JPH0610679B2 - Catalyst activity test equipment - Google Patents

Description

TECHNICAL FIELD The present invention relates to a catalyst activity test device for automatically performing reaction evaluation of a catalyst according to a preset schedule.

[Background Art and Problems] In catalyst development research, the reaction evaluation process is indispensable. When the reaction evaluation device is classified by the catalyst filling amount,
They are called microreactor, bench plant, and pilot plant in descending order of size.
In a microreactor that performs reaction evaluation on the experimental quality scale, that is, so-called primary cooling, a large number of trial catalysts must be evaluated efficiently.

Traditionally, automation of such small devices has been limited to program control of temperature and automatic gas sampling.
All other operations such as changing operating conditions and data processing have been performed manually. Therefore, in the research and development of catalysts, most of the effort is spent on the reaction evaluation.

[Object of the Invention] In view of the above points, an object of the present invention is to evaluate all reactions except catalyst filling, leak test, and withdrawal, such as pretreatment, gas switching, reaction, and analysis in the reaction evaluation of the catalyst. It is an object of the present invention to provide a catalytic activity test apparatus that can automate calculation, report generation, etc., can efficiently and accurately evaluate the reaction of a catalyst, and is economical.

[Means and Actions for Solving Problems] Therefore, in the present invention, a plurality of reaction devices having a plurality of reaction systems, and reactions produced by the corresponding reaction devices provided corresponding to the respective reaction devices A plurality of analyzers for analyzing products, and reaction products from any reaction system of the reactors respectively provided between these corresponding reactors and analyzers are selectively switched and injected into the analyzer. While switching the switching means and the respective reaction devices provided corresponding to the respective reaction devices according to a preset time schedule, at the same time, the operation state data of the reaction device at the time of sampling is filed,
A plurality of slave units that transmit the operation state data and the analysis result transferred from the analyzer corresponding to the reactor,
While giving an operation command to each slave unit, the master unit receives the operation state data and the analysis result transmitted from the slave unit and calculates the material balance from them and the data previously input, Each reaction system is a reactor filled with a test catalyst inside, a raw material selection valve for selecting the raw material supplied to the reactor from a plurality of types of raw materials, the pressure of the raw material selected by the raw material selection valve, Each of the analyzers is provided with a thermostatic chamber installed near the corresponding reactor, and a thermostatic chamber provided in the thermostatic chamber. And a sampling device for automatically injecting a reaction product from one of the reaction systems selected by the switching means into the analyzer.

[Example] FIG. 1 shows a catalyst activity testing apparatus of this example. The system includes one master device 1 including a computer, and six slave devices 11 to 16 each including a microcomputer or the like connected to the master device 1 via a communication line 10 so as to exchange information with each other. The reactors 21 to 26 whose operations are controlled by the respective slaves 11 to 16 and the reaction products generated in the respective reactors 21 to 26 are analyzed, and the analysis results are transferred to the slaves 11 to 16. Analyzer 3
1 to 36.

The master unit 1 has a time schedule (a selection of raw materials used in the reactors 21 to 26, a flow rate of the selected raw materials, a change time of set values such as pressure and temperature, sampling, etc., which is created in advance for performing the catalyst activity test. The time is set.) To any one of the slaves 11 to 16 designated by an address number, and sends a command to start or stop the experiment. In addition, the mass balance is calculated from the analysis results and operating conditions transferred from any one of the slaves 11 to 16 and the data input in advance, such as the catalyst weight, volume and raw material composition, and these results are stored in the floppy disk 2. Filing. At the same time, the operating state during the experiment is filed on the floppy disk 2 at regular time intervals. The operating state filed on the floppy disk 2 can be displayed on the green monitor 3 at any time and can be printed out by the printer 6. Further, the elapsed time data of the operating state can be displayed as a graph on the color monitor 4 and can be plotted on the XY plotter 5 at an arbitrary scale.

After receiving the time schedule transmitted from the master device 1, each of the slave devices 11 to 16 receives the experiment start command from the master device 1, and the corresponding reaction device 21 to 2 is received.
Drive 6 according to the time schedule. On the other hand, the operating state at the time of sampling based on the time schedule,
For example, the temperatures, pressures, and flow rates of the reaction devices 21 to 26 are stored in a file, and when the analysis results are transferred from the analysis devices 31 to 36, the analysis results and the operating state are combined to the master unit 1. It is supposed to be sent.

