A review on thermal performance enhancement of green cooling system using different adsorbent/refrigerant pairs

Abstract

Due to the ever-increasing cooling demand, alternative refrigeration is being explored for the last few decades that are less energy-intensive and can utilize ozoenvironmental friendly working fluid. Vapor adsorption refrigeration is one of the most promising alternatives among all heat-driven refrigeration systems. One of the most important requirements in an adsorption-based cooling system is to enhance the adsorption uptake capacity of the adsorbent materials for their impactful, effective, and economical operation. However, there are several working pairs explored during the recent decades but none of them could be suitable as an ideal one, for all the operating conditions. In this article, the various characteristics of different adsorbents including the highly porous activated carbons derived from waste biomass, the composites, and compounds developed, are thoroughly reviewed. Further, the synthesization, the optimal assortment, regeneration, coatings on adsorber, and commercial application of novel adsorbents including the advanced adsorption reactors and the current scenario of industrial adsorption chillers are discussed in detail. Finally, the impact of operating parameters, such as adsorbent-adsorbate mass ratio, desorption pressure, operating temperatures, and adsorption/desorption cycle time on the specific cooling power, coefficient of performance, and the chiller efficiency are summarized.

Full text

Energy Conversion and Management: X 14 (2022) 100225
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A review on thermal performance enhancement of green cooling system
using different adsorbent/refrigerant pairs
P.R. Chauhan , S.C. Kaushik , S.K. Tyagi
*
Department of Energy Science and Engineering, Indian Institute of Technology Delhi, Hauz Khas, New Delhi 110016, India
ARTICLE INFO
Keywords:
Ozoenvironmental friendly working pairs
Coated adsorber
Biomass-derived adsorbent
Metal-organic framework
Covalent-organic framework
ABSTRACT
Due to the ever-increasing cooling demand, alternative refrigeration is being explored for the last few decades
that are less energy-intensive and can utilize ozoenvironmental friendly working uid. Vapor adsorption
refrigeration is one of the most promising alternatives among all heat-driven refrigeration systems. One of the
most important requirements in an adsorption-based cooling system is to enhance the adsorption uptake capacity
of the adsorbent materials for their impactful, effective, and economical operation. However, there are several
working pairs explored during the recent decades but none of them could be suitable as an ideal one, for all the
operating conditions. In this article, the various characteristics of different adsorbents including the highly
porous activated carbons derived from waste biomass, the composites, and compounds developed, are thor-
oughly reviewed. Further, the synthesization, the optimal assortment, regeneration, coatings on adsorber, and
commercial application of novel adsorbents including the advanced adsorption reactors and the current scenario
of industrial adsorption chillers are discussed in detail. Finally, the impact of operating parameters, such as
adsorbent-adsorbate mass ratio, desorption pressure, operating temperatures, and adsorption/desorption cycle
time on the specic cooling power, coefcient of performance, and the chiller efciency are summarized.
Introduction
The efcient utilization of low-temperature thermal energy sources
such as solar energy [1,2], geothermal energy [3], industrial waste heat
[4], biomass combustion heat [5], and domestic waste heat is a major
concern for several engineering and industrial applications [6]. At pre-
sent, adsorption technology is recognized as realistic, environmentally
benign, and energy-efcient for utilizing low temperature [7] and ultra-
low temperature [8] heat energy to achieve some useful effects in the
domestic and industrial sectors: for example, the ice-making industry [9-
17], vaccine safety [18-22], fruits and vegetable storage [23], milk
storage [24], gas storage [25-30], food industry [31-33], CO
2
capturing
[34-41], and building cooling and air conditioning [42-49]. The peak
demand for electricity is increasing every year due to the heavy use of
airconditioning systems during the summer months, especially in loca-
tions with hot temperatures. Therefore, heat-driven cooling alternatives
such as an adsorption technology-based cooling system (ACS) could be
an effective option to reduce the peak demand for power that can pro-
duce the cooling effect using low-quality or waste thermal energy at a
heat source temperature of <100 ◦C. Though, the major hindrances in
the way of commercialization of ACS are its pitiable performance and
large size. This is because of the poor adsorption ability of adsorbent
material as well as the structure of the adsorption reactor which leads to
low heat and mass transfer performance of ACS. Therefore, the devel-
opment of compact thermal reactors [50], as well as the synthesization
and characterization of new adsorbent-adsorbate pairs with high
adsorption capacity or kinetics became a very attractive research topic
for the researchers.
Development of adsorption refrigeration systems
In 1848, the rst evidence of adsorption cooling was experienced in
Faraday’s laboratory. Later on, GE Hulse proposed an ACS using silica
gel-SO
2
working pair (WP) for storage of eatable items in a locomotive in
1920. After two decades, the waste heat from locomotive steam was
utilized as a heating source for the regeneration of the adsorbent bed.
Meanwhile, this technology could not compete with highly efcient
CFC-based VCRS as the freons and hermetically sealed mechanical
compressor were developed in 1930. In the 1970s, the adsorption system
has begun as an area of interest because of the oil crisis; later on, the
interest shifted towards the ecological problems like ozone depletion
* Corresponding author.
E-mail address: tyagisk@iitd.ac.in (S.K. Tyagi).
Contents lists available at ScienceDirect
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https://doi.org/10.1016/j.ecmx.2022.100225
Received 26 January 2022; Received in revised form 10 April 2022; Accepted 11 April 2022

Energy Conversion and Management: X 14 (2022) 100225
2
and global warming during the 1990s. Additionally, with a boost in
energy expenditure around the world, it is increasingly critical to nd
out solutions to make use of existing energy resources as economically as
possible. As a result, refrigeration systems like VAdRS have been
discovered which are capable of working with low grade waste heat (T
hs
≤50 ◦C) [51] and have emerged as a viable refrigeration option [52].
Adsorption process
The adsorption process is a surface phenomenon, in which a sub-
stance penetrates the pores of amorphous solids. It occurs due to the
interaction between adsorbent (solid material) and adsorbate/refrig-
erant (gaseous). However, the process in which the adsorbed molecules
break away from adsorbent pores is known as desorption. The molecules
of the adsorbate entrap on the pore’s textured surface of the adsorbent in
two different ways such as physisorption and chemisorption (refer
Fig. 1). The forces involved to attach the adsorbate (refrigerant) mole-
cules on the solid adsorbent surface in physical adsorption and chemical
adsorptions are intermolecular forces (Van der Walls) and valence
forces, respectively.
Adsorbents and adsorbates
The adsorbent is a solid and porous material, characterized as mac-
roporous (greater than50 nm), mesoporous (2–50 nm), and microporous
(<2 nm), should have a high specic surface area (m
2
/g), high
desorption capacity, high ability to adsorb a huge quantity of refrigerant
at a low cooling temperature, low specic heat capacity, high latent heat
of adsorption compared to its sensible heat, chemical stability, non-toxic
and non-corrosive, and inexpensive and easy to nd [54]. Though, a
good refrigerant should have a small molecule size to allow easy
adsorption, high thermal conductivity, high latent heat of vaporization,
Nomenclature
b
o
Equilibrium constant, (kPa
−1
)
E Activation energy, (kJ/kg)
h
fg
Latent heat of vaporization, (kJ/kg)
n, t Index parameter
P Pressure, (kPa)
Q
st
Isosteric heat of adsorption, (kJ/kg)
T Temperature, (K)
t Time, (sec)
W
o
Maximum adsorption uptake, (kg/kg)
Greek symbols
η
Efciency
ρ
Density, (kg/kg)
Abbreviation
AC Activated carbon
ACDS Adsorption cooling cum desalination system
ACF Activated carbon bre
ACS Adsorption cooling system
AHP Adsorption heat pump
COF Covalent organic framework
COP Coefcient of performance
CP Cooling power
EG Expanded graphite
GNP Graphene nanoplatelets
MOF Metal-organic framework
PVA Polyvinyl alcohol
SCE Specic cooling effect
SCP Specic cooling power
SDWP Specic daily water production
TCE Thermal conductivity enhancer
VAdRS Vapour adsorption refrigeration system
VCRS Vapour compression refrigeration system
WP Working pair
Subscripts
ads Adsorption
avg Average
chill Chilled
cond Condenser
cool Cooling
crc Critical
cyc Cycle
des Desorption
evap Evaporator
hs Heat source
in Inlet
max Maximum
min Minimum
opt Optimum
out Outlet
reg Regeneration
w Water
Fig. 1. Physical (a); and Chemical adsorption (b) [53].
P.R. Chauhan et al.

