JP2013087276A - Form of latent heat storage body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a form of a latent heat storage material, which uses a latent heat storage composition having harmonized various latent heat storage materials, has good efficiency of heat transfer applied to cooling and heating, air conditioning, and hot-water supply according to the aptitude of the heat storage materials, is compact, and exhibits a high-density and high-efficiency heat transfer function with the view of a heat source and the like for cooling and heating and hot-water supply, in housing, building, agriculture, and the like when necessary by storing atmospheric heat and solar heat in the heat storage body with inexpensive nighttime power.SOLUTION: The latent heat storage material is subjected to melting point adjustment so as to be applied to the purpose of applications, wherein in respective composition materials, transition points are changed in respective ranges, such as a range in which the melting point is 32°C or less (mainly 7-20°C), a range in which the melting point is 58.5°C or less (mainly 35-58°C), and a range in which the melting point is 93.5°C or less (mainly 70-85°C). An incision having a square-shaped or circular cross-sectional shape, proportional to the total thickness, is formed in the middle between soft, thin, lightweight, and impermeable synthetic resin sheets. A plurality of independent hollow structures are supported in a parallel state and constructed by monolithic injection molding. The latent heat storage body is obtained by injecting respective latent heat storage compositions into the hollow structures and filling and sealing the same.

Description

In the present invention, a sodium sulfate system having a solidification latent heat and a heat storage density of 389 (MJ / m ³ ), a melting point of 32.4 ° C., a heat of fusion 246 (KJ / Kg). Heat storage density 364 (MJ / m ³ ) Melting point 58.5 ° C melting heat 251 (KJ / Kg) peritectic type and various alum system heat storage density 400 (MJ / m ³ ) melting point 94 ° C melting A latent heat storage body using a latent heat storage composition having a harmonious type of heat 232 (KJ / Kg), and having a good heat transfer efficiency applied to heating / cooling air conditioning and hot water supply according to the suitability of each system It is a material form. Atmospheric and solar heat is stored in the heat storage body with low-cost nighttime electricity, and a small, high-density, high-efficiency heat transfer function is demonstrated for the purpose of air conditioning and hot water supply for houses, buildings, agriculture, etc. when necessary. Provide a form of latent heat storage material.

Conventionally, as a heat storage means, a container of a heat storage material is typically a blow-molded container made of a synthetic resin such as polyethylene or polypropylene, and a spherical, hollow plate, or an extrusion-molded packaging film is typical. . It has been put into practical use for floor heating, etc. that is directly attached using nighttime power. However, there is a problem in the heat transfer material inherent heat quantity and the temperature transferability related to the required performance, and the performance of the retained latent heat temperature has not been demonstrated. The reason is that the thermal conductivity is smaller than the stored heat capacity, and in order to secure the extraction heat flow, there is a temperature difference between the temperature intake and the outlet, and adjustment of the flow rate of the heat medium is necessary for adjustment, avoiding the enlargement of the storage device I couldn't. Further, as a hot water storage problem, it is known that the temperature loss due to natural heat dissipation is reduced by about 0.5 ° C. per hour in a hot water storage tank where the temperature difference is large in winter, especially when the outside air temperature is 0 ° C. If the characteristics of the hot water tank are temperature stratified, the heat loss per day is affected by the difference between the internal and external temperature, the surface area of the hot water tank and the contact area exposed to the outside air temperature, and the heat loss is proportional to the remaining hot water volume. It was increasing. Under the condition of ambient temperature = supply water temperature = 10 ° C., there is a study by the Architectural Institute of Japan that the heat loss actually reaches 38.8% of the theoretical required amount of heat Kcal. The demand trend was to make it difficult to select the installation location due to the increased functionality, increased demand for hot water, and larger tanks. Heat pumps that do not have heat storage alone have disadvantages in terms of performance, such as inconvenience that lacks convenience in use of temperature, such as a time lag in temperature follow-up.

