Chemical heat pump and chemical heat pump control method

Abstract

To provide a chemical heat pump and a response rate calculation method capable of smoothly switching between heat storage operation and heat radiation operation at suitable timing.SOLUTION: A chemical heat pump 11 includes an evaporator heating passage 21 having a heating flow passage 21a for supplying and discharging a first heat medium for heating an evaporator 14, and a recovery unit cooling passage 22 having a cooling flow passage 22a for supplying and discharging a second heat medium for cooling a recovery unit 15. A first calculation section of the chemical heat pump 11 calculates a reaction rate of hydration reaction of a chemical thermal storage medium 12 on the basis of a steam generation amount calculated from detection results of a supply temperature, a discharge temperature, and a supply flow rate of the first heat medium in the evaporator heating passage 21. A second calculation section of the chemical heat pump 11 calculates a reaction rate of dehydration reaction of the chemical thermal storage medium 12 on the basis of a steam recovery amount calculated from detection results of a supply temperature, a discharge temperature, and a supply flow rate of the second heat medium in the recovery unit cooling passage 22.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a chemical heat pump and Chemical heat pump control method Regarding. [Background technology]

[0002] As disclosed in Patent Document 1, a steam generator using a chemical heat pump is known. The chemical heat pump includes a reactor that houses a chemical heat storage material that stores heat through a dehydration reaction and releases heat through a hydration reaction. Also, as disclosed in Patent Document 2, a chemical heat storage system is known that includes a reactor that houses a chemical heat storage material and an evaporative condenser that condenses reaction vapor released from the reactor and supplies the reaction vapor to the reactor. The amount of steam generated in the evaporative condenser can be estimated from the temperature of the medium supplied to the evaporative condenser, the temperature of the medium recovered from the evaporative condenser, and the flow rate of the medium. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2019-158299 [Patent Document 2] Japanese Patent Application Laid-Open No. 2013-204856 Summary of the Invention [Problem to be solved by the invention]

[0004] As described above, a chemical heat pump has a reactor that contains a chemical heat storage material that stores heat through a dehydration reaction and releases heat through a hydration reaction. To improve the thermal efficiency of such a chemical heat pump, it is important to smoothly switch between heat storage and heat release operations at an appropriate timing. [Means for solving the problem]

[0005] A chemical heat pump that solves the above problem includes a chemical heat storage material that stores heat through a dehydration reaction and releases heat through a hydration reaction, a reactor that accommodates the chemical heat storage material, an evaporator that generates steam to be used in the hydration reaction, a collector that collects steam generated by the dehydration reaction, an evaporator heating path having a heating flow path that supplies and discharges a first heat medium that heats the evaporator, a collector cooling path having a cooling flow path that supplies and discharges a second heat medium that cools the collector, and at least one of a first calculation unit that calculates the reaction rate of the hydration reaction and a second calculation unit that calculates the reaction rate of the dehydration reaction, wherein the first calculation unit calculates the reaction rate of the hydration reaction based on the amount of steam generated that is determined from detection results of the supply temperature, discharge temperature, and supply flow rate of the first heat medium in the evaporator heating path, and the second calculation unit calculates the reaction rate of the dehydration reaction based on the amount of steam collected that is determined from detection results of the supply temperature, discharge temperature, and supply flow rate of the second heat medium in the collector cooling path.

[0006] According to this configuration, the chemical heat pump includes an evaporator that generates steam used in the hydration reaction and a collector that collects steam generated by the dehydration reaction, allowing the evaporator and the collector to be used alternately. This allows smooth switching between the heat storage operation and the heat dissipation operation. The chemical heat pump also includes at least one of the first and second calculation units. This allows switching between the heat storage operation and the heat dissipation operation based on the calculation results of at least one of the reaction rates of the hydration reaction and the dehydration reaction. This allows switching between the heat storage operation and the heat dissipation operation at an appropriate timing.

[0007] The chemical heat pump may include the first calculation unit, and the amount of steam generated calculated by the first calculation unit is the amount of steam generated excluding the amount of unreacted steam generated to create pressure conditions for the hydration reaction inside the reactor, and the amount of unreacted steam generated may be calculated based on a vapor pressure calculated from the supply temperature of the first heat medium and the supply temperature of the second heat medium.

[0008] According to this configuration, the first calculation unit uses the amount of vapor generated excluding the amount of unreacted vapor generated, thereby improving the accuracy of the reaction rate of the hydration reaction calculated by the first calculation unit. Here, the temperature inside the evaporator, for example, can be used to calculate the amount of unreacted vapor generated. However, the temperature inside a container such as an evaporator is not uniform, which may result in a low accuracy in calculating the reaction rate or complicated temperature sensor placement. In this regard, in the above-mentioned chemical heat pump, the amount of unreacted vapor generated is calculated based on the vapor pressure obtained from the supply temperature of the first heat medium and the supply temperature of the second heat medium. The supply temperatures of the first heat medium and the second heat medium can be measured simply and with relatively high accuracy, for example, by temperature sensors arranged in the flow paths. This allows the first calculation unit to calculate the amount of unreacted vapor generated simply and with relatively high accuracy.

[0009] The chemical heat pump may include the second calculation unit, and the amount of recovered vapor calculated by the second calculation unit is the amount of recovered vapor excluding the amount of recovered unreacted vapor required to create pressure conditions in the reactor for the dehydration reaction, and the amount of recovered unreacted vapor may be calculated based on a vapor pressure calculated from the supply temperature of the first heat medium and the supply temperature of the second heat medium.

[0010] According to this configuration, the second calculation unit uses the amount of recovered vapor excluding the amount of recovered unreacted vapor, thereby improving the accuracy of the reaction rate of the dehydration reaction calculated by the second calculation unit. Here, the amount of recovered unreacted vapor can be calculated using, for example, the temperature inside the recovery vessel. However, the temperature inside a container such as a recovery vessel is not uniform, which may result in a low accuracy in calculating the reaction rate or complicated temperature sensor placement. In this regard, in the above-mentioned chemical heat pump, the amount of recovered unreacted vapor is calculated based on the vapor pressure obtained from the supply temperature of the first heat medium and the supply temperature of the second heat medium. The supply temperatures of the first heat medium and the second heat medium can be measured easily and relatively accurately using, for example, temperature sensors disposed in the flow paths. This allows the second calculation unit to calculate the amount of recovered unreacted vapor easily and relatively accurately.

[0011] The chemical heat pump may include the first calculation unit, and the steam generation amount calculated by the first calculation unit is the steam generation amount after the pressure inside the reactor reaches the pressure condition for the hydration reaction, and the steam generation amount may be calculated based on detection results of the pressure inside the reactor and the pressure inside the evaporator.

[0012] According to this configuration, the amount of steam generated calculated by the first calculation unit can be made closer to the amount of steam used in the hydration reaction. This can improve the accuracy of the reaction rate of the hydration reaction calculated by the first calculation unit. Furthermore, the pressure in the reactor and the pressure in the evaporator can be measured easily and with relatively high accuracy by pressure sensors disposed in the reactor and the evaporator. This allows the first calculation unit to easily and with relatively high accuracy determine the amount of steam generated after the pressure in the reactor reaches the pressure condition for the hydration reaction.

[0013] The chemical heat pump may include the second calculation unit, and the amount of recovered vapor calculated by the second calculation unit may be the amount of recovered vapor after the pressure inside the reactor reaches the pressure condition for the dehydration reaction, and the amount of recovered vapor may be calculated based on detection results of the pressure inside the reactor and the pressure inside the recovery vessel.

[0014] According to this configuration, the amount of recovered steam calculated by the second calculation unit can be made closer to the amount of steam generated by the dehydration reaction. This can improve the accuracy of the reaction rate of the dehydration reaction calculated by the second calculation unit. Furthermore, the pressure in the reactor and the pressure in the recovery unit can be measured simply and with relatively high accuracy by pressure sensors disposed in the reactor and the recovery unit. This allows the second calculation unit to simply and with relatively high accuracy determine the amount of recovered steam after the pressure in the reactor reaches the pressure condition for the dehydration reaction.