Energy Conversion and Management: X 14 (2022) 100225
3
low specic volume, low viscosity, thermal and chemical stability within
the operating temperature range, non-corrosive, non-toxic, and non-
inammable. The meticulous discussion of the assortment of different
adsorbent-adsorbate pairs for ACS is systematically addressed by
Mahesh and Kaushik [61]. Table 1 shows the porous properties and
tting parameters of adsorbents; although Table 2 illustrates some
physical properties for various adsorbates applicable for ACS.
Adsorption cooling cycle
In the adsorption cooling cycle, the thermal compressor undergoes a
cooling and heating process intermittently [66]. The basic adsorption
refrigeration cycle contains an evaporator, an adsorbent bed, a
condenser, and a throttling valve. A schematic illustration of the
fundamental cycle and the Clapeyron diagram for VAdRS are shown in
Fig. 2.
Heating of sorption reactor: During this process, the temperature of the
adsorbent rst rises at the isosteric condition resulting in an increase in
pressure from the evaporator to the condenser level keeping all valves in
the closed position. Later on, the adsorbent temperature starts
increasing at the isobaric condition resulting in vapor desorption. Af-
terward, it goes to the condenser and then liquees. This process is
somehow similar to the condensation process in VCRS. The valve in
between the desorber and condenser remains open that allowing the
ow of vapor to the condenser.
Cooling of sorption reactor: In this process, the condenser pressure
drops to evaporator pressure by cooling down the adsorbent at isobaric
conditions keeping all valves in a closed state. Subsequently, the heat is
released from the adsorbent bed at a constant pressure which is attached
to the evaporator. This is due to the adsorption phenomenon. The valve
in between the adsorber and evaporator remains open that allowing the
ow of vapor from the evaporator to the adsorber.
Classication of adsorption cooling systems
The schematic representation of Fig. 3 explains the classication of
ACS into two categories; thermophysical adsorption, and physical
adsorption, which is further sub-divided into open systems, and closed
systems. In the case of physical adsorption, the open systems named
gas–solid desiccant systems are generally used for dehumidication and
air-conditioning purposes. However, closed systems are utilized for
freezing, chilling, and air-conditioning purposes.
Since the working conditions and environmental concerns are
heavily reliant on WPs, therefore a good and ideal combination of
adsorbate and adsorbent is the most signicant factor to achieve a
substantial increment in the performance of ACS. The afnity for each
other in a pair is determined by certain desirable features of their con-
stituents like thermodynamic and chemical properties, as well as their
physical properties. A lot of research attempts have been made, exper-
imentally, numerically, and theoretically, to determine the best pair of
Table 1
Porous properties and tting parameters of adsorbents for adsorption cooling system.
Adsorbents Porous Properties Adsorption Equilibrium Models Ref.
Total Surface area (m
2
/g) Total pore volume (cm
3
/g) Adsorption model Parameter Value
Silica gel
Type A 650 0.36 Freundlich W
o
(kg/kg) 0.346 [55]
n (-) 1.6
Type RD 636.4 0.314 D-A W
o
(kg/kg) 0.327 [56]
E (kJ/mol) 4.384
n (-) 1.35
Activated carbon (AC)
Maxsorb-III 3045 1.7 D-A W
o
(kg/kg) 1.2 [107]
E (kJ/mol) 5.538
n (-) 1.75
ACF(A-20) 1930 1.028 D-R W
o
(kg/kg) 0.797 [70]
D (K
−2
) 1.716 ×10
−6
WPT AC 2927 62.52 T´
oth W
o
(kg/kg) 1.9 [57]
b
o
(-) 4.09 ×10
−6
t (-) 3.88
Q
st
(kJ/mol) 44.23
M AC 2924 34.19 T´
oth W
o
(kg/kg) 1.65
b
o
(-) 2.37 ×10
−6
t (-) 3.42
Q
st
(kJ/mol) 46.30
Zeolite
Binderless 5A 526 0.25 T´
oth W
o
(mmol/kg) 5.11 [58]
b
o
(1/bar) 2.1 ×10
−5
t (-) 0.61
Q
st
(kJ/mol) 38.1
AQSOA-Z05 187.1 0.07 D-A W
o
(kg/kg) 0.22 [60]
E (kJ/mol) 2700
n (-) 6
Metal-organic framework (MOF)
MOF-801-U90
m
1151 1122 D-A W
o
(g/g) 0.454 [59]
E (J/mol) 285
n (-) 2.9
MOF-801-RT 976 954 D-A W
o
(g/g) 0.3272
E (J/mol) 286.37
n (-) 4.1945
Covalent-organic framework (COF)
COF-5 1943 1.23 Universal
ε
o
(J/mol) 4.75 ×10
3
[232]
m (J/mol) 1.57 ×10
3
α
0.35
MIL-101(Cr) 3358 2.09 Universal
ε
o
(J/mol) 3.92 ×10
3
m (J/mol) 8.92 ×10
3
α
0.67
P.R. Chauhan et al.

Energy Conversion and Management: X 14 (2022) 100225
4
adsorbent-refrigerant material; nonetheless, the expense of determining
the best adsorbent–refrigerant material is still prohibitive for commer-
cialization. As a result, certain investigations are centred on lowering
costs and enhancing the system’s performance. The most commonly
utilized WPs are zeolite–water, AC–methanol, silica gel–water, and
AC–ammonia, which are all summarised in the coming section.
Present scenario of industrial adsorption chillers
According to BP’s energy outlook, the global energy demand may
rise to 41% by 2035, out of which, more than 17% of electricity will be
consumed by refrigeration and airconditioning systems. In view of that,
several adsorption chiller manufacturing industries such as Mitsubishi,
Table 2
Physical properties of adsorbates for adsorption cooling systems.
Adsorbate/ Refrigerant Chemical formula Boiling point (◦C) Molecular weight h
fg
, (kJ/kg)
ρ
, (kg/m
3
) Ref.
Ammonia NH
3
−34 17 1368 681 [47]
Water H
2
O 100 18 2258 958
Methanol CH
3
OH 65 32 1102 791
Ethanol C
2
H
5
OH 79 46 842 789
TrichloroMonouoro Methane R-11 CCl
3
F 23.7 137.37 182.5 130.35 [62]
Dichloro Diuoro Methane R-12 CCl
2
F
2
−29.8 120.91 165.8 –
Methane CH
4
−161.6 16 511 422.6 [63]
HFC R507 −46.7 98.9 200 1050 [64]
Carbon dioxide CO
2
−78.0 44 321.3 1101
Tetrauoro ethane
R-134a
C
2
H
2
F
4
−14.94 102.03 93.28 4.25 [65]
Fig. 2. Basic cycle (a); and Clapeyron diagram (b) of VAdRS [67].
P.R. Chauhan et al.

Energy Conversion and Management: X 14 (2022) 100225
5
Bry Air, InvenSor GmbH, New Leaf, MAYEKAWA, and Bühler Motor
GmbH are serving the world for cooling and refrigeration purpose. In
1986, Nishiyodo Kuchouki Co. Ltd developed, rst of its kind, an
adsorption chiller driven at T
hs
of 50–900 ◦C using silica gel-water pair
for commercial applications. However, the use of solar energy as a heat
source for adsorption chiller was, rst in the world, brought to the notice
by Mitsubishi Plastics Inc. in partnership with MAYEKAWA
Manufacturing Co. In India, Bry Air Pvt. Ltd. was the rst manufacturing
industry that developed a low-grade thermal energy-driven (T
hs
=
50–100 ◦C) adsorption chiller having a cooling capacity of 40 kW using
silica gel-water as WP.
MAYEKAWA Manufacturing Co Ltd. Japan manufactured and
marketed different adsorption chiller models named ADR-Z3515, ADR-
Z3525, ADR-Z4520, and ADR-Z6025 having cooling capacities of 92 kW,
184 kW, 315 kW, and 369 kW, respectively, using zeolite–water pair for
cooling purposes in the pharmaceutical and beverage industries. To
compact design and performance enhancement, Mitsubishi Plastics Inc.
in collaboration with Union Industry Co. developed ACS containing an
extremely porous zeolitic AQSOA
TM
coated thermal compressor inte-
grated with a cooling tower for cooling applications in buildings, data
centres, chemical plants, warehouses, supermarkets, food plants, hos-
pitals, frozen storage, and welfare facilities. LTC30 and LTC90 e series
adsorption chillers with cooling capabilities ranging from 10 to 35 kW
and 30–105 kW commercialized by InvenSor GmbH Germany. These
Fig. 3. Classication of adsorption-based cooling systems [68].
Fig. 4. Structures of: (a) activated carbon; (b) silica gel [85]; crystal cell unit of zeolite type A (c1) and X, Y (c2) [86]; and MOF-801 (d) [59].
P.R. Chauhan et al.

