JP6099461B2 - Waste heat storage air-conditioning heat source system using chemical heat storage - Google Patents

Description

  The present invention relates to an exhaust heat storage air-conditioning heat source system that uses chemical heat storage that stores and dissipates heat by a chemical reaction that stores exhaust heat of 200 ° C. or less and makes it available as an air conditioning heat source with a time difference.

In recent years, global warming countermeasures have become an important issue on a global scale. In addition, there is an urgent need to realize a sustainable society through the efficient use of fossil energy in preparation for the depletion of finite energy resources.
Under such circumstances, “effective use of energy” that utilizes unused energy includes, for example, low-temperature exhaust heat (200 ° C.) generated from heat sources such as factories such as power plants and chemical plants, sewage sludge incineration plants, and waste incineration plants. The following is stored in latent heat storage material (PCM) and used in time- and location-mismatched usage facilities such as hospitals, offices, public facilities, etc. A latent heat storage device that can be used in the field has been proposed.
According to this latent heat storage device, the amount of fossil fuel used can be reduced by effectively using the low-temperature exhaust heat that has been mostly discarded in the environment. It is known that it can greatly contribute to the reduction of certain carbon dioxide gas.
However, when using the stored heat energy, we want to use it at a higher heat storage density. There is a request. The latent heat storage material cannot meet all of this request.
By the way, a chemical heat storage material is provided in the reactor, heat is released by reaction with water vapor in a pressure field lower than atmospheric pressure, and chemical heat storage is used to regenerate (that is, store heat) the chemical heat storage material by heating. Thermal storage systems are known.
As a feature of the chemical heat storage system, hydration and dehydration reactions are performed, so water sealed in a field lower than atmospheric pressure is handled, and its boiling point is not 100 ° C. under atmospheric pressure (absolute pressure of about 100 kPa), It can be raised to a low temperature (for example, 10 ° C. or less for about 1 kPa). At the water temperature in a pressure field lower than the atmospheric pressure, external heating is required in the case of the hydration reaction, that is, cold energy can be taken out.
For example, as a vehicle chemical heat storage system using the chemical heat storage in a vehicle, a reaction incorporating a chemical heat storage material that stores heat by performing a dehydration reaction by exhaust heat of an internal combustion engine mounted on the vehicle and dissipates heat by a hydration reaction An adsorber containing an adsorbent capable of adsorbing and desorbing the adsorbed water vapor from the reactor, adsorbed with the adsorbed water vapor, and desorbing the water vapor from the adsorbent of the adsorber There is a vehicle chemical heat storage system comprising: a desorption facilitating means; and a heat transfer structure that transfers heat radiated by the chemical heat storage material in the reactor to the object to be heated. (See Patent Document 1).
By the way, by using exhaust heat of 200 ° C. or less, air conditioning energy can be raised as energy that is easy to use as another energy and is used in a large amount as a society. Air conditioning heat source is chilled water (heating temperature of 7 ° C to 10 ° C, return temperature range of 12 ° C to 18 ° C) and air conditioning as heating use. If it can be taken out as hot water (a feed temperature of about 50 ° C. to 60 ° C. and a return temperature of about 45 ° C. to 50 ° C.) that is a heat medium sent to the hot water coil of the machine, it can be used for general-purpose air conditioning. .
In view of the pressure field of the hydration reaction (about 1 kPa) and the heating temperature of the dehydration reaction (desirably 150 ° C. or less), suitable chemical heat storage materials include gypsum, calcium chloride, calcium bromide, and the like.
Among them, calcium bromide having a high heat storage density (hydration heat of 480 kJ) except for inferior gypsum (hydration heat of 116 kJ / kg) as compared with high performance erythritol (latent heat of fusion of 320 kJ / kg) as a latent heat storage material. / Kg) and calcium chloride having a higher heat storage density (hydration heat of 890 kJ / kg), cold and warm heat can be used more efficiently as an air conditioning heat source.
However, since calcium chloride has deliquescence in the vicinity of the water temperature range of this cold extraction and in the pressure range of the hydration reaction, it is necessary to be careful not to deliquefy it in order to continue the reaction.

JP 2009-257239 A

The invention described in the cited document 1 is a chemical heat storage system for vehicles, configured so that the temperature of the chemical heat storage material becomes approximately 450 ° C. in accordance with the driving of the automobile, and the hydrated material also uses calcium oxide. Therefore, exhaust heat of 300 ° C. or higher is required.
As mentioned above, exhaust heat storage air conditioning heat source system using chemical heat storage of this time that takes out air conditioning energy as energy that is easy to use as another energy by using exhaust heat of 200 ° C or less Not applicable to
Waste heat storage air-conditioning heat source using chemical heat storage using calcium chloride that can be regenerated at a temperature of 100 and several tens of degrees, which is an economical temperature to use as waste heat, as a hydrated material. The system cannot be adopted because its basic structure, pressure field for hydration reaction (about 1 kPa), heating temperature for dehydration reaction (desirably 150 ° C. or less), and the like are different.
In view of the above facts, an object of the present invention is to obtain an exhaust heat storage air-conditioning heat source system using chemical heat storage that simultaneously uses heat and cold as heat sources.
In addition, the present invention is a waste heat utilizing chemical heat storage that can prevent the deliquescence of the hydrated material having deliquescence in the vicinity of the water temperature range of this cold heat extraction and the pressure region of the hydration reaction and can continue to use the waste heat. The purpose is to obtain a heat storage air conditioning heat source system.

The present inventors have solved the above problems by the following means.
(1) a granular heat storage material that dissipates heat by a hydration reaction and stores heat by a dehydration reaction by heating;
A heat transfer oil pipe that branches into and merges with a plurality of inlet headers and outlet headers so as to circulate heat transfer oil that heats the heat storage material and receives heat generated from the heat storage material;
A plurality of steam pipes that provide water vapor necessary for the hydration reaction of the heat storage material and have a large number of openings on the side surface that receives the water vapor extracted by the dehydration reaction of the heat storage material;
Fins fixed to the outer side surfaces of the heat transfer oil pipe and the steam pipe so as to be in contact with the direction perpendicular to the axis of the pipe, and the inside of the plurality of steam pipes communicate with the outside on the side surface A gas-liquid heat exchange coil-shaped heat exchanger to be fixed;
A heat exchanger lid that respectively closes an upper surface and a lower surface in a direction orthogonal to the fins of the heat exchanger;
After closing the heat exchange lid at the bottom, the heat storage material is filled between the fin gaps of the heat exchanger, and the heat exchanger closed by the upper heat exchange lid is built in. An end of the water vapor introduction pipe is positioned on the opposite side cover, and a reaction tank is provided for inserting the heat exchanger into one of the two side covers,
Furthermore, a water tank provided with an evaporation / condensation tube for heating the water stored therein and circulating a heat transfer water for cooling and condensing the water vapor generated in the heat exchanger;
In order to make the heat storage material react in an environment at a pressure lower than atmospheric pressure, a vacuum pump that eliminates air in the reaction tank and the water tank and makes the internal pressure lower than atmospheric pressure;
A heat medium oil inflow pipe for passing the heat medium oil through the reaction tank side wall and connected to the heat medium oil pipe of the heat exchanger via an inlet header, and a heat medium oil pipe connected to the heat medium oil pipe via an outlet header A heated heat oil discharge pipe,
An external steam pipe connecting the reaction tank and the water tank;
A vacuum pulling pipe for connecting the connecting portion of the external water vapor pipe and the vacuum pump;
A first vacuum valve provided in the external steam pipe on the water tank side as viewed from the connection part of the external steam pipe, and a second vacuum provided in the external steam pipe on the reaction tank side as viewed from the connection part of the external steam pipe A valve and a third vacuum valve provided in the vacuuming pipe;
With
The evaporation / condensation pipe of the water tank includes a cooling water circulation system that circulates cooling water using a cooling water pump to a cooling tower that exchanges heat with the atmosphere, and a chilled water circulation system that circulates cooling water using a cooling water pump to a cooling coil of an air conditioner. Switch to connect
The heat medium oil inflow pipe and the heat medium oil outflow pipe are connected by switching between a hot water circulation system for air conditioning and an exhaust heat recovery heat medium circulation system via a facility-side heat exchanger. Waste heat storage air conditioning heat source system using chemical heat storage.

(2) A heat medium oil inflow pipe connected to the heat medium oil pipe via an inlet header and allowing the heat medium oil to flow in is divided via an inflow side oil coupling,
Dividing the heat transfer oil discharge pipe connected to the heat transfer oil pipe via an outlet header via an outflow oil coupling;
After attaching an inflow side water coupling and an outflow side water coupling to the inlet / outlet tapping of the evaporation / condensation tube of the water tank, respectively, and enabling connection with an external flexible tube with a phase coupling,
The reaction tank, the water tank, and the vacuum pump;
An external steam pipe connecting the reaction tank and the water tank;
A vacuum pulling pipe for connecting the connecting portion of the external water vapor pipe and the vacuum pump;
A first vacuum valve provided in the external steam pipe on the water tank side as viewed from the connection part of the external steam pipe, and a second vacuum provided in the external steam pipe on the reaction tank side as viewed from the connection part of the external steam pipe A valve and a third vacuum valve provided in the vacuuming pipe;
A heat transfer oil inflow pipe from the inlet header of the heat transfer oil pipe to the inflow side oil coupling;
Heat medium oil outflow pipe from the outlet header of the heat medium oil pipe to the outflow side oil coupling,
On a movable base,
If you move to a waste heat facility,
The cooling water circulation system is connected to the evaporation / condensation pipe of the water tank via an inflow-side water coupling and an outflow-side water coupling, and the heating medium oil inflow pipe and the heating medium oil outflow pipe, through the inlet-side oil coupling and the outlet-side oil coupling connected to the thermal oil outlet pipe of the heat transfer oil inflow pipe of the facility and the facility by circulating oil to the facility-side heat exchanger, the facility heat Connected to the exhaust heat recovery heat medium circulation system through an exchanger,
If you move to a heat utilization facility,
The cold water circulation system is connected to the evaporation / condensation tube of the water tank via an inflow-side water coupling and an outflow-side water coupling, and to the heat-medium oil inflow tube and the heat-medium oil outflow tube, through the inlet-side oil coupling and the outlet-side oil coupling connected to the thermal oil outlet pipe of the heat transfer oil inflow pipe of the facility and the facility by circulating oil to the facility-side heat exchanger, the facility heat The exhaust heat storage air-conditioning heat source system using chemical heat storage according to (1), wherein the exhaust heat storage air-conditioning heat source system is connected to the hot water circulation system for air conditioning through an exchanger.

