Abstract:
A heat storage composition comprising sodium sulfate decahydrate as main component, a supercooling inhibitor, and a solid-liquid separation inhibitor, characterized in that hydraulic calcium sulfate and/or calcium sulfate dihydrate is contained as the solid-liquid separation inhibitor in an amount of 2-15% by weight based on the whole weight of the composition, whereby the solid-liquid separation, i.e. the sedimentation of the anhydrous sodium sulfate during the phase transition, is effectively prevented and the long-term stability is improved. The long-term stability of the composition can be more improved by addition of a silica series of thickener.

Description:
BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     The present invention relates to a heat storage composition superior in long-term stability, which is composed mainly of sodium sulfate decahydrate. More particularly, the invention relates to a heat storage composition characterized by additionally containing calcium sulfate as a solid-liquid separation inhibitor. 
     2. Description of the Prior Art 
     There has long been known the concept that thermal energy is stored and reproduced by utilizing the absorption and release of heat due to change in phase of a hydrate salt compound between fusion and solidification. According to results of studies reported up to now, it is pointed out that two problems arise when this method for heat storage is reduced into practical use. The first problem is that hydrate salts often show a so-called supercooling phenomenon without undergoing the phase transition of fusion or solidification at the respective fusion points or freezing points. Accordingly such supercooling needs to be prevented in order to cause the phase transition at a definite temperature. For example, U.S. Pat. No. 2,677,664 describes a method for preventing such supercooling which comprises addition of borax (Na 2  B 4  O 7  ·10H 2  O) as a supercooling inhibitor for Na 2  SO 4  ·10H 2  O. Crystals of Na 2  B 4  O 7  ·10H 2  O are reported to be in epitaxial relation with crystals of Na 2  SO 4  ·10H 2  O and when contained in a supersaturated solution of Na 2  SO 4  ·10H 2  O, promote the crystallization of Na 2  SO 4  ·10H 2  O, thus preventing the supercooling effectively (Industrial and Engineering Chemistry, Vol. 44, pp. 1308-1310 (1952)). The use of Ba(OH) 2  or Ba(OH) 2  ·8H 2  O (Japanese Patent Publication No. 9596/1978) and the use of BaI 2  or BaSO 4  (Japanese Patent Application Laid-Open No. 102675/1980) are also known as methods for preventing the supercooling of CaCl 2  ·6H 2  O. 
     The second problem is the occurrence of a solid-liquid separation phenomenon, that is, the sedimentation of an anhydrous salt during the phase transition of the hydrate salt thereof. For example, Na 2  SO 4  ·10H 2  O is decomposed at 32.4° C. to form an anhydrous salt thereof and this anhydrous salt settles on the bottom. On cooling to a temperature below 32.4° C., the anhydrous salt is recombined with water to become Na 2  SO 4  ·10H 2  O. However, crystals of Na 2  SO 4  ·10H 2  O cover the surface and hence the lower part of the anhydrous salt is inhibited from the water recombination, thus producing floating water, i.e., bleeding. Therefore, the anhydrous salt needs to be prevented from the sedimentation. In general a solid-liquid separation inhibitor is used for the purpose of preventing the sedimentation. In this case, the long-term stability of the resulting heat storage composition should be satisfied. The use of an organic material such as natural rubber or a synthetic high polymer as the solid-liquid separation inhibitor is undesirable since these organic materials can be gradually hydrolyzed or attacked by microorganisms to decomposition. The use of inorganic materials has been proposed such as a porous support (Japanese Patent Publication No. 6108/1978), a clay type of material having lath-like particles for providing a thixotropic property (Japanese Patent Application Laid-Open No. 34687/1978), and a superfine powder of anhydrous silicic acid (SiO 2 ) (Chemical Week, Mar. 1, 1978, p. 34). However, the use of these inorganic materials tends to result in a gradual reduction of the viscosity of the heat storage composition and leads to the solid-liquid separation during repetition of the heat absorption-radiation cycle for a long time, so that the ability thereof to prevent the solid-liquid separation cannot be said to be sufficient. Additionally, some of these inorganic materials are natural products yielding in special teritories and some of these are expensive. Thus, economy becomes an issue when these inorganic materials are practically used, since the original object of heat storage materials is energy conservation. 
