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WHAT IS THE BEST POSSIBLE HEAT STORAGE DENSITY FOR A SEASONAL ADSORPTIVE THERMAL ENERGY STORAGE

U. R. Fischer Brandenburg University of Technology Cottbus Department of Applied Physics/Thermophysics PF 101344, 03013 Cottbus, Germany Tel: +49-355-692315 fischer@tu-cottbus.de

ABSTRACT The heat storage density of a seasonal adsorptive TES depends on various factors such as the maximum desorption temperature TDES and the minimum condensation temperature TCOND during the desorption phase as well as the minimum adsorption temperature TADS and the maximum evaporation temperature TEVA during the adsorption phase. Changes of these temperatures alter immediately the storage density of the adsorption materials. The objective of this paper is to focus the attention not only on the adsorption capacity but also on a maximum binding energy and hence a maximum desorption temperature TDES. It is shown, that a high binding energy is advantageously for a maximum heat storage density, because more environmental heat is gained during the adsorption phase. For this purpose computer calculations of the heat storage density were performed for various zeolite water pairs using material data from own adsorption measurements as well as sorption isotherm data from the literature.

1.

BACKGROUND

In the last years several research projects were carried out to investigate the possibility of seasonal heat storage by adsorptive techniques. The advantage should be the loss free heat storage with a higher storage density compared to conventional sensible heat storage. It was expected to achieve energy densities up to about 170 kWh/m3 for an adsorptive heat storage with the pair water silica gel. This is a factor two or three in comparison to common sensible hot water storages. Up to now, these expectations are not fulfilled. Laboratory prototypes of adsorption storages give for instance storage densities (including all volumes of heat exchangers and separate vessels) of about 33 kWh/m3 for silica gel or about 58 kWh/m3 for zeolite 13X. The energy densities of the materials are 50 kWh/m3 for silica gel and 180 kWh/m3 for zeolite 13X in this cases [Bales 2007]. Due to the high costs for the adsorption materials, adsorptive heat pump processes with a shorter cycle time than seasonal storages are suggested to offer the better research perspective. Presently, seasonal heat storages require inexpensive materials. The more the price of fossil energy increases, the more a sorption seasonal heat storage becomes a better competitive position in comparison with a sorption heat pump driven by a gas burner. This is because the sorption heat pump with gas burner only gains a small part of the heat from the environment, but generates the main part from natural gas. The sorption seasonal heat storage automatically improves the amortisation and therefore more expensive materials become feasible. If an adsorbent with low binding enthalpy like silica gel is used, almost the entire adsorption enthalpy must be delivered for the evaporator of the storage system in the cold season. Also

the temperature lift (the difference between the adsorption temperature TADS and the temperature of the evaporator TEVA) is small. For adsorbents with greater specific inner surfaces and therefore smaller pore diameters also the binding enthalpy increases. In a comparison between two adsorbents with different inner surfaces but same porosity at an adsorption state with the same relative pressure, the adsorbent with the greater inner surface has a higher adsorption capacity with a greater release of binding enthalpy. In round terms, the fraction of binding enthalpy is direct proportional to the inner surface. The fraction of binding enthalpy is directly stored from summer to winter perfectly without losses [Fischer 2003]. On the one hand these adsorbents need a smaller fraction of heat for the evaporator and on the other hand the temperature lift increases. The latter fact in turn yields the possibility to use more environmental heat at low temperatures. For instance ground water with a temperature of about 10C is usable as heat source for the evaporator with zeolites, but disadvantageously with silica gels. Due to the higher binding forces between adsorbate and adsorbent in the case of zeolites, the desorption temperature increases up to 180C 250C. This temperature range is technically feasible with vacuum tube or concentrated solar collectors. In regard of the facts above, modifications of zeolites e.g. with ion exchange to decrease the desorption temperature should be deliberated against the disadvantages of the lower binding enthalpy.

2.