(3) The granular heat storage material that dissipates heat by the hydration reaction and stores heat by a dehydration reaction by heating is calcium chloride,
Filling the water tank with a predetermined amount of water,
After opening the third vacuum valve and the second vacuum valve, the vacuum pump is operated to reduce the internal pressure of the reaction tank to 2-50 Pa, then the second vacuum valve is closed and the first vacuum valve is opened to suck the vacuum pump. After deaeration operation to stop the vacuum pump after setting the water tank internal pressure to 1 to 3 kPa of the saturated water vapor pressure of the water temperature,
Connect the cold water circulation system to the evaporation / condensation pipe of the water tank to connect cold heat, and connect the hot water circulation system for air conditioning to the heat medium oil inflow pipe and the heat medium oil outflow pipe via a facility-side heat exchanger. Then, heat is taken out simultaneously as a heat source by hydration reaction,
Thereafter, the cooling water circulation system is connected to the evaporation / condensation tube of the water tank to dissipate heat of condensation in the water tank, and a facility-side heat exchanger is connected to the heat medium oil inflow pipe and the heat medium oil outflow pipe. Through the exhaust heat recovery heat medium circulation system through the exhaust heat of 200 ℃ or less, to store heat by dehydration reaction,
The exhaust heat storage air-conditioning heat source system using chemical heat storage according to (1) above, which can be repeated.

(4) The granular heat storage material that dissipates heat by the hydration reaction and stores heat by a dehydration reaction by heating is calcium bromide,
Filling the water tank with a predetermined amount of water,
After opening the third vacuum valve and the second vacuum valve, the vacuum pump is operated to reduce the internal pressure of the reaction tank to 2-50 Pa, then the second vacuum valve is closed and the first vacuum valve is opened to suck the vacuum pump. After deaeration operation to stop the vacuum pump after setting the water tank internal pressure to 1 to 3 kPa of the saturated water vapor pressure of the water temperature,
Connect the cold water circulation system to the evaporation / condensation pipe of the water tank to connect cold heat, and connect the hot water circulation system for air conditioning to the heat medium oil inflow pipe and the heat medium oil outflow pipe via a facility-side heat exchanger. Then, heat is taken out simultaneously as a heat source by hydration reaction,
Thereafter, the cooling water circulation system is connected to the evaporation / condensation tube of the water tank to dissipate heat of condensation in the water tank, and a facility-side heat exchanger is connected to the heat medium oil inflow pipe and the heat medium oil outflow pipe. Through the exhaust heat recovery heat medium circulation system through the exhaust heat of 200 ℃ or less, to store heat by dehydration reaction,
The exhaust heat storage air-conditioning heat source system using chemical heat storage according to (1) above, which can be repeated.

(5) An inflow heat medium oil thermometer that measures the temperature of the heat medium oil flowing into the heat medium oil inflow pipe, and an exhaust heat that measures the temperature of the heat medium oil discharged into the heat medium oil discharge pipe A medium temperature thermometer,
When the exhaust heat medium oil temperature measured by the exhaust heat medium oil thermometer falls below the set exhaust heat medium oil temperature obtained by adding a predetermined difference to the predetermined inflow heat medium oil temperature during the hydration reaction,
Judging that the heat storage material in the reaction tank has finished the hydration reaction at a predetermined rate,
The chemical heat storage according to (1), characterized in that the chemical heat storage is configured by a control unit that controls the first vacuum valve and the second vacuum valve to open and close to finish taking out the cold and hot heat. Waste heat storage air conditioning heat source system using

(6) a reaction vessel pressure gauge for measuring the internal pressure in the reaction vessel,
An inflow heat medium water thermometer that measures the temperature of the heat medium water that flows into the evaporation / condensation pipe, and an exhaust heat medium water thermometer that measures the temperature of the heat medium water that is discharged,
The water tank is equipped with a water level meter for measuring the water level of water stored therein, and a water tank pressure gauge for measuring the internal pressure,
During heat storage operation,
When the pressure value of the reaction tank pressure gauge becomes larger than the pressure value of the water tank pressure gauge by operating the first vacuum valve and the second vacuum valve from closed to open, the dehydration reaction is started,
When the water level measurement value of the water level gauge reaches a predetermined amount, the first vacuum valve and the second vacuum valve are operated from open to closed to control the heat storage operation to be completed. An exhaust heat storage air-conditioning heat source system using the chemical heat storage described in (1) above.

(7) After the deaeration operation,
When cooling and hot heat are taken out simultaneously by the hydration reaction, and when switching to each operation of storing heat by dehydration reaction using exhaust heat of 200 ° C or less, the reaction tank pressure gauge shows a measured value higher than the leak set pressure. In the case of measurement, the exhaust heat storage using the chemical heat storage according to (4), which is configured by a control unit that controls to perform each operation after performing the deaeration operation again. Air conditioning heat source system.

(8) The chemical according to any one of (1) to (5), wherein the heat storage material filled in the heat exchanger is made of a mixed material of a hydrated material and an adsorbent. Waste heat storage air conditioning heat source system using heat storage.

式中、h_adは吸着材の単位蓄熱量、ｈ_ｈｙは水和材の単位蓄熱量、αは水和材の混合比、ｔ_reは反応時間、ｔ_avは潮解を回避する時間、h_gは吸着材より追加的に得られる単位発熱量を示す。 (9) The chemistry according to any one of (1) to (6), wherein the hydrated material and adsorbent of the heat storage material are mixed at a mixing ratio based on the following formula (a): Waste heat storage air conditioning heat source system using heat storage.

In the formula, _ad is the unit heat storage amount of the adsorbent, h _hy is the unit heat storage amount of the hydrated material, α is the mixing ratio of the hydrated material, t _re is the reaction time, t _av is the time to avoid deliquescence, h _g Indicates the unit calorific value additionally obtained from the adsorbent.

(10) The diameter of the steam pipe and the heat transfer oil pipe provided in the heat exchanger is 16 mm to 22 mm, and the distance between the center of the steam pipe and the center of the heat transfer oil pipe is 40 mm to 60 mm. An exhaust heat storage air conditioning heat source system using the chemical heat storage according to any one of (1) to (7).

(11) The diameter of the particle | grains of the hydration material and adsorbent which comprise the said thermal storage material is 0.7 mm-2.5 mm, Any one of said (1)-(8) characterized by the above-mentioned. Waste heat storage air conditioning heat source system using chemical heat storage.

The following effects are exhibited by the exhaust heat storage air conditioning heat source system using chemical heat storage of the present invention.
<1> An exhaust heat storage air-conditioning heat source system using the chemical heat storage of the present invention,
A granular heat storage material that dissipates heat by a hydration reaction and stores heat by a dehydration reaction by heating,
A heat transfer oil pipe that branches into and merges with a plurality of inlet headers and outlet headers so as to circulate heat transfer oil that heats the heat storage material and receives heat generated from the heat storage material;
A plurality of steam pipes that provide water vapor necessary for the hydration reaction of the heat storage material and have a large number of openings on the side surface that receives the water vapor extracted by the dehydration reaction of the heat storage material;
Fins fixed to the outer side surfaces of the heat transfer oil pipe and the steam pipe so as to be in contact with the direction perpendicular to the axis of the pipe, and the inside of the plurality of steam pipes communicate with the outside on the side surface A gas-liquid heat exchange coil-shaped heat exchanger to be fixed;
A heat exchanger lid that respectively closes an upper surface and a lower surface in a direction orthogonal to the fins of the heat exchanger;
After closing the heat exchange lid at the bottom, the heat storage material is filled between the fin gaps of the heat exchanger, and the heat exchanger closed by the upper heat exchange lid is built in. An end of the water vapor introduction pipe is positioned on the opposite side cover, and a reaction tank is provided for inserting the heat exchanger into one of the two side covers,
Furthermore, a water tank provided with an evaporation / condensation tube for heating the water stored therein and circulating a heat transfer water for cooling and condensing the water vapor generated in the heat exchanger;
In order to make the heat storage material react in an environment at a pressure lower than atmospheric pressure, a vacuum pump that eliminates air in the reaction tank and the water tank and makes the internal pressure lower than atmospheric pressure;
A heat medium oil inflow pipe for passing the heat medium oil through the reaction tank side wall and connected to the heat medium oil pipe of the heat exchanger via an inlet header, and a heat medium oil pipe connected to the heat medium oil pipe via an outlet header A heated heat oil discharge pipe,
An external steam pipe connecting the reaction tank and the water tank;
A vacuum pulling pipe for connecting the connecting portion of the external water vapor pipe and the vacuum pump;
A first vacuum valve provided in the external steam pipe on the water tank side as viewed from the connection part of the external steam pipe, and a second vacuum provided in the external steam pipe on the reaction tank side as viewed from the connection part of the external steam pipe A valve and a third vacuum valve provided in the vacuuming pipe;
With
The evaporation / condensation pipe of the water tank includes a cooling water circulation system that circulates cooling water using a cooling water pump to a cooling tower that exchanges heat with the atmosphere, and a chilled water circulation system that circulates cooling water using a cooling water pump to a cooling coil of an air conditioner. Switch to connect
The heat medium oil inflow pipe and the heat medium oil outflow pipe are configured to switch and connect an air conditioning hot water circulation system and an exhaust heat recovery heat medium circulation system via a facility-side heat exchanger. So, it is easy to use for air-conditioning energy that has a large amount of use as a society, cold water that is a heating medium sent to the cooling coil of the air conditioner for cooling use (at a feed temperature of about 7 ° C to 10 ° C, about 12 ° C to 18 ° C) Range of return temperature), it can be taken out as warm water (heating temperature of about 50 ° C. to 60 ° C. and return temperature of about 45 ° C. to 50 ° C.) which is a heating medium sent to the hot water coil of the air conditioner for heating use.

