JP6540267B2 - Reactor and heat storage system - Google Patents

Description

  The present invention relates to a reactor and a heat storage system for effectively utilizing the generated heat.

  Conventionally, a reactor filled with alkaline earth metal oxide, a water tank for storing water, a water supply pipe for supplying water of the water tank to the reactor, and a reflux pipe for returning the water tank to the water tank A closed cycle, a water supply / supply means for controlling water supply / discharge to the reactor, a heating means for thermally decomposing the alkaline earth metal hydroxide in the reactor and regenerating it into an alkaline earth metal oxide, and the above A reaction control means is provided for controlling the water supply means and controlling the reversible reaction of the alkaline earth metal oxide with water, and utilizing the heat generated in association with the hydration reaction of the alkaline earth metal oxide. A chemical heating device is known (Patent Document 1).

  In this chemical heating device, since the alkaline earth metal oxide is stacked and filled in the form of a flat plate in the reactor, the filling rate is improved, and the reactor can be miniaturized. Further, since the heat resistant porous member is packed in the space between the lamination layers and in the direction parallel to the lamination direction, the water flow path can be secured for a long time, the area around water becomes better, and the reaction speed becomes faster. The reversibility of the reaction is also improved.

JP-A-7-180539

  In the technique described in the above-mentioned Patent Document 1, the water flowing through the porous space of the heat resistant porous member flows into the inside of the reactor and at the same time comes into contact with the calcium oxide molded body, so hydration immediately near the supply port is caused. A reaction occurs, and a part of the supplied water is vaporized to water vapor along with the heat of reaction. This vaporized water vapor inhibits the penetration of water into the interior, making it difficult to achieve uniform water supply to the entire calcium oxide compact. That is, in the prior art using a heat resistant porous member, the ability to generate water vapor is low.

  The present invention was made to solve the above problems, and it is an object of the present invention to provide a reactor and a chemical heat storage system which can suppress interference between chemical change and phase change and obtain high reaction rate and heat release rate. Is the purpose.

  The reactor according to the present invention performs desorption reaction or chemical reaction of a substance by heat supply to store heat, and a heat storage material that releases heat by adsorption reaction or chemical reaction of the substance, and liquid film evaporation of the supplied substance is possible. A heat exchange surface, a heat exchangeable partition wall provided between the heat storage material and the heat transfer surface, and for forming a heat conduction path, and the substance evaporated from the heat transmission surface And a mass transfer path different from the heat transfer path for transferring to the heat storage material.

  In the reactor according to the present invention, the heat storage material of the reactor receives the heat supplied from the heat source to store heat while causing the desorption reaction or the chemical reaction of the substance. When the heat stored in the heat storage material is released, the substance is supplied to the reactor to cause an adsorption reaction or a chemical reaction of the material of the heat storage material, and the heat stored in the heat storage material is released.

  Then, the heat released from the heat storage material is transferred to the heat transfer surface through the heat conduction path formed by the heat exchange partition, and the liquid film evaporation of the supplied material occurs on the heat transfer surface. The material evaporated from the heat transfer surface moves to the heat storage material through the mass transfer path, and the material is supplied to the reactor, so that the adsorption reaction or chemical reaction of the material of the heat storage material further occurs and the heat storage material The stored heat is released.

  As described above, since the heat transfer path and the mass transfer path act as a self-recirculating pressure rising mechanism, interference between the chemical change and the phase change can be suppressed, and a high reaction rate and heat release rate can be obtained.

  In the reactor according to the present invention, the thermal resistance of the heat conduction path may be set so as to obtain a relative vapor pressure equal to or higher than a predetermined relative vapor pressure when a weight change of the heat storage material occurs. it can. As a result, it is possible to act stably as a self-circulating pressure boosting mechanism.

  Further, the reactor according to the present invention includes a substance supply path for supplying the substance evaporated from the heat transfer surface to the outside, and a pressure measurement unit for measuring the pressure of the substance evaporated from the heat transfer surface. According to another aspect of the present invention, the apparatus may further include: a control unit provided in the substance supply path, which controls a valve for switching the supply of the substance, in accordance with the pressure measured by the pressure measurement unit. Thereby, high pressure steam can be supplied to the outside.

  The heat storage system according to the present invention is a heat storage material that releases heat by adsorption reaction or chemical reaction of the above-described reactor and the substance supplied by the reactor, and is more than the heat storage material of the reactor. And a high temperature reactor including a heat storage material having a high equilibrium temperature. Thereby, high temperature reaction heat can be obtained.

  Further, the heat storage system described above condenses the substance supplied by the desorption reaction or chemical reaction of the heat storage material of the reactor, and the substance supplied by the desorption reaction or chemical reaction of the heat storage material of the high temperature reactor. The heat storage material of the high temperature reactor causes desorption reaction or chemical reaction by heat supply from a heat source, and the heat storage material of the reactor causes desorption reaction or chemical reaction by heat supply from the high temperature reactor. can do. Thereby, the supplied heat can be recovered and used effectively.

  Further, the above-described reactor is provided in a pressure measurement unit that measures the pressure of the substance evaporated from the heat transfer surface, a temperature measurement unit that measures the temperature of the heat storage material, and the heat exchange partition wall. A medium flow path for flowing a medium as a heat exchangeable refrigerant, and when the pressure measured by the pressure measuring unit exceeds a target pressure, the temperature is measured according to the temperature measured by the temperature measuring unit. And a controller configured to control the flow rate of the medium flowing through the medium flow path. Thereby, the relative vapor pressure can be controlled while maintaining the balance between the amount of steam generation from the heat transfer surface and the amount of steam consumption due to the adsorption reaction or chemical reaction of the heat storage material, and the adsorption reaction can be maintained. .

  The above-mentioned reactor is a liquid film evaporation of the substance supplied by heat exchange between the heat medium medium flow path for flowing the medium as the heat exchangeable heat medium and the medium of the heat medium medium flow path. The heat storage material further includes a heat transfer surface for start-up that can be used, and a control unit that controls the medium to flow in the heat medium medium flow path when starting up, and when the heat storage material is started, Heat can be released by adsorption reaction or chemical reaction of the substance supplied from the heat transfer surface for starting. As a result, steam can be supplied at startup using an external heat medium.

