Energy 185, 19651970. In fact, since vapor-solid sorption is preferred to achieve larger heat storage density and improved adsorption/desorption dynamics, sorption heat storage systems typically require de-pressurized reactor vessels, vacuum pumps and various valves and tubes for managing the sorbate flow from/to the sorbent bed (Zettl et al., 2014). Westwood, NJ: Elsevier. Description and analysis of adsorption heat storage device. In these experiments, hydrated zeolite samples have been regenerated at 250C for 20 min. Eng. As the figures show, temperature has a strong effect on the regeneration grade, which, for e.g., water, increases from around 60% at 100C to 90% at 250C after 60 min. AL and MZ performed the experiments and wrote the first draft of the manuscript. (2016). Energy Fuels 27, 16251631. 42, 11061112. J. Prog. ethanol-water mixture. Typically, materials such as rock, concrete, steel, thermal oil and water are used for sensible heat storage (Hoogendoorn and Bart, 1992). Conclusions are finally drawn in section 5. A. Coffee-based colloids for direct solar absorption. Technology Brief. Such pre-heating of the lubricant would have a positive impact on the Friction Mean Effective Pressure (FMEP) required to overcome the engine friction during the cold-start, which would be lowered from 6 bar (20C) to either 3.5 bar (mixture) or 4 bar (ethanol) (Roberts et al., 2014). A. 1669. Figure 6. Flick, E. W. (1998). Eng. In detail, the mean hydration of regenerated zeolites is: = 0.42 0.04 for water, = 0.40 0.01 for ethanol, and = 0.47 0.02 for the mixture, where quantities are reported in terms of mean 2 standard deviation. 116, 364371. Twelve repetitions have been performed, using a new sample of zeolite for each test. However, in our case, the liquid water should be vaporized before being able to adsorb on the surface of zeolite pores: considering an enthalpy of vaporization equal to hvap = 2,454 kJ/kg (T = 20C) and = 0.34, the residual thermal energy available from the adsorption process is estimated to be E = 79 kWh/m3, in good agreement with our measures on new samples. Regeneration grade (Rg in Equation 2) as a function of time obtained by the experimental characterization tests on the 13X zeolite samples at different controlled temperatures for (A) distilled water, (B) ethanol, and (C) 30:70%wt. J. Phys. During the discharge phase (Figure 6A), the liquid sorbate hydrates the dry zeolite, the thermal energy released by the hydration process is collected by a heat transfer fluid and then exchanged with the fuel and/or oil and/or coolant tank via an heat exchanger. The surface barrier phenomenon at the loading of metal-organic frameworks. Jarrier, L., Champoussin, J., Yu, R., and Gentile, D. (2000). (1998). Since the capped flask has negligible heat losses with the surrounding environment (less than 5%), the system can be reasonably approximated as adiabatic. Energy Rev. doi: 10.1016/j.est.2018.02.014. In this work, we characterize the heat storage potential of various liquid sorbates (distilled water, ethanol and a mixture thereof) on a commercial 13X zeolite sorbent at ambient pressure. Figure 2. Energy Storage 17, 118128. Latent heat storage modules for preheating internal combustion engines: application to a bus petrol engine. Renew. Energy 190, 920948. (2014). For the sake of simplicity, heat losses are estimated parametrically as Qloss = 0.5 E Vzeo (to be conservative). 6:17. doi: 10.3389/fenrg.2018.00017, Heinke, L., Gu, Z., and Wll, C. (2014). Energy 203, 219239. Ther. Figure 4A shows that the best-fitted Rg,max are linearly dependent on temperature; whereas, no significant differences are observed between the three tested fluids. Energy 144, 341378. doi: 10.1016/j.rser.2011.04.018, Cot-Gores, J., Castell, A., and Cabeza, L. F. (2012). Prog. (2010). Eng. J. In general, thermo-chemical heat storage relies on the sorbent hydration by sorbate vapor to achieve larger heat storage density. To this, we consider a portable electric power generator operating in cold climates, and envision