Energy Conversion and Management: X 14 (2022) 100225
6
high-performance chillers with AQSOA
TM
coated heat exchangers,
compact size, low maintenance, and excellent energy-saving potential
are serving various sectors and industries around the world like Bühler
Motor GmbH, Miele & Cie. KG, Marburg in Germany, Turin in Italy, and
Cuiab´
a in Brazil for tool cooling, metal processing, machine cooling,
chilled air circulation, ofce space cooling, and hotel room cooling [6].
Activated carbon, zeolite, and silica gel-based adsorbents
The physical adsorbents such as AC and its ber, silica gel, and
zeolite rely on Van-der Waal’s forces to hold the refrigerant over its solid
surface. In the distant past, most of the ACs are prepared from coal
[69,70], municipal solid wastes [71], waste plastic [72], petroleum, and
coke [73-76]; however, in recent times a small number of adsorbents are
also made-up of biomass or renewable materials [77-84]. Fig. 4 shows
the physical structure of AC, silica gel, zeolite, and MOF. The bone-
derived AC microcrystal is a six-element carbon atomic ring [85], and
the adsorption properties are affected by the functional groups associ-
ated with the carbon atomic ring (see Fig. 4(a)). Silica gel, amorphous
synthetic silica, is a xed and uninterrupted set of connections of
colloidal silica that is allied to very ne hydrate grains of silicates (refer
Fig. 4(b)); however, zeolite adsorbent is alkali soil which is composed of
crystals of alumina silicate. An exchange process between the modulator
(formic acid) and the ligand (fumaric acid) is the basic mechanism for
MOF structure (see Fig. 4(d)).
From the existing works of literature, it has been found that around
40 natural and 150 articially synthesized zeolites are available now.
The AC-based adsorbents are different from other physical adsorbents in
terms of surface functioning. The entire surface of AC is roofed with
oxide matrix and inorganic materials that result in weak polarity. Also,
the requirement of adsorption heat for AC adsorbents is much lesser than
that of other physical adsorbents. Ramji et al. [87] numerically analyzed
the cooling performance of AC–methanol-based adsorption air-
conditioning system powered by exhaust gases under the inuences of
wall thickness. It is then computationally observed that on employing a
20 mm thick stainless-steel wall and at 473 K temperature of exhaust gas
as input, the temperature of the bed is found to be approximately 393 K.
Table 3 summarizes the various physical WPs for VAdRS highlighting
their performance parameters and working temperatures ranges.
An experimental work is performed to limit the range of maximum
regeneration temperature (T
reg
) for a manually prepared AC–methanol-
based solar-assisted ACS considering various mass ratios ranging from
0.25 to 2.50 [88]. When T
reg
exceeds 393 K, the breakdown of CH
3
OH
adsorbate into other compounds occurs, resulting in a performance loss
of the adsorption chiller. In their subsequent study, comparative per-
formance of glazed and unglazed cylindrical solar collectors under the
inuences of desorption temperature (T
des
), solar radiation intensity,
condenser temperature (T
cond
), and evaporator temperature (T
evap
) is
carried out [89]. The results revealed that the unglazed system is found
to be economically better in terms of efciency whereas COP values of
the adsorption cycle are calculated in the range of 0.57–0.73. The per-
formance of AC-CO
2-
based four-bed VAdRS at different cooling tem-
peratures (T
cool
) by adopting a transient mathematical model is
addressed numerically [90]. It is observed that at optimum desorption
pressure (P
des,opt
) of 79 bars and T
cool
of 300 K along with T
hs
of 368 K,
the COP and cooling power (CP) have resulted in 0.1 and 2 kW,
respectively.
Fig. 5 describes the pressure–temperature–concentration cycle and
effect of P
des
on performance parameters using MaxsorbIII-CO
2
as
adsorbent-adsorbate. A little climb is noticed at the closing stage due to
switching from adsorption to pre-heating. The COP and CP increase as
P
des
increase, but they decrease once they reach their greatest point.
Additionally, the CP values at different T
cool,w,in
attaining its greatest
values at t
opt,ads/des
of 11.7 min, 11.1 min, and 9.6 min. In order to make
use of waste biomass in form of highly porous AC, a waste matured
coconut shell made granular AC–NO
2
pair is studied for single bed
VAdRS at different pressures ranging from 6 to 18 kgf/cm
2
[91]. The
results demonstrated that the greatest heat of adsorption, highest
Table 3
An overview on physical adsorbent–adsorbate pairs for adsorption-based cooling systems.
Working
pairs
Approach of
work
No. of
beds
T
evap
(
o
C)
T
cond
(
o
C) T
des
(
o
C)
CP COP Featured highlights Ref.
AC –
methanol
Numerical
study
Four (2
×2)
– 15 – 25 200 650 W 0.25 The wall thickness of the adsorber plays a crucial role in the
cooling performance and T
des
.
[87]
AC –
methanol
Experimental
study
Single 12 31 80 –
120
2.5 kJ/kg 0.27 The methanol as refrigerant is decomposed into other
compounds at a temperature of more than 120 ◦C which
reduces the performance of VAdRS.
[88]
AC - CO
2
Numerical
study
Four 15 27 95 2 kW 0.1 The proposed system is appropriate for both housing and
transportable air-conditioning applications.
[90]
AC - N
2
Experimental
study
Single 1.7 28.2 – 415.4 W 1.32 The experimental analysis is having huge potential to
produce a cooling effect by employing the pressure swing
adsorption–desorption principle.
[91]
AC - R507a Theoretical
study
Four −5 30 72 1.55 kW 0.12 The proposed system is considerably useful in process
industries.
[93]
AC – ethanol Experimental
study
– 7 30 80 420 kJ/
kg
0.7 The proposed WP can be used as adsorbent-adsorbate pair
for solar VAdRS.
[107]
Carbon –
ammonia
Numerical
study
Two 0 30 100 104 W/
kg
0.43 The system is capable to generate a daily useful cooling of
2515 kJ per 0.8 m
2
of collector area.
[108]
Silica gel –
water
Experimental
study
Two 12 25 87 208 W/
kg
0.62 The proposed VAdRS can be driven by low-grade waste heat. [109]
Zeolite13X –
water
Experimental
study
Single 0.7 –
16.2
18 325 2 – 10.5
W
0.6 – 0.9 The proposed VAdRS is capable of air-conditioning purposes
in small vehicles and shing boats by reutilizing the waste
heat.
[110]
AC - R134a Experimental
study
Four 10.6 –
14.9
31.9–34.2 73 –
87
3.0 – 4.9
W
0.82 –
1.1
The experimental investigation is done for small cooling
applications in electronic devices.
[111]
Zeolite –
water
Experimental
study
Two 7 – 13 30 70 100 –
900 W/
kg
0.1–0.6 The derived analytical formulation is applicable for various
cyclic study state performances.
[112]
Silica gel –
water
Theoretical
study
Four 9 30 60 –
95
35 –
47.82 W/
kg
0.24 –
0.35
The proposed desalination system is having the potential to
provide a sufcient amount of drinkable water.
[113]
Silica gel –
water
Experimental
study
Two 15 40 85 57 W/kg 0.3 The proposed transient modeled VAdRS can be driven by
solar energy.
[114]
P.R. Chauhan et al.

Energy Conversion and Management: X 14 (2022) 100225
7
average refrigeration, and COP
avg
are calculated as 92.75 kJ at 15 kgf/
cm
2
, 0.42 kW at 18 kgf/cm
2,
and 1.32 at 12 kgf/cm
2
, respectively. The
coffee shell synthesized AC is also found to be useful as an adsorbent for
VAdRS [92].
Habib et al. [93] theoretically worked to investigate the thermal
performance of solar energy (using evacuated tube solar collectors)
assisted VAdRSs with the combination of two (top cycle and bottom
cycle) adsorption cycles in which the top cycle and bottom cycle are
operated using AC-R507A and AC-R134a as adsorbent-adsorbate pairs,
respectively for two different locations such as Singapore and Malaysia.
The proposed combined system is capable to bring the refrigeration load
to 283 K with a regeneration temperature of 349 K that could be useful
in industries for freezing applications. From Fig. 6, it is graphically
analyzed that both COP and
η
chill
are observed as consistently increasing
with an increase in t
cyc,ads/des
; however, the maximum CP is found to be
close to 1.55 kW in the bottoming cycle at t
cyc
ranging from 480 to 520 s.
The optimal values of
η
chill
and COP are evaluated as approximately 0.25
and 0.12, respectively.
The biomass is a highly porous material and it has adequate potential
to use as adsorbent material in VAdRS. In this list, the various precursor
materials of biomass waste like waste palm trunk, mangrove wood,
corncob, garlic peel, almond tree pruning, rice husk, sugarcane, almond
shell, coconut shell, walnut shell, and charcoal are used to synthesize AC
as adsorbent for cooling and heating applications using adsorption
technology. Singh and Kumar [94] theoretically investigated an ACS
using biomass-derived coconut shell-based AC-CO
2
as an adsor-
bent–refrigerant pair. The SCE
max
and COP
max
for the single-stage
adsorption cooling cycle at T
reg
of 80 ◦C are obtained as 9.26 kJ/kg
and 0.06, respectively. Though, in the case of a single-effect two-stage
adsorption cooling cycle at T
reg
of 65 ◦C, the maximal outcomes of SCE
and COP are evaluated as 8.85 kJ/kg and 0.04, respectively. Singh et al.
[95] experimentally worked on the adsorption kinetics of CO
2
refrig-
erant on indigenously developed coconut shell-based AC adsorbent at
different temperatures (273 to 368 K) using Linear Driving Force (LDF)
and Fickian Diffusion (FD) models. The results revealed that the SCE
max
(i.e., 12.52 kJ/kg) and COP
max
(i.e., 0.10) are evaluated at T
evap
of 15 ◦C
and T
des
of 80 ◦C.
For the adsorption-based cooling system, to compare biomass-
derived adsorbents with other traditional adsorbents under specied
operating conditions, the biomass-derived adsorbents are extensively far
above the ground in terms of maximal uptake to produce the cooling
effect at the high value of evaporator temperatures (for cooling and heat
pump application). Moreover, biomass-derived adsorbents (like WPT AC
and M AC) are observed with adequate potential in terms of uptake ef-
ciency and also require comparatively a lesser amount of temperature
of desorption (at T
des
<80 ◦C) to produce a cooling effect with T
evap
of
5 ◦C, and 10 ◦C. This is due to an extremely porous surface with a large
total surface area, high total pore volume, high micropore volume, more
pore width, and high values of tting parameters. The high carbon
content, large specic surface area as well as a highly porous structure
results in excellent use for synthesizing the adsorbent material. India is a
vast agricultural nation with considerable fruit and vegetable produc-
tion, and recycling such kind of biomass waste to manufacture adsorbent
material not only meets the needs of clean manufacturing, but it also
aids resource allocation and rural development.
Fig. 7 shows various steps involved in the preparation of AC adsor-
bent from two biomass precursors having low ash and high carbon
contents, named waste palm trunk (WPT) and mangrove wood (M) [96].
Initially, both the raw biomass materials were crushed and then dried at
100 ◦C for 48 h to remove water content and other gases. Later on,
vacuum drying at 105 ◦C followed by a carbonization process at
500–600 ◦C is performed for 1 h each at a temperature rate of 10 ◦C/min
with an N
2
ow of 100sccm. Though, in the case of KOH activation, the
temperature rises from 600 to 900 ◦C while the rate of temperature is
found to be diminished to half of the previous (i.e., 5 ◦C/min) for the
same duration keeping a constant ow of N
2
and KOH/carbon ratio of
4–6. After that, it washes away with HCl and DI water followed by air
oven dry at 100 ◦C for 3 h and vacuum oven-dried at 150 ◦C for 12 h. As a
result, the synthesized biomass-based AC can be useful as an adsorbent
(a)
3
4
5
6
7
8
9
10
270280290300310320330340350360370
P (MPa)
T (K)
Desorption
Adsorption
2
1
3
4
Critical Point
(b)
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
2
0
0.02
0.04
0.06
0.08
0.1
7.3 7.8 8.3 8.8 9.3
Tcooling = 300 K
Tcooling = 305 K
Tcooling = 310 K
COP
CP (kW)
Pdes (MPa)
Fig. 5. P–T–C diagram (a); and effect of P
des
(b) on performance [90].
Fig. 6. Effect of t
cyc,ads/des
on CP, COP, and
η
ch
[93].
P.R. Chauhan et al.

