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Abstract
Solar adsorption refrigeration devices are of significance to meet the needs for cooling requirements such as air-conditioning,
ice-making and medical or food preservation in remote areas. They are also noiseless, non-corrosive and environmentally
friendly. Various solar powered cooling systems have been tested extensively; however, these systems are not yet ready to
compete with the well-known vapor compression system. For these reasons, research activities in this sector are still increasing
to solve the technical, economical and environmental problems. The objective of this paper is to provide fundamental
knowledge on the adsorption systems and present a detailed review on the past efforts in the field of solar refrigeration systems.
A number of attempts have been made by researchers to improve the performance of the solar powered adsorption subsystems.
It is seen that, for successful operation of such systems, a careful selection of the adsorbent-adsorbate pair is essential apart from
the collector choice, system design and arrangement of subsystems.
q 2003 Elsevier Ltd. All rights reserved.
Keywords: Adsorbate; Adsorbent; Adsorption; Performance; Refrigeration; Solar energy
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2. Principle of adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1. Adsorption equilibria . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2. Refrigerants and adsorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3. Heat of adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3. Thermodynamics of adsorption cycles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1. Basic adsorption cycle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2. Heat recovery adsorption refrigeration cycle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3. Mass recovery adsorption refrigeration cycle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.4. Thermal wave cycle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.5. Convective thermal wave cycle. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.6. Multi-stage and cascading cycle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4. Solar cooling technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.1. Intermittent adsorption systems. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.1.1. Silica-gel/water and silica-gel methanol systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.1.2. Zeolite water systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.1.3. Activated carbon methanol systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.1.4. Activated carbon ammonia systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
* Corresponding author. Tel.: 852-2859-2632; fax: 852-2858-5415.
E-mail address: ksumathy@hku.hk (K. Sumathy).
0360-1285/03/$ - see front matter q 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/S0360-1285(03)00028-5
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1. Introduction
2. Principle of adsorption
Nomenclature
A
Cm
Cms
E
E0
H
k
K
l
l0
n
P
PC
21
PE
Ps
Rg
T
TA
TC
TE
TR
Ts
W
W0
W00
303
Greek symbol
b
affinity coefficient
d
variance
u
fractional loading
and several state equations known as isotherms of adsorption are proposed [2,4]. Several basic theories have been
proposed and ussed to define the main isotherms of an
adsorption process and are listed below:
Henrys law. For an adsorption process on a uniform
surface at sufficiently low concentrations (such that all
molecules are isolated from their nearest neighbors), where,
Table 1
Heat of adsorption of some adsorbent/adsorbate pairs
Adsorbent
Adsorbate
Activated
alumina
Water
3000
Zeolite
(various
grades)
Water
3300 4200
Ammonia
Carbon
dioxide
Methanol
Methyl
alcohol
Water
4000 6000
800 1000
Silica gel
Charcoal
Heat of
adsorption
(kJ kg21)
2300 2600
1000 1500
2800
C2H4
1000 1200
Ammonia
Water
Methanol
C2H5OH
2000 2700
2300 2600
1800 2000
1200 1400
Remarks
Water is applicable
except for very low
operating pressures
Natural zeolites have
lower values than
synthetic zeolites
304
K
l
where m 1=bk2
In order to obtain an equation for a heterogeneous solid,
the above adsorption equation is differentiated to obtain
micropore volume element dW :
dW dW0 exp2ml2 A2
305
10
306
bE0 n dT
nAn21
12
n
u
u
13
where the fractional loading u can be expressed as Cm =Cms :
The above expressions (11) (13) are often used in the
study of adsorption refrigeration system and the detail of
adsorption equilibria, working pair and heat of adsorption is
summarized in Table 2.
Table 2
A review of adsorption equilibrium equations used in different models.
