14 ASHRAE Jour nal ashr ae.

or g Sept ember 2011

A
dsorption (also called solid sorption) refrigeration systems use
solid sorption material such as silica gel and zeolite to produce
cooling effect. These systems are attracting increasing attention because
they can be activated by low-grade thermal energy and use refriger-
ants having zero ozone depletion potential and low global warming
potential. The adsorption refrigeration system has several advantages
compared to the absorption refrigeration system.
Wide range of operating tempera-
tures.
1
Adsorption systems can be acti-
vated by a heat source with a temperature
as low as 50C (122F), while the heat
source temperature for an absorption
system should be at least 90C (194F).
Also, adsorption systems have less cor-
rosion issues for the adsorbentrefriger-
ant working pairs when they incorporate
high temperature heat sources compared
to an absorption system, while severe
corrosion might occur in absorption sys-
tems when the regeneration temperature
is greater than 200C (392F).
No crystallization issue. In the lith-
ium bromide (LiBr) /water absorption
system, there is a specic minimum solu-
tion temperature for any given LiBr solu-
tion concentration below which the salt
begins to crystallize out of the solution.
2

Crystallization results in interruption of
machine operation and possible damage
to the unit. By contrast, in adsorption
systems the adsorbent remains in a solid
state, which means no crystallization is-
sues.
Suitability for application where se-
rious vibration occurs.
3,4
Absorption
systems cannot operate normally under
conditions where serious vibration oc-
curs, such as in shing boats and loco-
motives, because the absorbent in these
systems, which is in a liquid state, may
ow from the generator to the condenser
or from the absorber to the evaporator.
Adsorption systems are suitable for such
applications, because their adsorbents
stay in a solid state.
Depending on the nature of attractive
forces existing between the adsorbate
and adsorbent, adsorption can be clas-
sied as physical adsorption or chemi-
About the Authors
Kai Wang, Ph.D., is a postdoctoral research associ-
ate, and Edward A. Vineyard, P.E., is group man-
ager of the Building Equipment Research Group at
Oak Ridge National Laboratory, Oak Ridge, Tenn.
By Kai Wang, Ph.D., Member ASHRAE; Edward A. Vineyard, P.E., Fellow ASHRAE
Adsorption
Refrigeration
New Opportunities for Solar
This article was published in ASHRAE Journal, September 2011. Copyright 2011 American Society of Heating, Refrigerating and Air-Conditioning
Engineers, Inc. Posted at www.ashrae.org. This article may not be copied and/or distributed electronically or in paper form without permission
of ASHRAE. For more information about ASHRAE Journal, visit www.ashrae.org.
Sept ember 2011 ASHRAE Jour nal 15
cal adsorption. In physical adsorption, the forces of attraction
between the molecules of the adsorbate and the adsorbent
are of the Van der Waals type. Since the forces of attraction
are weak, the process of physical adsorption can be easily re-
versed by heating. In chemical adsorption, the forces of attrac-
tion and chemical bonds between the adsorbate and adsorbent
molecules are strong. The adsorbate and adsorbent molecules
change their original state after the adsorption process, e.g.,
complexation occurs between chlorides and ammonia. More-
over, chemical adsorption also exhibits the phenomena of salt
swelling and agglomeration, which are critical to heat and
mass transfer performance.
1
The major drawbacks of adsorp-
tion systems are their low energy efciency, the COP (coef-
cient of performance: the ratio of cooling capacity to thermal
energy supplied to the system) is usually less than 0.4, due to
the thermal coupling irreversibility.
5
Adsorbents and Refrigerants
The adsorbents used in adsorption systems are categorized
as physical, chemical, or composite adsorbents, according to
the nature of the forces involved in the adsorption process. The
types, characteristics, advantages, and disadvantages of differ-
ent adsorbents are summarized in this section. Two parameters
are widely used to evaluate the performance of an adsorption
system and adsorbents, namely, COP and SCP (specic cool-
ing power: the ratio of cooling capacity to mass of adsorbent
in the adsorbers).
