Renewable Energy 30 (2005) 81–96

www.elsevier.com/locate/renene

Technical note
Thermodynamic design procedure for solid
adsorption solar refrigerator
E.E. Anyanwu
, N.V. Ogueke
Mechanical Engineering Department, Federal University of Technology,
P.M.B. 1526, Owerri, Imo State, Nigeria
Received 2 July 2003; accepted 27 December 2003

Abstract

The thermodynamic design procedure for solid adsorption solar refrigeration is presented
and applied to systems using activated carbon/methanol, activated carbon/ammonia and
zeolite/water adsorbent/adsorbate pairs. The results obtained showed that zeolite/water is
the best pair for air conditioning application while activated carbon/ammonia is preferred
for ice making, deep freezing and food preservation. In all cases, the system depends
strongly on adsorption and condensation temperatures and weakly on the evaporator tem-
perature. The maximum possible net solar COP was found to be 0.3, 0.19 and 0.16 for zeo-
lite/water, activated carbon/ammonia and activated carbon/methanol, respectively, when a
conventional flat plate solar collector is used.
# 2004 Elsevier Ltd. All rights reserved.

1. Introduction

The major attraction of solid adsorption refrigeration technology for cold pro-
duction is that it can be powered entirely or partly by low grade energy such as
solar energy, bioenergy, etc. Its working fluids satisfy the Montreal protocol on
ozone layer depletion and the Kyoto protocol on global warming [1]. The con-
sumption of low grade energy by the units does not pose any problems of emission
of greenhouse gases (hydrofluorocarbon, carbon dioxide, nitrous oxide, methane,
perfluorocarbon and sulphur hexafluoride). Furthermore, solar powered refriger-
ation based on adsorption cycle is simple, quiet in operation and adaptable to

Corresponding author. Tel.: +234-83-231343; fax: +234-83-233228.
E-mail address: dreeanya@yahoo.com (E.E. Anyanwu).

0960-1481/$ - see front matter # 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.renene.2004.05.005
82 E.E. Anyanwu, N.V. Ogueke / Renewable Energy 30 (2005) 81–96

Nomenclature

Cp specific heat capacity (kJ/kg K)

D constant in D–A equation
h enthalpy (kJ/kg)
hsg isosteric heat (kJ/kg)
L latent heat of vapourization (kJ/kg)
m mass (kg)
P pressure (mbar)
Ps saturation pressure (mbar)
Q heat flow (kW)
S entropy (kJ/kg K)
T temperature (K)
W0 maximum capacity of sorbent (m3/kg)
X concentration (kg/kg)

Greek symbols
q density (kg/m3)
g efficiency

Subscripts
a adsorbent
c condenser
ct Carnot
e evaporator
f final
g generator; generated
i initial
r refrigerant
u universe
th thermodynamic
1st first law
2nd second law

Superscript
n constant index in D–A equation

small, medium or large systems [2]. Thus, adsorption refrigeration is considered

alternative to the conventional vapour compression refrigerator, especially in
remote areas of the world without grid connected electricity.
Activated carbon/methanol, activated carbon/ammonia, zeolite/water and silica
gel/water are the adsorbent/adsorbate pairs commonly used in practically realized
 E.E. Anyanwu, N.V. Ogueke / Renewable Energy 30 (2005) 81–96 83

adsorption refrigeration cycles. Tchernev [3], Pons and Grenier [4], Critoph [5] and
Anyanwu and Ezekwe [6] have all reported successful testing of units utilizing these
pairs. However, the overall performance of solar adsorption systems so far pro-
duced is very low; the order being around 10%. The prohibitive cost of the system
has hindered efforts to commercialize them. For example, the unit cost of about
US$ 1500 for BLM company of France manufactured system for a daily ice pro-
duction of 5.5 kg was considered too high by about 30% to get a real market [7].
More developmental research is therefore required for improvement in existing
designs either to increase overall performance significantly or reduce cost or both.
In spite of the technical success of solid adsorption refrigeration, it is difficult to
use the same performance parameter to evaluate the performances of machines
using various adsorbent/adsorbate pairs. This is mainly because the units present
marked differences in their design (dimension and weight), efficiency and cost. Cor-
bella and Garibotti [8] reported that the efficiency of the second law of thermo-
dynamics, sometimes referred to as availability, effectiveness or exergy efficiency
rather than just the first law COP is the appropriate parameter for comparing the
solar performances of solar powered absorption and the conventional vapour com-
pression machines. This efficiency of the second law is related to efficiency of the
first law by:
g1st
g2nd ¼ ð1Þ
gc

