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Chemical Engineering and Processing 47 (2008) 484489

Design of a thermochemical process for deep freezing using solar low-grade heat
Le Pierr` es Nolwenn , Stitou Driss, Mazet Nathalie
PROMES (Laboratory PROcesses, Materials and Solar Energy), CNRS Rambla de la Thermodynamique, Tecnosud, 66100 Perpignan, France Available online 12 January 2007

Abstract A deep-freezing process has been designed and experimented to cool a cold box down to about 30 C using only low-grade heat produced by simple at plate solar collectors operating at 70 C. The original process involves two cascaded thermochemical systems using BaCl2 salt reacting with ammonia. It works discontinuously, with one day phase of regeneration at high pressure and one night phase of cold production at low pressure. A global dynamic model allows the simulation of the different system components functioning depending on the hourly weather conditions. It takes into account the transient periods and shows the temperature changes of the components, the chemical reactions in the system and its performances. This system will cover the cooling needs of a 560 L cold box at 20 C during the 3 sunniest months of the year and provide more than 60% of the total yearly cooling needs of this box for the weather conditions of Perpignan (South of France). The prototype is expected to show a system coefcient of performance (COP) of about 0.07 over the 10 sunniest months of the year, and a net solar COP of 0.05, taking into account the collectors efciencies. 2007 Elsevier B.V. All rights reserved. R esum e t ` basse Un syst` eme de production de froid tr` es basse temp erature (de lordre de 30 C) a e e conc u. II utilise uniquement de la chaleur a temp erature (de lordre de 70 C) issue de capteurs solaires plans. Le proc ed e original d eni dans ce but met en oeuvre 2 dip oles thermochimiques fonctionnant en parall` ele et produisant du froid en cascade (Figs. 1 et 2). Le sel r eactif s electionn e est le BaCl2 , reagissant avec 1ammoniac. Le proc ed e fonctionne de fac on discontinue, avec une phase diurne de r eg en eration (haute pression) et une phase nocturne de production de froid (basse pression). Au cours de la phase de nuit, la chaleur produite par la r eaction chimique au sein du reacteur R1 est absorb ee par 1 evaporation ` environ 5 C. Ainsi, l ` tr` de 1ammoniac au sein de l evaporateur E2, et ce r eacteur est descendu a evaporation de lammoniac au sein de E1 a es basse temp erature est possible. Aucun transfert de masse na lieu entre les deux syst` emes, le transfert est seulement thermique. volution sur une Une mod elisation dynamique mettant en uvre lensemble des diff erents composants du syst` eme permet de simuler son e t journ ee puis sur lensemble de lann ee en prenant en compte les phases transitoires du fonctionnement. La simulation du proc ed eae e confront ee ` un prototype (Fig. 3 et dimensions Table 1) et une bonne concordance a e t aux r esultats exp erimentaux obtenus gr ace a e obtenue. A partir de cette tre e tudi ` partir des conditions m simulation valid ee, le fonctionnement thermique du proc ed e peut e e (exemple a et eorologiques mesur ees le 10 juin 2005, Fig. 4). La simulation d ebute au lever du soleil et pr esente la phase de chauffage solaire des r eacteurs jusqu` a la temp erature d equilibre ` 5) et de d ` 13) suivies de celles de refroidissement nocturne des r denviron 50 C (heures 0 a ecomposition (heures 5 a eacteurs et de production de froid ` 24). Les puissances mises en uvre sont pr par l evaporateur 1 (heures 13 a esent ees Fig. 5. La chaleur rec ue par les capteurs solaires est seulement ` la n en partie utilis ee par la r eaction chimique. La diff erence est due en partie au rendement des capteurs solaires et en partie a ecessit e de chauffer les masses thermiques des r eacteurs. Parall` element, les puissances de condensation sont environ deux fois plus faibles que les puissances de r eaction, en raison de la diff erence denthalpie des deux processus. L evaporation et donc la production de froid a lieu en continu au cours de la phase de nuit. De plus, la simulation du syst` eme sur lensemble de lann ee a permis d evaluer ses performances. Le froid produit pour des journ ees moyennes de chaque mois est compar e aux besoins de froid dune chambre froide de 560 L perdant 60 W en continu (Fig. 6). Le COP syst` eme de ce proc ed e ` 30 C est e galement pr original de production de froid a esent e Fig. 6 en fonction du mois. Sa valeur moyenne atteint 0.07 sur les 10 mois les plus ensoleill es et celle du COP solaire correspondant, 0.05, ce qui est comparable aux performances des proc ed es de production de froid solaire existants, mais pour des temp eratures de lordre de 10 C. 2007 Elsevier B.V. All rights reserved.
Keywords: Solar thermochemical process; Deep freezing; Low-grade heat; Experimentation