Each of the reaction devices 21 to 26 is, for example, shown in FIG. 2 (only the reaction device 21 is shown in FIG.
The same applies to 26. ) As shown in FIG.
1 to 16 through a switching cock 40 that constitutes switching means that is switched by a switching signal from the analyzers 31 to 31.
Two reaction systems A and B selectively connected to 36 are provided. Each of the reaction systems A and B is provided with a reactor 41 filled with a test catalyst. The reactor 41 is provided with an electric heater 42 as a heater that is heated by a signal from the slave unit 11 based on the temperature T in the reactor 41 on the outer periphery thereof, and a raw material supply line on the inlet side thereof. 43 is different types of four introducing a raw material gas feed introduction line 44 _{1-44 4} through the other end of the product discharge line 45 having one end to the outlet side is connected to the selector valve 40, respectively It is connected. Electromagnetic valves 46 _{1 to} 46 ₄ as raw material selection valves that are selectively opened / closed by selection signals from the slave unit 11 are provided on the respective raw material introduction lines 44 _{1 to 4} 44, respectively. Further, a pressure adjusting valve 48 having a pressure sensor 47 and a flow rate adjusting valve 50 having a flow meter 49 are inserted in the middle of the raw material supply line 43. Here, the pressure data P ₁ detected by the pressure sensor 47
When the flow rate data F detected by the flow meter 49 is fed back to the slave unit 11, the slave unit 11 receives the fed back pressure data P ₁ and flow rate data F.
Is equal to the preset pressure and flow rate, and a signal corresponding to the difference is given to the pressure regulating valve 48 and the flow rate regulating valve 50 to control them. A back pressure valve 52 having a pressure sensor 51 is inserted between the flow rate control valve 50 and the inlet side of the reactor 41 in the middle of the product withdrawal line 45. When the pressure data P ₂ detected by the pressure sensor 51 is input to the slaves 11 to 16, the pressure difference P between the pressure P ₁ detected by the pressure sensor 47 and the pressure P ₂ detected by the pressure sensor 51. _The pressure regulating valve 48 and the back pressure valve 52 are controlled so that ₁₋ P ₂ becomes a preset pressure.

Each analyzer 31 to 36, and two gas chromatographs 62 _1, 62 ₂ as analyzers, one of the reactions is actuated by the switching signal from the slave device 11 taken out through the selector valve 40 The gas chromatographs 62 ₁ and 62 ₂ are composed of two sampling cocks for automatically injecting reaction products from the vessel 41 into the gas chromatographs 62 ₁ and 62 ₂ and an integrator 63 that processes the analysis results of the gas chromatographs 62 ₁ and 62 _2. Has been done. The sampling device 61 includes the reaction devices 21 to 26.
It is provided in a constant temperature bath (not shown) installed close to. The indexer 63 multi-calculates the waveform processing device 64 that processes the waveform data of the gas chromatographs 62 ₁ and 62 ₂ and the result processed by the waveform processing device 64 to obtain the composition of the reaction product and store it. And a waveform storage device 65 that operates. Waveform storage device 65
After the analysis is completed, the analysis result stored in is transmitted to the slave unit 11 through the signal line 66.

Next, the operation of this embodiment will be described. First, in the master device 1, a time schedule for automatically performing the catalyst activity test is created for each of the reaction devices 21 to 26. In creating the time schedule, for example, as shown in FIG. 3, the temperature T, the flow rate F, the pressure P of each of the reaction devices 21 to 26,
Electromagnetic valves 46 _{1 to} 46 ₄ corresponding to the raw material gas used
ON / OFF, ON / OFF of the switching cock 40, ON / OFF of the sampling device 61, switching of the switching cock 40, etc. are set in accordance with the elapsed time. The time schedule set in this way is transferred to each of the slaves 11 to 16 through the communication line 10.

