JP2016090172A - Chemical heat storage device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To surely detect leakage of NHfrom a reactor.SOLUTION: A chemical heat storage device 10 includes a reactor 11, an adsorber 12, a supply pipe 15 connecting the reactor 11 and the adsorber 12, a solenoid valve 16 disposed in the supply pipe 15 and opening and closing a flow channel of NH, a pressure sensor 43 detecting a pressure in the adsorber 12, and a leakage determination portion 24 for determining whether NHleaks from the reactor 11 on the basis of the pressure in the adsorber 12 detected by the pressure sensor 43. The leakage determination portion 24 determines the leakage of NHfrom the reactor 11 in a case when the pressure in the adsorber 12 detected by the pressure sensor 43 becomes lower than an abnormality determination threshold value S after the lapse of an abnormality determination time ΔT from the opening of the solenoid valve 16 for exothermic reaction to supply NHfrom the adsorber 12 to the reactor 11.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a chemical heat storage device.

As a conventional chemical heat storage device, for example, a device described in Patent Document 1 is known. The chemical heat storage device described in Patent Document 1 uses the heat generated by the chemical reaction between the reaction material and the reaction medium (NH ₃ ) when the temperature of the exhaust gas discharged from the internal combustion engine is low, and the exhaust system of the internal combustion engine of the vehicle The heat exchanger provided in the heat exchanger is heated, and the exhaust gas passing through the heat exchanger is raised to a temperature (activation temperature) at which the downstream exhaust gas purification catalyst exhibits the purification capability, and the temperature of the internal combustion engine sufficiently rises Is applied to an exhaust gas purification system in which the reaction medium is desorbed from the reaction material by applying heat of the exhaust gas to the reaction material via a heat exchanger, and the desorbed reaction medium is recovered again. .

In such a chemical heat storage device, when the temperature of the exhaust gas discharged from the internal combustion engine is lower than the warm-up start temperature, NH ₃ stored in the reservoir is supplied to the reactor through the supply pipe, and the supplied NH ₃ and The reaction material in the reactor reacts chemically and heat is generated. The heat exchanger is heated by this heat, and the exhaust gas in the exhaust pipe is warmed through the heat exchanger. Further, when the temperature of the exhaust gas discharged from the internal combustion engine becomes higher than the regeneration temperature, the reaction material in the reactor is heated by the heat of the exhaust gas through the heat exchanger, and NH ₃ is desorbed from the reaction material in the reactor. To do. Then, the desorbed NH ₃ is collected in the reservoir through the supply pipe.

JP 2014-85093 A

  In the above prior art, the reactor and the supply pipe are connected by welding. For example, the reaction medium is supplied from the reservoir to the reactor due to the influence of the vibration of the vehicle or the vehicle coming into contact with the obstacle. In this case, the reaction medium may leak from the welded part. Further, the reaction medium may leak from the reactor due to, for example, a hole in the reactor itself. If the reaction medium leaks from the reactor, the amount of the reaction medium for generating heat by chemically reacting with the reactants in the reactor decreases, so that the exhaust gas in the exhaust pipe cannot be sufficiently warmed, and the catalyst warms up. There is a risk that the machine performance will deteriorate. For this reason, it is necessary to detect leakage of the reaction medium from the reactor. However, since the outside of the reactor is an open system, it is difficult to detect the reaction medium itself that has leaked to the outside of the reactor.

  An object of this invention is to provide the chemical thermal storage apparatus which can detect the leak of the reaction medium from a reactor reliably.

  A chemical heat storage device according to the present invention includes a reactor having a reaction material that generates heat by chemical reaction with a reaction medium and desorbs the reaction medium by heat storage, a reservoir that stores the reaction medium, and a reactor and a reservoir. Based on the pressure in the reservoir that is detected by the pressure sensor, the pressure sensor that detects the pressure in the reservoir, the valve that is disposed in the supply tube and opens and closes the flow path of the reaction medium A leakage determination unit that determines whether or not the reaction medium is leaking from the reactor, and the leakage determination unit opens a valve to perform an exothermic reaction in which the reaction medium is supplied from the reservoir to the reactor. It is determined that the reaction medium is leaking from the reactor when the pressure in the reservoir detected by the pressure sensor becomes lower than the abnormality determination threshold value after the abnormality determination time has elapsed.

