Energy Conversion and Management 44 (2003) 301312

www.elsevier.com/locate/enconman

Review of solid adsorption solar refrigerator I:

an overview of the refrigeration cycle
E.E. Anyanwu

Department of Mechanical Engineering, Federal University of Technology, P.M.B. 1526, Owerri, Imo State, Nigeria
Received 18 August 2001; accepted 26 December 2001

Abstract
A review of the practically realized solid adsorption solar refrigeration cycles is presented. The cycles also
have potentials for use as heat pumps. They have been classied according to the adsorbate utilized as: cycles
with water as refrigerant, cycles using uorocarbon as refrigerant, cycles using ammonia as refrigerant and
cycles with alcohols as refrigerant. The performances of these refrigeration cycles, drawn from experiences
worldwide, are also reported. The actual eld testing experiences, together with the technical and economic
constraints that aect popularization of the systems are reviewed, and their possible solutions are suggested.
2002 Elsevier Science Ltd. All rights reserved.
Keywords: Adsorption; Refrigeration; Solar energy review; Cycles; Performance; Data; Adsorbent; Refrigerant;
Cooling; Ice

1. Introduction
Solid adsorbents, such as zeolites, activated carbon, silica gel etc., in combination with suitable
refrigerants can be used in refrigeration systems to manufacture ice. Such materials possess a
permanent porous structure that, at low temperatures, act like a sponge, soaking up or adsorbing
the refrigerant. At elevated temperatures, the refrigerant is released or desorbed. The refrigeration
cycle can be powered by purely thermal energy, and therefore, they are silent in operation and
most suited for remote locations without rm electricity supply.
Adsorption cycles are only intermittent in operation, since the adsorbent cannot move through
the components, and the cycle comprises two phases: heatingdesorptioncondensation phase and
*

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E-mail address: eanyanwu@futo.edu.ng (E.E. Anyanwu).

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E.E. Anyanwu / Energy Conversion and Management 44 (2003) 301312

Fig. 1. PTX or Clapeyron diagram of adsorption cycle.

coolingadsorptionevaporation phase. When the thermal energy supply is solar energy, the
phases correspond to the natural diurnal and nocturnal solar radiation periods, respectively. In
this case, the demand for energy is in phase with its supply. Adsorption cycles have been considered for use in heat pump systems, as have many dierent absorption cycles [1].
Solar powered adsorption refrigeration contains only three major components (container of
adsorbents, condenser and evaporator) and functions as follows. The adsorbent is packed in a
hermetically sealed container painted black for solar radiation absorption. During the day, solar
energy heats the high concentration of adsorbent and container to the maximum cycle temperature. At its condensing pressure corresponding to a particular temperature, the refrigerant starts
desorbing from the adsorbent. As the refrigerant vapour is changed to liquid in the condenser,
heat is dissipated to the surroundings. The condensate ows by gravity into a liquid receiver or
directly into the evaporator.
During the night cycle, the adsorbent is cooled to near ambient temperature, thus reducing the
pressure of the entire system. When the adsorbent pressure equals the saturated vapour pressure
of the refrigerant, the refrigerant boils in the evaporator and causes heat to be absorbed from the
immediate environment. The resulting refrigerant vapour is readsorbed into the adsorbent, while
cooling is produced. The pressuretemperatureconcentration (PTX) diagram of Fig. 1 illustrates the above processes and their typical operating temperatures.
Practically realised solar energy powered solid adsorption refrigeration cycles based on the
above principles may be classied according to the adsorbent/refrigerant combination used.
ii(i)
i(ii)
(iii)
(iv)

Adsorption cycles with water as the refrigerant,

adsorption cycles with uorocarbon as the refrigerant,
adsorption cycles with ammonia as the refrigerant,
adsorption cycles with alcohol as the refrigerant.

