A Stand-Alone Solar Adsorption Refrigerator For Humanitarian Aid

Download as pdf or txt
Download as pdf or txt
You are on page 1of 7

Available online at www.sciencedirect.

com

ScienceDirect
Solar Energy 100 (2014) 172–178
www.elsevier.com/locate/solener

A stand-alone solar adsorption refrigerator for humanitarian aid


Giulio Santori a,c,⇑, Salvatore Santamaria b, Alessio Sapienza b, Stefano Brandani a,
Angelo Freni b
a
Institute for Materials and Processes, School of Engineering, The University of Edinburgh, Mayfield Road, The King’s Buildings, EH9 3JL, Edinburgh, UK
b
CNR-Istituto di Tecnologie Avanzate per l’Energia “Nicola Giordano”, S. Lucia sopra Contesse 5, 98126 Messina, Italy
c
GreenTech Srl, Via Brecce Bianche, 60131 Ancona, Italy1

Received 19 August 2013; received in revised form 20 September 2013; accepted 10 December 2013
Available online 28 December 2013

Communicated by: Associate Editor P. Gandhidasan

Abstract

Solar adsorption ice makers are devices which could prove a great help in sustaining the cold chain in third world countries. The use of
such devices could be extended also in supporting humanitarian aid actions for vaccines storage. However, further development and opti-
mization of the system design are still required. In this paper a new, versatile, solar driven ice maker operating with the activated carbon/
methanol adsorption pair has been developed and tested. The field tests carried out on February and March 2013, showed that the pro-
totype is able to produce up to 5 kg of ice, with a solar Coefficient Of Performance (COPs) of about 0.08, and to preserve it for whole next
day. The overall dimensions of the realized prototype are 1.7  1.5  0.95 m. Solar radiation is collected by a solar collector with an
exposed area of 1.2 m2.
Ó 2013 Elsevier Ltd. All rights reserved.

Keywords: Adsorption ice maker; Experimental test; Stand alone refrigerator; Solar cooling

1. Introduction Vaccine sample container The largest difficulty affecting the impact of every immu-
nization programs consists in keeping stored the vaccines
Every day thousands of children die also because of vac- at the right temperature until the administration.
cination-preventable diseases (You et al., 2012). Immuniza- The majority of vaccines have to be kept between 2 °C
tion is a milestone for the economic development and and 8 °C preventing any crossing of these limits (WHO-
poverty reduction in the third world countries. Following UNICEF, 2005). Such conditions can be easily kept storing
this believe, UNICEF has promoted the Global Alliance ice in a highly insulated boxes. For this reason research in
for Vaccines and Immunization (GAVI). The GAVI Alli- ice making technology could be an important impact on
ance aims at saving children’s lives and protecting people’s vaccines savings, increasing the number of vaccines
health by increasing access to immunization in poor coun- available for administration and consequently reducing
tries (GAVI Alliance, 2011). mortality.
The countries needing of such kind of humanitarian aid
usually have not a fully-developed electrical grid, therefore
⇑ Corresponding author at: Institute for Materials and Processes, School the traditional vapor compression refrigeration systems
of Engineering, The University of Edinburgh, Mayfield Road, The King’s have to be driven by internal combustion engines. This
Buildings, EH9 3JL, Edinburgh, UK. Tel.: +44 0131519043. involves a series of drawbacks and problems concerning
E-mail address: [email protected] (G. Santori). fuel supply and maintenance.
1
www.greentechsrl.com.

0038-092X/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.solener.2013.12.012
G. Santori et al. / Solar Energy 100 (2014) 172–178 173

Nomenclature

COPs solar coefficient of performance Tw water temperature (K)


Qe useful effect (heat of cooling) (J) mi mass of ice (kg)
Qt solar energy incident on the surface of the solar DL latent heat of liquefaction (J/kg)
collector (J) cpi specific heat of the ice in ambient conditions
Qsw sensible heat of cooling of the water (J) (J/kg K)
QL latent heat of liquefaction of water (J) Ti temperature of the ice (K)
Qsi sensible heat of sub-cooling for the ice (J) I(t) global solar radiation incident on the tilted
mw mass of water in the bins (kg) plane of the solar collector (W/m2)
cpw specific heat of water in ambient conditions A incident surface of the solar radiation (m2)
(J/kg K)