  Special Notice 2890197   Special Notice 2566445   JP-A-10-237433   JP 2006-75579 A   JP-A-57-198780   JP 59-197486   JP 57-074380   JP 57-074380   JP-A-63-135747   JP 2010-121814 A   The Architectural Institute of Architectural Institute of Japan

  The latent heat storage material employed in the heat storage device of the present invention does not change the specific melting point of the substance, and when the temperature falls below the melting point from the liquefied state, it dissipates the latent heat until the solidification entropy generation state ends, Release and absorb energy according to mass. Moreover, at the time of melting, it retains the reversibility of the property of absorbing heat until the heat storage material (1) is completely liquefied. The system of the electrolytic hydration composition (1) used in the heat storage device has a difference of ΔT / 10 ° C. when the specific gravity is 1.45 times or more in comparison with the capacity of water and the ambient temperature = feed water temperature = 10 ° C. The unit heat quantity is about three times that of water, and there is an advantage that the heat quantity is compact and the heat quantity is large, and the heat radiation surface load can be reduced by downsizing the container. The heat storage composition is supported in each of the independent hollow layer structures (1) to improve the contact area between the heat medium (2) and the heat storage body and the heat transfer resistance value of the cross section, thereby promoting the temperature transfer efficiency. This attempt reduces the thermal resistivity load, improves the temperature transfer efficiency, and improves the heat supply function. Further, downsizing of the apparatus has the advantage of reducing the heat loss and providing an inexpensive apparatus. There is a basis for trial calculation that it can be reduced by about 70% compared to the required amount of heat compared with the existing conventional hot water tank, which contributes to space and energy savings.

  As for the kind of the latent heat storage composition (1) of the present invention, the sodium sulfate type employed in the low temperature range has a melting point of 32 ° C. or lower to 7 ° C. In the middle temperature range, the sodium acetate type has a transition point range from a melting point of 57.5 ° C. or less to 35 ° C., and in the high temperature range, various alum hydrates have a melting point of 94 ° C., from 94 ° C. or less to 75 ° C. Useful for use in ° C. Of the various heat sources, especially the low temperature 5 ° C by the refrigeration heat pump chiller, the solar heat, the heat recovery from the compression heat pump 70 to 90 ° C is required for adaptability, and the cooling for dehumidification drying Useful as a heat storage device for heating / heating / hot water.

  Each of the latent heat storage hydrate substances of the present invention has an average density ratio of 1.4 times or more with water, and the required heat and heat release at ΔT / 10 ° C. are as large as 1.6 to 5.0 times. The size of the device related to heat storage can be reduced. Each of these heat storage materials absorbs and melts at the specific melting point of the substance, reveals the thermal reaction action of solidification while dissipating the latent heat below the melting point, so that the endothermic and heat dissipation is complete until the reversible state (phase) change is completed. It exhibits the property of maintaining a constant temperature of latent heat release near the required melting point. The present invention is applicable to hydrates of each system prepared by cooking with a main material of a single or a mixed mixture. Among the heat radiating body as an example of the present invention, the theoretical value of sodium acetate hydrate has a melting point of 58.5 ° C., a latent heat of 60 Kcal / kg is a peritectic type, and the melting process is a high temperature. As a result, supercooling related to intermolecular separation or supersaturation occurs in the process of thermal history such as melting / solidification, and the thermal conductivity of the solid is 0.35 m. The heat transfer coefficient due to the thermal resistance of about k was about 35% of ice, and had problems related to efficiency.

  Since the latent heat storage composition material is a heat storage body (1), the temperature transfer efficiency is determined in proportion to the product of the contact surface by the contact surface area ratio of the heat medium (2) and the thermal conductivity inherent to the heat storage material. As effective means for alleviating the transfer resistance, the latent heat storage composition and the external load contact value, that is, the container thickness has been optimized, and the heat transfer efficiency of the latent heat storage material has been an issue. By reducing the container thickness, it is possible to improve the temperature transfer efficiency, but there is a shortage of required heat. The means for securing the deficiency is supplemented by stacking a number of layers of the heat storage body to be the container. To improve temperature transfer efficiency: 1. Enlarge and secure container surface area. Achieved by the synergistic effect of increasing and securing mass. As a result, the generation of entropy is shortened by means for reducing the inherent heat conduction resistance of the system, which contributes to the improvement of COP. However, among the electrolytic hydrates, sodium acetate hydrate is generally subject to phase separation and supercooling, and cannot function as a heat storage material because of its unique molecular structure. As a countermeasure, it is solved by a blending means in a purified product such as palyskite, smectite, zeolite, sepiolate as an additive having a common chain function in other systems. Also, as a nucleation material to prevent the supercooling phenomenon that does not solidify even when the temperature falls below the melting point, various heat-resistant succinic acid, lithium fluoride, lithium acetate, potassium fluoride composites, alum, cobalt sulfate, boric acid, etc. Establishing the effectiveness of adapting to each system alone or in combination. On the other hand, the solution is acidic and the solution to the corrosion resistance problem has been preceded. However, by replacing the heat storage body and heat storage tank with synthetic resin, the maintenance of heat history and heat storage device equipment is ensured and low cost is achieved. To do.

