Bergamasco, L., Alberghini, M., and Fasano, M. (2019). Sensible heat storage is the most common and simple method, and relies on the capacity of a storage mediume.g., solid or liquidto store thermal energy by changing temperature. The effects of cooling structure and li-ion battery specification on the cooling performance of a passive thermal management system, in Sensing, Diagnostics, Prognostics, and Control (SDPC), 2017 International Conference on (IEEE), 662669. Daz-Gonzlez, F., Sumper, A., Gomis-Bellmunt, O., and Villaffila-Robles, R. (2012). doi: 10.1016/j.applthermaleng.2016.02.015, Fasano, M., Humplik, T., Bevilacqua, A., Tsapatsis, M., Chiavazzo, E., Wang, E. N., et al.
doi: 10.4271/2017-01-0150, Stritih, U., and Bomba, A. Ther. The dots correspond to the best-fitted values of Rg,max or for the different temperatures and fluids, while the dotted lines are their linear fit. J. When thermal equilibrium is reached, the paper sheet is removed from the cap and the zeolite released into the flask. The average quantity of loaded liquid over the twelve repetitions is = 0.500.02 for water, = 0.400.02 for ethanol, and = 0.480.04 for their mixture, where quantities are reported in terms of mean 2 standard deviation. Sci. Pinheiro, J. M., Salstio, S., Valente, A. Dehydration tests have shown that ethanol and mixture tend to dehydrate faster and at lower temperatures than water, due to the higher affinity of water molecules with the surface of zeolite pores with respect to ethanol. doi: 10.4271/2017-01-0183, Xue, J., Walnum, H. J., Aall, C., and Nss, P. (2016). Prog. 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). Appl. This different release rate could be attributed to the different affinity of the fluid molecules with the surface of the zeolite pores.
(2015). Thermal Energy Storage. Available online at: http://www.cwk-bk.de/en/. Protocols for atomistic modeling of water uptake into zeolite crystals for thermal storage and other applications. In the followings, a TES system based on the tested 13X zeolite hydrated by ethanol (E = 49 kWh/m3; = 0.40 after multiple regenerations at 250C) or the 30:70%wt. Although the thermal performance of zeolite-liquid hydration is lower than those typically reported for vapor hydration, using liquids may still represent an option when simple design and long-term storage are required. 82, 327350. Lithium in thermal energy storage: a state-of-the-art review. The proportion between ethanol and water in the mixture has been chosen to achieve a good compromise between higher heat storage density and lower freezing temperature. The sorbent reacts with the liquid sorbate, producing an exothermic reaction that releases heat (hydration process). Temperature dependence of the viscosity of hydrocarbon fractions. The experimental results are then reported in section 3, where the properties of different sorbent-sorbate pairs are compared.
Numerical investigation on sensible thermal energy storage with porous media for high temperature solar systems. doi: 10.1016/j.pecs.2015.10.003, Zhao, R., Liu, J., and Gu, J. Therefore, the thermal energy released by the hydration process can be estimated as: being Ti the initial temperature measured by the thermocouple inside the flask (before the hydration process), Te the equilibrium temperature (when the hydration is complete), mliq,t = kliqmliq,fh is the total mass of the liquid sorbate, cp,zeo and cp,liq the specific heat capacity of the sorbent and sorbate, respectively. Thermal energy storage also finds application in the transport sector, for which a reduction of greenhouse gas emissions is foreseen by the recent international agreements on climate change mitigation (Schleussner et al., 2016; Xue et al., 2016). doi: 10.1016/j.rser.2014.10.096, Calabrese, L., Brancato, V., Bonaccorsi, L., Frazzica, A., Capr, A., Freni, A., et al. Rg is measured as a function of different regeneration temperatures and for the different tested sorbates. The considered zeolite, 13X type, has been chosen for its suitability to long-term thermal energy storage even after multiple hydration/dehydration cycles. Front.