  In the chemical heat storage device according to the present invention, when performing an exothermic reaction in which the reaction medium is supplied from the reservoir to the reactor through the supply pipe, the pressure in the reservoir is determined to be the abnormality determination threshold after the abnormality determination time has elapsed since the valve was opened. If it is lower, it is determined that the reaction medium is leaking from the reactor. As described above, by using the pressure in the reservoir during the exothermic reaction as an index, leakage of the reaction medium from the reactor can be reliably detected.

  The abnormality determination threshold is set to a value lower than the pressure in the reservoir when the reaction system is in an equilibrium state in a normal state where the reaction medium does not leak from the reactor, and the abnormality determination time is set from the reactor to the reaction medium. It may be set as a time longer than the time until the reaction system is in an equilibrium state at the normal time when there is no leakage. Under normal conditions, when the exothermic reaction is in an equilibrium state, the pressure in the reservoir and the pressure in the reactor become a constant equilibrium pressure. Therefore, according to this configuration, the pressure in the reservoir after the abnormality determination time has elapsed since the valve was opened is lower than the abnormality determination threshold that is lower than the equilibrium pressure when the reaction system is in an equilibrium state in the normal state. If it becomes, it is determined that the reaction medium is leaking from the reactor. Thus, leakage of the reaction medium from the reactor can be easily detected based on the equilibrium pressure during the exothermic reaction in the normal state.

  ADVANTAGE OF THE INVENTION According to this invention, the chemical heat storage apparatus which can detect reliably the leak of the reaction medium from a reactor is provided.

It is a schematic block diagram which shows the exhaust gas purification system provided with the chemical heat storage apparatus which concerns on one Embodiment of this invention. It is a conceptual diagram which shows the exothermic reaction and regeneration reaction in the chemical thermal storage apparatus shown in FIG. Is a flow diagram illustrating the processing procedure of the control unit for detecting the leakage of NH ₃ from the reactor. It is a graph which shows the pressure change in an adsorber after abnormality determination time progress after an electromagnetic valve is opened.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the description, the same reference numerals are used for the same elements or elements having the same function, and redundant description is omitted.

  FIG. 1 is a schematic configuration diagram showing an exhaust gas purification system apparatus according to an embodiment of the present invention. In FIG. 1, an exhaust gas purification system 1 is disposed in an exhaust system of a diesel engine 2 (hereinafter simply referred to as an engine 2) that is an internal combustion engine of a vehicle, and contains harmful substances (environment) contained in exhaust gas discharged from the engine 2. Purify (pollutants).

  An exhaust gas purification system 1 includes a heat exchanger 4, an oxidation catalyst (DOC: Diesel Oxidation Catalyst) 5, which are arranged in order from an upstream side to a downstream side in an exhaust pipe 3 that is an exhaust passage connected to an engine 2. A diesel exhaust particulate filter (DPF) 6, a selective catalytic reduction (SCR) 7, and an oxidation catalyst (ASC: Ammonia Slip Catalyst) 8 are provided.

The heat exchanger 4 transfers heat between the exhaust gas from the engine 2 and a reaction material 13 described later. The heat exchanger 4 has a honeycomb structure, for example. The DOC 5 oxidizes and purifies HC and CO contained in the exhaust gas. The DPF 6 collects and removes particulate matter (PM) contained in the exhaust gas. The SCR 7 reduces and purifies NOx contained in the exhaust gas with urea or ammonia (NH ₃ ). The ASC 8 oxidizes and purifies NH ₃ that has passed through the SCR 7 and has flowed downstream of the SCR 7.

