International Journal of Air-Conditioning and Refrigeration

Vol. 20, No. 1 (2012) 1130001 (16 pages)

World Scientic Publishing Company
DOI: 10.1142/S2010132511300011

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ENHANCEMENT OF HEAT AND MASS TRANSFER

IN SOLID GAS SORPTION SYSTEMS
J. K. KIPLAGAT*, R. Z. WANG*,, T. X. LI* and R. G. OLIVEIRA
*Institute of Refrigeration and Cryogenics
Shanghai Jiao Tong University, 800 Dongchuan Road
Shanghai 200240, P. R. China

Federal University of Santa Catarina

Campus Ararangu

a , 88900-000, Brazil
rzwang@sjtu.edu.cn

Received 15 March 2011

Accepted 14 September 2011
Published 31 March 2012
Solid gas sorption systems driven by heat have gained much attention due to their energy conservation and environmental benets. These sorption machines can be driven by waste heat or
renewable energy source such as solar energy, and can utilize natural working uids with no GWP
and ODP, such as water, methanol, and ammonia. However, poor heat transfer process and slow
diusion rate of the refrigeration gas in the adsorber have been identied as the main drawbacks
limiting the cooling density performance, and consequently, commercialization of sorption machines. This paper provides a review of techniques that have been applied to enhance heat and
mass transfer in solid gas sorption systems. These techniques mainly include the use of materials
with high thermal conductivity, consolidation of adsorbents, and the use of specially designed
heat exchangers in the adsorbers. The eect of these methods on the coecient of performance
and the specic cooling power is also discussed.
Keywords: Adsorption refrigeration; solid
gas reaction; heat transfer; mass transfer; heat
exchangers.

1. Introduction
Sorption machines utilize a reversible physisorption
or chemisorption process to deliver useful cooling or
heating, for refrigeration or heat pump applications.
These solid sorption devices contain a porous solid
(the adsorbent) which has the ability to adsorb vapor
(the adsorbate or refrigerant) at ambient temperature and to desorb it when heated. The operation
principle of sorption system has been discussed
extensively in literature.1,2 The commonly utilized
working pairs are ammoniated salts (chlorides

in connection with ammonia), zeolites (with water),

activated carbon (with methanol or ammonia), and
metal hydrides (with hydrogen).3
5
Unlike the conventional compressor-based heat
or cold producing systems powered by electricity,
the use of sorption machines can help in energy
conservation and can have direct positive eects on
the environment. This is because sorption cycles can
be driven by heat rather than work; hence, they may
reduce CO2 emissions since they can make use of
renewable energy sources such as solar and biomass,
as well as waste heat. In addition, sorption devices

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J. K. Kiplagat et al.

can utilize natural working uids with no GWP and

ODP such as water, methanol and ammonia.1
In order to produce useful cooling or heating,
sorption system must undergo a thermodynamic
cycle where the adsorbent bed is heated during
desorption phase and cooled to the initial temperature during adsorption phase. Each complete cycle
results in addition and removal of a given amount
of heat into/from the adsorption bed as well as
adsorption and desorption of refrigerant gas. The
main drawbacks responsible for the low specic
cooling power and cooling power density, are slow
heat transfer process and poor diusion of the
refrigeration gas within the porous solid reactant.
These drawbacks lead to bulky and costly machines.
The slow heat transfer occurs due to high thermal
resistance along the heat ow path. There are two
main types of thermal resistances in solid gas
adsorption systems.1 The rst one occurs at the
interface between the metal and the adsorbent,
which mainly depends on the physical contact of
the adsorbent material and the wall of the reactor.
If the thermal contact between the metal surface
and the adsorbent materials is not good, a low
contact heat transfer coecient and a high-temperature gradient will occur at the interface.
The absence of gas convection at the interface
also contributes to low heat transfer coecient,
which in the case of low evaporating pressure
working uids (such as water or methanol), may
become extremely low. The second resistance to
heat transfer occurs inside the adsorption bed due to
poor thermal conductivity of adsorbents. Granular
adsorbents have low eective thermal conductivity
because of the high porosity and discontinuity of the
solid material. For example, the eective heat conductivity of zeolite is about 0:1 W=m  K, for ammonia salts or active carbon is about 0.3
0:5 W=m  K,
whereas for metal hydrides is about 1 W/m  K.6
Poor mass transfer of the refrigerant gas occurs
mainly due to low permeability in the reaction bed,
which may become more critical in machines utilizing low evaporating pressure refrigerants. The rate
of diusion of the refrigerant gas into and from the
adsorbent inuences the duration needed for adsorption and desorption; and hence the cycle time. It is
therefore necessary that an acceptable level of gas
permeability inside the adsorbent bed is attained for
high system performance.
When evaluating the performance of adsorption
systems, three performance indicators are usually

