BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a heat storage material utilizing the latent heat of fusion of CH₃ CO₂ Na·3H₂ O.

2. Description of the Prior Arts

Known heat storage materials utilize the sensible heat or the latent heat. A heat storage material utilizing the latent heat has a larger heat storage capacity per volume or mass than that utilizing the sensible heat, and can store a necessary amount of heat in a smaller quantity, permitting smaller size of the heat storage device. A heat storage material utilizing the latent heat can store and release heat at a constant transition temperature. A heat storage material which utilizes the latent heat of fusion of a hydrate, in particular, is known to have a larger heat storage capacity per unit volume.

CH₃ CO₂ Na·3H₂ O is heretofore known to have a particularly larger latent heat of fusion among hydrates. However, since the melting point of CH₃ CO₂ Na·3H₂ O is not a congruent melting point but a peritectic point, "phase separation" phenomenon proceeds in which CH₃ CO₂ Na deposits on the bottom of the vessel as the fusion and solidification are repeated. For this reason, the latent heat of fusion of CH₃ CO₂ Na·3H₂ O is decreased naturally by repeated storage and release of heat. This decrease of the latent heat accompanying the phase separation has been a major problem when CH₃ CO₂ Na·3H₂ O is used as the heat storage material.

SUMMARY OF THE INVENTION

This invention provides a heat storage material having stable performance and little change of heat storage capacity even under repeated storage and release of heat, comprising sodium acetate and water, admixed with a thickener comprising polyvinyl alcohol, paraffin and one or two components selected from the group consisting of formaldehyde and acetone.

Further, the heat storage material in accordance with the present invention comprises a sodium acetate-water system containing at least 53-69% by weight sodium acetate (CH₃ CO₂ Na), wherein said heat storage material is mixed with a thickener comprising polyvinyl alcohol, paraffin and one or two components selected from the group consisting of formaldehyde and acetone.

DESCRIPTION OF THE PREFERRED EMBODIMENT

The invention is characterized in that a system comprising sodium acetate and water containing at least 53-69% by weight of CH₃ CO₂ Na is mixed with a thickener comprising polyvinyl alcohol (PVA), paraffin and one or two components selected from the group consisting of formaldehyde and acetone; preferably, 100 parts by weight of a system of CH₃ CO₂ Na and H₂ O is mixed with 0.5-20 parts by weight of PVA and 0.1-5 parts by weight of one or two components selected from the group consisting of formaldehyde and acetone.

Reagents on the market, CH₃ CO₂ Na·3H₂ O, PVA, formaldehyde, acetone and paraffin were compounded with H₂ O in specified amounts into the compositions as shown in Table 1 and Table 2. Three types of PVA; about 500, 1500 and 2000 in polymerization degree and three types of paraffin; liquid paraffin, paraffin with a melting point of 42°-44° C., and one with an m.p. of 54°-56° C. were used.

                                  TABLE 1__________________________________________________________________________                     Form-Composition com-          alde-prising CH3 CO2 Na           PVA       hydeand H2 O   Degree    Quan-                          Paraffin      Quantity           of poly-                Quantity                     tity     QuantitySampleCH3 CO2 Na      (weight           meriza-                (weight                     (weight  (weightnumber(weight %)      part)           tion part)                     part)                          Kind*                              part)__________________________________________________________________________ 1   52    100  500  2    0.5  a   1.0 2   54    100  500  2    0.5  a   1.0 3   56    100  500  2    0.5  a   1.0 4   58    100  500  2    0.5  a   1.0 5   60    100  500  2    0.5  a   1.0 6   62    100  500  2    0.5  a   1.0 7   64    100  500  2    0.5  a   1.0 8   66    100  500  2    0.5  a   1.0 9   68    100  500  2    0.5  a   1.010   70    100  500  2    0.5  a   1.011   56    100  500  2    0.5  a   012   56    100  500  2    0.5  a   0.113   56    100  500  2    0.5  a   0.514   56    100  500  2    0.5  a   1.515   56    100  500  2    0.5  a   3.016   56    100  500  2    0.5  a   5.017   56    100  500  2    0.5  a   10.018   56    100  500  2    0    a   1.019   56    100  500  2    0.1  a   1.020   56    100  500  2    0.2  a   1.021   56    100  500  2    5.0  a   1.022   56    100  500  2    10.0 a   1.023   56    100  500  0    0.5  a   1.024   56    100  500  0.1  0.5  a   1.025   56    100  500  0.5  0.5  a   1.026   56    100  500  2.5  0.5  a   1.027   56    100  500  10   0.5  a   1.028   56    100  500  20   0.5  a   1.029   56    100  500  30   0.5  a   1.030   56    100  500  2    0.5  b   1.031   56    100  500  2    0.5  c   1.032   56    100  1500 2    0.5  a   1.033   56    100  2000 2    0.5  a   1.0__________________________________________________________________________ *a: Liquid paraffin b: Paraffin having melting point of 42-44° C. c: Paraffin having melting point of 54-56° C.