Third world country


Despite the situation described above, the majority of Therefore the versatility of the prototype, its main strength,
the third world countries benefit of high power solar radi- permits an overall sensitivity analysis, useful for the devel-
ation. These features make the third world countries partic- opment of optimized units.
ularly attractive for solar adsorptive cooling. In the first part of the paper, the operating principle and
Nowadays, thermally-driven adsorption cooling systems the design criteria are described. Afterwards experimental
have been extensively studied and can be considered as a results of two typical operational days under winter/spring
viable alternative to traditional electric-driven vapor com- Mediterranean conditions are provided.
pression systems (Critoph et al., 2005). Their operating
principle is based on the reversible adsorption of vapor
(water, ammonia, methanol) on a porous media (zeolite, 2. Operational phases of the solar powered adsorption ice
silica gel, activated carbon). Exhaustive details concerning maker
the adsorption heat transformers and their applications can
be found elsewhere (Cacciola and Restuccia, 1999). The conceptual scheme of an adsorption ice-maker is
This technology sounds particularly attractive when an presented in Fig. 1. The machine operates with a 24-h inter-
high amount of low temperature heat is available, such as mittent cycle and consists of the following main compo-
solar energy (Wang and Oliveira, 2006). nents: a solar collector, in which the adsorbent (activated
Accordingly, the current R&D is focused on the devel- carbon) is integrated, an air-cooled condenser for the rela-
opment of adsorption and absorption solar-powered chill- tive adsorbate (methanol) phase transition and an evapora-
ers to be used for ice making or food storage (Dieng and tor placed inside an insulated box where cold is produced.
Wang, 2001; Luo et al., 2005). Many off-grid solar refriger- During the daytime, the solar energy received by the col-
ator devices have been realized and successfully tested in lector allows the methanol desorption from the activated
rural areas where solar radiation is widely available (Any- carbon. The methanol vapor is condensed via the
anwu and Ezekwe, 2003; Buchter et al., 2003; Erickson,
2009; Hildbrand et al., 2004; Lemmini and Errougani,
2007; Li et al., 2004; Leite et al., 2007), demonstrating
the feasibility of this technology. However, further devel-
opment and optimization of the system design are still
required in order to realize compact, cheap and efficient
units with the aim to make them more market-attractive.
This paper presents a new solar-powered adsorption ice
maker using the working pair activated carbon (adsorbent)
and methanol (adsorbate). The prototype was designed on
the basis of the result of a mathematical model developed
and optimized in previous works (Freni et al., 2008; Mag-
gio et al., 2009; Vasta et al., 2008). This paper represents an
experimental follow up of that previous activity.
The prototype has been developed with the aim to study
the influence of some different, modifiable aspects (i.e. heat
transfer surfaces areas, type of adsorbent, adsorbent mass
and adsorbent grain size) on the overall performance. Fig. 1. Operational phases of an intermittent solar adsorption ice maker.
174 G. Santori et al. / Solar Energy 100 (2014) 172–178