Equilibrium equation
Adsorbent-adsorbate pair
Adsorption heat
lnp aw bw=T aw a0 a1 w a2 w2 a3 w3 ;
bw b0 b1 w b2 w2 b3 w3 DHw=R
Simplified Freundlichs equation: simplified Freundlichs
equation: q qsat P=Psat 1=n ; qsat 0:522 kg kg21, n 1:6
D-A equation: q W0 rT exp2A=bE0 n
Enthalpy of adsorption:
bw b0 b1 w b2 w2 b3 w3 DHw=R
[14]
[43]
Gui, 2001, 2002,
Chahbani, 2002 [38,75]
Guilleminot, 1987,
Boubakri, 2000, Passos, 1989,
Mhimid, 1998, [41]
Modified DR equation
Modified D-A equation: q q0 exp2kT=Tsat 2 1n
P T n
q W0 r exp 2D T ln sat
Psat Tcond
Llobet, 2000
D-A equation
Luo, 2000
Sakoda, 1984,1986,
Saha, 1995, Alam, 2000
Sami, 1996
Shelton, 1990, Fuller, 1994
Sward, 2000 [41,52]
[40]
[74]
Constant
Constant
Clapeyron equation for ideal gas:
DH RT 2 lnp=T
Qst T; Pevap RT 2 lnp=T
DHNH3 A 2:5 1023 T bn E0n A12n =n
p
DH RT L 2303b= k ln1=2 1=u
aT=2ln21=2 1=u k; b are coefficients,
a is the thermal expansion coefficient of
liquid, and u q=q0
Constant
Constant
Clapeyron equation for ideal gas
Constant
References
Constant
Constant
Constant
307
308
309
which the heat recovery state for a two bed system is shown
by the state points e 2 e0 :
The mass recovery cycle a2 2 a3 2 g01 2 g1 2 g2 2
g3 2 a01 2 a1 2 a2 is an extended form of a two bed
basic cycle or two bed heat recovery cycle
(a2 2 g1 2 g2 2 a1 2 a2 shown in Fig. 3), and the cycled
mass is increased from Dx to Dx dx; which causes the
refrigeration effect to increase. The principle of these cycles
can be described using Fig. 3. The very first part of each half
cycle is the mass recovery process (path g2 2 g3 and
a2 2 a3 ). Then the heat recovery process proceeds: heat is
transferred from the hot adsorber to the cold one (path
g3 2 e0 ). As a consequence, the hot adsorber is first
depressurized (path g03 2 a01 ), it then adsorbs vapor from
the evaporator (path ). Meanwhile, the cold adsorber is first
pressurized (path a3 2 g01 ), and then vapor that is desorbed
passes into the condenser (path g01 2 e). Theoretically, the
heat recovery process develops until the adsorbers reach the
same temperature. Actually, there still remains a temperature difference between the adsorbers at the end of this
period. Then, for closing each half cycle, the adsorbers are,
respectively, connected to the heat source and heat sink
(path e 2 g2 and e0 2 a2 ). The second half-cycle is
performed the same way except that the adsorbers now
exchange their roles. Due to this process, about 35% of the
total energy transmitted to each adsorber can be internally
recovered, including part of the latent heat of sorption.
3.4. Thermal wave cycle
To further improve the heat regenerative ratio, Shelton
[39] had proposed an attractive cycle called thermal wave
cycle. In this process, it is assumed that a large temperature
gradient exists along an adsorption bed.
Heating and cooling of the adsorbent beds is achieved
via a heat transfer fluid such as high temperature oil. The
system consists of two adsorber beds and two heat
310
exchangers connected in series (Fig. 4) to effect semicontinuous process. The function of the bed and heat
exchanger is to combine a large area of heat transfer surface
with a low oil flow rate.
