Oven 5a upstream furnace 5b downstream furnace 61 Supply-side switching valve 62 Supply-side switching valve 63 Drain-side switching valve 64 Selection valve 65 Intermediate valve 66 Drain-side switching valve 67 Connection target switching valve 701, 701a, 701b Sampling line 702 Drain pipe 7 Analyzer QUOTES INCLUDED IN THE DESCRIPTION

[0000] This list of documents cited by the applicant was automatically generated and is included solely for the reader's convenience. The list is not part of the German patent or utility model application. The DPMA accepts no liability for any errors or omissions. Cited patent literature

[0000] US 2002 / 0141900 A

[0004] JP 2021-159910 A

[0004]

Claims

[1] Test apparatus for performing a rate test of a chemical reaction taking place in the presence of a catalyst, the test apparatus comprising: a sample feeder that supplies a sample to be fed to the catalyst at a preset flow rate; a multitude of reaction vessels, each containing a catalyst layer filled with the catalyst; a temperature control mechanism that sets the temperature of the reaction vessels; a feed-side switching valve that connects a feed flow path, through which the sample is fed from the sample feeder, to a feed target reaction vessel selected from the multitude of reaction vessels; a drain-side switching valve connecting a sample flow path, designed to collect the sample for analysis that has passed through the catalyst layer, to a drain-source reaction vessel from which the sample flows out of the catalyst layer; and a control unit that performs switching control of the feed target and outflow source reaction vessels with the feed-side switching valve and the outflow-side switching valve, so that the reaction rate test is carried out under at least three conditions with different residence times in the catalyst layer. [2] Test apparatus according to claim 1, wherein at least three reaction vessels with different volumes of catalyst layer must be provided, the control unit performs the switching control in such a way that the feed target reaction vessel and the outflow source reaction vessel are identical. [3] Test apparatus according to claim 1, wherein the temperature control mechanism is configured to set the temperature while the reaction vessels are housed in a temperature control chamber, the test apparatus further comprises: an upstream temperature control chamber and a downstream temperature control chamber, each accommodating a plurality of reaction vessels with different volumes of catalyst layer; and an intermediate valve connecting an upstream reaction vessel, housed in the upstream temperature control chamber and through which the sample flows out of the catalyst layer, and a downstream reaction vessel, selected from the multitude of reaction vessels housed in the downstream temperature control chamber and to which the sample flowing out of the upstream reaction vessel is fed, and In addition to switching the reaction vessels, the control unit performs a connection control between the upstream reaction vessel and the downstream reaction vessel with the intermediate valve. [4] Test apparatus according to claim 1, wherein the temperature control mechanism is configured to control the temperature while a multitude of reaction vessels with different volumes of catalyst layer are in a housed state within a temperature control chamber, the test apparatus further comprises: a connection target switching valve that connects a reaction vessel, through which the sample flows from the catalyst layer, to another reaction vessel selected from the reaction vessels that are not the one reaction vessel from the multitude of reaction vessels; and a selection valve that selects a discharge destination for the sample from one reaction vessel, between the sample flow path and the other reaction vessel via the connection destination switching valve and The control unit is configured to: a control process is carried out to select the discharge destination of the sample using the selection valve; the switching control is carried out with the outflow-side switching valve, so that one reaction vessel operates as an outflow-source reaction vessel when the connection to the sample flow path is selected; and The switching control is carried out with the drain-side switching valve, so that the other reaction vessel operates as the drain-source reaction vessel when the connection to the other reaction vessel is selected. [5] Test apparatus according to claim 1, wherein the control unit performs the switching control to a next of the feed target reaction vessel and a next of the outflow source reaction vessel after a preset settling period has elapsed since a feed of the sample from the feed flow path to the feed target reaction vessel was started and the sample that was collected from the outflow source reaction vessel via the sample flow path. [6] Test apparatus according to claim 1, wherein the control unit performs the switching control to a next of the feed target reaction vessel and a next of the outflow source reaction vessel after the sample flowing from the outflow source reaction vessel via the sample flow path has been collected in each sampling period, determined based on a preset rule, since a feed of the sample from the feed flow path to the feed target reaction vessel was started and a concentration change index of a focused component contained in the sample has become equal to or less than a preset threshold based on a result of a concentration analysis performed on the focused component. [7] Test apparatus according to claim 1, wherein the