  The heat transfer surface may be formed such that the diffusion rate of the substance is higher than the reaction rate of the heat storage material. Thereby, reaction nonuniformity of the heat transfer surface can be suppressed.

  As described above, the reactor and the chemical heat storage system according to the present invention act as a self-circulating pressure rising mechanism by the heat conduction path and the mass transfer path, thereby suppressing the interference between the chemical change and the phase change, It has the excellent effect that high reaction rate and heat release rate can be obtained.

It is a perspective view showing composition of a steam generator concerning a 1st embodiment of the present invention. It is a side view sectional view showing the composition of a steam generator. It is a figure for demonstrating in-plane temperature distribution of a heat-transfer surface. It is a figure which shows the thin tube group model which modeled the heat transfer surface. It is a graph which shows the liquid diffusion rate to a contact angle. It is a graph which shows the liquid diffusion rate to the porosity. It is a figure for demonstrating a hydration reaction position. It is a graph for demonstrating the relative vapor pressure which a thermal storage material weight change becomes remarkable. It is a figure for demonstrating the relative vapor pressure which a thermal storage material weight change becomes remarkable. It is a figure showing the composition of the steam generator concerning a 3rd embodiment of the present invention. It is a figure showing control composition of a steam generator concerning a 3rd embodiment of the present invention. It is a figure which shows the flow of the vapor | steam in the steam generator concerning the 3rd Embodiment of this invention. It is a figure which shows the steam generation processing routine performed by thermal storage ECU of the steam generator which concerns on the 3rd Embodiment of this invention. It is a figure for demonstrating the heat feeder in driving | operation * thermal storage mode. It is a figure for demonstrating the heat supply device in start / warm air mode. It is a figure for demonstrating the chemical reaction in a reactor and a high temperature reactor in start-up / warm air mode. It is a figure for demonstrating the chemical reaction in the reactor in a driving | operation * thermal storage mode, and a high temperature reactor. It is a side view sectional view showing the composition of the heat exchanger concerning a 5th embodiment of the present invention. It is a figure which shows the structure of the heat supply device which concerns on the 5th Embodiment of this invention. It is a figure which shows the heat supply processing routine performed by heat storage ECU of the heat feeder which concerns on the 5th Embodiment of this invention. It is a side view sectional view showing the composition of the heat exchanger concerning a 6th embodiment of the present invention. It is a figure which shows the structure of the heat feeder which concerns on the 6th Embodiment of this invention. It is a figure which shows the heat supply processing routine performed by heat storage ECU of the heat feeder which concerns on the 6th Embodiment of this invention.

First Embodiment
A steam generator 10 according to a first embodiment of the present invention will be described based on FIGS. 1 to 6.

  A perspective view of the steam generator 10 is shown in FIG. 1 and a cross-sectional view of the steam generator 10 is shown in FIG. As shown in this figure, the steam generator 10 is a heat transfer auxiliary material (carbon fiber, sintered copper, graphite carbon, etc.) which is highly thermally conductive to a chemical heat storage material in a container 12 made of a metal material such as stainless steel. And a reactor 16 provided with a heat storage material molded body 14 obtained by mixing them. The chemical thermal storage material contained in the thermal storage material molded body 14 is configured to store heat (heat absorption) with dehydration and release heat (heat generation) with hydration (restoration to calcium hydroxide).

In this embodiment, calcium hydroxide (Ca (OH) ₂ ), which is one of alkaline earth metal hydroxides, is employed as the chemical heat storage material. Therefore, the heat storage material molded body 14 in the reactor 16 is configured to be capable of reversibly repeating heat storage and heat release by the reaction shown below.

Ca (OH) ₂ ⇔ CaO + H ₂ O

  When the heat storage amount and the calorific value Q are shown together with this equation, it is represented by the following equation.

Ca (OH) ₂ + Q → CaO + H ₂ O
CaO + H ₂ O → Ca (OH) ₂ + Q

  In the reactor 16, a heat transfer surface 18 capable of evaporating a liquid film of water supplied from the water supply port 17 is provided. The heat transfer surface 18 is a structured heat transfer surface in which a porous body is formed on the surface, and a hydrophilic treatment using an inorganic slurry colloidal solution is applied to the surface. Although the case where the porous body is formed on the surface of the heat transfer surface 18 has been described as an example, etching, fins or the like may be formed on the surface.

  Further, in the reactor 16, a heat exchange partition wall 20 capable of heat exchange is provided between the heat storage material molded body 14 and the heat transfer surface 18 to form a heat conduction path.

  Further, in the reactor 16, a mass transfer path 22 different from the heat transfer path for transferring the water vapor evaporated from the heat transfer surface 18 to the heat storage material molded body 14 is provided.

  The container 12 is provided with an initial steam inlet 24 for supplying initial steam to the heat storage material molded body 14, and a steam supply path 26 for supplying water vapor evaporated from the heat transfer surface 18 to the outside.

  Here, the principle in which the reactor 16 in the present embodiment supplies water vapor as a self-circulating pressure raising mechanism will be described.

The reactor 16 is a heat storage material molded body 14 in which a heat conduction material of high thermal conductivity (carbon fiber, sintered copper, graphite carbon, etc.) is mixed with a heat storage material of hydration reaction system (CaO / Ca (OH) ₂ ) The heat exchange partition wall 20 is provided between the heat transfer surface 18 capable of evaporating the liquid film, and a circulation path connecting the heat conduction path and the mass transfer path is formed, thereby generating the chemical reaction of the heat storage material and the adsorption reaction. The heat Qc [W] is transferred to the evaporation interface through the heat exchange partition wall 20 and the heat transfer surface 18. As a result, the difference Qc-Qe [W] between the exothermic Qc [W] and the latent heat of vaporization Qe [W] due to a chemical reaction is consumed in the rise of the sensible heat of the reactor 16 and the reaction medium, and the vapor temperature and vapor pressure are increased. be able to. On the other hand, by supplying the vapor generated from the evaporation interface to the heat storage material molded body 14 through the mass transfer path 22, it becomes possible to have the heat transfer path and the mass transfer path 22 independently. While this prevents the performance deterioration of the heat storage material that tends to deliquesce due to the reaction medium (liquid), and enables uniform in-plane supply of reaction medium vapor in the thickness direction of the heat storage material, the evaporation field due to the formation of a liquid film of uniform thickness The reaction temperature controllability is improved by the expansion of the area and the in-plane uniformity of latent heat cooling, etc. While suppressing the mutual interference between the chemical reaction and the phase change phenomenon, the calorific difference ΔQ (= Qc-Qe) By utilizing it for the sensible heat increase, steam pressure can be increased, and high pressure steam can be supplied from the steam supply path 26.