Physical Adsorbents
The commonly used physical adsorbents for adsorption re-
frigeration systems are activated carbon, silica gel and zeolite.
Activated carbon is a form of carbon that has been pro-
cessed to make it extremely porous, and it has a large
surface area available for adsorption. Methanol and am-
monia are the most common refrigerants paired with ac-
tivated carbon. Activated carbonmethanol is one of the
most promising working pairs in practical systems because
of its large adsorption quantity and low adsorption heat
(about 1800 to 2000 kJ kg
1
(773.9 to 859.8 Btu/lb).
1
Low
adsorption heat is beneficial to the systems COP because
the majority of heat consumption in the desorption phase
is the adsorption heat. Another advantage of activated car-
bonmethanol is low desorption temperature (about 100C
[212F]), which is within a suitable temperature range for
using solar energy as a heat source. However, activated
carbon will catalyze methanol to decompose into dimethyl
ether when the temperature is higher than 120C (248F).
6

Since typical pressures in an activated carbonmethanol
system are subatmospheric, a hermetically sealed outer
vessel is required.
Activated carbonammonia has almost the same adsorp-
tion heat as the activated carbonmethanol working pair. The
main difference is the much higher operating pressure (about
1600 kPa [232 psia] when the condensing temperature is 40C
[104F]) of activated carbonammonia. The high operating
pressure leads to rather small pipe diameters and relatively
compact heat exchangers, as compared to activated carbon
methanol. Another advantage of activated carbonammonia
is the possibility of using heat sources at 200C (392F) or
above.
7
The drawbacks of this working pair are the toxicity
and pungent smell of ammonia.
Silica gel is a granular, highly porous form of silica made
synthetically from sodium silicate. For the silica gelwa-
ter working pair, the adsorption heat is about 2500 kJ /kg
(1074.8 Btu/lb) and the desorption temperature could be
as low as 50C (122F).
1
Such a low desorption tempera-
ture makes it suitable for solar energy use. There is about
4% to 6% (by weight) of water connected with a single hy-
droxyl group on the surface of a silica atom, which cannot
be removed; otherwise the silica gel would lose its adsorp-
tion capability. Thus, the desorption temperature cannot be
higher than 120C (248F), and it is generally lower than
90C (194F).
1
One of the drawbacks of the silica gelwater
working pair is its low adsorption quantity (about 0.2 kg
water/kg [0.2 lb water/lb] silica gel). Another drawback is
the limitation of evaporating temperature due to the freezing
point of water.
Zeolite is a type of alumina silicate crystal composed of
alkali or alkali soil. The adsorption heat of zeolitewater is
higher than that of silica gelwater, at about 3300 to 4200
kJ kg
1
(1418.7 to 1805.7 Btu/lb).
1
The desorption tempera-
ture of zeolitewater is higher than 200C (392F) due to its
stable performance at high temperatures. The drawbacks of
zeolitewater are the same as for silica gelwater, low adsorp-
tion quantity and inability to produce evaporating tempera-
tures below 0C (32F).
Chemical Adsorbents
Chemical adsorption is characterized by the strong chemical
bond between the adsorbent and the refrigerant. The chemical
bond mainly includes the functions of complexation, coordi-
nation, hydrogenation and oxidization.
1
The chemical adsorp-
tion reaction is represented in Equation 1:
8
(1)
The equilibrium of this reaction is monovariant. Since the
liquid-vapor equilibrium is also monovariant, the solidgas
and liquidvapor equilibrium lines can be calculated using the
Clausius-Clapeyron equation,
8
Ln P
H
RT
S
R
eq
( )
=

+

(2)
H is the reaction enthalpy, S is the reaction entropy, R is
the gas constant. The most commonly used chemical adsor-
bentrefrigerant pair is metal chlorides and ammonia, which
exhibits the complexation force. The metal chlorides include
calcium chloride (CaCl
2
), strontium chloride (SrCl
2
), magne-
sium chloride (MgCl
2
), barium chloride (BaCl
2
), manganese
chloride (MnCl
2
), and cobalt chloride (CoCl
2
), among others.