condenser and then flows into the evaporator. During this materials for a screening on the more suitable material
process, valves V1 and V0 depicted in the scheme are for ice making, its optimal grain size, etc.
opened, while valve V2 is closed. Overnight, the positions The specifically designed air-cooled condenser consists
of valves V0, V1 and V2 are inverted. As a consequence, of seven finned tubes connected to a cylindrical receiver
the activated carbon adsorbs methanol from the evapora- for collection of the condensate methanol (Fig. 2). When
tor, where the useful cooling effect is produced. If liquid the desorption phase is completed, the liquid methanol col-
water is placed inside the insulated box, it can be converted lected into the receiver is passed to the evaporator through
into ice. The heat of condensation and of adsorption are an automatic valve.
released to the ambient during the day/night cycle. The evaporator (Fig. 2) consists of eighteen finned tubes
organized in two interconnected levels. This configuration
3. Realization of the prototype offers large heat exchange surface and high heat transfer
rate. All finned tubes convey the refrigerant to two cylindri-
The most important part of the system is the adsorbent cal collectors. The tubes can be partially disassembled from
bed where the pressure gradients, resulting from its thermal the collectors for sensitivity analysis purposes.
conditions, drive the vapor transfer through the other com- The evaporator is located inside a highly insulated box
ponents. Adsorbent bed consists of a tube bundle made of where the cooling effect is achieved by natural convection
10 pipes where about 20 kg of adsorbent are loaded. and that can be opened to insert/remove the substance to
Activated carbon SRD 1352/3 (origin Coconut Shell, be cooled (food, medicines, water). In the presented tests,
manufactured by Chemviron Carbons Ltd.) (Tamainot- water to be iced has been located in four bins. In one of
Telto et al., 2009) has been suitably selected to work in pair these a thermocouple is devoted to monitor the tempera-
with methanol. Its grain size ranges between 0.6 and ture evolution during the tests.
1.7 mm. These values should make the interparticle diffu- Regarding the construction material, stainless steel AISI
sion resistances reduced to guarantee a sufficient mass 304 has been selected as most suitable metal to avoid cor-
transport through the tube length. The adsorbent bed is rosion problems on the methanol used as refrigerant (Hu,
integrated with a flat-type solar collector with an exposed 1998).
area of 1.2 m2. The advantage of this configuration is the Fig. 3 shows a 3D computerized view of the prototype
compactness of the component and the reduction of the and the real apparatus equipped with the auxiliary devices.
heat transfer resistances from solar collector to the acti- The three main components previously described, mounted
vated carbon. The tubes are coated with a high absorptivity on a proper metallic framework, are suitably intercon-
and low-emissivity layer in order to maximize the absorbed nected by a pipe system and a set of vacuum valves. The
solar energy and reduce thermal energy losses. Fig. 2 shows system is equipped with pressure (piezoresistive) and tem-
the integrated system “adsorber/solar collector”, installed perature sensors (thermocouple type T, class 1), with accu-
inside an insulated metallic housing. This is equipped with racy respectively of ±2 mbar and ±0.5 °C. They allow to
shutters that can be opened during the adsorption phase, monitor the evolution of the ad/desorption cycle as well
allowing the adsorption heat dissipation from the activated as of the most relevant operational variables. A pyranom-
carbon to the external ambient. Moreover, the tilt angle of eter for the measurement of the global radiation is also
the adsorber/solar collector can be adjusted in order to set installed on the same plane of the solar collector.
its optimal value on the basis of the installation latitude All sensors and automatic valves have been interfaced
and of the time of year. with a data acquisition and control system. A specific soft-
The present adsorber can be partially disassembled for ware developed in LabviewÒ environment, allows to oper-
tests with a variable number of tubes and material mass ate the ice maker automatically. The overall dimensions of
in order to understand the sensitivity of these parameters the machine are approx. 1.7  1.5  0.95 m, while the total
on the machine performance. In addition, this design weight is about 500 kg. The main features of the prototype
allows the refilling the tubes with different adsorbent are reported in Table 1.

Fig. 2. Schematic of the adsorber/solar collector (a), condenser/receiver (b), and evaporator (c).
G. Santori et al. / Solar Energy 100 (2014) 172–178 175

Fig. 3. The solar-powered adsorption ice maker in a rendering design (a) and a real (b) view.

climatic operational conditions are reported in Fig. 4.


Table 1
Main features of the ice maker. The solar energy provided is quite similar, even though a
slightly higher cloudiness is recorded on the March test.
Solar collector
Exposed area 1.2 m2 The ambient temperatures range between a minimum
Selective surface SolMax Foil (a = 95–99%; e = 4–10%) difference of 0.3 °C during the night and a maximum differ-
Tube bundle 5 tubes DN 60  1.73 m + 5 tubes DN ence of 4.3 °C during the day. These features of the selected
60  1.63 m days make them useful for comparison purposes about the
Total surface 3.7 m2
influence of the condensing temperature on the perfor-
Adsorbent material SRD 1352/3 Chemviron Carbons Ltd.
Adsorbent mass 20 kg mance of the system. Table 2 resumes the phases schedul-
Grain size 0.6–1.7 mm ing of the thermodynamic cycles performed.
Condenser Air-cooled, 7 finned tubes DN 16, length 1 m
During the diurnal time, the solar radiation is effectively
Cylindrical receiver (DN100, 6.5 l) captured allowing to reach high temperatures on the adsor-
Total surface 4.08 m2 bent grains in both the days. It can be seen from Fig. 5 that
Evaporator 18 finned tubes DN 25, length 1 m in 2 carbon temperature rises steadily until to achieve its maxi-
interconnected levels mum, near to 93 °C and 85 °C respectively on February
Total surface 18.45 m2 and March test. These values guarantee a sufficient desorp-
Insulated box tion of refrigerant, especially in the first case. The time shift
Internal volume 1000  640  500 mm = 0.32 m3 between the tube temperature and the activated carbon
External volume 1.3 m3 temperature reflects the thermal inertia of the adsorbent
Insulation material Polyurethane foam bed, giving a measure of the system heating dynamics
and of the efficiency in the solar tubes/adsorbent material