  Next, the principle of suppressing the reaction nonuniformity by the generation of the in-plane temperature distribution of the heat transfer surface 18 will be described.

  As shown in FIG. 3, by adjusting the material thermal conductivity, mixing ratio, orientation, and thickness of the heat conduction aid to be mixed with the heat storage material, and making the heat storage material molded body 14 of high density, the thickness direction of the heat storage material Control of the thermal resistance of the On the other hand, the heat transfer surface 18 can be formed as a liquid film which can be evaporated by coating an inorganic hydrophilic material on a structured heat transfer surface composed of a porous body, etching, fins, etc. by a slurry, sol gel or colloidal solution method. The thermal resistance of the evaporation heat transfer surface in the thickness direction can be controlled by adjusting the porosity of the heat transfer surface, the material thermal conductivity, and the thickness of the structure. Thereby, the temperature difference between the heat storage material reaction temperature and the evaporation interface temperature can be set independently of the movement of the substance (reaction medium).

The heat flux q _w passing through the heat exchange partition wall 20 is determined by the reaction rate of the heat storage material and the vapor diffusion rate determined by the density, thickness and vapor diffusion pore size setting of the heat storage material molded body 14. On the other hand, the liquid diffusion rate to the heat transfer surface 18 is determined by the structure void diameter, the contact angle of the solid-liquid interface, and the gravity, and the extremely high diffusion rate is obtained by the hydrophilization treatment (reduction of the contact angle). For this reason, it is possible to control the liquid diffusion rate independently of heat transfer (heat conduction), and by setting the liquid diffusion rate to be larger than the reaction rate, the reaction non-uniformity due to the generation of the in-plane temperature distribution is realized. It can be suppressed.

Further, FIG. 4 shows a thin tube group model (normal temperature, non-evaporation) in which the heat transfer surface 18 is modeled. Assuming the kinematic viscosity coefficient [[m ² / s], surface tension T [N / m] and density ρ [kg / m ³ ], the following equation consisting of inertia term, viscosity term, gravity and capillary force term is obtained .

  From analysis by the above-mentioned capillary group model (normal temperature, non-evaporation), contact angle α (wettability improvement by hydrophilic treatment), gravity utilization (the reaction liquid is supplied from the vertical upper part, gravity and capillary force are used), void diameter The liquid diffusion rate can be controlled by the size (see FIGS. 5 and 6), and the liquid diffusion rate can be set larger than the reaction rate. For example, the hydrophilization treatment can reduce the contact angle α and increase the diffusion rate. This is because the decrease in the contact angle α increases the capillary force term B. In addition, compared with the case where the reaction solution is supplied from the lower side, when the reaction solution is supplied from the upper side, the liquid diffusion rate can be increased by utilizing gravity. In addition, when the reaction solution is supplied from the top, the diffusion speed can be improved by setting the pore size to a large pore (d = 0.5 mm).

  Next, the operation of the first embodiment will be described.

  First, when the initial steam is supplied from the initial steam inlet 24, heat is generated by the hydration reaction of the heat storage material molded body 14, and the generated heat is transmitted to the evaporation interface through the heat exchange partition wall 20 and the heat transfer surface 18. . At this time, the water supplied from the water supply port 17 is evaporated at the evaporation interface of the heat transfer surface 18, and the water vapor is supplied.

  The water vapor supplied from the heat transfer surface 18 is transferred to the heat storage material molded body 14 along the mass transfer path 22 and generates heat due to the hydration reaction of the heat storage material molded body 14.

  Thus, the heat supplied from the heat transfer surface 18 is gradually boosted by the circulation of the heat moving in the heat transfer path formed by the heat exchange partition 20 and the water vapor moving in the mass transfer path 22. The pressurized steam is supplied to the outside by the steam supply path 26.

  Then, when the heat storage material molded body 14 is regenerated, heat is supplied to the heat storage material molded body 14 from the outside, and the heat storage material molded body 14 performs a desorption reaction of water to store heat. The water generated by the desorption reaction of the heat storage material molded body 14 may be recovered by a recovery mechanism.

  As described above, according to the steam generator according to the first embodiment, since the heat transfer path and the mass transfer path are provided independently to act as a self-circulating pressure boosting mechanism, chemical change and phase change are realized. The interference between them can be suppressed, and a high reaction rate and heat release rate can be obtained.

  Moreover, reaction nonuniformity of the heat transfer surface can be suppressed by setting the liquid diffusion rate of the heat transfer surface to be larger than the reaction speed.

Second Embodiment
A steam generator 10 according to a second embodiment of the present invention will be described. In addition, since it becomes the structure similar to 1st Embodiment, the steam generator 10 which concerns on 2nd Embodiment attaches | subjects the same code | symbol, and abbreviate | omits description.

  Here, the principle of controlling the relative vapor pressure by setting of the thermal resistance in the heat transfer path in the present embodiment will be described.

The heat of chemical reaction of the heat storage material is transported to the gas-liquid evaporation interface of the heat transfer surface 18 via the heat conduction of the heat storage material molded body 14, the heat exchange partition wall 20, and the heat transfer surface 18. Here, when the steam passage resistance of the heat storage material molded body 14 is sufficiently small compared to the steam diffusion resistance inside the heat storage material, the hydration reaction proceeds from the interface of the steam passage and the heat storage material, and the reaction distribution is uniform in the thickness direction It becomes. For this reason, as shown in FIG. 7, the reaction vapor is diffused from the heat storage material interface at the hydration reaction position z (τ) expressed by the following equation, and the reaction from the hydration reaction position to the heat exchange partition wall 20 is a reaction The heat is conducted to the heat exchange partition wall 20 at a heat flux q _w [W / m ² ].

z (τ) = δ _s · X (τ)

However, τ [s] is time, δ _s [m] is the thickness of the heat storage material molded body 14, and X (τ) [m] is the hydration reaction rate.