Corresponding author. Tel.: +33 4 79 44 45 58; fax: +33 4 79 68 80 49. E-mail address: nolwenn.le-pierres@univ-savoie.fr (N. Le Pierr` es).

0255-2701/$ see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.cep.2007.01.011

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1. Introduction The increasing use of air conditioning in developed areas and the growth of refrigeration and deep-freezing needs in developing countries are the cause of peaks in electricity consumption during summer months. To cover these cooling needs, new technologies with low environmental impacts (greenhouse gas emission and ozone depletion) are thus needed. The development of solar cold production sorption systems is then a promising solution, as sorption systems only use heat sources and environmentally friendly refrigerants (no CFC or HCFC). Today, sorption systems are used to produce cold for air conditioning and refrigeration purpose, at cooling temperatures around respectively, 10 and 0 C [1,2]. These processes need heat sources with temperatures higher than 80 and 100 C, respectively. Complex and costly solar collectors are necessary to produce heat at these temperature levels. The implementation of these technologies in housing is thus slow and difcult. Moreover, no deep-freezing system has been developed using sorption technologies. The aim of this project was to design a thermochemical process producing cold at deep-freezing temperatures (lower than 18 C), and using only low-grade solar heat from simple at plate solar collectors (below 70 C). This system should be as cheap as possible and should work without any moving parts. 2. Description of the process 2.1. Thermochemical processes The thermochemical process used is based on a reversible reaction between a solid reactant S and a refrigerant gas G: S1 + G2 1 S2 + Hr (1)

an example of a thermochemical dipole [3]. These two processes are monovariant and their equilibrium conditions follow the ClausiusClapeyron equation: ln(p) = Si Hi + (2) RT R Thus, the thermodynamic equilibrium conditions of the reactors are determined by only one parameter (p or T). The degree of conversion of the reaction, X, determines the quantity of solid which has reacted with the gas. For these thermochemical processes, the solids reactants (chloride) are inserted in consolidated blocs of natural expanded graphite (GNE). This implementation was developed to enhance heat transfer in the reactors [4]. 2.2. Solar process The cold production system associates two thermochemical dipoles, which are thermally connected. The primary dipole (which produces cold in the cold box) is cooled during the night phase by evaporation of ammonia in the secondary evaporator (Fig. 1). This thermally cascaded process was obtained through an original exergetic analysis of ideal processes [5]. The two systems (primary (1) and secondary (2)) work in parallel during the daily and night periods. They contain the same reactants BaCl2 and ammonia. During the day phase, the two reactors R1 and R2 are heated by solar radiation and decomposition occurs. Ammonia desorbed by the salt is condensed in condensers C1 and C2, respectively, both at ambient temperature. Liquid ammonia is accumulated in tanks 1 and 2 (Fig. 2). During the night period, both reactors are rst cooled by natural convection with outside air and radiation toward the nocturnal sky and their pressure decreases. When pressure in evaporator E2 becomes lower than pressure in tank 2, ammonia which was stored in tank 2 ows to E2 through the check-valves. R2 is then in synthesis conditions. Ammonia evaporates in E2, which is located inside R1. This evaporation absorbs heat from R1 through the evaporator walls. The temperature of R1 then decreases to about 5 C and R1 is then brought to synthesis conditions. Ammonia can thus evaporate in E1 at very low temperatures, down to 33 C. Evaporation of ammonia in E2 is continuous during the night phase. This evaporation maintains

In direction 1, called synthesis, gas G is xed on solid S1 . This chemical reaction is exothermic and releases Hr . In direction 2, called decomposition, S2 releases the gas G. This endothermic reaction needs the heat quantity Hr . The simplest thermochemical cold production system associates a solid/gas reaction with a liquid/gas phase change. This connection between a reactor and an evaporator/condenser is

Fig. 1. The cascaded cycle during the day (decomposition) and night (synthesis and cold production) phases in the ClausiusClapeyron diagram.