< > < > S v G S v H + ( ) +
16 ASHRAE Jour nal Sept ember 2011
As an example, the complexation reaction of CaCl
2
and am-
monia (NH
3
) can be written as
CaCl NH NH CaCl NH
2 1 2 3 2 3 2 1 3 2
( ) + + n n n n n H (3)
where the numbers of n
1
and n
2
could be 2, 4 and 8.
The advantage of metal chlorideammonia working pairs
is the higher adsorption quantity than that of physical adsor-
bentrefrigerant pairs. The drawbacks of metal chlorideam-
monia pairs are: 1) they require more energy to remove the
adsorbed molecules than in physical adsorption, and 2) ad-
sorption performance is degraded because of salt swelling and
agglomeration in repeated adsorption/desorption processes.
Composite Adsorbents
The composite adsorbents (or complex compounds)
9,10
are
made from porous media, and chemical sorbents are commonly
a combination of metal chlorides and expanded graphite, acti-
vated carbon, active carbon ber, zeolite or silica gel. The ob-
jectives of using composite adsorbents are: 1) improve heat and
mass transfer of chemical adsorbents
11
, 2) increase the adsorp-
tion quantity of physical adsorbents.
12
The addition of chemi-
cal sorbents to the physical adsorbents could result in higher
adsorption quantity than that of physical adsorbents alone.
The main composite adsorbentsrefrigerants in the recent
literature can be categorized as silica gel and chloridewater,
and chlorides and porous mediaammonia.
Composite adsorbents of silica gel and chloride are usually
produced using the impregnation method. The silica gel is im-
mersed in a chloride salt solution and is then dried to remove
the water. The adsorption characteristics of silica gel and chlo-
ride composite adsorbents could be modied by 1) changing
the silica gel pore structure, 2) changing the type of salt, and
3) changing the proportions of chloride and silica gel.
13
Daou,
et al.,
14
impregnated silica gel with calcium chloride, which
improved the COP by 25% and increased the SCP by 283%
compared to pure microporous silica gel.
Four types of porous media reported in the recent literature
were used to produce composite adsorbents with chlorides: ex-
panded graphite,
11,12,15
activated carbon,
16
and activated car-
bon ber as well as vermiculite.
17,18
Han, et al.,
19
measured
the effective thermal conductivity and gas permeability of a
composite adsorbent made from expanded graphite impreg-
nated with MnCl
2
using the consolidation method. The mea-
sured effective thermal conductivities ranged from 14.0 to 25.6
Wm
1
K
1
(8.1 to 14.8 Btu/hftF) and permeability ranged
from 8.110
15
to 2.510
13
m
2
(8.710
14
to 2.710
12
ft
2
).
Wang, et al.,
11
used the same method to produce the composite
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Sept ember 2011 ASHRAE Jour nal 17
adsorbent of expanded graphite and CaCl
2
. Effective thermal
conductivities of the expanded graphiteCaCl
2
consolidated
composite adsorbent are in the range of 7.05 to 9.2 Wm
1
K
1

(4.07 to 5.3 Btu/hftF). The obtained results indicated that the
thermal conductivity of the composite adsorbent has a strong
dependence on the bulk density, the mass fraction of expanded
graphite and the ammoniated state of CaCl
2
. Wang, et al.,
20

investigated the effective thermal conductivity of a compos-
ducing the desired refrigeration effect. This step is equivalent
to the evaporation in the vapor-compression cycle. The ba-
sic adsorption refrigeration cycle is an intermittent system
and the cooling output is not continuous. A minimum of two
adsorbers are required to obtain a continuous cooling effect
(when the rst adsorber is in the adsorption phase, the second
adsorber is in desorption phase). These adsorbers will sequen-
tially execute the adsorption-desorption process.
ite consolidated adsorbent of expanded
graphite and activated carbon, and test
results showed that its thermal conductiv-
ity could reach as high as 30 Wm
1
K
1

(17.3 Btu/hftF).