     In view of the present situation noted above, the present inventors made extensive studies on the long-term stability of heat storage materials composed mainly of Na 2  SO 4  ·10H 2  O, and as a result have found that the stability is markedly improved by addition of calcium sulfate as a solid-liquid separation inhibitor to Na 2  SO 4  ·10H 2  O. Based on this finding, the present invention has been accomplished. 
     SUMMARY OF THE INVENTION 
     The first object of the invention is to provide a novel heat storage composition which utilizes the phenomenon of absorption and release of heat due to change in phase of a hydrate salt compound. 
     The second object of the invention is to provide a heat storage composition superior in anti-supercooling property, which is composed mainly of Na 2  SO 4  ·10H 2  O. 
     The third object of the invention is to provide a heat storage composition composed mainly of Na 2  SO 4  ·10H 2  O, which is improved in the solid-liquid separation inhibiting property and superior in long-term stability. 
     According to the invention, there is provided a heat storage composition comprising sodium sulfate decahydrate as main component, a supercooling inhibitor, and a solid-liquid separation inhibitor, characterized in that calcium sulfate is contained as the solid-liquid separation inhibitor in an amount of 2 to 15% by weight based on the whole weight of the composition. 
     DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS 
     The heat storage composition of the invention comprises sodium sulfate decahydrate as main component, a supercooling inhibitor, and a solid-liquid separation inhibitor and is characterized in that the solid-liquid separation inhibitor is hydraulic calcium sulfate and/or calcium sulfate dihydrate. 
     The main component sodium sulfate decahydrate termed in the invention consists of Na 2  SO 4  ·10H 2  O with or without some additional water, and for example, is formed from Na 2  SO 4  ·10H 2  O or from Na 2  SO 4  and H 2  O. The H 2  O/Na 2  SO 4  molar ratio is in the range of 10 to 15. When it is lower than 10, the heat storage capacity will be insufficient because of the lack of the water to be recombined with Na 2  SO 4 . When the ratio is higher than 15, the heat storage capacity will be also insufficient because of the low concentration of Na 2  SO 4 . 
     The calcium sulfate used as the solid-liquid separation inhibitor, the characteristic of this invention, includes those of hydraulic type such as a hydraulic anhydrous calcium sulfate (CaSO 4  of type III) and α-type and β-type of calcium sulfate hemihydrates (α-type and β-type of CaSO 4  ·1/2H 2  O); and those in dihydrate form such as synthetic gypsum and by-product gypsum. Suitable contents of such a calcium sulfate in the heat storage composition are 2-15%, particularly 3-7%, by weight. The content less than 2% by weight is too low for the sufficient formation of the matrix and the effect of preventing the solid-liquid separation is poor. The content more than 15% by weight results in an undesirably low capacity of heat storage because of the decreased concentration of Na 2  SO 4 , though the formation of the matrix is satisfactory. 
     Hydraulic calcium sulfate in water is hydrated into calcium sulfate dihydrate (CaSO 4  ·2H 2  O). It is well known that calcium sulfate dihydrate is reacted with sodium sulfate in an aqueous solution thereof to form double salts. For example, &#34;Gypsum&#34; by Michio Sekiya (published by Gihodo Co., Ltd., 1965, p. 104) describes the formation of the following double salts: 
     