  The container used for the latent heat storage body of the present invention is a container in which a heat storage composition is inserted and filled into a hollow (2) in which a middle space is integrally formed between soft sheets, and a built-in support (1) is made of polyethylene (PE ), Polypropylene (PP), polycarbonate (PC), polyphthalate, and hard aluminum.

  The main materials used are sodium sulfate hydrate, sodium acetate hydrate, and various alum hydrates. Each system composition (1c) liquefies above its inherent melting point, below which it generates reversible entropy of coagulation. Energy transmitted from the heat source and the load is transmitted to the heat storage material through the heat medium. That is, if the temperature (2) of the heat medium is higher than the specific melting point of the heat storage composition, the heat storage body (1) liquefies while absorbing the heat of heat, maintains the heat storage state, and if it is lower than the melting point temperature of the system, The recombination of the atoms releases the solidification latent heat at the melting point of the substance, and the heat release completes with solidification. The latent heat that enters and exits the entropy generation process is used for air conditioning and hot water supply. After heat dissipation, it has reversibility of repeated melting by reheating.

  In other words, heat is absorbed and released in a reversible manner through a temperature difference between the latent heat storage material (1) and the heat medium (2) of the system. Therefore, by varying the required amount (number) of the heat storage body, it is possible to appropriately cope with the load and to achieve efficient heat transfer between the heat medium (2) and the heat storage material (1). Combined with the increase in required heat, it effectively demonstrates the heat transfer function and the temperature and flow capacity corresponding to the heat flow load.

  Heat is transferred by transferring the temperature to the heat storage material through the contact surface between the heat medium and the heat storage body. As a means for improving the heat conduction efficiency, the thickness of the heat accumulator that comes into contact with the heat medium is set to a favorable allowable thickness to suppress the temperature transfer resistance. In addition, it is possible to achieve an increase in the contact surface with the heat medium, an increase in the amount of retained heat, and an improvement in temperature transmission efficiency due to the effect of stacking the heat storage elements. Generally, melting is proportional to thermal conductivity, and inversely proportional to thermal resistance. Thermal conduction λ and temperature conductivity are related to the increase / decrease of the unit quantity of the heat accumulator due to the principle of a = λ / PC. Contributes to the improvement of COP of installed equipment, etc. by increasing the density of heat storage and high input / output. Compared to conventional spherical synthetic resin pro-molded capsules and boards, the heat transfer capacity of heat storage per unit is improved from about 5 times to 16 times to promote space saving. In the implementation, the heat quantity of high-temperature water 70 ° C. for comparing the latent heat quantity of the heat storage material with a volume of 140 l and the specific heat quantity of water is 7,000 Kcal / Kl at an internal / external temperature difference ΔT 20 ° C. The latent heat of 5 mm at 58 ° C × 135 l of the container amount is 13.800 Kcal / Kl, and the difference in the amount of heat held in the density is about twice as great, and space saving and energy saving results can be expected. .

  The latent heat storage material (1) related to the heat source and load is not limited to the container volume, but the heat resistance width when using a 5 mm thickness as an example of thickness selection is almost equal to or close to that of water, and good heat absorption and radiation An effect is obtained. The efficiency of transmission of melting / dissipating heat (1) can be improved by thermal contact with the heat medium on both surfaces of the latent heat storage container (1). The adopted heat storage material sodium acetate type (1) obtained a heat supply function in a large amount within a fixed amount of time with a predetermined heat amount of 60 Kcal / Kg at 56 ° C. In general, the hydrate salt has many peritectic types and requires heating higher than the melting point for melting, but means for reducing the thermal resistance by the combined use of the harmonic change treatment (1c) is effective. Although experimental values are not described, the alum system is particularly harmonious, and the desired heating temperature can be close to the temperature lowering treatment melting point. It has also been demonstrated that the system can withstand high temperatures of 100 ° C. or higher by using polycarbonate resin or metallic aluminum. As a means for storing atmospheric heat in the heat storage container using solar heat or nighttime power, it is easy to construct a latent heat storage device having a large unit latent heat amount and excellent temperature conductivity. It will contribute to the space-saving of air conditioning and hot water supply equipment in various fields by expanding the range of use by supplying low-priced equipment and downsizing with mass production merit.

