JP2007246372A - CO shift catalyst system, reformed gas generation system, and CO shift catalyst regeneration method - Google Patents

Abstract

A CO shift catalyst system capable of recovering the catalytic activity of a CO shift catalyst contained in a CO shift reactor without having to stop the operation of the apparatus, a reformed gas generation system including the CO shift catalyst system, and a CO To provide a method for regenerating a shift catalyst.
A CO shift reactor containing a CO shift catalyst, used in a gas flow path, an oxidant supply means for supplying an oxidant to the CO shift reactor, and an oxidant supply means A CO shift catalyst system comprising start-up criterion determining means having a start reference and stop criterion determining means having a stop reference for an oxidant supply means. The CO shift catalyst system activates and operates the oxidant supply unit when the activation criterion determination unit determines that the activation criterion is satisfied, and when the stop criterion determination unit determines that the activation criterion is satisfied, Stop the oxidant supply means.
[Selection figure] None

Description

  The present invention relates to a CO shift catalyst system, a reformed gas generation system, and a CO shift catalyst regeneration method, and more specifically, a CO shift catalyst that supplies an oxidant to a CO shift reactor provided under predetermined conditions. The present invention relates to a system, a reformed gas generation system including the system, and a CO shift catalyst regeneration method.

Conventionally, in a device equipped with a CO shift catalyst, as a method for recovering the catalytic activity of the CO shift catalyst, after the CO shift catalyst is brought to a temperature of 200 to 700 ° C., the CO shift catalyst is changed to an oxidizing atmosphere or CO is oxidized in an oxidizing atmosphere. A method of bringing the shift catalyst to a temperature of 200 to 700 ° C. has been proposed (see Patent Document 1).
Japanese Patent Laid-Open No. 2002-3205

  However, in the apparatus for carrying out the method described in Patent Document 1, it is necessary to stop the operation of the apparatus when recovering the catalytic activity of the CO shift catalyst.

  The present invention has been made in view of such problems of the prior art, and the object of the present invention is to eliminate the CO shift contained in the CO shift reactor without requiring the operation of the apparatus to be stopped. An object of the present invention is to provide a CO shift catalyst system capable of recovering the catalytic activity of the catalyst, a reformed gas generation system including the CO shift catalyst system, and a method for regenerating the CO shift catalyst.

  The present inventor has intensively studied to achieve the above object. As a result, the present inventor has found that the above object can be achieved by supplying an oxidant to a CO shift reactor provided under predetermined conditions. It came to complete.

  That is, the CO shift catalyst system of the present invention is used by being disposed in a gas flow path, and includes a CO shift reactor containing a CO shift catalyst, and an oxidant supply for supplying an oxidant to the CO shift reactor. Means, a starting reference determining means having a starting reference for the oxidizing agent supplying means, and a stopping reference determining means having a stopping reference for the oxidizing agent supplying means, and the starting reference determining means satisfies the starting reference When the determination is made, the oxidant supply unit is activated and operated, and when the stop criterion determination unit determines that the stop criterion is satisfied, the oxidant supply unit is stopped.

  A first preferred embodiment of the CO shift catalyst system of the present invention is characterized in that the oxidant supply means is an oxidant pulse supply means for supplying an oxidant in pulses to the CO shift reactor.

  Furthermore, the second preferred embodiment of the CO shift catalyst system of the present invention is a temporary stop criterion determining means having a temporary stop criterion for the oxidant supplying means, and a temporary stop cancellation criterion determination having a temporary stop cancellation criterion for the oxidant supplying means. Means for temporarily stopping the oxidant supply means when the stop criterion determination means determines that the temporary stop criterion is satisfied, and reducing the oxidant supply amount, and the temporary stop release criterion. When the determination means determines that the stop cancellation criterion is satisfied, the oxidant supply means is restarted with the oxidant supply amount reduced.

  The third preferred embodiment of the CO shift catalyst system of the present invention further includes an operation stop criterion determining unit having an operation stop criterion for the oxidant supply unit, and the operation stop criterion determining unit satisfies the operation stop criterion. When judged, the operation of the oxidant supply means is stopped.

  Furthermore, the reformed gas generation system of the present invention includes the above-described CO shift catalyst system of the present invention.

  On the other hand, according to the CO shift catalyst regeneration method of the present invention, when the regeneration process of the CO shift catalyst is necessary, the oxidant is supplied to the CO shift catalyst when performing the regeneration process using the CO shift catalyst. It is characterized by doing.

  According to the present invention, since the oxidizing agent is supplied to the CO shift reactor provided under predetermined conditions, the CO shift reactor contains CO without requiring the operation of the apparatus to be stopped. A CO shift catalyst system that can recover the catalytic activity of the shift catalyst, a reformed gas generation system including the CO shift catalyst system, and a CO shift catalyst regeneration method can be provided.

Hereinafter, the CO shift catalyst system of the present invention will be described in detail. In the present specification and claims, “%” for concentration, content and the like represents mass percentage unless otherwise specified.
As described above, the CO shift catalyst system of the present invention is used by being disposed in a gas flow path, and an oxidation that supplies a CO shift reactor containing a CO shift catalyst and an oxidant to the CO shift reactor. An oxidant supply means, a start reference determination means having a start reference for the oxidant supply means, and a stop reference determination means having a stop reference for the oxidant supply means.
And when this CO shift catalyst system judges that the starting reference | standard judgment means to satisfy | fill a starting reference | standard, it determines that the oxidant supply means to equip | provides and operates, and the stop reference | standard judging means to equip with a stop | fastening reference | standard When this happens, the oxidant supply means provided is stopped.
By adopting such a configuration, the catalytic activity of the CO shift catalyst contained in the CO shift reactor can be recovered (regenerated) without the need to stop the operation of the apparatus, that is, stop using the CO shift catalyst. ).
In the present invention, the operation of the apparatus can be stopped and the oxidant can be supplied, and such a CO shift catalyst system is also included in the scope of the present invention.

Here, FIG. 1 is a graph showing an example of the change over time of the CO shift performance of the CO shift catalyst and the conventional CO shift catalyst in the CO shift catalyst system of the present invention.
As shown in the figure, in the conventional CO shift catalyst, the CO shift performance decreases with time ((1) in the figure). On the other hand, in the CO shift catalyst in the CO shift catalyst system of the present invention, although the CO shift performance has a tendency to decrease with the passage of time, the catalyst of the CO shift catalyst can be obtained by supplying an oxidizing agent as shown by an arrow A. The activity can be recovered (regenerated) ((2) in the figure).
In the figure, (3) shows the initial CO shift performance of the CO shift catalyst.

In the present invention, the oxidant supply means can be oxidant pulse supply means for supplying an oxidant pulse to the CO shift reactor.
By using the oxidant pulse supply means that can supply such an oxidizer in a pulsed manner, not only a small amount of oxidant can be supplied, but also the catalyst regeneration can be determined by determining that the stop criterion determination means satisfies the stop criterion. At the end of the process, this can be executed with high accuracy.
“Oxidizing agent pulse supply” indicates that, for example, an oxidizing agent having a volume flow rate of about 0.01 to 10% by volume is supplied for 0.001 to 60 seconds. However, the present invention is not necessarily limited to this. Moreover, either continuous supply or discontinuous supply may be sufficient. Furthermore, as such an oxidant pulse supply means, for example, one provided with a valve mechanism capable of ejecting an oxidant can be mentioned.

Furthermore, in the present invention, the oxidant to be supplied is not particularly limited as long as it can recover (regenerate) the catalytic activity of the CO shift catalyst. However, oxygen, hydrogen peroxide, or at least one of these can be used. A mixed gas containing seeds (for example, air) can be used.
As will be described in detail later, in recovering (regenerating) the catalytic activity of the CO shift catalyst by oxidizing and removing the cerium (Ce) site carbonate contained in the CO shift catalyst, oxygen or peroxidation that generates oxygen by thermal decomposition. It is particularly desirable to use hydrogen.