A typical thermal wave cycle is shown in Fig. 4. The
cycle consists of two phases: In the first phase, the oil
recovers heat from bed 2 (hot), has a further heat addition
from the heat exchanger and then proceeds to heat bed 1
(cold). As the heating of the bed proceeds, bed 1 desorbs
refrigerant which passes to the condenser (giving a useful
heat output in the case of a heat pump) and bed 2 adsorbs gas
from the evaporator which provides cooling. In the
following phase (second phase) of the cycle the pump is
reversed, and hence, bed 1 is cooled (adsorbing) and bed 2 is
heated (desorbing) in a similar fashion until the original
conditions are reached and the pump can again be reversed.
Though the procedure is simple, significant heat recovery
can be achieved. Further, the system would achieve much
better performance due to the combination of the special
nature of the internal bed heat exchangers and the low flow
rate.
Although many researchers have studied the cycle, up to
now, there is no report of a successful prototype adopting
thermal wave cycle. Also, some experimental reports had
shown that the performance of the thermal wave cycle is not
very good. The efficiency of the thermal wave regenerative
system depends on a relatively large number of parameters:
for example, rates of various heat transfer processes, the
flow rate of the circulating fluid, the cycle time, the adsorber
configuration, etc. A numerical analysis of adsorptive heat
pumps with thermal wave heat regeneration had been
presented by Sun et al. [40]. They had derived two time
constants which can be used directly to quantify the relative
importance of the two heat transfer processes. This allows
ready determination of which of the two processes is rate
limiting and needs to be improved. The work has also
confirmed that the performance of an adsorptive heat pump
system using a traditional packed-bed would be too low,
even with a heat regeneration, and therefore a significant
enhancement of heat transfer properties inside the adsorber
is necessary.
Similar to the above numerical study, the effect of
various operating parameters on the performance of an
adsorptive thermal wave regenerative heat pump had been
studied by Ben Amar et al. [41], theoretically. They had
developed a two-dimensional model which simultaneously
considers heat and mass transfer in the bed. The results have
shown that under ideal conditions, the performance of a
thermal wave regenerative heat pump is considerably better
than that of a basic uniform temperature heat pump. The
study showed that a COP greater than 1 and a power of cold
production of near 200 W per kg of adsorbent could be
obtained. For air-conditioning applications, these figures are
slightly higher than those obtained with other single-stage
solid-gas systems as chemical heat pumps [42].
3.5. Convective thermal wave cycle
Thermal wave cycles normally suffer from low power
density because of poor heat transfer through the adsorbent
bed. Rather than attempting to heat the bed directly, it is
possible to heat the refrigerant gas outside the bed and to
circulate it through the bed in order to heat the sorbent. The
high surface area of the grains leads to very effective heat
transfer with only low levels of parasitic power needed for
pumping. Hence, Critoph [43,44] has presented a modified
version of a thermal wave cycle, known as convective
thermal wave cycle. The concept is the same as thermal
wave cycle, however, the thermal fluid for heating and
cooling to the beds is initiated by the refrigerant itself, thus
the heat transfer between thermal fluid and adsorption bed is
a direct contact heat transfer, which is incorporated with
mass transfer in the system.
A practical schematic of the proposed system is shown in
Fig. 5. The two active beds are packed with activated
311
carbon and the two inert beds are packed with non-reactive
particles such as steel balls. The diagram shows the first half
of the cycle, during which Active bed 1 is heated and
desorbs ammonia while Active bed 2 is cooled, adsorbing
ammonia.
In the fluid circulation loop shown on the left, a low
power pump circulates ammonia steam through inert bed 1
which is initially hot. The gas stream is heated by the bed
and a cold wave passes through the bed from right to left.
Having been preheated by the inert bed, the ammonia stream
is heated to the maximum cycle temperature (150 200 8C)
in a heat exchanger. The ammonia gas then passes to active
bed 1 where it heats the carbon. A hot thermal wave passes
from left to right through the active bed. As the temperature
of the active bed rises it desorbs ammonia which first
increases the pressure in the left hand loop and then
condenses in the condenser, rejecting heat to the environment. The mass flow rate of circulating ammonia is typically
ten times that of the condensing stream of ammonia and it
may take about ten minutes for the two thermal waves to
travel the length of their respective beds. In similar fashion
to the left hand loop the circulating flow might be ten times
the adsorption flow from the evaporator.