<2> A heat medium oil inflow pipe connected to the heat medium oil pipe via an inlet header and allowing the heat medium oil to flow in is divided through an inflow side oil coupling,
Dividing the heat transfer oil discharge pipe connected to the heat transfer oil pipe via an outlet header via an outflow oil coupling;
After attaching an inflow side water coupling and an outflow side water coupling to the inlet / outlet tapping of the evaporation / condensation tube of the water tank, respectively, and enabling connection with an external flexible tube with a phase coupling,
The reaction tank, the water tank, and the vacuum pump;
An external steam pipe connecting the reaction tank and the water tank;
A vacuum pulling pipe for connecting the connecting portion of the external water vapor pipe and the vacuum pump;
A first vacuum valve provided in the external steam pipe on the water tank side as viewed from the connection part of the external steam pipe, and a second vacuum provided in the external steam pipe on the reaction tank side as viewed from the connection part of the external steam pipe A valve and a third vacuum valve provided in the vacuuming pipe;
A heat transfer oil inflow pipe from the inlet header of the heat transfer oil pipe to the inflow side oil coupling;
Heat medium oil outflow pipe from the outlet header of the heat medium oil pipe to the outflow side oil coupling,
On a movable base,
If you move to a waste heat facility,
The cooling water circulation system is connected to the evaporation / condensation pipe of the water tank via an inflow-side water coupling and an outflow-side water coupling, and the heating medium oil inflow pipe and the heating medium oil outflow pipe, through the inlet-side oil coupling and the outlet-side oil coupling connected to the thermal oil outlet pipe of the heat transfer oil inflow pipe of the facility and the facility by circulating oil to the facility-side heat exchanger, the facility heat Connected to the exhaust heat recovery heat medium circulation system through an exchanger,
If you move to a heat utilization facility,
The cold water circulation system is connected to the evaporation / condensation tube of the water tank via an inflow-side water coupling and an outflow-side water coupling, and to the heat-medium oil inflow tube and the heat-medium oil outflow tube, through the inlet-side oil coupling and the outlet-side oil coupling connected to the thermal oil outlet pipe of the heat transfer oil inflow pipe of the facility and the facility by circulating oil to the facility-side heat exchanger, the facility heat Since it is configured to be connected to the hot air circulation system for air conditioning through an exchanger, the spatial mismatch between the exhaust heat facility and the heat utilization facility is eliminated, and exhaust heat of 200 ° C. or less, which was conventionally discarded, is eliminated. It can be used to circulate and use air-conditioning energy, which is used in large quantities as a society, to store, transport, and store waste heat.

<3><4> The granular heat storage material that dissipates heat by the hydration reaction and stores heat by a dehydration reaction by heating is calcium chloride (or calcium bromide),
Filling the water tank with a predetermined amount of water,
After opening the third vacuum valve and the second vacuum valve, the vacuum pump is operated to reduce the internal pressure of the reaction tank to 2-50 Pa, then the second vacuum valve is closed and the first vacuum valve is opened to suck the vacuum pump. After deaeration operation to stop the vacuum pump after setting the water tank internal pressure to 1 to 3 kPa of the saturated water vapor pressure of the water temperature,
Connect the cold water circulation system to the evaporation / condensation pipe of the water tank to connect cold heat, and connect the hot water circulation system for air conditioning to the heat medium oil inflow pipe and the heat medium oil outflow pipe via a facility-side heat exchanger. Then, heat is taken out simultaneously as a heat source by hydration reaction,
Thereafter, the cooling water circulation system is connected to the evaporation / condensation tube of the water tank to dissipate heat of condensation in the water tank, and a facility-side heat exchanger is connected to the heat medium oil inflow pipe and the heat medium oil outflow pipe. Through the exhaust heat recovery heat medium circulation system through the exhaust heat of 200 ℃ or less, to store heat by dehydration reaction,
Since it is configured to repeat this,
Despite a large amount of exhaust heat, waste heat of 200 ° C or less with low temperature potential is used, and it is sent to the cooling coil of an air conditioner as a cooling application that is easy to use for air conditioning energy that is used in large quantities as a society. Cold water (heating temperature of about 7 ° C to 10 ° C, return temperature range of about 12 ° C to 18 ° C), which is a heating medium, hot water (50 ° C to about 50 ° C to about 18 ° C) It can be taken out at a feed temperature of about 60 ° C and a return temperature of about 45 ° C to 50 ° C).

<5> An inflow heat medium oil thermometer that measures the temperature of the heat medium oil flowing into the heat medium oil inflow pipe, and an exhaust heat that measures the temperature of the heat medium oil discharged into the heat medium oil discharge pipe A medium temperature thermometer,
When the exhaust heat medium oil temperature measured by the exhaust heat medium oil thermometer falls below the set exhaust heat medium oil temperature obtained by adding a predetermined difference to the predetermined inflow heat medium oil temperature during the hydration reaction,
Judging that the heat storage material in the reaction tank has finished the hydration reaction at a predetermined rate,
Since the first vacuum valve and the second vacuum valve are operated from open to closed, and the control unit is configured to control the end of the extraction of the cold and hot heat,
It is possible to control the extraction of cold and hot heat efficiently by evacuation so that the hydration reaction whose reaction is difficult to understand can be reliably grasped with an inexpensive measuring instrument.

<6> a reaction vessel pressure gauge for measuring an internal pressure in the reaction vessel,
An inflow heat medium water thermometer that measures the temperature of the heat medium water that flows into the evaporation / condensation pipe, and an exhaust heat medium water thermometer that measures the temperature of the heat medium water that is discharged,
The water tank is equipped with a water level meter for measuring the water level of water stored therein, and a water tank pressure gauge for measuring the internal pressure,
During heat storage operation,
When the pressure value of the reaction tank pressure gauge becomes larger than the pressure value of the water tank pressure gauge by operating the first vacuum valve and the second vacuum valve from closed to open, the dehydration reaction is started,
Since the water level measurement value of the water level meter reaches a predetermined amount, the first vacuum valve and the second vacuum valve are operated from open to closed, and the control unit is configured to control the heat storage operation to be finished.
The heat storage can be controlled efficiently so that the dehydration reaction whose reaction is difficult to understand by evacuation can be surely grasped by an inexpensive measuring instrument.

<7> When cooling and warm heat are simultaneously taken out by hydration reaction and switching to each operation of storing heat by dehydration reaction using exhaust heat of 200 ° C. or less, the reaction vessel pressure gauge is higher than the leak set pressure When the measured value is measured, it consists of a control unit that controls each operation after deaeration operation again,
The hydration reaction and dehydration reaction of the reaction tank and water tank can be controlled at a predetermined pressure temperature, and the heat storage and the extraction of cold / hot heat can be controlled efficiently.

<8> Since the heat storage material filled in the heat exchanger is made of a mixed material of a hydrated material and an adsorbent, deliquescence can be suppressed even if calcium chloride is used as the hydrated material.

<9> Since the hydrated material and the adsorbent of the heat storage material are mixed at a mixing ratio based on the following formula (a), the mixing ratio of the hydrated material and the adsorbent is obtained from the time t _av to avoid deliquescence. be able to.

In the formula, _ad is the unit heat storage amount of the adsorbent, h _hy is the unit heat storage amount of the hydrated material, α is the mixing ratio of the hydrated material, t _re is the reaction time, t _av is the time to avoid deliquescence, h _g Indicates the unit calorific value additionally obtained from the adsorbent.

<10> The diameter of the steam pipe and the heat transfer oil pipe provided in the heat exchanger is 16 mm to 22 mm, and the distance between the center of the steam pipe and the center of the heat transfer oil pipe is 40 mm to 60 mm. The pressure loss of the passing water vapor can be suppressed within a necessary range.

<11> Since the diameter of the particles of the hydrated material and the adsorbent constituting the heat storage material is 0.7 mm to 2.5 mm, the pressure loss of water vapor passing through the layer of the heat storage material is suppressed within a necessary range. be able to.

System configuration diagram showing schematic overall configuration of waste heat storage air conditioning heat source system using chemical heat storage System configuration diagram showing the schematic central configuration of an exhaust heat storage air-conditioning heat source system using chemical heat storage External view of reaction tank The perspective view which shows the structure of a heat exchanger Plan sectional view of heat exchanger and reaction tank The figure which shows the relationship between water vapor | steam and heat | fever transfer with respect to a hydration material and an adsorbent in the cross section orthogonal to the axis | shaft of the heat-medium oil pipe and water vapor | steam pipe | tube in a heat exchanger. Reaction explanatory diagram of heat storage material (PT diagram) Explanatory diagram of the operating state of a chemical heat storage system that uses cold and heat simultaneously Explanatory diagram showing stable and deliquescent areas of calcium chloride with pressure and temperature as axes Explanatory diagram of hydration reaction and moisture content ratio of hydrated material and adsorbent with respect to temperature The figure which shows the suppression effect of deliquescence by including adsorbent Illustration of dehydration reaction of hydrated material and adsorbent mixed material Diagram showing the mixing ratio of adsorbent to hydrated material in terms of heat storage and heat generation Figure showing the steam pipe pressure loss and occupancy Diagram showing dimensions and positional relationship between steam pipe and heat transfer oil pipe The figure which shows the pressure loss of the water vapor which passes through the particle layer with respect to the particle diameter System configuration diagram showing a schematic overall configuration using an exhaust heat storage air conditioning heat source system that uses chemical heat storage in a mobile manner