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N. Le Pierr` es et al. / Chemical Engineering and Processing 47 (2008) 484489 Table 1 Technical specications of the main components of the prototype Reactive medium (BaCl2 + GNE) mass system 1 Area of solar collector 1 Reactive medium (BaCl2 + GNE) mass system 2 Area of solar collector 1 Volume of tank 1 Volume of tank 2 Area of evaporator 1 Area of condenser 1 Area of condenser 2 15.3 kg 2 m2 30.6 kg 3.8 m2 15 L 20 L 5 m2 9 m2 22 m2

Fig. 2. Schematic representation of the cascaded cold production freezing process.

the temperature of R1 low enough to ensure an efcient synthesis reaction in R1 and thus an efcient evaporation of ammonia in E1. A cold storage is included in the cold box to manage the day/night discontinuous cold production of the process and the inefcient operating conditions during bad weather. For the meteorological conditions of Perpignan (Mediterranean climate) and a process working during the 6 sunniest months of the year, cold storage for 3 days is necessary. This cold storage is provided by a phase change material (PCM) (salt solution [6]). To ensure a cold box temperature always lower than 18 C, the phase change temperature is around 20 C. This process does not involve any rotating part. The only moving components are four check valves in the secondary system, which regulate the ow of ammonia within the system [7]. The opening and closing of these check-valves is controlled by the pressure difference between both sides of the valves. The system operation is thus totally autonomous (no electricity or human intervention for its functioning), robust and silent. 3. Process simulation A dynamic simulation of the process has been developed [7]. Simulations describe the process evolutions, depending on the weather conditions and on the sizes of the different components. They take into account the transient periods of the process operation, the inuence of the inert material masses and the kinetics of the chemical reactions, according to kinetic equations derived for this type of solidgas reactions [8]. For the solidgas monovariant reversible reactions, the kinetics depend linearly on the

local equilibrium drop, pop peq and this is presented in (3) for the decomposition and in (4) for synthesis reactions. pop peq dX = kcin X dt pop pop peq dX = kcin (1 X) dt pop (3) (4)

These simulations were used to size a prototype, which was built in Perpignan (Fig. 3) and has been running since May 2005. Its dimensions are presented in Table 1. Simulation results have been compared to experimental ones and the model parameters have been adjusted [9]. The efcient solar at plate collectors have an optical efciency of 0.85 and a heat losses coefcient of 2 W/(m2 K). The kinetic coefcient kcin of the reaction between BaCl2 and NH3 is of 104 s1 . The cold box of 560 L loses 1.4 W/K. When the cold box at 20 C is located in a room at 20 C, the cold power needed is thus 60 W. 3.1. Temperature evolution An example of simulation results is presented in Fig. 4. It is based on measured hourly weather conditions (solar radiation, ambient temperature and wind speed) on 10 June 2005. Simulation begins at sunrise, at 6:00 a.m. These simulations were performed assuming an empty cold box (without PCM or ice inside). The evolution can be separated into two phases: between 0 and 15 h, the day phase (sunrise to sunset) during which decomposition occurs, and between 15 and 24 h the night phase with synthesis in the reactors. During the rst hours (between 0 and

Fig. 3. Pictures of the solar deep freezing prototype. (A) Front side and (B) back side.

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Fig. 4. Temperatures and degrees of conversion of the system for the weather conditions of the 10 June 2005 in Perpignan (South of France).

Fig. 5. System power for the weather conditions of the 10 June 2005 in Perpignan.