  An exhaust gas temperature sensor 18 is disposed on the upstream side and the downstream side of the heat exchanger 4 in the exhaust pipe 3. The exhaust gas temperature sensor 18 detects the temperature of exhaust gas from the engine 2 flowing in the exhaust pipe 3. The temperature information of the exhaust gas detected by the exhaust gas temperature sensor 18 is output to the control unit 20 described later. The upstream side and the downstream side in the present embodiment are the upstream side and the downstream side in the direction in which the exhaust gas flows through the exhaust pipe 3.

Further, the exhaust gas purification system 1 includes a chemical heat storage device 10 that heats (warms up) the heat exchanger 4 that is a heating target without using external energy by utilizing a reversible chemical reaction. Specifically, the chemical heat storage device 10 stores heat (exhaust heat) of the exhaust gas inside by separating a reaction material 13 and a reaction medium described later from each other. The chemical heat storage device 10 supplies the reaction medium to the reaction material 13 when necessary, causes the reaction medium and the reaction material 13 to chemically react (chemical adsorption), and uses the reaction heat at the time of the chemical reaction to generate heat. The exchanger 4 is heated. In this embodiment, ammonia (NH ₃ ) is used as a reaction medium.

  The chemical heat storage device 10 includes a reactor 11, an adsorber (storage device) 12, a supply pipe 15 that connects the reactor 11 and the adsorber 12, and an electromagnetic valve (valve) 16 disposed in the supply pipe 15. And a control unit 20, a temperature sensor 41, and a pressure sensor 43.

The reactor 11 is disposed around the exhaust pipe 3 so as to correspond to the portion of the exhaust pipe 3 where the heat exchanger 4 is provided. The reactor 11 includes a reaction material 13 that generates heat by chemically reacting with NH ₃ that is a gaseous reaction medium, and desorbs NH ₃ by receiving exhaust heat. The reaction material 13 disposed inside the reactor 11 has a heat conductivity higher than that of the reaction material 13, and is a heat conduction material that serves as a heat conduction path for transferring heat generated in the reaction material 13 to the heat exchanger 4. (Not shown) may be mixed to form a molded pellet.

  As the reaction material 13, a halide represented by the composition formula MXa is used. Here, M is an alkaline earth metal such as Mg, Ca, or Sr, or a transition metal such as Cr, Mn, Fe, Co, Ni, Cu, or Zn. X is Cl, Br, I or the like. a is a number specified by the valence of M, and is 2-3. In addition, as the heat conducting material, a material such as carbon fiber, carbon black, or graphite sheet is used. The molded pellets are produced by simultaneously pressing and solidifying the reaction material 13 and the heat conductive material in a mold and mixing them. Note that the molded pellets may be press-molded in a state where a plurality of types of heat conductive materials are mixed in the reaction material 13.

Adsorber 12, elimination of the holding and NH ₃ by physical adsorption of NH ₃ contains an adsorbent 14 capable. As the adsorbent 14, activated carbon, carbon black, mesoporous carbon, nanocarbon, zeolite, or the like is used. Adsorber 12, by physically adsorbed NH ₃ to the adsorbent 14, storing NH _3.

The supply pipe 15 constitutes a supply flow path in which NH ₃ can flow between the reactor 11 and the adsorber 12. The electromagnetic valve 16 is an open / close valve that opens and closes the NH ₃ flow path between the reactor 11 and the adsorber 12. The electromagnetic valve 16 is controlled by the control unit 20.

  The temperature sensor 41 and the pressure sensor 43 are disposed in the adsorber 12, for example. The temperature sensor 41 detects the temperature in the adsorber 12. The pressure sensor 43 detects the pressure in the adsorber 12. The temperature information in the adsorber 12 detected by the temperature sensor 41 and the pressure information in the adsorber 12 detected by the pressure sensor 43 are output to the control unit 20.