the improvement of the efficiency of its Diesel engine during the cold-start using waste heat recovered from the exhaust gases and stored using the proposed TES system. Simulation of a seasonal, solar-driven sorption storage heating system. At 100C, for example, the amount of water released from the zeolite is about 45% respect to fully hydrated conditions, while this quantity is close to 60% for the ethanol and mixture sorbates. Here, the regeneration of the zeolite is intended as the dehydration process, which restores the heat storage potential of the sorbent material, and it is quantified by the following parameter: where the mass of loaded liquid (mliq) is compared with that in case of fully hydrated conditions (mliq,fh) at ambient pressure. Compendium of Chemical Terminology, Vol. 132, 308320. Baerlocher, C., McCusker, L., and Olson, D. (2007). While distilled water-zeolite is one of the most common working pairs for sorption heat storage (Mir et al., 2016), hereconsidering potential outdoor applicationsfluids with lower freezing point have been also tested. Appl. Nanoscale Res. Experimental and numerical investigations of different reactor concepts for thermochemical energy storage. Sustain. 38, 98104. Eng. doi: 10.1016/j.ijheatmasstransfer.2013.12.061, Mir, L., Gasia, J., and Cabeza, L. F. (2016). A few works have also studied possible solar (Gaeini et al., 2018; Shere et al., 2018) or automotive (Gardie and Goetz, 1995; Narayanan et al., 2017) applications of TES based on sorption processes; however, a broader diffusion of this heat storage approach may be limited by the complexity of the required technology and auxiliary systems. Figure 4. doi: 10.1109/SDPC.2017.131, Keywords: thermal energy storage, adsorption, zeolite, water, ethanol, experimental characterization, Citation: Fasano M, Bergamasco L, Lombardo A, Zanini M, Chiavazzo E and Asinari P (2019) Water/Ethanol and 13X Zeolite Pairs for Long-Term Thermal Energy Storage at Ambient Pressure. Energy 179, 284301. 126, 509516. (2018). doi: 10.1016/j.enconman.2003.09.015, Fasano, M., Borri, D., Cardellini, A., Alberghini, M., Morciano, M., Chiavazzo, E., et al. Qr is obtained via calorimetric measurements, while Vzeo = mzeo/zeo with zeo = 800 kg/m3. Energy Storage 13, 4047. J. Ther. Diesel Engine: Experiment and Modeling. with Rg,max being the maximum regeneration grade and the characteristic regeneration time per each sorbent-sorbate pair and temperature. Renew. Technical report, SAE Technical Paper. doi: 10.1016/j.applthermaleng.2018.03.091, Piperel, A., Perrin, H., Walter, B., Crepeau, G., and Starck, L. (2013). Low Temperature Thermal Energy Storage (TES) System for Improving Automotive HVAC Effectiveness. Sensible and latent TES systems recovering the thermal energy from the exhausts have been demonstrated to improve the cold-start performance of engines (Jarrier et al., 2000; Vasiliev et al., 2000); however, they may not be suitable for emergency power systems where the engine operates just a few hours per year and thus successive heat charge/discharge phases could be far in time. (A) Heat discharge phase: the liquid sorbate (S) is released into the chamber containing the zeolite (Z), thus hydrating it (Z/S). Besides chemical reactions (Donkers et al., 2016), thermo-chemical storage can be based also on sorption processes. All tests are carried out for the three considered fluids, that is, water, ethanol and their mixture. (A) Maximum regeneration grade (Rg,max) and (B) characteristic time (or time constant, ) of the dehydration process for the tested sorbates, obtained by best-fit of Equation (5) on the experimental series in Figures 3AC. 40, 11761181. Energy Convers. The characteristic regeneration time is the time constant of the exponential-decay term in the above equation, and represents the time at which the regeneration grade is around 63% its maximum value. Figure 3. The different sorption pairs have been experimentally characterized in terms of hydration capacity, dehydration dynamics and heat storage density at ambient pressure. Rep. 9:4701. doi: 10.1038/s41598-019-39032-5, PubMed Abstract | CrossRef Full Text | Google Scholar, Alva, G., Lin, Y., and Fang, G. (2018). 