Here, in the CO shift catalyst system of the present invention, the procedure for recovering the catalytic activity of the CO shift catalyst (CO shift catalyst regeneration method) will be described in detail with reference to a flow chart.
FIG. 2 is a flowchart showing an example of a procedure (a method for regenerating the CO shift catalyst) when recovering the catalytic activity of the CO shift catalyst in the CO shift catalyst system of the present invention.

As shown in the figure, the CO shift catalyst system of this example satisfies the start criteria that the start criteria judgment means has at Step 1 (hereinafter abbreviated as “S1”) during operation of the CO shift catalyst system. When it is determined, the process proceeds to S2.
In S2, the CO shift catalyst system starts the oxidant supply means and starts the catalyst regeneration process.
In S3, the CO shift catalyst system operates the oxidant supply means to recover the catalytic activity of the CO shift catalyst contained in the CO shift reactor, that is, performs a catalyst regeneration process.
In S4, the CO shift catalyst system proceeds to S5 when the stop criterion determining means determines that the stop criterion is satisfied.
In S5, the CO shift catalyst system stops the oxidant supply means and ends the catalyst regeneration process.

In S1, the CO shift catalyst system does not perform the catalyst regeneration process when it is determined that the activation criterion determination means does not satisfy the activation criterion.
Furthermore, in S4, when the CO shift catalyst system determines that the stop criterion determination means does not satisfy the stop criterion, the process proceeds to S3.

Further, in the present invention, as an example of the activation reference determination means, a gas flow rate detector that detects a gas flow rate to the CO shift reactor, and an inlet side CO detector that detects the CO concentration on the gas inlet side of the CO shift reactor; And an outlet side CO detector that detects the CO concentration on the gas outlet side of the CO shift reactor, and an arithmetic processing unit that stores the CO detector type activation reference data.
In order to determine that the activation criterion determination means satisfies the activation criterion, the arithmetic processing unit performs arithmetic processing on data input from the gas flow rate detector, the inlet side CO detector, and the outlet side CO detector. The calculation data obtained in this way is compared with the CO detector type activation reference data stored in the arithmetic processing unit itself, and it is determined that the CO detector type activation reference data is satisfied.
By using such start-up criterion determination means, it becomes possible to respond more quickly to fluctuations in the flow rate of gas flowing into the CO shift reactor and CO concentration.
As such a gas flow rate detector, for example, a conventionally known gas flow meter can be used, and as the CO detector, for example, a conventionally known CO sensor can be used, and various data are stored. As the arithmetic processing unit, a conventionally known microcomputer, an electronic control unit equipped with an arithmetic unit, or the like can be used.

At this time, in the present invention, as an example of a combination of the above-described calculation data and CO detector type activation reference data, the arithmetic processing unit inputs from the gas flow rate detector, the inlet side CO detector, and the outlet side CO detector. A combination of a cumulative CO processing amount obtained by arithmetic processing of the data to be processed and a preset cumulative CO processing amount of the CO shift reactor can be mentioned.
Here, the “cumulative CO processing amount of the CO shift reactor set in advance” is specifically obtained in advance through experiments or the like to obtain a relationship between the cumulative CO processing amount of the CO shift reactor and the CO shift performance. Is. Then, the CO shift performance is determined according to the performance required in the CO shift reactor, and the accumulated CO processing amount that becomes the CO detector type activation reference data is determined from this.
In addition, when the performance required in the CO shift reactor is high, it is also possible to suppress a decrease in the catalytic activity of the CO shift catalyst by reducing the cumulative CO processing amount that becomes the CO detector type activation reference data. It is.

Here, the calculation method of the cumulative CO processing amount described above will be described in detail with reference to the drawings.
FIG. 3 is an explanatory diagram showing a conceptual calculation method of the cumulative CO throughput of the CO shift reactor. The line graph shown by the solid line in FIG. 3 shows an example of the relationship between time (t) and time CO processing amount [F × (CO _in −CO _out )]. Here, F is the gas flow rate flowing into the CO shift reactor, CO _in is the CO concentration on the inlet side of the CO shift reactor, and CO _out is the CO concentration on the outlet side of the CO shift reactor.
Then, at time _{[T 0],} to exit the catalyst regeneration process, assuming that resets the accumulated CO throughput, the cumulative CO throughput from time _{[T 0]} to time _{[T 1],} the time _{[T 0} ] Is the integral value of the time CO processing amount [F × (CO _in −CO _out )] from time [T ₁ ], and corresponds to the area indicated by hatching the dot pattern in the figure.

Furthermore, in the present invention, as another example of the activation reference determination means, there can be mentioned one provided with a time measuring device and an arithmetic processing device for storing time measuring device type activation reference data.
In determining that the activation criterion determination means satisfies the activation criterion, the arithmetic processing device includes calculation data obtained by performing arithmetic processing on data input from the time measuring device, and the arithmetic processing device itself. The time measurement type activation reference data to be stored is compared, and it is determined that the time measurement type activation reference data is satisfied.
By using such a starting reference determination means, the above-described gas flow rate detector and CO detector are not required, the configuration of the CO shift catalyst system can be simplified, and the cost can be reduced. There is an advantage.
In addition, such a CO shift catalyst system is particularly suitable when the decrease in CO shift performance in the CO shift reactor is only related to time (for example, when the CO amount defined by the inflowing gas flow rate and the CO concentration is constant). Etc.).
As such a time measuring device, for example, various conventionally known timers can be used, and such a timer may be incorporated in the arithmetic processing unit.

At this time, in the present invention, as an example of a combination of the above-described calculation data and time measuring device type activation reference data, an oxidant obtained by processing the data input from the time measuring device by the arithmetic processing unit A combination of the accumulated time from the latest stop of the supplying means and the preset accumulated time from the most recent stop of the oxidant supplying means can be mentioned.
Here, the “integrated time from the most recent stop of the oxidant supply means set in advance” specifically refers to the accumulated time from the most recent stop of the oxidant supply means in advance and the CO shift reactor. The relationship with the CO shift performance can be obtained by experiments or the like. Then, the CO shift performance is determined in accordance with the performance required in the CO shift reactor, and the accumulated time from the most recent stop time of the oxidant supply means serving as the time measurement type start reference data is determined. Good.
In addition, when the performance requested | required in a CO shift reactor is high, it is also possible to suppress the fall of the catalytic activity of a CO shift catalyst by shortening the integration time used as time measuring device type starting reference data. .
Moreover, it is also possible to use a combination of these start-up criterion determination means, and thereby it is possible to perform more accurate recovery (regeneration) of the catalytic activity of the CO shift catalyst.

Furthermore, the CO shift catalyst system of the present invention has an oxidizer when the load applied to the CO shift reactor is large and the start-up criterion determination means determines that the start-up criterion is satisfied. It is desirable to start and operate the supply means.
When the load applied to the CO shift reactor is large, the gas flow rate flowing into the CO shift reactor is large, and hydrogen burnout is relatively small. Further, since the temperature is high and the reaction activity is increased, the catalyst regeneration process can be completed in a short time.
The load applied to such a CO shift reactor can be measured using, for example, the gas flow rate detector described above, and the reference for the load is appropriately set according to the use mode of the CO shift catalyst system. be able to.