Table 1. doi: 10.1016/j.rser.2012.04.007, CWK-BK datasheets (2019). Warm-up of a D.I. Energy 189, 3143. The heat storage density of the considered working pairs has been first measured on new samples of zeolite, which, therefore, did not experience any hydration/dehydration cycles before. 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). (2017). An overview of thermal energy storage systems. J. Mech. This calculation also proofs that the higher water load observed in our experiments ( = 0.50) could be explained by a residual quantity of liquid water on the surface of the zeolite bead after the hydration process, which is not involved in the adsorption process. doi: 10.1016/j.tsep.2018.02.003, Andreozzi, A., Buonomo, B., Manca, O., Mesolella, P., and Tamburrino, S. (2012). Acta Chimica Slovaca 1, 4357. Sustain. Energy Rev. In general, thermo-chemical heat storage relies on the sorbent hydration by sorbate vapor to achieve larger heat storage density. 38, 98104. Appl. doi: 10.1016/j.apenergy.2015.10.126. Technical report, SAE Technical Paper, Valeo Climate Control; CNRS/IMP. being Qr the thermal energy released in the hydration process and Vzeo the volume of dry zeolite. (B) Overview of the material and instruments used for the experimental characterization of the sorption working pairs: (1) Dewar flask, (2) insulated tap, (3) K-type thermocouple, (4) zeolite containers, (5) precision balance. 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. For the considered tests, the hydration process typically completes in less than 10 s. The experimental values of sorbate loaded in zeolite are shown in Figure 2 for the three tested liquids, at p = 1 bar and T = 20C. In this sense, some preliminary tests using water-ethylene glycol mixtures led us to exclude their utilization, as they carbonize at 150C therefore clogging and wasting the zeolite during the dehydration phase. 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. Appl. Thermal energy storage: recent developments and practical aspects. Received: 23 April 2019; Accepted: 02 December 2019; Published: 18 December 2019. Membranes 9:76. doi: 10.3390/membranes9070076, Lehmann, C., Beckert, S., Glser, R., Kolditz, O., and Nagel, T. (2017). Sorption thermal storage for solar energy. In the third application case, the whole tank of the coolant (11.4 L) could be pre-heated by the zeolite at the engine starting. Front. Sustain. doi: 10.1061/(ASCE)0887-381X(1992)6:3(124), Dimian, A. C., Bildea, C. S., and Kiss, A. Flick, E. W. (1998). 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. (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). 
7:12762. doi: 10.1038/ncomms12762, First, E. L., Gounaris, C. E., Wei, J., and Floudas, C. A. Experimental studies for the cyclability of salt hydrates for thermochemical heat storage. J. Industrial Solvents Handbook. doi: 10.1016/S0035-3159(99)80020-8, Vasta, S., Brancato, V., La Rosa, D., Palomba, V., Restuccia, G., Sapienza, A., et al. Eng. A 6, 1152111530. Clim. 42, 11061112. Conclusions are finally drawn in section 5. Ginley, D., and Parilla, P. (2013). Copyright 2019 Fasano, Bergamasco, Lombardo, Zanini, Chiavazzo and Asinari. 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. Mette, B., Kerskes, H., and Drck, H. (2014a). A review on long-term sorption solar energy storage. Oxford: Blackwell Science. Simulation of a seasonal, solar-driven sorption storage heating system. Development and Optimization of PCM Based Technology for Cooling Applications for Improvement of Fuel Efficiency in Commercial Vehicle. Heat Transf. The weight of the zeolite sample is monitored at different time intervals, thus obtaining the sorbate release rate with time. 16, 21542171. In this work, we report the experimental characterization of working pairs made of various liquid sorbates (distilled water, ethanol and their mixture) and a 13X zeolite sorbent at ambient pressure. Three laboratory tests are set up to characterize the zeolite properties for heat storage, namely: liquid sorbate hydration, dehydration and heat storage density. Solar energy: a common-sense vision. Renew. Hot tap water production by a 4 kw sorption segmented reactor in household scale for seasonal heat storage. As reported in Table 1, this would lead to a potential increase of approximately 5C in the coolant temperature, namely from 20C to either 15.0C (mixture) or 15.6C (ethanol), with a limited change in the viscosity. The dehydration temperature has been made vary in a large range of values, to assess the release dynamics of the different sorption pairs. The Use of Flow Improved Diesel Fuel at Extremely Low Temperatures. All the obtained experimental series (dots in Figures 3AC) have been best-fitted with the proposed exponential form in Equation (5), obtaining the maximum regeneration grade and characteristic time (constant) per each tested temperature. 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). Eng. doi: 10.1016/j.apenergy.2016.12.148, Schleussner, C.-F., Rogelj, J., Schaeffer, M., Lissner, T., Licker, R., Fischer, E. M., et al. At a given temperature, water presents a slower liquid release than ethanol and mixture, which have instead similar characteristic regeneration times.