The advantages of this system are:
The four packed beds are in effect heat exchangers of
very high surface areas but at minimal cost. They are not
only cheap but very compact.
There are only four conventional heat exchangers and
this is the minimum number allowed by thermodynamics. These are the evaporator and condenser, a gas
heater whereby high-grade heat is input and a gas cooler
whereby the low grade heat of adsorption is rejected to
the environment.
312
intermittent adsorption;
continuous adsorption;
diffusion; and
absorption systems;
313
and was found that the COP tends to rise with cycle time
above 5 min and with the flow rate of chilled water.
A solar powered refrigeration system with a 0.25 m2 flat
plate collector has been developed [53]. This system would
realize an evaporating temperature of 5 8C when the
condensation temperature was around 35 8C and the attained
regeneration temperature was 100 8C. Ortel and Fischer [54]
used methanol with silica gel instead of water, so that the
system could operate at an evaporating temperature below
0 8C. It was found that a two-chamber silica-gel/water
system could be operated by methanol also, but because of
methanols inferior thermodynamic properties the COP of
the system was considerably reduced by about 30%.
4.1.2. Zeolite water systems
Since the late 1970s, significant efforts were made by
Tchernev [55] to develop a solar-powered natural-zeolite/
water system. Natural zeolites, with a heat of adsorption of
2.8 MJ kg21, were found to be more suitable for cooling
systems than synthetic zeolites having a heat of adsorption
of 4.2 MJ kg21. This is due to the fact that with lower heat
of adsorption the adsorbent bed can be cooled more
effectively, which in turn results in better adsorption of
refrigerant. This air-conditioning system with the exposed
collector area of 1 m2 could produce ice at a rate of
6.8 kg day21. Tchernev [55] also designed and tested a solar
adsorption machine with different combinations of working
media. Flat plate collector having an exposed area of
2.44 m2 was used to produce 100 kg of ice per day. An
additional 1.5 m2 flat plate collector was used along with the
system to refrigerate milk. However, its performance
314
315
316
317
318
Fig. 11. Schematic of the ejection refrigeration and adsorption refrigeration systems.
Fig. 12. Schematic of the hybrid system: (1) solar collector; (2)
water tank; (3) adsorber; (4) condenser; (5) receiver; (6) valve; (7)
evaporator; (8) refrigerator.
319
320
Fig. 13. Schematic of the solar cooling system with rotary desiccant dehumidification and solar adsorption refrigeration [78].
Fig. 14. Schematic of the solar house with enhanced natural ventilation driven by solar chimney and adsorption cooling cavity [80].
