JPH067030B2 - Forward and reverse mutual drive type heating and refrigerating method and apparatus - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a heating and refrigerating method and apparatus, and more particularly to a heating and refrigerating container and a heat generating container, which accompanies storage and release of hydrogen in a metal hydride. The present invention relates to a forward-reverse mutual drive type heating and refrigerating method and apparatus which utilize heat generation and heat absorption to alternately repeat the heat generation / heat absorption reaction and the reversible reaction of the reaction to continuously obtain high temperature or low temperature continuously.

[Prior Art] Conventionally, as a heating and refrigerating method and apparatus, a heat source method in which a heat source such as hot water or a heater or a cold heat source such as ice or dry ice is housed in an adiabatic container, a low temperature storage method using liquefied nitrogen, and a Peltier device are used. An electric system is known in which the element is arranged in a heat insulating container. According to the heat source method, it is very inconvenient that a heat source must be prepared each time it is used. Further, the temperature of a heating source such as hot water drops in a short time, and the cooling source such as ice or dry ice is consumed over time, so that it does not exhibit stable heating and refrigerating capacity. While a large and complicated structure is required because a mechanism and space for storing and discharging them are required, the low-temperature storage method that uses liquefied nitrogen allows liquefied nitrogen to pass through a pipe from a container and be insulated from a spray header to be refrigerated.・ It is directly injected into the freezing container and maintains a good low temperature state, but in the case of long-term storage, it is necessary to replenish liquefied nitrogen, and it is difficult to maintain a constant low temperature continuously for a long time, and the cost is high. It has the drawback of being expensive. Further, according to the electric method, it is possible to stably heat and refrigerate for a long time, but it cannot be used in a place without a power source. These require larger and more complex and expensive mechanisms and space, as well as operation monitoring functions, resulting in large and complex configurations.

[Problems to be Solved by the Invention] Each of the heating and refrigerating devices described above has its own characteristics.
Generally, the temperature of a heating source such as hot water decreases in a short time, and ice,
Cold heat sources such as dry ice and liquefied nitrogen are consumed over time, so in order to maintain a low temperature continuously,
There is a problem that the heat source must be replenished, the cost becomes high, and the heater and the refrigerator cannot be used in a place without a power source.

[Means for Solving Problems] An object of the present invention is to provide a forward-reverse mutual drive type heating and refrigerating method and device which eliminates and solves various drawbacks and problems of the conventional heating and refrigerating method and device. is there. The present inventors have found that certain alloys rapidly occlude hydrogen, generate heat to form metal hydride, and this metal hydride reversibly releases hydrogen and absorbs heat. A heating and refrigerating method and device capable of continuously heating or refrigerating for a long time without providing a heating or refrigerating heat source for use by providing a heat generating container utilizing Newly found,
The present invention has been completed here.

According to the method of the present invention, the first container loaded with the first metal hydride is arranged so as to exchange heat with the heating and refrigerating container space.
And a second container loaded with the second metal hydride are connected to each other to provide a heat generation container, and the two containers loaded with the metal hydride and the hydride-forming alloy are charged with hydrogen by a pressure change. The energy required for these reactions and this reversible reaction is exchanged and exchanged quickly and without waste in order to charge and discharge alternately and continuously, and to effectively utilize the heat of reaction obtained thereby to obtain high temperature or low temperature. Along with this, the positive reaction of the other party is widened by the temperature change caused by the reverse reaction of the other party to widen the temperature difference between each pair of containers to promote the reaction.

Further, as the first metal hydride, a misch metal-nickel hydride is used, and as the second metal hydride, a misch metal-nickel-aluminum hydride is used, and the reaction heat obtained by the combination is used to obtain high temperature or It is characterized by obtaining a low temperature.

In addition, in a heat generation container in which a pair of first and second containers are connected, the heat of reaction between the alloy in the second container and hydrogen can be used for heating the metal hydride in another second container. It is characterized by installing a heat exchange plate.

The present invention will be described below with reference to the drawings illustrating an embodiment.

[Example] FIG. 1 shows an example of a heating and refrigerating apparatus used directly for carrying out the method of the present invention. The heating and refrigerating apparatus A of the present invention comprises a heat insulating and refrigerating container 1 and a heat insulating and heat generating container 2 which is fitted into the lower opening of the heating and refrigerating container 1 and can be freely detached.