Therefore, considering zeo = 800 kg/m3, the ideal heat storage density of the water-13XBFK pair would be equal to Eid= 265 kWh/m3 in case of purely vapor hydration. Energy Proc. Sustainable freshwater production using passive membrane distillation and waste heat recovery from portable generator sets. The experimental regeneration grade as a function of time obtained on the fully hydrated zeolite samples is reported in Figures 3AC (dots) for the three tested fluids. Latent heat storage shows typically larger energy density than sensible one (about 30100 kWh/m3, Lizana et al., 2017) and, thus, has been widely explored in solar (Andreozzi et al., 2018; Buonomo et al., 2018) and automotive applications (Jaguemont et al., 2018). Adsorbent working pairs for solar thermal energy storage in buildings. Synthesis and characterization of thermochemical storage material combining porous zeolite and inorganic salts. Eng. 6:17. doi: 10.3389/fenrg.2018.00017, Heinke, L., Gu, Z., and Wll, C. (2014). Ther. Nat. Cambridge, UK: Woodhead Publishing. Sci. In particular, the negligible heat losses of sorption technologies during the storing period make them ideal for applications where long-term storage is required. Energy Convers. Experimental and numerical investigations on the water vapor adsorption isotherms and kinetics of binderless zeolite 13x. Nanomaterials 8:522. doi: 10.3390/nano8070522, Wang, M., Craig, T., Wolfe, E., LaClair, T. J., Gao, Z., Levin, M., et al. 1669. Owe to these peculiar properties, and to the large range of potential applications, several working pairs have been extensively investigated: for example, sorbents like silica gel, zeolite, metal-organic framework or hygroscopic salts; sorbates as water or organic solvents (Scapino et al., 2017). 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. Int. Change 6:827. doi: 10.1038/nclimate3096, Shere, L., Trivedi, S., Roberts, S., Sciacovelli, A., and Ding, Y. doi: 10.1016/j.applthermaleng.2009.11.008, Kohler, T., and Mller, K. (2017). Note that the first regeneration cycle reports the heat storage density and hydration capacity of pristine zeolite samples, as provided by the manufacturer. Improving Engine Pre-start and After-start Heating by Using the Combined Heating System. Different application cases of a TES system based on 13X zeolite and liquid sorbate (MIX: 30:70%wt. 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). Advances in thermal energy storage materials and their applications towards zero energy buildings: a critical review. doi: 10.1016/j.enconman.2003.09.015, Fasano, M., Borri, D., Cardellini, A., Alberghini, M., Morciano, M., Chiavazzo, E., et al. Appl. (2016). 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). Appl. doi: 10.1016/j.apenergy.2017.06.008. The zeolite samples are supplied as spherical beads with diameter in the range 2.53.5 mm (see Figure 1A). 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. Nat. A zeolite volume of Vzeo = 2 L is taken for all the analyses, therefore leading to a storable thermal energy equal to 98 Wh (ethanol) or 112 Wh (mixture). A dewar flask has been employed for the calorimetric tests [see (1) in Figure 1B]. (2016b). As a first approximation, the energy provided to the engine fluids during the discharge phase can be estimated as: being Qloss the heat losses in the system, mf, cp,f and Tf the mass, specific heat capacity and temperature increase of the engine fluid (i.e., coolant, oil or fuel). 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. Energy Storage 17, 118128. Health, safety and environment, in Computer Aided Chemical Engineering, Vol. Zeolite 13X has average pore size around 9 , which allows intrusion of both molecules; however, also because of their smaller size, water molecules can achieve larger adsorption on the zeolite structure. (2017). Energy 110, 8794. 101, 762769. 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).