[0015] The chemical heat pump may include a recovery material disposed in the recovery vessel for recovering vapor generated by the dehydration reaction. With this configuration, even if the steam generated from the chemical heat storage material in the reactor is at a relatively low pressure, the dehydration reaction of the chemical heat storage material can be promoted by using a recovery material that can undergo a hydration reaction with the low-pressure steam.

[0016] A reaction rate calculation method that solves the above problem is a reaction rate calculation method that calculates the reaction rate of at least one of the hydration reaction and the dehydration reaction of a chemical heat pump that includes a chemical heat storage material that stores heat through a dehydration reaction and releases heat through a hydration reaction, a reactor that accommodates the chemical heat storage material, an evaporator that generates steam to be used in the hydration reaction, a recovery device that recovers the steam generated by the dehydration reaction, an evaporator heating path having a heating flow path that supplies and discharges a first heat medium that heats the evaporator, and a recovery device cooling path having a cooling flow path that supplies and discharges a second heat medium that cools the recovery device, wherein the reaction rate of the hydration reaction is calculated based on the amount of steam generated obtained from detection results of the supply temperature, discharge temperature, and supply flow rate of the first heat medium in the evaporator heating path, and the reaction rate of the dehydration reaction is calculated based on the amount of steam recovered obtained from detection results of the supply temperature, discharge temperature, and supply flow rate of the second heat medium in the recovery device cooling path. [Effects of the Invention]

[0017] According to the present invention, it is possible to smoothly switch between the heat storage operation and the heat dissipation operation at an appropriate timing. [Brief explanation of the drawings]

[0018] [Figure 1] FIG. 1 is a schematic diagram showing a chemical heat pump according to a first embodiment. [Figure 2] FIG. 2 is a block diagram showing a control unit of the chemical heat pump. [Figure 3] FIG. 10 is a flow chart illustrating a heat dissipation operation and a heat storage operation. [Figure 4] 4 is a time chart illustrating a heat dissipation operation and a heat storage operation. [Figure 5] FIG. 4 is a schematic diagram showing a chemical heat pump according to a second embodiment. [Figure 6] FIG. 10 is a flow chart illustrating a heat dissipation operation and a heat storage operation. [Figure 7] FIG. 10 is a schematic diagram showing a part of a chemical heat pump in a modified example. DETAILED DESCRIPTION OF THE INVENTION

[0019] (First embodiment) A first embodiment of a chemical heat pump and a reaction rate calculation method will be described below with reference to FIGS.

[0020] 1 and 2, the chemical heat pump 11 of the first embodiment includes a chemical heat storage material 12 and a reactor 13 in which the chemical heat storage material 12 is accommodated. The chemical heat pump 11 includes an evaporator 14, a recovery device 15, an evaporator heating path 21, and a recovery device cooling path 22. The chemical heat pump 11 includes a control device 16. The control device 16 includes a first calculation device 31 and a second calculation device 32. The chemical heat pump 11 is a system that stores exhaust heat generated from a factory or the like in the chemical heat storage material 12, and is able to radiate heat at a temperature higher than the temperature of the exhaust heat from the chemical heat storage material 12, for example.

[0021] <Chemical heat storage material 12 and reactor 13> The chemical heat storage material 12 is a material that stores heat through a dehydration reaction and releases heat through a hydration reaction. Well-known solid materials can be used as the chemical heat storage material 12. The chemical heat storage material 12 may be composed only of a chemical heat storage substance that undergoes a reaction, or may be a material in which a particulate chemical heat storage substance is bound with a water vapor permeable binder such as a water vapor permeable resin. Examples of chemical heat storage substances include calcium chloride and calcium sulfate. One type of chemical heat storage material 12 may be used, or multiple types may be used in combination. The chemical heat storage material 12 may be placed in a container having a water vapor permeable portion.

[0022] The dehydration reaction during the heat storage operation of calcium chloride, which is a type of chemical heat storage material, is expressed by, for example, the following formula (a). CaCl2·2H2O→CaCl2·H2O+H2O···(a) For example, when the water vapor pressure is 1 kPa, calcium chloride can store heat by utilizing exhaust heat of 80°C.

[0023] The hydration reaction of calcium chloride during heat dissipation is expressed by, for example, the following formula (b). CaCl2·H2O+H2O→CaCl2·2H2O···(b) For example, calcium chloride releases heat of 170°C when the water vapor pressure is 100 kPa.

[0024] That is, for example, if the temperature condition for the heat storage operation is 80°C and the temperature condition for the heat dissipation operation is 170°C, the heat dissipation operation is started by increasing the water vapor pressure in the calcium chloride atmosphere from 1 kPa to 100 kPa.

[0025] The reactor 13 is equipped with a heat exchanger that exchanges heat between the chemical heat storage material 12 and the heat medium. During heat storage operation, a heating medium that heats the chemical heat storage material 12 is supplied from the outside to the heat exchanger. In detail, the heating medium is supplied from the exhaust heat source HS through a heating medium supply path L1 to the heat exchanger of the reactor 13. The heating medium supply path L1 is equipped with a heating medium temperature sensor L1a.

[0026] During the heat dissipation operation, the heat generated from the chemical heat storage material 12 is transported from the reactor 13 to the outside. In detail, the chemical heat pump 11 is provided with a heat transport path (not shown). The heat transport path can be configured to transport heat using, for example, water vapor as the heat medium. As the heat medium, steam generated by utilizing the exhaust heat may be used, or water or water vapor remaining in the heat exchanger in the reactor 13 or in the heating medium supply path L1 may be used.

[0027] <Evaporator 14 and evaporator heating path 21> As shown in Fig. 1, water 14a is stored in the evaporator 14. The evaporator 14 includes a heat exchanger that exchanges heat between the water 14a and a first heat medium. The evaporator heating path 21 includes a heating flow path 21a that supplies and discharges the first heat medium from a heat source HS of exhaust heat to the evaporator 14. The evaporator heating path 21 includes a first supply temperature sensor 21b that detects the supply temperature of the first heat medium and a first discharge temperature sensor 21c that detects the discharge temperature of the first heat medium. The evaporator heating path 21 also includes a first flow rate sensor 21d that detects the supply flow rate of the first heat medium.

[0028] <Collector 15 and collector cooling path 22> The recovery device 15 recovers steam generated by a dehydration reaction of the chemical heat storage material 12 in the reactor 13 during heat storage operation of the chemical heat pump 11. The recovery device 15 includes a heat exchanger that exchanges heat between the steam generated by the dehydration reaction and a second heat medium supplied to the recovery device 15. The chemical heat pump 11 of this embodiment includes a recovery material that is disposed in the recovery device 15 and recovers steam generated by a dehydration reaction of the chemical heat storage material 12.

[0029] As the recovery material, a material that can undergo a hydration reaction with steam (water) generated by the dehydration reaction of the chemical heat storage material 12 in the reactor 13 can be used. The recovery material is placed in the recovery vessel 15 so that it is heated or cooled by the heat exchanger. Recovery of steam by the recovery material is promoted by cooling the recovery material with the second heat medium supplied to the recovery vessel 15.

[0030] The hydration reaction of the recovery material in the recovery vessel 15 can reduce the pressure in the recovery vessel 15. As a result, even if the steam generated from the chemical thermal storage material 12 in the reactor 13 is at a relatively low pressure (low temperature), the dehydration reaction of the chemical thermal storage material 12 can be advanced by using a recovery material that can undergo a hydration reaction with the low-pressure steam.

[0031] The recovery material may be a known solid material, which may consist solely of a recovery substance capable of undergoing hydration and dehydration reactions, or may be a material in which particulate recovery substances are bound together with a water vapor-permeable binder such as a water vapor-permeable resin.

[0032] As the recovery material (recovery substance), for example, a substance that undergoes a hydration reaction at a temperature higher than the temperature at which steam condenses under pressure conditions below atmospheric pressure can be suitably used. This makes it possible to set the operating conditions of the chemical heat pump 11 to below atmospheric pressure (reduced pressure) and use cold water at a temperature higher than the temperature at which steam condenses under these pressure conditions as the second heat medium.