Further, in the present invention, as an example of the stop reference determination means, an oxygen detector for detecting the oxygen concentration inside the CO shift reactor and / or the gas outlet side, and oxygen detector type stop reference data are stored. And an arithmetic processing unit.
When determining that the stop criterion determination means satisfies the stop criterion, the arithmetic processing unit includes calculation data obtained by arithmetic processing of data input from the oxygen detector, and the arithmetic processing unit itself. The stored oxygen detector stop reference data is compared to determine that the oxygen detector stop reference data is satisfied.
By using such a stop criterion judgment means, when the oxidizing agent such as oxygen or hydrogen peroxide that generates oxygen is used in the catalyst regeneration process, the catalytic activity of the CO shift catalyst is recovered by the catalyst regeneration process. The degree of (regeneration) can be estimated, and a more accurate catalyst regeneration process can be performed.
In addition, for example, in a reformed gas generation system including a CO shift catalyst system, which will be described in detail later, there is also an advantage that the reaction in the CO selective oxidation reactor disposed downstream of the CO shift reactor can be easily stabilized. is there.

At this time, in the present invention, as an example of a combination of the above-described calculation data and oxygen detector type stop reference data, the arithmetic processing unit performs arithmetic processing on data input from the oxygen detector of the CO shift reactor. And a combination of the oxygen concentration of the CO shift reactor set in advance.
Here, the “preliminarily set oxygen concentration of the CO shift reactor” is specifically obtained in advance by an experiment or the like from the oxygen concentration on the gas outlet side of the CO shift reactor during normal operation. For example, this may be set to zero or a reference value may be set.
In addition, as such an oxygen detector, a conventionally well-known oxygen sensor etc. can be used, for example.

Here, the configuration of the CO shift catalyst system of the present invention will be described in detail with reference to the drawings.
FIG. 4 is a block diagram showing an embodiment of the CO shift catalyst system of the present invention. As shown in the figure, the CO shift catalyst system 1a of this example is disposed in a gas flow path and is used with respect to a CO shift reactor 10 containing a CO shift catalyst 12 and a CO shift reactor 10. An oxidant pulse supply means 22, which is an example of the oxidant supply means 20 for supplying the oxidant, a gas flow rate detector 32, and an inlet side CO detector 34 for detecting the CO concentration on the gas inlet side of the CO shift reactor 10. A CO detector 36 for detecting the CO concentration on the gas outlet side of the CO shift reactor 10, an oxygen detector 42 for detecting the oxygen concentration on the gas outlet side of the CO shift reactor 10, and a CO detector type And an arithmetic processing unit 70 that stores start reference data and oxygen detector type stop reference data.

In addition, the gas flow rate detector 32, the inlet side CO detector 34, the outlet side CO detector 36, and the arithmetic processing device 70 function as the activation reference determination means 30. Further, the oxygen detector 42 and the arithmetic processing unit 70 work together to function as the stop reference determination unit 40.
In addition, the arrow A in a figure shows a gas flow direction.

Here, an example of a procedure (regeneration method of the CO shift catalyst) when recovering the catalytic activity of the CO shift catalyst 12 in the CO shift catalyst system 1a of the present example will be described with reference to a flowchart.
FIG. 5 is a flowchart showing an example of a procedure (regeneration method of the CO shift catalyst) when recovering the catalytic activity of the CO shift catalyst 12 in the CO shift catalyst system 1a of this example.

  As shown in the figure, the CO shift catalyst system 1a uses the CO detector type start reference data as CO detector type start reference data in advance in S11 according to the CO shift performance required in the CO shift reactor 10. The cumulative CO processing amount (in the figure, (trigger amount: X)) is set.

In S12, the CO shift catalyst system 1a proceeds to S13 when it is determined that the activation reference determination means 30 satisfies the CO detector type activation reference data that it has.
Specifically, during operation of the CO shift catalyst system 1a, in S12, the arithmetic processing unit 70 is changed from the gas flow rate detector 32, the inlet side CO detector 34, and the outlet side CO detector 36 to the arithmetic processing unit 70, respectively. Cumulative CO processing amount as calculation data obtained by arithmetic processing of input data and cumulative CO processing amount serving as CO detector type activation reference data stored in the arithmetic processing unit 70 itself ((Trigger amount in the figure) : X)) is compared, and when the accumulated CO processing amount as the calculation data exceeds the trigger amount, it is determined that the CO detector type activation reference data is satisfied, and the process proceeds to S13.

In S13, the CO shift catalyst system 1a activates the oxidant pulse supply means 22 and starts the catalyst regeneration process.
In S14, the CO shift catalyst system 1a operates the oxidant pulse supply means 22 to recover the catalytic activity of the CO shift catalyst 12 of the CO shift reactor 10, that is, to perform a catalyst regeneration process.

In S15, the CO shift catalyst system 1a proceeds to S16 when it is determined that the stop criterion determination means 40 satisfies the oxygen detector type stop criterion data that it has.
Specifically, in S15, the calculation processing device 70 performs calculation processing on the data input from the oxygen detector 42, and oxygen detector type stop reference data stored in the calculation processing device 70 itself. When unreacted oxygen (O ₂ ) is detected, it is determined that the oxygen detector type stop reference data is satisfied, and the process proceeds to S16.

In S16, the CO shift catalyst system 1a resets the cumulative CO processing amount as calculation data obtained by performing arithmetic processing on the data input to the arithmetic processing unit 70 (specifically, the cumulative CO processing amount = 0). .)
In S17, the CO shift catalyst system 1a stops the oxidant pulse supply means 22 and ends the catalyst regeneration process.

In S12, the CO shift catalyst system 1a does not perform the catalyst regeneration process when the activation reference determination unit 30 determines that the CO detector type activation reference data is not satisfied.
Further, when the stop criterion determining means 40 determines in S15 that the oxygen detector type stop criterion data is not satisfied, the process proceeds to S14.

The CO shift catalyst system of the present invention further includes a temporary stop criterion determining unit having a temporary stop criterion for the oxidant supply unit, and a temporary stop cancellation criterion determining unit having a temporary stop cancellation criterion for the oxidant supply unit. It may be.
In such a CO shift catalyst system, when the stop criterion determining unit once determines that the stop criterion is satisfied, the oxidant supplying unit is temporarily stopped, the oxidant supply amount is reduced, and the stop is temporarily stopped. When the release criterion determining means once determines that the stop release criterion is satisfied, the oxidant supply means is restarted while reducing the oxidant supply amount as described above.
Here, “stop” means complete stop of the catalyst regeneration process, and indicates a situation in which, for example, the key is removed from the vehicle. “Temporary stop” means a momentary stop during the execution of the catalyst regeneration process, and is approximately 0.5 hour or less in a vehicle.
By further providing such a temporary stop criterion determination means and a temporary stop cancellation criterion determination means, for example, the combustion of hydrogen generated by a CO shift catalyst or the like is effectively suppressed or prevented, and deterioration of the CO shift catalyst due to heat is suppressed. be able to.
When reducing the oxidant supply amount, the reduction amount may be adjusted as appropriate according to the required CO shift performance and system usage.

Furthermore, in the present invention, as an example of the stop reference determination means, a temperature detector for detecting the temperature of either or both of the inside of the CO shift reactor and the gas inlet side, and temperature detector type temporary stop reference data are provided. And a stored arithmetic processing unit.
When such a temporary stop criterion determining means determines that the temporary stop criterion is satisfied, the arithmetic processing unit includes calculation data obtained by performing arithmetic processing on data input from the temperature detector, and such arithmetic processing. The temperature detector type temporary stop reference data stored in the apparatus itself is compared, and it is determined that the temperature detector type temporary stop reference data is satisfied.
By further providing such a stop criterion determination means, for example, deterioration of the CO shift catalyst due to heat can be suppressed.
As such a temperature detector, for example, a temperature sensor equipped with a conventionally known thermocouple can be used.