EMBODIMENT OF THE INVENTION The form for implementing the waste heat storage air-conditioning heat source system using the chemical heat storage of this invention is demonstrated based on the figure of an Example.
FIG. 1 is a system configuration diagram showing a schematic overall configuration of an exhaust heat storage air conditioning heat source system using chemical heat storage. As shown in this figure, the waste heat storage air conditioning heat source system 1 using chemical heat storage basically includes a water tank 10, a vacuum pump 20, a reaction tank 30, an external water vapor pipe 22, a vacuum pipe 23, a first vacuum. A valve 25, a second vacuum valve 26, a third vacuum valve 27, a vacuum pump 20, a heat medium oil inflow pipe 35, a heat medium oil outflow pipe 35 ', the water tank 10, the reaction tank 30, the first vacuum valve 25, the first A system center having two vacuum valves 26, a third vacuum valve 27 and a control unit 2 for controlling the vacuum pump 20, and
A cooling tower 60, a cooling water pump 63, a cooling water return pipe 61 that circulates the cooling water of the cooling tower 60, a cooling water forward pipe 62, and a cooling water circulation system 67 having a common piping section connected to the evaporation / condensation pipe;
A water-water heat exchanger 68, an evaporation / condensation tube for exchanging heat between minute high-temperature cold water sent to a chilled water coil using a chilled water coil or the like incorporated in an air conditioner (not shown) as a cooling load and a heat transfer medium and the chilled water flowing to the evaporation / condensation tube A cold water circulation system 69 having a common water pipe line connected to the water circulation pipe 89, the cold water pump 88, and the evaporation / condensation pipe,
Facility side heat exchanger 70 for exchanging heat between the exhaust heat transfer medium (exhaust gas or liquid with exhaust heat) carrying exhaust heat and the heat transfer oil introduced into the reaction tank 30, and the primary side of the facility side heat exchanger 70 An exhaust heat recovery heat medium circulation system 86 having a heat medium oil outflow exhaust heat recovery utilization secondary pipe 72, a heat medium oil inflow exhaust heat recovery utilization secondary pipe 71, and an exhaust heat recovery heat medium oil pump 73;
A facility-side heat exchanger 77 that exchanges heat between hot water that uses a hot water coil or the like incorporated in an air conditioner (not shown) as a heat load and heat medium oil that is introduced into the reaction tank 30, and a primary of the facility-side heat exchanger 77. A heating medium oil outflow hot water use secondary pipe 81 provided on the side, a heat medium oil inflow hot water use secondary pipe 78, and a hot water use system heat medium oil pump 79, and a hot water heating circulation system 87 for air conditioning.
It is composed of the whole structure including the above.
The water tank 10 is a vacuum vessel, which heats the water stored in the water tank and stores the heat transfer water that cools and condenses the water vapor sent from the reaction tank, and is stored in the water tank. A water level gauge 12 for measuring the water level and a water tank pressure gauge 13 for measuring the pressure in the water tank are provided. The evaporation / condensation pipe 11 includes an inflow heat medium water thermometer 14 for measuring the temperature of the heat medium water flowing into the water tank and a discharge heat medium water thermometer 15 for measuring the temperature of the discharged heat medium water. Is provided. The inflow heat medium water thermometer 14 and the exhaust heat medium water thermometer 15 are monitoring instruments that check whether the operation of the exhaust heat storage air conditioning heat source system using chemical heat storage is normally performed. Output as a display signal.
The water tank 10 and the reaction tank 30 are connected by an external water vapor pipe 22, and when heat radiation (heat generation) operation is performed, water vapor is sent from the water tank 10 to the reaction tank 30 through the external water vapor pipe 22 to store heat (heat absorption). When the operation is performed, water vapor is sent from the reaction tank 30 to the water tank 10 through the external water vapor pipe 22.
In this embodiment, two external steam pipes are provided so that steam can be supplied and taken out from the front side and the rear side of the reaction tank 30 so that the heat storage material in the reaction tank 30 can uniformly perform hydration and dehydration reactions. 22 is connected to the reaction tank 30.

The vacuum pump 20 sucks (unnecessary) air from the reaction tank 30 and the water tank 10 to ensure a vacuum state, and connects a vacuum drawing pipe 24 extended from a connection point between the external steam pipe 22 and the external steam pipe 23. The vacuum tank 24 and the external steam pipe 22 are connected to the water tank 10, and the vacuum pipe 24 and the external steam pipe 23 are connected to the reaction tank 30.
The external water vapor pipe 22, the external water vapor pipe 23 and the vacuum pipe 24 are provided with a first vacuum valve 25, a second vacuum valve 26 and a third vacuum valve 27 in the middle of the pipe, respectively. When the (unnecessary) air is sucked from 10 or when water vapor is exchanged between the water tank 10 and the reaction tank 30, it is opened and closed by an output signal from the control unit 2 according to each application.

The cooling tower 60 and the water tank 10 are connected by an evaporation / condensation pipe 11, a cooling water return pipe 61, and a cooling water forward pipe 62. The cooling water return pipe 61 is provided with a cooling water pump 63 and a switching valve 64, and the cooling water forward pipe 62 is provided with a switching valve 65, thereby constituting a cooling water circulation system 67.
The cold heat that can be taken out during the hydration reaction is a water-water heat exchanger that exchanges heat between the chilled water coil that is installed in the air conditioner (not shown) and the chilled water that is sent to the cold water coil and the cold water that flows to the evaporation / condensation tube. 68 and the water tank 10 are connected to each other by a water circulation pipe 89 that flows to the evaporation / condensation pipe and a cold water pump 88 provided in the middle of the water circulation pipe 89, thereby constituting a cold water circulation system 69.
The steam tank circulation system 67 and the cold water circulation system 69 are connected to the water tank 10 so as to be switched by a group of a switching valve 64 and a switching valve 65 and a group of a switching valve 84 and a switching valve 85.
The heat medium oil inflow pipe 35 and the heat medium oil outflow pipe 35 ′ are used to recover the heat medium oil outflow exhaust heat provided on the primary side of the facility side heat exchanger 70 connected to the facility side heat exchanger 70. Heat medium oil is circulated through the secondary pipe 72, the heat medium oil inflow exhaust heat recovery utilization secondary pipe 71 provided on the primary side of the facility-side heat exchanger 70, and the exhaust heat recovery heat medium oil pump 73. These are connected, and these constitute the exhaust heat recovery heat circulation system 86.
The cold heat that can be taken out during the hydration reaction uses a hot water coil incorporated in an air conditioner (not shown) as a thermal load, and heat exchange between the hot water and the heat transfer oil introduced into the reaction tank 30 is performed on the facility side heat exchanger 77 and the facility side. The facility-side heat exchanger 77 and the reaction tank are connected to each other via a heat medium oil outflow hot water secondary pipe 81 provided on the primary side of the heat exchanger 77, and thereby the hot water heating circulation system 87 for air conditioning is connected. It is composed.
The tip of the heat transfer oil outflow pipe 35 ′ is branched and provided with a switching valve 83 and a changeover valve 82, and the end of the heat transfer oil inflow pipe 35 is branched and provided with a changeover valve 74 and a changeover valve 80. A heat transfer oil pump 79 is provided, and the exhaust heat recovery heat circulation system 86 or the hot water heating circulation system 87 for air conditioning is switched by switching them.

FIG. 2 shows a schematic central configuration of an exhaust heat storage air conditioning heat source system using chemical heat storage.
The description of the same configuration as in FIG. 1 is omitted.
As shown in the figure, a waste heat storage air conditioning heat source system 1 using chemical heat storage includes a water tank water level meter 12 for measuring the water level of water stored in the water tank, and a pressure gauge for measuring the pressure in the water tank. 13, the evaporating / condensing pipe 11 includes an inflow heat medium water thermometer 14 for measuring the temperature of the heat medium water flowing into the water tank, and an exhaust heat medium water thermometer for measuring the temperature of the discharged heat medium water. 15, an inflow heat medium oil thermometer 51 that measures the temperature of the heat medium oil sent to the heat exchanger 40 in the reaction tank 30 is connected to the heat medium oil inflow pipe 35 ′. Is provided with an exhaust heat medium oil thermometer 52 for measuring the temperature of the heat medium oil discharged from the reaction tank 3, and the reaction tank 30 is provided with a pressure gauge 38 for measuring the pressure in the reaction tank 30 as a measuring instrument. , Based on measurement signals from those instruments,
The second vacuum valve 26, the third vacuum valve 27, the vacuum pump 20, and the control unit for controlling the water tank 10, the reaction tank 30, the first vacuum valve 25, the second vacuum valve 26, the third vacuum valve 27, and the vacuum pump 20. 2 and.
The water tank 10 is a vacuum vessel, which heats the water stored in the water tank and stores the heat transfer water that cools and condenses the water vapor sent from the reaction tank, and is stored in the water tank. A water level gauge 12 for measuring the water level and a pressure gauge 13 for measuring the pressure in the water tank are provided. The evaporation / condensation pipe 11 includes an inflow heat medium water thermometer 14 for measuring the temperature of the heat medium water flowing into the water tank and a discharge heat medium water thermometer 15 for measuring the temperature of the discharged heat medium water. Is provided.
The inflow heat medium water thermometer 14 and the exhaust heat medium water thermometer 15 are monitoring instruments that check whether the operation of the exhaust heat storage air conditioning heat source system using chemical heat storage is normally performed. Output as a display signal.

The vacuum pump 20 sucks (unnecessary) air from the reaction tank 30 and the water tank 10 to ensure a vacuum state, and connects a vacuum drawing pipe 24 extended from a connection point between the external steam pipe 22 and the external steam pipe 23. The vacuum tank 24 and the external steam pipe 22 are connected to the water tank 10, and the vacuum pipe 24 and the external steam pipe 23 are connected to the reaction tank 30.
The external water vapor pipe 22, the external water vapor pipe 23 and the vacuum pipe 24 are provided with a first vacuum valve 25, a second vacuum valve 26 and a third vacuum valve 27 in the middle of the pipe, respectively. When the (unnecessary) air is sucked from 10 or when water vapor is exchanged between the water tank 10 and the reaction tank 30, it is opened and closed by an output signal from the control unit 2 according to each application.

FIG. 3 shows the appearance of the reaction tank 30.
The reaction tank 30 is a vacuum vessel and is composed of a rectangular main body 31 and vacuum flange lids 32 and 33.
The vacuum flange lids 32 and 33 have a water vapor pipe 34 for flowing in and out water vapor, a heat medium oil inflow pipe 35 for flowing heat medium oil, and a heat medium oil discharge pipe 35 'for flowing out heat medium oil. A vacuum joint 36 is provided. In the present embodiment, the external steam pipe 23 and the steam pipe 34 are described with different reference numerals, but the external steam pipe 23 may also serve as the steam pipe 34.
As shown in the enlarged cross-sectional view of FIG. 3B, the vacuum joint 36 is a sheath pipe through which the heat transfer oil inflow pipe 35 and the heat transfer oil discharge pipe 35 ′ pass, and an O-ring 37 provided at the tip thereof. Thus, the gap between the heat transfer oil inlet pipe 35 and the heat transfer oil discharge pipe 35 'is closed to keep the reaction tank 30 airtight, and water vapor does not leak from the reaction tank.
The reaction tank 30 is provided with a pressure gauge 38 (see FIG. 2) for measuring the pressure in the reaction tank 30.