control unit performs the switching control to a next feed target reaction vessel and a next outflow source reaction vessel after a feed of the sample from the sample feeder has been stopped. [8] Test procedure for performing a reaction rate test of a chemical reaction taking place in the presence of a catalyst, the test procedure comprising: a feeding step of a sample that is to be fed to the catalyst at a preset flow rate; a step to adjust the temperature of a plurality of reaction vessels, each containing a catalyst layer filled with the catalyst; a step of connecting a feed flow path, through which the sample is fed, to a feed target reaction vessel selected from the multitude of reaction vessels; and a step of connecting a sample flow path designed to collect the sample for analysis that has passed through the catalyst layer to a drain source reaction vessel from which the sample flows out of the catalyst layer; where The step of connecting the feed flow path and the step of connecting the sample flow path are carried out by switching the feed target and outflow source reaction vessels, so that the reaction rate test is performed under at least three conditions with different residence times in the catalyst layer. [9] Test method according to claim 8, wherein the step of connecting the feed flow path and the step of connecting the sample flow path are switched and performed on at least three reaction vessels having different volumes of catalyst layer, such that the feed target reaction vessel and the outflow source reaction vessel are identical. [10] Test method according to claim 8, wherein the step of adjusting the temperature of the reaction vessels is carried out while the reaction vessels are in a housed state within a temperature adjustment chamber, The test procedure further comprises: a use step of an upstream temperature control chamber and a downstream temperature control chamber, each accommodating a plurality of reaction vessels with different volumes of the catalyst layer, and a connection step of an upstream reaction vessel, which is accommodated in the upstream temperature control chamber and through which the sample flows out of the catalyst layer, and a downstream reaction vessel, which is selected from the plurality of reaction vessels accommodated in the downstream temperature control chamber and to which the sample flowing out of the upstream reaction vessel is fed, and a step of connecting the upstream reaction vessel and the downstream reaction vessel, which is carried out in addition to switching the feed target and outflow source reaction vessel in the step of connecting the feed flow path and the step of connecting the sample flow path. [11] Test method according to claim 8, wherein The step of adjusting the temperature of the reaction vessels is carried out while a multitude of reaction vessels with different volumes of catalyst layer are in a housed state within a temperature adjustment chamber, the test procedure further includes: a step of connecting a reaction vessel through which the sample flows from the catalyst layer to another reaction vessel selected from the reaction vessels that are not the one reaction vessel from the multitude of reaction vessels; and a step of selecting a discharge destination for the sample from one reaction vessel between the sample flow path and the other reaction vessel, and In the step of selecting the sample flow path, the step of connecting the sample flow path is performed in such a way that one reaction vessel acts as the drain source reaction vessel when a connection with the sample flow path is selected, and the step of connecting the sample flow path is performed in such a way that the other reaction vessel acts as the drain source reaction vessel when a connection with the other reaction vessel is selected. [12] Test method according to claim 8, wherein by performing the step of connecting the feed flow path and the step of connecting the sample flow path, the step of connecting the feed flow path and the step of connecting the sample flow path are performed for a next of the feed target reaction vessel and a next of the outflow source reaction vessel after a preset settling period has elapsed since a feed of the sample to the feed target reaction vessel was started and the sample flowing from the outflow source reaction vessel via the sample flow path has been collected. [13] Test method according to claim 8, wherein by performing the step of connecting the feed flow path and the step of connecting the sample flow path, the step of connecting the feed flow path and the step of connecting the sample flow path are performed for a next of the feed target reaction vessel and a next of the outflow source reaction vessel after the sample flowing out of the outflow source reaction vessel via the sample flow path has been collected in each sampling period determined based on a preset rule since a feed of the sample from the feed flow path to the feed target reaction vessel was started and a concentration change index of a focused component contained in the sample has become equal to or less than a preset threshold based on a result of the concentration analysis performed on the focused component. [14] Test method according to claim 8, wherein the step of connecting the feed flow path and the step of connecting the sample flow path are performed for a next of the feed target reaction vessel and a next of the outflow source reaction vessel after a feed of the sample to a preceding feed target reaction vessel has been stopped.

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