  The control unit 20 includes a valve opening / closing unit 21, an adsorption amount calculation unit 22, a leak determination unit 24, and a display output unit 25. The valve opening / closing unit 21 controls the open / close state of the electromagnetic valve 16 based on the temperature of the exhaust gas indicated by the temperature information output from the exhaust gas temperature sensor 18 described above.

The adsorption amount calculation unit 22 is based on the temperature in the adsorber 12 indicated by the temperature information output from the temperature sensor 41 and the pressure in the adsorber 12 indicated by the pressure information output from the pressure sensor 43. The amount of adsorption of NH ₃ existing in the inside (hereinafter referred to as “NH ₃ adsorption amount”) is calculated. NH ₃ adsorption amount is an amount of NH ₃ adsorbed in the adsorbent 14 within the adsorber 12.

The leak determination unit 24 determines whether NH ₃ is leaking from the reactor 11 based on the pressure in the adsorber 12 detected by the pressure sensor 43. Thereby, the leakage of NH ₃ from the reactor 11 is detected. When the leakage determination unit 24 determines that NH ₃ is leaking from the reactor 11, the display output unit 25 outputs the determination result to, for example, the display unit 30 mounted on the vehicle. By displaying information indicating the determination result output from the display output unit 25 on the display unit 30, the vehicle driver can recognize that NH ₃ is leaking from the reactor 11. The details of the operation of the control unit 20 for detecting the leakage of NH ₃ from the reactor 11 will be described later.

In such a chemical heat storage device 10, when the temperature of the exhaust gas from the engine 2 is lower than the warm-up start temperature, NH ₃ is supplied from the adsorber 12 to the reactor 11 through the supply pipe 15, and the reaction material of the reactor 11 13 (for example, MgCl ₂ ) and NH ₃ are chemically reacted and chemisorbed (coordinated bond), and heat is generated from the reaction material 13. That is, a reaction (exothermic reaction) from the left side to the right side in the following reaction formula (A) occurs (see FIG. 2A). The heat exchanger 4 is heated by the heat generated in the reactor 11, and the exhaust gas is warmed through the heat exchanger 4. Then, the DOC 5 is heated by the warmed exhaust gas.
MgCl ₂ + xNH ₃ ＭｇMg (NH ₃ ) xCl ₂ + heat (A)

On the other hand, when the temperature of the exhaust gas from the engine 2 becomes higher than the warm-up start temperature, the exhaust heat is given to the reaction material 13 of the reactor 11 through the heat exchanger 4, so that NH ₃ is desorbed from the reaction material 13. To do. That is, a reaction (regeneration reaction) occurs from the right side to the left side in the above reaction formula (A) (see FIG. 2B). Then, NH ₃ desorbed from the reaction material 13 returns from the reactor 11 to the adsorber 12 through the supply pipe 15 and is physically adsorbed (recovered) by the adsorbent 14 of the adsorber 12.

Next, referring to FIG. 3, the operation of the control unit 20 for detecting leakage of NH ₃ from the reactor 11 in the exothermic reaction in which NH ₃ is supplied from the adsorber 12 to the reactor 11 will be described in detail. explain. FIG. 3 is a flowchart showing the processing procedure of the control unit 20 for detecting the leakage of NH ₃ from the reactor 11.

As shown in FIG. 3, the valve opening / closing unit 21 determines whether or not the temperature of the exhaust gas indicated by the temperature information output from the exhaust gas temperature sensor 18 after the engine start is equal to or lower than the warm-up start temperature at which catalyst warm-up is required. Is determined (S1). When the temperature of the exhaust gas is equal to or lower than the warm-up start temperature (S1; YES), the valve opening / closing unit 21 transmits a signal for opening the electromagnetic valve 16 to the electromagnetic valve 16 to open the electromagnetic valve 16 (S2). . As a result, NH ₃ moves from the adsorber 12 to the reactor 11 through the supply pipe 15, the pressure in the adsorber 12 decreases, and an exothermic reaction between the reactant 13 and NH ₃ occurs in the reactor 11 (FIG. 2 (see (a)). On the other hand, when the temperature of the exhaust gas is higher than the warm-up start temperature (S1; NO), the process returns to S1, and the valve opening / closing unit 21 maintains the electromagnetic valve 16 in the closed state and the exhaust gas temperature is the warm-up start temperature. The determination of S1 is repeated until the following is reached.