Adsorption Cycle Description
Basic Adsorption Cycle
A basic adsorption cycle consists of
four steps (Figure 1): heating and pres-
surization, desorption and condensa-
tion, cooling and depressurization, and
adsorption and evaporation. In the rst
step, the adsorber is heated by a heat
source at a temperature of T
H
. The pres-
sure of the adsorber increases from the
evaporating pressure up to the condens-
ing pressure while the adsorber temper-
ature increases. This step is equivalent
to the compression in the vapor-com-
pression cycle. In the second step, the
adsorber continues receiving heat and
its temperature keeps increasing, which
results in the desorption (or generation)
of refrigerant vapor from adsorbent in
the adsorber. This desorbed vapor is
liqueed in the condenser and the con-
densing heat is released to the rst heat
sink at a temperature of T
C
. This step
is equivalent to condensation in the
vapor-compression cycle.
At the beginning of the third step, the
adsorber is disconnected from the con-
denser. Then, it is cooled by heat trans-
fer uid at the second heat sink tempera-
ture of T
M
. The pressure of the adsorber
decreases from the condensing pressure
down to the evaporating pressure due
to the decrease in the adsorber tem-
perature. This step is equivalent to the
expansion in the vapor-compression
cycle. In the last step, the adsorber keeps
releasing heat while being connected to
the evaporator. The adsorber tempera-
ture continues decreasing, which results
in the adsorption of refrigerant vapor
from the evaporator by adsorbent, pro-
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18 ASHRAE Jour nal ashr ae. or g Sept ember 2011
Advanced Adsorption Cycle
Since the efciency of the basic adsorption refrigeration
cycle is low, and the cooling output is not continuous, many
advanced adsorption refrigeration cycles (such as the heat re-
covery cycle, mass recovery cycle, thermal wave cycle, forced
convective thermal wave cycle, etc.) have been developed to
improve efciency and practicability.
The heat recovery cycle is an advanced adsorption cycle used
in a system with two or more adsorbers. Figure 2 shows the
heat recovery system on the P-T diagram. After the adsorption
phase and desorption phase are nished in the adsorbers, the
heat from the hot adsorber is transferred to the cold adsorber
by circulating heat transfer uid between them in a closed loop.
The experimental results show that the COP of the system will
increase by up to 25% with the heat recovery cycle.
21,22
The mass recovery cycle uses refrigerant mass recovery
between two adsorbers to effectively increase cooling output
and COP of the system. Figure 3 presents a diagram of the
mass recovery cycle of an adsorption system. In the end of
the desorptionadsorption phase, the high-pressure adsorber
Figure 1: Basic adsorption refrigeration system. A. Heating and pressurization. B. Desorption and condensation. C. Cooling and
depressurization. D. Adsorption and evaporation.
29
1/T
P
c
P
E
P
c
P
E
1/T
Adsorption and
Evaporation
T
H
T
M
T
C
T
E
T
H
T
M
T
C
T
E
Throttling
Valve
Throttling
Valve
Adsorber Condenser
Absorbed Vapor
Evaporator
Absorbed Vapor
Evaporator
Adsorber Condenser
Q
H
Q
M
Q
E
Q
C
Q
H
Q
M
Q
E
Q
C
1/T
Ln(P)
P
c
P
E
Ln(P)
P
c
P
E
Heating and Pressurization
1/T
T
H
Desorption and
Condensation
T
M
T
C
T
E
T
H
T
M
T
C
T
E
Desorber Condenser
Throttling
Valve
Throttling
Valve
Desorber Condenser
Desorbed
Vapor
Desorbed
Vapor
Q
H
Q
M
Q
E
Q
C
Q
H
Q
M
Q
E
Q
C
B
C D
A
Ln(P)
Ln(P)
Cooling and
Depressurization
20 ASHRAE Jour nal ashr ae. or g Sept ember 2011
is connected to the low-pressure adsorber in a closed loop. The
refrigerant in the high-pressure adsorber will be re-adsorbed
by the adsorbent in the low-pressure adsorber due to the pres-
sure difference between the two adsorbers. In a mass recov-
ery process, the adsorption quantity of adsorbent is increased,
which causes the cooling capacity and COP to increase. The
experimental results showed the mass recovery cycle may help
obtain a COP increase of more than 10%.