                                  TABLE 2__________________________________________________________________________Composition com-prising CH3 CO2 Na           PVA            Paraffinand H2 O   Degree    Acetone  Quan-      Quantity           of poly-                Quantity                     Quantity titySampleCH3 CO2 Na      (weight           meri-                (weight                     (weight  (weightnumber(weight %)      part)           zation                part)                     part)                          Kind*                              part)__________________________________________________________________________34   52    100  500  2    0.5  a   1.035   54    100  500  2    0.5  a   1.036   56    100  500  2    0.5  a   1.037   58    100  500  2    0.5  a   1.038   60    100  500  2    0.5  a   1.039   62    100  500  2    0.5  a   1.040   64    100  500  2    0.5  a   1.041   66    100  500  2    0.5  a   1.042   68    100  500  2    0.5  a   1.043   70    100  500  2    0.5  a   1.044   56    100  500  2    0.5  a   045   56    100  500  2    0.5  a   0.146   56    100  500  2    0.5  a   0.547   56    100  500  2    0.5  a   1.548   56    100  500  2    0.5  a   3.049   56    100  500  2    0.5  a   5.050   56    100  500  2    0.5  a   10.051   56    100  500  2    0    a   1.052   56    100  500  2    0.1  a   1.053   56    100  500  2    0.2  a   1.054   56    100  500  2    5.0  a   1.055   56    100  500  2    10.0 a   1.056   56    100  500  0    0.5  a   1.057   56    100  500  0.1  0.5  a   1.058   56    100  500  0.5  0.5  a   1.059   56    100  500  2.5  0.5  a   1.060   56    100  500  10   0.5  a   1.061   56    100  500  20   0.5  a   1.062   56    100  500  30   0.5  a   1.063   56    100  500  2    0.5  b   1.064   56    100  500  2    0.5  c   1.065   56    100  1500 2    0.5  a   1.066   56    100  2000 2    0.5  a   1.0__________________________________________________________________________ *a: Liquid paraffin b: Paraffin having melting point of 42-44° C. c: Paraffin having melting point of 54-56° C.

A mixture of a specified composition was heated to 70° C. and vigorously stirred using a stirrer for about 60 minutes. A viscous white liquid was obtained. About 100 g of the sample was sealed in a capsule together with 0.5 g of Na₄ P₂ O₇ ·10H₂ O, an anti-supercooling agent for CH₃ CO₂ Na·3H₂ O, and the latent heat of the sample was determined by the dropping method. The capsule containing the sample was heated at 70° C. for about 3 hours to melt the sample, and held further 4 hours at the temperature dropped to 60° C. The capsule was then put into a thermos containing water at about 30° C., and the latent heat of the sample was determined from the rising water temperature caused by it. Then, the capsule containing the sample was put in a water bath and repeatedly heated and cooled 1000 times between 70° C. and 35° C. The latent heat of the sample after 100 times and 1000 times of melting-solidification repetitions was determined by the above dropping method. The results are shown in Table 3. As the evaluation, they are marked in Table 3 with ○ when the latent heat after 1000 melting-solidification repetitions is 45 cal/g or more, with Δ when it is in a range from 40 cal/g to 45 cal/g and with × when less than 40 cal/g. Those marked with ○ can be used practically having a large heat storage capacity, and those marked with Δ can also be put to practical use with stabilized action, though the heat storage capacity is not so large.