Energy Conversion and Management: X 14 (2022) 100225
8
(a) (b)
Fig. 7. Preparation steps of AC adsorbent from biomass material [96].
P.R. Chauhan et al.

Energy Conversion and Management: X 14 (2022) 100225
9
for cooling and heating application in VAdRS.
In another investigation addressed by Pal et al. [97], the thermo-
dynamic performance in terms of SCE and COP of single-stage VAdRS
using biomass-derived AC and CO
2
pair is studied considering T
evap
of 5,
10, and 15 ◦C, T
des
ranging from 50 to 100 ◦C, and T
ads
of 30 ◦C. The
SCE
max
and COP
max
are found to be 109 kJ/kg and 0.13 for WPT AC
(C500) followed by 108 kJ/kg and 0.13 for M AC (C500), 94 kJ/kg and
0.12 for WPT AC (C600), and 90 kJ/kg and 0.12 for M AC (C600) with
T
evap
of 15 ◦C and T
reg
of 100 ◦C, respectively. Many research efforts [98-
106] have also been made on the adsorption analysis of R114, methanol,
N
2
, n-butane, H
2
, Diethyl ether, n-butane, methanol, and n-butane on
the AC composite adsorbent for various cooling applications.
Metal chlorides, hydrides, and oxides-based adsorbents
The chemical adsorbent primarily comprises chlorides, oxides, and
hydrides of metal, of which, metal chlorides are generally chlorides of
calcium, strontium, magnesium, and barium [115]. In general, ammonia
is used as the refrigerant or adsorbate with metal chlorides as adsorbent
that results in agglomeration and salt swelling in the adsorption process.
Similarly, the hydrides of salt and metal, having hexagonal crystal lat-
tice structures with large density, are applicable as chemical adsorbents
to produce the cooling effect in VAdRS. In the case of metal oxides as
adsorbents, the coordination number, direction of the chemical bond,
the arrangement of active canters, and unsaturated degree of coordi-
nation are the key elements that affect the adsorption performance
[116]. A dynamic examination of the thermal performance of solar
energy-powered chemical refrigeration is reported to adopt barium
chloride–ammonia as adsorbent-adsorbate pair [117]. The COP value is
evaluated as 0.63 at T
reg
of 52 ◦C for ice-making application.
A kinetic study of chemical heat pumps using calcium oxide–water
WPs is discussed by Kanamori et al. [118]. This system has been used as
heat storage for the consumption of excess electrical energy, later on;
Ogura et al. [119] experimentally examined it for drying application.
The energy consumption of a cogeneration system is experimentally
reduced by adopting magnesium oxide–water pair [120]. Metal hy-
drides put forward wider applicability at equilibrium temperatures
ranging from −113 to 527 ◦C [121]. Three different schemes of solid
sorption systems are theoretically analyzed using metal hydride–hy-
drogen pair for cooling and heating applications [122]. It is found that
the SCP values for single stage and double stage are obtained as
100–200 W/kg and 150–300 W/kg, respectively. Moreover, it is pre-
dicted that the lowest amount of T
evap
could be achieved at −50 ◦C at
T
reg
ranging from 85 to 215 ◦C.
An experimental investigation of an adsorption-based refrigeration
system is carried out using MIL-101(Cr) as an adsorbent and water as a
refrigerant. The results showed that the optimal value of activation
temperature is calculated as 140 ◦C at which the synthesized adsorbent
gives the maximum adsorption performance. It is then concluded that it
could be a promising adsorbent to generate fresh water from air for
coastal areas [123]. The lowest temperature for regeneration of MIL-101
(Cr) adsorbent is obtained as 94 ◦C [124]. In another experimental
investigation [125], ethanol is chosen as a refrigerant with MIL-101
adsorbent for cooling application. In which, the adsorption isotherm
and desorption performance of ethanol refrigerant on MIL-101(MIL-
101-3) are examined using the high vacuum gravimetric method and
Thermo Gravimetric Analyzer, respectively. It is then observed that the
equilibrium adsorption capacity (at 298 K) and peak T
des
(in Kelvin) are
found to be 0.74 kg/kg and 327 K, respectively. The typical trend of type
I and VI isotherms are noticed for adsorption isotherms.
The adsorption phenomenon of water refrigerant over the surface of
metal–organic frameworks (MOFs) adsorbents such as Basolite™ A100
and Basolite™ F300 is addressed by Henninger et al. [126]. The inves-
tigation observed that Basolite™ F300 gives a higher amount of
adsorption uptake (0.37 kg/kg) than the adsorption uptake (0.34 kg/kg)
of Basolite™ A100. Similarly, another MOF adsorbent (i.e., CAU-10-H)
is also considered for the examination of water adsorption behavior
[127,128]. The S-shape isotherm with a sudden rise in uptake value up
to 0.3 kg/kg at relative pressure ranging from 0.15 to 0.25 is examined
for CAU-10-H adsorbent. Rezk et al. [129] measured the adsorption of
ethanol refrigerant on several MOFs such as MIL-100, MIL-101Cr, MIL-
53Cr, Fe-BTC, CPO-27Ni, and Cu-BTC. The greatest value of ethanol
uptake (i.e., 1.2 kg/kg at 25 ◦C of saturation condition) is achieved for
MIL-101Cr adsorbent. In another existing literature [130], the
maximum BET surface area is obtained for MIL-101 (3017 m
2
/g) fol-
lowed by MIL-100(Fe) (1549 m
2
/g), DUT-4 (1360 m
2
/g), HKUST-1
(1340 m
2
/g), and ZIF-8 (1255 m
2
/g). Moreover, DUT-4 and HKUST-1
own unsteadiness towards the water refrigerant, but the former ex-
hibits hydrophobic character at the same time the latter is extremely
hydrophilic. Amongst all the assorted MOFs, the MIL-101 provides the
greatest water adsorption of 1.34 kg/kg.
A group of researchers reported the comparative effect of alkali
metal ions on water adsorption using modied MIL-101(Cr) and its
parent MOF. The pore volume and BET surface area turn out to be less
when doping the alkali metal ions such as lithium, sodium, and potas-
sium. At high-pressure conditions, the parent adsorbent shows a higher
value of adsorption uptake of water at saturation conditions of 25 ◦C
[131]. Although in a different investigation, the nitro functionalities and
amino are doped in MIL-101Cr to augment the adsorption capacity of
water [132]. The results revealed that the amino-functionalized MIL-
101Cr-NH
2
owns superior adsorption uptake followed by non-modied
MIL-101Cr and nitro-functionalized MIL-101Cr-NO
2
. This is because of
the huge difference in their porous properties like pore volume and BET
surface area.
Adsorption of methanol vapor over the solid surface of porous
crystalline solids (MIL-101(Cr)) is addressed by Solovyeva et al. [133].
The calculated values of specic heating power (0.65–1.95 kW/kg) and
specic heat (385 kJ/kg) encourage the possible use of the MIL-101(Cr)–
methanol pair for adsorption heating. Ma et al. [134] reported work on
the performance of adsorption refrigeration using the MIL-101-
isobutane pair. It is summarised that the SCE for assorted pair is
almost 1.7 times more than that of AC-isobutene pair at T
des
of 95 ◦C,
T
cond
of 30 ◦C, and t
des
of 1800 s. To get better thermal conductivity (i.e.,
approximately 14 times more than that of MIL-101 powder), the MIL-
101(CFCM) adsorbent is cured by copper foam using the binderless
dip-coating method [135]. This investigation using MIL-101 (CFCM)-
isobutene pair showed a reduction of 50% in heating time and an
improvement of 2.6 times in cooling rate; however, the cooling capacity
and volumetric CP are found to be enhanced by 1.8 and 4 times,
respectively.
The MIL-100(Fe) and MIL-100(Al) adsorbents, which possess surface
area of 1917 m
2
/g and 1814 m
2
/g, respectively, are investigated for heat
transformation application by Jeremias et al. [136]. The adsorption
uptake of water refrigerant is obtained greater (0.77 kg/kg) in the case
of MIL-100(Fe) adsorbent in comparison to MIL-100(Al) (0.51 kg/kg) at
25 ◦C. Kim et al. [137] performed work using similar MOFs with iden-
tical isotherms of type IV and observed that these kinds of unsaturated
metals such as Fe, Cr, and Al-doped in MIL-100(M) adsorbent do not
have a noticeable impact on its water adsorption capacity. In another
study, the decrements in the BET surface area and pore volume are
observed while activated MIL-100(Cr) adsorbent is grafted with dieth-
ylene glycol, ethylene glycol, tri-ethylene glycol, and ethylenediamine.
However, it shows a minor upgrade in the adsorption uptake of water in
comparison with non-modied MIL-100(Cr) [138]. It is, most likely,
owing to the augmentation in hydrophilicity of adsorbent material after
grafting with diethylene glycol, ethylene glycol, tri-ethylene glycol, and
ethylenediamine. Many other researchers and pioneers (shown in Fig. 8)
have also contributed their best efforts in the domain of chemical
adsorbent-based adsorption systems with different adsorbates for
various cooling or heating applications.
A comparative graphical investigation in terms of chilling tempera-
ture and regeneration temperature for different chemical WPs has been
P.R. Chauhan et al.