On the other hand, at the heat transfer surface 18, the evaporation interface is formed at the interface between the heat transfer surface 18 and the mass transfer path 22 by the high liquid diffusion rate by the hydrophilic treatment, and the apparent thermal conductivity to the evaporation interface is the structure thermal conductivity The combined thermal conductivity λ _comp [W / m / K] of the thermal conductivity λ _liq [W / m / K] of λ _metal [W / m / K] is obtained.

For this reason, the relative vapor pressure R _p is expressed by the following equation: physical properties of the material (thermal conductivity λ _s of the heat storage material molded body 14, thermal conductivity λ _metal of the heat transfer surface 18, air gap of the heat transfer surface 18 It is possible to set from the ratio ε [-] and the shape specification (the thickness δ _s of the heat storage material molded body 14, the thickness δ _e [m] of the heat transfer surface 18, the thickness δ _w [m] of the heat exchange partition 20) .

However, P _e [kPa] is the vapor pressure, P _s [kPa] is the vapor pressure at the heat storage material temperature, P (T) [kPa] is the saturated vapor pressure at temperature T, ΔP ₁ [kPa] Is the pressure drop of the mass transfer path 22, and ΔP ₁ [kPa] is the pressure drop from the surface of the heat storage material molded body 14 to the hydration reaction position. ΔT [K] is the temperature difference between the hydration reaction position and the evaporation interface, and T _s [K] is the heat storage material temperature.

On the other hand, the relative vapor pressure _{RP, T} at which the heat storage material weight change becomes remarkable due to hydration / dehydration differs depending on the heat storage material (see FIGS. 8 and 9).

Therefore, by setting the thermal resistance of the heat transfer path, the relative vapor pressure R _P can be made continuous by setting it to the relative vapor pressure R _{P, T} (eg, 0.45 to 0.55) that can cause hydration reaction. Steam pressure can be generated. The reaction temperature is too high below the relative vapor pressure R _{P, T} , and the hydration reaction stops.

As described above, in the reactor 16 of the steam generator 10 according to the second embodiment, the relative vapor pressure R _{P, T} or more relative to the predetermined relative vapor pressure when the weight change of the heat storage material molded body 14 occurs In order to obtain the pressure R _P , the physical properties of the material (thermal conductivity λ _s of the heat storage material molded body 14, thermal conductivity λ _metal of the heat transfer surface 18, void ratio ε [−] of the heat transfer surface 18) The thermal resistance of the heat conduction path is set from the elements (thickness δ _s of the heat storage material molded body 14, thickness δ _e [m] of the heat transfer surface 18, and thickness δ _w [m] of the heat exchange partition 20).

  Next, the operation of the second embodiment will be described.

  First, when the initial steam is supplied from the initial steam inlet 24, heat is generated by the hydration reaction of the heat storage material molded body 14, and the generated heat is transmitted to the evaporation interface through the heat exchange partition wall 20 and the heat transfer surface 18. . At this time, the water supplied from the water supply port 17 is evaporated at the evaporation interface of the heat transfer surface 18, and the water vapor is supplied.

Since the relative vapor pressure R _P is equal to or higher than the relative vapor pressure R _{P, T} (eg, 0.45 to 0.55) capable of hydration reaction due to the water vapor supplied from the heat transfer surface 18, the heat storage material molded body A hydration reaction of 14 occurs and produces an exotherm.

  Thus, by circulating the heat moving in the heat transfer path formed by the heat exchange partition 20 and the steam moving in the mass transfer path 22, the steam supplied from the heat transfer surface 18 is continuously pressurized. The pressurized steam is supplied to the outside by the steam supply path 26.

As described above, according to the steam generator according to the second exemplary embodiment, the predetermined relative vapor pressure of R _{P, T} or more relative vapor pressure R _P is obtained when the weight change of the heat storage material occurs As described above, by setting the thermal resistance of the heat conduction path, it stably acts as a self-circulating pressure boosting mechanism, and steam pressure boosting is possible.

Third Embodiment
A steam generator 310 according to a third embodiment of the present invention will be described. In addition, about the part which becomes the structure similar to 1st Embodiment and 2nd Embodiment, the same code | symbol is attached | subjected and description is abbreviate | omitted.

  As shown in FIG. 10, the steam supply passage 26 of the reactor 16 of the steam generator 310 according to the third embodiment is provided with an on-off valve 320 for switching the supply of steam. In addition, the water supply port 17 is in communication with the water tank 326 via the water supply line 322. The water supply line 322 is provided with a water pump 324. The initial steam inlet 24 is also in communication with the initial steam generator 332 via a steam supply line 330. The steam supply line 330 is provided with an on-off valve 334 for switching the supply of steam.

  The steam generator 310 also includes a pressure sensor 340 that outputs a signal corresponding to the pressure of the mass transfer path 22 in the reactor 16. The pressure sensor 340 is an example of a pressure measurement unit.

  Further, as shown in FIG. 11, the steam generator 310 includes a heat storage ECU 350. The heat storage ECU 350 is electrically connected to the on-off valves 320 and 334 and the water pump 324, and controls the operation of these. The heat storage ECU 350 is an example of a control unit.

  The heat storage ECU 350 is electrically connected to the pressure sensor 340.

As shown in FIG. 12, the heat storage ECU 350 controls the on-off valve 320 to close until the pressure detected by the pressure sensor 340 reaches the target pressure P _target to pressurize the steam. When the pressure detected by the pressure sensor 340 reaches the target pressure P _target , the heat storage ECU 350 controls the open / close valve 320 to open to connect the steam supply path 26 to supply high pressure steam to the outside. .

  Here, the principle of generating high-pressure steam in the third embodiment will be described.

In order to raise the temperature of the heat storage material, the initial hydration reaction is started by the supply of initial start steam, and the heat from the heat storage material to the evaporation interface is set such that relative vapor pressure R _P ≧ R _{P, T} by the supply of reaction water. Vapor generation from the gas-liquid interface is performed by conduction (temperature difference ΔT). After the heat storage material temperature rise and internal steam pressure increase by steam self-circulation, the internal steam pressure reaches P _target and at the same time the steam supply side on-off valve 320 is opened to supply high pressure steam. As a result, it is possible to generate high-pressure steam with low input energy from the outside (the latent heat of vaporization required for the initial hydration reaction, electric heater heating, etc.).