At this time, in the present invention, as an example of the combination of the above-described calculation data and the temperature detector type temporary stop reference data, a CO obtained by the arithmetic processing unit arithmetically processing the data input from the temperature detector A combination of the catalyst temperature of the shift reactor and the preset catalyst temperature of the CO shift reactor can be mentioned.
Here, the “preliminarily set catalyst temperature of the CO shift reactor” is specifically obtained from the catalyst temperature during normal operation in advance through experiments or the like. Then, an allowable temperature increase range may be determined according to the catalyst regeneration process and the CO shift reactor.

Furthermore, in the present invention, as another example of the stop reference determination means, a hydrogen detector for detecting the hydrogen concentration on the gas outlet side of the CO shift reactor, and a calculation process storing the hydrogen detector type stop reference data And a device provided with a device.
When such a temporary stop criterion determining means determines that the temporary stop criterion is satisfied, the arithmetic processing unit includes calculation data obtained by performing arithmetic processing on data input from the hydrogen detector, and such arithmetic processing. The hydrogen detector type temporary stop reference data stored in the apparatus itself is compared to determine that the hydrogen detector type temporary stop reference data is satisfied.
By further providing such a stop criterion determination means, it is possible to effectively suppress or prevent the combustion of hydrogen generated by, for example, a CO shift catalyst.
In addition, as such a hydrogen detector, a conventionally well-known hydrogen sensor etc. can be used, for example.

At this time, in the present invention, as an example of the combination of the above-described calculation data and the hydrogen detector type temporary stop reference data, a CO obtained by the arithmetic processing unit operating the data input from the hydrogen detector is used. A combination of the hydrogen concentration on the gas outlet side of the shift reactor and the hydrogen concentration on the gas outlet side of the CO shift reactor set in advance can be mentioned.
Here, the “predetermined hydrogen concentration on the gas outlet side of the CO shift reactor” is specifically obtained from the hydrogen concentration on the gas outlet side during normal operation in advance by experiments or the like. Then, an allowable hydrogen concentration reduction rate may be determined in accordance with the catalyst regeneration process and the CO shift reactor.
Note that these temporary stop criterion determination means can also be used in combination, thereby making it possible to more accurately recover (regenerate) the catalytic activity of the CO shift catalyst.

On the other hand, in the present invention, as an example of the stop release criterion determination means, a temperature detector that detects the temperature of at least one of the inside of the CO shift reactor, the gas inlet side, and the gas outlet side, and the temperature detector type once And an arithmetic processing unit that stores stop cancellation reference data.
And when such a temporary stop cancellation reference determination means determines that the temporary stop cancellation criterion is satisfied, the arithmetic processing unit includes calculation data obtained by performing arithmetic processing on data input from the temperature detector, and The temperature detector type temporary stop release reference data stored in the arithmetic processing unit itself is compared to determine that the temperature detector type temporary stop release reference data is satisfied.
By further providing such a stop cancellation criterion determination means, the combustion of hydrogen generated by the CO shift catalyst or the like is effectively suppressed or prevented, and the catalyst is efficiently regenerated while suppressing the deterioration of the CO shift catalyst due to heat. Processing can be executed.

Here, the configuration of the CO shift catalyst system of the present invention will be described in detail with reference to the drawings.
FIG. 6 is a block diagram showing another embodiment of the CO shift catalyst system of the present invention. As shown in the figure, the CO shift catalyst system 1b of the present example is disposed and used in a gas flow path, and a CO shift reactor 10 containing a CO shift catalyst 12 and a CO shift reactor 10 are used. An oxidant pulse supply means 22, which is an example of the oxidant supply means 20 for supplying the oxidant, a gas flow rate detector 32, and an inlet side CO detector 34 for detecting the CO concentration on the gas inlet side of the CO shift reactor 10. An outlet side CO detector 36 for detecting the CO concentration on the gas outlet side of the CO shift reactor 10, an oxygen detector 42 for detecting the oxygen concentration on the gas outlet side of the CO shift reactor 10, and a CO shift reactor 10, a temperature detector 52 for detecting the internal temperature of the gas detector 10, a hydrogen detector 62 for detecting the hydrogen concentration on the gas outlet side of the CO shift reactor 10, CO detector type start reference data, oxygen detector type stop reference data Comprises a temperature detector type temporarily stop cancellation reference data and the processing unit 70 which stores the stop criterion data hydrogen-detector once a.

  Further, the gas flow rate detector 32, the inlet side CO detector 34, the outlet side CO detector 36, and the arithmetic processing device 70 work together to function as the activation reference determination means 30, and operate with the oxygen detector 42. The processing device 70 cooperates to function as the stop reference determination means 40, and the hydrogen detector 62 and the arithmetic processing device 70 cooperate to function as the stop reference determination means 60, and the temperature detector 52 and the arithmetic processing. In cooperation with the device 70, the device once functions as the stop cancellation reference determination means 50.

Here, an example of a procedure (regeneration method of the CO shift catalyst) when recovering the catalytic activity of the CO shift catalyst 12 in the CO shift catalyst system 1b of the present example will be described with reference to a flowchart.
FIG. 7 is a flowchart showing an example of a procedure (regeneration method of the CO shift catalyst) when recovering the catalytic activity of the CO shift catalyst 12 in the CO shift catalyst system 1b of this example.

As shown in the figure, the CO shift catalyst system 1b uses the CO detector type start reference data as the CO detector type start reference data in advance in S21 according to the CO shift performance required in the CO shift reactor 10. The cumulative CO processing amount (in the figure, (trigger amount: X)) is set. Further, as the oxidant supply amount, an initial oxidant supply amount ((pulse supply amount: P ₀ in the figure)) is set in advance according to the CO shift performance required in the CO shift reactor 10.

In S22, the CO shift catalyst system 1b proceeds to S23 when it is determined that the activation reference determination means 30 satisfies the CO detector type activation reference data that it has.
Specifically, during operation of the CO shift catalyst system 1b, in S22, the arithmetic processing unit 70 is changed from the gas flow rate detector 32, the inlet side CO detector 34, and the outlet side CO detector 36 to the arithmetic processing unit 70, respectively. Cumulative CO processing amount as calculation data obtained by arithmetic processing of input data and cumulative CO processing amount serving as CO detector type activation reference data stored in the arithmetic processing unit 70 itself ((Trigger amount in the figure) : X)), and when the accumulated CO processing amount as the calculation data exceeds the trigger amount, it is determined that the CO detector type activation reference data is satisfied, and the process proceeds to S23.

In S23, the CO shift catalyst system 1b determines whether or not the oxidant supply unit has been temporarily stopped. When it is determined that the oxidant supply unit has not been temporarily stopped, the process proceeds to S24.
Specifically, in S23, the arithmetic processing unit 70 once reads the number of stops: n from the storage area that can be stored, and once the number of stops: n is n = 0, it is determined that the stop has not been temporarily performed. , Go to S24.

In S24, CO shift catalyst system 1b sets the oxidizing agent supply amount of the oxidizing agent pulse supply unit 22 to the _{P 0.}
In S25, the CO shift catalyst system 1b activates the oxidant pulse supply means 22 and starts the catalyst regeneration process.
In S26, the CO shift catalyst system 1b operates the oxidant pulse supply means 22 to recover the catalyst activity of the CO shift catalyst 12 of the CO shift reactor 10 provided, that is, performs a catalyst regeneration process.

In S27, the CO shift catalyst system 1b proceeds to S28 when the stop criterion determining unit 60 determines that the hydrogen detector type temporary stop criterion data is not satisfied.
Specifically, in S27, the arithmetic processing unit 70 performs arithmetic processing on the data input from the hydrogen detector 62, and the hydrogen detector type temporary stop reference data stored in the arithmetic processing unit 70 itself. When the hydrogen concentration reduction rate is less than 5% in normal operation, it is determined that the hydrogen detector type temporary stop reference data is not satisfied, and the process proceeds to S28.