considered, viz., the coecient of performance

(COP), the specic cooling power (SCP), and the
cooling power density (CPD). The COP shows how
ecient (according to the rst law of thermodynamics) the adsorption machine is in transforming
the heat input into useful cooling or heating output.
The SCP indicates how much cooling power can be
expected from a certain mass of adsorbent. Low
SCP machines need a large amount of adsorbent to
achieve a certain cooling power, which increases the
cost of the machine per kW of cooling output. The
CPD is the ratio between the cooling power output
and the volume of the adsorbent. Low CPD machines are bulky, which increases the cost of the
adsorber, and limits the installation places.
Poor thermal conductivity of an adsorption bed
causes slow heat addition/removal rates, resulting
in slower reaction rates, long cycle times, low SCP,
and CPD. For instance, in the exothermic reaction
between a sorbent and a gas, the heat produced
must be dissipated so as to maintain a low temperature in the sorbent, which is necessary for higher
reaction rate. If the reactive medium is a poor heat
conductor, it is not able to quickly release the heat
produced, and the temperature of the sorbent will
rise near to equilibrium condition, which can result
to an almost zero reaction rate.
Considerable eorts have been done by dierent
research groups to enhance the heat transfer in
sorption machines with the aim of improving specic
power performance to a level where they can compete eectively with conventional electricity powered systems. In the following sections, we review
various techniques that have been developed and
applied to enhance the heat transfer and mass
transfer in solid
gas reactor beds, and discuss their
eects of the performance on sorption machines.

2. Techniques to Enhance Heat and

Mass Transfer within the Adsorbent
2.1. Use of materials with high
conductivity or high porosity
In the absence of any technique for heat transfer
enhancement, granular adsorbent beds exhibit low
thermal conductivities and wall heat transfer coefcients. Furthermore, some of the adsorbents, such
as metal chlorides, experience poor mass transfer
due to agglomeration of the sorbents after a few
adsorption cycles. Thus, to achieve higher SCP,

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Enhancement of Heat and Mass Transfer in Solid Gas Sorption Systems

alternatives to enhance heat transfer without depleting mass transfer are necessary; and in this section, we
present various materials that have been suggested
for use as additives to enhance heat transfer, mass
transfer or both, in sorption beds.

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2.1.1. Metal additives and metal inserts

Eltom and Sayigh7 added copper powder into activated carbon and lump wood charcoal, and
measured the conductivity at temperatures ranging
from 30  C to 95  C, in the absence of adsorbate. The
improvement in the conductivity for the two
sorbents varied from 2%
25%, according to the
sorbent temperature. Higher thermal conductivity
was observed at low sorbent temperature, and
sharply decreased at relatively high temperatures.
Demir et al.8 tested the eect of various metal
additives on the heat transfer rate of unconsolidated
silica gel. The silica gel granules were mixed with
four dierent metal pieces: (i) aluminum, (ii) copper,
(iii) brass, and (iv) stainless steel (Fig. 1). Results
showed that the addition of metal pieces in the
granular adsorbent increased considerably the heat
transfer rate in the adsorbent and led to a reduction
in the cycle time and an increase in the SCP. The
bed with 15% loading of aluminum particles
1.0
2.8 mm wide had the highest eective thermal
conductivity and diusivity, which were respectively

242% and 157% higher than those of the bed with

pure silica gel. The increment in conductivity was
inuenced by three parameters, which are as follows:
loading amount, shape of the metal pieces, and
size of the metal pieces. The authors emphasized
the need for proper selection of shape and size of the
metal additives in order to avoid an increase in the
mass transfer resistance, and optimization of
the weight fraction of silica-gel
Al mixture.
Wu et al. used copper nanopowder to enhance the
heat transfer performance of silica gel. Composite
bricks of an adsorbent consisting of silica gel with
copper nanopowders were prepared by the sol
gel
process and compressed at 2 MPa. A 20% increase in
the thermal conductivity was observed, when compared to pure silica gel without compression, and the
thermal conductivity also varied according to the
amount of copper nanopowder in the adsorbent.
The breakthrough curves showed an apparent
increase in the mass transfer resistance with the
metal additive, however, high water vapor uptakes
were reported which correlated well with the structure of silica gel. The results showed that the heat
and mass transfer properties were reproducible and
consistent, and the water vapor uptake, thermal
conductivity, and eective intra particle diusivity
values are suitable for adsorption refrigeration
systems.9

(a)

(b)

(c)

(d)

Fig. 1. Photographs of metal pieces used to enhance thermal conductivity of silica gel: (a) Copper, (b) aluminum, (c) stainless steel,
and (d) brass.8
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J. K. Kiplagat et al.

Khattab studied four approaches to improve the

thermal properties of the adsorbent bed of a solar
powered system as follows: (i) Black metallic meshes
on both faces of a glass adsorber and granular carbon inside; (ii) black metallic plates on both faces
of a glass adsorber and granular carbon inside;
(iii) granular carbon mixed with small pieces of
blackened steel; and (iv) granular carbon bonded
with small pieces of blackened steel. The glass
adsorber enhanced the eectiveness of solar energy
absorption by allowing the adsorbent to receive
solar energy on both sides. The bed with granular
carbon bonded with blackened steel achieved the
best results among the tested beds, and the machine
COP reached 0.16 with a daily ice production of
9.4 kg/m2 of adsorber when the insolation was about
20 MJ/m2 and the average outdoor temperature was
29  C.10

2.1.2. Expanded graphite additives

Expanded graphite can be used as an inert material
to provide a support matrix for reactive materials in
solid
gas reactors. Expanded graphite originates
from the exfoliation of graphite intercalation compounds submitted to a brutal thermal shock.11 The
result is the creation of worm-like or accordion-like
particles, which have very low apparent density, in
the range of 6
45 kg/m3, depending on the temperature and length of the thermal treatment.12 The
major elements in expanded graphite are C, S, and
O (Table 1).
Researchers in France are among the pioneers in
the use of expanded graphite to improve the kinetics
in solid
gas reactions.14 Various methods of mixing
expanded graphite with reactive adsorbents have
been developed, which included direct mixing and
consolidation, and impregnation of graphite matrix
with an aqueous solution of reactive salt.
Lin and Yuan15 mixed calcium chloride and
expanded graphite for use in chemical heat pump
with ammonia as the gas, and obtained a reduction
in synthesis and desorption time, from 10 h without
additives to 3 h with additive. The authors also
investigated the eect of two mixing methods
Table 1.
Elements
wt%

(direct mixing and mixing by salt solution), and

results showed no signicant eect of the mixing
method on the heat and mass transfer enhancement.