         Na.sub.2 SO.sub.4 ·CaSO.sub.4, 
    
     
         Na.sub.2 SO.sub.4 ·CaSO.sub.4 ·4H.sub.2 O, 
    
     
         2Na.sub.2 SO.sub.4 ·CaSO.sub.4 ·2H.sub.2 O, 
    
     
         Na.sub.2 SO.sub.4 ·5CaSO.sub.4 ·3H.sub.2 O 
    
     Accordingly, an Na 2  SO 4  --H 2  O system on stirring with hydraulic calcium sulfate and/or calcium sulfate dihydrate yields CaSO 4  ·2H 2  O and/or the above double salts. The resulting CaSO 4  ·2H 2  O and/or the above double salts are in the form of fine acicular crystals. These crystals are entangled and distributed throughout the mixed system to form a matrix. The thus formed matrix exhibits the effect of preventing the solid-liquid separation in the heat storage composition of the invention. In such a mixed system as stated above, considerable time is required for completing the hydration of hydraulic calcium sulfate or for completing the double salt-producing reaction of calcium sulfate dihydrate, because the reaction is completed through the steps of dissolution of calcium sulfate→reaction→crystallization of dihydrate or double salts. Therefore, the stirring needs to be continued from the addition of the hydraulic calcium sulfate and/or calcium sulfate dihydrate to the Na 2  SO 4  --H 2  O system until some amounts of dihydrate or double salt crystals appear and the viscosity of the slurry is raised thereby. The sedimentation of the unreacted calcium sulfate is prevented by these partially appearing crystals, and crystals are formed uniformly throughout the system. 
     It should be noted that the effect of the invention cannot be obtained by dissolving the above double salts in a water-sodium sulfate mixture, since the matrix is not formed thereby. 
     It is desirable to add a thickener to the heat storage composition of the invention for the purpose of preventing the unreacted calcium sulfate from sedimentation. Suitable thickeners for this purpose include silica thickeners, for example, amorphous silica in fine powder and polysilicic acid. Both the thickeners are effective in raising the viscosity of the Na 2  SO 4  --H 2  O system, and preventing the sedimentation of the unreacted calcium sulfate, and additionally have in the themselves the effect of preventing the solid-liquid separation, thus more improving the long-term stability of the composition. 
     Fine powders of amorphous silica which can be added as desired for the thickening include those produced by the dry process and the wet process, which are well known by the common name of white carbon. These are readily available as sold under the tradenames Aerosil® (Nippon Aerosil Co., Ltd.), Tokusil® (Tokuyama Soda Co., Ltd.), Nipsil® (Nippon Silica Co., Ltd.), and Syloid® (Fuji-Davison Chemical, Ltd.). Suitable contents of the thickener are 0.5-10%, particularly 1-7%, by weight. The content, when less than 0.5% by weight, is too low for exhibiting the thickening effect, and when more than 10% by weight, reduces the heat storage capacity undesirably because of the decreased concentration of Na 2  SO 4  and raises the cost considerably. 
     When polysilicic acid is formed by mixing sodium silicate with sulfuric acid, water glass or sodium metasilicate is used for the sodium silicate. Desirably, water glass is used after being diluted with about the same weight of water and the concentration of sulfuric acid used is also lowered. For mixing sodium silicate with sulfuric acid, the way of feeding sodium silicate into surfuric acid is preferred to the way of the reverse feeding since polysilicic acid produced in an acidic medium is superior in thickening effect. Sodium silicate and sulfuric acid are used in such amounts as to be just neutralized and to give a silicic acid concentration in terms of SiO 2  lying within the same range as of the above fine powder of amorphous silica, that is, the range of 0.5 to 10% by weight. 
     Suitable supercooling inhibitors for use in the heat storage composition of the invention include ammonium borate, lithium borate, and borax. In particular, borax (Na 2  B 4  O 7  ·10H 2  O) is effective. The content of borax is in the range of 2 to 15% by weight. 
     Furthermore, a fusion point requlator may be added if necessary. Examples thereof are inorganic salts including NaCl, KCl, NH 4  Cl, and NaNO 3 . The amount of the regulator to be added is in the range of 0.2 to 1.0 mole per 1 mole of Na 2  SO 4 . With the regulator in an amount in this range, an intended fussion point can be obtained. 
     According to the present invention, there is provided, as described above, a heat storage composition which is effectively protected from the solid-liquid separation and markedly improved in stability. Thus, the invention much contributes to putting heat storage compositions into practical use. 
    