EXPERIMENTAL

For the calculation of the storage density the knowledge of the minimal and maximal adsorbed water mass Xmin and Xmax (in kgwater/kgadsorbent) and of the specific binding enthalpy hbind(X) (in kJ/kgwater) as a function of the adsorbed water mass X is necessary. The masses Xmin and Xmax were gained from the data from the sorption isotherms with the relative p (T ) humidities MIN = pS (TCOND ) and MAX = S EVA under the assumption of pressure pS (TADS ) pS (TDES ) equilibrium between adsorber/desorber and evaporator/condenser with the temperatures of desorption TDES, adsorption TADS, condensation TCOND and evaporation TEVA. From the equilibrium of the specific free enthalpies (under the presumption that only physical adsorption and no chemical reaction takes place) between the vapor and the adsorbed liquid phase follows the equation for the calculation of the specific binding enthalpy hbind

h (ln ) = bind 1 R T X = const

(1)

with the relative humidity, T the adsorption temperature (in K), X the adsorbed water mass (in kgwater/kgadsorbent) and R the gas constant of water. Especially in the case of organic adsorbents with additional heat of hydration or heat of solution measurements of several adsorption isotherms at different temperatures are necessary to obtain the specific binding enthalpy hbind(X) as a function of the adsorbed mass X. A plot of ln versus T-1 at constant X gives a straight line, the slope being direct proportional to the specific binding enthalpy hbind. In the case of inorganic adsorbents it is often sufficient to use directly the equation

hbind = RT ln

(2)

Equations (1) and (2) do not hold for very low relative humidities with an adsorption coverage of less than a monolayer (Eq. (2) would give hbind for 0). I this case the binding enthalpy of the monolayer can derived e.g. from the Langmuir isotherm or if applicable from the BET C-value with hbind = RT ln C [Webb, Orr 1997]. Due to the assumptions of these models, the real surface area and the binding enthalpy of the monolayer of zeolites are higher than the data derived from the BET-model but lower than the data derived from the Langmuir model. For instance in the case of surfaces of metals or metal oxides the binding enthalpy of the monolayer exceeds the condensation enthalpy up to a factor of four [Ruthven 1984]. The calculation of the integral binding enthalpy was performed with

H bind =

X MAX

X MIN

bind

( X )dX

(3)

with hbind derived from eq. (2). In the case the zeolite is dried during the desorption step to a water mass X lower than the monolayer coverage, the calculation was performed according

H bind = H bind ( X MONO ) +

X MAX

X MONO

bind

( X )dX

(4)

The total integral adsorption enthalpy is the sum of integral binding and condensation enthalpy. For various zeolites the adsorption isotherms were gravimetrically measured using saturated salt solutions. Additional data from sorption isotherms for the calculations were selected from literature [Stach 2001/2003, Krischer 1992]. Especially faujasite type and A-zeolite materials with both high binding enthalpy and adsorption capacity were chosen. The zeolite 4A (Nr. 1 in table 1) is Kstrolith 4A from Chemiewerk Bad Kstritz, Germany. The 4A-materials Nr. 2 and 3 from table 1 are different 4A-zeolites measured by other authors. Both measured 13-zeolites (Nr. 4 and 5 in table 1) are also from Chemiewerk Bad Kstritz, the first in granular the latter in powder constitution.

3.

RESULTS AND DISCUSSION

Table 1 contains an overlook over all calculated integral binding enthalpies, condensation enthalpies, adsorption enthalpies and storage densities for different sets of TDES, TCOND, TADS and TEVA. The calculated storage densities are in all cases the energy densities of the adsorptive material itself. The condenser temperature was set for all calculations to TCOND = 10C. This is a practical condensation temperature level, delivered by a buried ground heat exchanger. For the calculation of the condensation enthalpy the temperature TADS was used (TADS = 35C and TADS = 60C resp.). For all zeolite materials the optimal case at TDES = 250C, TCOND = 10C, TADS = 35C and TEVA = 20C is printed bold. Due to the longterm storage times over several months, all sensible heat was neglected. The calculation results show, that the faujasite type 13X and LiLSX zeolites exhibit the best performance under most temperature conditions. Figure 1 illustrates a comparison of the storage densities with different desorption and evaporation temperatures. On the on hand there is plotted the optimal case with TDES = 250C and TEVA = 20C, on the other hand the more practical case with TDES = 180C and TEVA = 10C. It can be seen, that especially with the 13X materials there is only a slight decrease in the storage densities with the drop of TDES and TEVA. The decrease of the storage densities is still smaller, if in the comparison the evaporator temperature TEVA is held constant. This case with TEVA = 10C is shown in Figure 2. Figure 3 compares the storage densities with equal desorption temperature TDES = 180C but different adsorption temperatures of TADS = 35C and TADS = 60C. The first adsorption temperature is sufficient for a low temperature heating, the latter is necessary for hot water supply. It is obvious from the chart, that many zeolite materials are able to deliver this high temperature lift T= TADS TEVA due to the high binding enthalpy with resulting storage densities of more than 100 kWh/m3. Lower binding enthalpy materials like silica gel fail in this respect. In Figure 4 the ratio of the binding enthalpy to the whole adsorption enthalpy of the material is depicted. The data underline the fact, that zeolites under the presumption of sufficient high desorption temperatures exhibit a high fraction of binding enthalpy up to 30 % of the total adsorption enthalpy. One has to bear in mind, that this part is really stored from summer to winter and has not to be delivered from the low temperature heat source e.g. the ground heat exchanger or the solar collector at the temperature level TEVA. This in turn reduces the exhaust of the low temperature source and therefore the efficiency of the whole storage system. The significance of the part of the binding enthalpy is often underestimated. There is furthermore an additional benefit of adsorbents with high binding enthalpy as shown in figure 5. For the calculation of the data in this chart it is assumed, that a part of the storage volume is recharged a second time during the storage year. After a complete desorption of the partial volume the binding enthalpy is activated again. The sorption storage has to be divided into at least 2 separate vessels to enable this mode. The second time activated binding enthalpy is higher than in the case of e.g. silica gels. Figure 5 gives additional storage densities of up to 16 kWh/m3 only due to the binding enthalpy if a third of the storage volume is recharged twice.