[0033] Here, the hydration reaction of the recovery material referred to in this specification also includes the adsorption of steam (moisture) using a porous material as a recovery material. In other words, the reaction between the recovery material and water also includes the desorption of steam (moisture) using a porous material as a recovery material. Examples of recovery materials include zeolite, lithium hydroxide, magnesium sulfate, strontium bromine, activated carbon, and porous metal oxides (MOFs). One type of recovery material may be used, or multiple types may be used in combination. The recovery material may be placed in a container having a water vapor permeable section.

[0034] The collector cooling path 22 has a cooling flow path 22a that supplies and discharges the second heat medium from the cooling source CS to the collector 15. The collector cooling path 22 is equipped with a second supply temperature sensor 22b that detects the supply temperature of the second heat medium and a second discharge temperature sensor 22c that detects the discharge temperature of the second heat medium. The collector cooling path 22 is equipped with a second flow rate sensor 22d that detects the supply flow rate of the second heat medium.

[0035] <Flow path configuration for heat storage and heat release operations> The chemical heat pump 11 has a heat release flow path L2 that sends steam from the evaporator 14 to the reactor 13 during heat release operation, and a heat release on-off valve V1 that opens and closes the heat release flow path L2. The chemical heat pump 11 has a heat storage flow path L3 that sends steam from the reactor 13 to the recovery device 15 during heat storage operation, and a heat storage on-off valve V2 that opens and closes the heat storage flow path L3.

[0036] <First Calculation Unit 31 and Second Calculation Unit 32 of Control Unit 16, and Reaction Rate Calculation Method> 2, the first calculation unit 31 of the control unit 16 calculates the reaction rate of the hydration reaction based on the amount of steam generated that is determined from the detection results of the supply temperature T1_in, the discharge temperature T1_out, and the supply flow rate F1 of the first heat medium in the evaporator heating path 21. The progress of the heat dissipation operation of the chemical heat pump 11 can be estimated from this reaction rate of the hydration reaction.

[0037] The supply temperature T1_in of the first heat medium is detected by the first supply temperature sensor 21b. The discharge temperature T1_out of the first heat medium is detected by the first discharge temperature sensor 21c. The supply flow rate F1 of the first heat medium is detected by the first flow rate sensor 21d.

[0038] The reaction rate of the hydration reaction can be calculated, for example, according to the following formulas (1) to (3).

[0039]

number

[0040] N eva is the amount of vapor produced in the evaporator 14 [mol]. n HM is the value [mol] obtained by multiplying the amount of chemical heat storage material filled by the hydration number. Q eva is the sensible heat change amount [kJ] of the first heat medium supplied to the evaporator 14.

[0041] H wis the latent heat of vaporization of water [kJ / mol]. ρ f1 is the density of the first heat transfer medium [kg / L]. C pf1 is the specific heat of the first heat medium [kJ / kg / K].

[0042] F1 is the flow rate [L / sec] of the first heat medium. ΔT1 is the temperature difference [K] between the supply temperature T1_in [K] and the discharge temperature T1_out [K] of the first heat medium.

[0043] The second calculation unit 32 of the control unit 16 calculates the reaction rate of the dehydration reaction based on the amount of recovered steam determined from the detection results of the supply temperature T2_in, discharge temperature T2_out, and supply flow rate F2 of the second heat medium in the recovery vessel cooling path 22. The progress of the heat storage operation of the chemical heat pump 11 can be estimated from this reaction rate of the dehydration reaction.

[0044] The supply temperature T2_in of the second heat medium is detected by the second supply temperature sensor 22b. The discharge temperature T2_out of the second heat medium is detected by the second discharge temperature sensor 22c. The supply flow rate F2 of the second heat medium is detected by the second flow rate sensor 22d.

[0045] The reaction rate of the dehydration reaction can be calculated, for example, according to the following formulas (4) to (6).

[0046]

number

[0047] N rec is the amount of vapor recovered [mol]. n HM is the value [mol] obtained by multiplying the amount of chemical heat storage material filled by the hydration number. Q rec is the sensible heat change [kJ] of the second heat medium supplied to the recovery device 15.

[0048] H LM is the heat of hydration reaction of the recovered material per 1 mol of water [kJ / mol]. ρ f2 is the density [kg / L] of the second heat medium supplied to the recovery device 15. C pf2 is the specific heat [kJ / kg / K] of the second heat medium supplied to the recovery device 15.

[0049] F2 is the flow rate of the heat transfer medium [L / sec]. ΔT2 is the temperature difference [K] between the supply temperature T2_in and the discharge temperature T2_out of the second heat medium.

[0050] <Amount of unreacted steam generated and amount of unreacted steam recovered> The amount of steam generated calculated by the first calculation unit 31 is preferably the amount of steam generated excluding the amount of unreacted steam generated to create the pressure conditions for the hydration reaction inside the reactor 13. In this case, the accuracy of calculating the reaction rate of the hydration reaction can be improved.

[0051] The amount of unreacted vapor generated can be calculated based on the vapor pressure determined from the supply temperature T1_in of the first heat medium and the supply temperature T2_in of the second heat medium. The amount of unreacted vapor generated can be calculated, for example, by the following formula (7).

[0052]

number

[0053] P c1 is the maximum pressure in the reactor 13, and is the pressure of the steam supplied from the evaporator 14 during the heat dissipation operation. c1 is the saturated vapor pressure [Pa] of water at the supply temperature T1_in of the first heat medium supplied to the evaporator 14. For example, when the supply temperature T1_in of the first heat medium is 80°C (353 [K]), the maximum pressure P c1 is 48 [kPa] (4.8 × 10 3 [Pa]).

[0054] P c2 is the minimum pressure in the reactor 13, and is the pressure [Pa] in the recovery device 15 during the heat storage operation. c2 is the equilibrium vapor pressure [Pa] of the recovered material when the supply temperature T2_in of the second heat medium supplied to the recovery device 15 is T2_in. c2 For example, when the supply temperature T2_in of the second heat medium supplied to the recovery device 15 is 30°C (303 [K]) and strontium bromide is used as the recovery material, the pressure is 0.5 [kPa] (5 × 10 2 [Pa]).

[0055] It is preferable to use the supply temperature T2_in of the second heat medium during the immediately preceding heat storage operation as the supply temperature T2_in of the second heat medium supplied to the recovery device 15. In this case, the accuracy of calculating the amount of unreacted steam generated is improved, and the accuracy of calculating the reaction rate of the hydration reaction can be further improved.

[0056] V rea is the volume [m 3 ]. R is the gas constant [J / (mol·K)]. T(P c1 ) is the supply temperature T1_in [K] of the first heat medium supplied to the evaporator 14.

[0057] The amount of recovered steam calculated by the second calculation unit 32 is preferably the amount of recovered steam excluding the amount of recovered unreacted steam required to achieve the pressure conditions for the dehydration reaction inside the reactor 13. In this case, the accuracy of the reaction rate of the above-mentioned dehydration reaction can be improved.

[0058] The amount of unreacted vapor recovered can be calculated based on the vapor pressure determined from the supply temperature T1_in of the first heat medium and the supply temperature T2_in of the second heat medium. That is, this amount of unreacted vapor recovered can also be calculated as the amount of unreacted vapor recovered SP1, for example, in the same way as the amount of unreacted vapor recovered SP1 in the above formula (7). c1It is preferable to use the supply temperature T1_in of the first heat medium during the immediately preceding heat dissipation operation as the supply temperature T1_in of the first heat medium for calculating ( ). In this case, the accuracy of calculating the amount of recovered unreacted vapor is improved, thereby further improving the accuracy of calculating the reaction rate of the dehydration reaction.

[0059] <Storage section and comparison section of control section 16> As shown in Fig. 2, the control unit 16 includes a memory unit 33 and a comparison unit 34. The memory unit 33 stores a preset reaction rate of a hydration reaction and a preset reaction rate of a dehydration reaction. The comparison unit 34 compares the reaction rate of the hydration reaction stored in the memory unit 33 with the reaction rate of the hydration reaction calculated by the first calculation unit 31. The comparison unit 34 also compares the reaction rate of the dehydration reaction stored in the memory unit 33 with the reaction rate of the dehydration reaction calculated by the second calculation unit 32.