Energy Conversion and Management: X 14 (2022) 100225
10
done in this work (refer to Fig. 9(a)). It can be concluded evidently from
the graph (see Fig. 9) that the lowest T
evap
can be achieved at −50 ◦C
using the chemical adsorbent–adsorbate pair i.e., metal hydride–hy-
drogen WP. Also, the metal chloride–ammonia-based adsorption
refrigeration system is capable to produce a refrigeration effect at
−10 ◦C using a heat source at a temperature of 52 ◦C only. Fig. 9(b)
illustrates the comparison based on performance parameters among the
different chemical WPs. The COP and CP values for the metal chloride-
ammonia WP are found to be comparatively much higher than that of
the metal hydride-hydrogen pair. Furthermore, the COP value is noticed
as more than one in the case of the metal chloride-ammonia pair.
Recent updates on composite and compound adsorbents
To improve the thermal performance of a system, composite adsor-
bents are becoming more popular due to their improved thermophysical
and porous properties such as high packing density, thermal conduc-
tivity, and volumetric adsorption capacity. These improved character-
istics craft it very constructive to build up a compact and efcient
system. There are several physical (AC, silica gel, and zeolite) and
chemical (Metal oxide, metal hydride, and metal carbide) parent ad-
sorbents available with high porous structures and high surface area but
low heat transfer and low packing density to develop composite adsor-
bents. These characteristics can be enhanced by incorporating thermal
conductivity enhancers (TCEs) such as expanded graphite (EG), gra-
phene nanoplatelets (GNPs) [160], carbon nanotube, ZnO, SiC, and
boron nitride. Further, the binder materials such as polyvinyl alcohol
(PVA), polyvinyl pyrrolidone (PVP), polytetrauoroethylene (PTFE),
hydroxyethyl cellulose (HEC), and polymerized ionic liquid (PIL) also
improve the packing density and thermal conductivity. In Fig. 10, a
conceptual schematic diagram is shown for the development of a
consolidated composite adsorbent. Table 4 summarizes the comparative
investigation in terms of COP and CP at different T
cond
, T
reg
, and T
evap
for
various composite adsorbents.
Composites and compounds of silica gel, activated carbon, and zeolites
To achieve a signicant improvement in thermal performance of
ACS, a double effect cascading adsorption cycle using Silica-gel/FAM-
Z01 composite adsorbent is numerically performed [171]. The pro-
posed system utilizes the heat produced during condensation in the top
cycle as the driving heat source for the bottom cycle. It is then observed
that at T
chill,w
of 10 ◦C and T
reg
between 90 and 150 ◦C, the COP and SCP
are found to be superior to that of the silica-gel/silica-gel double effect
cycle. Akisawa et al. [172] presented a static analysis of double stage
VAdRS using two dissimilar adsorbents like FAMZ01 and FAMZ05. A
new design of three beds systems is introduced instead of four beds
conventional system for FAMZ01 and FAMZ05 adsorbent combination
at low- and high-pressure sides, respectively. The uptake values for silica
gel, FAMZ01, and FAMZ05 are calculated using Langmuir expression,
the revised expression addressed by Marlinda et al. [171], and the
revised model of Watanabe and Akisawa [173] with adding the third
term, respectively. The SCE at T
des
of 328 K for a proposed cycle is found
to be greater than that of the conventional silica gel-water adsorption
cycle. Therefore, with an aim to enhance the cooling performance per
adsorbent quantity, the three bed-two stages ACS are recognized as
Fig. 8. Existing chemical WPs for adsorption-based cooling or heating system [139–159].
Fig. 9. T
evap
and T
reg
(a) [102], [132], [159], [120]; and COP and CP [144],
[148] (b) for chemical adsorption working pairs.
P.R. Chauhan et al.

Energy Conversion and Management: X 14 (2022) 100225
11
Fig. 10. Conceptual diagram of consolidated composite adsorbent.
Table 4
Literatures on composite adsorbents for adsorption cooling systems.
Working pairs Approach of
study
No. of
beds
T
evap
(
o
C)
T
cond
(
o
C)
T
reg
(
o
C)
CP COP Applications Ref.
Silica gel and chlorides –
water
Experimental
study
– 5 40 100 – 0.8 * The assorted composite is superior for
various applications at low T
hs
.
[161]
CaCl
2
and AC – NH
3
Experimental
study
Two −15 23 –
27
135 731 W/
kg
0.41 * The proposed ice-making system is
designed for shing boats.
[162]
CaCl
2
and EG – NH
3
Numerical study Two −10 &
−15.6
25 550 5.1 kW 0.94 * This WP requires high temperature of heat
source.
[163]
Silica gel and LiCl –
methanol
Numerical study Single −10 18–24 47 –
57
– 0.33 * A quantity of 20 kg/m
2
of ice can be
produced daily.
[164]
Zeolite & foam Al – water Experimental
study
Two 10 40 400 650 W/
kg
0.55 * More appropriate for trucks or long-
distance coaches.
[165]
Silica gel and LiCl – water Numerical study Two 20 30 90 5.295
kW
0.43 * To resolve the refrigerant unbalance that is
because of mass recovery.
[166]
Silica-AC and CaCl
2
–
water
Numerical study Two 9 30 85 380 W/
kg
0.65 * The proposed composite adsorbent is
greatly efcient for VAdRS.
[167]
LiNO
3
and vermiculite –
water
Experimental
study
Single 10 35 90 230 W/
kg
0.66 * Capable for air conditioning and heat
storage purposes at low T
hs
.
[168]
Barium halides and
vermiculite – NH
3
Experimental
study
– −5 30 90 –
100
1.2 W/g – * The rate of ice making is obtained as 2 kg/
(kg-h).
[169]
NaBr and EG - NH
3
Experimental
study
Single 10 – 85 3.16 kW 0.28 –
0.48
* More useful for air conditioning purposes at
low T
hs
.
[170]
P.R. Chauhan et al.