The reaction tank 30 is provided with a heat exchanger 40. FIG. 4 is a perspective view showing the configuration of the heat exchanger 40. FIG. 5 is a plan sectional view of the heat exchanger 40 and the reaction tank 30.
As can be seen in both figures, the heat exchanger 40 is composed of a rectangular main body 41, a heat exchanger bottom plate 42 as a heat exchanger lid, and a heat exchanger lid plate 43 as a heat exchanger lid. . The heat exchanger 40 has a gas-liquid heat exchanger shape, a so-called coil shape, and is filled with a granular heat storage material 47 that dissipates heat by a hydration reaction filled therein and stores heat by a dehydration reaction by heating. doing.
The heat exchanger 40 has a structure in which an inlet header 50 and an outlet header 50 ′ are branched into a plurality of pipes and joined so as to circulate heat transfer oil that heats the heat storage material 47 and receives heat generated from the heat storage material 47. A plurality of steam pipes 49 having a large number of openings on the side surface for receiving steam necessary for the hydration reaction of the heat storage material 47 and receiving the water vapor taken out by the dehydration reaction of the heat storage material 47. A plurality of fins 44 fixed so as to be in contact with the outer surfaces of the heat transfer oil pipe 48 and the water vapor pipe 49 fixed in a direction perpendicular to the axis of each pipe, and orthogonal to the fins 44. The upper surface and the lower surface in the direction have open surfaces, and the upper surface and the lower surface in the direction orthogonal to the fins are closed after the heat exchanger bottom plate 42 serving as the heat exchange lid at the bottom is closed. The heat storage material 4 7 is filled between the fins 44 and further closed by a heat exchanger cover plate 43 which is an upper heat exchange cover.
The heat storage material 47 filled between the fins 44 is a hydrated material 45, or when the hydrated material 45 is, for example, calcium chloride, it is made of a mixed material of the hydrated material 45 and the adsorbent 46.
The heat exchanger 40 is provided with a heat medium oil header 50 that is connected to the heat medium oil inflow pipe 35 and distributes and supplies the heat medium oil to the plurality of heat medium oil pipes 48. The oil enters the heat medium oil header 50 from the heat medium oil inflow pipe 35, is divided into a plurality of heat medium oil pipes 48, joins at the other heat medium oil header 50 ′, and then passes through the heat medium oil discharge pipe 35 ′. It is carried out of the reaction tank 30.
The heat medium oil inflow pipe 35 has an inflow heat medium oil thermometer 51 for measuring the temperature of the heat medium oil sent to the heat exchanger 40 in the reaction tank 30, and the heat medium oil discharge pipe 35 ′ has a reaction tank. An exhaust heat medium oil thermometer 52 for measuring the temperature of the heat medium oil discharged from 3 is provided.
The inflow heat medium oil thermometer 51 and the exhaust heat medium oil thermometer 52 output respective measurement signals to the control unit 2, and set discharge in which a predetermined difference is added to a predetermined inflow heat medium oil temperature during the hydration reaction. When the exhaust heat medium oil temperature measured by the exhaust heat medium oil thermometer 52 falls below the heat medium oil temperature, it is determined that the heat storage material 47 in the reaction tank 30 has finished the hydration reaction at a predetermined rate. Then, the first vacuum valve 25 and the second vacuum valve 26 are operated from the open state to the closed state, and control is performed so as to end the extraction of the cold heat and the hot heat.
The inflow heat transfer oil thermometer 51 is also used for judging the risk of deliquescence of calcium chloride, which will be described later.

  The control unit 2 is provided in a reaction tank pressure gauge 38 provided in the reaction tank 30, an inflow heat medium oil thermometer 51 provided in the heat medium oil inflow pipe 35, and the heat medium oil discharge pipe 35 ′. The exhaust heat medium oil thermometer 52, the water level meter 12 and water tank pressure gauge 13 provided in the water tank 10, the inflow heat medium water thermometer 14 and the exhaust heat medium water thermometer 15 provided in the evaporation / condensation pipe 11. Based on the measured value from each measuring instrument, the operation of the vacuum pump 20, the first vacuum valve 25, the second vacuum valve 26 and the third vacuum valve 27 is controlled, and the exhaust heat storage air conditioning heat source using chemical heat storage Control the operating status of the system.

FIG. 6 is a view showing the relationship between the transfer of water vapor and heat to the hydrated material 45 and the adsorbent 46 in the heat exchanger 40. In the figure, the transfer of heat and water vapor in the hydration reaction for extracting heat is indicated by arrows. In the hydration reaction, water vapor is supplied from the water vapor pipe 49 to the hydrating material 45 and the adsorbent material 46, and the generated heat is supplied to the reaction tank through the heat medium oil pipe 48, the heat medium oil header 50 ', and the heat medium oil discharge pipe 35'. 30 is carried out.
The heat storage material 47 is configured to dissipate heat (heat generation) with a hydration reaction and store heat (heat absorption) with dehydration.
In this embodiment, as the heat storage material 47, a hydrated material 45 made of calcium chloride (CaCl ₂ ) capable of dehydration reaction (regeneration) at 100 degrees tens of degrees, and an adsorbent made of synthetic zeolite that can be regenerated at 100 ° C. or less. 46 mixed materials are used.
Therefore, in the reaction tank 30, it is set as the structure which can reversibly repeat heat storage and heat dissipation by the reaction shown below.
CaCl ₂ (s) + H ₂ O (g) ⇔ CaCl ₂ · H ₂ O (s) + Q1 (653 kJ / kg) Non-hydrate ⇔ Monohydrate
CaCl ₂ · H ₂ O (s) + H ₂ O (g) ⇔CaCl ₂ · 2H ₂ O (s) + Q2 (409 kJ / kg) Monohydrate⇔Dihydrate For reaction heat Q1 and Q2, Not based on mol, but on a mass basis based on the mass on the side with the lower hydration number (left side of the formula).

FIG. 7 shows an outline of the above reaction on an Arrhenius plot. Here, the reaction equilibrium of calcium chloride and the saturated water vapor pressure (reaction equilibrium of water vapor and water) are shown.
In the figure, the vertical axis represents absolute pressure and the horizontal axis represents temperature. The line X (the leftmost solid line from the left) represents the temperature and pressure conditions for changing from the anhydride to the monohydrate, and the line Y (the second dotted line from the left) is The temperature and pressure conditions that change from monohydrate to dihydrate are represented, and the line Z (the third solid line from the left) represents the conditions under which water boils at the water saturation line in terms of pressure and temperature. .

About the operation (heat dissipation / heat storage) of the exhaust heat storage air conditioning heat source system 1 using the chemical heat storage of the present embodiment, the case where calcium chloride is used for the hydrated material 45 based on FIGS. 8 (a) to (c). This will be described with reference to FIG. In FIG. 8, the control unit 2 is omitted.
Further, the temperature and pressure in the driving operation are an example of the operating conditions, and are not limited thereto.
First, the deaeration operation (a) is performed according to the following procedure.
After closing the heat exchanger bottom plate 42 which is the heat exchange lid on the bottom, the calcium chloride (anhydride) which is the hydrated material 45 and the heat storage material 47 which is the adsorbing material 46 are fins 44 of the heat exchanger 40. Two vacuum flanges which are side lids facing the side surfaces of the heat exchanger 40 so as to incorporate the heat exchanger 40 which is filled between the gaps and closed by the heat exchanger lid plate 43 which is an upper heat exchange lid In the central portion 1 where the reaction tank 30 into which the heat exchanger is inserted through either one of the lids 32 is set,
The water tank 10 is filled with water. With the vacuum pump 20 in operation, the second vacuum valve 26 and the third vacuum valve 27 are opened, and the air in the reaction vessel 30 is discharged. This is because the air is accumulated in the fine holes of the granular heat storage material 47, the gaps of the heat exchanger 40, etc., so that the vacuum is drawn for a certain period of time. After the controller 2 determines that the internal pressure is reduced to 2 to 50 Pa based on the measured value of the reaction vessel pressure gauge 38, the operation proceeds to the next operation. The value of the internal pressure of 2 Pa to 50 Pa is a value that can be evacuated economically so that air, which is a factor that hinders the reaction, can be discharged out of the system as much as possible. 47, and can impart a moving force of water vapor from the water tank 10 to the reaction tank 30 in the hydration reaction.
Next, the vacuum valve 26 is closed, 25 is opened, and the air in the water tank 10 is discharged.
In order to extract the air contained in the water surface of the water tank 10 as a gas or melted in the stored water by vacuuming out of the system, the air is evacuated for a certain period of time. After the controller 2 determines that the internal pressure is reduced to 1 to 3 kPa of the saturated water vapor pressure of the water temperature based on the measured value of the water tank pressure gauge 13, the operation proceeds to the next operation. The saturated water vapor pressure of 1 to 3 kPa is obtained when the water temperature of the above-mentioned cold water system of water temperature 8 ° C. to 25 ° C. and the water temperature cooled to some extent in the cooling water circulation system to the cooling tower performing heat exchange in the atmosphere are This is the saturated water vapor pressure at the water temperature in the aquarium where only heat is indirectly applied by the condenser tube.
After the controller 2 determines that the internal pressure of the water tank 10 is reduced to 1 to 3 kPa of the saturated water vapor pressure of the water temperature, the first vacuum valve 25 and the third vacuum valve 27 are closed, and the vacuum pump 20 is stopped.