              TABLE 3______________________________________Sample Latent heat            Latent heat Latent heatnum-  after a first            after 100 times                        after 1000 times                                  Evalu-ber   time (cal/g)            (cal/g)     (cal/g)   ation______________________________________ 1    55         43          37        X 2    57         53          50        ○ 3    58         57          57        ○ 4    59         57          56        ○ 5    55         53          52        ○ 6    54         53          50        ○ 7    54         50          48        ○ 8    52         50          46        ○ 9    47         45          43        Δ10    45         43          39        X11    57         50          38        X12    57         53          49        ○13    56         54          53        ○14    57         56          55        ○15    56         54          54        ○16    53         53          52        ○17    50         47          44        Δ18    58         48          38        X19    57         55          48        ○20    57         55          52        ○21    53         52          52        ○22    48         47          44        Δ23    58         45          34        X24    57         51          43        Δ25    57         56          54        ○26    57         56          56        ○27    53         52          52        ○28    48         46          46        ○29    43         43          43        Δ30    57         56          56        ○31    57         55          55        ○32    56         55          55        ○33    56         55          55        ○34    53         43          38        X35    56         54          52        ○36    57         57          57        ○37    58         57          56        ○38    55         54          53        ○39    53         53          52        ○40    50         48          48        ○41    49         47          46        ○42    47         44          43        Δ43    44         43          39        X44    58         52          39        X45    57         53          50        ○46    56         54          54        ○47    58         56          55        ○48    57         57          55        ○49    53         51          50        ○50    50         48          43        Δ51    58         48          38        X52    56         54          49        ○53    56         55          53        ○54    54         54          52        ○55    49         47          44        Δ56    59         43          32        X57    57         53          45        Δ58    57         55          55        ○59    58         56          55        ○60    54         53          52        ○61    50         48          47        ○62    45         44          43        Δ63    58         56          56        ○64    57         56          56        ○65    58         57          55        ○66    56         56          56        ○______________________________________

In Table 3, samples 1 to 10 are prepared from 100 parts by weight of a system of CH₃ CO₂ Na and water containing a variable quantity of CH₃ CO₂ Na in a range from 52 to 70% by weight, mixed with 2 parts by weight of PVA, 0.5 parts by weight of formaldehyde, and 1.0 part by weight of paraffin. Sample 1 whose CH₃ CO₂ Na-water system contains 52% by weight CH₃ CO₂ Na releases as large as 55 cal/g heat at the first solidification, but after 1000 times of melting-solidification repetitions, the latent heat is decreased to 37 cal/g. Sample 2 whose CH₃ CO₂ Na--H₂ O system contains 54 parts by weight CH₃ CO₂ Na has a latent heat of 50 cal/g after 1000 times of melting-solidification repetitions, considerably larger than sample 1. Samples 2-6 whose CH₃ CO₂ Na-- H₂ O systems contain CH₃ CO₂ Na in a range from 54 to 68% by weight have latent heats of 50 cal/g or more even after 1000 times of melting-solidifications repetitions. However, sample 10 whose CH₃ CO₂ Na-water system contains 70% by weight CH₃ CO₂ Na has a latent heat of 39 cal/g after 1000 times of melting-solidification repetitions, rather smaller than sample 3. It is found that a heat storage material containing such a thickener shows a maximum latent heat when the composition of CH₃ CO₂ Na-water system is in H₂ O rich side than the given proportion, 60.28% by weight, of CH₃ CO₂ Na in the CH₃ Na·3H₂ O composition, that is, about 56-58% by weight CH₃ CO₂ Na.

Samples 11 to 17 are prepared from 100 parts by weight of a system comprising 50% by weight CH₃ CO₂ Na and water, 2 parts by weight of PVA, and 0.5 parts by weight of formaldehyde mixed with paraffin in a range from zero to 10% by weight. Sample 11 which is free of paraffin has a large initial latent heat of 57 cal/g, but the latent heat largely decreases to 50 cal/g after 100 times and 38 cal/g after 1000 times of melting-solidification. Sample 12 containing 0.1 parts by weight of paraffin has a latent heat of 49 cal/g after 1000 times, considerably larger than that of sample 11. Samples 13 to 16 containing paraffin in a range from 0.5 to 5 parts by weight have larger latent heats of 50 cal/g or more after 1000 melting-solidification repetitions. In sample 17 which is mixed with 10 parts by weight of paraffin, however, the latent heat after 1000 melting-solidification repetitions is decreased to 44 cal/g.