4. Experimental results and discussion

The prototype is installed on the roof of the CNR-ITAE


building in Messina (38°110 latitude N). In order to maxi-
mize the collected solar energy, the prototype is oriented
towards south with an angle of inclination of about 38°.
A complete adsorbent evacuation to flush out air and resid-
ual gases has been performed using a vacuum pump for 8 h
and heating the carbon in a sunny day until to reach a max-
imal temperature of about 95 °C. Seven liters of methanol
have been loaded in the system. This quantity represents an
optimal value, obtained using the developed model. It is
able to produce the cooling effect required as well as to pro-
duce a constant reservoir in the evaporator of almost 2 l,
useful to promote the evaporation process.
The presented field tests have been performed during
two typical days, respectively on 11 February 2013 (winter Fig. 4. Climatic conditions in Messina during 11 February 2013 and 20
season) and on 20 March 2013 (spring season). The March 2013.
176 G. Santori et al. / Solar Energy 100 (2014) 172–178

Table 2
Scheduling of the phases of the thermodynamic cycles performed.
Start time of the operational phase Solar radiation (W/m2)
11 February 2013 (Sunrise: 6:54; Sunset: 17:30)
Isosteric heating 7:30 (+0:36 sunrise) 0
Desorptiona + cold box opening 9:30 (+2:36 sunrise) 145 (at 9:30); 1081 (Peak)
Isosteric cooling + water substitution 18:30 (+1:00 sunset) 0
Adsorptionb 19:15 (+1:45 sunset) 0
20 March 2013 (Sunrise: 6:00; Sunset: 18:10)
Isosteric heating 7:00 (+1:00 sunrise) 0
Desorption 9:30 (+3:30 sunrise) 225 (at 9:30); 1024 (Peak)
Cold box opening 10:40 430
Isosteric cooling + water substitution 18:40 (+0:30 sunset) 80
Adsorption 20:00 (+1:50 sunset) 0
a
Valve V1 open, V2 closed.
b
Valve V1 closed, V2 open.

Fig. 5. Dynamic profile of the operational temperatures of the system in 11 February 2013 and 20 March 2013.

heat transfer. About 6 h are requested to reach the maxi- the barely warm condensed refrigerant moves from the
mal tubes temperature while another hour is needed to condenser to the evaporator.
get the adsorbent temperature peak. During the night time (adsorption phase) the external
At the end of the isosteric heating phase the cold box is temperature permits to cool down the adsorbent bed pro-
opened to check the quantity of ice produced during the moting the methanol adsorption and the consequent useful
previous night. Since air at ambient temperature replaces cooling effect in the cold box.
the cold one inside the box, an increase of evaporator tem- The evaporator temperature (measured on the external
perature is observed. This increase is not registered in the surface of the heat exchanger) decreases respectively to
ice temperature profile thanks to its high latent heat of 13.6 °C on 11 February and 5.3 °C on 20 March allow-
fusion and to the good cold box thermal insulation. In fact ing the cooling of the air closed in the box and the subse-
the ice temperature remains constant equal to around 0 °C quent ice production (Fig. 6). These minimal temperature
until the start of isosteric cooling, which is the moment of values are reached in about 5 h since the beginning of the
the ice substitution with fresh water. At the same time a adsorption phase. This confirms the sufficient heat transfer
steep increase of the evaporator temperature occurs as performance of the evaporator. In the presented test 5 kg
G. Santori et al. / Solar Energy 100 (2014) 172–178 177

coupled with a slight decrease in the desorption tempera-


tures, leads to a plentiful decrease in the machine
performance.
First tests conducted in real operating conditions high-
light as a great care should be taken in the system design,
tailoring the components on the local climate of the instal-
lation, in order to develop high performance units.
Optimized condensers should be designed in climate
with high diurnal average ambient temperature, while areas
with partially cloudy weather need solar collectors able to
capture efficiently the solar radiation and to store it power-
fully in the absorbed heat.