Next, the heat release (hydration reaction) operation (b) will be described.
As described above, in the state where the inside of the reaction tank 30 and the water tank 10 are in a certain vacuum state due to the above-described internal pressure, the heat medium oil of 50 ° C. is fed from the heat medium oil inflow pipe 35 of the reaction tank 30 into the reaction tank 30. It feeds into the heat exchanger 40 and circulates in the heat transfer medium oil pipe 48. Further, 12 ° C. heat transfer water is sent to the evaporation / condensation tube 11 in the water tank 10 to circulate the evaporation / condensation tube 11. In this initial state, for example, the pressure in the water tank 10 is about 1.4 kPa at a saturated water vapor pressure of 12 ° C. water, and the reaction tank 30 is a low pressure of about several Pa.
The heat transfer oil at 50 ° C is heated to 55 ° C or higher in the reaction tank as a heating source of hot water having a return temperature of 44 ° C from the hot water coil of the heat load through the facility-side heat exchanger at a supply temperature of 54 ° C. To be used. The heat transfer water of 12 ° C. in the evaporation / condensation tube has a return temperature of cold water, and a return cold water temperature of 12 ° C., which is a design value of an evaporator of a general-purpose refrigerator.
Next, when the first vacuum valve 25 and the second vacuum valve 26 are opened, as shown in FIG. 7, the reaction tank 30 is connected from the water vapor pipe 34 connected to the water tank 10 by the pressure difference ΔP1 between the water tank 10 and the reaction tank 30. When water vapor is supplied into the inner heat exchanger 40 and water is adsorbed by the left side anhydrous product from the line X in FIG. 7, a hydration reaction occurs and changes to the right side monohydrate of the same line X. At this time, the heat Q1 is dissipated (heated). Although the reaction part at this time becomes high temperature, the measured value of the exhaust heat medium oil thermometer 52: the heat medium oil outlet temperature is raised to a temperature of about 70 ° C., and the pressure in the reaction tank in which the hydration reaction occurs is 1 kPa (point c). Heat generation on the line X occurs between the various heat storage materials 47 in the reaction tank 30 and the water vapor, and the heat medium oil outlet temperature and the pressure in the reaction tank continue, so that a large amount of heat can be taken out.
Furthermore, in the process in which the anhydride in the reaction tank 30 is changed to monohydrate to some extent, this time, when water is adsorbed to the monohydrate (between the lines X and Y), the hydration reaction occurs. It changes to the dihydrate on the right side of the generated line Y. At this time, the heat Q2 is dissipated (heated). The measured value of the exhaust heat medium oil thermometer 52 at this time: the heat medium oil outlet temperature is 55 ° C., and the pressure in the reaction tank in which the hydration reaction is occurring is 1 kPa (point b).

On the other hand, on the reaction tank 30 side, heats Q1 and Q2 due to the hydration reaction of calcium chloride are taken out by heat transfer oil through the pipe side surface of the heat transfer oil pipe 48 in the heat exchanger 40, and the heat transfer oil discharge pipe 35 ′ is connected. Through the reaction tank 30. This heat is used as warm heat. At this time, the temperature of the heat transfer oil discharged from the heat transfer oil discharge pipe 35 ′ is initially 70 ° C. to 55 ° C. during the dihydration reaction.
Further, in the water tank 10, the steam moves to the reaction tank 30 and changes in the pressure direction. However, since the water boils at 7 to 10 ° C. using the heat transfer water at 12 ° C. as the heat source, The pressure in the water tank 10 is balanced.
At this time, the temperature in the water tank 10 is about 10 ° C., and the pressure is 1.2 kPa (point a).
Then, the heat transfer water is deprived of the evaporation heat Q3 by the water boiling in the water tank 10, becomes a low temperature of 10 ° C. or less, is carried out of the water tank, and is used as cold heat.
When about 80% of the heat storage material filled in the reaction tank 30 becomes dihydrate, the temperature of the heat transfer oil discharged from the heat transfer oil discharge pipe 35 ′ becomes 54 ° C. When the temperature of the heat transfer oil discharged from the heat transfer oil discharge pipe 35 ′ is confirmed to be 54 ° C. by the discharge heat transfer oil thermometer 52 provided in the heat transfer oil discharge pipe 35 ′, the vacuum valve 25 and 26 are closed, the supply of water vapor from the water tank 10 to the reaction tank 30 is stopped, and the heat radiation operation is terminated.

The heat storage operation after the heat radiation operation will be described with reference to FIG. First, air that has entered the reaction tank 30 and the water tank 10 due to leakage during the heat radiation operation is discharged by the vacuum pump 20.
Next, the heat transfer oil in the reaction tank 30 is exchanged from the heat transfer oil inflow pipe 35 of the reaction tank 30 through the facility-side heat exchanger of the exhaust heat facility with the heat transfer oil at about 130 ° C. exchanged with the exhaust heat transfer medium. It is sent to the vessel 40 and circulated in the heat transfer oil pipe 48. Further, a 20 ° C. heat transfer water is sent to the evaporation / condensation tube 11 in the water tank 10 and circulated in the evaporation / condensation tube 11.
The heat transfer water at 20 ° C in the evaporation / condensation tube is the return temperature of the cooling water cooled by the outside air heat by the cooling tower that exchanges heat with the outside air. It can be cooled, and in summer, it is further cooled to 20 ° C. with a heat medium cooled in a refrigerator as additional cooling.
At this time, the calcium chloride dihydrate in the heat exchanger 40 receives heat from the heat transfer oil pipe 48 and first changes to a monohydrate (point e), and then becomes an anhydride (point f). And dewatered to discharge water vapor. The heat absorbed at this time is Q2 and Q1, respectively.
As described above, when the heat storage material 47 is heated, dehydration from the dihydrate and monohydrate of calcium chloride becomes water vapor, and the pressure in the reaction tank 30 increases. When the vacuum valves 25 and 26 are opened when the pressure in the reaction tank 30 is higher than the pressure in the water tank 10 by the pressure gauge 38 provided in the reaction tank 30, the water vapor discharged into the reaction tank 30 is pressurized. It moves to the water tank 10 by the difference ΔP2. In the water tank 10, the water vapor moved from the reaction tank 30 is cooled and condensed on the surface of the evaporation / condensation tube 11 (point d). The water level in the water tank 10 is confirmed by a water level meter 12 provided in the water tank 10, and when the dehydration is completed, the first vacuum valve 25 and the second vacuum valve 26 are closed, and the heat storage operation is finished.

As described above, when the heat of Q2 is applied to the dihydrate on the right side of the line Y in FIG. 7 from the heat transfer oil pipe, a dehydration reaction occurs and water is removed from the dihydrate to change to a monohydrate. The temperature at this time is 100 ° C., and the pressure is 8 kPa.
Further, when the heat of Q1 is applied from the heat transfer oil pipe 48 to the monohydrate, a dehydration reaction takes place and water is removed from the monohydrate to change to an anhydrous form. The temperature at this time is 130 ° C., and the pressure is 10 kPa.

As described above, the hydration state of calcium chloride changes depending on the ambient temperature and water vapor pressure. In addition, calcium chloride has a deliquescent (aqueous solution) boundary at a certain temperature and water vapor pressure. FIG. 9 is an explanatory diagram showing the stable region and deliquescent region of calcium chloride, with the vertical axis representing water vapor pressure (absolute pressure Pa) and the horizontal axis representing temperature (° C.).
The aa line shown in FIG. 9 is a line that separates the state of calcium chloride anhydrate and monohydrate, and the left side of the aa line is a stable region as the anhydrate CaCl ₂ , aa The region between the line and the bb line is stable as the monohydrate CaCl ₂ · H ₂ O, and the region between the line bb and the cc line is stable as the dihydrate CaCl ₂ · 2H ₂ O It is. The area on the right side of the line cc is the deliquescent area.

In this embodiment, at the time of the hydration reaction for extracting heat from the heat exchanger 40, first, the heat Q1 due to the reaction (CaCl ₂ → CaCl ₂ · H ₂ O) at point A shown in FIG. Heat Q2 due to reaction at point B (CaCl ₂ · H ₂ O → CaCl ₂ · 2H ₂ O) is taken out. Temperature of the heat transfer oil at the point B is 50 ° C. in a normal state, CaCl ₂ · 2H ₂ O hydration reaction is complete is also stable as a state in the case if CaCl ₂ · 2H ₂ O in this temperature. However, when CaCl ₂ · 2H ₂ O, which has completed the hydration reaction under the steam pressure condition, is cooled, the condition moves in the direction of the arrow, so that it enters the deliquescence zone beyond the point C. When deliquescent, what has been a stable shape as a granular layer until then flows, moves to the lower part of the heat exchanger 40, the material is unevenly distributed inside the heat exchanger 40, and heat exchange becomes impossible. Furthermore, since the deliquescent calcium chloride is highly corrosive, there is a problem that the heat transfer oil pipe 48 and the water vapor pipe 49 of the heat exchanger 40 are corroded.

FIG. 10 is a graph showing the water content ratio of the hydrated material and the adsorbent with respect to the temperature when the water vapor pressure is constant. In the figure, the vertical axis represents the water content ratio, and the horizontal axis represents the temperature.
In this embodiment, an adsorbent 46 is mixed with calcium chloride in order to suppress deliquescence of calcium chloride. The effect of mixing the adsorbent 46 will be described with reference to FIG.
The figure shows the water content ratio with respect to temperature when the water vapor pressure is constant, as a step-like line for calcium chloride, and as a curve rising to the left for the adsorbent 46.
Here, the water content ratio between the calcium chloride and the adsorbent 46 is shown based on the state (a) dehydrated at 130 ° C. (zero).

When the heat storage material 47 in the reaction tank 30 is cooled by the heat transfer oil flowing into the heat transfer oil pipe 48, the temperature of calcium chloride decreases. At this time, when the vacuum valves 25 and 26 are released and water vapor is supplied from the water tank 10 to the heat storage material 47, the water vapor is adsorbed by the adsorbent 46, and the water content ratio of calcium chloride does not increase and maintains a zero level. When the temperature of calcium chloride drops to about 70 ° C, it causes a hydration reaction with water vapor and the water content ratio rises to 0.16, changing from the anhydrous CaCl2 to the monohydrate CaCl2 · H2O and generating heat. Do (a state).
Furthermore, when the temperature drops due to the heat transfer oil and the temperature drops below 60 ° C, the hydration reaction of calcium chloride occurs again, and the water content ratio is increased to 0.32 from the monohydrate CaCl2 · H2O to the dihydrate CaCl2・ Changes to 2H2O and generates heat (U state).
At this time, the water vapor pressure in the reaction tank 30 is 1.2 kPa.