2.1.3. Activated carbon or carbon bers

Activated carbon is produced from a wide variety of
carbonaceous materials, which have been activated
by chemical or physical means to make them porous.
Hence, they have extremely high internal surface
area within its intricate network of pores. Total
surface area ranging from 450 to 1800 m2/g has been
estimated.16 Activated carbon typically comes in
three general types: Granular or natural grains,
pellets, and powders. Graphite bers have very high
axial thermal conductivities which vary with the ber
type and quality. Values as high as 500 W=m  K for
ex-pitch carbon P120, and 1100 W=m  K for K1100
type have been reported.17
Dellero and co-authors17 used carbon bers to
improve the performance of a metallic salt
ammonia
chemical heat pump. They compared the performance of the heat pump with dierent methods of
combining carbon bers with manganese chloride
salt, viz., simple mixing, impregnation, and intercalation. The results obtained by the later two
methods were much superior to those obtained by
simple mixing, in that they exhibited faster reaction
rates, complete reaction, and avoided the agglomeration phenomenon. However, some drawbacks of
the two methods were observed; for the impregnation
method, the salts appear to attach less well to the
bers after few reactions, and there is a risk of the salt
grains dropping to the bottom of the reactor. The
drawback of the intercalation method is the diculty
in controlling the quantity of salt used, and the length
of the preparation, which is longer than that by the
other methods.
Dellero and Touzain18 studied the eect of ber
disposition on the reaction kinetics (Fig. 2). They
compared bers 30 cm and 3 cm long impregnated
with MnCl2. Results showed that, in the case of
short bers, the reaction kinetics was faster than in
the long bers case. When using short bers the
reaction could be completed after 15 min, whereas

Chemical analysis of expanded graphite powders.13

Ca

Mn

Cr

Al

Cu

Ti

Si

Zn

Mg

Fe

74.2

2.82

0.16

0.55

0.003

0.56

0.001

0.026

0.13

1.82

0.084

0.15

0.5

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Remainder
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Enhancement of Heat and Mass Transfer in Solid Gas Sorption Systems

the chiller using this material exhibited a COP

of 0.54 and SCP ranging from 300 to 680 W/kg,
when driven by a low temperature heat source of
80  C
90  C.

2.2. Consolidated beds

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Fig. 2.

Fiber disposition in reactor.18

with long bers, the reaction took 60 min to be

completed. They attributed the dierence to the fact
that the short bers could stay in the radial direction, which was the same direction of heat transfer;
and thus, providing a heat ow path, unlike in the
case of the long bers, which tended to wind round
near the centre of the adsorber.

Consolidated adsorbent beds are obtained from the

powders of solid sorbents, which may be combined
by a binder or other materials with higher thermal
conductivity. Consolidation can produce continuous
solid adsorbent blocks with reduced void spaces,
which provides heat conduction path; therefore, can
lead to compact adsorbers with increased thermal
conductivity and improved surface heat transfer
coecient. However, consolidation should be used
with caution to avoid a situation where improvement in the heat transfer is achieved, at the expense
of intolerable reduction in the mass transfer.

2.2.1. Consolidated activated carbon

2.1.4. Other additives
Polyaniline belongs to a family of conductive polymers, and has electrical properties similar to those of
some metals. The advantages of its use as additive
include the simplicity to combine with the sorbent,
good stability, and high electric conductivity.19
Various researchers19,20 introduced polyaniline into
zeolite to enhance the conductivity of the sorbent
bed. The composite of polyaniline and adsorbent
was prepared by chemical oxidation and in situ
polymerization of aniline onto the surface of adsorbent particles. A thin thermal conducting layer on
the surface of adsorbent particles was grown. The
process of preparing the composite involved four
materials which were aniline, zeolite 13X, HCl, and
NH4 2 S2 O8 . The results showed that the thermal
conductivity of the zeolite
polyaniline composite
was four times higher than that of untreated zeolite.19 Hu et al.20 reported a two to three fold
increase in the eective thermal conductivity, and a
near constant adsorption performance for zeolite
coated with polyaniline.
Veselovskaya et al.21 used expanded vermiculite
as a porous matrix for the composite sorbent
(BaCl2/vermiculite) to prevent agglomeration of the
salt and improve mass transfer, due its macroporous
structure. The performance of this composite sorbent was tested in a lab-scale adsorption chiller with
ammonia as the refrigerant. Results showed that