  In the present invention, a liquid vacuum filling method, a drip nozzle injection method, or a resolidified filling method can be adopted as means for injecting the heat storage material into the hollow tube to obtain the latent heat storage body (1). In the liquid method, the prepared liquid having the latent heat storage composition is applied to the liquid composition by applying a vacuum replacement function. The solid method can cope with the productivity by adopting a solidified tablet method in which the dissolved material having the latent heat storage composition prepared in advance is shaped into a solid and then inserted into the container space. In addition, the heat storage body can be easily formed into a laminated unit that combines a plurality of units, and the device constituted by the heat storage body can be easily simplified, such as divided installation or compaction, by a process such as increase or decrease in the amount of heat, and has a large heat capacity. It has the characteristics of. Furthermore, the efficiency improvement of the function of the apparatus constructed | assembled by increase / decrease in a thermal storage body is improved. For example, if the material of the heat storage device is made of a composite resin such as FRP or a single plastic tank, corrosion can be prevented at low cost, and if it is buried directly in the soil or installed under the floor or basement, the heat insulation effect and unused space Various heat insulation methods such as the use of hot water are possible, and there is a demand effect in cold regions. It is incorporated as a heat pump or a waste heat utilization device, and is useful as a heat storage device that compensates for the time lag of the dehumidifying and cooling function using a cold district or solar heat as a heat source.

  The protrusion (3) of the heat storage body prevents adhesion of the heat storage body (1) stacked and installed in the heat storage device, and serves as a gap action of the contact flow path (2) with the heat medium between the stacks. Attached to. In proportion to the contact area, the efficiency of heat conduction between the heat storage material and the heat medium can be improved by ensuring the contact temperature flow rate. The setting means for the projection (3) is not limited to its shape, number, front-end and / or front-end / post-end means.

FIG. 3 is an enlarged cross-sectional view of a structure of an integrally formed hollow hole that houses a latent heat storage material that performs heat input and heat dissipation. It is opening sectional drawing filled with a thermal storage material (1c) in the space which consists of a soft sheet | seat (1a) and the pillar (1b) which supports and partitions a hollow hole. These are the oblique views which show the whole structure of the thermal storage body filled with the latent heat storage material. Although not shown here, the latent heat storage body (1) is shielded at both inlets. Indicates a state in which a plurality of heat accumulators (1) are laminated, indicates the laminated adhesion prevention part (3), secures a flow path of the heat medium (2), and is laminated or parallel to the outside or a load. The state which formed the temperature transmission flow path of this is shown.

It is an Example of this invention.
It is an Example of the composition which adjusted the sodium acetate type | system | group chosen among AB employ | adopted to this invention appropriately. The specific heat is 0.35 [Kcal / Kg / ° C.] The average heat density is 1.42, and the conversion to heat release is shown in Table 1 as the heat storage material weight. A heat storage material (1) was filled and sealed in the middle space of the sheet to prepare a sample. The flow rate of hot water heated to 75 ° C with a heated hot water heater is set to a constant flow rate with an electromagnetic pump, and the inlet and outlet temperatures of the heater are measured with a data logger for the characteristics of heat absorption and heat dissipation. Table 1 shows the measured values. The amount of heat required is almost the same as the DSC measurement method, and the amount of heat of the system (1) employed in the examples is close to the original phase theoretical value. In addition, a composition sample (1) that adjusts the melting point of sodium acetate trihydrate is prepared, and in the repeated examples, a thermal history test is performed assuming practical use. Show.
ΔT = 20 ° C. The measurement result of the latent heat storage body implemented by taking into account the environmental temperature difference showed a value almost close to the original theoretical value of the system. The symbol A shown in Table 1 is a sodium acetate trihydrate composition as the heat storage material of the sample 1 holding container, and the symbol B is a sample prepared for the implementation of the sample 2 same blow-molded structure and sodium acetate trihydrate. S, indicating tap water.