  Next, the operation of the third embodiment will be described.

  Control of the heat storage ECU 350 will be described with reference to a steam generation processing routine shown in FIG. When the start of operation of the steam generator 310 is instructed, the heat storage ECU 350 executes a steam generation processing routine.

  First, in step 100, the initial steam generator 332 is operated for a predetermined time, and the on-off valve 334 is opened. Thereby, steam is supplied from the initial steam generator 332 to the heat storage material molded body 14 in the reactor 16 through the steam supply line 330 and the initial steam inlet 24. In the heat storage material molded body 14, a hydration reaction is started, and the heat is released along with the hydration reaction. This heat is transferred to the heat transfer surface 18 through the heat exchange partition wall 20.

  Then, in step 102, the water pump 324 is operated. Thus, water is supplied from the water tank 326 to the heat transfer surface 18 through the water supply line 322 and the water supply port 17.

At this time, the temperature T _s of the heat storage material molded body 14 is raised by the hydration reaction, the heat storage material molded body 14 to heat transfer surfaces 18, heat conduction occurs at a temperature difference [Delta] T. And

Since the relative vapor pressure R _P becomes higher than the relative vapor pressure R _{P, T} capable of hydration reaction by the water vapor P _e = P (T _s + ΔT) −ΔP ₁ supplied from the heat transfer surface 18, the heat storage material The hydration reaction of the molded body 14 further occurs to generate heat, and the water vapor supplied from the heat transfer surface 18 is pressurized.

In the next step 104, it is determined whether the pressure detected by the pressure sensor 340 exceeds the target pressure P _target . When the detected pressure is equal to or less than the target pressure P _target , the on-off valve 320 is kept closed, and the heat moving in the heat transfer path formed by the heat exchange partition 20 and the mass transfer path 22 are moved. Continue self-circulation with water vapor.

On the other hand, if the detected pressure exceeds the target pressure P _target , the process proceeds to step 106, the on-off valve 320 is opened, and the pressurized steam is supplied to the outside through the steam supply path 26.

  As explained above, according to the steam generator concerning a 3rd embodiment, high-pressure steam can be supplied outside so that desired steam pressure may be obtained.

Fourth Embodiment
A heat supply device 410 according to a fourth embodiment of the present invention will be described. In addition, about the part which becomes the structure similar to 1st Embodiment-3rd Embodiment, the same code | symbol is attached | subjected and description is abbreviate | omitted.

  As shown in FIG. 14, the heat supplier 410 according to the fourth embodiment further includes a high temperature reactor 416 and a condenser 430, and the reactor 16, the high temperature reactor 416, and the condenser 430 are steams. It is in communication via the supply path 26. The steam supply path 26 is provided with on-off valves 421 and 422 for switching the supply of steam. The heat supplier 410 is an example of a heat storage system.

In the thermal storage material molded body 14 of the reactor 16, for example, M · xH ₂ O is used as a chemical thermal storage material.

The high temperature reactor 416 mixes a high thermal conductivity heat conduction aid (carbon fiber, sintered copper, graphite carbon, etc.) with a chemical heat storage material (for example, calcium hydroxide (Ca (OH) ₂ )) in a container 412. Two heat storage material molded bodies 414 are provided, and further, a heat exchange partition 420 capable of exchanging heat between the two heat storage material molded bodies 414 for forming a heat conduction path is provided.

In the heat storage material molded body 414 of the high temperature reactor 416, for example, Ca (OH) ₂ is used as a chemical heat storage material having a higher equilibrium temperature than the chemical heat storage material of the heat storage material molded body 14.

  In the high temperature reactor 416, there is a mass transfer path 432 for transferring the water vapor supplied from the outside to the heat storage material molded body 414 and supplying the water vapor desorbed from the heat storage material molded body 414 to the outside. A mass transfer path 432 is provided in communication with the vapor supply path 26.

  In the heat exchange partition 20 of the reactor 16 and in the heat exchange partition 420 of the high temperature reactor 416, heat exchange channels 440 and 442 for recovering the heat (system exhaust heat etc.) necessary for dehydration of the heat storage material are provided The exhaust heat outlet (not shown) communicates with the heat exchange channel 442 of the high temperature reactor 416, and the heat exchange channel 442 of the high temperature reactor 416 communicates with the heat exchange channel 440 of the reactor 16. Thereby, the heat storage material molded body 414 of the high temperature reactor 416 is dewatered by the high temperature exhaust heat, and the heat storage material molded body 14 of the reactor 16 is dewatered by the low temperature exhaust heat discharged from the high temperature reactor 416 Thermal storage is possible.

  The principle for obtaining the heat of hydration reaction at high temperature will be described.

  A high-pressure vapor is generated by the heat storage material molded body 14, the heat exchange partition wall 20, and the reactor 16 constituted by the heat transfer surface 18 capable of evaporating a liquid film, and the chemical heat storage material having a higher reaction equilibrium temperature than the reactor 16 is mounted. By supplying steam to the high temperature reactor 416 through the steam supply passage 26, the heat of hydration reaction higher than the reaction equilibrium temperature of the reactor 16 can be obtained, and the reaction rate of the high temperature reactor 416 can be It is possible to improve (see FIGS. 15 and 16). In addition, by increasing the pressure of the vapor generated in the reactor 16, the equilibrium temperature of the high temperature reactor 416 can be shifted to the high temperature side, and a higher heat of hydration reaction can be obtained.

  Next, the principle of effectively recovering exhaust heat will be described.

  Heat exchange channels 440 and 442 for recovering heat (system exhaust heat etc.) necessary for heat storage material dehydration are provided in the high temperature reactor 416 and the reactor 16, and the exhaust heat outlet is in the heat exchange channel 442 of the high temperature reactor 416 The heat exchange flow path 442 of the high temperature reactor 416 is connected to the heat exchange flow path 440 of the reactor 16 so that the high temperature reactor 416 is dewatered by high temperature exhaust heat (for example, 650 ° C.). By dehydrating the reactor 16 by the low temperature exhaust heat (for example, 450 ° C.) discharged from the exhaust gas, it is possible to perform cascaded heat storage (see FIGS. 14 and 17). As a result, the heat discharged from the system can be effectively recovered and used from high temperature to low temperature, and system efficiency can be improved.