2. Adsorption cycles with water as the refrigerant

Tchernev [2] observed that a naturally occurring mineral, called zeolite, adsorbs large amounts
of water vapour when cooled and desorbs the water vapour when heated, thus providing a unique

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303

Fig. 2. Adsorption isotherms of water vapour on zeolite-13X.

opportunity for its utilization in refrigeration applications. Natural zeolite, placed in a hermetically sealed metal container, performs the functions of energy collection and those of mechanical
compressor in the conventional refrigerator but without any moving parts. Fig. 2 shows that the
quantity of water adsorbed by zeolite is strongly dependent on temperature and only weakly
dependent on vapour pressure [3]. Therefore, during the refrigeration process at night, when the
collector containing zeolite is near ambient temperature, the water is readily adsorbed, keeping the
pressure below 0.055 kPa and making the evaporator water freeze. During the day, the regeneration process is only slightly aected by the condensation pressure.
Using this principle, Tchernev [4] fabricated and tested a 100 dm3 zeolitewater solar energy
powered refrigerator. The collector/generator/absorber component contained 5 cm thick, 50 kg
zeolite per square meter. For a solar energy input of 6 kW h, the refrigerator produced 900 Wh of
cooling per square meter of collector area with a coecient of performance (COP) of 0.15. Fig. 3
shows a schematic diagram of Tchernevs refrigerator. Successful eld testing of this unit sparked
interests world wide in solar powered solid adsorption refrigeration. However, natural zeolites
are dicult to obtain in sucient quantities in many countries. Consequently synthetic zeolite,

Fig. 3. Tchernevs refrigerator.

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E.E. Anyanwu / Energy Conversion and Management 44 (2003) 301312

particularly molecular sieve 13X, which are easily manufactured, are commonly used. Dupont et al.
[5] investigated two solar powered solid adsorption refrigerators: one utilizing a water cooled
condenser, while the other used an air cooled condenser. The working pair for both is zeolite
13Xwater. Test results showed that in the water cooled condenser model, the solar COP varied
over the range 0.040.14 with ice production in the range 3.718.14 kg/m2 of collector area. For the
air coded condenser refrigerator, the solar COP of 0.10 was achieved with 7.0 kg/m2 of ice produced.
Grenier et al. [6] built a large cold store of volume 12 m3 powered by solar energy using a zeolite
13Xwater combination. The adsorbent granules were distributed in 24 at plate type collectors,
each of area 0.83 m2 . The evaporator temperature achieved was as low as 2.5 C, corresponding to
a solar COP of 0.086. Comparing these results with those of Refs. [4,5] above reveals that the
technology does not show any size advantages and, therefore, could be adaptable to large, small
and medium size refrigerators.
Phillip et al. [7] also built a at plate solar collector operated, intermittent zeolite 13Xwater
refrigerator. Their system comprised a box type solar collector of surface area 0.25 m2 containing
about 5 kg of adsorbents, tube-in-stagnant water condenser of 0.4 m2 heat transfer area, a two
litre evaporator constructed from brass and diaphragm valves for isolating the components. Field
tests in actual day and night conditions of India indicated that about 3% desorption was obtained,
and the maximum cycle temperature was 130 C. Evaporator temperatures as low as
8 C could
be attained with 1 kg of ice produced during the night cycle.
Apart from zeolite, another adsorbent which adsorbs water is silicagel. Sakoda and Suzuki [8]
constructed and tested a laboratory scale closed adsorption cooling system employing a silicagel
water combination. The refrigerator consisted of ve T-type tubes used as packed bed of adsorbents, a condenser, an evaporator, infrared lamp and a vacuum pump system. The successful
operation of this unit demonstrated clearly both the experimental and technical feasibility of solid
adsorption refrigeration. Kluppel and Gurgel [9] built two prototypes of solar powered solid
adsorption cooling systems using a silicagelwater combination. The prototypes (small domestic
refrigerator and portable water cooler) used a solar collector/generator in which the adsorbents
are packed in the annular space between copper tubes that were connected to a manifold. The
tubes were then juxtaposed in order to present a continuous surface to the solar radiation. A solar
COP of 0.055 was obtained for the small domestic refrigerator prototype with evaporator temperatures below 277 K, while it reached a COP of 0.077 for the portable water cooler with
evaporator temperatures around 285 K.
Water appears to be the best refrigerant because of its high latent heat of vaporization,
abundance and zero hazard in use. However, its low vapour pressure near 0 C and 0 C freezing
temperature make it dicult to use as refrigerant at sub-zero evaporating temperatures. Water, of
course, enjoys useful applications as refrigerant in the lithium bromide-water absorption air
conditioning units and other refrigeration systems requiring evaporation temperatures greater
than or equal to 10 C.