  1.2g x 3 pieces (3 units of sample: width 300mm / length 600mm / thickness 0.5mm) in a 6L sample volume made of FRP (4) in a heat storage device in which the latent heat storage body (1) adjusted to suitability is laminated .6 kg), and a mounting that secures the flow path of the heat medium at a gap of 2 mm or between the layers is selected from Table 1. The latent heat radiation composition (1) prepared by adjusting sodium acetate hydrate having the inherent melting point of the system was charged into a 6 l apparatus. Similarly, a latent heat dissipating composition (1) prepared by adjusting sodium acetate hydrate having a unique melting point of the system was filled in a synthetic resin blow container with a unit of 3000 ml (4.3 kg) and a total weight of 4.3 kg with a water volume of 6 liters. It was attached to a container and the calorie volume was 6 l. It shows in Table 1 about the latent heat storage material of an Example. A heater is installed in each of the A, B, and S devices, the water temperature is set to 75 ° C., the heated water is circulated to each sample by an electric pump, and the heat exchange function of A and B is measured in terms of thermal conductivity in Table 2. The difference shown was made. A temperature sensor is connected to the hot water outlet and intake port of the heating device, the incoming water of the device, the outlet, and the main body, and measurement is performed with a temperature data logger. n Amount of water flow meter installed at the water outlet, measuring the outlet n water volume / second of the water collection header, items A, B, S of the heat quantity, melting point, and internal temperature of the system related to the function of heat dissipation / endotherm Table 2 shows the average numerical values.

As a latent heat storage material that uses solar heat, atmospheric heat, waste heat, etc., it has a high heat retention characteristic and improved temperature heat transfer efficiency. Contributes to power saving and the effect of suppressing greenhouse gases. Supplied as heat storage facilities for air conditioning and hot water supply for industrial and agricultural facilities and houses.

1 to 3 reference numeral 1-latent heat storage body / 1a-soft sheet-1b-pillar supporting an independent medium space-1c-latent heat storage composition-2 heat medium and flowing water path-3 projection parts [Sequence Listing Free Text]

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Claims (5)

  Each composition material used as a latent heat storage material has a melting point in the range of 32 ° C. or lower (mainly 7 ° C. to 20 ° C.), 58.5 ° C. or lower (mainly 35 ° C. to 58 ° C.), or 93.5 ° C. or lower. Between the impervious synthetic resin sheets that are soft, light, thin, and lightweight, using a latent heat storage material that has a transition point changed in each range (mainly 70 ° C to 85 ° C) and the melting point adjusted to suit the purpose of use. In the middle of the hollow structure formed by integral injection molding in which the diameter of the cross section proportional to the total thickness forms a square or circular cut, and a plurality of independent hollow structures are supported in parallel, each latent heat It is a latent heat storage body that is filled with a heat storage composition and sealed. The present invention relates to a claim related to a latent heat storage body in which a protrusion is disposed on one surface of the sheet.   A composition having a melting point of 32 ° C. is sodium sulfate hydrate, a composition having a melting point of 57.5 ° C. is sodium acetate hydrate, and a composition having a melting point of 94 ° C. is alum hydrate. For each purpose of use of the composition, the amount of addition of the phase separation inhibitor, the breakthrough cooling inhibitor, and the preparation agent for changing the transition point is 0.1% by weight with respect to 100 parts by weight of the main component for each functional ingredient. The present invention relates to claim 1 relating to a latent heat storage material obtained by adding and mixing the range of 30% by weight or more.   Anti-separation agents are synthetic zeolite, palygorskite, attapulgite, sepiolite, synthetic smectite, fine porous and fibrous ceramics, each having a particle size in the range of 0.1 μ to 100 mesh. The present invention relates to claims 1 and 2 relating to a latent heat storage material prepared in a range of 1 wt% to 30 wt%.   Boronic acid, succinic acid, fluoride (lithium, potassium, sodium), lithium acetate, alum, chelate material (cuberon ethylenediaminetetraacetic acid / 2Na salt nitrilotriacetic acid, 2Na salt triethanolamine) A suitable amount is added to each composition in the range of 0.1 wt% to 30 wt% selected from potassium chloride / lithium / sodium) and mixed to obtain a latent heat storage material. The present invention relates to claims 1 and 3 relating to preparation of a heat storage material using ammonium salt / sodium nitrate as a temperature modulation material.   The container is a single-piece molded product having a structure in which a plurality of the same spaces are arranged in parallel between the hollow spaces between the soft, light and light synthetic resin sheets. Single or / or different synthetic resin processing by extrusion injection molding Effective total thickness of 2.5 mm to 15 mm, and a synthetic resin such as polyethylene, polypropylene, polycarbonate, polyphthalate, etc. Alternatively, hard aluminum is used as the material. The present invention relates to claim 1 relating to a heat storage material container in which a protrusion for securing a flow path of a heat medium during lamination is attached to a plate surface.

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