[0060] The heat release on-off valve V1 and the heat storage on-off valve V2 are configured to close based on the comparison result in the comparison section . A display unit 35 may be connected to the control unit 16. The display unit 35 can display the operating status of the chemical heat pump 11, such as the progress of the reaction rate of the hydration reaction, the progress of the reaction rate of the dehydration reaction, etc.

[0061] <Heat dissipation operation of chemical heat pump 11> 3, in the heat dissipation operation of the chemical heat pump 11, first, a first heat medium is supplied to the evaporator 14 (step S11). In step S11, water 14a stored in advance in the evaporator 14 is heated by the first heat medium. Note that step S11 may be omitted by constantly supplying the first heat medium into the evaporator 14.

[0062] In step S12, it is confirmed whether or not the generation of steam in the evaporator 14 has been completed. In this step S12, for example, if the value of "supply temperature T1_in - discharge temperature T1_out of first heat medium" is equal to or less than a predetermined value, it is determined that the inside of the evaporator 14 reaches saturated vapor pressure and the generation of steam in the evaporator 14 has been completed (step S12: YES). If this determination is made, the process proceeds to step S13. On the other hand, for example, if the value of "supply temperature T1_in - discharge temperature T1_out of first heat medium" exceeds a predetermined value, it is determined that the generation of steam in the evaporator 14 has not been completed (step S12: NO). If this determination is made, step S12 is repeated.

[0063] In step S13, as shown in Figures 3 and 4, the heat release on-off valve V1 that opens and closes the heat release flow path L2 is opened to open the heat release flow path L2. In step S13, the supply of steam from the evaporator 14 to the reactor 13 is started. The steam generation amount N eva Start calculating.

[0064] In step S14, the unreacted vapor generation amount SP1 is updated. Here, the supply temperature T2_in of the second heat medium during the immediately preceding heat storage operation is used as the supply temperature T2_in of the second heat medium for calculating the unreacted vapor generation amount SP1. In this way, by updating the unreacted vapor generation amount SP1 for each heat dissipation operation, the calculation accuracy of the unreacted vapor generation amount can be improved. Note that step S14 may be omitted, and the previously calculated unreacted vapor generation amount SP1 may continue to be used.

[0065] In step S15, the steam generation amount N eva In step S15, for example, it is determined whether the amount of steam generated N eva = unreacted steam generation amount SP1” is satisfied, the steam generation amount N evaIt can be determined that the amount of unreacted steam generated has reached the amount SP1 of unreacted steam generated (step S15: YES). If this determination is made, the process proceeds to step S16. On the other hand, for example, eva = unreacted steam production amount SP1” is not satisfied, the steam production amount N eva It can be determined that the amount of unreacted vapor produced has not reached the amount of unreacted vapor produced SP1 (step S15: NO). If this determination is made, step S15 is repeated.

[0066] In step S16, as shown in FIGS. 3 and 4, the steam generation amount N eva is cleared once, and the process proceeds to step S17. eva = 0”, and then the steam generation rate N eva Start calculating.

[0067] In step S17, the reaction rate of the hydration reaction is calculated based on the amount of steam generated, and it is determined whether the reaction rate of the hydration reaction has reached a predetermined reaction rate. hyd =1.0" is satisfied, it can be determined that the reaction rate of the hydration reaction has reached a predetermined reaction rate (step S17: YES). If this determination is made, the process proceeds to step S18. At this time, the steam generation amount N eva Cleared, that is, "steam generation amount N eva =0”.

[0068] On the other hand, for example, "response rate X hyd =1.0" is not satisfied, it can be determined that the reaction rate of the hydration reaction has not reached the predetermined reaction rate (step S17: NO). If this determination is made, step S17 is repeated.

[0069] 3 and 4, in step S18, the heat dissipation on-off valve V1 that opens and closes the heat dissipation flow path L2 is closed, thereby closing the heat dissipation flow path L2. In step S18, the supply of steam from the evaporator 14 to the reactor 13 is stopped, thereby ending the heat dissipation operation.

[0070] <Heat storage operation of chemical heat pump 11> 3, in the heat storage operation of the chemical heat pump 11, first, the second heat medium is supplied to the recovery device 15 (step S21). In step S21, the recovery material in the recovery device 15 is cooled by the second heat medium. Note that step S21 may be omitted by constantly supplying the second heat medium into the recovery device 15.

[0071] 3 and 4, in step S22, the heat storage on-off valve V2 that opens and closes the heat storage flow path L3 is opened to open the heat storage flow path L3. In step S22, the recovery of steam in the reactor 13 by the recovery device 15 is started. In step S22, the amount of steam recovered N rec Start calculating.

[0072] In step S23, the steam recovery amount N rec In step S23, for example, it is determined whether the amount of recovered vapor N rec = unreacted steam recovery amount SP1" is satisfied, the steam recovery amount N rec It can be determined that the unreacted vapor recovery amount SP1 has been reached (step S23: YES). If this determination is made, the process proceeds to step S24. On the other hand, for example, rec If the relationship of "= unreacted vapor recovery amount SP1" is not satisfied, the vapor recovery amount N rec It can be determined that the amount of unreacted vapor recovered has not reached the unreacted vapor recovery amount SP1 (step S23: NO). If this determination is made, step S23 is repeated.

[0073] Here, the unreacted vapor recovery amount SP1 may be updated for each heat storage operation, similar to the unreacted vapor generation amount SP1 during the heat dissipation operation. That is, for example, the supply temperature T1_in of the first heat medium during the immediately preceding heat dissipation operation is used as the supply temperature T1_in of the first heat medium for calculating the unreacted vapor recovery amount SP1. In this way, by updating the unreacted vapor recovery amount SP1 for each heat storage operation, the calculation accuracy of the unreacted vapor recovery amount can be improved. Note that such unreacted vapor recovery amount SP1 may be omitted, and the previously calculated unreacted vapor recovery amount SP1 may be continued to be used.

[0074] In step S24, as shown in FIGS. 3 and 4, the amount of steam recovered N rec is cleared once, and the process proceeds to step S25. rec = 0”, and again the steam recovery amount N rec Start calculating.

[0075] In step S25, it is determined whether or not heating of the chemical heat storage material 12 in the reactor 13 is necessary. Here, the temperature of the chemical heat storage material 12 generated by the heat generation reaction during the heat dissipation operation may be higher than the temperature of the heat medium supplied from the heat source HS of the exhaust heat. In this case, when the heat medium supplied from the heat source HS of the exhaust heat is supplied to the reactor 13, the chemical heat storage material 12 is cooled by the heat medium, and the dehydration reaction of the chemical heat storage material 12 is delayed. In step S25, for example, when the relationship "temperature of the chemical heat storage material 12≦temperature of the heating medium supplied to the reactor 13" is satisfied, it can be determined that heating of the chemical heat storage material 12 in the reactor 13 is necessary (step S25: YES). If this determination is made, the process proceeds to step S26.

[0076] The above "temperature of the chemical heat storage material 12≦temperature of the heat medium of the heat source HS" is expressed by the following formula (8). T HM (P c1 )-ΔT≦T3 (8) T HM (P c1 ) [K] is the maximum temperature of the chemical heat storage material 12. T HM (P c1) can be calculated from the supply temperature T1_in [K] of the first heat medium supplied to the evaporator 14. As described above, the saturated vapor pressure [Pa] of water at the supply temperature T1_in of the first heat medium is equal to the maximum pressure P c1 [Pa]. This P c1 When the equilibrium vapor pressure is T HM (P c1 )[K].

[0077] ΔT[K] can be calculated using the following formulas (9) and (10). ΔT=Qrec' / Cp (9) Qrec'=N rec ×H HM ···(10) Cp is the heat capacity of the heat storage material [kJ / K].

[0078] H HM is the heat of hydration reaction [kJ / mol] for 1 mol of water in the heat storage material. T3 [K] is the temperature of the heating medium that heats the chemical thermal storage medium 12 in the reactor 13, and can be detected by the heating medium temperature sensor L1a shown in FIG.