5 h), the degrees of conversion of the reactors X1 and X2 remain approximately constant while the temperatures of the reactors increase. Once these temperatures reach about 55 C, reactions begin. There is a plateau in the temperature evolution, as the heat absorbed by the solar collectors is mainly used by the endothermic decomposition process. After about 9 h, the reaction kinetics in R1 decreases (following equation (3)) and the degree of conversion X1 reaches zero, the decomposition process in this reactor is thus nished. As solar radiation goes on, the temperature of R1 further increases, up to about 110 C. As reaction is not completed in R2, the temperature in this reactor is maintained approximately at the equilibrium value. After about 11 h, the solar radiation decreases and becomes too low to counteract the heat losses of the collector to the surrounding air. Thus, the temperatures of the reactors decrease progressively. This cooling changes the pressure conditions in the different parts of system 2 and the ammonia contained in tank 2 ows to E2. Thus, the wall temperature of evaporator 2 decreases strongly at 14 h. During the day phase, evaporator E2 is empty and its temperature follows exactly R1 temperature. The cold box and E1 heat up slowly from 23 to 0 C: this is the natural temperature evolution of the empty box when cold production is stopped. The night phase begins at sunset (15 h) with the opening of the side walls of the secondary solar collector in order to increase natural convection and cooling of R2. Thus, there is a step in the evolution of reactor R2 temperature at 15 h on Fig. 4. The salt in R2 reacts with gaseous ammonia and the reaction heat is rejected to the environment. Pressure then decreases in system 2 and the evaporation of ammonia in E2 increases. Consequently, the primary reactor R1 is cooled, R1 is brought to synthesis conditions and the reaction heat of the exothermic reaction in R1 is transferred to E2. The temperature of R1 thus decreases below the outside temperature (18 h). The synthesis reaction continues also in R1 and X1 increases steeply. The ammonia temperature in E1 decreases to about 30 C during the night phase (23 h). The temperature of the air in the cold box is about 10 C higher, due to the low heat transfer coefcient with E1. However, the temperature of the air in the box decreases to 23 C during this night.

3.2. Power study Fig. 5 shows the simulation of the power involved in the system on 10 June 2005, as in Fig. 4. The heat received by the solar collectors follows the radiative heat ux received by the Earth surface at this point. As solar collector 2 is twice as large as collector 1, heat absorbed is also twice as large. Only a part of the input heat is used for salt decomposition, as the collector efciency is lower than 1 and a part of this energy is needed to heat up the metal walls of the reactor. Moreover, as decomposition in R1 is already complete after only 10 h, the whole solar energy received by collector 1 after that decomposition period is lost and only used to heat up the collector parts over the decomposition temperature. For R2, as the decomposition is not complete before the end of the day, the reaction power follows the evolution of the received solar power. During the day phase, condensation occurs at outside temperature. Thus, condensing heat is rejected to the condensers surrounding air. This heat is about two times smaller than the reaction heat, according to the ratio of ammonia latent heat to enthalpy of ammonia/BaCl2 reaction. During the following night phase, synthesis occurs in the reactors and evaporation produces cold in the evaporators. The reaction and evaporation rates are almost constant, except a small peak at the beginning of the night (15 h). This is due to the opening of the collectors side walls at sunset to increase convection with outside air, and the enhancement of the ow of ammonia from tank 2 to evaporator 2 to cool R1. After that peak, the reaction rates decrease very slowly until the sunrise. During the night phase, this process can provide an average cooling power of 110 W to the cold box during 10 h for that day of June. 4. Performances 4.1. Cooling needs coverage The simulation results show the efciency of the process during the whole year. Simulations are obtained for average days for each month of the year. These average days weather conditions are calculated from the hourly weather data of years 1996 and 1997 in Perpignan. The cooling needs of the cold box and