Energy Conversion and Management: X 14 (2022) 100225
12
protable in comparison to the conventional four bed-two stage system.
Two consolidated carbon-based composite adsorbents are synthe-
sized having different densities, grain size, and volumetric fractions,
later on; thermo-physical properties are also evaluated [174]. The steps
for production of composite adsorbent are shown in Fig. 11 which
consists of drying processes of granular expanded natural graphite
treated with sulphuric acid (ENG-TSA) (a), granular AC (b), a combi-
nation of water and granular AC (c), composite adsorbent of AC, water,
and ENG-TSA (d), compression of composite (e), drying of consolidated
composite adsorbent (f), consolidated composite adsorbent for investi-
gation (g). Scanning Electron Microscopy (SEM) images are shown in
Fig. 12 for consolidated composite adsorbents. The wormlike structure
(Fig. 12(a) and (b)) is observed for low-density samples; however,
layered structure (Fig. 12(c) and (d)) is noticed for large density samples
of ENG-TSA. The results demonstrated that the greatest thermal diffu-
sivity and effective thermal conductivity of carbon-based consolidated
composite are estimated as 72 times and 150 times greater than that of
regular granular AC, respectively. Moreover, it can be concluded that
the accumulation of ENG-TSA can enhance the system performance by
raising the concentration swing.
An adsorption uptake behavior of AQSOA using water as adsorbate is
studied for ACS [175]. The property analysis of AQSOA zeolite is
completed by numerous experimental technologies like Field Emission
Scanning Electron Microscopy, X-ray diffraction, thermo gravimetric
analysis, and nitrogen adsorption/desorption isotherms. Though, the
adsorption enthalpies are determined with the help of Clausius Cla-
peyron formulation. It is investigated that at the low-pressure side, the S-
shape isotherm is observed for water vapor adsorption on AQSOA-Z01
with a hydrophobic phenomenon. Moreover, at T
des
of 338 K, a high
value (0.1 kg of water per kg of zeolite) of H
2
O vapor uptake is found
from the porous surface of AQSOA-Z01 for a single adsorp-
tion–desorption cycle. Pal et al. [176] experimentally worked on the
characterization and synthesis of GNP (H & C grade) and PVA-contained
AC composite adsorbent to get better the performance and compactness
of the cooling system. The effect of GNP on the thermal conductivity,
porous properties, and ethanol adsorption characteristics of composites
is also observed. It is concluded that the porous properties of composite
employing C-grade GNP are found to be more than that of H-grade (40
wt%) contained composite. The thermal conductivity is observed high-
est (1.55 W/m-K and 23.5 times greater than that of powder AC) for H-
grade composite. The effective volumetric uptake for H25 (20 wt%)
contained composite is calculated as 23% greater compared to the
parent AC. A comparative investigation in terms of COP, chilling tem-
perature, and regeneration temperature has been done in this work as
shown in Fig. 13. It can be addressed that the best performance is
observed in the case of CaCl
2
and EG-ammonia pair; however, silica gel
and LiCl-methanol pair show the great potential to generate the refrig-
eration effect at much lower regeneration temperature.
An experimental work is performed on the N
2
gas adsorption fol-
lowed by water uptake behavior on FAMZ01 at a temperature ranging
from 293 K to 353 K for the potential use in adsorption cum desalination
system (ACDS) [177]. Furthermore, a hybrid AIM (combination of
Henry and the Sips isotherms) for water adsorption on the FAM-Z01
adsorbent is proposed. The comparison of adsorption isotherm curves
for type–A5BW silica gel, FAM Z01, and type–RD2560 silica gel adsor-
bents are studied at different T
ads
and T
des
. The equilibrium uptake of
water vapor on FAM-Z01 adsorbent is found to be 2, 3, and 5 times
greater compared to Type-A5BW silica gel, Type-A++ silica gel, and
Type-RD 2560 silica gel, respectively. Al-zareer et al. [178] theoretically
investigated a novel thermo-chemical energy storage system using
strontium chloride ammonia as a solid gas couple for various heating
and cooling applications. It is evaluated that the greatest exergy and
energy efciencies for cooling applications are calculated as 22.9% at
T
chill
of −35 ◦C and 29.3% at T
chill
of 0 ◦C, respectively. Goldsworthy
[179] studied various adsorption isotherms of water vapor (adsorbate)
on RD silica gel, CECA zeolite 3A, and AQSOA series like Z01, Z02, and
Z05 at partial vapor pressures between 1 and 500 bar and temperatures
ranging from 293 K to 443 K. The least-square tting approach is applied
to calculate the variations in isosteric heat and compared over a wide
range of adsorption uptake for all assorted adsorbents. It is observed that
for uptake beyond 10% of the greatest value, the adsorption heats are
found to be 1 and 1.6 times more than the vaporization heat for all
working pairs.
Regarding the performance enhancement of VAdRS, the adsor-
bent–adsorbate pair acts as a key function. Therefore, the selection of
good quality WP is becoming a most important task. The present section
aims to recapitulate the novel research and developments on the
application of composite adsorbent-adsorbate pairs in VAdRS. Also, the
size and work efciency of the VAdRS depend on specic heat capacity,
surface area, adsorption capacity, packing density, and pore volume. An
experimental investigation is performed to improve specic heat ca-
pacity [180]. To make the system compact, lightweight, and more ef-
cient, the design of the thermal compressor needs to be modied by
improving the heat transfer mechanism using various approaches like
coatings on adsorber/desorber [181], which includes binder-based,
thick, and crystallization. At micro level investigations, the particle
size [182], and thickness of the coating layer [183] are critical param-
eters for lowering the heat barriers existing in the adsorbent material,
resulting in faster overall adsorption dynamic. Also, covalent-organic
frameworks (COFs) with large pores and MOFs with small pores have
unique and enhanced adsorption properties that make them more suit-
able for the high and low-temperature stages of cascade adsorption heat
pumps (AHPs) [184].
The various steps for synthesizing the composite adsorbent are
depicted in Fig. 14. The MaxsorbIII is assorted as parent adsorbent;
however, the water, PVA, and EG are used as a solvent, binder, and TCE,
Fig. 11. Synthesis action of carbon-based consolidated adsorbent [174].
P.R. Chauhan et al.

Energy Conversion and Management: X 14 (2022) 100225
13
respectively. Initially, the moisture and unwanted gases are removed
from the parent adsorbent and TCE by drying at 120 ◦C for 6 h. On the
other hand, the solvent is poured into the binder powder to make a
solution. Afterward, a predened fraction of parent adsorbent and TCE
are mixed properly, later on; this mixture is added with the solution of
binder and solvent. The pressure of 15 MPa is applied to this mixture
using a compression machine and then dried at 120 ◦C for 24 h. Several
composite adsorbents can be synthesized by altering the mass propor-
tion of the ingredients, which can be further useful for cooling appli-
cations. Berdenova et al. [185] comprehensively investigated CO
2
adsorption-based novel small-sized VAdRS using a new composite
adsorbent which is made up of AC (as a parent adsorbent), GNP (to
improve the thermal conductivity), and hydroxyl cellulose (as a binder).
The consolidated adsorbent with improved thermal conductivity (i.e.,
233% higher than that of parent AC), uptake capacity, pore-volume, and
surface area is accountable to reduce the overall size of the VAdRS. The
uptake of CO
2
is evaluated at the temperature ranging from 293 to 343 K
from an excess amount of adsorption quantity by averaging two methods
((a) V
a
=V
pore
, and (b) V
a
=0 at P → 0 and/or T → ∞).
An experimental investigation on thermodynamic performance
assessment of MaxsorbIII-HFC404A pair-based VAdRS is performed at a
temperature ranging from 25 ◦C to 75 ◦C [186]. The optimal values of
SCP and COP are estimated as 275 W/kg and 0.23, respectively. The
enhancement in uptake value of water adsorption on zeolite and GNP
synthesized composite adsorbent is estimated at up to 42.8% [187]. The
cost optimization analysis for a VAdRS using two different WPs such as
AC-R134a and AC-diethyl ether is carried out [188-190]. It is expressed
that the optimum value of exergetic efciency for the AC-R134a pair is
found to be 79% greater than that of the AC-diethyl ether pair. The
thermodynamic assessment of VAdRS for three different temperature
limits (T
reg,min
, T
reg,max
, and T
reg,opt
) of heat sources using two dissimilar
adsorbent–adsorbate pairs like MaxsorbIII–ethanol and
MaxsorbIII–R134a is performed by Banker et al. [191], statistically. The
overall cost values for AC-R134a and AC-diethyl ether pairs are dimin-
ished by 1% and 0.57%, respectively.
Composites and compounds of COFs
Many research attempts [187,192-206] have been carried out to
develop innovative composite and compound materials that may be
employed as an adsorbent to increase the performance of AHPs and
ACSs. A unique material containing zeolite 13X and LiCl and CaCl
2
is
synthesized and afterward offered as an adsorbent with water adsorbate
[195]. The D-A isotherm model is determined to be the ttest, with
water uptake 5.3 times that of zeolite 13X. Additionally, an increase in
LiCl content in composite adsorbent boosts adsorption capability. P´
erez
et al. [196] used the Crank-Nicholson technique with a nite-difference
mechanism to perform a time-dependent analysis on a two-dimensional
axisymmetric thermodynamic model of a thermal compressor having
ns on its exterior. Experimentally, a composite consisting of AC, EG,
and LiCl with ammonia refrigerant gives SCP up to 30 W/kg. The heat
and mass transfer phenomena of ammonia refrigerant are investigated
in a thermal compressor containing a composite of CaCl
2
and EG [197].
According to the research ndings, with rising temperature, the rate of
adsorption reduces, whereas the rate of desorption decreases. Using a
hydrothermal technique, Liu et al. [198] successfully prepared a com-
posite material having MIL-101(Cr)/CaCl
2
for the application as an
adsorbent in AHPs. At 25 ◦C, the COP and SCP values are 0.172 and
136.9 W/kg, respectively; however, lowering the T
ads
by 5 ◦C increases
both parameters to 0.18 and 142.4 W/kg, respectively. Also, both COP
and SCP improve as T
evap
rises. A cost model of the complete adsorption-
based refrigeration system is also given in terms of economic analysis
[199].
Elsayed et al. [207] numerically addressed the water adsorption on a
Fig. 12. Scanning Electron Microscopy (SEM) pictures of consolidated composite adsorbents: (a) AC 33%, 278 kg/m
3
, 50.3×; (b) AC 67%, 250 kg/m
3
, 53×; (c) AC
33%, 430 kg/m
3
, 50.6×; (d) AC 67%, 448 kg/m
3
, 49.7×[174].
P.R. Chauhan et al.