    
     The invention is illustrated in more detail with reference to the following example; however the invention is not limited by any of these examples. In the examples, &#34;parts&#34; are all by weight. The heat of fusion of heat storage compositions was measured as follows: A polyethylene pouch packed with 30 g of each specimen was put into 300 ml of warm water contained in a Dewar vessel. The change in the temperature of the water was measured to calculate the heat of fusion therefrom. The hardness was measured by placing a round rod with a weight of 500 gr. on the same specimen and determining the depth of the round rod penetrating into the specimen in 30 secs. When the depth is above 5 mm, the hardness is herein referred to as &#34;bad&#34;, and when the depth is below 5 mm, the hardness is referred to as &#34;good&#34;. 
     EXAMPLE 1 
     A viscous composition was obtained by stirring the following mixture at 30° C. for 130 minutes and adding 3 parts of borax to the mixture. 
     Anhydrous sodium sulfate: 31.60 parts 
     Water: 52.15 parts 
     Sodium chloride: 6.50 parts 
     α-Hemihydrate gypsum (α-type of CaSO 4  ·1/2H 2  O): 6.75 parts 
     In one-day standing at about 30° C., the composition turned into a non-thixotropic solid without bleeding. 
     EXAMPLE 2 
     A viscous composition was obtained by stirring the following mixture at 35° C. for 80 minutes and adding 3 parts of borax. 
     Anhydrous sodium sulfate: 37.27 parts 
     Water: 57.03 parts 
     α-Hemihydrate gypsum (α-type of CaSO 4  ·1/2H 2  O): 2.53 parts 
     Fine powder of silica (Tokusil®P, supplied by Tokuyama Soda Co., Ltd.): 3.0 parts 
     In one-day standing at 35° C., the composition turned into a non-thixotropic solid without bleeding. The found heat of fusion of the composition was 49.6 Cal/g. 
     EXAMPLE 3 
     Similarly to Example 2, a viscous composition was obtained by stirring the following mixture for 80 minutes and adding 3 parts of borax. 
     Anhydrous sodium sulfate: 35.29 parts 
     Water: 54.97 parts 
     α-Hemihydrate gypsum (α-type of CaSO 4  ·1/2H 2  O): 6.74 parts 
     Fine powder of silica (Tokusil®P, supplied by Tokuyama Soda Co., Ltd.): 3.0 parts 
     After one-day standing, the composition showed a hardness higher than that of the composition of Example 2. The found heat of fusion of the composition was 43.7 Cal/g. 
     EXAMPLE 4 
     Similarly to Example 2, a viscous composition was obtained by stirring the following mixture for 80 minutes and adding 3 parts of borax. 
     Anhydrous sodium sulfate: 36.47 parts 
     Water: 56.30 parts 
     α-Hemihydrate gypsum (α-type of CaSO 4  ·1/2H 2  O): 4.22 parts 
     Fine powder of silica (Tokusil®P, supplied by Tokuyama Soda Co., Ltd.): 3.0 parts 
     After one-day standing, the composition was exposed to temperature cycles of 40° C.⃡10° C. 28 times, and the hardness, the state of bleeding and the heat of fusion were measured. Results thereof are shown in Table 1. 
     EXAMPLE 5 
     A viscous composition was obtained by stirring the following mixture at 25° C. for 80 minutes and adding 3 parts of borax. 
     Anhydrous sodium sulfate: 33.73 parts 
     Water: 52.12 parts 
     Sodium chloride: 6.94 parts 
     α-Hemihydrate gypsum (α-type of CaSO 4  ·1/2H 2  O): 4.22 parts 
     Fine powder of silica (Tokusil®P, supplied by Tokuyama Soda Co., Ltd.): 3 parts 
     In one-day standing at about 25° C., the composition turned into a non-thixotropic solid. It was exposed to temperature cycles of 35° C.⃡10° C. 28 times, and the hardness, the state of bleeding, and the heat of fusion were measured. Results thereof are shown in Table 1. 
     EXAMPLE 6 
     A composition was prepared in the same manner from the same material mixture as in Example 5, except that Aerosil®200 (supplied by Nippon Aerosil Co., Ltd.) was substituted for the fine powder of silica. The composition showed a sufficient hardness and no bleeding. 
     The composition was exposed to temperature cycles of 35° C.⃡10° C. 28 times, and the hardness, the state of bleeding, and the heat of fusion were measured. Results thereof are shown in Table 1. 
     EXAMPLE 7 
     A composition was prepared by adding 30.15 parts of anhydrous sodium sulfate to 43.64 parts of a 1.54 wt% concentration of sulfuric acid with stirring at about 30° C., gradually adding 10.20 parts of a 1:1 (weight ratio) water glass No. 3-water mixture, further adding 6.40 parts of sodium chloride and 6.55 parts of α-hemihydrate gypsum (α-type of CaSO 4  ·1/2H 2  O), stirring the mixture for 20 minutes, adding then 3 parts of borax, and continuing stirring further for 60 minutes. In one-day standing at about 30° C., the composition was solidified without bleeding. 
     COMPARATIVE EXAMPLE 1 
     In accordance with the same procedures as in Example 4, a composition was prepared from the following mixture. 
     Anhydrous sodium sulfate: 42.76 parts 
     Water: 54.23 parts 
     Fine powder of silica (Aerosil®200, supplied by Nippon Aerosil Co., Ltd.): 7.0 parts 
     Borax: 3.0 parts 
     The composition was exposed to temperature cycles of 40° C.⃡10° C. 12 times, and the hardness, the state of bleeding, and the heat of fusion were measured. Results thereof are shown in Table 1. 
     