Samples 18-22 comprise 100 parts by weight of a system of 56% by weight CH₃ CO₂ Na and water, 2 parts by weight of PVA, and 1 part by weight of paraffin, mixed with a varying amount of formaldehyde in a range from zero to 10 parts by weight. Sample 18 which is free of formaldehyde has a large initial latent heat of 58 cal/g, but it decreases to 48 cal/g after 100 times and to 38 cal/g after 1000 times. Sample 19 which contains 0.1 parts by weight of formaldehyde has a latent heat of 48 cal/g after 1000 melting-solidification repetitions, a considerably smaller decrease in comparison with sample 18. Samples 20 and 21 containing formaldehyde in a range from 0.2 to 5 parts by weight have latent heats of 50 cal/g or more after 1000 melting-solidification repetitions. However, sample 22 which contains 10 parts by weight of formaldehyde has a latent heat after 1000 melting-solidification repetitions decreased to 44 cal/g.

Samples 23-29 comprise 100 parts by weight of a system comprising 56% by weight CH₃ CO₂ Na and water, 0.5 parts by weight of formaldehyde, and 1 part by weight of paraffin mixed with PVA in varying amounts in a range from zero to 30 parts by weight. Sample 23 which is free of PVA has the initial latent heat as large as 59 cal/g, but it decreases to 45 cal/g after 100 times and to 34 cal/g after 1000 times of melting-solidification repetition. In sample 24 which contains 0.1 part by weight of PVA, the latent heat after 1000 times is 43 cal/g, considerably larger than that of sample 23. Samples 25-27 containing PVA in a range from 0.5 to 10 parts by weight have latent heat after 1000 times of melting-solidification repetition as large as 50 cal/g or more. However, sample 29 containing 30 parts by weight of PVA has a latent heat after 1000 times of melting-solidification repetition of 43 cal/g, considerably smaller in comparison with that of sample 26.

Samples 30 and 31 use paraffin having melting point higher than room temperature, instead of liquid paraffin on the market used so far. Little difference is found in their latent heat from that of samples using liquid paraffin.

Samples 32 and 33 use PVA of about 1500 and about 2000 in polymerization degree, respectively. Little difference of latent heat is found in these cases from that when PVA of 500 in polymerization degree is used.

Data in Table 4 are then analyzed. Samples 34-43 comprise 100 parts by weight of a CH₃ CO₂ Na--H₂ O system containing a variable quantity of CH₃ CO₂ Na in a range from 52 to 70% by weight, mixed with 2 parts by weight of PVA, 0.5 parts by weight of acetone, and 1.0 part by weight of paraffin. Sample 34 which contains 52% by weight CH₃ CO₂ Na in the CH₃ CO₂ Na system releases at the first solidification a large heat quantity of 53 cal/g, but it is decreased to 38 cal/g after 1000 times of melting-solidification repetitions. In sample 35 containing 54 parts by weight of CH₃ CO₂ Na in the CH₃ CO₂ Na--H₂ O system, the latent heat after 1000 times of melting-solidification repetition is 52 cal/g, considerably larger than sample 1. Samples 35-39 which contain CH₃ CO₂ Na in a range 54-68% by weight have latent heat larger than 50 cal/g even after 1000 times of melting-solidification repetition. However, sample 10 which contains 70% by weight CH₃ CO₂ Na in the CH₃ CO₂ Na--H₂ O system has a latent heat of 39 cal/g after 1000 times of repetition, considerably small in comparison with sample 36 which has a large latent heat. It is found in the heat storage material containing such thickeners that the maximum latent heat appears when the composition of the CH₃ CO₂ Na--H₂ O system is in H₂ O-rich side than the given ratio of CH₃ CO₂ Na·3H₂ O composition, 60.28% by weight CH₃ CO₂ Na, that is, about 56-58% by weight CH₃ CO₂ Na.

