3. 0 Adsorption Working Pairs
Compared to activated carbon/ammonia or methanol,
Working pairs are very important components in
adsorption refrigeration system. The performance of
adsorption refrigeration system mostly depends on the
properties of a working pair[23]. A wide variety of
working pairs can be applied into adsorption system
and further developments of working pairs are
necessary to enhance the efficiency of the adsorption
refrigeration system.
3.1 Selection of working pairs
For proper selection of working pairs, its chemical,
physical, availability and thermodynamic properties
should be considered[23]. Working pairs are classified
into three categories with respect to its adsorption
process such as physical, chemical and composite
adsorption[5]
3.1.1 Physical adsorption
Adsorption forces involve in physical adsorption are
intermolecular forces (Van de Walls forces) and the
individuality of the adsorbate and the adsorbent are
preserved. Commonly used physical adsorption
working pairs are activated carbon/methanol and
activated/ammonia[5,23]. Activated carbon are made of
materials such as wood, coal, fossil fuel, coconut shell
and nut stone. Ammonia is a good adsorbate because it
has high latent heat[23] and has high adsorption
capacity with activated carbon[5], stable, wide
temperature range and low freezing temperature but a
disadvantage for its toxicity and corrosiveness[23].
Activated carbon/ammonia can operate at higher
pressure which improves adsorption performance of
the system. It can also operate on a very high heat
source of above 200°C [23].
Similar to activated carbon/ammonia, activated
carbon/methanol is also commonly used working pair
due to its high adsorption capacity with lower
adsorption heat requirement, which is good for its
COP[5]. Activated Carbon/Methanol working pair is
good in solar application because of its low desorption
temperature of about 100°C[5]. Its unavailability to
operate at sub atmospheric pressure is its primary
drawback due to the necessity of vacuum inside the
machine[5]. A desorption temperature of higher than
120°C should be avoided because of decomposition of
methanol to another compound [5,24].
Another working pair that is good in adsorption
refrigeration is Silica Gel and Water due to their
environmentally friendly characteristic that can be
operated by a low-grade source. Silica gel is made from
silicon dioxide hydrosol and an amorphous form of
silicon dioxide. It has a very low desorption
temperature of 50°C and cannot be higher than 120°C
making it as a good choice for solar energy application.
silica gel/water working pair has a low adsorption
capacity and cannot produce cooling at temperature
below 0°C [5].
3.1.2 Chemical Adsorption
Similar to physical adsorption, chemical adsorption has
four processes desorption, condensation, evaporation
and adsorption; but unlike physical adsorption which
retains its individuality, chemical adsorption has
transfer or sharing of electron. Metal
Chlorides/ammonia is one of the most used chemical
adsorption working pair due to its large adsorption
capacity among chlorides but has a disadvantage of salt
swelling and agglomeration during adsorption, which
affects the heat and mass transfer[5].
Another working pair that gained attention due to its
potential in low-risk and efficient storage due to its
large density is metal hydrides, which is a good storage
for hydrogen. Metal hydrides is a mixture of three metal
powders, titanium, chromium and manganese. The rates
of hydrogen desorption depends on the mass transfer,
heat transfer and the reaction kinetics of the metal
hydride bed[25].
4.1 Basic and modified cycle.
Clapeyron diagram shows the four stages of basic
adsorption cycle as shown on Fig. 3. The four processes
consist of two constant adsorbed phase concentration
process, Isosteric Heating(process a) and Isosteric
Cooling (process c) and two constant pressure process,
Isobaric desorption and condensation (process b) and
Isobaric cooling and evaporation (process d). The cycle
starts at a point where the adsorbate is at low
temperature (𝑇𝐿 ) and low pressure (𝑃𝐿 ) corresponding
to the evaporating temperature and pressure of the
adsorbate. Process (a) represents the heating of
adsorbate along with adsorbent by means of some
external sources. The continuous heating represented
by process b (left) causes the adsorbate to be desorbed.
At maximum temp (𝑇𝑚𝑎𝑥 ) the desorption stops. The
collector is connected to the condenser for
condensation of the adsorbate. After the condenser the
liquid phase adsorbate is transferred to evaporator via
pressure reducing valve; thus, decreasing its pressure
from Pc to Pe as represented by process c (left). During
this process, the collector is also closed and caused a
decrease in temperature and pressure of adsorbent as
represented by process c (right). Process d (right)
shows cooling of adsorbent by means of external
cooling sources while the adsorbate is being vaporized
by absorbing cooling load at the evaporate as
represented by process d (left).
Basic adsorption cycle is a single bed and single stage
adsorption refrigeration system. It has an advantage
due to its simple design but has lower efficiency. It is
not optimum for high temperature heat source. It is not
working well on a very low temperature and
intermittent in producing cooling load; hence, several
modified advance cycle is being introduced like multi