Consolidation of carbons has been used to produce

adsorption beds with high packing density and
improved conductivity. Mauran et al.22 reported a
value of bed thermal conductivity as high as
40 W=m  K, which is considerably larger than the
best values that have been obtained with unconsolidated beds. Tamainot-Telto and Critoph23 investigated activated carbon mixed with a polymeric
binder, compressed in a die and red to produce
monolith of a desired shape, with a density of
713 kg/m3 and conductivity of 0:33 W=m  K. The
system with the consolidated compound had a SCP
90% higher than the bed with granular carbon.
Cacciola et al.24 prepared carbon bricks using polytetrauoroethylene (PTFE) as a binder and tested
the conductivity and adsorption performance on
methanol. The adsorption capacity of the compound
was 40% higher, whereas its thermal conductivity
ranged between 0.13 and 0:20 W=m  K. The authors
observed that the low thermal conductivity of
PTFE (about 0.2 W=m  K) lowered the thermal
conductivity of solid grain from 1.06 W=m  K to
0.45 W=m  K, and hence a binder with a higher
thermal conductivity should be sought.
To reduce mass transfer resistance in consolidated beds, arteries or mass transfer channels
may be added within the bed. Wang et al.25 used
solidied activated carbon with mass ow channels
in an adsorption bed of a prototype ice maker using

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J. K. Kiplagat et al.

of
10  C, due to reduced mass transfer of the

refrigerant at low saturation pressure.28

2.2.3. Consolidated activated carbon salt

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Wang et al.29 mixed CaCl2 with activated carbon

and obtained 35% improvement in the volume
cooling density, in comparison to unconsolidated
adsorbent. Furthermore, the use of activated carbon
avoided salt agglomeration, and maintained a constant adsorption capacity. Lu and coworkers30 also
used activated carbon to enhance heat and mass
transfer of CaCl2 adsorbent (mass ratio 1:4) for use
in an adsorption ice maker, and the machine
achieved a SCP ranging from 111 to 161 W/kg.

2.2.4. Consolidated expanded graphite salt

Fig. 3.

Solidied activated carbon bed with gas channels.25

methanol as refrigerant (Fig. 3). The maximum

cooling power of the prototype was 2 kW, which
correspond to a specic cooling power of 17 W/kg.

2.2.2. Consolidated activated carbon with

expanded graphite
Biloe et al.26 evaluated the performance of consolidated activated carbon and expanded graphite
composite for natural gas storage, and found that
the thermal conductivity was 30 times higher than
that of activated carbon packed bed. The addition
of graphite reduced the charge time of methane by a
factor of 10.
Py et al.27 prepared in situ composites of activated carbon and expanded natural graphite without any binder. The material had an adsorption
capacity up to 80 wt%, and presented high thermal
conductivities, which ranged from 1 to 32 W=m  K,
depending on the mass ratio between expanded
graphite and carbon. Recently, Wang et al. measured
the thermal conductivity, permeability, and the
adsorption rate of consolidated activated carbon and
expanded natural graphite composites. The use of
expanded graphite enhanced both the thermal conductivity and permeability of the composite, and the
highest values of each obtained were 2.47 W=m  K and
4:378  10
12 m 2 , respectively. However, the authors
reported lower performance of the consolidated
composite adsorbent at evaporation temperature

Mauran et al.31 patented a process of manufacturing

consolidated blocks impregnated with metallic salts.
The common preparation procedure incorporates an
aqueous solution of inorganic salt into expanded
graphite matrices, followed by drying and calcinations to deposit the salt inside the pores of expanded
graphite. Han et al.17 studied the thermal and
physical properties of expanded graphite matrix
with bulk densities ranging from 100 to 400 kg/m3,
which were fabricated by pressing expanded graphite
powders. The gas permeability of porous graphite
matrices was in the range of 10
12 to 10
15 m 2 , and
the thermal conductivity values in the axial and
radial directions were between 4.1 and 20 W=m  K,
and between 4.6 and 42.3 W=m  K, respectively.
Han et al.32 measured the eective thermal
conductivities of expanded graphite
CaCl2  nNH3
(n 8; 4; 2), MnCl2  nNH3 (n 6; 2), and BaCl2 
8NH3 . The eective thermal conductivities of the
graphite
metallic salt complexes were in the range
of 10
49 W=m  K, which are considerably higher
than the values of 0.1
0.5 W=m  K, normally found
in powder beds. The results showed that the eective thermal conductivity of a graphite
metallic
salt complex has a strong dependency on the bulk
density, the weight fraction of graphite, and the
ammoniated state of salt.
Wang et al.33 measured the eective thermal conductivity of consolidated composite adsorbent of CaCl2
and expanded graphite at xed pressure and
temperature under an atmosphere of ammonia. The
eective thermal conductivity ranged from 7.05

9.2 W=m  K depending on the mass fraction of
expanded graphite, bulk density, and the ammoniated

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Enhancement of Heat and Mass Transfer in Solid Gas Sorption Systems