  Following the processing of S2, the leakage determination unit 24 determines whether or not an abnormality determination time (for example, about 20 seconds) has elapsed since the electromagnetic valve 16 was opened (S3). When the abnormality determination time has elapsed since the solenoid valve 16 was opened (S3; YES), the process proceeds to S4. On the other hand, if the abnormality determination time has not elapsed since the solenoid valve 16 was opened (S3; NO), the process returns to S3, and the leak determination unit 24 repeats the determination of S3 until the abnormality determination time has elapsed.

In the process of S4, the leak determination unit 24 determines whether or not the pressure in the adsorber 12 detected by the pressure sensor 43 is lower than the abnormality determination threshold (S4). Here, the abnormality determination threshold is a value lower than the pressure in the adsorber 12 when the reaction system is in an equilibrium state, for example, when NH ₃ is not leaking from the reactor 11 in a normal state. When an exothermic reaction occurs at normal time, for example, since the equilibrium state is reached after about 10 seconds from the opening of the solenoid valve 16, the pressure in the adsorber 12 when the abnormality determination time elapses after the solenoid valve 16 is opened. Is kept at a constant equilibrium pressure (see FIG. 4A). Therefore, the abnormality determination threshold is a value lower than the equilibrium pressure, for example, a value about 10% lower than the equilibrium pressure. The abnormality determination threshold is confirmed in advance by experiments or the like. The details of the equilibrium pressure at the normal time will be described later with reference to FIG. The abnormality determination time is set as a time sufficiently longer than the time required for the reaction system to be in an equilibrium state at the normal time when NH ₃ is not leaking from the reactor.

When the pressure in the adsorber 12 after the abnormality determination time has elapsed after the solenoid valve 16 is opened is lower than the abnormality determination threshold (S4; YES), the leakage determination unit 24 leaks NH ₃ from the reactor 11. (S5). Subsequently, the display output unit 25 outputs the determination result to the display unit 30 (S6), and ends the process. On the other hand, when the pressure in the adsorber 12 is equal to or higher than the abnormality determination threshold (S4; NO), the leakage determination unit 24 determines that NH ₃ is not leaking from the reactor 11 (S7), and ends the process. Through the operation of the control unit 20 described above, leakage of NH ₃ from the reactor 11 is detected.

Next, with reference to FIG. 4, the pressure change in the adsorber 12 after the abnormality determination time has elapsed since the electromagnetic valve 16 was opened will be described. FIG. 4 is a graph showing the pressure change in the adsorber 12 after the abnormality determination time has elapsed since the electromagnetic valve 16 was opened. 4A shows a normal case where NH ₃ is not leaking from the reactor 11, and FIG. 4B shows an abnormal case where NH ₃ is leaking from the reactor 11. FIG. In the graph of FIG. 4, the horizontal axis indicates the time after engine start, and the vertical axis indicates the pressure in the adsorber 12. In the graph of FIG. 4, T1 indicates the time when the electromagnetic valve 16 is opened, and T2 is the time (for example, about 10 seconds) from when the electromagnetic valve 16 is opened until the electromagnetic valve 16 is in an equilibrium state. It shows the time when it has passed. T3 indicates a time when an abnormality determination time ΔT (for example, 20 seconds) for determining an abnormality after the electromagnetic valve 16 is opened has elapsed.