5. Conclusions
Fig. 6. Ice produced in the bins.

In this paper a novel experimental solar-powered


Table 3 adsorption ice maker, employing the working pair acti-
Performance of the ice maker. vated carbon/methanol, is presented. The prototype has
Day 11 February 2013 20 March 2013 been designed after an accurate optimization based on a
mathematical model. The latter was specifically developed
Solar radiation energy (kJ) 28,664 26,961
COPsolara 0.08 0.063 with the aim of performing experimental sensitivity analy-
Daily ice production (kg) 5 4.6 ses both on the components features and on climatic
Maximal carbon temperature (°C) 93.0 86.4 conditions.
Average ambient temperatureb (°C) 13.0 16.2 The first outdoor field tests, performed at CNR-ITAE in
Minimal evaporator temperature (°C) 12.4 5.7
Messina (38° latitude N), show that the system in its basic
a
COPsolar is calculated as reported in (Vasta et al., 2008). configuration is able to produce up to 5 kg of ice per day
b
Considering only the diurnal period affecting the desorption phase.
with a solar COP of 0.08. The produced ice is suitably
stored for all the following day, when a new cycle start.
and 4.6 kg of ice have been produced and suitably pre- This confirms the possibility to employ this technology
served for all the next day. for vaccines or foods conservation in remote areas.
The solar Coefficient Of Performance (COPs) of 0.08 on Furthermore the test have confirmed that the technol-
11 February and of 0.063 on 20 March are obtained. The ogy is compliant with the requirements of the main human-
COPs is defined in Eq. (1). itarian organizations in supporting aid operations.
The results suggest that great care must be taken in the
Qe Qs w þ QL þ Qs i design of the machine components about the operational
COPs ¼ ¼
Qt Qt weather conditions. In fact the performance drop when
mw cpw DT w þ mi DL þ mi cpi DT i the machine is operated with slightly higher diurnal tem-
¼ Rt ð1Þ
A 0 IðtÞdt peratures or less solar irradiation. Future activities concern
a deeper sensitive analysis aiming at identify the most
It is the ratio between the useful cooling effect Qe and relevant construction parameter where to focus the
the daily collected solar energy Qt, incident on the solar optimization efforts. On the basis of this study a new,
collector surface. The Qe value is a sum of the sensible heat more compact and market-attractive prototype can be
and the latent heat of liquefaction of the water. The global developed.
performance of the prototype are summarized in Table 3.
Results show the meaningful influence of the total radi- Acknowledgements
ation captured as well as of the diurnal ambient tempera-
ture. Decreasing by 7% the first parameter as well as This work has been partially founded by Rotary Inter-
increasing by 3 °C the second one, the overall system per- national Districts 2030, 2040, 2050, 2070, 2080, 2090,
formance show a reduction about equal to 20%. In fact 2100, 2110, 2120.
the solar radiation affects the maximum adsorbent temper-
ature reached, influencing the driving force for the desorp- References
tion stage. In general higher desorption temperatures are
desirable and this could be obtained reducing the thermal Anyanwu, E.E., Ezekwe, C.I., 2003. Design, construction and test run of a
solid adsorption solar refrigerator using activated carbon/methanol, as
inertia of bed. The diurnal ambient temperature is another
adsorbent/adsorbate pair. Energy Conv. Manage. 44, 2879–2892.
important operational parameter because it affects the Buchter, F., Dind, Ph., Pons, M., 2003. An experimental solar-powered
methanol condensation rate. Operating at slightly higher adsorptive refrigerator tested in Burkina-Faso. Int. J. Refrigeration 26,
ambient temperature then the design ambient temperature, 79–86.
178 G. Santori et al. / Solar Energy 100 (2014) 172–178