In S28, the CO shift catalyst system 1b proceeds to S29 when it is determined that the stop reference determination means 40 satisfies the oxygen detector stop reference data that it has.
Specifically, in S28, the calculation processing device 70 performs calculation processing on the data input from the oxygen detector 42, and oxygen detector type stop reference data stored in the calculation processing device 70 itself. When unreacted oxygen (O ₂ ) is detected, it is determined that the oxygen detector type stop reference data is satisfied, and the process proceeds to S29.

In S29, the CO shift catalyst system 1b resets the cumulative CO processing amount as calculation data obtained by arithmetic processing of the data input to the arithmetic processing unit 70 (specifically, the cumulative CO processing amount = 0). .)
In S30, the CO shift catalyst system 1b stops the oxidant pulse supply means 22 and ends the catalyst regeneration process.

  In S22, the CO shift catalyst system 1b does not perform the catalyst regeneration process when the activation reference determination unit 30 determines that the CO detector type activation reference data is not satisfied.

In S23, the CO shift catalyst system 1b determines whether or not the oxidizer pulse supply means 22 has been temporarily stopped. When it is determined that the oxidizer pulse supply unit 22 has been temporarily stopped, the process proceeds to S31.
Specifically, in S23, the arithmetic processing unit 70 once reads the number of stops: n from a storage area that can store, and once the number of stops: n is n ≠ 0 (specifically, n = 1, 2, 3, ..)), It is determined that the operation has been temporarily stopped, and the process proceeds to S31.

In S31, the CO shift catalyst system 1b sets the oxidant supply amount of the oxidant pulse supply means 22 to P ₀ × (1/2) ⁿ .

In S27, the CO shift catalyst system 1b proceeds to S32 when it is determined that the stop reference determination means 60 satisfies the hydrogen detector type temporary stop reference data.
Specifically, in S27, the arithmetic processing unit 70 performs arithmetic processing on the data input from the hydrogen detector 62, and the hydrogen detector type temporary stop reference data stored in the arithmetic processing unit 70 itself. When the hydrogen concentration reduction rate is 5% or more of the normal operation, it is determined that the hydrogen detector type temporary stop reference data is satisfied, and the process proceeds to S32.

In S32, the CO shift catalyst system 1b temporarily stops the oxidant pulse supply means 22. Although not shown in the figure, the number of times of stoppage of the arithmetic processing unit 70 is temporarily written in a storage area capable of storing n.
In S33, the CO shift catalyst system 1b reduces the oxidant supply amount of the oxidant pulse supply means 22.
Specifically, in S33, the oxidizing agent supply amount of the oxidizing agent pulse supply means 22 is halved.

In S34, the CO shift catalyst system 1b proceeds to S25 when it is determined that the stop cancellation reference means 50 satisfies the temperature detector type temporary stop cancellation reference data.
Specifically, in S34, the calculation processing device 70 performs calculation processing on the data input from the temperature detector 52, and the temperature detector type temporary stop cancellation reference stored in the calculation processing device 70 itself. When the catalyst temperature is in the range of ± 5 ° C. during normal operation, it is determined that the temperature detector type temporary stop release reference data is satisfied, and the process proceeds to S25.

In S34, the CO shift catalyst system 1b proceeds to S32 when it is determined that the stop cancellation reference means 50 does not satisfy the temperature detector type temporary stop cancellation reference data.
Specifically, in S34, the calculation processing device 70 performs calculation processing on the data input from the temperature detector 52, and the temperature detector type temporary stop cancellation reference stored in the calculation processing device 70 itself. When the catalyst temperature is not within the range of ± 5 ° C. during normal operation, it is determined that the temperature detector type temporary stop release reference data is not satisfied, and the process proceeds to S32.

  Furthermore, when the stop criterion determination means 40 determines in S28 that the oxygen detector type stop criterion data is not satisfied, the process proceeds to S26.

  Although not shown, in S27, determination may be made by applying temperature detector type temporary stop reference data. For example, the catalyst temperature obtained by computing the data input from the temperature detector and the catalyst temperature during normal operation are measured in advance through experiments, etc., and the temperature rise is set from the catalyst temperature during normal operation. It can be judged by comparing with the temperature detector type temporary stop reference data. For example, when the temperature rise width is set to 20 ° C., it may be determined that the temperature detector type temporary stop reference data is satisfied when the temperature rise is more than 20 ° C. than during normal operation.

Further, the CO shift catalyst system of the present invention may further include an operation stop criterion determination unit having an operation stop criterion for the oxidant supply unit.
In such a CO shift catalyst system, the operation of the oxidant supply unit is stopped when the operation stop criterion determination unit determines that the operation stop criterion is satisfied.
By using such an operation stop criterion determination means, when the catalyst activity of the CO shift catalyst is completely deactivated so as not to be recovered (regenerated) even by the catalyst regeneration process, the unnecessary catalyst regeneration process is not performed. There is an advantage that it can be done.

Furthermore, in the present invention, as an example of the operation stop criterion determination means, an outlet side CO detector for detecting the CO concentration on the gas outlet side of the CO shift reactor, and an arithmetic processing device storing CO detector type operation stop criterion data; Can be mentioned.
Then, in determining that such an operation stop criterion determination means satisfies the operation stop criterion, the arithmetic processing unit calculates the data input from the outlet side CO detector and the calculation data obtained by the operation processing. The CO detector type operation stop reference data stored in the processing device itself is compared to determine that the CO detector type operation stop reference data is satisfied.
By using such an operation stop criterion determination means, the deactivation of the CO shift catalyst can be detected more accurately, and the execution of the catalyst regeneration process can be stopped.

  At this time, in the present invention, as an example of the combination of the above-mentioned CO detector type operation stop reference data and the calculated data, the data input from the outlet side CO detector at the start of the oxidant supply means is calculated. CO concentration obtained by the treatment and the outlet side CO when the oxidant supply means is stopped and the CO shift catalyst system is operated under the same conditions as when the oxidant supply means is started. A combination with a CO concentration obtained by arithmetic processing of data input from the detector can be given.

Here, an example of the procedure (regeneration method of the CO shift catalyst) for recovering the catalytic activity of the CO shift catalyst in the CO shift catalyst system provided with such an operation stop criterion determination means will be described with reference to a flow chart.
FIG. 8 is a flowchart showing an example of a procedure (a method for regenerating the CO shift catalyst) when recovering the catalytic activity of the CO shift catalyst in the CO shift catalyst system.

As shown in the figure, the CO shift catalyst system becomes CO detector type start reference data in advance in S41 as CO detector type start reference data according to the CO shift performance required in the CO shift reactor. The cumulative CO processing amount ((trigger amount: X) in the figure) is set. Further, as the oxidant supply amount, an initial oxidant supply amount ((pulse supply amount: P ₀ in the figure)) is set in advance according to the CO shift performance required in the CO shift reactor.

In S42, the CO shift catalyst system proceeds to S43 when it is determined that the activation reference determination means satisfies the CO detector type activation reference data that it has.
Specifically, during operation of the CO shift catalyst system, in S42, the arithmetic processing unit calculates data input to the arithmetic processing unit from each of the gas flow rate detector, the inlet side CO detector, and the outlet side CO detector. Comparing the accumulated CO processing amount as calculation data obtained by processing with the cumulative CO processing amount ((trigger amount: X) in the figure) as the CO detector type activation reference data stored in the arithmetic processing unit itself Then, when the cumulative CO processing amount as the calculation data exceeds the trigger amount, it is determined that the CO detector type activation reference data is satisfied, and the process proceeds to S43.

  In S43, the CO shift catalyst system writes the CO concentration obtained by arithmetic processing of the data input from the outlet side CO detector in the storage area of the arithmetic processing unit that can store the CO concentration (in the figure, CO Concentration: C).