21
The concept of thermal wave cycle, proposed by Shelton, et
al.,
23,24
is shown in Figure 4.
25
The heat transfer uid circu-
lates through four components: (1) Adsorber 1 in adsorption
phase, (2) the heat source; (3) Adsorber 2 in desorption phase,
and (4) heat sink. The adsorption heat released from Adsorber
1 is recovered by the heat transfer uid and transferred to Ad-
sorber 2, and only limited thermal energy is required from the
heat source since about 65% of the total energy received by
each adsorber can be internally recovered.
26
Experimental re-
sults showed the COP of a two-bed adsorption air conditioner
(zeolitewater) with thermal wave cycle was approximately
1.0 in cooling season.
27
Critoph
28
invented and theoretically
investigated the convection thermal wave cycle, which uses re-
frigerant as a heat transfer medium for internal heat recovery.
The simulation results predicted a COP of 0.95 for this system
when the evaporating temperature and condensing tempera-
ture are 0C and 42C (32F and 107.6F), respectively.
Performance of Adsorption Systems
Table 1
25
summarizes the performance of some typical ad-
sorption refrigeration systems that were manufactured and
tested in the last 20 years for use of waste heat and solar en-
ergy. These results were obtained under various operating con-
ditions; hence they should not be compared to one another.
However, they could be used as a reference to what can be
expected from adsorption refrigeration systems.
Summary
Compared to the vapor compression refrigeration systems,
adsorption systems have the following advantages: 1) they can
be driven by waste heat and low-grade heat such as solar en-
ergy; 2) they use environmentally friendly uids such as water
or ammonia as refrigerants. The major drawbacks of adsorption
systems are their low energy efciency (low COP and SCP).
Silica gelwater and activated carbonmethanol are suitable
working pairs for low temperature waste heat and solar energy
due to their relatively low desorption temperatures. Zeolite
water, activated carbonammonia, and metal chloridesam-
monia, as well as composite adsorbentsammonia can be used
in adsorption systems driven by high temperature waste heat.
Since the typical pressures in silica gelwater, zeolitewater,
and activated carbonmethanol systems are subatmospheric, a
hermetically sealed outer vessel is essential to maintain good
machine performance.
The basic adsorption refrigeration cycle is an intermittent
system and the cooling output is not continuous. A minimum
of two adsorbers are required to obtain a continuous cooling
effect (when the rst adsorber is in the adsorption phase, the
second adsorber is in the desorption phase). Several advanced
adsorption cycles (such as heat recovery cycle, mass recov-
Heating and Pressurization
Cold Adsorber 1/T
Hot Adsorber
1/T
Cooling and
Depressurization
Ln(P)
P
c
P
E
Ln(P)
P
c
P
E
Figure 2: Pressure-temperature diagram of heat recovery cycle.
High Pressure
Desorber
Low Pressure
Adsorber
Open
Refrigerant
Vapor
T
H
T
M
Figure 3: Diagram of mass recovery cycle.
Reversible Pump
T
e
m
p
e
r
a
t
u
r
e
A
Adsorber 1
Adsorber 2
Condenser
Evaporator
Energy Supplied by
The Heat Source
Heat
Source
Energy Released
To the Adsorber
Heat Sink
B C
D
Figure 4: Thermal wave adsorption cycle.