40, 11761181. Energy Storage 13, 4047. This reduction in heat storage density is associated with the residual sorbate in the zeolite after regeneration, which limits its successive hydration capability (see Figure 5C) and is clearly dependent on the considered regeneration protocol. Adsorption heat storage: state-of-the-art and future perspectives. In very cold climates indeed, low temperatures may lead to several issues, such as a large concentration of CO and CnHn in the exhausts, reduced engine resource time, high load on starter and accumulator and increased fuel consumption during the cold-start (Diemand, 1992), due to the high viscosity of fuel and lubricant and to the difficult ignition at low temperatures (Piperel et al., 2013). Remarkably, the mixture maintains similar hydration performance to that of the new samples of zeolite (only 2% reduction). Description and analysis of adsorption heat storage device. 53, 140. Appl. (2011). Nanoparticles and metal foam in thermal control and storage by phase change materials. doi: 10.4271/982576, Morciano, M., Fasano, M., Bergamasco, L., Albiero, A., Lo Curzio, M., Asinari, P., et al. 116, 364371. 
The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest. doi: 10.1016/j.applthermaleng.2017.01.112, Chidambaram, L., Ramana, A., Kamaraj, G., and Velraj, R. (2011). Energy 203, 219239. 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). Energy Sci. Sustain. Energy Rev. Note that, at ambient pressure, the freezing points of pure ethanol and 30:70%wt. The cap is then positioned on the top of the flask, with a thin paper sheet preventing the zeolite beads from falling into the flask. doi: 10.1016/j.egypro.2017.08.229, Fasano, M., Borri, D., Chiavazzo, E., and Asinari, P. (2016a). (2017). Ethanol, instead, has not shown significant detrimental effects on the zeolite beads. As reported in Table 1, this would lead to a potential increase of approximately 40C in the fuel temperature, which would sharply decrease its kinematic viscosity from 16.82 mm2/s (20C) to either 3.46 mm2/s (23.5C, zeolite hydrated by mixture) or 3.94 mm2/s (18.1C, zeolite hydrated by ethanol) (Dauk et al., 2008). The zeolite beads (10 g per test) are first placed into the adiabatic cap; the liquid sorbate is poured into the flask. Qr is obtained via calorimetric measurements, while Vzeo = mzeo/zeo with zeo = 800 kg/m3. Methodology for estimating the performance of fuels during cold start and idle with the adaptation of a gradation system. doi: 10.1016/j.enconman.2014.03.002, Scapino, L., Zondag, H. A., Bael, J. V., Diriken, J., and Rindt, C. C. (2017).
Mater. Chem. Thermal Management Solutions to Reduce Fuel Consumption. Thermo-chemical heat storage, instead, relies on reversible physical-chemical phenomena between compoundsnamely the working pairfor energy accumulation or release via endothermic or exothermic reactions, respectively. Moreover, Equation (7) also presents: Eid, that is the ideal thermal energy density of the sorption pair, as from the isosteric heat of adsorption (Fasano et al., 2017); cp,liq, Tliq and hvap,liq, namely the specific heat capacity, temperature increase and heat of vaporization of the excess liquid sorbate (e.g., ethanol or ethanol-water mixture), if any. This synthetic zeolite belongs to the Faujasite (FAU) family (Baerlocher et al., 2007; First et al., 2011) and presents a regular nanoporous structure with mean pore size equal to 9 (Fasano et al., 2016a, 2017), which makes it suitable for sorption of small molecules such as water or organic solvents (Fasano et al., 2016b; Bergamasco et al., 2019). Distilled water, ethanol (99.8%, Sigma-Aldrich) and a mixture thereof (30% ethanol, 70% water by weight) have been considered as sorbates. 70, 4249. Baerlocher, C., McCusker, L., and Olson, D. (2007). Such excess of sorbate guarantees that the sorbent material achieves full hydration at the considered ambient conditions. Latent heat storage modules for preheating internal combustion engines: application to a bus petrol engine. Integration and Validation of a Thermal Energy Storage System for Electric Vehicle Cabin Heating. Energy Fuels 27, 16251631. At fully hydrated conditions, the fraction between the mass of loaded liquid (mliq,fh) and the one of dry sorbent (mzeo) is here defined as.
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