[0079] On the other hand, in step S25, for example, if the relationship "temperature of the chemical thermal storage medium 12≦temperature of the heating medium supplied to the reactor 13" is not satisfied, it can be determined that heating of the chemical thermal storage material 12 in the reactor 13 is not necessary (step S25: NO). If this determination is made, step S25 is repeated.

[0080] In step S26, the heat medium from the exhaust heat source HS, that is, the heating medium for heating the chemical thermal storage medium 12, is supplied to the reactor 13. With the heating medium supplied to the reactor 13 in this way, the process proceeds to step S27.

[0081] In step S27, the reaction rate of the dehydration reaction is calculated based on the amount of recovered steam, and it is determined whether the reaction rate of the dehydration reaction has reached a predetermined reaction rate. dehydCalculate the "response rate X dehyd =1.0" is satisfied, it can be determined that the reaction rate of the dehydration reaction has reached a predetermined reaction rate (step S27: YES). If this determination is made, the process proceeds to step S28. At this time, the steam recovery amount N rec Cleared, that is, "steam recovery amount N rec =0”.

[0082] On the other hand, for example, "response rate X dehyd =1.0" is not satisfied, it can be determined that the reaction rate of the dehydration reaction has not reached the predetermined reaction rate (step S27: NO). If this determination is made, step S27 is repeated.

[0083] In step S28, the equilibrium vapor pressure of the recovered material is calculated from the temperature of the second heat medium supplied to the recovery device 15, and is stored as the pressure inside the recovery device 15. This pressure inside the recovery device 15 is used as the minimum pressure inside the reactor 13 to calculate the amount of unreacted vapor generated SP1 shown in the above formula (7).

[0084] In step S29, the supply of the second heat medium to the recovery vessel 15 is stopped, and the supply of the heating medium to the reactor 13 is stopped. 3 and 4, in step S30, the heat storage on-off valve V2 that opens and closes the heat storage flow path L3 is closed, thereby closing the heat storage flow path L3. In step S30, the recovery of steam in the reactor 13 by the recovery device 15 is stopped, thereby ending the heat storage operation.

[0085] After the above heat storage operation is completed, the process is repeated from step S12, whereby the heat dissipation operation and the heat storage operation can be performed in sequence. <Actions and Effects of the First Embodiment> The operation and effects of the first embodiment will be described.

[0086] (1-1) As described above, the chemical heat pump 11 includes the chemical heat storage material 12, the reactor 13, the evaporator 14, the recovery device 15, the evaporator heating path 21, and the recovery device cooling path 22. The chemical heat pump 11 includes a first calculation unit 31 that calculates the reaction rate of a hydration reaction, and a second calculation unit 32 that calculates the reaction rate of a dehydration reaction. The first calculation unit 31 calculates the reaction rate of the hydration reaction based on the amount of steam generated that is determined from the detection results of the supply temperature, discharge temperature, and supply flow rate of the first heat medium in the evaporator heating path 21. The second calculation unit 32 calculates the reaction rate of the dehydration reaction based on the amount of steam recovered that is determined from the detection results of the supply temperature, discharge temperature, and supply flow rate of the second heat medium in the recovery device cooling path 22.

[0087] According to this configuration, the chemical heat pump 11 is equipped with the evaporator 14 that generates steam to be used in the hydration reaction and the recovery device 15 that recovers the steam generated by the dehydration reaction, and therefore the evaporator 14 and the recovery device 15 can be used alternately. This allows smooth switching between the heat storage operation and the heat release operation.

[0088] Furthermore, since the chemical heat pump 11 includes the first calculation unit 31 and the second calculation unit 32, it is possible to switch between the heat storage operation and the heat release operation in both directions based on the calculation results of the reaction rates of the hydration reaction and the dehydration reaction, thereby enabling bidirectional switching between the heat storage operation and the heat release operation at an appropriate timing.

[0089] Therefore, it is possible to smoothly switch between the heat storage operation and the heat dissipation operation at an appropriate timing. (1-2) The amount of steam generated calculated by the first calculation unit 31 is preferably the amount of steam generated excluding the amount of unreacted steam generated to achieve the pressure conditions for the hydration reaction inside the reactor 13. The amount of unreacted steam generated is calculated based on the vapor pressure determined from the supply temperature of the first heat medium and the supply temperature of the second heat medium.

[0090] In this case, the first calculation unit 31 uses the amount of steam generated excluding the amount of unreacted steam generated, thereby improving the accuracy of the reaction rate of the hydration reaction calculated by the first calculation unit 31. Here, the temperature inside the evaporator 14, for example, can be used to calculate the amount of unreacted steam generated. However, the temperature inside a container such as the evaporator 14 is not uniform, which may result in a low accuracy in calculating the reaction rate or complicated temperature sensor placement. In this regard, in the chemical heat pump 11, the amount of unreacted steam generated is calculated based on the vapor pressure obtained from the supply temperature of the first heat medium and the supply temperature of the second heat medium. The supply temperatures of the first heat medium and the second heat medium can be measured simply and with relatively high accuracy, for example, by temperature sensors disposed in the flow paths. This allows the first calculation unit 31 to calculate the amount of unreacted steam generated simply and with relatively high accuracy.

[0091] (1-3) The amount of recovered steam calculated by the second calculation unit 32 is preferably the amount of recovered steam excluding the amount of recovered unreacted steam required to achieve the pressure conditions for the dehydration reaction inside the reactor 13. The amount of recovered unreacted steam is calculated based on the vapor pressure calculated from the supply temperature of the first heat medium and the supply temperature of the second heat medium.

[0092] According to this configuration, the second calculation unit 32 uses the amount of recovered vapor excluding the amount of recovered unreacted vapor, thereby improving the accuracy of the reaction rate of the dehydration reaction calculated by the second calculation unit 32. Here, the temperature inside the recovery unit 15, for example, can be used to calculate the amount of recovered unreacted vapor. However, the temperature inside a container such as the recovery unit 15 is not uniform, which may result in a low accuracy in calculating the reaction rate or complicated temperature sensor placement. In this regard, in the chemical heat pump 11, the amount of recovered unreacted vapor is calculated based on the vapor pressure obtained from the supply temperature of the first heat medium and the supply temperature of the second heat medium. The supply temperatures of the first heat medium and the second heat medium can be measured easily and with relatively high accuracy, for example, using temperature sensors disposed in the flow paths. This allows the second calculation unit 32 to calculate the amount of recovered unreacted vapor easily and with relatively high accuracy.

[0093] (1-4) The chemical heat pump 11 is provided with a recovery material that is disposed in the recovery vessel 15 and recovers the steam generated by the dehydration reaction. In this case, even if the steam generated from the chemical heat storage material 12 in the reactor 13 is at a relatively low pressure, the dehydration reaction of the chemical heat storage material 12 can be advanced by using a recovery material that can undergo a hydration reaction with the low-pressure steam.

[0094] (Second embodiment) The second embodiment of the chemical heat pump 11 will be described, focusing on the differences from the first embodiment.

[0095] 5, the chemical heat pump 11 of the second embodiment includes a first pressure sensor 41 that detects the pressure inside the evaporator 14. The chemical heat pump 11 also includes a second pressure sensor 42 that detects the pressure inside the recovery vessel 15. The chemical heat pump 11 also includes a third pressure sensor 43 that detects the pressure inside the reactor 13.

[0096] The steam production amount calculated by the first calculation unit 31 in the second embodiment is the steam production amount after the pressure condition for the hydration reaction is reached inside the reactor 13. The first calculation unit 31 calculates the steam production amount based on the detection results of the pressure inside the reactor 13 and the pressure inside the evaporator 14, and calculates the reaction rate of the hydration reaction based on this steam production amount.

[0097] The reaction rate of the hydration reaction can be calculated, for example, according to the formulas (1) and (3) of the first embodiment and the following formula (11).

[0098]

number

[0099] ΔP3 is the pressure difference [Pa] between the pressure in the reactor 13 and the pressure in the evaporator 14. V eva is the volume [m3 ]. R is the gas constant [J / (mol·K)].