state of CaCl2 . The thermal conductivity of the consolidated bed was about 30 times that of an unconsolidated bed. The CPD and the SCP of the consolidated
adsorbent was 52% and 353% higher than that of pure
CaCl2 powder, respectively, under the working conditions for ice making.34
In the work conducted by Fujioka et al.,35 the
authors showed that an uncompressed compound of
CaCl2 and expanded graphite in the proportion 15:1
had a thermal conductivity 60% higher than that of
powder CaCl2 . However, the same compound when
compressed to reduce the overall void fraction to
about 0.6 reached a thermal conductivity of about
1 W=m  K, which was 10 times that of powdered
CaCl2 . The same study also showed that the impregnation of CaCl2 in activated carbon bers followed by compression did not change considerably
the thermal conductivity when compared to that of
the powdered CaCl2 .
Other experimental results also showed that the
use of expanded graphite improves the mass transfer
performance and can control the phenomena of
swelling and agglomeration in reactive salts.12,36
38
In the experiments conducted by Oliveira and
Wang,12 the pressure drop across the bed made of
35% of expanded graphite and 65% of CaCl2 was
negligible, but the heat transfer although improved
when compared to the CaCl2 , still was the limiting
factor for the reaction rate. Further studies from the
same research group showed that the reaction rate
was improved when the mass fraction of expanded
graphite increases up to 50%.37
Li et al.39 produced a consolidated composite
sorbent made from manganese chloride and expanded graphite for sorption deep-freezing processes.
Experimental results showed that the SCP of the
machine varied from 200 W/kg to 700 W/kg when
the evaporation temperature ranged from
35  C to
0  C. The COP of the machine employing a basic
sorption thermodynamic cycle reached 0.34 at the
generation temperature of 180  C, the heat sink
temperature of 25  C, and the evaporation temperature of
30  C.

2.2.5. Consolidated expanded graphite

silica gel
Eun et al.40,41 reported the quantity of water adsorbed, thermal conductivity, and gas permeability for
consolidated composites of expanded graphite and
silica gel prepared with various compositions and

molding pressure. Expanded graphite in the composite blocks had no eects on the equilibrium adsorption amount of water on silica gel and increased the
rate of adsorption. The composite blocks of 20% to
30% of graphite mass fraction, and under the molding
pressure in the range of 4 to 40 MPa showed
permeability of 3  10
12 to 40  10
12 m 2 . The
permeability increased with graphite fraction at constant molding pressure. Thermal conductivity of the
composite blocks ranged between 10
20 W=m  K,
depending on the graphite bulk density in the block.
These values are much higher than the value of
0.17 W=m  K usually found for silica-gel packed bed.
The highest SCP obtained with the composites was
about 36 W/kg in a 20 min cycle, whereas that
obtained from silica gel bed was about 21 W/kg in a
60 min cycle.

2.2.6. Consolidated compounds

with zeolite
Poyelle et al.42 used a consolidated compound of
expanded graphite and zeolite in a prototype air
conditioner, and achieved an SCP four times higher
than that obtained using zeolite pellets. Guilleminot
et al.43 studied a consolidated compound made from
a mixture of zeolite and metallic foam (copper foam
and nickel foam). The consolidated adsorbent was
produced by rst suspending zeolite powder in a
silico
aluminate gel to obtain a paste, which was
lled in a metallic mesh. The resulting compound
was compressed at some tens of MPa and heated at
1000  C for 3 h. The composite with copper foam had
a thermal conductivity of 8 W=m  K, which was 22
times higher than that of the consolidated zeolite.
The wall heat transfer coecient also increased
signicantly to a value of 180 W/m 2  K. The thermal conductivity of the compound manufactured
with nickel foam was only 1.7 W=m  K, which
indicates that the metallic material property plays
an important role in the extent of the heat transfer
enhancement. Although good thermal conductivity
values were obtained, compression of the materials
at high temperature and pressure resulted in low
porosity in the zeolite, which aected the mass
transfer. Lang et al.44 enhanced the heat and mass
transfer in compact zeolite layers by using a metallic
matrix with a honeycomb-like structures, and a pore
forming material. The hexagonal aluminum honeycomb structure was clamped to the inside of a
cylinder and lled with zeolite to enhance heat

1130001-7

J. K. Kiplagat et al.

transfer. An amount of 5 wt% of melamine and 5 wt%

of tartaric acid were used to increase the macropore
fraction of the compacted zeolite layers. The results
showed that this approach improved the adsorption
rate by up to 110%.

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2.3. Sinterized metal foam beds

Heat exchangers based on open cell metal forms have
high surface area to metal mass ratio, which can
result in high adsorbent to metal mass ratio.
Bonaccorsi et al.45 developed a process to obtain
metal foams for thermal applications. The authors
proposed a heat exchanger made of copper metal
foam coated pipes on which zeolite 4A was deposited
by a direct hydrothermal synthesis process. The
copper foam obtained had a nal density of 0.5 g/cm3
with an open porosity close to 70%, and a maximum
pore size of 0.5 mm (Fig. 4). In another work of
Bonaccorsi et al.,46 the authors coated zeolite 4A on
copper foams, and zeolite Y on aluminum foams. The
compounds were characterized by SEM, XRD analysis, and the water equilibrium sorption curves were
measured by a thermogravimetric method. In both of
the cases, the zeolite layer had good bond properties
to the metal substrate, and up to 15%
17% (by
weight) of zeolite was deposited by a double synthesis process. The authors reported that the
adsorption capacity of the zeolite/foam composites
were comparable with those of commercial zeolites.