  Next, the operation of the fourth embodiment will be described.

  First, when the heat storage material molded body 14 or 414 is regenerated in the operation / heat storage mode, a high temperature heat medium is allowed to flow from the exhaust heat outlet to the heat exchange flow path 442 of the high temperature reactor 416. Heat is supplied to the heat storage material, and the heat storage material molded body 414 performs a desorption reaction of water to store heat. At this time, the heat storage ECU 350 controls the opening / closing valve 422 to open, and the water generated by the desorption reaction of the heat storage material molded body 414 is recovered by the condenser 430 via the steam supply path 26.

  Further, a heat medium is caused to flow from the heat exchange flow path 442 of the high temperature reactor 416 to the heat exchange flow path 440 of the reactor 16 to supply heat to the heat storage material molded body 14. To store heat. At this time, the heat storage ECU 350 controls the opening / closing valve 421 to open, and the water generated by the desorption reaction of the heat storage material molded body 14 is recovered by the condenser 430 via the steam supply path 26.

  Also, when transitioning to the start-up / warm-air mode, first, the initial steam is supplied from the initial steam inlet 24 of the reactor 16, heat is generated by the hydration reaction in the heat storage material molded body 14, and the generated heat is heat It is transmitted to the evaporation interface via the exchange bulkhead 20 and the heat transfer surface 18. At this time, the water supplied from the water supply port 17 is evaporated at the evaporation interface of the heat transfer surface 18, and the water vapor is supplied.

  The water vapor supplied from the heat transfer surface 18 is transferred to the heat storage material molded body 14 along the mass transfer path 22 and generates heat due to the hydration reaction of the heat storage material molded body 14.

  Thus, the heat supplied from the heat transfer surface 18 is gradually boosted by the circulation of the heat moving in the heat transfer path formed by the heat exchange partition 20 and the water vapor moving in the mass transfer path 22. The pressurized steam is supplied to the high temperature reactor 416 by the steam supply line 26.

  Then, the water vapor supplied to the high temperature reactor 416 moves to the heat storage material molded body 414 along the mass transfer path 432, and generates heat due to the hydration reaction in the heat storage material molded body 414. The high temperature heat thus generated is supplied to the warm air target.

  As described above, according to the heat supplier according to the fourth embodiment, exhaust heat recovery is performed by high-temperature heat storage and low-temperature heat storage, and heat from the system is effectively recovered and used from high temperature to low temperature. System efficiency can be improved.

  In addition, by supplying high pressure steam to the high temperature reactor by the low temperature reactor, high-speed heating can be performed, and high temperature reaction heat can be obtained.

Fifth Embodiment
A heat supply device 510 according to a fifth embodiment of the present invention will be described. In addition, about the part which becomes the structure similar to 1st Embodiment-4th Embodiment, the same code | symbol is attached | subjected and description is abbreviate | omitted.

  As shown in FIG. 18, the container 12 of the reactor 16 of the heat supply device 510 according to the fifth embodiment is not in communication with the steam supply path in the first to fourth embodiments. It is different from the form of

  The heat exchange partition wall 20 of the reactor 16 is provided with a medium flow passage 540 for flowing the refrigerant, and the medium flow passage 540 is in communication with the refrigerant supply device 550 via a refrigerant circulation line 552 as shown in FIG. ing. The refrigerant circulation line 552 is provided with an on-off valve 554 for switching the supply of refrigerant and adjusting the amount of supply. In addition, the water supply port 17 is in communication with the water tank 326 via the water supply line 322. The water supply line 322 is provided with a water pump 324. The initial steam inlet 24 is also in communication with the initial steam generator 332 via a steam supply line 330. The steam supply line 330 is provided with an on-off valve 334 for switching the supply of steam.

  Further, the heat supply device 510 includes a pressure sensor 340 that outputs a signal corresponding to the pressure of the mass transfer path 22 in the reactor 16 and a temperature sensor 560 that outputs a signal corresponding to the temperature of the heat storage material molded body 14. Have. The temperature sensor 560 is an example of a temperature measurement unit.

  Further, the heat supply device 510 includes a heat storage ECU 350, and the heat storage ECU 350 is electrically connected to each of the open / close valves 320, 334, 554 and the water pump 324, and controls the operation thereof. It has become.

  The heat storage ECU 350 is electrically connected to the pressure sensor 340 and the temperature sensor 560.

The heat storage ECU 350 controls the on-off valve 554 to close until the pressure detected by the pressure sensor 340 reaches the target pressure P _target to pressurize the steam. When the pressure detected by the pressure sensor 340 reaches the target pressure P _target , the heat storage ECU 350 controls the open / close valve 554 to open and causes the refrigerant to flow in the medium flow channel 540.

  Here, the principle of controlling the flow rate of the refrigerant in the fifth embodiment will be described.

By providing the medium flow path 540 in the heat exchange partition wall 20, a part of the heat obtained by the chemical reaction can be exchanged by the refrigerant. As a result, the pressure is raised to the target pressure P _target by self-steam circulation, and then heat is exchanged with the refrigerant to remove part of the heat obtained by the chemical reaction, and the amount of steam generated from the heat transfer surface 18 The temperature difference between the reaction temperature and the vapor temperature is set such that the relative vapor pressure R _P RR _{P, T} while maintaining the balance of the amount of vapor consumed in the chemical reaction (chemical reaction heat amount = heat of evaporation latent heat + medium heat release amount) Control to maintain the hydration reaction.

  Next, the operation of the fifth embodiment will be described.

  Control of the heat storage ECU 350 will be described with reference to a heat supply processing routine shown in FIG. When the start of operation of the heat supplier 510 is instructed, the heat storage ECU 350 executes a heat supply processing routine. In addition, about the process similar to 3rd Embodiment, the same code | symbol is attached | subjected and detailed description is abbreviate | omitted.

  First, in step 100, the initial steam generator 332 is operated for a predetermined time, and the on-off valve 334 is opened. Then, in step 102, the water pump 324 is operated.

In the next step 104, it is determined whether the pressure detected by the pressure sensor 340 exceeds the target pressure P _target . When the detected pressure is equal to or lower than the target pressure P _target , the on-off valve 554 is kept closed, and the heat moving in the heat transfer path formed by the heat exchange partition 20 and the mass transfer path 22 are moved. Continue self-circulation with water vapor.