In S44, the CO shift catalyst system determines whether or not the alarm is on. When determining that the alarm is not on, the process proceeds to S45.
Details of the alarm will be described later.

In S45, the CO shift catalyst system determines whether or not the oxidant supply unit has been temporarily stopped. When it is determined that the oxidant supply unit has not been temporarily stopped, the process proceeds to S46.
Specifically, in S45, the arithmetic processing unit once reads the number of stops: n from the storage area where it can be stored, and once determines that the number of stops: n is n = 0, it is not temporarily stopped. Proceed to S46.

In S46, CO shift catalyst system sets the oxidizing agent supply amount of the oxidizing agent pulse supply means to P _0.
In S47, the CO shift catalyst system activates the oxidant pulse supply means and starts the catalyst regeneration process.
In S48, the CO shift catalyst system operates the oxidant pulse supply means to recover the catalytic activity of the CO shift catalyst of the CO shift reactor, that is, to perform catalyst regeneration.

In S49, the CO shift catalyst system proceeds to S50 when it is determined that the stop reference determination means does not satisfy the hydrogen detector type stop reference data.
Specifically, in S49, the arithmetic processing unit compares the calculation data obtained by performing arithmetic processing on the data input from the hydrogen detector and the hydrogen detector type temporary stop reference data stored in the arithmetic processing unit itself. When the hydrogen concentration reduction rate is less than 5% during normal operation, it is determined that the hydrogen detector type temporary stop reference data is not satisfied, and the process proceeds to S50.

In S50, the CO shift catalyst system proceeds to S51 when it is determined that the stop reference determination means satisfies the oxygen detector type stop reference data that it has.
Specifically, in S50, the arithmetic processing unit compares the calculation data obtained by performing arithmetic processing on the data input from the oxygen detector and the oxygen detector type stop reference data stored in the arithmetic processing unit itself. When unreacted oxygen (O ₂ ) is detected, it is determined that the oxygen detector type stop reference data is satisfied, and the process proceeds to S51.

In S51, the CO shift catalyst system resets the cumulative CO processing amount as calculation data obtained by performing arithmetic processing on the data input to the arithmetic processing device (specifically, the cumulative CO processing amount = 0). To do.
In S52, the CO shift catalyst system stops the oxidant pulse supply means and ends the catalyst regeneration process.
In S53, the CO shift catalyst system performs processing on the data input from the outlet side CO detector when operated under the same conditions as when the data input from the outlet side CO detector is taken in S43. The CO concentration obtained in this way (in the figure, CO concentration: C ′) is written in the storage area of the arithmetic processing unit where CO concentration can be stored.

In S54, the CO shift catalyst system determines that the operation stop criterion determination means satisfies the CO detector type operation stop criterion data that it has.
Specifically, in S54, the CO concentration: C, which is the CO detector type operation stop reference data written in the storage area where the CO concentration of the arithmetic processing unit can be stored, and the time when the oxidant supply means is stopped. When the CO shift catalyst system is operated again under the same conditions, the CO concentration obtained by calculating the data input from the outlet side CO detector (in the figure, the CO concentration is C ′). ) And C ′ ≠ C, it is determined that the CO detector type operation stop reference data is not satisfied.

  In S42, the CO shift catalyst system does not perform the catalyst regeneration process when it is determined that the start reference determination means does not satisfy the CO detector type start reference data.

  Further, in S44, the CO shift catalyst system does not perform the catalyst regeneration process when the alarm is on.

In S45, the CO shift catalyst system determines whether or not the oxidant supply unit has been temporarily stopped. When it is determined that the oxidant supply unit has been stopped, the process proceeds to S55.
Specifically, in S45, the arithmetic processing unit once reads the number of stops: n from a storage area that can store, and once the number of stops: n is n ≠ 0 (specifically, n = 1, 2, 3,... ), It is determined that the operation has been temporarily stopped, and the process proceeds to S55.

In S55, the CO shift catalyst system sets the oxidant supply amount of the oxidant pulse supply means to P ₀ (1/2) ⁿ .

In S49, the CO shift catalyst system proceeds to S56 when it is determined by the stop criterion determining means that the hydrogen detector type temporary stop reference data is satisfied.
Specifically, in S49, the arithmetic processing unit compares the calculation data obtained by performing arithmetic processing on the data input from the hydrogen detector and the hydrogen detector type temporary stop reference data stored in the arithmetic processing unit itself. When the outlet hydrogen concentration reduction rate is 5% or more of the normal operation, it is determined that the hydrogen detector type temporary stop reference data is satisfied, and the process proceeds to S56.

In S56, the CO shift catalyst system temporarily stops the oxidant supply means. Although not shown in the drawing, the number of times of temporary stop of the arithmetic processing unit is temporarily written in a storage area capable of storing n.
In S57, the CO shift catalyst system reduces the oxidant supply amount of the oxidant supply means.
Specifically, in S57, the oxidant supply amount of the oxidant pulse supply means is halved.

In S58, the CO shift catalyst system proceeds to S47 when it is determined that the stop cancellation reference means satisfies the temperature detector type temporary stop cancellation reference data.
Specifically, in S58, the arithmetic processing unit calculates the calculation data obtained by performing arithmetic processing on the data input from the temperature detector, and the temperature detector type temporary stop release reference data stored in the arithmetic processing unit itself. In comparison, when the catalyst temperature is in the range of ± 5 ° C. during normal operation, it is determined that the temperature detector type temporary stop release reference data is satisfied, and the process proceeds to S47.

In S58, when the CO shift catalyst system determines that the temporary stop cancellation reference means does not satisfy the temporary stop cancellation criterion, the process proceeds to S56.
Specifically, in S58, the arithmetic processing unit calculates the calculation data obtained by performing arithmetic processing on the data input from the temperature detector, and the temperature detector type temporary stop release reference data stored in the arithmetic processing unit itself. In comparison, when the catalyst temperature is not within the range of ± 5 ° C. during normal operation, it is determined that the temperature detector type temporary stop release reference data is not satisfied, and the process proceeds to S56.

  Further, when the stop criterion determining means determines in S50 that the oxygen detector type stop criterion data is not satisfied, the process proceeds to S48.

In S54, the CO shift catalyst system proceeds to S59 when it is determined that the operation stop criterion determination means satisfies the CO detector type operation stop criterion data that it has.
Specifically, in S54, the CO concentration: C that is the operation stop reference data written in the storage area where the CO concentration of the arithmetic processing unit can be stored is the same condition again when the oxidant supply means is stopped. When the CO shift catalyst system is operated, the CO concentration (CO concentration: C ′ in the figure) obtained by calculating the data input from the outlet side CO detector is compared. When C = C ′, it is determined that the CO detector type operation stop reference data is satisfied, and the process proceeds to S59.

In S59, the alarm is turned on.
Although not shown, in S49, determination may be made by applying temperature detector type temporary stop reference data. For example, the catalyst temperature obtained by computing the data input from the temperature detector and the catalyst temperature during normal operation are measured in advance through experiments, etc., and the temperature rise is set from the catalyst temperature during normal operation. It can be judged by comparing with the temperature detector type temporary stop reference data. For example, when the temperature rise width is set to 20 ° C., it may be determined that the temperature detector type temporary stop reference data is satisfied when the temperature rise is more than 20 ° C. than during normal operation.

  Further, in the CO shift catalyst system of the present invention, conventionally known ones can be used as the CO shift catalyst included in the CO shift reactor. For example, noble metals, cerium, titanium, zirconium, vanadium, niobium are usable. Or the thing containing the component element which concerns on a tantalum and these arbitrary combinations can be mentioned.

  Furthermore, in the present invention, the noble metal contained in the CO shift catalyst is not particularly limited as long as it can promote the CO shift reaction, and examples thereof include platinum, palladium, and rhodium. From the viewpoint of suppressing the by-product reaction that generates methane, platinum is desirable.