3. Reactors with Enhanced Heat

and Mass Transfer
3.1. Specially designed heat exchangers
Specially designed heat exchangers with nonconventional geometry and shape have been used in
adsorbers of solid gas systems to enhance heat

(a)

transfer. These heat exchangers were designed with

extended surfaces to increase the heat transfer areas,
and granular adsorbents were distributed uniformly
into the heat exchanger.
Plate type heat exchanger (Fig. 5) with ns has
been applied in an adsorption bed of a solar ice maker
using activated carbon and methanol as the working
pair.47,48 The use of ns and thin wall in the adsorbent improved the performance of the ice maker,
when compared to a previous prototype. Experimental results showed that 4 to 5 kg of ice could be
produced by the ice maker with an area of 0.75 m2,
when the insolation ranged between 14 and 16 MJ/m2,
whereas 7 to 10 kg of ice could be produced when
the insolation ranged between 28 and 30 MJ/m2.
Tchernev and Emerson49 utilized serpentine atpipe heat exchanger (Fig. 6) which winds its way
between consolidated sorbent bricks in a prototype
of a regenerative heat pump. The at pipes were
fabricated from two thin sheets of metal foil (0.1 mm
thick) that were laid over one another and joined at
the edges. The use of consolidated bricks showed
higher thermal conductivity than a poured bed of
spherical adsorbent pellets, although the low porosity of the bricks degraded the performance,
the prototype yielded a high COP of 1.1 with 70%
regeneration.
Wang et al.50 developed a spiral plate heat
exchanger and applied it in a regenerative adsorption
refrigerator using activated carbon methanol pair
(Fig. 7). Improved heat transfer in the adsorbers
allowed cycle time of 40 min. The distinct advantages
of this type of heat exchanger include the compact
size, the small temperature dierence between the
sorbent and the heat transfer uid, and a more uniform temperature distribution within the bed.
Wang et al. applied a plate-nned tubes adsorber
in an activated carbon
methanol adsorption air

(b)

(c)

Fig. 4. SEM images of copper foam (a) without adsorbent (X 35), (b) without adsorbent (X 400), and (c) after two depositions with
zeolite 4A (X500).45
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Fig. 5.

Plate heat exchanger type adsorber with ns.47

Fig. 7. Spiral plate type adsorber: 1. Spiral plate, 2. vapor

outlet, 3. solid adsorbent, 4. uid ow passage, 5. thermal uid
outlet, 6. thermal uid inlet, and 7. support rod.50

Fig. 6. Serpentine at pipe heat exchanger: 1. Fluid ow

channel. 2. Embedded adsorbent.49

conditioner. Tubes with a diameter of 9.5 mm were

used for heat transfer from the thermal uid to the
adsorption bed, and aluminum plates were attached
outside the tubes to increase the heat transfer area.
The adsorbent bed with the heat exchanger tubes
was packed inside a metallic mesh, and the void
space between the mesh and the shell was used as a
gas ow channels to enhance the mass transfer
(Fig. 8). This heat exchanger exhibited a low thermal capacity associated to the metallic parts. The
adsorber heat capacity ratio (ratio of adsorber material to adsorbent) was 1.36, whereas the thermal
uid heat capacity ratio (thermal uid to adsorber)
was 1.5 for water and 0.53 for oil.51
Kanamori et al.52 proposed a disk-module-type
adsorber with 1.35 mm consolidated carbon adsorbent made of activated carbon with carbon ber. It
was found that the cycle period was about 10 times

Fig. 8.

Plate-nned tubes absorber.51

shorter than that of the packed-bed-type adsorber of

activated carbon without carbon ber.
Linder et al.53 presented experimental analysis of
a metal hydride sorption system using a reaction bed
with a capillary tube bundle heat exchanger (Fig. 9).

Fig. 9. Capillary tube bundle reaction bed of a metal hydride

sorption system (length: 135 mm, diameter (max.): 65 mm).53

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J. K. Kiplagat et al.

It consisted of 372 small tubes with an inner diameter of 1.4 mm made of stainless steel. The heat
carrier owed through the tubes that were surrounded by the metal powder. Due to the high heat
and mass transfer rates within the adsorber, cycle
time around 200 s were realized, and leading to
specic cooling power up to 780 W/kg depending on
the temperature boundary conditions.

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3.2. Coated heat exchangers and other

methods to decrease contact
resistance at the reactor
adsorbent
interface
Another method used to increase the wall heat transfer
coecient is the adhesion of the adsorbent on the wall
of the heat exchanger tube or plate. Various coating
methods leading to uniform surface have been applied.
They include slip coating, spray coating, curtain
coating, coil coating, and electrically assisted coating.54 Pretreatment of the metal surface before coating
with adsorbent is necessary in order to improve
the wetting of the metal surface by synthesis mixture,
and to promote physical and chemical interactions
between growing crystals and metal surface.55
Dunne56 proposed carousel-type heat exchanger consisting of tubes coated with zeolite monolayer crystal
(about 5 mm thick) for air conditioning or with wasteheat recovery systems. Good contact between the
heat transfer uid and the adsorbent was achieved
and improved cooling performance ranging from
1400
1800 W/kg was reported.
Restuccia et al.57 used a thin adsorbent coating of
zeolite around a metal tube (Fig. 10). The preparation process involved several steps. Initially, an
aqueous solution of zeolite powder and an inorganic
binder (alumina gel precipitated in situ) was homogenized. Afterwards, the slurry was layered on the
metal support, properly pretreated, to obtain a
homogenous coating of desired thickness. A nal
thermal treatment in air allowed the stabilization of
the adsorbent. This technique of coating can be
applied to dierent types of heat exchangers (e.g.,
tube and shell). The authors reported a slight
increase of the adsorbent thermal conductivity and
a large increase in the metal
adsorbent heat
transfer coecient, due to the metal/adsorbent adhesion. The improvement in the global heat transfer
coecient resulted in a system with higher specic
cooling power. Calculated results showed that the
bed with coated adsorber could have a specic