In each of the slaves 11 to 16, as shown in the flowchart of FIG. 4, after receiving the time schedule transmitted from the master 1, storing it in a preset filing area, an experiment is performed from the master 1. Monitor whether a start command has been sent. Here, when the experiment start command is received from the base unit 1, it is subsequently determined whether or not the experiment end time is reached, and if the experiment end time is not reached, proceed to the next step and move to the filing area. Reactors 21-26 according to the stored time schedule
The temperature T, the pressure P, and the flow rate F are controlled. That is, the electric heater 42 and the pressure P of the pressure sensor 51 are set so that the temperature of the reactor 41 matches the temperature data T of the time schedule.
_The back pressure valve 52 is set so that 2 matches the time schedule pressure data P, and the flow rate adjustment valve 5 is set so that the value of the flow meter 49 matches the time schedule flow rate data F.
0 is controlled respectively. At the same time, the elapsed time is counted.

After that, the process proceeds to the next step on condition that the optimum control mode is not set, that is, the time schedule mode is set, and the temperature T, the pressure P, and the flow rate F of the reaction devices 21 to 26 are set to values corresponding to the elapsed time. Determine whether or not. Here, when the temperature T, the pressure P, and the flow rate F are not the values corresponding to the elapsed time, the control signals for the temperature T, the pressure P, and the flow rate F corresponding to the elapsed time are sent to the electric heater 42, the back pressure. To the valve 52 and the flow control valve 50,
Return to the judgment of the end time of the experiment. On the other hand, when the temperature T, the pressure P, and the flow rate F are values corresponding to the elapsed time, it is subsequently determined whether or not the sampling time has been reached. If the sampling time has not been reached, the process returns to the judgment of the experiment end time, but if the sampling time has been reached, the sampling device 61 is switched to perform sampling. Then, the reaction product from any one of the reactors 41 is passed through the switching cock 40 and the gas chromatograph 6
2 ₁ and 62 ₂ are automatically injected, and the reaction products are analyzed in the gas chromatographs 62 ₁ and 62 ₂ .
The waveform data analyzed by the gas chromatographs 62 ₁ and 62 ₂ is processed by the integrator 63 and then stored.

In this way, the temperature T, the flow rate F, and the pressure P are sequentially changed according to the time schedule until the experiment end time is reached, and the samples are sampled at predetermined time intervals. And are transmitted to base unit 1.

Then, in the master unit 1, the mass balance is calculated from the analysis results and the operating conditions transferred from the slave units 11 to 16 and the previously input data, such as the catalyst weight, the volume and the raw material composition, and these results are calculated. Filing to floppy disk 2. The operating state filed on the floppy disk 2 can be displayed on the green monitor 3 at any time and can be printed out by the printer 6. Further, it is possible to display a graph on the color monitor 4 and to plot on the XY plotter 5 at an arbitrary scale.

On the other hand, in the optimum control mode, the operation is performed according to the flowchart of FIG. First, after reading the initial value in the time schedule, sampling is performed under the condition that one hour has passed after the setting value was changed. Sampling procedure opens the sampling device 61 similarly to the foregoing operation a predetermined time, the reaction product produced by any one of the reactor 41 was automatically injected into the gas chromatograph 62 _1, 62 _2, the gas chromatograph 62 ₁ , the analysis of the reaction product in 62 _2. Then, the concentration of a specific peak is detected from this analysis result. The concentration can be represented by the product of the peak area and the factor. The factor is a value calibrated with a standard gas before the start of the experiment. In addition,
When a plurality of types of gas chromatographs are used for the analysis of the produced gas, the respective analysis results can be transmitted to the parent device 1 and the composition of the produced gas can be calculated from the analysis results.

Next, the selectivity is calculated from the raw material gas and the number of moles of the product, and after filing the results, it is judged whether or not the experiment is completed. As a determination condition for this end, the selectivity is M
When the temperature reaches the ax, the temperature T exceeds the set range, or the conversion rate exceeds the set range, the process is considered to be finished and the process shown in the flowchart of FIG. 6 is performed. On the other hand, in the state before the end condition is not reached, the temperature T is plus 5 ° C. when the previous data is 1 or less, and the temperature T is minus 5 when the previous data is 2 or more and the tendency is decreasing.
C. If there are two or more previous data and there is an increasing tendency, the temperature T is changed by plus 5.degree. C., and then the process returns to the judgment as to whether or not one hour has elapsed after the setting value was changed. In this way, depending on the number of collected data and the changing direction of the data, the temperature T
By changing each of the temperature ranges by a predetermined temperature range, sampling for 1 hour after the change, and performing the sampling until the end condition is reached, the reaction evaluation test of the catalyst can be performed.