  Furthermore, in the present invention, niobium is desirable as the above-described component element contained in the CO shift catalyst from the viewpoint that the CO shift reaction can be further promoted.

Next, the reformed gas generation system of the present invention will be described in detail.
As described above, the reformed gas generation system of the present invention includes the CO shift catalyst system of the present invention.

Here, the configuration of the reformed gas generation system of the present invention will be described in detail with reference to the drawings.
FIG. 9 is a configuration diagram showing an embodiment of the reformed gas generation system of the present invention.
As shown in the figure, the reformed gas generation system 100 includes a reforming reactor 80, a high temperature CO shift reactor 10a, and a low temperature CO shift reactor 10b on the gas flow channel from the upstream side in the gas flow direction. , The CO selective oxidation reactor 90 in this order, and an oxidant pulse supply which is an example of an oxidant supply means 20 for supplying an oxidant to the high temperature type CO shift reactor 10a and the low temperature type CO shift reactor 10b. Means 22, a gas flow rate detector 32, an inlet side CO detector 34 for detecting the CO concentration on the gas inlet side of the high temperature CO shift reactor 10a, and a CO concentration on the gas outlet side of the low temperature CO shift reactor 10b. , An oxygen detector 42 for detecting the oxygen concentration on the gas outlet side of the low temperature CO shift reactor 10b, a high temperature CO shift reactor 10a, and a low temperature CO shift counter. Temperature detectors 52a and 52b for detecting the temperature inside the reactor 10b, a hydrogen detector 62 for detecting the hydrogen concentration on the gas outlet side of the low-temperature CO shift reactor 10b, CO detector type activation reference data, oxygen detection And an arithmetic processing unit 70 which stores the temperature-type stop reference data, the temperature detector-type temporary stop release reference data, and the hydrogen detector-type temporary stop reference data.

  Further, the gas flow rate detector 32, the inlet side CO detector 34, the outlet side CO detector 36, and the arithmetic processing device 70 work together to function as the activation reference determination means 30, and operate with the oxygen detector 42. The processing device 70 cooperates to function as the stop reference determination means 40, the hydrogen detector 62 and the arithmetic processing device 70 cooperate to function as the stop reference determination means 60, and the temperature detectors 52a and 52b. The arithmetic processing unit 70 cooperates to function as the stop cancellation reference determination unit 50 once.

In such a reformed gas generation system 100, when a mixture of air, fuel and water is passed through the reforming reactor 80, a reformed gas is generated from the mixture by the reforming reaction.
Next, when the obtained reformed gas added with water is passed through the high temperature CO shift reactor 10a and the low temperature CO shift reactor 10b, a hydrogen rich reformed gas is generated by the CO shift reaction. .
Next, when the obtained hydrogen-rich reformed gas added with air is passed through a CO selective oxidation reactor, the CO-selective oxidation reaction causes a low CO concentration or a hydrogen-rich reformation from which CO has been removed. Gas is generated.
In the figure, arrow A indicates the reformed gas, arrow B indicates air, arrow C indicates water or water vapor, and arrow D indicates the fuel flow direction.

The hydrogen-rich reformed gas having a low CO concentration or CO removed in this way is suitable as a fuel to be supplied to the polymer electrolyte fuel cell 200 as shown in FIG. is there.
Further, as described above, such a reformed gas generation system 100 does not need to stop the operation of the apparatus when the CO shift catalyst system incorporated therein recovers the catalytic activity of the CO shift catalyst. There is an advantage.

Next, a method for regenerating the CO shift catalyst of the present invention will be described.
As described above, the method for regenerating a CO shift catalyst according to the present invention provides that when the regeneration process of the CO shift catalyst is necessary, the regeneration process using the CO shift catalyst is performed by oxidizing the CO shift catalyst. Supply agent.
The above-described CO shift catalyst system of the present invention is an example of a system that can realize such a CO shift catalyst regeneration method. The CO shift catalyst regeneration method of the present invention uses the above-described CO shift catalyst system of the present invention. It is not limited to that.
Note that “using a CO shift catalyst” refers to a use of demonstrating the CO shift performance of the CO shift catalyst.

In the present invention, it is desirable to supply a pulse when supplying the oxidizing agent to the CO shift catalyst.
By supplying the oxidant in this way, not only a small amount of oxidant can be supplied, but also when the regeneration process of the CO shift catalyst is not necessary, the oxidant can be supplied with high accuracy when the supply of the oxidant is terminated. Can be executed.

Furthermore, in the present invention, when supplying the oxidizing agent to the CO shift catalyst, it is desirable to reduce the supply amount of the oxidizing agent according to the active state of the CO shift catalyst.
By reducing the supply amount of the oxidant, it is possible to execute a more accurate regeneration process of the CO shift catalyst.

Furthermore, in the present invention, it is desirable to match the time when the oxidizing agent is supplied to the CO shift catalyst with the time when the load applied to the CO shift catalyst is large.
When the load applied to the CO shift catalyst is large, the gas flow rate flowing into the CO shift catalyst is large, and hydrogen burnout is relatively small. Further, since the temperature is high and the reaction activity is increased, the catalyst regeneration process can be completed in a short time.

It is a graph which shows an example of the time-dependent change of CO shift performance of the CO shift catalyst in the CO shift catalyst system of this invention, and the conventional CO shift catalyst. It is a flowchart which shows an example of the procedure at the time of recovering the catalyst activity of a CO shift catalyst in the CO shift catalyst system of this invention. It is explanatory drawing which shows the conceptual calculation method of the accumulation CO processing amount of a CO shift reactor. It is a block diagram which shows one Embodiment of the CO shift catalyst system of this invention. It is a flowchart which shows an example of the procedure at the time of recovering the catalyst activity of the CO shift catalyst in one Embodiment of the CO shift catalyst system of this invention. It is a block diagram which shows other one Embodiment of the CO shift catalyst system of this invention. It is a flowchart which shows an example of the procedure at the time of recovering the catalyst activity of the CO shift catalyst in other one Embodiment of the CO shift catalyst system of this invention. It is a flowchart which shows an example of the procedure at the time of recovering the catalyst activity of the CO shift catalyst in other one Embodiment of the CO shift catalyst system of this invention. It is a block diagram which shows one Embodiment of the reformed gas production | generation system of this invention.

Explanation of symbols

1a, 1b CO shift catalyst system 10 CO shift reactor 10a High temperature type CO shift reactor 10b Low temperature type CO shift reactor 12 CO shift catalyst 20 Oxidant supply means 22 Oxidant pulse supply means 30 Start standard judgment means 32 Gas flow rate detection 34 Inlet side CO detector 36 Outlet side CO detector 40 Stop reference judgment means 42 Oxygen detector 50 Temporary stop release reference judgment means 52, 52a, 52b Temperature detector 60 Temporary stop reference judgment means 62 Hydrogen detector 70 Arithmetic processing Apparatus 80 reforming reactor 90 CO selective oxidation reactor 100 reformed gas generation system 200 polymer electrolyte fuel cell

Claims (24)