As shown in FIG. 4A, under normal conditions, the pressure in the adsorber 12 is maintained at the initial pressure P1 until the electromagnetic valve 16 is opened after the engine is started. From this state, when the solenoid valve 16 is opened (that is, when time T1 is reached), NH ₃ in the adsorber 12 moves to the reactor 11 due to a pressure difference, and the pressure in the adsorber 12 decreases. At time T2, the movement of NH ₃ from the adsorber 12 to the reactor 11 is stopped, and an equilibrium state is reached. That is, the pressure in the adsorber 12 and the pressure in the reactor 11 are the same pressure. The pressure in the adsorber 12 in the equilibrium state at the normal time is defined as an equilibrium pressure P2. Under normal conditions, the pressure in the adsorber 12 is maintained at the equilibrium pressure P2 even after the time T2 has elapsed. Therefore, even after the abnormality determination time ΔT has elapsed since the electromagnetic valve 16 was opened, the equilibrium pressure P2 is maintained. Is maintained. For example, a value about 10% lower than the equilibrium pressure P2 is set as the threshold value (abnormality determination threshold value) S used for the determination by the leak determination unit 24 described above. After that, when the exhaust gas temperature becomes equal to or higher than the regeneration temperature, a regeneration reaction occurs in the reactor 11, and NH ₃ is desorbed from the reaction material 13, so that the solenoid valve 16 is opened and the reactor 11 is passed through the supply pipe 15. NH ₃ moves to the adsorber 12. Thereby, the pressure in the adsorber 12 rises from the equilibrium pressure P2, and becomes constant again when it reaches the initial pressure P1.

On the other hand, as shown in FIG. 4B, when the solenoid valve 16 is opened from the state of the initial pressure P1 (that is, when the time T1 is reached) from the initial pressure P1, it is normal until the time T2 is reached. In the same manner, the pressure in the adsorber 12 decreases. However, at the time of abnormality such as NH ₃ leaking from the reactor 11, the reactor 11 and the adsorber 12 are composed even after the abnormality determination time ΔT has elapsed since the electromagnetic valve 16 was opened. The reaction system does not reach an equilibrium state, and the pressure in the adsorber 12 continues to decrease. Therefore, at the time of abnormality, the pressure in the adsorber 12 after the abnormality determination time ΔT has elapsed after the electromagnetic valve 16 is opened becomes lower than the abnormality determination threshold S set as described above. From the above, the leakage determination unit 24 determines whether or not the pressure in the adsorber 12 after the abnormality determination time ΔT has elapsed is lower than the abnormality determination threshold S set as described above. The leakage of NH ₃ from 11 can be detected.

As described above, according to the chemical heat storage device 10 according to the present embodiment, when performing an exothermic reaction in which NH ₃ is supplied from the adsorber 12 to the reactor 11 through the supply pipe 15, the abnormality determination time after the electromagnetic valve 16 is opened. When the pressure in the adsorber 12 becomes lower than the abnormality determination threshold S after the lapse of ΔT, it is determined that NH ₃ is leaking from the reactor 11. Thus, by using the pressure in the adsorber 12 during the exothermic reaction as an index, leakage of NH ₃ from the reactor 11 can be reliably detected.

In particular, in the prior art, since the outside of the reactor 11 is an open system, it is difficult to detect NH ₃ itself leaking to the outside of the reactor 11. For example, when the chemical heat storage device 10 is mounted on a vehicle, NH ₃ leaking from the reactor 11 is diffused by the air flow generated while the vehicle is running. In this case, there is a problem that it is difficult to detect the NH ₃ itself leaked to the outside of the reactor 11. On the other hand, according to the present embodiment, as described above, it is possible to reliably detect the leakage of NH ₃ from the reactor 11 without detecting the NH ₃ itself leaking to the outside.

In addition, according to the present embodiment, since the leakage of NH ₃ from the reactor 11 is detected using the pressure in the adsorber 12 detected by the pressure sensor 43 as an index, the pressure sensor detects the pressure in the reactor 11. Without using the pressure sensor 43, the leak amount of the NH ₃ from the reactor 11 can be easily detected by using the pressure sensor 43 for calculating the NH ₃ adsorption amount by the adsorption amount calculation unit 22.