On the other hand, if the detected pressure exceeds the target pressure P _target , the process proceeds to step 570, the on-off valve 554 is opened, and the refrigerant is fed from the refrigerant feeder 550 by the initial flow rate Fc via the refrigerant circulation line 552 It flows in the flow path 540.

Then, in the next step 572, the ratio | T−T _target | / T of the absolute value of the difference between the temperature T detected by the temperature sensor 560 and the heating temperature target T _target, and the heating temperature target T _target It is determined whether _target is less than a threshold (for example, 0.1). If | T−T _target | / T _target is less than the threshold (eg, 0.1), the process proceeds to step 576, while | T−T _target | / T _target is the threshold (eg, If it is 0.1 or more, in step 574, the flow rate of the refrigerant to be supplied to the medium flow channel 540 is determined according to the magnitude relationship between the temperature T detected by the temperature sensor 560 and the temperature release target T _target. The on-off valve 554 is controlled to increase or decrease by ΔFc, and the process returns to step 572.

  In step 576, it is determined whether or not the hydration reaction of the heat storage material molded body 14 is completed, and if it is determined that the hydration reaction of the heat storage material molded body 14 is not completed, the process returns to the above step 572 On the other hand, when it is determined that the hydration reaction of the heat storage material molded body 14 is completed, the heat supply processing routine is ended.

  As described above, according to the heat supplier according to the fifth embodiment, control is performed to a constant temperature by balancing heat of hydration reaction (warm heat) and latent heat of evaporation (cold heat) by heat radiation from the medium. be able to. As a result, the relative vapor pressure can be controlled while maintaining the balance between the amount of steam generation from the heat transfer surface and the amount of steam consumption due to the adsorption reaction of the heat storage material, and the adsorption reaction can be maintained.

Sixth Embodiment
A heat supply device 610 according to a sixth embodiment of the present invention will be described based on FIG. 21 and FIG. In addition, about the part which becomes the structure similar to 1st Embodiment-5th Embodiment, the same code | symbol is attached | subjected and description is abbreviate | omitted.

  As shown in FIG. 21, the point that the container 12 of the reactor 16 of the heat supplier 610 according to the sixth embodiment is not in communication with the steam supply path is that the first to fourth embodiments described above. It is different from the form of Further, two sets of the heat storage material molded body 14, the heat transfer surface 18, and the heat exchange partition wall 20 are provided in the reactor 16, and two heat transfer for initial startup between the two heat transfer surfaces 18. A surface 618 and a heat exchange bulkhead 620 for initial start are provided.

  The two heat transfer surfaces for initial start 618 are provided to face the two heat transfer surfaces 18 respectively, and the heat exchange partition 620 for initial start is provided between the two heat transfer surfaces for initial start 618 ing. The heat transfer surface for initial start 618 is a structured heat transfer surface in which a porous body, etching, fins and the like are formed on the surface, and the surface is subjected to a hydrophilic treatment using an inorganic slurry colloidal solution.

  In addition, the heat exchange partition wall 620 for starting initial stage is provided with a heat medium channel 640 for flowing the heat medium, and the heat medium channel 640 is, as shown in FIG. It communicates through 652. The heat medium circulation line 652 is provided with an on-off valve 654 for switching the supply of the heat medium.

  A water supply port 617 is provided in the heat exchange partition 620 for start-up, and the water supply port 617 is in communication with the water tank 326 via the water supply line 622. A water pump 626 is provided in the water supply line 622.

  Further, a medium flow passage 540 is provided in the heat exchange partition wall 20 of the reactor 16, and the medium flow passage 540 is in communication with the refrigerant supply device 550 via a refrigerant circulation line 552. The refrigerant circulation line 552 is provided with an on-off valve 554. In addition, the water supply port 17 is in communication with the water tank 326 via the water supply line 322. The water supply line 322 is provided with a water pump 324.

  The heat supplier 610 also includes a pressure sensor 340 and a temperature sensor 560.

  Further, the heat supply device 610 is provided with a heat storage ECU 350, and the heat storage ECU 350 is electrically connected to the on-off valves 554, 652 and the water pumps 324, 624, respectively, to control their operation. ing.

  Here, the principle of controlling the heat supply in the present embodiment will be described.

  A heat storage material molded body is provided with a heat transfer surface 618 having a hydrophilic treatment applied to the surface provided on both sides of the heat exchange partition 620 for the initial start provided with the heat medium flow path 640 capable of external heat exchange. 14, by sandwiching between self-circulating vapor pressure raising mechanism consisting of heat transfer surface 18 and heat exchange partition 20, initial steam supply by external heat source (air heat @ environmental temperature, heat mass etc) is possible It becomes. As a result, input energy due to electric heater heating and the like can be reduced, system efficiency can be improved, and continuous sequential operation from initial start up to high pressure steam generation becomes possible.

  Next, the operation of the sixth embodiment will be described.

  Control of the heat storage ECU 350 will be described with reference to a heat supply processing routine shown in FIG. When the start of operation of the heat supplier 610 is instructed, the heat storage ECU 350 executes a heat supply processing routine. In addition, about the process similar to 5th Embodiment, the same code | symbol is attached | subjected and detailed description is abbreviate | omitted.

  First, in step 700, the on-off valve 654 is opened, and the heat medium is flowed from the heat medium supply device 650 to the heat medium channel 640 via the heat medium circulation line 652. Then, in step 702, the water pump 624 is operated. Thus, water is supplied from the water tank 326 to the heat transfer surface for initial start 618 through the water supply line 622 and the water supply port 617.

In the next step 704, it is determined whether the pressure detected by the pressure sensor 340 has exceeded the target pressure P1 _target at the start of startup. If the detected pressure is less than or equal to the target pressure P1 _{target at} the start of startup, the heat medium and water are kept supplied. On the other hand, if the detected pressure is higher than the target pressure P1 _{target at} the start of startup, in step 706, the on-off valve 654 is closed to stop the supply of the heat medium from the heat medium supplier 650. Then, in step 708, the operation of the water pump 624 is stopped, and the water supply to the heat transfer surface for initial start 618 is stopped.

  When the start-up initial steam generation sequence is completed by the above-described steps 700 to 708, the high-pressure steam generation sequence of steps 102 to 576 is executed.