Fig. 10. Finned tubes heat exchanger coated with zeolite.57

power 20 times higher than that of the bed with

sorbent grains.
Further research of this same team58 tested experimentally a lab-scale adsorption chiller, in which
the adsorber was a shell and tube heat exchanger,
with nned tubes coated with a zeolite layer (Fig. 11).
The machine achieved a specic power between 30
and 60 W/kg of adsorbent (binder included), operating under a cycle 15
20 min cycle. A machine using
the same type of zeolite, but in the form of pellets had
to operate under a cycle 60 to 120 min longer, and
delivered a specic cooling power of about 10 W/kg.
No major improvements in the COP were observed,
although the COP obtained with the coated adsorbed
was about 0.02 higher.
Tatlier and Erdem-Senatalar59 studied the eect
of zeolite coating thickness and wall thickness of a
stainless steel heat exchanger on the performance of
an adsorption heat pump. They showed that there
exists an optimum zeolite layer thickness that

Fig. 11. Photograph of the metal-bound zeolite layer.58

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Enhancement of Heat and Mass Transfer in Solid Gas Sorption Systems

maximizes the output heating power of an adsorption

heat pump. Moreover, the authors observed a general
trend whereby very high power and quite low cycle
COP values are obtained when zeolite coatings are
synthesized on metal heat exchanger. In another study
by the latter research group,60 the authors proposed a
scheme to decrease the temperature and concentration
gradient of a solar adsorption heat pump. The scheme
included the use of zeolite 4A synthesized on stainless
steel wire gauzes, which were placed vertically in the
collector, to form a rm contact with the absorber
plate. The authors estimated that a zeolite 4A coating
thickness value of 50
100
m was sucient to remove
the adverse eects originating from the metal mass in
the collector.
Maier-Laxhuber and Engelhardt61 described an
adsorbent bed coating process for use on metallic
surface of lamella heat exchangers. The method used
a high temperature adhesive and enabled good
adherence of the adsorbent (preferably a zeolite) to
the heat exchanger during very rapid temperature
increase and decrease. Chung et al.62 developed a
consolidated copper nanopowder/silica gel layer and
coated directly onto the surface of a metal heat
exchanger in the adsorption cooling system. The
thermal conductivity of the silica gel was improved
by the addition of copper nanopowder and a binder,
and was further improved by compression of the
consolidated copper nanopowder/silica gel layer.
The German company SorTech AG developed and
patented two innovative techniques of pasting adsorbent on the heat exchanger surface. The rst technique
enabled silica gel to be pasted directly on the surface of
the adsorber heat exchanger with the aid of epoxy
resin (Fig. 12(a)).63 Based on this technology, SorTech
AG was able to manufacture a compact adsorption
chiller with a nominal cooling capacity of 5.5 kW for
use in solar air-conditioning in private homes and
small oces. The second technique was based on a
direct crystallization of zeolite on the surface of the
heat exchanger (Fig. 12(b)). Compared to the epoxy
resin coating, the direct crystallization technology has
the following advantages:
.
.

High mechanical stability of the coated layer due to

strong binding forces at the zeolitemetal interface.
Enhanced adsorption kinetics, because of good heat
and mass transport caused by the very compact
layers containing only active material.
Reduction of material synthesis and coating to a
one-step process.

(a)

(b)
Fig. 12. (a) Photo of a silica gel coated tube and n adsorber
heat exchanger. (b) REM picture of the cross-section of an
aluminum n coated with zeolite by direct crystallization. The
overall thickness of the n is about 500 microns.63

Zhu and Wang64 investigated the eect on the

interface contact resistance caused by exerting
pressure and using high thermal conductive (HTC)
adhesive. The eect of pressure was determined by
use of dierent weights. The HTC adhesive was
made from epoxy, butyl gum, ethylated resin, and
sinterized copper powder, and it was spread at the
interface between the adsorber and the adsorbent.
Experimental results showed that the contact resistance decreased by 86% when the pressure
applied increased from 0 kPa to 50 kPa. However, to
avoid problems caused by high mass transfer resistance, the applied pressure should be optimized.
The spreading of the HTC adhesive over the interface between the adsorbent granule and the adsorber reduced the contact resistances by 40% and by
30% at the interface between the adsorbent block
and the adsorber. These experimental results show
that exerting certain amount of pressure or spreading adhesive on the interface can reduce the contact
resistance signicantly.

3.3. Heat pipes

When thermal resistance within adsorbent
reactor
is small, the thermal resistance between the heat
transfer uid and the reactor wall may become the

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J. K. Kiplagat et al.

limiting factor. Meunier1 suggested the application

of heat pipe technology in the adsorber to reduce the
thermal resistance in the adsorber, because of the
high heat transfer coecient that could be obtained
during the evaporation and condensation of the heat
transfer uid in the heat pipe. Heat pipes can
transfer a considerable amount of heat using a small
area because the heat transfer coecient in the
evaporator and condenser zones of these devices
ranges from 10 3
10 5 W=m 2  K, whereas the thermal resistance usually range from 0.01
0.03 K/W.65
Vasiliev66 proposed a multi-channel pulsating
heat pipe for adsorption systems (Fig. 13), whereby
propane was used as the heat transfer uid. Wang
et al.67 applied a split heat pipe type in an adsorber
containing a compound adsorbent for an adsorption
ice maker (Fig. 14). During desorption phase, the
lower part of the split heat pipe, which was connected to the heating boiler, served as evaporator,
and the adsorber served as condenser. During cooling phase, the adsorber served as evaporator for the
upper part of the split heat pipe.