On the other hand, in the flowchart of FIG.
After lowering the temperature at ℃ / min and reducing the pressure P at 10 kg / cm ² / min, the temperature T is 100 ° C. or less and the pressure P is 1
Judge whether it is 0 kg / cm ² G or less. Temperature T is 1
When the temperature is not lower than 00 ° C. and the pressure P is not lower than 10 kg / cm ² G, the above-mentioned process is repeated, but the temperature T is 10
When the temperature is 0 ° C. or less and the pressure P is 10 kg / cm ² G or less, the flow rate F is 0 / hr. That is, the electromagnetic valve 4
6 _{1 to} 46 ₄ are closed. Finally, after the end message is printed out from the printer 6, the process ends.

In addition to the processing shown in FIG. 4 to FIG. 6, the present apparatus is adapted to perform the alarm processing shown in FIG. In this alarm processing, the temperature T, the pressure P, and the flow rate F are constantly monitored, and when these values exceed preset values, predetermined alarm processing is performed according to those values. . Specifically, when the temperature T, the pressure P, and the flow rate F exceed preset upper limit values, an alarm is output to warn that these values exceed the upper limit values. Further, when the temperature T, the pressure P, and the flow rate F exceed preset lower limit values, an alarm is output to warn that these values have exceeded the lower limit values. Furthermore,
When the temperature T, the pressure P, and the flow rate F exceed the maximum upper limit values higher than the above-mentioned upper limit values, an alarm is output, and then the control output of the temperature T, the pressure P, and the flow rate F is controlled to be 0 in 5 minutes. It is supposed to do. As a result, the safety of the entire device is ensured.

Therefore, according to the present embodiment, the catalyst activity test is automatically performed according to the previously created time schedule. Therefore, if the time schedule is created in advance, the catalyst activity test can be faithfully performed according to the time schedule. Therefore, the reaction evaluation test can be efficiently processed, and as a result, significant labor saving can be achieved.

In addition, even if you do not create a time schedule, if you switch to automatic mode, the conditions are sequentially changed according to the number of collected data and the change tendency of the data, and sampling is performed after each change, so The activity test of the catalyst can be automatically performed without creating a time schedule, and as a result, significant labor saving can be achieved.

The system also uses catalyst loading, leak testing,
All operations except extraction, ie pretreatment, gas switching,
Since reaction, analysis, calculation, and report creation can all be automated, it is possible to greatly reduce labor.

Further, the values of the temperature T, the pressure P, and the flow rate F are constantly monitored, and when the temperature T, the pressure P, and the flow rate F exceed preset values, an alarm output is issued to warn that.
When the maximum upper limit is exceeded, the operation of the device is stopped so that safety can be achieved.

Also, each reactor 21 to 2 having two reaction systems A and B
6, the slave units 11 to 16, the generated gas sampling device 61, and the analyzers 31 to 36 are shared,
Not only can the equipment investment be reduced, but the accuracy of the experiment when comparing a plurality of catalyst activities can be improved.

Further, in the above-mentioned embodiment, a constant temperature bath is installed close to each of the reaction devices 21 to 26, and a sampling device 61 such as a sampling cock is provided in the constant temperature bath so that the sampling gas is sampled by the sampling device 61. Since the reaction device and the constant temperature bath are close to each other, the sampling device 61 can be brought close to the reaction devices 21 to 26, and as a result, the proportion of the low pressure part of the product gas line to the analysis devices 31 to 36 is small. More and more analyzers 31-3
The response to 6 can be improved. This means that the catalyst filling amount of the reactors 21 to 26 is small (for example, 1
If possible, the activity evaluation can be carried out. Moreover, it becomes possible to match the sampling conditions by sharing the sampling device 61 with the plurality of reaction devices 21 to 26, and there is an advantage that the activities of the catalysts packed in the reaction devices 21 to 26 can be compared more strictly. is there.