[0100] T(P3) is the temperature [K] at the pressure inside the reactor 13. The amount of recovered steam calculated by the second calculation unit 32 in the second embodiment is the amount of recovered steam after the pressure condition for the dehydration reaction is reached inside the reactor 13. The second calculation unit 32 calculates the amount of recovered steam based on the detection results of the pressure inside the reactor 13 and the pressure inside the recovery unit 15, and calculates the reaction rate of the dehydration reaction based on this amount of recovered steam.

[0101] The reaction rate of the dehydration reaction can be calculated, for example, according to the formulas (4) and (6) in the first embodiment and the following formula (12).

[0102]

number

[0103] ΔP3 is the pressure difference [Pa] between the pressure in the reactor 13 and the pressure in the evaporator 14. V rec is the volume [m 3 ]. R is the gas constant [J / (mol·K)].

[0104] T(P3) is the temperature [K] at the pressure inside the reactor 13. <Heat dissipation operation of chemical heat pump 11> 6, in the heat dissipation operation of the chemical heat pump 11, first, a first heat medium is supplied to the evaporator 14 (step S41). In step S41, water 14a stored in advance in the evaporator 14 is heated by the first heat medium. Note that step S41 may be omitted by constantly supplying the first heat medium into the evaporator 14.

[0105] In step S42, it is confirmed whether or not the generation of steam in the evaporator 14 has been completed. In this step S42, for example, if the relationship "pressure P1 in the evaporator 14 ≧ SP2" is satisfied, the evaporator 14 reaches saturated vapor pressure, and it can be determined that the generation of steam in the evaporator 14 has been completed (step S42: YES). SP2 is the saturated vapor pressure of water at the supply temperature T1_in of the first heat medium supplied to the evaporator 14. For example, when the temperature of the first heat medium is 80°C, SP2 is 48 kPa. If this determination is made, the process proceeds to step S43. On the other hand, for example, if the relationship "pressure P1 in the evaporator 14 ≧ SP2" is not satisfied, it can be determined that the generation of steam in the evaporator 14 has not been completed (step S42: NO). If this determination is made, step S42 is repeated.

[0106] In step S43, it is confirmed whether steam can be supplied from the evaporator 14 to the reactor 13. In this step S43, for example, if the relationship "pressure P1 in the evaporator 14 > pressure P3 in the reactor 13" is satisfied, it can be determined that steam can be supplied from the evaporator 14 to the reactor 13 (step S43: YES). If this determination is made, the process proceeds to step S44. On the other hand, for example, if the relationship "pressure P1 in the evaporator 14 > pressure P3 in the reactor 13" is not satisfied, it can be determined that steam cannot be supplied from the evaporator 14 to the reactor 13 (step S43: NO). If this determination is made, step S43 is repeated.

[0107] In step S44, the heat release on-off valve V1 that opens and closes the heat release flow path L2 is opened, thereby opening the heat release flow path L2. In step S44, the supply of steam from the evaporator 14 to the reactor 13 is started.

[0108] In step S45, the reaction rate of the hydration reaction is calculated based on the amount of steam generated, and it is determined whether the reaction rate of the hydration reaction has reached a predetermined reaction rate. hyd Calculate the "response rate X hyd=1.0" is satisfied, it can be determined that the reaction rate of the hydration reaction has reached a predetermined reaction rate (step S45: YES). If this determination is made, the process proceeds to step S46. At this time, the steam generation amount N eva Cleared, that is, "steam generation amount N eva =0”.

[0109] On the other hand, for example, "response rate X hyd =1.0" is not satisfied, it can be determined that the reaction rate of the hydration reaction has not reached the predetermined reaction rate (step S45: NO). If this determination is made, step S45 is repeated.

[0110] In step S46, the heat dissipation on-off valve V1 that opens and closes the heat dissipation flow path L2 is closed, thereby closing the heat dissipation flow path L2. In step S46, the supply of steam from the evaporator 14 to the reactor 13 is stopped, thereby ending the heat dissipation operation.

[0111] <Heat storage operation of chemical heat pump 11> In the heat storage operation of the chemical heat pump 11, first, the second heat medium is supplied to the recovery device 15 (step S51). In step S51, the recovery material in the recovery device 15 is cooled by the second heat medium. Note that step S51 may be omitted by constantly supplying the second heat medium into the recovery device 15.

[0112] In step S52, it is confirmed whether or not the steam from the reactor 13 can be recovered by the recovery device 15. In this step S52, for example, if the relationship "pressure P3 in the reactor 13 > pressure P2 in the recovery device 15" is satisfied, it can be determined that the steam from the reactor 13 can be recovered by the recovery device 15 (step S52: YES). If this determination is made, the process proceeds to step S53. On the other hand, for example, if the relationship "pressure P3 in the reactor 13 > pressure P2 in the recovery device 15" is not satisfied, it can be determined that the steam from the reactor 13 cannot be recovered by the recovery device 15 (step S52: NO). If this determination is made, step S52 is repeated.

[0113] In step S53, the heat storage on-off valve V2 that opens and closes the heat storage flow path L3 is opened to open the heat storage flow path L3. By this step S53, the recovery of steam in the reactor 13 by the recovery device 15 is started.

[0114] In step S54, it is determined whether or not it is necessary to heat the chemical thermal storage material 12 in the reactor 13. In step S54, for example, if the relationship "temperature of the chemical thermal storage material 12≦temperature of the heating medium supplied to the reactor 13" is satisfied, it can be determined that it is necessary to heat the chemical thermal storage material 12 in the reactor 13 (step S54: YES). If this determination is made, the process proceeds to step S55. Here, the temperature of the chemical thermal storage material 12 can be found from the pressure P3 inside the reactor 13. That is, the temperature of the chemical thermal storage material 12 is the temperature of water vapor found with the pressure P3 inside the reactor 13 as the saturated vapor pressure.

[0115] On the other hand, in step S54, for example, if the relationship "temperature of the chemical thermal storage medium 12≦temperature of the heating medium supplied to the reactor 13" is not satisfied, it can be determined that heating of the chemical thermal storage material 12 in the reactor 13 is not necessary (step S54: NO). If this determination is made, step S54 is repeated.

[0116] In step S55, the heat medium from the exhaust heat source HS, that is, the heating medium for heating the chemical thermal storage medium 12, is supplied to the reactor 13. With the heating medium supplied to the reactor 13 in this way, the process proceeds to step S56.

[0117] In step S56, the reaction rate of the dehydration reaction is calculated based on the amount of recovered steam, and it is determined whether the reaction rate of the dehydration reaction has reached a predetermined reaction rate. dehyd Calculate the "response rate X dehyd =1.0" is satisfied, it can be determined that the reaction rate of the dehydration reaction has reached a predetermined reaction rate (step S56: YES). If this determination is made, the process proceeds to step S57. At this time, the steam recovery amount N rec Cleared, that is, "steam recovery amount N rec =0”.

[0118] On the other hand, for example, "response rate X dehyd =1.0" is not satisfied, it can be determined that the reaction rate of the dehydration reaction has not reached the predetermined reaction rate (step S56: NO). If this determination is made, step S56 is repeated.

[0119] In step S57, the supply of the second heat medium to the recovery vessel 15 is stopped, and the supply of the heating medium to the reactor 13 is stopped. In step S58, the heat storage on-off valve V2, which opens and closes the heat storage flow path L3, is closed to close the heat storage flow path L3. In step S58, the recovery of steam from inside the reactor 13 by the recovery device 15 is stopped, thereby ending the heat storage operation.

[0120] After the above heat storage operation is completed, the process is repeated from step S42, whereby the heat dissipation operation and the heat storage operation can be performed in sequence. <Actions and Effects of the Second Embodiment> (2-1) The steam generation amount calculated by the first calculation unit 31 of the chemical heat pump 11 is the steam generation amount after the pressure inside the reactor 13 reaches the pressure condition for the hydration reaction. The chemical heat pump 11 calculates the steam generation amount based on the detection results of the pressure inside the reactor 13 and the pressure inside the evaporator 14.