3. Adsorption cycles with uorocarbon as the refrigerant

Measurements of the adsorptive properties of zeolite-5A, Zeolite-13X and activated carbon
have been made by Critoph and Vogel [10] for the organic refrigerants: R11, R12, R22 and R114

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305

as possible combinations for solar cooling. Even though an activated carbonR22 combination
was reported to give the best COP of 0.2, the only such adsorption refrigerator in the literature
used R114 as refrigerant.
Critoph [11] considered the use of a high pressure refrigerant R114activated carbon combination for the operation of a solar powered adsorption cycle. He built a small scale refrigerator to
produce about 300 kJ of cooling. The solar collector/generator/absorber component comprised 9
lengths of 700  1 mm2 wall thickness steel tube containing 24.2 kg of activated carbon, with a
plan area of 1.02 m2 coated with maxorb solar lm. The air cooled condenser was integrated into
the underside of the collector/generator/absorber component. Experimental results with this
system were less than satisfactory, as the refrigerator only cooled from an ambient temperature of
30 C down to 13 C before adsorption was completed. It was concluded that the losses into the
cold box consumed most of the available cooling, which meant that ice could not be produced.
The main problem with uorocarbon refrigerants is their depleting eect on the ozone layer.
Edmunds et al. [12] have found that uorocarbon refrigerants used in refrigeration machines
contribute up to 50% of the chlorouorocarbon emission in the atmosphere and, thus, accounts
for about 33.3% of the greenhouse eect. As a result of this, the Montreal protocol on substances
that deplete the ozone layer has proposed phasing out fully halogenated uorocarbon refrigerants, such as R11, R12, R21 etc. currently used on large scale in refrigeration industries [13]. This
condition will undoubtedly aect most of the o-the-shelf refrigeration technologies and boost
eorts at substitution with new technologies utilizing environmentally friendly working substances. Fig. 4 shows the main features of the R114activated carbon refrigerator.

Fig. 4. Photograph of the experimental R114charcoal refrigerator.

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4. Adsorption cycles with ammonia as the refrigerant

In furtherance of the eorts to develop a high pressure adsorbentrefrigerant solar energy
operated refrigerator, Critoph [14] also built a laboratory scale activated carbonammonia refrigerator. The generator, of exposed surface area 1.4 m2 , consisted of an array of 15 stainless
steel tubes, each of 2 m length, 42 mm outside diameter and 1.1 mm thick, rated to 30
bar pressure. About 17 kg of 208 C activated carbon granules were packed in the tubes. The
condenser was a 4 m length of 12.5 mm diameter stainless steel tube coiled within a 100 litre
water tank. The evaporator was a 10 mm diameter stainless steel coil immersed in 4 litres of
water. The evaporator temperature attained was up to
1 C and about 3 kg of ice was manufactured. The peak collector temperature for the simulated day tests was 115 C, and the solar
COP was 0.04.
However, the diculties and practical disadvantages of activated carbonammonia systems are
the high pressure requirement, resulting in the bulkiness of the refrigerator, and the corrosive
nature of the refrigerant, ammonia. The problem of great bulk in large systems can be avoided by
the development of rapid cycling units, as have been done by Ref. [15]. In this version, two
separate adsorption cycles are operated out of phase such that when one adsorber is being
heated by the energy source, the other cools to ambient temperature, readsorbing its refrigerant and producing useful cooling in the evaporator. The laboratory prototype rapid cycling
ice maker consisted of two adsorbers: each consisting of seven 2 m long stainless steel tubes, with
1.04 kg of activated carbon in each tube, packed in a hexagonal cell and manifolded together.
Each hexagonal cell was contained in an outer copper shell of 150 mm diameter that contained steam at 2 bar pressure during the heating phase. Each individual tube had a smaller
diameter concentric tube that carried cooling water during the cool down mode. The condenser
was water cooled and the evaporator consisted of a simple stainless steel coil soldered around a
copper box containing up to 5 litres of water. The results of experiments conducted with this unit
showed that the half cycle times for optimum ice production varied from 16 min with steam at
150 C to 26 min with steam at 100 C. Fig. 5 illustrates the main features of the rapid cycling
refrigerator.