Further, according to the present embodiment, the abnormality determination threshold value S is a value lower than the equilibrium pressure P2 at the normal time. Therefore, the leakage of NH ₃ from the reactor 11 is easily detected based on the equilibrium pressure P2. be able to.

  As mentioned above, although various embodiment of this invention was described, this invention is not limited to the said embodiment, It deform | transformed in the range which does not change the summary described in each claim, or applied to others It may be a thing.

In the above embodiment, the leakage of NH ₃ from the reactor 11 is detected using the pressure sensor 43. However, in addition to the pressure sensor 43, a pressure sensor for detecting the pressure in the reactor 11 may be provided separately. Good.

  The position of the exhaust gas temperature sensor 18 is not limited to the upstream side and the downstream side of the heat exchanger 4 in the exhaust pipe 3, and may be arranged at any position in the exhaust pipe 3. Further, instead of the exhaust gas temperature sensor 18 or in addition to the exhaust gas temperature sensor 18, a heater temperature sensor is provided in the reactor 11, and the valve opening / closing part 21 is provided based on the temperature of the reactor 11 detected by the heater temperature sensor. The open / close state of the electromagnetic valve 16 may be controlled.

In the above embodiment, by the information indicating the determination result output from the display output unit 25 is displayed on the display unit 30, the driver of the vehicle was able to recognize that the leak NH ₃ from adsorber 12 However, the method of notifying the driver of NH ₃ leakage from the adsorber 12 is not limited to this. For example, the driver may be notified of NH ₃ leakage from the adsorber 12 by voice or buzzer.

The reaction medium introduced into the reactor 11 is not limited to NH ₃ and may be, for example, H ₂ O, alcohol, CO ₂ or the like. Note that CaO, MnO, CuO, Al ₂ O ₃ or the like is used as a reaction material that is chemically reacted with H ₂ O.

  In the above embodiment, the exhaust gas is heated via the heat exchanger 4 provided in the exhaust system of the diesel engine 2, but the present invention is not particularly limited thereto, and is provided in the exhaust system of the gasoline engine. A device that heats exhaust gas via a heat exchanger, or a device that heats a heat medium via a heat exchanger other than the exhaust system of the engine may be used. Further, a catalyst coat layer may be formed on a part or all of the surface of the heat exchanger provided in the exhaust system of the engine. That is, the catalyst may be directly warmed up by a chemical heat storage device instead of warming up the catalyst via a heat exchanger.

  DESCRIPTION OF SYMBOLS 10 ... Chemical thermal storage apparatus, 11 ... Reactor, 12 ... Adsorber (reservoir), 13 ... Reaction material, 15 ... Supply pipe, 16 ... Solenoid valve (valve), 24 ... Leak determination part, 43 ... Pressure sensor, S ... Abnormality determination threshold, ΔT: Abnormality determination time.

Claims (2)

A reactor having a reaction material which generates heat by chemical reaction with the reaction medium and desorbs the reaction medium by storing heat;
A reservoir for storing the reaction medium;
A supply pipe connecting the reactor and the reservoir;
A valve disposed in the supply pipe to open and close the flow path of the reaction medium;
A pressure sensor for detecting the pressure in the reservoir;
A leakage determination unit for determining whether or not the reaction medium is leaking from the reactor, based on the pressure in the reservoir detected by the pressure sensor;
With
The leak determination unit is configured to detect the internal pressure of the reservoir detected by the pressure sensor after an abnormality determination time has elapsed since the valve was opened to perform an exothermic reaction in which the reaction medium is supplied from the reservoir to the reactor. A chemical heat storage device that determines that the reaction medium is leaking from the reactor when the pressure of is lower than an abnormality determination threshold. The abnormality determination threshold is set to a value lower than the pressure in the reservoir when the reaction system is in an equilibrium state at a normal time when the reaction medium does not leak from the reactor,
2. The chemical heat storage device according to claim 1, wherein the abnormality determination time is set as a time longer than a time until the reaction system is in an equilibrium state at a normal time when the reaction medium does not leak from the reactor.

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