In the heat generation container 2, a first metal hydride loaded first
2 and 3 and the second containers 5 and 6 loaded with the second metal hydride are arranged, and the heat generation container 2 defines an adiabatic partition 7 to allow the reaction of the first containers 3 and 4. The heat is prevented from conducting between the first containers 3 and 4, and the first container 4
So that the reaction heat of the first container 3 can be exchanged with the atmosphere and the reaction heat of the remaining first container 3 can be exchanged with the accommodation space 8 of the heating and refrigerating container 1. , 10 are further opened, and the heat generation container 2 surrounds the second containers 5 and 6 with a heat insulating outer wall 11 to prevent the heat of reaction of the second containers 5 and 6 from being transferred to the outside. , 6 for interposing a heat transfer plate 12 having a good thermal conductivity between the opposite surfaces of the second container 5 and the heat source for causing a reversible reaction in the other second container 6 which remains. As soon as possible, the transmission and exchange are performed without waste, and the temperature difference between the containers of each group is widened,
By accelerating the reaction of each other, the hydrogen pressure of the container 6 is maintained while apparently continuously generating heat and absorbing heat because it operates simply and alternately without providing a space for placing a cold heat source such as a heater or dry ice. Increase.

The first container 3 and 4 and the second container 5 and 6 are communication pipes 1 having filters 13, 14, 15 and 16 attached to both ends, respectively.
7, 18 and connecting valves 19 and 20 for controlling the flow and stop of hydrogen between the first containers 3 and 4 and the second containers 5 and 6 are provided in the communication pipes 17 and 18, respectively. There is. The filters 13, 14, 15 and 16 prevent metal hydrides from being entrained during the flow of hydrogen and block the communication pipes 17 and 18, and for example, a porous sintered metal having a pore diameter of 10 μm or less is used.

The first container 3 and 4 and the second container 5 and 6 are preferably, but not limited to, formed of a plurality of tubular containers, and a plurality of sets are arranged in parallel in upper and lower two stages. The communication pipes 17 and 18 are connected to each other. Alternatively, a plurality of sets may be arranged in parallel in one stage and each pair may be connected by the communication pipes 17 and 18. This second
The containers should be placed side by side as close as possible so that heat can be transferred quickly and without waste.

The heat generating container 2 including the first container 3 and 4 and the second container 5 and 6 is detachable from the heating and refrigerating container 1 as one set so that the mesh window 10 faces the inside of the heating and refrigerating container 2. It can be installed by reversing.

A temperature sensor 21 is arranged in the heat-insulated refrigerating container 1 so that the respective communication valves 19 and 20 can be opened and closed by the temperature detected by the temperature sensor 21, and the hydrogen passing through the communication valves 19 and 20 can be opened and closed. The distribution volume of is controlled.

First metal hydride M ₁ H and second metal hydride M ₂ H
Are used that have different equilibrium decomposition pressure characteristics.
Specifically, as M ₁ H, LaNi ₅ , LaNi ₅ z are used.
Az, MmNi ₅ , MmNi ₅ -zAz, MmxT
iyNi ₅ , MmxZryNi ₅ , MmxNbyNi ₅
(However, 0.75 <x <1.2, 0 <y <0.25,
0 <z ≦ 0.5) and LaN as M ₂ H
_{i 5 -zAz, MmNi 5 -zAz,} MmxTiy
_{Ni 5 -zAz, MmxZryNi 5 -zAz,} M
mxNbyNi ₅ -zAz (where 0.75 <x <
A combination with a hydride such as 1.2,0 <y <0.25, 0 <z ≦ 0.5) is used.

[Operation] When the device A of the present invention is used as a refrigerating device,
As shown in the figure, the first containers 3 and 4 are filled with M ₁ H having a high equilibrium decomposition pressure at T _M = 20 ° C. under a high-pressure hydrogen atmosphere, and the second containers 5 and 6 are filled with T _M. = M ₂ H having a low equilibrium decomposition pressure at 20 ° C. is preferably filled in a hydrogen-releasing alloy state under a low-pressure hydrogen atmosphere. That is, the state of M ₁ H corresponds to the point, and the state of M ₂ H corresponds to the point.