A
22 ASHRAE Jour nal ashr ae. or g Sept ember 2011
ery cycle, and thermal wave adsorption cycle) have been de-
veloped to improve efciency and practicality. Although the
advanced cycles can improve the adsorption system perfor-
mance, the complexity and the initial costs of the system also
increase. In these advanced cycles, the mass recovery cycle
has the potential to be a cost-effective way to boost the COP
and SCP of the adsorption systems.
25

Although the adsorption refrigeration systems have several
advantages over vapor compression refrigeration systems,
there are several challenges (such as improvement in systems
energy efciency and/or reduction of manufacturing costs, ad-
vanced cycles with less thermal coupling irreversibilities, and
formulation of new composite adsorbents with enhanced ad-
sorption capacity and improved heat and mass transfer prop-
erties) to overcome before they can be considered as possible
alternatives to replace the present vapor compression systems,
especially in regions with abundant waste heat or solar en-
ergy resources available. These challenges also point to new
research and development opportunities and leave opportunity
for considerable creativity.
Application Heat Source Temperature or Insolation Working Pair COP SCP or Ice Production Year
Ice Making
20 MJ m
2
day
1
AC Methanol 0.12 6 kg day
1
m
2
1986
105C AC NH
3
0.10 35 W kg
1
1997
18.1 to 19.2 MJ m
2
day
1
AC Methanol 0.12 to 0.14 5.0 to 6.0 kg day
1
m
2
2002
17 to 20 MJ m
2
day
1
AC Methanol 0.13 to 0.15 6.0 to 7.0 kg day
1
m
2
2004
15.4 MJ m
2
day
1
Silica Gel Water 0.16
a
2.05 MJ m
2
day
1
2004
20 MJ m
2
day
1
AC Blackened Steel Methanol 0.16 9.4 kg day
1
m
2 b
2004
<120C AC Methanol 0.18 27 W kg
1
2005
115C AC+CaCl
2
NH
3
0.39 770 W kg
1 c
2006
Chilled Water
55C Silica Gel Water 0.36 3.2 kW Unit
1
2001
100C AC Methanol 0.40 73.1 W kg
1
2001
65C Silica Gel Water 0.28 12.0 kW Unit
1
2004
75 to 95C Silica Gel Water 0.35 to 0.60 15.0 kW m
3
2004
80 to 95C Silica Gel Water 0.30 to 0.60 20 W kg
1 d
2004
80C Silica Gel Water 0.33 to 0.50 91.7 to 171.8 W kg
1
2005
Air Conditioning
232C AC NH
3
0.42 to 1.19 NI
e
1996
204C Zeolite Water 0.60 to 1.60 36 to 144 W kg
1
1988
230C Zeolite Water 0.41 97 W kg
1
1999
310C Zeolite Water 0.38 25.7 W kg
1
2000
100C AC NH
3
0.20 600 W kg
1
2003
230 to 300C Zeolite Water 0.20 to 0.21 21.4 to 30 W kg
1
2004
a
Average value obtained during 30 days of continuous operation;
b
Based on the area of the adsorber, which was different from the area of the reector panels;
c
The SCP is based on the mass of CaCl
2
inside one adsorbent bed and only for the duration of the adsorption phase;
d
At generation temperature of 95C;
e
Not informed.
Table 1: Performance of adsorption refrigeration systems for different applications.
25
Acknowledgments
The authors would like to acknowledge Dr. Liwei Wang
and Dr. Ruzhu Wang of Shanghai J iao Tong University,
Shanghai, and Dr. Abdolreza Zaltash, Dr. Moonis R. Ally
and Erica Atkin of Oak Ridge National Laboratory, Oak
Ridge, Tenn., for their support, enlightening discussions and
insights.
Note
Figure 4 and Table 1 are reprinted from Progress in Energy
and Combustion Science, 32(4), R.Z. Wang, R.G. Oliveira,
Adsorption refrigerationAn efcient way to make good
use of waste heat and solar energy, pp. 424 458 with per-
mission from Elsevier.
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