321
322
Table 3
An overview of developments in adsorption technologies
System
Performancea
TA
COP
SCP
Ice
(W kg21) (kg)
2129
0.12
Solar heat
0.090.13
Measured solar
irradiation
Solar heat
0.92
33
20.9
105
26
Quartz lamp
28 35
40
35
3
0
1
1
Working pairs
Investigators
Remarks
Activated carbon/methanol
Boubakri [94]
Activated carbon/methanol
7.3
Activated carbon/methanol
7078
613
0.10.12
45
Activated carbon/methanol
120
0.11
0.15
0.750.85
56
Activated carbon/methanol
Zeolite 13-X/water
Activated carbon/methanol
Buchter
et al. [95]
Leite and
Daguenet [96]
Li and
Sumathy [63]
Li et al. [97]
Tchernev [55]
Cacciola and
Restuccia [61]
Collectorcondenser
technology
Experiment
Experiment
Zeolite/water
Cascading
Cascading
Thermal
wave
Boiler
Heater
0.210.48
0.30.5
0.320.4
133 151
Silica gel/water
Silica gel/water
Activated carbon/methanol
30
80120
0.60.8
Activated carbon/methanol
Wang [27]
Generator
38
8.9
0.60
142
Critoph [38]
Thermostated
bath
35
25
1.06
Zeolite/water activated
Douss and
carbon/methanol
Meunier [67]
Zeolite/water LiBr water Shu et al. [68]
35
Ditto
Heater
40
Zeolite NaX/ammonia
Miles and
Shelton [66]
Sun et al. [40]
Simulation
Experiment
Experiment
Simulation
Single stage
system
Experiment
Simulation
Experiment
Mass
recovery
Simulation
Mass
recovery
Experimental
simulation
Multi-bed
system
Experiment
Simulation
of COP
Multi effect
Simulation
Heat
recovery
Heat source
Convective
thermal
wave
Hybrid
Heater
42
0.95
Carbon/methanol
Critoph [43,44]
20
22.5
0.064 0.067
10 10.5
Activated carbon/methanol
Assumed solar
irradiation
1535
210
84.9100
0.039 0.046
Binary
coupling
a
0.4
30
0.18
0.33
87.8
5.67
Activated carbon/methanol
Zeolite 13-X/water
Zhang and
Wang [98]
Zhang and
Wang [99]
Generator
40
10
120
0.4
Zeolite 13-X/water
Li et al. [76]
Electric heater
130
Zeolite/Ammonia/water
Wang and
Zhu [100]
Heating
ice making
Simulation
Hybrid
collector
Simulation
Adsorptionejection
technology
Experiment
Adsorptionejection
technology
Adsorption
absorption
Experiment
Experiment
323
324
(as only air and water are needed); low pressure operation;
improved indoor air quality; potential for high energy
savings; and operation with potential use of diverse energy
sources such as solar energy, natural gas and bio-gas. Their
major limitation is that their performance may be influenced
by variations in weather conditions. Their COP ranges from
0.5 to 1.0, although analytical models for modified systems
have predicted that COP values greater than 2.0 are possible.
An experimental investigation with a lithium-chlorideimpregnated wheel regenerated, by solar energy (using a
commercially available evacuated tube collector) showed
that 0.5 units of cooling can be obtained per unit of solar
energy incident on solar collectors. In summer, an average
cooling of 10 MJ m21 per day could be achieved [87]. The
use of desiccant wheels for humidity control has been tried
successfully in applications such as the prevention of metal
corrosion in storage, and in photolithography, by Harriman
[88,89]; their potential has been evaluated by Banks [90,91]
for use in applications including ice rinks and supermarkets.
Hybrid systems, which integrate desiccant dehumidifiers
with conventional cooling systems are proven to provide
substantial energy savings. The required energy can be
supplied by low temperature heat sources for the regeneration if the rotary dehumidifier matrix is properly constructed and appropriate selections are made for the type and
amount of the desiccant. The thermal energy can be
provided by a combination of an array of solar flat plate
collectors and natural gas [92].
5. Conclusions
The development of adsorption system for refrigeration
is promising. An overall thermodynamics-based comparison
of sorption systems shows that the performance of
adsorption systems depend highly on both the adsorption
pairs and processes [93]. The technology continues to
develop, and the cost of producing power with solar thermal
adsorption refrigeration is falling. If the costs of fossil fuels,
transportation, energy conversion, electricity transmission
and system maintenance are taken into account, the cost of
energy produced by solar thermal adsorption systems would
be much lower than that for conventional refrigeration
systems. This paper presents an overall review on the
fundamental understanding on the various adsorption
refrigeration cycles and the applicability of solar adsorption
both in air conditioning and refrigeration, with the
improvement of the COP.
Of the several kinds of adsorption systems analyzed in
this paper, the intermittent system has been extensively
studied both theoretically and experimentally, owing to its
simplicity and cost effectiveness. However, the main
disadvantages such as long adsorption/desorption time
have become obstacles for commercial production of the
system. Hence, to compete with conventional absorption
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