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night. This increases the boiling temperature of ammonia in E1 and, consequently, the cold box temperature; during the day time, the high outside temperature increases the condensing temperature of ammonia in the air-cooled condensers. Thus, to counteract this high temperature, the equilibrium temperature of the reactors must also be high. As the solar collectors efciencies are low in these conditions and as a large amount of input radiation is used after decomposition to warm up the metal parts of the process to temperature peaks of the reactors, the net solar COP is low. The net solar COP of the solar system (Fig. 6) is dened as the ratio of the heat extracted by evaporator E1 in the cold box to the solar energy input received by the solar collectors. This COP takes into account the efciency of the solar collectors. Its average over the 10 sunniest months of the year is 0.047. This is close to the COP obtained by other solar cold production systems but for a higher evaporation temperature of about 10 C [1012]. The average ratio of the system and the solar COP is 67% and approximately constant for the different months. It results from the solar collectors efciencies. For this deep freezing thermochemical system, the ideal COP [8] is 0.23. It is dened as the ratio of cold produced by evaporator E1 in the ideal thermodynamic cycle to the heat required for regeneration of the salt. The COP of 0.071 obtained by simulations of the experimental prototype takes into account the dynamics of the process and both the sensible heats of the salts, ammonia and of the inert components of the process. 5. Conclusion and outlooks A new thermochemical process has been designed and studied, to produce cold at low temperature (below 20 C) using low-grade heat from simple at plate solar collectors. This process associates two cascaded cycles working in parallel with BaCl2 and NH3 . The numerical simulation of this process and the construction of a prototype: proved the feasibility of this new concept of solar freezing, to produce cold at a temperature as low as 30 C using low temperature solar heat in the range of 6080 C; demonstrated its potential use in housing, by the simplicity of its cheap and efcient at plate collector technology and by the acceptable size and weight of the system; showed the system performances during the year in a chosen location with a system COP of about 0.07 over the 10 sunniest months of the year and a net solar COP of 0.05. Further work will be carried out by considering different weather conditions and locations for implementation of this solar deep freezing system. The potential use of other types of low-grade heat (such as waste or geothermal heat) as energy sources for this process will also be considered. Another point under study is the use of PCM in the cold box to ensure a low temperature over the whole day from a discontinuous cold production.

Fig. 6. Cold production and needs of the cold box, system and net solar COP during the different months in Perpignan for the system described in Table 1.

the cooling capacity of the process are compared in Fig. 6. Simulations show that the system could cover at least 100% of the cooling needs of the cold box during the 3 sunniest months of the year (from May to July). The results obtained for the other months are also shown. During these months, the process provides an average of 53% of the cooling needs. Globally, the process should provide more than 65% of the total yearly cooling needs of this box for the weather conditions of Perpignan. An auxiliary cooling system would be needed to maintain the cold box temperature low enough for food storage. 4.2. Coefcient of performance The system coefcient of performance (COP) is dened as the ratio of the heat extracted by evaporator E1 in the cold box to the heat absorbed by the reactors of both systems. It is calculated for the same time sequence as presented above. Results are shown in Fig. 6. The average system COP over the 10 sunniest months of the year given by the simulations is 0.071. The system COP evolution is slightly different from the cold production. It remains approximately constant from February to November, with a small increase in MarchMay and SeptemberOctober. Indeed, during January and December, the daily solar energy input received by the solar collectors is not sufcient to cover both the heating of the collectors to over the decomposition temperature and the reaction heat. Most of the heat received is used to heat up the walls and inert components of the reactor. From February to November, the most favourable months are not the sunniest in Mediterranean conditions, as the outside temperatures are also the highest during these months. The increase in outside air temperatures decreases the system performances for two reasons: at night time, the high outside air temperature slows down the cooling of the solar collectors and indeed of the reactors. Thus, both time available for the synthesis reactions and the reaction rates are low and this process can be stopped before completion. Moreover, the synthesis temperature for reactor R2 is high, thus increasing the boiling temperature of ammonia in evaporator E2, and the temperature of R1 during the

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Acknowledgements This work was supported by the French governmental Agency for Energy Management and Environment (ADEME) and the ENERGIE program of the CNRS through the project PRI Froid Solaire 6.1. Appendix A. Nomenclature

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C E G H kcin p R R S S T X

condenser evaporator gas enthalpy change (J mol1 ) kinetic coefcient (s1 ) pressure (Pa) reactor ideal gas constant (J mol1 K1 ) solid entropy change (J mol1 K1 ) temperature (K) degree of conversion

Greek letter stoechiometric coefcient Subscripts amb ambient eq equilibrium i reaction, evaporation or condensation op operatoring r reaction