In a more recent study, Pons et al. [9] used cooling (heating) COP, second law effi-
ciencies, and cooling (heating) capacities per unit volume (or weight) as figures of
merit for thermodynamic based comparison of sorption systems for cooling and
heat pumping. These studies reveal the urgent need to evolve means of comparing
different sorption refrigeration on the one hand, and sorption and shelf vapour
compression refrigeration on the other hand.
In this paper, we set out thermodynamic design procedure for the analysis of
solid adsorption refrigeration systems. Two performance parameters developed
from the first and second laws of thermodynamics were used to obtain the thermo-
dynamic efficiency relation for comparing different adsorption systems over speci-
fied operating conditions. These performance indices are considered adequate to
measure the performances of such systems.

2. Thermodynamic design procedure

Fig. 1 shows a simple adsorption cycle indicating all the heat transfer for a com-
plete cycle. Its principle of operation involves the processes of isosteric heating,
desorption, isosteric cooling and resorption. A comprehensive review of its mode
of operation is given in Ref. [2].
84 E.E. Anyanwu, N.V. Ogueke / Renewable Energy 30 (2005) 81–96

Fig. 1. A simple adsorption refrigerator.

2.1. First law considerations

The assumptions made for this analysis are that the specific heat and density of
the adsorbed refrigerant are those of the bulk liquid adsorbate. Applying the
steady flow energy equation to Fig. 2, for each stage of the refrigeration cycle, the
energy transfers are as follows.

2.1.1. Collector/generator/adsorber
The quantity of energy used to generate refrigerant vapour from the adsorbent
during the generation process is given by Eq. (2)
Qg ¼ ma Cpa DTa þ ðmr;i  mr;g ÞCpr DTr þ mr;g ðh2  h1 Þ þ mr;g hsg ð2Þ

Fig. 2. P–T–X diagram of an adsorption system showing the theoretical refrigeration cycle.
 E.E. Anyanwu, N.V. Ogueke / Renewable Energy 30 (2005) 81–96 85

The total mass of refrigerant charged into the system, mr,i is given by
mr;i ¼ ma Xi ð3Þ
The concentration, X, of the adsorbate in the adsorbent can be obtained from
the equation of state of the bivariant solid–vapour equilibrium given in functional
form as [10]:
X ¼ CðlnP; TÞ ð4Þ
The Dubinin–Astakhov (D–A) equation (Eq. (5)) [10] relates concentration, press-
ure and temperature in the form:
   
Ps ðTÞ n
X ¼ qr ðTÞW0 exp D Tln ð5Þ
P
The initial concentration of adsorbate in adsorbent, Xi, is given by the equilib-
rium state equation
Xi ¼ CðlnPe ; Te Þ ð6Þ
During the adsorption/refrigeration phase, Ps ðTi Þ ¼ Pe . Thus,
Xi ¼ qr ðTi ÞW0 ð7Þ
The mass of refrigerant generated, mr,g, is obtained from,
mr;g ¼ ðmr;g  mr;f Þ ð8Þ
where
mr;f ¼ ma Xf ð9Þ
and Xf, the concentration of adsorbate in the adsorbent at the end of generation, is
obtained from
Xf ¼ CðlnPc ; Tf Þ ð10Þ
Pc is obtained from Ref. [11] as:
Pc ¼ exp½17:75  ð3800=Tc Þ ð11Þ

2.1.2. Evaporator
The quantity of heat transferred in the evaporator during refrigeration process is
given by Eq. (12) below.
Qe ¼ mr;g ðh1  h3 Þ ð12Þ

2.1.3. Condenser
The quantity of heat dissipated by the hot refrigerant vapour to change to liquid
form is:
Qc ¼ mr;g ðh2  h3 Þ ð13Þ
86 E.E. Anyanwu, N.V. Ogueke / Renewable Energy 30 (2005) 81–96

2.1.4. Refrigerator coefficient of performance

For a batch refrigeration process, as in the case of the intermittent adsorption
cycle, the assessment parameter is the coefficient of performance (COP) defined as
Qe
COP1 ¼ ð14Þ
Qg
where Qe and Qg are the heat transferred during refrigeration and the heat used to
generate refrigerant during generation, respectively.
Eqs. (1)–(14) may be solved once the operating conditions such as Te, Tc, L and
X are specified. In order to completely evaluate these equations for particular
adsorbent/adsorbate pair, information on the adsorbent properties is required.
2.2. Second law considerations