A CO shift reactor containing a CO shift catalyst, used in a gas flow path, an oxidant supply means for supplying an oxidant to the CO shift reactor, and a starting reference for the oxidant supply means A CO shift catalyst system comprising: a start reference determination means having a stop reference determination means having a stop reference for the oxidant supply means;
The CO shift catalyst system determines that the oxidant supply unit is activated and operated when the activation criterion determining unit determines that the activation criterion is satisfied and that the stop criterion determining unit satisfies the stopping criterion. The oxidant supply means is stopped when
CO shift catalyst system characterized by the above.   2. The CO shift catalyst system according to claim 1, wherein the oxidant supply means is an oxidant pulse supply means for supplying an oxidant pulse to the CO shift reactor.   The CO shift catalyst system according to claim 2, wherein the oxidizing agent contains oxygen and / or hydrogen peroxide. The starting reference determination means includes a gas flow rate detector that detects a gas flow rate to the CO shift reactor, an inlet side CO detector that detects a CO concentration on the gas inlet side of the CO shift reactor, and the CO shift reaction. An outlet-side CO detector that detects the gas outlet-side CO concentration of the gas detector, and an arithmetic processing unit that stores the CO detector-type activation reference data,
In determining that the start-up criterion determination means satisfies the start-up criterion, the arithmetic processing unit is obtained by performing arithmetic processing on data input from the gas flow rate detector, the inlet side CO detector, and the outlet side CO detector. The calculated calculation data is compared with the CO detector type activation reference data stored in the arithmetic processing unit to determine that the CO detector type activation reference data is satisfied.
The CO shift catalyst system according to any one of claims 1 to 3, wherein: The calculation data is a cumulative CO processing amount obtained by the arithmetic processing unit performing arithmetic processing on data input from the gas flow rate detector, the inlet side CO detector, and the outlet side CO detector, and the CO The detector-type activation reference data is a cumulative CO processing amount of the CO shift reactor set in advance.
The CO shift catalyst system according to claim 4. The activation reference determining means includes a time measuring device, and an arithmetic processing device for storing time measuring device type activation reference data,
In determining that the activation criterion determination means satisfies the activation criterion, the arithmetic processing device stores calculation data obtained by performing arithmetic processing on data input from the time measuring device, and the arithmetic processing device stores the calculation data. Compare the time measuring instrument type activation reference data and determine that the time measuring instrument type activation reference data is satisfied.
The CO shift catalyst system according to any one of claims 1 to 5, wherein: The calculation data is an accumulated time from the most recent stop of the oxidant supply means obtained by the arithmetic processing unit performing arithmetic processing on data input from the time measuring instrument, and the time measuring instrument type The starting reference data is a cumulative time from the latest stop time of the oxidant supply means set in advance.
The CO shift catalyst system according to claim 6.   The CO shift catalyst system starts up and operates the oxidant supply means when the load applied to the CO shift reactor is large and the start reference judgment means judges that the start standard is satisfied. The CO shift catalyst system according to any one of claims 1 to 7, wherein The stop criterion determining means comprises an oxygen detector for detecting the oxygen concentration inside the CO shift reactor and / or the gas outlet side, and an arithmetic processing device storing oxygen detector type stop criterion data,
When the stop criterion determining means determines that the stop criterion is satisfied, the arithmetic processing unit stores calculation data obtained by arithmetic processing of data input from the oxygen detector, and the arithmetic processing device stores Compare with the oxygen detector type stop reference data and determine that the oxygen detector type stop reference data is satisfied.
The CO shift catalyst system according to any one of claims 1 to 8, wherein A CO shift catalyst system further comprising: a temporary stop reference determining means having a temporary stop reference of the oxidant supplying means; and a temporary stop cancellation reference determining means having a temporary stop cancellation reference of the oxidant supplying means,
The CO shift catalyst system temporarily stops the oxidant supply unit when the temporary stop criterion determination unit determines that the temporary stop criterion is satisfied, reduces the oxidant supply amount, and releases the temporary stop. When it is determined that the criterion determination means satisfies the stop release criterion, the oxidant supply means is restarted with its oxidant supply amount reduced;
The CO shift catalyst system according to any one of claims 1 to 9, wherein The temporary stop reference judging means comprises a temperature detector for detecting the temperature inside the CO shift reactor and / or the gas inlet side, and an arithmetic processing unit storing temperature detector type temporary stop reference data,
When the temporary stop criterion determining means determines that the temporary stop criterion is satisfied, the arithmetic processing unit stores calculation data obtained by arithmetic processing of data input from the temperature detector, and the arithmetic processing unit stores The temperature detector type temporary stop reference data is compared to determine that the temperature detector type temporary stop reference data is satisfied.
The CO shift catalyst system according to claim 10. The temporary stop reference determination means comprises a hydrogen detector that detects the gas outlet side hydrogen concentration of the CO shift reactor, and a processing unit that stores hydrogen detector type temporary stop reference data.
When the temporary stop criterion determining means determines that the temporary stop criterion is satisfied, the arithmetic processing unit stores calculation data obtained by arithmetic processing of data input from the hydrogen detector, and the arithmetic processing unit stores Comparing with the hydrogen detector type temporary stop reference data to determine that the hydrogen detector type temporary stop reference data is satisfied,
The CO shift catalyst system according to claim 10 or 11, wherein The temporary stop cancellation reference judgment means stores a temperature detector for detecting the temperature of at least one of the inside of the CO shift reactor, the gas inlet side and the gas outlet side, and temperature detector type temporary stop cancellation reference data. An arithmetic processing unit,
When the temporary stop cancellation criterion determining means determines that the temporary cancellation criterion is satisfied, the arithmetic processing unit calculates calculation data obtained by calculating data input from the temperature detector, and the arithmetic processing Compare the temperature detector type temporary stop release reference data stored in the device, and determine that the temperature detector type temporary stop release reference data is satisfied.
The CO shift catalyst system according to any one of claims 10 to 12, wherein: A CO shift catalyst system further comprising an operation stop criterion judgment unit having an operation stop criterion of the oxidant supply unit,
The CO shift catalyst system stops the operation of the oxidant supply unit when the operation stop criterion determination unit determines that the operation stop criterion is satisfied.
The CO shift catalyst system according to any one of claims 1 to 13, characterized in that The operation stop criterion judgment means comprises an outlet side CO detector that detects the gas outlet side CO concentration of the CO shift reactor, and an arithmetic processing unit that stores CO detector type operation stop reference data.
In determining that the operation stop criterion determination means satisfies the operation stop criterion, the arithmetic processing unit includes calculation data obtained by performing arithmetic processing on data input from the outlet side CO detector, and the arithmetic processing unit. Is compared with the CO detector type operation stop reference data stored in the above, and it is determined that the CO detector type operation stop reference data is satisfied.
The CO shift catalyst system according to claim 14. The operation stop reference data is a CO concentration obtained by arithmetic processing of data input from the outlet side CO detector at the time of starting the oxidant supply means, and the calculated data is the oxidant supply means. The CO concentration obtained by calculating the data input from the outlet side CO detector when the CO shift catalyst system is operating under the same conditions as when the oxidant supply means is started. is there,
The CO shift catalyst system according to claim 15.   The CO shift catalyst contains a noble metal, cerium, and at least one component element selected from the group consisting of titanium, zirconium, vanadium, niobium and tantalum. A CO shift catalyst system according to any one of the preceding paragraphs.   The CO shift catalyst system according to claim 17, wherein the noble metal is platinum.   The CO shift catalyst system according to claim 17 or 18, wherein the component element is niobium.   A reformed gas generation system comprising the CO shift catalyst system according to any one of claims 1 to 18.   A method for regenerating a CO shift catalyst, which comprises supplying an oxidizing agent to the CO shift catalyst when performing the regeneration process using the CO shift catalyst when the regeneration process of the CO shift catalyst is required.   The method for regenerating a CO shift catalyst according to claim 21, wherein a pulse is supplied when supplying the oxidizing agent to the CO shift catalyst.   23. The method for regenerating a CO shift catalyst according to claim 21 or 22, wherein when supplying the oxidant to the CO shift catalyst, the supply amount of the oxidant is reduced according to the active state of the CO shift catalyst.   24. The CO shift catalyst according to any one of claims 21 to 23, wherein the time when the oxidizing agent is supplied to the CO shift catalyst is combined with the time when the load applied to the CO shift catalyst is large. Playback method.

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