1:3. doi: 10.3389/fenrg.2013.00003. Energy 189, 3143. An adiabatic cap [see (2) in Figure 1B] has been designed to allow the insertion of zeolite beads into the dewar flask while minimizing thermal losses. 57, 23802389. Appl. Renew. Energy Rev. doi: 10.1080/01457632.2018.1457266, Shukla, A. K., Dhami, R., Bhargava, A., and Tiwari, S. (2017). Thermal Management Solutions to Reduce Fuel Consumption. The weight of the zeolite sample is monitored at different time intervals, thus obtaining the sorbate release rate with time. Among the different regeneration options in terms of temperature and time, we decidedfor illustrative purposesto regenerate the zeolite for 20 min at 250C. (2014). doi: 10.1016/S1359-4311(99)00061-7, Vasiliev, L. L., Burak, V. S., Kulakov, A. G., Mishkinis, D. A., and Bohan, P. V. (1999). Nat. (A) Sample of the commercial 13X zeolite used in the experimental characterization as sorbent material: Kstrolith 13XBFK by Chemiewerk Bad Kstritz GmbH (CWK-BK datasheets, 2019). Given their auxiliary scope, these generators are not typically subject to frequent start-stop cycling, which makes them lend to a TES system able to store thermal energy for long periods with negligible losses. Ther. This latter technique relies on the capacity of a sorbent material to take up a sorbate in the vapor or liquid phase. 71, 555561. The editor and reviewer's affiliations are the latest provided on their Loop research profiles and may not reflect their situation at the time of review. Experiments show that the heat storage density of the first hydration is significantly higher than the ones from regenerated zeolite samples. TES has recently attracted particular attention in the renewable energy field, to match periodical or intermittent availability of renewable sources (e.g., solar) with continuous energy demand (Daz-Gonzlez et al., 2012; Engel et al., 2017; Bocca et al., 2018). The resulting functions are shown in Figure 3A (water, R2 0.98), Figure 3B (ethanol, R2 0.85), and Figure 3C (mixture, R2 0.92) using solid lines. Since water sorbate requires higher regeneration temperatures (see Figure 3D) and has slower dehydration kinetics (see Figure 4B) than ethanol and mixture ones, the zeolite samples regenerated from water show more pronounced degradation of heat storage density with successive cycles (see Figure 5B) (Kohler and Mller, 2017). Purification of pharmaceutical solvents by pervaporation through hybrid silica membranes. doi: 10.1016/B978-0-444-62700-1.00016-4, Donkers, P., Pel, L., and Adan, O. Appl. Dauk, P., Viovsk, J., Ambro, J., and Hjekov, E. (2008). At a given temperature, water presents a slower liquid release than ethanol and mixture, which have instead similar characteristic regeneration times. Distilled water, ethanol (99.8%, Sigma-Aldrich) and a mixture thereof (30% ethanol, 70% water by weight) have been considered as sorbates. Clearly, large heat capacity is desirable to achieve high sensible heat storage density, namely the amount of stored energy in a given system per unit volume (Chidambaram et al., 2011). 13, 1733917358. Technical report, SAE Technical Paper, The University of Leeds. Copyright 2019 Fasano, Bergamasco, Lombardo, Zanini, Chiavazzo and Asinari. doi: 10.1016/j.pecs.2015.10.003, Zhao, R., Liu, J., and Gu, J. Interplay between hydrophilicity and surface barriers on water transport in zeolite membranes. Solar energy: a common-sense vision. Renew. (2011). Int. No use, distribution or reproduction is permitted which does not comply with these terms. Energy Proc. Assessment of adsorbate density models for numerical simulations of zeolite-based heat storage applications. 395:012150. doi: 10.1088/1742-6596/395/1/012150, Andrews, G. E., Ounzain, A. M., Li, H., Bell, M., Tate, J., and Ropkins, K. (2007). The assembled measurement system is left to relax to ambient temperature. (B) Heat charge phase: the thermal energy recovered from the exhaust gases is employed to dehydrate the sorbate from the zeolite. All authors contributed to manuscript revision, read, and approved the final version. 