Table 1: Integral adsorption enthalpies and storage densities of zeolites derived from sorption isotherm data. Temperature of the condenser TCOND = 10C in all cases. Zeolite type
TDES TADS TEVA Integral binding enthalpy Integral condensation enthalpy Integral adsorption enthalpy Storage density

Nr

C
250

C
35 60

C
10 20 10 20 10 20 10 20 10 20 10 20 10 20 10 20 10 20 10 20 10 20 10 20 10 20 10 20 10 20 10 20 10 20 10 20 10 20 10 20 10 20 10 20 10 20 10 20 10 20 10 20 10 20 10 20

kJ kg ZEO
203,9 205,4 199 201,8 203,9 205,4 199 201,8 149,7 152,3 146,5 148,4 97,6 100,1 96,1 96,3 127,3 128,5 123,1 126,3 124,5 125,7 120,8 123,5 249,6 252,2 240,9 246,1 249,6 252,2 240,9 246,1 219,6 221,8 212,2 216,4 219,6 221,8 212,2 216,4 127,6 130,3 98,9 105,2 74,2 75,3 43,6 49,9 152,1 155,2 146,8 150,5 97,4 100 91,6 95,3

kJ kg ZEO
423,7 445,5 374,5 393,8 402,0 423,8 353,3 372,6 454,6 495,7 415,1 431,6 328,8 370,0 292,5 309,0 471,5 488,4 424,5 448,1 449,7 466,7 403,3 426,9 570,9 611,5 487,3 521,7 549,2 589,7 466,0 500,5 493,5 526,6 423,9 451,9 471,8 504,9 402,7 430,7 413,5 444,9 250,0 273,6 282,9 314,3 122,6 146,2 483,6 524,7 424,5 455,2 357,9 399,0 301,9 332,5

kJ kg ZEO
627,6 650,9 573,5 595,6 605,9 629,2 552,3 574,4 604,3 648,0 561,6 580,0 426,4 470,1 388,6 405,3 598,8 616,9 547,6 574,4 574,2 592,4 524,1 550,4 820,5 863,7 728,2 767,8 798,8 841,9 706,9 746,6 713,1 748,4 636,1 668,3 691,4 726,7 614,9 647,1 541,1 575,2 348,9 378,8 357,1 389,6 166,2 196,1 635,7 679,9 571,3 605,7 455,3 499,0 393,5 427,8

kWh 3 mZEO
122,0 126,6 111,5 115,8 117,8 122,3 107,4 111,7 117,5 126,0 109,2 112,8 82,9 91,4 75,6 78,8 116,4 120,0 106,5 111,7 111,7 115,2 101,9 107,0 159,5 167,9 141,6 149,3 155,3 163,7 137,5 145,2 138,7 145,5 123,7 129,9 134,4 141,3 119,6 125,8 105,2 111,8 67,8 73,7 69,4 75,8 32,3 38,1 123,6 132,2 111,1 117,8 88,5 97,0 76,5 83,2