Fig. 5. The sectional view of the solar adsorption refrigerator.

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307

5. Adsorption cycles with alcohol as the refrigerant

The most detailed design of a practical solid adsorption refrigerator so far reported in the
literature is that of Pons and Guilleminot [16] that used an activated carbonmethanol combination. This system consisted of four solar collectors of total exposed area 6 m2 , containing a total
of 130 kg of adsorbent, two air cooled condensers and an evaporator with a net production of 30
35 kg of ice per sunny day. Analysis of the experimental data on this ice maker showed the
performance to be in the range 0:10 < COP < 0:12 when the incident solar energy lies between 16
and 19 MJ/m2 [17]. They concluded that this performance could be improved by reducing the
sensible heat of the evaporator, improving the cooling of the collectors and making all their
collectors identical.
Exell et al. [18] designed and fabricated a charcoalmethanol solar refrigerator with the reactor
consisting of an array of 15 copper tubes 54 mm in diameter and 1.2 m long with eective collecting area of about 1 m2 . The reactor tubes contained 17.8 kg of activated charcoal 207E3,
manufactured by Sutclie Speakman Carbons Ltd., United Kingdom. The condenser was water
cooled with a heat transfer area of 0.35 m2 , and the liquid receiver and evaporator were designed
as a single unit housed in a lagged box. Test results showed that the eciency of the reactor varied
between 33% and 44%, and a peak temperature of 122 C was attained during clear days [19]. The
net solar COP obtained was above 0.10 and sometimes reached 0.123. The maximum evaporator
temperature during most nights was below
7 C, but during some nights it was as low as
12 C.
The refrigerator was able to manufacture up to 4 kg ice after a clear day. Fig. 6 is a schematic
diagram of this unit. Quite recently, Headley et al. [20] built a charcoalmethanol adsorption
refrigerator having a cylindro-parabolic reector which concentrated solar heat onto an adsorbent
copper tube at the focal line. The tube, of length 2.44 m was packed with 2.6 kg of activated
carbon 207E3 and coupled to an air cooled condenser, liquid reservoir and 1.2 litre capacity
evaporator. Fig. 7 illustrates this refrigerator. It manufactured up to 1 kg of ice at an evaporator
temperature of
6 C, and the net solar COP was of the order of 0.02. The maximum cycle
temperature achieved was 154 C on a day when the ambient solar energy was 26.8 MJ/m2 . The

Fig. 6. Schematic diagram of the New Solar Refrigerator model developed at AIT (Exell [3]).