Considering Fig. 2 and performing the second law of thermodynamics analysis,

the entropy change of the universe becomes:
Qg Qe Qc Qa
DSu ¼   þ þ ð15Þ
Tg Te Tc Ta
Qc and Qa are often transferred to the same heat sink and therefore Tc may be
assumed equal to Ta and
Qg Qe Qc þ Qa
DSu ¼   þ ð16Þ
Tg Te Ta
The lost energy is given by
QL ¼ Ta DSu ð17Þ
Hence,
 
Qg Qe
QL ¼ ðQc þ Qa Þ  Ta þ ð18Þ
Tg Te
Since there is no external power source, one can write
Qg þ Qe ¼ Qa þ Qc ð19Þ
Substituting Eq. (19) into Eq. (18) and dividing the resulting equation by Qe gives
 
QL Qg Qg 1
¼ þ 1  Ta þ ð20Þ
Qe Qe Qe Tg Te
By the second law of thermodynamics, QL > 0. If we assume QL ¼ 0, then
ð1  ðTa =Tg ÞÞ
COP6 ð21Þ
ððTa =Te Þ  1Þ
When the equality sign is used, Eq. (21) gives the maximum possible coefficient of
performance for the adsorption cycle which is also the Carnot coefficient of per-
formance, COPct.
 E.E. Anyanwu, N.V. Ogueke / Renewable Energy 30 (2005) 81–96 87

2.3. Thermodynamic efficiency

The thermodynamic efficiency relates the actual performance of a system to its

expected maximum performance as determined from its ideal Carnot cycle. It is
obtained from a relation proposed by Pons et al. [9] as
COP1
gth ¼ : ð22Þ
COPct

3. Thermodynamic design analysis for adsorbent/adsorbate pairs

The set of Eqs. (1)–(22) together with the appropriate adsorbent/adsorbate pro-
perty data have been used to carry out the thermodynamic analysis of activated
carbon/methanol, activated carbon/ammonia and zeolite/water refrigeration sys-
tems with the aid of the computer. Four evaporator temperatures representing air
conditioning, food storage, ice making and deep freezing applications and three
condenser temperatures representing water and air cooled condensers were ana-
lysed (see Table 1). The results are presented in Figs. 3–11.
The COP of the refrigerators is observed to be strongly influenced by the
adsorption and condensation temperatures and only affected weakly by evaporator
temperature. Similar trend is deducible for the thermodynamic efficiency which
increases with an increase in condenser temperature. A closer study of Eq. (21)
shows that COPct decreases with an increase in condenser temperature, thus justi-
fying reasonably the observed thermodynamic efficiency trend.
From Figs. 3–11, it is evident that water cooled condensers are preferable from
the COP point of view. This is expected because air cooled condensers discharge
into the atmosphere even at the hottest times of the day. In Owerri, Nigeria, for
v
instance, the average ambient temperature varies over 25–38 C [12]. Because on a
typical hot day during the dry season in Nigeria, tap water is almost as warm as
the atmospheric air, evaporatively cooled water condenser is preferred. Simple
v
evaporative coolers have been reported to yield 5–7 C below ambient tempera-
tures in the country [13]. If, however, air cooling of the condenser is desired, higher
condensing temperatures than the ambient must be tolerated. For solar driven
adsorption refrigerators, air cooling of the collector/generator/adsorber is impera-
tive. Since resorption of the vapour resulting from the evaporation process occurs

Table 1
Prescribed temperatures for different applications
v
Application Evaporator tempera- Condenser temperature ( C)
v
ture ( C)
Water cooled Water cooled Air cooled
Air conditioning 5 27 37 47
Food storage 0 27 37 47
Ice making 10 27 37 47
Deep freezing 20 27 37 47
88 E.E. Anyanwu, N.V. Ogueke / Renewable Energy 30 (2005) 81–96

v
Fig. 3. Coefficient of performance and thermodynamic efficiency curves of AC/methanol at 5 C evapor-
ator temperature.

v
Fig. 4. Coefficient of performance and thermodynamic efficiency curves of AC/methanol at 0 C evapor-
ator temperature.
 E.E. Anyanwu, N.V. Ogueke / Renewable Energy 30 (2005) 81–96 89

v
Fig. 5. Coefficient of performance and thermodynamic efficiency curves of AC/methanol at 10 C
evaporator temperature.

v
Fig. 6. Coefficient of performance and thermodynamic efficiency curves of AC/methanol at 20 C
evaporator temperature.
90 E.E. Anyanwu, N.V. Ogueke / Renewable Energy 30 (2005) 81–96

v
Fig. 7. Coefficient of performance and thermodynamic efficiency curves of zeolite/water at 5 C evapor-
ator temperature.