4A*
180

35 60

250

35 60

4A**
180

35 60

250

35 60

4A***
180

35 60

250

35 60

13X*
180

35 60

250

35 60

13X*
180

35 60

250

35 60

NaLSX**
180

35 60

250

35 60

LiLSX**
180

35 60

*)

own measurements sorption isotherm data from literature [Stach 2001, 2003] ***) sorption isotherm data from literature [Krischer 1992]
**)

TDES=250C, TADS=35C, TEVA=20C TDES=180C, TADS=35C, TEVA=10C LiLSX (7) NaLSX (6)

zeolite type

13X (5) 13X (4) 4A (3) 4A (2) 4A (1) 0 40 80 120


3

160

storage density, kWh/m

Figure 1: Storage densities at different desorption and evaporation temperatures

TDES=250C, TADS=35C, TEVA=10C TDES=180C, TADS=35C, TEVA=10C LiLSX (7) NaLSX (6)

zeolite type

13X (5) 13X (4) 4A (3) 4A (2) 4A (1) 0 40 80 120


3

160

storage density, kWh/m

Figure 2: Storage densities at different desorption temperatures

TDES=180C, TADS=60C, TEVA=10C, TDES=180C, TADS=35C; TEVA=10C, LiLSX (7) NaLSX (6)

zeolite type

13X (5) 13X (4) 4A (3) 4A (2) 4A (1) 0 40 80 120


3

160

storage density, kWh/m

Figure 3: Storage densities at different adsorption temperatures

TDES=250C, TADS=35C, TEVA=20C LiLSX (7) NaLSX (6)

zeolite type

13X (5) 13X (4) 4A (3) 4A (2) 4A (1) 0 5 10 15 20 25 30

fraction of binding enthalpy, %

Figure 4: Ratio of binding enthalpy to the total adsorption enthalpy

1/4 volume recharged 1/3 volume recharged LiLSX (7) NaLSX (6)

TDES=250C, TADS=35C, TEVA=20C

zeolite type

13X (5) 13X (4) 4A (3) 4A (2) 4A (1) 0 5 10


3

15

additional storage density, kWh/m

Figure 5: Additional storage density (only the part from binding enthalpy) under the presumption of recharging 1/4 or 1/3 of the volume twice within one year

4.

CONCLUSIONS

It was shown, that an adsorbent with a high binding enthalpy is advantageously for a seasonal heat storage. The adsorbent should not be selected only under the aspect of a high adsorption capacity, but also a high binding enthalpy. A ratio of up to 30 % binding enthalpy to the total adsorption enthalpy can be attained. For an almost complete use of the binding enthalpy a desorption temperature TDES 180C available from vacuum tubes or concentrated solar collectors is necessary. Under these conditions with an adsorptive seasonal storage with TDES = 180C, TADS = 35C, TCOND = 10C, TEVA = 10C a storage density of about 160 kWh/m3 can be achieved.

REFERENCES
Bales, Ch., Gantenbein, P., Jaenig, D., Weber, R., (2007). Laboratory Prototypes of Thermo-Chemical and Sorption Storage Units. Report of IEA Solar Heating and Cooling programme Task 32, Advanced storage concepts for solar and low energy buildings, Report B3 of Subtask B. Fischer, U., (2003). The determination of the heat of adsorption in dependence of the water vapour partial pressure of zeolites for heat storage purposes. Proc: FUTURESTOCK 2003, Warsaw, 431-436. Krischer, O., Kast, W., (1997). Die wissenschaftlichen Grundlagen der Trocknungstechnik. Springer Verlag Berlin Heidelberg New York. Ruthven, D. M., (1984). Principles of adsorption and adsorption processes. John Wiley & Sons, New York. Stach, H., Ackermann, D., Brsicke, W., Jnchen, J., Weiler, E., (2003). Erprobung der thermochemischen Wrmespeicherung mit neuen Speichermaterialien. Schlussbericht BMWi-Forschungsprojekt 0329525D, FHTW Berlin, ZeoSYS GmbH.

Stach, H., Ackermann, D., Brsicke, W., Jnchen, J., Weiler, E., (2001). Entwicklung und Charakterisierung von mikroporsen Festkrpern fr die adsorptive Langzeitspeicherung von Niedertemperaturwrme. Schlussbericht BMWi-Forschungsprojekt 0329525C, FHTW Berlin, ZeoSYS GmbH. Webb P. A., Orr C., (1997). Analytical Methods in Fine Particle Technology, Micromeritics Instrument Corporation, Norcross, GA.

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