  At step 102, the water pump 324 is operated.

In the next step 104, it is determined whether the pressure detected by the pressure sensor 340 has exceeded the target pressure P2 _target for steam pressure increase. When the detected pressure is equal to or lower than the target pressure P2 _{target for} steam pressure, the on-off valve 554 is kept closed, and the heat transferred through the heat transfer path formed by the heat exchange partition 20 and the mass transfer path 22 Continue self-circulation with moving steam.

On the other hand, if the detected pressure exceeds the target pressure P2 _target of the steam pressure increase, the process proceeds to step 570, the on-off valve 554 is opened, and the refrigerant circulation line 552 It flows into the medium channel 540 through

Then, in the next step 572, the ratio | T−T _target | / T of the absolute value of the difference between the temperature T detected by the temperature sensor 560 and the heating temperature target T _target, and the heating temperature target T _target It is determined whether _target is less than a threshold (for example, 0.1). If | T−T _target | / T _target is less than the threshold (eg, 0.1), the process proceeds to step 576, while | T−T _target | / T _target is the threshold (eg, If it is 0.1 or more, in step 574, the flow rate of the refrigerant to be supplied to the medium flow channel 540 is determined according to the magnitude relationship between the temperature T detected by the temperature sensor 560 and the temperature release target T _target. The on-off valve 554 is controlled to increase or decrease by ΔFc, and the process returns to step 572.

  In step 576, it is determined whether or not the hydration reaction of the heat storage material molded body 14 is completed, and if it is determined that the hydration reaction of the heat storage material molded body 14 is not completed, the process returns to the above step 572 On the other hand, when it is determined that the hydration reaction of the heat storage material molded body 14 is completed, the heat supply processing routine is ended.

  As described above, according to the heat feeder of the sixth embodiment, after the start-up initial steam generation sequence for generating the start-up initial steam by external heat exchange is executed, the process is switched to the high pressure steam generation sequence. By doing this, continuous sequence operation from initial start up to high pressure steam generation becomes possible.

  In the first to third embodiments described above, the case where the present invention is applied to the steam generator has been described as an example, but the present invention is not limited to this and the fifth embodiment The present invention may be applied to a heat supply device as in the sixth embodiment. In this case, the steam supply path communicating with the vessel of the reactor becomes unnecessary.

Moreover, although the case where calcium hydroxide (Ca (OH) ₂ ) was used as a chemical thermal storage material was demonstrated to the example, it is not limited to this, For example, MgO / Mg (OH) _{2 of a} hydration reaction system A coordination reaction system such as Mg or Ca hydrate may be used.

When MgO / Mg (OH) ₂ of the hydration reaction system is used, the following chemical reaction occurs.

MgO + H ₂ O ⇔ Mg (OH) ₂ + Q

  Moreover, when using a coordination reaction system, it becomes the following chemical reactions.

_{M + xH 2 O⇔M · xH 2} O + Q

  Further, zeolite-based, silica-based or carbon-based adsorbents may be used.

  Moreover, although the case where water was used as a reaction liquid was demonstrated to the example, it is not limited to this, Another reaction liquid may be sufficient. For example, ammonia may be used.

10, 310 Steam generator 14, 414 Heat storage material molding 16 Reactor 17, 417 Water supply port 18 Heat transfer surface 20, 420 Heat exchange partition wall 22, 432 Mass transfer path 24 Initial steam inlet 26 Steam supply path 320, 334, 421, 422, 554, 654 on-off valve 340 pressure sensor 350 heat storage ECU
410, 510, 610 Heat feeder 416 High temperature reactor 430 Condenser 440, 442 Heat exchange flow path 540 Media flow path 560 Temperature sensor 618 Heat transfer surface for start up 620 Heat exchange partition for start up 640 Heat medium flow path

Claims (6)

A heat storage material that performs desorption reaction or chemical reaction of a substance by heat supply to store heat, and releases heat by adsorption reaction or chemical reaction of the substance;
A heat transfer surface capable of evaporating a liquid film of a substance to be supplied;
A heat exchange partition wall which is provided between the heat storage material and the heat transfer surface and which forms a heat conduction path;
A mass transfer path different from the heat transfer path for transferring the substance evaporated from the heat transfer surface to the heat storage material;
Containing reactors. A substance supply path for supplying the substance evaporated from the heat transfer surface to the outside;
A pressure measurement unit that measures the pressure of the substance evaporated from the heat transfer surface;
A control unit provided in the substance supply path for controlling a valve for switching the supply of the substance, according to the pressure measured by the pressure measurement section;
The reactor of claim 1 Symbol mounting further comprises a. A reactor according to claim 1 or 2 ;
A heat storage material that releases heat by adsorption reaction or chemical reaction of the substance supplied by the reactor, and a high temperature reactor including a heat storage material having a higher equilibrium temperature than the heat storage material of the reactor;
Thermal storage system including. The system further includes the substance supplied by the desorption reaction or the chemical reaction of the heat storage material of the reactor, and a condenser for condensing the substance supplied by the desorption reaction or the chemical reaction of the heat storage material of the high temperature reactor.
The heat storage system according to claim 3 , wherein the heat storage material of the high temperature reactor is desorbed or chemically reacted by heat supply from a heat source, and the heat storage material of the reactor is desorbed or chemically reacted by heat supply from the high temperature reactor. A pressure measurement unit that measures the pressure of the substance evaporated from the heat transfer surface;
A temperature measurement unit that measures the temperature of the heat storage material;
A medium flow path provided in the heat exchange partition wall for flowing a medium as a heat exchangeable refrigerant;
A control unit configured to control the flow rate of the medium to be flowed through the medium flow path according to the temperature measured by the temperature measurement unit, when the pressure measured by the pressure measurement unit exceeds a target pressure;
The reactor according to claim 1 or 2 , further comprising A heat medium medium flow path for flowing a medium as a heat exchangeable heat medium;
A heat transfer surface for start-up capable of evaporating a liquid film of a supplied substance by heat exchange with the medium of the heat medium medium flow channel;
And a control unit that controls the medium to flow in the heat medium flow path when starting up the heat medium.
The reactor according to claim 1, 2, or 5 , wherein the heat storage material releases heat due to an adsorption reaction or a chemical reaction of the substance supplied from the heat transfer surface for startup when the heat storage material is started.

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