                       TABLE 1______________________________________Before temperature  After temperaturecycle test          cycle test              Heat of              Heat ofHard-      Bleed-  fusion   Hard- Bleed-                                   fusionness       ing     (Cal/g)  ness  ing   (Cal/g)______________________________________Example  Good    None    45.5   Good  None  43.9Example  Good    None    33.5   Good  None  31.15Example  Good    None    33.9   Good  None  31.56Com-   Good    None    49.7   Bad   Ca. 10                                     37.4parative                            vol %Example1______________________________________ 
    
     EXAMPLE 8 
     A viscous composition was obtained by stirring the following mixture at 35° C. for 60 minutes. 
     Anhydrous sodium sulfate: 300.0 parts 
     Water: 483.3 parts 
     Sodium chloride: 61.7 parts 
     Synthetic gypsum (CaSO 4  ·2H 2  O): 40.0 parts 
     Borax: 30.0 parts 
     Fine powder of silica (Aerosil®200, supplied by Nippon Aerosil Co., Ltd.): 20.0 parts 
     After one-day standing, the composition was exposed to temperature cycles of 40° C.⃡10° C. 48 times. The results showed neither the appearance of bleeding nor the sedimentation of anhydrous sodium sulfate. 
     EXAMPLE 9 
     A viscous composition was obtained by stirring the following mixture at 35° C. for 50 minutes. 
     Anhydrous sodium sulfate: 36.37 parts 
     Water: 46.14 parts 
     Sodium chloride: 7.48 parts 
     Synthetic gypsum (CaSO 4  ·2H 2  O): 7.00 parts 
     Borax: 3.00 parts 
     In one-day standing at about 30° C., the composition turned into a non-thixotropic solid. It was exposed to temperature cycles of 40° C.⃡10° C. 78 times, and the hardness, the state of bleeding, and the heat of fusion were measured. Results thereof are shown in Table 2. 
     EXAMPLE 10 
     A viscous composition was obtained by stirring the following mixture at 35° C. for 40 minutes. 
     Anhydrous sodium sulfate: 35.56 parts 
     Water: 45.12 parts 
     Sodium chloride: 7.32 parts 
     Synthetic gypsum (CaSO 4 .2H 2  O): 9.00 parts 
     Borax: 3.00 parts 
     In one-day standing at about 30° C., the composition turned into a non-thixotropic solid. It was exposed to temperature cycles of 40° C.⃡10° C. 78 times, and the hardness, the state of bleeding, and the heat of fusion were measured. Results thereof are shown in Table 2. 
     EXAMPLE 11 
     A viscous composition was obtained by stirring the following mixture at 35° C. for 50 minutes. 
     Anhydrous sodium sulfate: 39.67 parts 
     Water: 50.33 parts 
     Synthetic gypsum (CaSO 4  ·2H 2  O): 7.00 parts 
     Borax: 3.00 parts 
     In one-day standing at about 30° C., the composition turned into a non-thixotropic solid. It was exposed to temperatures cycles of 40° C.⃡10° C. 78 times, and the hardness, the state of bleeding, and the change in the heat of fusion were measured. Results thereof are shown in Table 2. 
     COMPARATIVE EXAMPLE 2 
     Similarly to Examples 9, a composition was prepared from the following mixture. 
     Anhydrous sodium sulfate: 38.80 parts 
     Water: 49.22 parts 
     Sodium chloride: 7.98 parts 
     Synthetic gypsum (CaSO 4  ·2H 2  O): 1.00 part 
     Borax: 3.00 parts 
     The composition was exposed to temperature cycles of 40° C.⃡10° C. 78 times, and the hardness, the state of bleeding and the heat of fusion were measured. Results thereof are shown in Table 2. 
     
                       TABLE 2______________________________________Before temperature  After temperaturecycle test          cycle test              Heat of              Heat ofHard-      Bleed-  fusion   Hard- Bleed-                                   fusionness       ing     (Cal/g)  ness  ing   (Cal/g)______________________________________Example  Good    None    30     Good  None  30Example  Good    None    27     Good  None  2710Example  Good    None    48     Good  None  4811Com-   Bad     5 vol   38     Bad   20 vol                                     31parative       %                    %Example2______________________________________