A heating / refrigerating container 1 insulating the operating temperature of the temperature sensor 21.
When the required cooling temperature T _L inside is set to 0 ° C., the second container is cooled by air to lower the dissociation pressure of M ₁ H, and the state is set to a point. The communication valve 19 is opened until the temperature inside the heating / refrigerating container 1 reaches the set temperature, and the first container 3 and the second container 5 are opened.
, The hydrogen moves from the high-pressure first container 3 to the low-pressure second container 5, and M ₁ H absorbs heat and releases hydrogen to reach the temperature T _L = 0 ° C., thereby heating and refrigerating. The inside of the container 1 is cooled. This is the point state, which is the low temperature generation step. On the other hand, M ₂ H in the second container 5 absorbs hydrogen to generate heat, which is generated by the heat transfer plate 1 made of aluminum or copper.
While heating the other container 6 remaining through ₂ , heat the M ₂ H filled inside. When the temperature in the heat-insulated heating and refrigerating container 1 reaches the set temperature T _L = 0 ° C., the temperature sensor 21 operates to close the communication valve 19, and the flow of hydrogen between the first container 3 and the second container 5 is prevented. Suspended. When the temperature in the heating / refrigerating container 1 rises above a predetermined temperature, the temperature sensor 21 is activated again and the communication valve 19 is opened, so that the flow of hydrogen occurs and the inside of the heating / refrigerating container 1 is cooled to the predetermined temperature.

In the first container 4 and the second container 6 that remain while the first container 3 and the second container 5 perform the above-described low temperature generation operation, regeneration using a reversible reaction that is a property of a hydrogen storage metal. The operation of. That is, hydrogen is stored in M ₂ H on the low pressure side of the second container 6 to generate a hydride. The heat generated by the operation of generating the low temperature is heated in the second container through the heat transfer plate 12. This state corresponds to the point (the state where the equilibrium partial pressure of M2H is higher than that of M1H). Communication valve 20
Is opened and the second container 6 and the first container 4 communicate with each other, so that hydrogen is transferred from the high-pressure second container 6 to the low-pressure first container 4
And M ₁ H in the first container 4 absorbs hydrogen to generate heat. This heat is dissipated into the atmosphere from the first container 4 through the window 10. This is the initial state of the point, the regeneration process.

The heat generation container 2 is replaced so that the series of the first container 3 and the second container 5 of the heat generation container 2 and the series of the first container 4 and the second container 6 are reversed, and low temperature generation and re-generation are performed. By alternately operating the two series of formation processes, it is possible to continuously cool the heating and refrigerating vessel 1, and there is no need for a mechanism to control the operation of the storage space for the cold heat source, the heater, etc. The heat generated by the device itself can be effectively used.

Such a chemical reaction is continued until an equilibrium state is reached, but the reaction rate and intensity at each time are farther from the equilibrium state, that is, faster and stronger as there is a temperature difference. Therefore, it is better to increase the temperature difference between the respective containers, and in the present invention, the temperature reduction of the other container is achieved by rapidly transmitting the cold heat and the heat generated from the respective second containers which carry out the forward and reverse reactions. The other exothermic heat is used to suppress the temperature increase by using the other cold heat reaction to promote the mutual reaction.

When the heating and refrigerating apparatus A of the present invention is used as a heating apparatus, conversely to the above, the second container 5 is filled with M ₁ H under a high-pressure hydrogen atmosphere, and the first container 3 is filled with M ₂ Fill with H under a low pressure hydrogen atmosphere. The communication valve 19 is opened until the inside of the insulated heat-refrigerating container 1 reaches a predetermined temperature, and the second container 5 is opened.
And the first container 3 communicate with each other, hydrogen moves from the high-pressure second container 5 to the low-pressure first container 3, and M ₂ H in the first container 3 absorbs hydrogen exothermically, Heat is applied to the heating and refrigerating container 1 through the mesh window 9 to heat it. This is the high temperature generation process. In the regenerating process, the heat absorption of the second container 5 obtained in the high temperature generating process is converted into a hydride-forming alloy through the heat transfer plate 12, and the other second container 6 is cooled and filled therein. M ₁ H absorbs hydrogen. Therefore, when the communication valve 20 is opened, hydrogen moves from the high pressure first container 4 to the low pressure second container 6. At this time, the cold heat generated in the first container 4 is dissipated into the atmosphere through the mesh window 10.

Continuous heating is possible by replacing the heat generation container 2.

[Example] A small heating and refrigerating apparatus having an insulated heating and refrigerating vessel having an inner volume of about 36 was used, and about 1 kg of MmNi _4.7 A was used.
_A pair of a first container filled with _0.3 and a second container filled with about 1 Kg of LaNi ₅ are arranged, and the first container is 20 ° C.
Hydrogen at a temperature of about 7 atm was occluded in LaNi ₅ hydride while the second container was at a temperature of 20 ° C. of about 1.
When the pressure is reduced to 2 atm, the set temperature is set to 0 ° C, and the temperature in the container is about 0 when connected to the sensor placed in the heating and refrigerating container.
C., and the heating and refrigerating container was continuously kept at about 0.degree. C. thereafter.