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E.E. Anyanwu / Energy Conversion and Management 44 (2003) 301312

Fig. 7. The main refrigerator power by cylindro-parabolic solar reector.

twin advantages of this refrigerator are the capacity to produce ice even on overcast days and
lightness of the entire system compared to other designs. However, concentrating solar collectors
are expensive and complex in structure, as they need to always track the path of the sun to capture
only the direct component of solar radiation.
The peak cycle temperature for the activated carbonmethanol combination is limited to 150
C because of methanol instability above it. The methanol breakdown that might occur at such
elevated temperature is:
2CH3 OH ) CH3 OCH3 H2 O
It is seen that activated carbon acts as a catalyst for the reaction.
Exploiting this regenerating temperature limitation, of the activated carbonmethanol pair and
the freezing temperature limitation, as well as the high regenerating temperatures of the zeolite
water pair, Meunier and Douss [1] designed and tested cascading adsorption heat pump cycles
using the two pairs. The entire laboratory system was comprised of a two adsorber zeolitewater
cycle topping an intermitted activated carbonmethanol cycle. The cooling obtainable was 1.06,
which corresponded approximately to more than 100% enhancement compared to only an intermittent cycle. The regeneration parameter reached 57%. This sort of cycle appears very
promising for air conditioning applications, but dierent heat management may be needed to
satisfy other applications, such as cogeneration of chilled water at 2 C and hot water at 70 C,
cogeneration of refrigeration at
10 C and hot water at 70 C. Ethanol has also been investigated
as a possible refrigerant with activated carbon as the adsorbent [21,22]. The results of tests on
some solar adsorption refrigeration cycles [4,14,16,17] are presented in Table 1. They show, at a
glance, their operating parameters and performances.
The activated carbonmethanol combination is preferred to other solid adsorbentrefrigerant
combinations due to several advantages: chemical stability, enhanced COP, inexpensive materials
easily available or produceable in most developing countries where such refrigerators are urgently
required and relative lightness of construction because the pressure inside is low. For these reasons, a compact activated carbonmethanol solid adsorption refrigerator powered by solar energy
was designed, fabricated and is being tested by the author at the Centre for Energy Research and
Development, University of Nigeria, Nsukka. Fig. 8 illustrates the general layout of the refrigerator. The results of tests conducted with this unit will be reported in future communications.

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309

Table 1
Test result for some solar adsorption refrigeration cycles
CarbonMethanol
cycle [16,17]

ZeoliteWater
cycles [4]

CarbonAmmonia cycles [14]

Generator/Adsorption/Collector Area (m2 )

1.51

1.4

Generation phase
Duration (h)
Mass of adsorbent (kg/m2 )
Adsorbent thickness (m)
Mass of generator/adsorber/collector (kg)
Adsorbate distillate (kg)
Total incident solar radiation

6
24
0.06
114
1620
120,000 kJ

7.5
50
0.05
149.69

22,360.67 kJ/m2

12
12.14

33
1.38
1000 W/m2

Cool down/Adsorption phase

Duration (approximately) (h)
Initial Temp. of evaporator water (C)
Minimum evaporator temperature (C)
Mass of ice produced (kg)
Eective cooling (kJ/m2 )

12
20

3
37
2583.3

12

2.8
6.80
4508.48

12
20
0
4
1069

Performance ratios
Cycle COP
Net solar COP

0.43
0.12

0.8
0.109

0.25
0.05

Fig. 8. Solid adsorption solar powered refrigerator.

6. Problems and prospects of solar adsorption refrigeration technology

6.1. Field experiences
The most signicant work on testing and evaluating commercially produced solid adsorption
solar refrigerators in the eld has been undertaken by Boubakri et al. [23] in Agadir, Morocco.
The results of eld monitoring of such systems in several locations of possible application are
important to establish system reliability as well as provide operating data. This is also expected to
provide experience of user reactions to the system as in the case with photovoltaic (PV) powered
refrigerators. By the end of the 1980s, more than 800 PV powered medical refrigerators were
installed and evaluated throughout the developing world by the World Health Organisation

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E.E. Anyanwu / Energy Conversion and Management 44 (2003) 301312