Assuming that the temperature of the heat transfer oil flowing into the reaction tank 30 (T1in in FIG. 8) is 50 ° C., calcium chloride CaCl 2 .2H 2 O exists stably as a granular material at this temperature. However, when the temperature of the heat transfer oil flowing into the reaction tank 30 decreases to about 30 ° C. (T1in ′) due to a change in conditions on the heat utilization side (change in heat load) (in FIG. 10, (D)), CaCl ₂・ The temperature of 2H ₂ O also decreases to 30 ° C. At this temperature, as described above with reference to FIG. 8, CaCl ₂ .2H ₂ O is deliquescent.
This deliquescence of calcium chloride can be suppressed by mixing the adsorbent 46 with calcium chloride. The adsorbent 46 has a characteristic that, when the temperature is lowered under the condition of a constant water vapor pressure, the water content ratio (adsorption amount) is increased and heat is generated by the adsorption, as indicated by the water content ratio line in FIG. Due to this feature, when the temperature of the heat transfer oil flowing into the reaction tank 10 decreases, the adsorbent 46 increases the amount of water that can be adsorbed as indicated by the arrow in the figure, and therefore adsorbs water simultaneously with the temperature decrease. It generates heat and has the function of suppressing the temperature drop of the entire heat storage material. That is, as shown in FIG. 11, when T1in (temperature of the heat transfer oil flowing into the reaction tank) drops below the deliquescence temperature, if the adsorbent 46 is mixed with calcium chloride, the heat storage material falls below the deliquescence temperature. The time until the temperature of 47 decreases can be delayed as compared with the case of calcium chloride alone (about 10 minutes in FIG. 11), which has the effect of improving the safety against temperature fluctuations of T1in.
As described above, in this embodiment, when T1in (the temperature of the heat transfer oil flowing into the reaction tank) is lowered below the deliquescence temperature, the time until the temperature of the heat storage material 47 falls below the deliquescence temperature is extended. However, if the inflow heat transfer oil thermometer 51 confirms that the low temperature has continued for a certain period of time (for example, 10 minutes in FIG. 13), the inflow of T1in is closed to avoid deliquescence. Is configured to do.

The dehydration of the heat storage material 47 of the hydrate material 45 and the adsorbent material 46 is shown in FIG. The temperature of the hydrating material 45 and the adsorbent 46 is almost the same as the temperature of the heat transfer oil (T1in) 50 ° C. flowing into the reaction tank 10 at the time of heat release with the reaction almost completed, and a vacuum valve ( Dehydration is started from the state in which FIGS.
First, the temperature (T1in) of the heat transfer oil flowing into the reaction tank 30 is set to 130 ° C., and circulation is started. Further, the heat medium water inflow temperature (T2in) into the water tank 10 is set to 25 ° C. to circulate. The temperature of the hydrated material 45 and the adsorbent 46 in the reaction tank 30 rises, and water vapor is generated only from the adsorbent 46 up to about 100 ° C. (ki), and the pressure in the reaction tank 30 rises. When the pressure in the reaction tank 30 becomes higher than the pressure in the water tank 10, the vacuum valve (FIGS. 825 and 26) is opened. Thereafter, CaCl ₂ · 2H ₂ O changes to CaCl ₂ · H ₂ O at about 100 ° C. (ki), and further changes to CaCl ₂ at 130 ° C.

As shown in FIG. 11, when the temperature of the heat transfer medium oil (T1in) flowing into the reaction tank 30 is lowered to a temperature at which there is a risk of deliquescence, a certain amount of adsorption is required to suppress the liquefaction of the hydrated material 45 for a certain period of time. Mixing of the material 46 is required.
In FIG. 13, when the ratio of the hydrated material 45 is plotted on the horizontal axis and the heat storage amount is plotted on the vertical axis, the heat stored in the hydrated material 45 and the adsorbent 46 and the heat transfer oil temperature are additionally obtained from the adsorbent 46. Indicates the amount of heat storage.
This relationship will be described using equations (i to iv).

Formula (i) is a formula for obtaining the unit heat storage amount (q _mix ) of the heat storage material 47, (h _ad ) is the unit heat storage amount of the adsorbent (600 kJ / kg), and h _hy is the unit heat storage amount of the hydrated material (1,130 kJ / kg), α represents the mixing ratio of the hydrated material 45. Next, a formula for obtaining the heat release rate (v) from the formula (ii), _tre represents a reaction time. Equation (iii) is a relational expression that cancels the amount of heat (vt _av ) for avoiding deliquescence for a certain time (t _av ) by the amount of heat additionally obtained from the adsorbent 46, and h _g is added from the adsorbent 46. Unit calorific value (230 kJ / kg) obtained. Equation (iv) is obtained from these equations (i) to (iii), and the mixing ratio α of the hydrated material 45 is obtained from the equation.
For example, assuming that the heat storage material 47 is dissipated in 2.5 hours, the ratio for avoiding deliquescence due to a decrease in the temperature of the heat transfer oil at the heat release rate for 10 minutes is 72% of the hydrated material 45 from the formula (iv). On the other hand, the adsorbent 46 is 28%.

The diameter of the steam pipe 49 has a suitable range depending on the pressure loss of the steam passing through the steam pipe. The pressure difference (ΔP1) in the hydration reaction of FIG. 7 is about 230 Pa, and is between the water tank 10 and the reaction tank 30, the steam pipe 49 in the reaction tank 30, the steam pipe 49, the heat transfer oil pipe 48, and the heat distribution fin. Therefore, it is necessary to suppress the pressure loss passing through each of the granular material layers, which are the heat storage material layers filled in the voids 44, to 230 Pa or less. Especially, the pressure loss is large in the steam pipe 49, and the outer diameter of the steam pipe 49 is shown in FIG. 14 showing the outer diameter of the steam pipe, the pressure loss in the steam pipe and the occupation ratio of the heat transfer oil pipe / steam pipe. Was about 16-22 mm. When the diameter of the steam pipe 49 is enlarged, as shown in FIG. 14, the occupation ratio of the steam pipe 49 and the heat transfer oil pipe 48 with respect to the entire container is increased, and the filling amount of the heat storage material 47 is reduced. The diameter of 49 is suitably 16 to 22 mm. At this time, the pressure loss of water vapor passing through the water vapor pipe 48 is 170 to 22 Pa.
Moreover, since the pressure loss of the water vapor | steam which passes the piping 22 and 23 between the reaction tank 30 and the water tank 10 is 24 Pa when the diameter of a pipe | tube is 250 mm, it is necessary to make the pressure loss of the water vapor | steam which passes a granular material layer about 30 Pa or less. There is.

  FIG. 15 shows the dimensions of the water vapor pipe 49 and the heat transfer oil pipe 48, and FIG. 16 shows the pressure loss of water vapor passing through the particle layer with respect to the particle diameter and particle layer thickness. The distance between the steam pipe 49 and the heat transfer oil pipe 48 is 40 to 60 mm, and the distance from the steam pipe 49 to the farthest point due to the diameter 16 to 22 mm of the steam pipe 49 is 40 mm and the diameter of the steam pipe 49 is 16 mm. In this case, the distance is 27 mm, and when the interval between the heat transfer oil pipes 48 is 60 mm and the diameter of the water vapor pipe 49 is 45 mm, the width is 45 mm. The thickness of the granule layer is 27 to 45 mm. The diameter of the granule that results in a pressure loss of 30 Pa or less with the thickness of this granule layer is 0.7 mm or more when the interval between the heat medium oil tubes 48 is 27 mm, and about 1.2 mm or more when the interval between the heat medium oil tubes 48 is 45 mm. It becomes. In this embodiment, since the pitch of the heat distribution fins 44 is 4 to 10 mm, the maximum value of the diameter of the particles is set to about 1/4 or less of the pitch of the heat distribution fins 44, and the pressure loss as the diameter of the particles. It was set to 0.7 mm to 2.5 mm which is low and appropriate.

With reference to FIG. 17, a schematic overall configuration using an exhaust heat storage air-conditioning heat source system using chemical heat storage in a mobile manner will be described as another embodiment.
The same parts as described in the description of FIG. 1 are omitted.
In this embodiment, a water tank 10, a vacuum pump 20, a reaction tank 30, an external water vapor pipe 22, a vacuum pipe 23, a first vacuum valve 25, a second vacuum valve 26, The chemical heat storage comprising the third vacuum valve 27, the vacuum pump 20 and the water tank 10, the reaction tank 30, the first vacuum valve 25, the second vacuum valve 26, the third vacuum valve 27, and the controller 2 that controls the vacuum pump 20. The exhaust heat storage air conditioning heat source system used is installed and is detachable from the exhaust heat recovery heat medium circulation system 86 and the cooling water circulation system 67 of the exhaust heat facility, and the hot water heating circulation system 87 and the cold water circulation system for air conditioning of the heat utilization facility 69, the inflow side oil coupling is connected to the heat medium oil inflow pipe, the outflow side oil coupling is connected to the heat medium oil outflow pipe, and the inlet / outlet tapping of the evaporation / condensation pipe of the water tank is detachable. Side water coupling, by comes the outflow side water coupling, made to travel between the exhaust heat Facilities heat utilization facilities, by detachable coupling, exhaust heat, is intended to efficiently utilize the cold.
In the same figure (A), a dehydration reaction is performed in order to store heat by connecting to an exhaust heat facility, and in the same figure (b), a hydration reaction is performed in order to connect to a heat utilization facility and release heat. It shows a state.

1: Cold and hot simultaneous use chemical heat storage device 2: Control unit
10: Aquarium
20: Vacuum pump
22, 23, 24: Piping 25, 26, 27: Vacuum valve 30: Reaction tank 31: Reaction layer body 32, 33: Vacuum flange lid 34: Steam pipe 35: Heat transfer oil inflow pipe 35 ': Heat transfer oil discharge pipe 36: Vacuum joint 38: Pressure gauge 40: Heat exchanger 41: Heat exchanger body 42: Heat exchanger bottom plate 43: Heat exchanger cover plate 44: Heat distribution fin 45: Hydrated material
46: Adsorbent 47: Heat storage material 48: Heat transfer oil pipe 49: Steam pipe 50, 50 ': Heat transfer oil header

Claims (11)