Energy Conversion and Management: X 14 (2022) 100225
14
novel MIL-101(Cr)/CaCl
2
composite adsorbent. MIL-101(Cr) having an
excellent thermal property is used as a parent adsorbent, while the
incorporation of calcium chloride improves its water uptake value. The
numerical results revealed that at the denite values of T
w,in
(i.e. 283 K)
and T
des
(i.e. 363 K), the SCP values are found to be 168 W/kg, 248 W/
kg, and 388 W/kg for pure MIL-101(Cr), Comp_1:5 (one part of MIL-101
(Cr) and 5 parts of CaCl
2
salt), and Comp_1:8 (one part of MIL-101(Cr)
and 8 parts of CaCl
2
salt), respectively. Moreover, at a half t
cyc
of 500
s and T
chill,w,in
of 288 K, the COP values are calculated as 0.247, 0.262,
and 0.35 for pure MIL-101(Cr), Comp_1:5, and Comp_1:8, respectively.
It is stated that with an increase in T
evap
the SCP and COP values are
found to be improved; however, it is reverse in the case of T
ads
[208].
The effect of the dynamical adjustment in half t
cyc
on the thermal
performance of a solar-driven single-stage two-bed VAdRS is also
numerically investigated [209]. Sinha et al. [210] performed numerical
work on a solar-powered VAdRS using a new combination of composite
absorbents and heat transfer uid under unsteady state conditions. The
assorted coolant is the mixture of Graphene nanoakes (GNF) and multi-
walled carbon nanotubes (MWCNT); however, the activated carbon
ber (ACF) with either nickel chloride salt or barium chloride salt are
used as an adsorbent. It is analyzed that the greatest COP and the
maximum CP for ACF with nickel chloride salt-ammonia, ACF with
barium chloride salt-ammonia, and silica gel-water are calculated as
0.58 & 14.7 kW, 0.92 & 14.7 kW, and 0.47 & 12.6 kW, respectively.
Moreover, the COP values are found to be enhanced by 23.4% and
95.7% for ACF with nickel chloride salt and ACF with barium chloride
salt, respectively. A novel solid composite, a combination of UiO-66 and
CaCl
2
, is used as an adsorbent in adsorber to improve the uptake mass of
water without dissolutions [211]. It is observed that the COP and SCP for
composite adsorbents having UiO-66 and CaCl
2
(53%w/w) are found to
be 0.83 and 631 W/kg, respectively.
Thermal energy-assisted single effect VAdRS functioning with the
combination of n-butane (adsorbate) and different hydrocarbons
(adsorbent) is investigated computationally [212]. It is concluded that
the butane-heavy naphtha pair shows the greatest performance in terms
of COP value (i.e., 0.78) among all the assorted WPs. Gao et al. [213]
experimentally analyzed an adsorption-based chilling system with a new
multi-salt adsorbent of CaCl
2
/MnCl
2
over a wide range of temperatures.
The proposed system is powered by exhaust gas recirculation to cut
down the excess fuel requirement under different operating circum-
stances for chilling purposes in a lightweight refrigerated truck. The
design of the adsorber is modied in such a way that the exchange of
heat from the engine’s outgoing gases and atmospheric air can easily go
on. It is then noticed that at T
reg
of 473 K and T
amb
of 298 K, the greatest
CP is calculated as approximately 2.4 kW for t
cyc,opt
of 65 min.
Furthermore, the desired temperature of the air to be supplied is ach-
ieved within three minutes of the start, while the greatest value of SCP (i.
e., 260 W/kg) is obtained at a COP of around 0.4 for the T
chill
ranging
from −15 ◦C to 5 ◦C. The performance of VAdRS can also be boosted by
synthesizing the alumina-phosphate with the parent adsorbent [214].
Tso et al. [215] numerically worked on the performance enhancement of
an ACDS by employing a new composite adsorbent (MWCNT-embedded
zeolite 13X/CaCl
2
). The SCP and specic daily water production (SDWP)
under the inuence of different variables like T
cool,w,in
, T
des
, T
chill,w,in
,
t
cyc,des
, and t
cyc,ads
are investigated computationally. The result
demonstrated that the SCP and SDWP using the synthesized composite
adsorbent are improved by 40% and 190%, respectively.
Raya et al. [216] experimentally addressed an investigation on
adsorption technology-based heat pumps (AHPs) using CPO-27(Ni),
MIL-100(Fe), and aluminum fumarate adsorbents. Among all the
cases, the maximum SCP is achieved as 226 W/kg for MIL-100(Fe) at
95 ◦C followed by aluminum fumarate. As far as the water production is
concerned, the SDWP is also accomplished the greatest (19 m
3
/ton/day)
for MIL-100(Fe). The effect of saltwater salinity on the thermal perfor-
mance of a novel composite adsorbent (MWCNT embedded zeolite13X-
CaCl
2
) based low-grade energy powered ACDS is studied,
Fig. 13. COP (a); T
evap
and T
reg
(b) for various composite adsorbents.
Fig. 14. Steps for manufacturing the composite adsorbent [180].
P.R. Chauhan et al.

Energy Conversion and Management: X 14 (2022) 100225
15
experimentally [217]. The results demonstrated that the SCP and SDWP
values are found to be 490 W/kg and 18 m
3
/tonne-adsorbent/day at
denite operating conditions (t
cyc
=1140 s, T
des
=85 ◦C, T
cool,w,in
=
24 ◦C, and T
evap
=14 ◦C). Additionally, a mathematical model is also
developed by considering mass recovery and variable properties of sa-
line water. Recently, many research attempts [218-223] have been
made towards cooling and water production using adsorption
technology.
Composites and compounds of MOFs
Owing to their target-oriented design, structural diversity, and
extraordinary adsorption properties, a new adsorbent known as MOFs
has recently been synthesized, attracting thermal scientists to use it for
numerous purposes such as water harvesting [224] and energy con-
version. For the rst time, the MOF materials are used as an adsorbent to
replace the traditional adsorbent in adsorption-based heat pumps, with
improved results by implementing a computational uid dynamic
[225]. Other new MOF adsorbents like UiO-66 (Zr) [226], CPO-27(Ni)
[227] with water are utilized for cooling and desalination purposes,
with enhanced adsorption characteristics. Gordeeva et al. [228] give a
thorough assessment that bridges the gap between material science and
thermal research. For analyzing cooling efcacy, a cascade adsorption
cooling system using UiO-66, DUT-67, and NU-1000 MOFs, as adsor-
bents along with water refrigerant is studied [229]. In terms of the
highest COP, the DUT-67 - water pair is discovered to be the best. In
terms of techno-economic analysis, a computational investigation is also
available for two distinct MOFs as adsorbent materials in VAdRS [230].
A schematic representation of the modulated synthesis of MOF and COF
is shown in Fig. 15.
The development and employment of COFs as an adsorbent is fuel-
ling attention to do research in the eld of AHPs. To determine the most
efcient with improved adsorption characteristics COFs for various
cooling and refrigeration purposes, Li et al. [231] introduced machine
learning and grand canonical Monte Carlo computational techniques.
Xia et al. [232] created a COF-5 material including hexahydrox-
ytriphenylene, benzenediboronic acid, and methanol, that has been
later employed as an adsorbent with ethanol adsorbate in AHP. The
COF-5 – ethanol pair had the highest cooling and heating COPs of all the
pairs evaluated. P´
erezCarvajal et al. [233] conducted research and
concluded that imine-based COF can substitute typical composite ad-
sorbents in VAdRS. The results showed that employing T
hs
below 65 ◦C
and TpPa-1 and water pair can generate a cooling effect with a COP of
0.77.
Coated and nned tube adsorption reactors
In ACS, the poor heat and mass transfer difculties can be mitigated
by improving the thermal conductivity of the adsorbent and heat
exchanger material and by increasing the surface area of the heat
exchanger elements or modifying the bed structure to reduce the contact
thermal resistance. In view of the that, an innovative and coated
adsorber [234], two innovative coating processes [235], different
coating materials such as Cu, Al, and stainless steel [236], and a micro-
size at plate type plastic adsorber [237] are proposed to improve the
performance of ACS. The ndings of the experiments show that a higher
COP value can be reached with a lower sorbent particle size. According
to the numerical data, Al adsorber has the best performance in terms of
COP, SCP, and ex, followed by Cu and stainless steel. The coating
thickness is also an important parameter in adsorber design [238]. It is
noticed that the COP is maximized corresponding to a 1.75 mm coating
thickness. With the intention of improvement in system performance, a
ned tube adsorption reactor is computationally addressed along with
heat and mass recovery schemes [266]. The various published pieces of
Fig. 15. Modulated synthesis of MOF (a) [59]; and COF (b) [232].
P.R. Chauhan et al.