[Effect] In the present invention, since heating or cooling is carried out by utilizing the hydrogen absorption / desorption reaction of metal hydride, no power source is required, and moreover, as seen in the conventional heating / cooling method and apparatus, a heat source is used. It does not need to be consumed or replenished, it does not need a space to store this cold heat source, it can be downsized, and it does not require expensive mechanisms such as heaters, so it is inexpensive, and the heat generated by the device itself can be regenerated. Since the reaction between the vessels is promoted by utilizing it, a highly efficient operation can be performed, and further, a required temperature can be taken out and used stably for a long period of time as needed, which is an excellent effect.

[Brief description of drawings]

FIG. 1 is a sectional view showing an embodiment of the heating and refrigerating apparatus of the present invention, and FIG. 2 is M ₁ H and M for explaining the operation.
The relationship diagram of the equilibrium decomposition pressure of ₂ H and temperature is shown. A ... Heating / refrigerating device 1 ... Heating / refrigerating container 2, 2 ... Heat generating container 3, 4 ... First container, 5, 6 ... Second container 7 ... Insulating partition wall, 8 ... Storage space 9, 10 ... Net window, 11 ... Insulation outer wall 12 ... Heat transfer plate 13,14,15,16 ... Filter 17,18 ... Communication pipe, 19,20 ... Communication valve 21 ... Temperature sensor

Claims (5)

[Claims] 1. A pair of at least two pairs of a first container and a second container, each pair of which are connected to each other by aeration, are arranged in parallel, and the first container and the second container of each pair have different equilibrium decomposition pressure characteristics. Hydrogen is added to the metal hydride by alternately loading and discharging hydrogen into the first container and the second container of each pair due to a pressure change due to a difference in decomposition pressure. In alternately carrying out the occlusion and release of the, between the first containers of the pair, while blocking heat transfer by the first container group, one container is in contact with the outside air to radiate and absorb heat, The other container is in contact with the inside air of the accommodation space of the heating and refrigerating container, which is insulated from the outside air, so as to radiate and absorb heat, the second container groups are closely arranged side by side, and the second container is located between the second containers. Heat is efficiently exchanged between the groups only and is also insulated from the outside. The first container and the second container of the pair are ventilated and communicated with each other to control the flow rate of the gas stored in the first container and the second container at a predetermined temperature. The heating and cooling reaction is performed in the first container and the second container, and the reversible regeneration reaction of the heating and cooling reaction is performed in parallel in the other pair of the first container and the second container, respectively. Forward and reverse mutual drive type heating and refrigerating, characterized in that the temperature difference between the first and second containers of each pair is widened to promote the reaction and continuously generate hot or cold heat. Method 2. A metal hydride loaded in each of the first container and the second container is a mischmetal-nickel hydride and a mischmetal-nickel-aluminum hydride. Forward / reverse mutual drive type heating / refrigerating method according to item 1. 3. A heating / refrigerating container having a heat-insulated accommodation space therein, a plurality of pairs of a first container and a second container respectively loaded with metal hydrides having different equilibrium decomposition pressure characteristics, and a plurality of sets in the accommodation space. Each pair is interconnected so as to be freely ventilated through a connection valve that is controlled to be opened and closed by a temperature sensor installed, and a plurality of sets of adjacent first containers are insulated from each other and the adjacent one is exposed to the outside air. While the other one is in open contact with the air in the accommodation space so that it can radiate and absorb heat, the plurality of sets of adjacent second containers mutually interpose a heat transfer plate and transfer the other outside. A forward-reverse mutual drive type heating and refrigerating apparatus, which comprises a heat generating container that is heat-insulated and is fitted in the heating and refrigerating container 1 side so as to be freely replaceable. 4. The metal hydride loaded in the first container and the second container, respectively, is a mischmetal-nickel hydride or a mischmetal-nickel-aluminum hydride. Forward-reverse mutual drive type heating and refrigerating apparatus according to item 3. 5. The heat generating container is formed in a heating / refrigerating container so that it can be reversed and replaced.
Alternatively, the forward / reverse mutual drive type heating / refrigerating apparatus according to item 4.