(WHO), Centre for Disease Control, US Agency for International Development, European
Community and other agencies [22]. This enabled the WHO to specify a requirement for solar
refrigeration in its Expanded Programme on Immunization because of its important role in
maintaining the vaccine cold chain [25] in Third World rural clinics. Sponsored widespread eld
testing of all solar refrigeration technologies are considered complete solutions to the problems of
maintaining the vaccine cold chain in rural clinics of developing countries.
6.2. Technical problems
The major technical problem associated with solar powered adsorption technology is its poor
heat and mass transfer characteristics. The adsorbents, such as activated carbon, zeolite and
silicagel, in use have low thermal conductivity and poor porosity characteristics. The eect is the
bulky collector/generator/adsorber component and, thus, its excessive heating capacity, leading to
rather low system COP. Spinner [26] reported a slight improvement of the system performance
from adsorbent stabilization with graphite binders. Munyebvu [27] produced activated carbon
from monolithic discs housed in a tube with internal ns to improve both its thermal conductivity
and thermal contact with metal elements. Other possible solutions suggested by researchers [28,29]
include:
i(i) Use of two cycles with dierent adsorbent/adsorbate combinations
(ii) Use of regenerative cycles, in which two adsorption cycles are operated out of phase such that
when one is being heated, the other is being cooled.
None of these possible solutions, however, is yet to be adopted in commercially tried solar adsorption refrigeration to permit evaluation of the eectiveness.
6.3. Economic problem
The principal challenge for adsorption refrigerators powered by solar energy is to overcome
several failed attempts to commercialize them. Commercialization of the silicagel/sulphur dioxide refrigerator in the 1930s [30] and the activated carbonmethanol refrigerator in 1960 [31],
both of which used a fossil fuel based heat source, were unsuccessful because of the emergence of
more ecient vapour compression refrigerators using cheap conventional energy, including
electrical energy. More recently, the commercially tried adsorbent/adsorbate combination of activated carbonmethanol and zeolitewater refrigerators proved to be technically successful but
too expensive to penetrate the market. The BLM company of France and Comesse Soudure of
South Africa produced the activated carbonmethanol refrigerators. The Zeopower company of
the USA manufactured the zeolitewater refrigerators. However, the unit price of about US$ 1500
for the BLM system for a daily ice production of 5.5 kg was considered too high by about 30% to
get a real market [32]. In Nigeria, ice packs produced by vapour compression refrigerators cost
about thirty (30) Naira per kg. PV refrigerators widely used in the vaccine cold chain have had
better commercial success than the solar sorption systems. An installed PV refrigerator cost about
US$ 6000.00. The Platen-Munters (Electrolux) diusion absorption systems, particularly for the
preservation of vaccines and drugs, have an installed cost of US$ 1500.00, considerably less than

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311

the PV refrigerators. However, the operation and maintenance cost of Electrolux systems are
high, and their reliability is low, sometimes resulting in an availability of only about 50% [24]. For
solar adsorption units, the commercialization potential may be boosted by either a considerable
reduction in unit cost or remarkable improvements in its performances at existing costs.

7. Conclusion
Solar powered refrigeration based on adsorption cycles is simple, quiet in operation and
adaptable to small or medium or large systems. Application potentials include storage of vaccines
for immunization against killer diseases in remote areas, preservation of foodstu for future use
and manufacture of ice.
Already solar adsorption refrigeration is a technical success, but it is not commercially competitive with either the conventional vapour compression or PV refrigerators. Further developmental research is, therefore, required for improvements in existing designs either to increase
system overall performances signicantly or to reduce system unit cost or both.

Acknowledgements
The author acknowledges the nancial support provided, at various times, by the Federal
University of Technology, Owerri, Nigeria, under its Senate research grant scheme and the National Centre for Energy Research and Development, (NCERD), University of Nigeria, Nsukka.
The author is also grateful to Professors C.I. Ezekwe and O.C. Iloeje of the Department of
Mechanical Engineering, University of Nigeria, Nsukka, for their helpful comments.

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