Energy Conversion and Management: X 14 (2022) 100225
16
literature are also available on the effect of n thickness, radius, and
spacing. It is observed that the smaller ns are predominantly better
[239]. Fig. 16 depicts schematics of several externally coated metal
tubes adsorber and rectangular, wire nned, and microchannel adsorber
to improve heat and mass transfer mechanism.
The feasibility of a unique design and conguration that includes an
embedded condenser inside the shell and a tube-type sorption reactor is
being examined [240]. A multi-objective genetic algorithm, as well as a
new design of three axial nned tubes adsorber, are used to improve
operating parameters [241]. This algorithm is then determined to be
useful in solving difcult optimization issues, as well as improving the
COP and SCP by 21% and 51.7%, respectively. Experimental work has
been carried out on simple, annulus, modied annulus sorption reactors,
individually as well as in combination [242]. Also, the increment in bed
aspect ratio increases the uptake value resulting in further enhancement
in the thermal performance by improving the HT rate up to 22.2% [243].
Based on the available works of literature, it can be concluded that the
conguration of the adsorbent material, as well as the sorption reactor,
is also benecial in achieving the high performance of ACS.
Conceptual design of biomass gasication powered adsorption chiller
In hot regions of the world or India where there is a lack of elec-
tricity, the heating unit is necessary to meet the energetic expectations
for the regeneration process in VAdRS. The thermal energy from sun-
light, biomass combustion, or a collection of both can be an option. In
view of that, a conceptual schematic of biomass-powered VAdRS is
presented in Fig. 17. In which the biomass-derived pellets are used to
Fig. 16. Schematics of several externally coated metal tubes adsorber (a) [238]; rectangular, wire nned, and microchannel adsorber (b) [239].
P.R. Chauhan et al.

Energy Conversion and Management: X 14 (2022) 100225
17
produce the heat energy caused by combustion inside the combustion
devices like biomass boilers, biomass stoves, particularly for small
prototypes [244-247], biomass gasiers, and CO
2
-based energy storage
systems [248,249]. This energy is further utilized to increase the tem-
perature of hot uid that ows inside the adsorber/desorber tubes for
the regeneration of refrigerant vapor. Biomass refers to various organ-
isms formed through photosynthesis, including all animals, plants, and
microorganisms. It has the advantages of abundance, low pollution, and
renewability, and is an important biological resource on the earth. The
term biomass generally refers to all plants such as tobacco stems, wood
chips, bagasse, fruit shells, and microbes such as algae and fungi. It is an
important biological resource on the planet, with advantages such as
abundance, low pollution, and renewability. These materials not only
work well in the medicine and waste water treatment eld but also has a
good impact on composites for various applications in cooling and
heating. Therefore, it can be inferred that the biomass material, which is
highly porous and abundantly available in nature, is a sustainable, eco-
friendly option to meet the requirements of adsorbent as well as a
combustion fuel for a heat source for adsorption technology-based AHPs
and ACSs.
It is well known that millions of tons of biomass are being burnt
annually around the globe particularly, in the open eld, releasing
millions of tons of harmful pollutants (ne and ultra-ne particulate
matters, carbon monoxide, oxides of Nitrogen, etc.). For which the sci-
entic community and policy makers are looking for sustainable
disposal including, the value-added products, waste to wealth, etc.
Further, some useful applications are being thought of and authors are
trying to develop suitable adsorbents in the laboratory using different
types of biomasses available locally. With a focus on further enhance-
ment in thermal performance of VAdRS, the various strategies along
with highly porous adsorbent materials like heat recovery [250,251],
mass recovery [252-254], and combined heat and mass recovery [255-
260], multi-bed [261-266], multi-stage [267-270], hybrid and inte-
grated systems [271-283], and coatings of composite materials [284-
287], desiccant materials [288-290], and hybrid materials [291] on
adsorber/desorber, have also been thoroughly investigated experimen-
tally as well as numerically for low-temperature refrigeration, cooling,
and heat pump application in industrial sectors [292,293], space heating
[294-296], ofce buildings [297], and domestic sectors [298-300].
Conclusions and future perspectives
In the previous two decades, the research on adsorption technology-
based cooling and heating systems has promptly increased because of
ecological and power consumption issues. The consolidated composite
adsorbents are gaining more attention as parent adsorbents have less
packing density and pitiable heat transfer performance. Though, the
overall performance of the composite adsorbents has not yet reached the
expected point. Finding the best working pair for a distinctive adsorp-
tion cooling application is always a challenge. Therefore, the present
review article focuses on the enhancement of performance of green
cooling systems using physical/chemical, composite, compound adsor-
bents considering physical structure, adsorption equilibrium, the inter-
action between sorbate and sorbent, and various working parameters.
The major ndings derived from this review study are given below:
•The COP, SCP, and chiller efciency are noted as increasing with a
rise in heat source temperature.
•After attaining a zenith, the COP is found to be diminishing with an
increase in adsorbent–adsorbate mass ratio; however, a signicant
decrement in SCP is observed with an increase in mass ratio at
constant desorption temperature.
•At a constant value of cooling temperature, both COP and SCP attain
a peak later on decreases with an increase in desorption pressure.
•Both COP and chiller efciency is found to be consistently improved
with increment in cycle time; however, the cooling power achieves a
peak before decreasing with an increase in cycle time for adsorption/
desorption.
•The maximum adsorption uptake (2.34 kg/kg) is observed for R-32
adsorption onto phenol resin-based AC at 303 K and 16.70 bar.
Fig. 17. Proposed schematic diagram of biomass-powered adsorption cooling system.
P.R. Chauhan et al.

Energy Conversion and Management: X 14 (2022) 100225
18
Maxsorb-III, on the other hand, is highly microporous and has a
greater surface area, resulting in strong adsorption uptakes for the
majority of the adsorbate.
•The COP and SCP values are found to be enhanced with enhancement
in refrigeration temperature at a constant value of cycle time.
•The biomass-derived adsorbents show the substantial potential to use
as an adsorbent in VAdRS for producing a signicant cooling effect.
•The composite adsorbent of silica gel and LiCl with methanol as
adsorbate is noticed capable to produce the refrigeration effect at the
lowest regeneration temperature of 58 ◦C.
•The lowest refrigeration temperature can be achieved at −50 ◦C
using the chemical adsorbent–adsorbate pair i.e., metal hydri-
de–hydrogen pair.
•The incorporation of CaCl
2
into MOF such as MIL-101(Cr) is
accountable for considerably enhancing the system performance.
•The COP values are found to be enhanced by 23.4% and 95.7% for
ACF with nickel chloride salt and ACF with barium chloride salt,
respectively.
•S-type or type V adsorption isotherms can be seen in zeolite-water
combinations like AQSOA-Z01, AQSOA-Z02, and AQSOA-Z05, indi-
cating pore lling processes that allow for increased adsorption up-
take over a small pressure range.
•MIL series-based MOFs, such as MIL-101(Cr) and MIL-53(Al), have
stable structures and show type-IV and type-V adsorption isotherms,
and have been identied as potential adsorbents for ACDS.
•In terms of SCP and SDWP, the coated wire nned tube performs
better than the packed and combined packed/coated adsorber beds.
Furthermore, it is observed that the TCEs (EG and GNP) and binder
(PIL) have more impact on the thermophysical characteristics of
consolidated composite adsorbent. Thus, future research should be
conducted on the production of promising TCEs and binders that will
lead to synthesizing efcient and next-generation composite adsorbents.
Although, a lot of investigations are still required to be made in the
adaption of new composite adsorbent and adsorbate pairs for extensive
applications of cooling in various sectors like industry, automobile, and
agriculture. Also, the performance of adsorbents in the adsorption
cooling system depends upon micro- and macro pores, their surface area,
the size of granules in powder, etc. Therefore, the various parameters
such as heat of adsorption, the heat of desorption, adsorption uptake,
BET surface area, a quantity of refrigerant adsorbed/desorbed at a
particular time, and adsorption–desorption characteristics, pore size and
pore volume, and cycle time are still needed to be explored compre-
hensively. Concerning some issues of ACS like low efciency, bulkiness,
and high initial cost, the scientists and researchers have been motivated
to develop the carbons-based adsorbent from biomass waste that could
be a promising adsorbent material in the near future due to its well-
dened heterogeneous micro/nanostructures and morphology. Also,
the biomass material, which is carbon neutral and abundantly available
in nature, could be utilized as a combustion fuel for heating units. As a
result, biomass can be utilized as an adsorbent as well as the combustion
fuel for the heating source in ACS. In view of heavy size, and poor heat
and mass transfer mechanism, the adsorbent material is not only a
concern but there is another aspect in form of the design of the sorption
reactor which needs to be further considered. The sorption reactors used
in research are typically enormous and heavy and occupy a huge space
in automobiles. Therefore, designing a compact-sized thermal
compressor for air-conditioning purposes in vehicles is still a current
challenge for the researcher and scientic community in the eld of
adsorption technology-based cooling systems. The authors expect that
this review contribution will be benecial for researchers and scientists
in the development of compact and efcient adsorption refrigeration
systems.
CRediT authorship contribution statement
P.R. Chauhan: Investigation, Formal analysis, Resources, Writing –
original draft. S.C. Kaushik: Supervision. S.K. Tyagi: Conceptualiza-
tion, Writing – review & editing, Supervision.
Declaration of Competing Interest
The authors declare that they have no known competing nancial
interests or personal relationships that could have appeared to inuence
the work reported in this paper.
Acknowledgements
One of the authors (PRC) thankfully acknowledges the nancia-
l assistance in the form of fellowship due to Indian Institute of Tech-
nology Delhi. Sincere thanks are also due to learned Reviewers for their
critical review and suggestions to improve the manuscript in the present
form.
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