A granular heat storage material that dissipates heat by a hydration reaction and stores heat by a dehydration reaction by heating,
A heat transfer oil pipe that branches into and merges with a plurality of inlet headers and outlet headers so as to circulate heat transfer oil that heats the heat storage material and receives heat generated from the heat storage material;
A plurality of steam pipes that provide water vapor necessary for the hydration reaction of the heat storage material and have a large number of openings on the side surface that receives the water vapor extracted by the dehydration reaction of the heat storage material;
Fins fixed to the outer side surfaces of the heat transfer oil pipe and the steam pipe so as to be in contact with the direction perpendicular to the axis of the pipe, and the inside of the plurality of steam pipes communicate with the outside on the side surface A gas-liquid heat exchange coil-shaped heat exchanger to be fixed;
A heat exchanger lid that respectively closes an upper surface and a lower surface in a direction orthogonal to the fins of the heat exchanger;
After closing the heat exchange lid at the bottom, the heat storage material is filled between the fin gaps of the heat exchanger, and the heat exchanger closed by the upper heat exchange lid is built in. An end of the water vapor introduction pipe is positioned on the opposite side cover, and a reaction tank is provided for inserting the heat exchanger into one of the two side covers,
Furthermore, a water tank provided with an evaporation / condensation tube for heating the water stored therein and circulating a heat transfer water for cooling and condensing the water vapor generated in the heat exchanger;
In order to make the heat storage material react in an environment at a pressure lower than atmospheric pressure, a vacuum pump that eliminates air in the reaction tank and the water tank and makes the internal pressure lower than atmospheric pressure;
A heat medium oil inflow pipe for passing the heat medium oil through the reaction tank side wall and connected to the heat medium oil pipe of the heat exchanger via an inlet header, and a heat medium oil pipe connected to the heat medium oil pipe via an outlet header A heated heat oil discharge pipe,
An external steam pipe connecting the reaction tank and the water tank;
A vacuum pulling pipe for connecting the connecting portion of the external water vapor pipe and the vacuum pump;
A first vacuum valve provided in the external steam pipe on the water tank side as viewed from the connection part of the external steam pipe, and a second vacuum provided in the external steam pipe on the reaction tank side as viewed from the connection part of the external steam pipe A valve and a third vacuum valve provided in the vacuuming pipe;
With
The evaporation / condensation pipe of the water tank includes a cooling water circulation system that circulates cooling water using a cooling water pump to a cooling tower that exchanges heat with the atmosphere, and a chilled water circulation system that circulates cooling water using a cooling water pump to a cooling coil of an air conditioner. Switch to connect
The heat medium oil inflow pipe and the heat medium oil outflow pipe are connected by switching between a hot water circulation system for air conditioning and an exhaust heat recovery heat medium circulation system via a facility-side heat exchanger. Waste heat storage air conditioning heat source system using chemical heat storage. A heat medium oil inflow pipe connected to the heat medium oil pipe via an inlet header and allowing the heat medium oil to flow in is divided through an inflow side oil coupling,
Dividing the heat transfer oil discharge pipe connected to the heat transfer oil pipe via an outlet header via an outflow oil coupling;
After attaching an inflow side water coupling and an outflow side water coupling to the inlet / outlet tapping of the evaporation / condensation tube of the water tank, respectively, and enabling connection with an external flexible tube with a phase coupling,
The reaction tank, the water tank, and the vacuum pump;
An external steam pipe connecting the reaction tank and the water tank;
A vacuum pulling pipe for connecting the connecting portion of the external water vapor pipe and the vacuum pump;
A first vacuum valve provided in the external steam pipe on the water tank side as viewed from the connection part of the external steam pipe, and a second vacuum provided in the external steam pipe on the reaction tank side as viewed from the connection part of the external steam pipe A valve and a third vacuum valve provided in the vacuuming pipe;
A heat transfer oil inflow pipe from the inlet header of the heat transfer oil pipe to the inflow side oil coupling;
Heat medium oil outflow pipe from the outlet header of the heat medium oil pipe to the outflow side oil coupling,
On a movable base,
If you move to a waste heat facility,
The cooling water circulation system is connected to the evaporation / condensation pipe of the water tank via an inflow-side water coupling and an outflow-side water coupling, and the heating medium oil inflow pipe and the heating medium oil outflow pipe, through the inlet-side oil coupling and the outlet-side oil coupling connected to the thermal oil outlet pipe of the heat transfer oil inflow pipe of the facility and the facility by circulating oil to the facility-side heat exchanger, the facility heat Connected to the exhaust heat recovery heat medium circulation system through an exchanger,
If you move to a heat utilization facility,
The cold water circulation system is connected to the evaporation / condensation tube of the water tank via an inflow-side water coupling and an outflow-side water coupling, and to the heat-medium oil inflow tube and the heat-medium oil outflow tube, through the inlet-side oil coupling and the outlet-side oil coupling connected to the thermal oil outlet pipe of the heat transfer oil inflow pipe of the facility and the facility by circulating oil to the facility-side heat exchanger, the facility heat The exhaust heat storage air conditioning heat source system using chemical heat storage according to claim 1, wherein the exhaust heat storage air conditioning heat source system is connected to the hot water circulation system for air conditioning via an exchanger. The granular heat storage material that dissipates heat by the hydration reaction and stores heat by a dehydration reaction by heating is calcium chloride,
Filling the water tank with a predetermined amount of water,
After opening the third vacuum valve and the second vacuum valve, the vacuum pump is operated to reduce the internal pressure of the reaction tank to 2-50 Pa, then the second vacuum valve is closed and the first vacuum valve is opened to suck the vacuum pump. After deaeration operation to stop the vacuum pump after setting the water tank internal pressure to 1 to 3 kPa of the saturated water vapor pressure of the water temperature,
Connect the cold water circulation system to the evaporation / condensation pipe of the water tank to connect cold heat, and connect the hot water circulation system for air conditioning to the heat medium oil inflow pipe and the heat medium oil outflow pipe via a facility-side heat exchanger. Then, heat is taken out simultaneously as a heat source by hydration reaction,
Thereafter, the cooling water circulation system is connected to the evaporation / condensation tube of the water tank to dissipate heat of condensation in the water tank, and a facility-side heat exchanger is connected to the heat medium oil inflow pipe and the heat medium oil outflow pipe. Through the exhaust heat recovery heat medium circulation system through the exhaust heat of 200 ℃ or less, to store heat by dehydration reaction,
The exhaust heat storage air-conditioning heat source system using chemical heat storage according to claim 1, wherein this can be repeated. The granular heat storage material that dissipates heat by the hydration reaction and stores heat by the dehydration reaction by heating is calcium bromide,
Filling the water tank with a predetermined amount of water,
After opening the third vacuum valve and the second vacuum valve, the vacuum pump is operated to reduce the internal pressure of the reaction tank to 2-50 Pa, then the second vacuum valve is closed and the first vacuum valve is opened to suck the vacuum pump. After deaeration operation to stop the vacuum pump after setting the water tank internal pressure to 1 to 3 kPa of the saturated water vapor pressure of the water temperature,
Connect the cold water circulation system to the evaporation / condensation pipe of the water tank to connect cold heat, and connect the hot water circulation system for air conditioning to the heat medium oil inflow pipe and the heat medium oil outflow pipe via a facility-side heat exchanger. Then, heat is taken out simultaneously as a heat source by hydration reaction,
Thereafter, the cooling water circulation system is connected to the evaporation / condensation tube of the water tank to dissipate heat of condensation in the water tank, and a facility-side heat exchanger is connected to the heat medium oil inflow pipe and the heat medium oil outflow pipe. Through the exhaust heat recovery heat medium circulation system through the exhaust heat of 200 ℃ or less, to store heat by dehydration reaction,
The exhaust heat storage air-conditioning heat source system using chemical heat storage according to claim 1, wherein this can be repeated. Before SL thermal oil inflow pipe, flows heat transfer oil thermometer to measure the temperature of the heat transfer oil that flows in the heat transfer oil discharging pipe, exhaust heat transfer oil to measure the temperature of the thermal oil discharged A thermometer,
When the exhaust heat medium oil temperature measured by the exhaust heat medium oil thermometer falls below the set exhaust heat medium oil temperature obtained by adding a predetermined difference to the predetermined inflow heat medium oil temperature during the hydration reaction,
Judging that the heat storage material in the reaction tank has finished the hydration reaction at a predetermined rate,
The chemical heat storage according to claim 1, further comprising: a control unit that controls the first vacuum valve and the second vacuum valve to open and close to finish taking out cold and hot heat. Used exhaust heat storage air conditioning heat source system. A reaction vessel pressure gauge for measuring the internal pressure of the reaction vessel,
An inflow heat medium water thermometer that measures the temperature of the heat medium water that flows into the evaporation / condensation pipe, and an exhaust heat medium water thermometer that measures the temperature of the heat medium water that is discharged,
The water tank is equipped with a water level meter for measuring the water level of water stored therein, and a water tank pressure gauge for measuring the internal pressure,
During heat storage operation,
When the pressure value of the reaction tank pressure gauge becomes larger than the pressure value of the water tank pressure gauge by operating the first vacuum valve and the second vacuum valve from closed to open, the dehydration reaction is started,
When the water level measurement value of the water level gauge reaches a predetermined amount, the first vacuum valve and the second vacuum valve are operated from open to closed to control the heat storage operation to be completed. The exhaust heat storage air-conditioning heat source system using chemical heat storage according to claim 1. After the deaeration operation,
When cooling and hot heat are taken out simultaneously by the hydration reaction, and when switching to each operation of storing heat by dehydration reaction using exhaust heat of 200 ° C or less, the reaction tank pressure gauge shows a measured value higher than the leak set pressure. The exhaust heat storage air-conditioning system using chemical heat storage according to claim 4, wherein the exhaust heat storage air conditioning system uses chemical heat storage according to claim 4. Heat source system. The chemical heat storage according to any one of claims 1 to 5, wherein the heat storage material filled in the heat exchanger is a mixture of a hydrated material and an adsorbent. Waste heat storage air conditioning heat source system. The hydrated material of the heat storage material and the adsorbent are mixed at a mixing ratio based on the following formula (a), and the chemical heat storage according to any one of claims 1 to 6 is used. Waste heat storage air conditioning heat source system.

In the formula, _ad is the unit heat storage amount of the adsorbent, h _hy is the unit heat storage amount of the hydrated material, α is the mixing ratio of the hydrated material, t _re is the reaction time, t _av is the time to avoid deliquescence, h _g Indicates the unit calorific value additionally obtained from the adsorbent.   The diameter of the steam pipe and the heat transfer oil pipe provided in the heat exchanger is 16 mm to 22 mm, and the distance between the center of the steam pipe and the center of the heat transfer oil pipe is 40 mm to 60 mm. Item 8. A waste heat storage air-conditioning heat source system using the chemical heat storage according to any one of Items 7.   The chemical heat storage according to any one of claims 1 to 8, wherein a diameter of particles of the hydrated material and the adsorbent constituting the heat storage material is 0.7 mm to 2.5 mm. Waste heat storage air conditioning heat source system.

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