4. Eects on the COP, Specic Cooling

Power, and Cooling Power Density
4.1. Use of materials with high
thermal conductivity
Materials with high thermal conductivity that have
been used as additives to enhance thermal conductivity

Fig. 14. Adsorption bed with application of split heat pipe.67

of granular beds include metallic pieces or metal

powders, akes of expanded graphite mixed or impregnated with salt, carbon and carbon bers, polyaniline, and vermiculite. The use of these materials
has various eects on the performance of adsorption
machines; however, they introduce additional costs
that could reach about 10 times the conventional
material cost.68
Some of the additives such as metallic pieces,
expanded graphite, and polyaniline do not take part
in the adsorption process, and therefore increases
the dead mass in the reactor. Cacciola et al.69 studied the eect of increased amount of metal in the
adsorbent bed on the COP and on the specic
cooling power. They observed that such additives
increased the ratio of dead mass to the adsorbent
mass and reduced the SCP; thereby, requiring more
mass of adsorbent and expensive adsorbers.

4.2. Consolidated beds

Fig. 13. Multi-channel pulsating heat pipe type adsorber.66

The use of consolidated beds have been successful in

enhancing the heat transfer especially in high
pressure machines, such as those using salts and
ammonia as the working pair. However, for lowpressure systems, such as those using water and
methanol as working uid, consolidation can have
serious eects on mass transfer which in turn, may
reduce the performance of the machine. For example, the water vapor pressure in a typical cycle of
an adsorption refrigerator working with water as
refrigerant is about 8 to 12 mbar during the cooling
period. Thus, a small increase in the mass transfer
resistance of the bed caused by the consolidation
can greatly compromise the adsorption capacity.

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Enhancement of Heat and Mass Transfer in Solid Gas Sorption Systems

However, in a study using silica-gel as sorbent, Eun

et al.40 showed that when the molding pressure on
the block and the proportion between expanded
graphite and silica-gel are carefully chosen, the
consolidated block can lead to specic cooling power
up to 75% higher than that obtained with nonconsolidated silica-gel.
Aristov et al.70 compared the specic cooling
power and the global heat transfer coecient of the
adsorber with pelletized zeolite, consolidated zeolite,
and consolidated silica-gel impregnated with CaCl2 .
The consolidation of the zeolite produced a four-fold
increase in the cooling power and a six-fold increase
in the global heat transfer coecient. Because the
consolidated compound of silica-gel impregnated
with CaCl2 had thermal conductivity higher than
that of the consolidated zeolite, the global heat
transfer coecient of the former compound could
reach 130 W=m 2  K and the calculated specic
cooling power was 480 W/kg.
Klein and Groll71 showed that consolidated compound beds with metal hydrides in the proportion
20:1 to expanded graphite can be an economically
competitive alternative to metal-hydrides
Al-foams
beds. The metal hydrides
expanded graphite consolidated beds tested by these researchers had thermal conductivity higher than 8 W=m  K and wall
heat transfer coecient ranging between 1500 and
3000 W=m 2  K.
The consolidation process also showed to be
eective to enhance the specic cooling power of
activated carbon
ammonia systems. The thermal
conductivity of the consolidated carbon block developed by Tamainot-Telto and Critoph23 was twice the
original thermal conductivity of the carbon without
consolidation, and could lead to an improvement in
the cooling power of about 90%.

The authors analyzed numerically several congurations of reactors employing such element, and
reported that it is possible to expect cooling production at
60  C, with ammonia reacting at 0.2 bars.
Specially designed heat exchangers may use several ns, and the major drawback of this approach is
that they increase the thermal capacity of the
adsorber due to the increase of the metallic mass. A
heat recovery process between adsorbers is therefore
necessary to reduce the heat input load; otherwise,
the energy consumed by the sensible heat will be
too large, and the COP of the system will be severely
aected. Wang51 recommended a thermal capacity
ratio between the metallic mass of the heat exchanger and the adsorbent mass up to 5, ensure reasonable COP.

4.3. Reactors with enhanced heat

and mass transfer

Acknowledgment

Reactors with enhanced heat and mass transfer

include specially designed heat exchangers for the
adsorber, use of coated heat exchangers and application of heat pipes. Mazet and Lu72 showed that
specially designed reactors as those presented by
these authors can help reduced mass transfer problems at low pressure, and enhance the specic
cooling power in the range of 100% to 200%. In their
work, they studied an adsorber whereby the heat
exchanger and the gas diuser were a single element.

5. Conclusion
Various techniques have been employed to enhance
heat and mass transfer in sorption beds, which
include use of materials with high conductivity,
consolidation of adsorbents, and use of specially
designed adsorbers. Most of these techniques have
resulted to great improvements in the heat and mass
transfer and increase in specic power of the systems. However, more eorts and new innovative
techniques are necessary to further enhance cooling
power performance of sorption machines, and lead
to more compact machines that can compete eectively with conventional electricity powered refrigerators. These eorts should be guided to the
optimization of the proportion and density between
high thermal conductivity inert materials and high
adsorption capacity adsorbents, in order to achieve
adsorbent beds with little mass transfer and heat
transfer resistances.

This work was supported by the Key Project of the

Natural Science Foundation of China under contract No. 50736004.

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