v
Fig. 8. Coefficient of performance and thermodynamic efficiency curves of AC/ammonia at 5 C evapor-
ator temperature.
 E.E. Anyanwu, N.V. Ogueke / Renewable Energy 30 (2005) 81–96 91

v
Fig. 9. Coefficient of performance and thermodynamic efficiency curves of AC/ammonia at 0 C evapor-
ator temperature.

v
Fig. 10. Coefficient of performance and thermodynamic efficiency curves for AC/ammonia at 10 C
evaporator temperature.
92 E.E. Anyanwu, N.V. Ogueke / Renewable Energy 30 (2005) 81–96

v
Fig. 11. Coefficient of performance and thermodynamic efficiency curves of AC/ammonia at 20 C
evaporator temperature.

under exothermic conditions, cool down of the collector/generator/adsorber is

very important for the adsorbent temperature to be as close to ambient tempera-
ture as practicable to enhance adsorption of large quantity of refrigerant in the
adsorbent porous matrix [14]. Additional cooling arrangement should therefore be
incorporated if desired performance is to be achieved. Suggested approaches
include opening the end insulation covers to allow ambient air come in contact
with the collector plate and adsorbent tubes [4,6].
v
At generating temperatures above the range of 90–110 C, the refrigerator COP
for activated carbon/methanol and zeolite/water did not change significantly. The
activated carbon/ammonia system showed no appreciable change in COP over the
entire operating temperature range. This behaviour is easily attributable to the
higher generating temperature required of activated carbon/ammonia system. The
cost of constructing a system that can operate at higher generator temperature far
exceeds the gain in COP achieved. This is so because the COP depends on the mass
of adsorbate generated which in turn is a function of not only the generation tem-
perature but also the sorption characteristics of the adsorbent. Furthermore, too
high a generator temperature will delay the time to cool the collector/generator/
adsorber to the temperature for re-adsorption/refrigeration to commence, and
hence will reduce the refrigeration time.
An optimum generation temperature is therefore apparent. This can be fixed
from the COP and thermodynamic efficiency curves for the activated carbon/meth-
anol and zeolite/water systems (see Figs. 3–7). It is the point where the increasing
COP curves intercept the decreasing thermodynamic efficiency curves. For acti-
 E.E. Anyanwu, N.V. Ogueke / Renewable Energy 30 (2005) 81–96 93
v
vated carbon/methanol pair at evaporator temperature of 10 C, the values are
v v
75, 103 and 134 C for the condenser temperatures of 27, 37 and 47 C, respect-
ively. The left hand side of these points reveals high thermodynamic efficiency
values with correspondingly low COP values. Here, while the system utilizes a high
percentage of the heat supplied for useful cooling, the amount of cooling produced
is quite small. On the other hand, the right hand side of the points shows low ther-
modynamic efficiency with high COP values. This means that even though the sys-
tem produced a reasonable amount of cooling, the percentage of the applied total
heat used in producing the cold is quite small. The rest of the heat energy is used in
the wasteful heating of the adsorbent and the metal components to the high gener-
ator temperature achieved. However, similar remarks cannot be made for the acti-
vated carbon/ammonia system since both the COP and thermodynamic efficiency
decrease with an increase in generator temperature. Judging from the curves
(Figs. 8–11), low generating temperature may be recommended. However, this does
not seem plausible considering the fact that ammonia systems, being high pressure
systems, require high generator temperatures to operate. Thus, the concept of ther-
modynamic efficiency may not be adequately used to predict the optimum gener-
ator temperature for the activated carbon/ammonia systems.
Equally apparent from the study is the fact that the lost energy increases with an
increase in generator temperature. This is also evident from the thermodynamic
efficiency curve which decreases with an increase in generator temperature. For the
v
activated carbon/ammonia system at evaporator temperature of 20 C, the lost
v
energy increases more rapidly for the condenser temperatures of 37 and 47 C,
which is responsible for the apparent convergence of the thermodynamic efficiency
curves. While the convergence is more pronounced in activated carbon/ammonia
systems, a close inspection of Figs. 3–11 indicate a similar trend for the other pairs
(activated carbon/methanol and zeolite/water). This trend is best understood by
considering thermodynamic efficiency relation in the form given in Eq. (23)
Qe ðð1=Te Þ  ð1=Ta ÞÞ
gth ¼ ð23Þ
Qg ðð1=Ta Þ  ð1=Tg ÞÞ
In any application, Te and Ta are fixed. The COP and thermodynamic efficiency
depend on the mass of adsorbate generated and the generation temperature, Tg.
Unfortunately, above a certain generator temperature, the mass of adsorbate gen-
erated is no longer a direct function of the temperature. In fact, in some cases, con-
tinued increase in generator temperature does not yield any adsorbate. Thus, an
improved COP and consequently the thermodynamic efficiency will only come
from an adsorbent that will readily desorb the adsorbate in its pores up to a low
level of about 20–25 g of adsorbate per kilogram of adsorbent for the range of
temperature obtainable using a conventional flat plate solar collector. This, how-
ever, is with the understanding that the refrigerant will have a high latent heat of
vapourization.
v
The activated carbon/ammonia for 0, 10 and 20 C evaporator temperatures
v
and 47 C condenser temperature gave thermodynamic efficiency values above
94 E.E. Anyanwu, N.V. Ogueke / Renewable Energy 30 (2005) 81–96
v
100% at generator temperatures of about 70 C (see Figs. 9–11). This implies that
for those conditions, the activated carbon/ammonia system cannot be used for
cold production. Thus, the minimum generator temperature for cold production
v
for any activated carbon/ammonia system should be between 75 and 80 C when
operated at the above specified evaporator temperatures and condenser tempera-
ture.