bed/multi stage cycle, heat recovery cycle, heat and
mass recovery cycle, thermal wave cycle, hybrid and
cascade cycle[26].
FIG. 3. Clapeyron diagram of Absorbate cycle(left) and
absorbent cycle(right)[26].
4.1.1 Heat recovery cycle
Heat recovery cycle is composed of two identical
collectors (collector 1 and collector 2), heater, cooler,
condenser, evaporator, 4sets valves and reversible
pump as shown in FIG. 4. Both collectors are filled with
adsorbent that will undergo heating and cooling. While
collector 1 is undergoing heating by a hot heat transfer
fluid, collector 2 is simultaneously undergoing cooling
by a cool heat transfer fluid. After completing this
process, collector 1 and 2 will interchange process.
Initially collector 1 is at evaporator temperature and
pressure while collector 2 is at condenser temperature
and pressure with all valves closed. To begin the cycle,
the hot heat transfer fluid from the heater, where it is
heated to maximum temperature (𝑇𝑚𝑎𝑥 ) for
regeneration, is forced to enter the collector 1 then goes
out to the cooler for cooling and at the same time the
cold heat transfer fluid is forced to enter to the
collector 2 then goes out to the heater for heating.
During this stage, the collector 1 initiates desorption
and collector 2 initiates the adsorption. The valve (V1)
before the condenser will be opened if the pressure of
the collector 1 increases up to the condensing pressure
(Pc) to allow the condensation of the adsorbate; and,
also the valve before the evaporator (V2) will be opened
if the pressure of the collector decreases down to the
evaporating pressure (Pe) to allow the evaporation of
adsorbate. When all this processes are completed and
both collectors have enough heating and cooling, the
process will be reversed. Collector 1 and collector 2 will
interchange process and heat transfer fluid will reverse
direction.
FIG. 4. Schematic diagram of Adsorption Refrigeration
with heat recovery cycle[27].
The result of the study for heat recovery adsorption
refrigeration with two adsorption beds shows
improvements on the system’s performance compared
to single stage adsorption refrigeration system. The
parameters used in the comparison were based on the 4.1.3 Thermal wave cycle.
optimum condition of each system. Single stage system
held a best result of COP=0.483 and double adsorption Thermal regeneration can be achieved using thermal
bed of COP=0.682, a significant increase in COP of wave cycle to reduce the heat input of the system. FIG. 6
41.2% [27]. shows the schematic of a thermal wave cycle. It has
condenser, evaporator, throttling device the same as a
4.1.2 Heat and Mass Recovery simple adsorption cycle; only the collectors are different
from the simple adsorption cycle. A reversible heat
This heat recovery cycle recovers heat from the transfer fluid is thermally connecting the collectors by
temperature difference between collectors and mass heating or cooling either of the collectors. The collector
recovery increase cycled refrigerant mass between in a thermal wave cycle is a concentric tube heat
evaporators. The schematic diagram was shown at FIG transfer with heat transfer fluid flowing axially at the
5. It includes two independent sorption chambers and inner part and the adsorbate and its adsorbent are
each chamber has a collector, a condenser, evaporator flowing at the annulus. At the beginning, the heat
and eight valves [28]. This system has three phases; transfer fluid is circulated through the collector creating
heating, mass recovery and cooling[29]. During the a thermal wave, which is created by heating the
desorption of collector 1 its temperature is increased collector 1 and cooling the collector 2. After desorption
(heating) while simultaneously collector 2 doing the valve connecting the condenser and collector 1 is
adsorption and its temperature is decreased (cooling) . closed and the heat transfer fluid flow is reversed. The
The heat recovery utilizes some energy during phase thermal wave results into a wave adsorption. A system
change of adsorption and desorption. A heat transfer of adsorption cycle with thermal regeneration such as
fluid will circulate from heated collector through the thermal wave(COP’s 2.5-3.5) are predicted to be higher
cooled collector; thus, utilizing the heat of the heated than simple cycle even if using multi bed system (COP’s
collector. During mass recovery phase, no collectors are 1.25-2.75) [30].
connected to neither evaporator nor condenser. In the
beginning, the heated collector has high pressure which
is equal to the condenser pressure, and the cooled
collector has low pressure which is equal to the
evaporating pressure. By connecting the two collectors
the vaporized absorbate will naturally flow from high
pressure heated collector to the low pressure cooled
collector; thus, drying more the heated collector. By the
next cycle, the dried collector will adsorb more during
next desorption phase. Utilizing chilled water to flow
from collector 1 to collector 2 to cool the collector 1 and
heating collector 2 could create more pressure
difference and mass recovery. For optimum results, a
heat recovery time of 25sec to 45sec is recommended
and a mass recovery time of 5 to 50sec[28]. An increase
of 4.8 percent in cooling capacity and 6.4 percent in COP
were reported with mass recovery compared to with
heat recovery only[29]. FIG. 6. Schematic diagram of Thermal Wave Adsorption
Refrigeration [30]