[0121] In this case, the amount of steam generated calculated by the first calculation unit 31 can be made closer to the amount of steam used in the hydration reaction. This can improve the accuracy of the reaction rate of the hydration reaction calculated by the first calculation unit 31. Furthermore, the pressure inside the reactor 13 and the pressure inside the evaporator 14 can be measured simply and with relatively high accuracy by pressure sensors disposed inside the reactor 13 and the evaporator 14. This allows the first calculation unit 31 to simply and with relatively high accuracy determine the amount of steam generated after the pressure inside the reactor 13 reaches the pressure condition for the hydration reaction.

[0122] (2-2) The amount of recovered steam calculated by the second calculation unit 32 of the chemical heat pump 11 is the amount of recovered steam after the pressure inside the reactor 13 reaches the pressure condition for the dehydration reaction. The chemical heat pump 11 calculates the amount of recovered steam based on the detection results of the pressure inside the reactor 13 and the pressure inside the recovery vessel 15.

[0123] In this case, the amount of recovered steam calculated by the second calculation unit 32 can be made closer to the amount of steam generated by the dehydration reaction. This can improve the accuracy of the reaction rate of the dehydration reaction calculated by the second calculation unit 32. Furthermore, the pressure in the reactor 13 and the pressure in the recovery unit 15 can be measured simply and with relatively high accuracy by pressure sensors disposed in the reactor 13 and the recovery unit 15. This allows the second calculation unit 32 to simply and with relatively high accuracy determine the amount of recovered steam after the pressure in the reactor 13 reaches the pressure condition for the dehydration reaction.

[0124] (Example of change) The above embodiment may be modified as follows: The above embodiment and the following modifications may be implemented in combination with each other within the scope of technical compatibility.

[0125] The chemical heat pump 11 may omit either the first calculation unit 31 or the second calculation unit 32. In this case, it is possible to switch from the heat storage operation to the heat dissipation operation, or from the heat storage operation to the heat dissipation operation, based on the calculation results of the calculation unit.

[0126] In the first and second embodiments, the first flow rate sensor 21d and the second flow rate sensor 22d may be omitted. For example, the chemical heat pump 11 shown in Fig. 7 includes a first pump 51 provided in the evaporator heating path 21 to supply a first heat medium, and a second pump 52 provided in the recovery device cooling path 22 to supply a second heat medium. The supply flow rate of the first heat medium supplied to the evaporator 14 can be calculated from the drive frequency of the first pump 51. Furthermore, the supply flow rate of the second heat medium supplied to the recovery device 15 can be calculated from the drive frequency of the second pump 52.

[0127] More specifically, the supply flow rate F can be calculated, for example, by the following equations (13) and (14).

[0128]

number

[0129] N is the pump rotation speed [r / min]. f is the pump operating frequency [Hz]. P is the number of poles.

[0130] s is the slippage [%]. For example, the supply flow rate of the first heat medium may be detected by the first flow rate sensor 21d, and the supply flow rate of the second heat medium may be determined from the drive frequency of the second pump 52. Alternatively, for example, the supply flow rate of the first heat medium may be determined from the drive frequency of the first pump 51, and the supply flow rate of the second heat medium may be detected by the second flow rate sensor 22d.

[0131] The number of evaporators 14 may be one, or two or more. The number of collectors 15 may be one, or two or more. The recovery material disposed in the recovery vessel 15 may be omitted. That is, the vapor pressure in the recovery vessel 15 can be adjusted by using a lower temperature second heat medium or by reducing the pressure in the recovery vessel 15 with a pressure reducing pump, in addition to using a recovery material.

[0132] Hydration reaction rate X hyd The threshold value is not limited to 1.0, but can be set to any value, such as 0.8. Dehydration reaction rate X dehyd The threshold value is not limited to 1.0, but can be set to any value, such as 0.8.

[0133] The heat dissipation operation can be temporarily stopped before the reaction rate of the hydration reaction reaches a predetermined rate. The heat storage operation can also be temporarily stopped before the reaction rate of the dehydration reaction reaches a predetermined rate.

[0134] A step of setting the pressure inside the reactor 13 to a predetermined value may be provided as a preceding step to step S11 in the first embodiment. That is, for example, when starting to use the chemical heat pump 11, the inside of the reactor 13 may be evacuated in order to promote the dehydration reaction of the chemical heat storage material 12. In this case, step S11 may be started after the pressure inside the reactor 13 has been increased to a predetermined pressure by, for example, using a connection to the recovery vessel 15.

[0135] The chemical heat pump 11 of the first and second embodiments has a reaction rate X of the hydration reaction. hyd The chemical heat pump 11 has a control unit 16 that automatically switches from the heat dissipation operation to the heat storage operation based on, for example, the reaction rate X of the hydration reaction displayed on the display unit 35. hyd The heat dissipation operation can be manually switched from the heat storage operation to the heat release operation based on the reaction rate X of the dehydration reaction displayed on the display unit 35. dehyd It is also possible to manually switch from the heat dissipation operation to the heat storage operation based on the above. [Explanation of symbols]

[0136] 11...Chemical heat pump 12...Chemical heat storage material 13...Reactor 14...Evaporator 15...Collector 21...Evaporator heating path 21a...Heating channel 22...Collector cooling path 22a...cooling channel 31...First calculation unit 32...Second calculation unit F1: Supply flow rate of first heat medium F2: Second heat transfer medium supply flow rate Neva…steam production Nrec: steam recovery amount T1_in: Supply temperature of first heat medium T1_out…Discharge temperature of the first heat medium T2_in: Second heat transfer medium supply temperature T2_out…Discharge temperature of second heat medium X dehyd …Dehydration reaction rate X hyd …Hydration reaction rate

Claims

1. A chemical heat storage material that stores heat through a dehydration reaction and releases heat through a hydration reaction; A reactor in which the chemical heat storage material is accommodated; an evaporator for generating steam used in the hydration reaction; a recovery vessel for recovering steam generated by the dehydration reaction; an evaporator heating path having a heating flow path that supplies and discharges a first heat medium that heats the evaporator; a collector cooling path having a cooling flow path that supplies and discharges a second heat medium that cools the collector; a control unit having a first calculation unit that calculates the reaction rate of the hydration reaction, the first calculation unit calculates a reaction rate of the hydration reaction based on a steam generation amount determined from detection results of a supply temperature, a discharge temperature, and a supply flow rate of the first heat medium in the evaporator heating path, and the control unit determines whether or not the reaction rate of the hydration reaction has reached a predetermined reaction rate, and when it is determined that the reaction rate of the hydration reaction has reached the predetermined reaction rate, stops the supply of steam from the evaporator to the reactor, thereby terminating the heat dissipation operation and switching to a heat storage operation; the steam generation amount calculated by the first calculation unit is a steam generation amount excluding an unreacted steam generation amount for setting the inside of the reactor to a pressure condition for the hydration reaction, a supply temperature of the first heat medium and a supply temperature of the second heat medium in the recovery vessel cooling path;

2. A chemical heat storage material that stores heat through a dehydration reaction and releases heat through a hydration reaction; A reactor in which the chemical heat storage material is accommodated; an evaporator for generating steam used in the hydration reaction; a recovery vessel for recovering steam generated by the dehydration reaction; an evaporator heating path having a heating flow path that supplies and discharges a first heat medium that heats the evaporator; a collector cooling path having a cooling flow path that supplies and discharges a second heat medium that cools the collector; a control unit having a second calculation unit that calculates the reaction rate of the dehydration reaction, the second calculation unit calculates a reaction rate of the dehydration reaction based on a steam recovery amount determined from detection results of a supply temperature, a discharge temperature, and a supply flow rate of the second heat medium in the recovery device cooling path, the control unit determines whether or not the reaction rate of the dehydration reaction has reached a predetermined reaction rate, and when it is determined that the reaction rate of the dehydration reaction has reached the predetermined reaction rate, stops recovery of the steam in the reactor by the recovery device, thereby terminating the heat storage operation and switching to a heat dissipation operation, the amount of recovered steam calculated by the second calculation unit is an amount of recovered steam excluding an amount of recovered unreacted steam required to set the inside of the reactor under a pressure condition for the dehydration reaction, the chemical heat pump calculating the amount of unreacted vapor recovered based on a vapor pressure determined from a supply temperature of the first heat medium and the supply temperature of the second heat medium in the evaporator heating path.