4. Net solar coefficient of performance

From the thermodynamic analysis presented using Figs. 3–11, it is observed that
COP values of about 0.38, 0.31, and 0.60 is possible for the activated carbon/
ammonia, activated carbon/methanol and zeolite/water pairs, respectively. Since
the systems are solar energy powered, a net solar COP is defined as
Qe Qe Qg
COPN ¼ ¼ ð24Þ
Qs Qg Qs
The ratio, Qg =Qs , gives the solar collector efficiency. Duffie and Beckman [15] give
the best solar collector efficiency for a conventional flat plate solar collector as 0.5.
Thus, COPN is
Qe
COPN ¼ 0:5 ð25Þ
Qg
Results obtained for all the conditions tested using Eq. (25) are presented in
Table 2. It is evident from the table that for air conditioning, zeolite/water pair is
the best. For the other applications, activated carbon/ammonia pair is preferable.
A similar trend can be observed when comparing the different pairs using their
thermodynamic efficiencies. Interestingly for activated carbon/methanol and acti-
vated carbon/ammonia pairs, the net solar COP for all the applications, i.e. air
conditioning, food storage, ice making and deep freezing, are equal at the respect-
ive condenser temperatures. It follows therefore that the net solar COP that can be
theoretically achieved using the activated carbon/methanol, activated carbon/
ammonia and zeolite/water pairs is in the range of 0.13–0.16, 0.16–0.19 and
0.27–0.3, respectively.

Table 2
Net solar coefficient of performance of the adsorbent/adsorbate pairs for different applications
v
Adsorbent/ Net solar coefficient of performance at condenser temperature ( C)
adsorbate pair
Air conditioning Food storage Ice making Deep freezing
27 37 47 27 37 47 27 37 47 27 37 47
Zeolite/water 0.3 0.29 0.27
Activated carbon/ 0.19 0.18 0.16 0.19 0.18 0.16 0.19 0.18 0.16 0.19 0.18 0.16
ammonia
Activated carbon/ 0.16 0.15 0.13 0.16 0.15 0.13 0.16 0.15 0.13 0.16 0.15 0.13
methanol
 E.E. Anyanwu, N.V. Ogueke / Renewable Energy 30 (2005) 81–96 95

5. Conclusion

A thermodynamic design procedure used for the analysis of solid adsorption

refrigeration systems has been outlined. From the result of analysis using three dif-
ferent working pairs (activated carbon/ammonia, activated carbon/methanol and
zeolite/water), the following conclusions could be drawn:

1. Adsorption systems are generally poor thermal machines,

2. When the interest is air conditioning, the zeolite/water pair is preferred while
activated carbon/ammonia is the preferred pair for other applications,
3. The performance of adsorption systems depend strongly on the adsorption and
condensation temperatures and weakly on the evaporator temperature,
4. Optimum generation temperature exist for activated carbon/methanol and zeo-
lite/water pairs at the various condenser and evaporator temperatures, and
5. The maximum net solar coefficient of performance that can be achieved when
using a conventional flat plate solar collector is 0.16, 0.19, and 0.3 for acti-
vated carbon/methanol, activated carbon/ammonia and zeolite/water pairs,
respectively.

Acknowledgements

The authors acknowledge the financial support provided by the Federal Univer-
sity of Technology, Owerri, Nigeria, under its Senate Research Grant Scheme.

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