4.2 Other Adsorption Cycle Modification

4.2.1 Cascaded Cycle

Cascading of adsorption system into another system is

one way to enhance the performance and to counter the
major drawback of adsorption refrigeration which is its
low COP. Dakkama et al. investigated the performance

FIG. 5. Schematic diagram of Adsorption Refrigeration of different working pairs in a cascade adsorption

with heat and mass recovery cycle[27]. system with integrated condenser/evaporator as shown
in FIG. 7. It is composed of two pairs of adsorbent beds, cascade refrigeration with similar configuration,
condenser, evaporator and an integrated concluded that an electrical savings of 35% is
condenser/evaporator heat exchanger. The working obtainable compared to vapor compression system
principles are similar with basic adsorption cycle for alone[33].
each system and the only difference is 1st stage
condenser acting as the 2nd stage evaporator. Based on
the results for this system, a high pressure and high
latent heat working pairs are recommended. The
system utilized a low temperature heat source, low
evaporation temperature and high condensing
temperature which result into a very low COP of about
0.04. [31].

FIG. 8. Schematic diagram of Hybrid Refrigeration

System[32]

FIG. 7. Schematic diagram of Cascaded Adsorption

Refrigeration System[31]

4.2.2 Hybrid and Cascade System

Vasta et al. investigated the performance of a chiller

composed of adsorption refrigeration unit cascaded to
a vapor compression unit as shown in FIG. 8. The
adsorption cycle which operates on high pressure
receives heat from an external source and produces
cooling in the evaporator of about 20°C. The evaporator
of the adsorption cycle which operates on high pressure
is used as the heat rejection component of the vapor
compression cycle which operates on low pressure. The
vapor compression system is consist of electric
compressor, condenser, throttling valve and evaporator.
The experiment shows that for cascade system in the
presence of waste or free heat available, an electrical
savings of 50% can be obtained compared to a vapor
compression system alone[32]. Another experiment of
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http://dx.doi.org/10.1016/ j.applthermaleng.2016.11.138 efficient combination of natural working fluids.
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