13, 23852396. Heat is stored in a narrow temperature range; therefore, PCM must have phase-transition temperature in the range of practical interest, besides being chemically stable, non-toxic and non-corrosive (Farid et al., 2004). Nat. A review of energy storage technologies for wind power applications. The latter applications span from battery thermal management (Zhao et al., 2017) to engine pre-heating at start-up (Vasiliev et al., 1999; Gritsuk et al., 2016), from temperature optimization of engine for fuel saving (Kauranen et al., 2010; Shukla et al., 2017) to vehicle climate conditioning (Fleming et al., 2013; Jha and Badathala, 2015; Wang et al., 2017). Renew. Sorption heat storage for long-term low-temperature applications: a review on the advancements at material and prototype scale. doi: 10.1016/j.apenergy.2016.06.147, Mitchell, K., and Chandler, J. This progressive reduction in the heat storage density denotes a degradation of the zeolite sorbent, which has been associated by previous works with a minor structure decomposition and formation of amorphous non-porous portions in the sorbent material (Risti et al., 2018). doi: 10.1016/j.apenergy.2016.12.148, Schleussner, C.-F., Rogelj, J., Schaeffer, M., Lissner, T., Licker, R., Fischer, E. M., et al. doi: 10.1016/S0035-3159(99)80020-8, Vasta, S., Brancato, V., La Rosa, D., Palomba, V., Restuccia, G., Sapienza, A., et al. Sci. In fact, the ideal performance of water vapor adsorption on 13XBFK zeolite are (Mette et al., 2014b; Pinheiro et al., 2018): heat of adsorption approximately equal to hads = 3,500 kJ/kg (released energy per kilogram of adsorbed water, that is 63 kJ/mol); maximum water vapor load on zeolite = 0.34. Science and policy characteristics of the paris agreement temperature goal. In fact, the amount of loaded sorbate depends on the affinity between its fluid molecules and the zeolite surface, and on the size of the fluid molecules with respect to that of the pores and cages in the zeolite framework. Appl. One thermocouple [K-type, RS Pro, Alberghini et al., 2019, see (3) in Figure 1B] is located inside the dewar flask, being initially immersed in the liquid sorbate. Ethanol and water are both polar liquids; yet, the kinetic diameter of water molecules is about 2.96 , while ethanol ones about 4.30 (La Rocca et al., 2019). doi: 10.1016/j.pecs.2013.05.004, Zettl, B., Englmair, G., and Steinmaurer, G. (2014). doi: 10.1016/0038-092X(92)90176-B. Note that the considered dehydration temperature is kept far from the autoignition temperature of ethanol, that is 425C (Dimian et al., 2014). Appl. The obtained heat storage densities per each regeneration cycle are reported in Figure 5A; whereas, Figure 5B shows their values averaged over the 9 regeneration cycles following the first hydration. Hence, heat storage systems based on sorption processes present the advantage of having: a large range of operating temperatures, depending on the chosen working pair; a larger heat storage density with respect to sensible and latent heat storage; negligible heat losses during the storing period, which makes them particularly suitable for long-term energy storage (Stritih and Bomba, 2014). The use, distribution or reproduction in other forums is permitted, provided the original author(s) and the copyright owner(s) are credited and that the original publication in this journal is cited, in accordance with accepted academic practice. Sci. The zeolite beads (10 g per test) are first placed into the adiabatic cap; the liquid sorbate is poured into the flask. Pinheiro, J. M., Salstio, S., Valente, A. The sorption process may occur according to two different phenomena: absorption, if the structure of the sorbent is modified by the sorbate sorption; adsorption, if the sorbate does not modify its structure during the process (N'Tsoukpoe et al., 2009). doi: 