Cacciola, G., Restuccia, G., 1999. Adsorption heat pumps: a new way for Maggio, G., Gordeeva, L.G., Freni, A., Aristov, Yu.I., Santori, G.,
energy saving and CFCs replacement. In: Dabrowski, A. (Ed.), Polonara, F., Restuccia, G., 2009. Simulation of a solid sorption ice-
Adsorption and its Application in Industry and Environmental maker based on the novel composite sorbent “lithium chloride in silica
Protection. Elsevier Science, Amsterdam, pp. 949–978. gel pores”. Appl. Therm. Eng. 29, 1714–1720. http://dx.doi.org/
Critoph, R.E., Zhong, Y., 2005. Review of trends in solid sorption 10.1016/j.applthermaleng.2008.07.026.
refrigeration and heat pumping technology. Proc. Inst. Mech. Eng. Leite, A.Pralon Ferreira, Grilo, M.Bezerra, Andrade, R.Ronelli Duarte,
Part E: J. Proc. Mech. Eng. 219, 285–300. Belo, F.A., Meunier, F., 2007. Experimental thermodynamic cycles
Dieng, A., Wang, R.Z., 2001. Literature review on solar adsorption and performance analysis of a solar-powered adsorptive icemaker in
technologies for ice-making and air conditioning purposes and recent hot humid climate. Renew. Energy 32, 697–712.
developments in solar technology. Renew. Sust. Energy Rev. 5, 313– Tamainot-Telto, Z., Metcalf, S.J., Critoph, R.E., Zhong, Y., Thorpe, R.,
342. 2009. Carbon–ammonia pairs for adsorption refrigeration applica-
Erickson, C., 2009. Rural milk preservation with the ISAAC solar tions: ice making, air conditioning and heat pumping. Int. J.
icemaker. Energy Sust. Dev. 13, 287–291. Refrigeration 32, 1212–1229.
Freni, A., Maggio, G., Polonara, F., Restuccia, G., Santori, G., Vasta, S., Vasta, S., Maggio, G., Santori, G., Freni, A., Polonara, F., Restuccia, G.,
2008. Optimization of a solar-powered adsorptive ice-maker by a 2008. An adsorptive solar ice-maker dynamic simulation for north
mathematical method. Sol. Energy 82, 965–976. http://dx.doi.org/ mediterranean climate. Energy Conv. Manage. 49, 3025–3035. http://
10.1016/j.solener.2008.05.002. dx.doi.org/10.1016/j.enconman.2008.06.020.
GAVI Alliance, Progress report 2011. Available at (14.08.13): Wang, R.Z., Oliveira, R.G., 2006. Adsorption refrigeration-an efficient
<www.gavialliance.org>. way to make good use of waste heat and solar energy. Prog. Energy
Hildbrand, C., Dind, Ph., Pons, M., Buchter, F., 2004. A new solar Combust. Sci. 32, 424–458.
powered adsorption refrigerator with high performance. Sol. Energy WHO-UNICEF Joint Statement on Effective Vaccine Store Management,
77, 311–318. WHO/IVB/04.16 UNICEF/Immunization/04.01, Printed: January
Hu, E., 1998. A study of thermal decomposition of methanol in solar 2005. Available at (14.08.13) <http://whqlibdoc.who.int/hq/2005/
powered adsorption refrigeration systems. Sol. Energy 62, 325–329. WHO_IVB_04.16-20.pdf>.
Lemmini, F., Errougani, A., 2007. Experimentation of a solar adsorption You, D., New, J.R., Wardlaw, T., Inoue, M., Mathers, C., Boerma, T.,
refrigerator in Morocco. Renew. Energy 32, 2629–2641. Suzuki, E., Pelletier, F., Heilig, G., Andreev, K., Gerland, P., Gu, D.,
Li, M., Sun, C.J., Wang, R.Z., Cai, W.D., 2004. Development of no valve Li, N., Sawyer, C., Spoorenberg, T., Bay, G., Miller, T., Jaspers Faijer,
solar ice maker. Appl. Therm. Eng. 24, 865–872. D., 2012. Levels & Trends in Child Mortality, Report 2012. Estimates
Luo, H.L., Dai, Y.J., Wang, R.Z., Tang, R., Li, M., 2005. Year round test Developed by the UN Inter-agency Group for Child Mortality
of a solar adsorption ice maker in Kunming. China. Energy Conv. Estimation. Available at (14.08.13) <http://www.unicef.org/videoau-
Manage. 46, 2032–2041. dio/PDFs/UNICEF_2012_child_mortality_for_web_0904.pdf>.

You might also like