In the above embodiment, in the process of the optimum control shown in FIG. 5, when the end condition is satisfied, that is, the selectivity is Max.
When the temperature T or the conversion rate exceeds the set range, the process proceeds to the shutdown process shown in FIG. 6, but when any of these elements becomes the termination condition. For example, when the selectivity reaches Max, the process may return to the main routine shown in FIG.

In addition, if the gas flow rate and control are performed using a thermal flow meter and the true gas flow rate is calculated based on the flow rate factor set in advance in the slave units 11 to 16 according to the type of gas, the experiment Even if the type of gas is changed, the true gas flow rate can be continuously obtained with one gas flow meter.

Further, although gas is used as a raw material in the above embodiment, the present invention can also be applied to a chemical reaction using a liquid raw material.

An optical modem and an optical fiber may be used for data communication between the master unit 1 and the slave units 11 to 16.

[Effects of the Invention] As described above, according to the present invention, all operations except for catalyst filling, leak test, and withdrawal, that is, pretreatment, gas switching, reaction, analytical calculation, and report preparation can be automated. Thus, it is possible to efficiently and accurately evaluate the reaction of the catalyst and to provide an economical catalyst activity testing device.

[Brief description of drawings]

FIG. 1 shows an embodiment of the present invention. FIG. 1 is a block diagram showing the whole of the present apparatus, FIG. 2 is a block diagram showing the relationship between a reaction device, an analysis device and a slave unit, and FIG. FIG. 4 and FIG. 7 are flowcharts showing an example of the time schedule. 1 ... Parent unit, 11, 12, 13, 14, 15, 16 ...
Handset, 21,22,23,24,25,26 ...... reactor, 31,32,33,34,35,36 ...... analyzer 40 ...... selector valve (switching _means), 46 1-46 ₄
...... Electromagnetic valve, 48 …… Pressure control valve, 50 …… Flow control valve, 52 …… Back pressure valve, A, B …… Reaction system.

Claims (4)

[Claims] 1. A plurality of reactors having a plurality of reaction systems,
A plurality of analyzers which are provided corresponding to the respective reactors and which analyze the reaction products produced by the respective reactors, and the reactors which are respectively provided between the corresponding reactors and the analyzers. Switching means for selectively switching and injecting a reaction product from any one of the reaction systems into the analyzer, and operating the corresponding reactor provided corresponding to each reactor according to a preset time schedule. At the same time, while storing the operating state data of the reactor at the time of sampling, a plurality of slave units transmitting the operating state data and the analysis results transferred from the analyzer corresponding to the reactor, and each slave unit. While giving the operation command to the operation status data and the analysis result transmitted from the slave unit, A master unit for calculating a mass balance, and each reaction system is a reactor having a test catalyst filled therein, and a raw material selection for selecting a raw material supplied into the reactor from a plurality of types of raw materials. A valve, an adjusting valve for adjusting the pressure and flow rate of the raw material selected by the raw material selection valve, and a heater for changing the temperature of the reactor are provided, and each analyzer is installed close to a corresponding reactor. And a sampling device for automatically injecting a reaction product from one of the reaction systems selected by the switching means provided in the constant temperature bath into the analyzer. Activity test equipment. 2. The catalyst activity test apparatus according to claim 1, wherein the slave unit monitors pressure, flow rate and temperature in the reactor, and at least one of these pressure, flow rate and temperature is previously set. A catalyst activity testing device having a function of outputting an alarm when a set upper limit value or a lower limit value is exceeded. 3. The catalyst activity test apparatus according to claim 2, wherein the slave unit monitors the pressure, the flow rate and the temperature in the reactor, and at least one of the pressure, the flow rate and the temperature is preset. A catalyst activity testing device having a function of outputting an alarm and stopping the operation of the reaction device when a set upper limit value higher than the upper limit value is exceeded. 4. In the catalyst activity test apparatus according to claim 1, when a gas is used as the raw material, when the flow rate of the gas is measured and controlled by a thermal flow meter, the slave unit is set in advance. A catalyst activity test apparatus, which is configured to calculate a true gas flow rate based on a flow rate factor set according to a gas type.