10.1007/978-3-319-26695-4_39. Eng. Dry zeolite beads (10 g per test) are first fully hydrated according to the previously described protocol, and then introduced in an oven with controlled temperature and ambient pressure. The material is non-toxic, low-cost (about 1 per liter) and particularly suitable for adsorption processes, since no inert binder components are included (Gaeini et al., 2018). In this section, we provide an illustrative example application of the proposed thermal energy storage system in practice. Eng. doi: 10.4271/982576, Morciano, M., Fasano, M., Bergamasco, L., Albiero, A., Lo Curzio, M., Asinari, P., et al. Energy 112, 160169. Aguiar, P., Miyauchi, E., and Baumgartner, L. (2013). Kauranen, P., Elonen, T., Wikstrm, L., Heikkinen, J., and Laurikko, J. The dots correspond to the experimental data points, while solid lines show the best-fit of Equation (5). Lindl, B., and Schmitz, H.-G. (1999). (2018). The dotted lines show the mean value over the repetitions for the three different fluids. Sci. Furthermore, the handling of zeolite samples during the successive tests may eventually lead to the generation of diffusion resistances (surface barriers) related to surface pore blockage or narrowing, which may hinder the sorbate intrusion into the zeolite framework (Heinke et al., 2014; Fasano et al., 2016b). Ethanol, instead, has not shown significant detrimental effects on the zeolite beads. 1, 859883. The Use of a Water/Lube Oil Heat Exchanger and Enhanced Cooling Water Heating to Increase Water and Lube Oil Heating Rates in Passenger Cars for Reduced Fuel Consumption and CO2 Emissions During Cold Start. Thermal energy storage is a key technology to increase the global energy share of renewablesby matching energy availability and demandand to improve the fuel economy of energy systemsby recovery and reutilization of waste heat. The Use of Flow Improved Diesel Fuel at Extremely Low Temperatures. doi: 10.4271/2017-01-0150, Stritih, U., and Bomba, A. Rg is measured as a function of different regeneration temperatures and for the different tested sorbates. Sci. Received: 23 April 2019; Accepted: 02 December 2019; Published: 18 December 2019. *Correspondence: Pietro Asinari, pietro.asinari@polito.it, Creative Commons Attribution License (CC BY), Department of Energy, Politecnico di Torino, Turin, Italy. Cabeza, L. F., Gutierrez, A., Barreneche, C., Ushak, S., Fernndez, G., Ferndez, A. I., et al. As a representative application example of long-term storage, we verify the feasibility of a sorption heat storage system with liquid sorbate, which could be used to improve the cold-start of stand-by generators driven by internal combustion engines. Lithium in thermal energy storage: a state-of-the-art review. Acta Chimica Slovaca 1, 4357. MF and LB analyzed the data and wrote the manuscript. This is the case of the proposed solution that, relying on a simplified thermo-chemical heat storage approach, has the pivotal advantage of long-term heat storage over technologies based on sensible/latent heat. Energy Res. doi: 10.1016/j.energy.2017.12.037, Andreozzi, A., Buonomo, B., Ercole, D., and Manca, O. Nanomaterials 8:522. doi: 10.3390/nano8070522, Wang, M., Craig, T., Wolfe, E., LaClair, T. J., Gao, Z., Levin, M., et al. In this work, we aim at characterizing the feasibility of a sorption TES cycle with liquid sorbates at ambient conditions, thus not requiring auxiliary systems for vapor generation. The authors acknowledge Antonino Monteleone and Paride Ottaviani for supporting the experimental activity; Marco Rossetto, Cristiano Massano, Matteo Biglia, and Domenico Vitali for technical discussions. While chemical reactions allow to achieve the highest energy densities (about 150400 kWh/m3 Lizana et al., 2017) but also require large reaction temperatures, sorption processes generally provide a good compromise between high heat storage density (about 50300 kWh/m3 Lizana et al., 2017), moderate reaction temperatures and cyclability (Cot-Gores et al., 2012).
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