3. A chemical heat storage material that stores heat through a dehydration reaction and releases heat through a hydration reaction; A reactor in which the chemical heat storage material is accommodated; an evaporator for generating steam used in the hydration reaction; a recovery vessel for recovering steam generated by the dehydration reaction; an evaporator heating path having a heating flow path that supplies and discharges a first heat medium that heats the evaporator; a collector cooling path having a cooling flow path that supplies and discharges a second heat medium that cools the collector; a control unit having a first calculation unit that calculates the reaction rate of the hydration reaction, the first calculation unit calculates a reaction rate of the hydration reaction based on a steam generation amount determined from detection results of a supply temperature, a discharge temperature, and a supply flow rate of the first heat medium in the evaporator heating path, and the control unit determines whether or not the reaction rate of the hydration reaction has reached a predetermined reaction rate, and when it is determined that the reaction rate of the hydration reaction has reached the predetermined reaction rate, stops the supply of steam from the evaporator to the reactor, thereby terminating the heat dissipation operation and switching to a heat storage operation; the steam generation amount calculated by the first calculation unit is the steam generation amount after the pressure in the reactor reaches the pressure condition for the hydration reaction, The chemical heat pump calculates the amount of steam generated based on detection results of the pressure in the reactor and the pressure in the evaporator.

4. A chemical heat storage material that stores heat through a dehydration reaction and releases heat through a hydration reaction; A reactor in which the chemical heat storage material is accommodated; an evaporator for generating steam used in the hydration reaction; a recovery vessel for recovering steam generated by the dehydration reaction; an evaporator heating path having a heating flow path that supplies and discharges a first heat medium that heats the evaporator; a collector cooling path having a cooling flow path that supplies and discharges a second heat medium that cools the collector; a control unit having a second calculation unit that calculates the reaction rate of the dehydration reaction, the second calculation unit calculates a reaction rate of the dehydration reaction based on a steam recovery amount determined from detection results of a supply temperature, a discharge temperature, and a supply flow rate of the second heat medium in the recovery device cooling path, the control unit determines whether or not the reaction rate of the dehydration reaction has reached a predetermined reaction rate, and when it is determined that the reaction rate of the dehydration reaction has reached the predetermined reaction rate, stops recovery of the steam in the reactor by the recovery device, thereby terminating the heat storage operation and switching to a heat dissipation operation, the vapor recovery amount calculated by the second calculation unit is a vapor recovery amount after the pressure inside the reactor reaches a pressure condition for the dehydration reaction, The chemical heat pump calculates the amount of recovered vapor based on detection results of the pressure in the reactor and the pressure in the recovery vessel.

5. The chemical heat pump according to claim 1 , further comprising a recovery material disposed in the recovery vessel and configured to recover the vapor generated by the dehydration reaction.

6. A chemical heat storage material that stores heat through a dehydration reaction and releases heat through a hydration reaction; A reactor in which the chemical heat storage material is accommodated; an evaporator for generating steam used in the hydration reaction; a recovery vessel for recovering steam generated by the dehydration reaction; an evaporator heating path having a heating flow path that supplies and discharges a first heat medium that heats the evaporator; a collector cooling path having a cooling flow path that supplies and discharges a second heat medium that cools the collector, the chemical heat pump being controlled based on calculating a reaction rate of at least one of the hydration reaction and the dehydration reaction of the chemical heat pump, calculating a reaction rate of the hydration reaction based on a steam generation amount obtained from detection results of the supply temperature, discharge temperature, and supply flow rate of the first heat medium in the evaporator heating path, determining whether or not the reaction rate of the hydration reaction has reached a predetermined reaction rate, and when it is determined that the reaction rate of the hydration reaction has reached the predetermined reaction rate, stopping the supply of steam from the evaporator to the reactor, thereby terminating the heat dissipation operation and switching to a heat storage operation; The steam production amount is calculated by subtracting the amount of unreacted steam produced to maintain the pressure condition in the reactor for the hydration reaction, a control method for a chemical heat pump, the control method comprising: calculating the amount of unreacted vapor generated based on a vapor pressure determined from the supply temperature of the first heat medium and the supply temperature of the second heat medium in the recovery vessel cooling path;

7. A chemical heat storage material that stores heat through a dehydration reaction and releases heat through a hydration reaction; A reactor in which the chemical heat storage material is accommodated; an evaporator for generating steam used in the hydration reaction; a recovery vessel for recovering steam generated by the dehydration reaction; an evaporator heating path having a heating flow path that supplies and discharges a first heat medium that heats the evaporator; a collector cooling path having a cooling flow path that supplies and discharges a second heat medium that cools the collector, the chemical heat pump being controlled based on calculating a reaction rate of at least one of the hydration reaction and the dehydration reaction of the chemical heat pump, calculating a reaction rate of the dehydration reaction based on a vapor recovery amount determined from detection results of the supply temperature, discharge temperature, and supply flow rate of the second heat medium in the recovery device cooling path, determining whether or not the reaction rate of the dehydration reaction has reached a predetermined reaction rate, and when it is determined that the reaction rate of the dehydration reaction has reached the predetermined reaction rate, stopping the recovery of the vapor in the reactor by the recovery device, thereby terminating the heat storage operation and switching to a heat dissipation operation; The amount of recovered steam is determined by subtracting the amount of unreacted steam recovered for maintaining the pressure condition in the reactor for the dehydration reaction, a control method for a chemical heat pump, the unreacted vapor recovery amount being calculated based on a vapor pressure determined from a supply temperature of the first heat medium and the supply temperature of the second heat medium in the evaporator heating path;

8. A chemical heat storage material that stores heat through a dehydration reaction and releases heat through a hydration reaction; A reactor in which the chemical heat storage material is accommodated; an evaporator for generating steam used in the hydration reaction; a recovery vessel for recovering steam generated by the dehydration reaction; an evaporator heating path having a heating flow path that supplies and discharges a first heat medium that heats the evaporator; a collector cooling path having a cooling flow path that supplies and discharges a second heat medium that cools the collector, the chemical heat pump being controlled based on calculating a reaction rate of at least one of the hydration reaction and the dehydration reaction of the chemical heat pump, calculating a reaction rate of the hydration reaction based on a steam generation amount obtained from detection results of the supply temperature, discharge temperature, and supply flow rate of the first heat medium in the evaporator heating path, determining whether or not the reaction rate of the hydration reaction has reached a predetermined reaction rate, and when it is determined that the reaction rate of the hydration reaction has reached the predetermined reaction rate, stopping the supply of steam from the evaporator to the reactor, thereby terminating the heat dissipation operation and switching to a heat storage operation; The steam generation amount is the steam generation amount after the pressure in the reactor reaches the pressure condition for the hydration reaction, A method for controlling a chemical heat pump, the method comprising: calculating the amount of steam generated based on detection results of the pressure in the reactor and the pressure in the evaporator.

9. A chemical heat storage material that stores heat through a dehydration reaction and releases heat through a hydration reaction; A reactor in which the chemical heat storage material is accommodated; an evaporator for generating steam used in the hydration reaction; a recovery vessel for recovering steam generated by the dehydration reaction; an evaporator heating path having a heating flow path that supplies and discharges a first heat medium that heats the evaporator; a collector cooling path having a cooling flow path that supplies and discharges a second heat medium that cools the collector, the chemical heat pump being controlled based on calculating a reaction rate of at least one of the hydration reaction and the dehydration reaction of the chemical heat pump, calculating a reaction rate of the dehydration reaction based on a vapor recovery amount determined from detection results of the supply temperature, discharge temperature, and supply flow rate of the second heat medium in the recovery device cooling path, determining whether or not the reaction rate of the dehydration reaction has reached a predetermined reaction rate, and when it is determined that the reaction rate of the dehydration reaction has reached the predetermined reaction rate, stopping the recovery of the vapor in the reactor by the recovery device, thereby terminating the heat storage operation and switching to a heat dissipation operation; The amount of steam recovered is the amount of steam recovered after the pressure in the reactor reaches the pressure condition for the dehydration reaction, A method for controlling a chemical heat pump, comprising: calculating the amount of recovered vapor based on detection results of the pressure in the reactor and the pressure in the recovery vessel.

Images