Samples 44-50 comprise 100 parts by weight of a CH₃ CO₂ Na--H₂ O system containing 56% by weight of CH₃ CO₂ Na, 2 parts by weight of PVA, and 0.5 parts by weight of acetone, mixed with paraffin in a varied quantity in the range from zero to 10% by weight. In sample 44 which is free of paraffin, the latent heat at the first solidification is as large as 58 cal/g, but it largely decreases to 52 cal/g after 100 times, and to 39 cal/g after 1000 times of melting-solidification repetition. In sample 45 containing 0.1 parts by weight of paraffin, the latent heat after 1000 melting-solidification repetitions is 50 cal/g, considerably larger than that in sample 44. In samples 46-49 which contain paraffin in a range of 0.5-5 parts by weight, the latent heat after the 1000 repetitions is as large as 50 cal/g or more. However, in sample 50 which contain 10 parts by weight of paraffin, the latent heat after the 1000 repetitions decreases to 43 cal/g.

Samples 51-55 comprise 100 parts by weight of a CH₃ CO₂ Na--H₂ O system containing 56% by weight CH₃ CO₂ Na, 2 parts by weight of PVA, and 1 part by weight of paraffin, mixed with acetone in a varied quantity in a range from zero to 10 parts by weight. In sample 51 which is free of acetone, the latent heat at the first solidification is as large as 58 cal/g, but it decreases to 48 cal/g after 100 times and to 38 cal/g after 1000 times of melting-solidification repetition. In sample 52 containing 0.1 part by weight of acetone, the latent heat after the 1000 repetitions is 49 cal/g, considerably smaller decrease in comparison with sample 51. Samples 53 and 54 containing 0.2 to 5 parts by weight of acetone have large latent heats of 50 cal/g or more after 1000 times of melting-solidification repetition. However, in sample 56 containing 10 parts by weight of acetone, the latent heat after 1000 times of the repetition is decreased to 44 cal/g.

Samples 56-62 comprise 100 parts by weight of a CH₃ CO₂ Na--H₂ O system containing 56% by weight of CH₃ CO₂ Na, 0.5 parts by weight of acetone, and 1 part by weight of paraffin, mixed with a varied quantity of PVA in a range from zero to 30 parts by weight. In sample 56 which is free of PVA, the latent heat at the first solidification is as large as 59 cal/g, but it is decreased to 43 cal/g after 100 times and to 32 cal/g after 1000 times of melting-solidification repetition. In sample 57 containing 0.1 parts by weight of PVA, the latent heat after the 1000 repetitions is 45 cal/g, considerably large in comparison with sample 56. In sample 58-60 containing PVA in a range of 0.5-10 parts by weight, the latent heat after 1000 melting-solidification repetitions is as large as 50 cal/g or more. However, sample 62 containing 30 parts by weight of PVA has a latent heat of 43 cal/g after 1000 times of the repetition, considerably reduced in comparison with sample 59.

Samples 63 and 64 use PVA of about 1500 and 2000 in polymerization degree, respectively. In these cases, the latent heat is little different from that in the case where PVA of 500 in polymerization degree is used.

As shown above, a CH₃ CO₂ Na system containing CH₃ CO₂ Na in a range from 53 to 69% by weight provides, when admixed with a thickener comprising PVA, paraffin and one or two components selected from the group consisting of formaldehyde and acetone give a heat storage material which has a stabilized heat storage capacity little changed even after being subjected to repeated melting and solidification. A preferable composition of the heat storage material is in the range marked by ○ in Tables 3 and 4, that is, 100 parts by weight of the system comprising CH₃ CO₂ Na and H₂ O, 0.5-20 parts by weight of PVA, 0.1-5 parts by weight of one or two components out of formaldehyde and acetone, and 0.1-5 parts by weight of paraffin.

INDUSTRIAL UTILITY

The heat storage material according to the invention is provided with a very stable performance of heat storage with little change of the capacity even after repeated melting and solidification, being composed of a CH₃ CO₂ Na--H₂ O system containing 53-69% by weight of CH₃ CO₂ Na and mixed with a thickner comprising PVA, paraffin and one or two components selected from the group consisting of acetone and formaldehyde to prevent phase separation as described above. Therefore, it can be widely applied to a field using heat storage including a heat storage device for air conditioning.