1

CHAPTER 1
INTRODUCTION
Nature works much like a heat engine, heat flows from high temperature
elements to low temperature elements. As it does this, work is also done on its
environment. Refrigeration is a process to keep an element cool or to reduce the
temperature of one element below that of the other. The refrigeration process is
like a reverse heat engine, where heat is taken from a cold element to be
transferred to a warmer element, generally by adding work to the system. In a
heat engine, work is done by the system so in order to do the reverse work must
be done on the system.

This work input is traditionally mechanical work, but it can also be driven by
magnetism, lasers, acoustics, and other means. Several different types of
refrigeration systems which utilize different work input were considered for this
work. They are the vapor compression system and the absorption/adsorption
refrigeration system. In recent developments of thermal engineering the
refrigeration technologies play an important role in today's industrial
applications. But as far as COP of this refrigeration system is concerned, it is
always a challenge to the researchers to significantly increase the COP for these
systems. The most popular refrigeration and air conditioning systems at present
are those based on the vapor absorption/adsorption systems. These systems are
popular because they are reliable, relatively inexpensive and their technology is
well established. However, these systems do not require high-grade energy
(mechanical or electrical) for their operation.

Apart from this, the recent discovery that the conventional working fluids of
vapour compression systems are causing the ozone layer depletion and
greenhouse effects has forced the scientific researchers to look for alternative
systems for cooling applications. The natural alternative is of course the
adsorption system, which mainly uses heat energy for its operation. Heat can be
a waste heat in engines, power plants, geothermal energy, Solar energy, ..etc.
Moreover, the working fluids of these systems are environment friendly. A
suitable working fluid is probably the single most important factor in any
refrigeration system. The cycle efficiency and operation characteristics of an
adsorption refrigeration system depend on the properties of refrigerant, adsorbent
and their mixtures. The most important thermo-physical properties are heat of
vaporization of refrigerant, vapour pressure of refrigerant and adsorbent,
solubility of refrigerant in solvent, heat capacity of solution, viscosity of solution
and surface tension and thermal conductivity of the solution. Apart from this, the
other selection criteria for the working fluids are their toxicity, chemical stability
and corrosiveness. Simultaneous heating and cooling are required in many
industries such as dairy plant, pharmaceutical, chemical etc. Adsorption systems
have been extensively paid attention in recent years due to the potential for CFC
and HCFC replacements in refrigeration, heating and cooling applications.
 2

Despite a lower coefficient of performance (COP) as compared to the vapour

compression cycle, adsorption refrigeration systems are promising for using
inexpensive waste energy from industrial processes, geothermal energy, solar
energy etc.

1.1 CLASSIFICATION OF SOLAR REFRIGERATION CYCLE

FIG.1.1 CLASSIFICATION OF SOLAR REFRIGERATION CYCLE

Each of the methods, except the adsorption cooling technique, maintains the
advantages of its conventional type but suffers from certain limitations. PV
refrigerators, in spite of their commercial success among solar refrigerators, have
high installed cost and bleak prospects for on the rural site manufacture. Liquid
absorption units have the problem of generating some absorbent with the
refrigerant during generation, thus requiring rectification. Solid absorbents
characteristically disintegrate after repeated cycles of operation, as in the case of
the CaCl2/NH3 pair. Most often, special treatments of the absorbents are needed
to obtain hard porous granules, thereby increasing the system first cost. Solar
adsorption refrigerators do not possess these disadvantages. The concept of using
solar energy for powering a refrigerator arose 40 years ago. Besides conventional
refrigerators powered by photovoltaic cells, heat powered machines work with
either liquid or solid sorption cycles. Solar refrigerators with liquid sorption, Li-
Br + water or water + ammonia, have been studied by many authors.

However, the use of liquid sorption for solar cooling induces two features. First,
liquid sorption cycles operate continuously, while solar energy is inherently
transient during the day and vanishes during the night. A large heat-storage must
then be installed between the solar collectors and the generator. Second, the
solution is most often circulated by a pump working all day long. This pump
consumes electricity that must be supplied by photovoltaic cells or a reliable
electricity network. It therefore results that hybrid power (solar + fuel) suits liquid
sorption well. Solid sorption works differently. First, the cycles are by principle
 3

transient: heat is accumulated in the sorbent resulting in desorption of refrigerant

vapour and only a cold-storage is necessary for providing refrigeration over the 24
h period. Second, the cycle itself works without any mechanical input or moving
parts. In addition to reliability, full autonomy with solar energy should be
achievable, which is very attractive for installation in remote areas. There are two
solid sorption systems likely to be solar-powered: chemical reaction and
adsorption. After pioneering works, chemical reaction solar refrigerators are
evoking new interest thanks to novel composite materials impregnated with
chloride salts. Solar-powered adsorption systems have been investigated by
several groups.

In addition to models, real machines have been developed. Some of them use
sophisticated solar collectors with concentration, others use the adsorbent itself,
contained in a transparent tube, as the solar-energy-absorbing material, but the
most efficient configuration seems to consist of metallic flat-plate solar collectors,
single- or double-glazed, covered with a selective surface and filled with the
adsorbent bed.

1.2 NEED OF SOLAR ENERGY DRIVEN REFRIGERATION

Most of the cooling systems operate on vapour compression refrigeration cycle.
This system generally consumes electrical energy that is high-graded and costlier
too. Also, large-scale consumption of electricity from conventional resources like
fossil fuels poses serious problems to be solved with utmost care and concern.
The immediate solution to mitigate from environmental issues is to emphasize all
energy-consuming sectors to utilize renewable energy sources such as solar
energy, wind energy and so on in addition to waste heat from industrial processes.
Among the known alternate energy sources, solar energy is proved to be easily
accessible for electricity-starved places located in tropical regions (on our mother
planet, the Earth). Though solar energy is dilute and intermittent, its choice for
refrigeration is attributed to its availability in abundance and non-polluting nature.
In recent years, heat-driven refrigeration systems have drawn significant
consideration due to their lesser environmental impact and large energy-
equivalent potential. The common heat-operated cooling system(s) that can be
operated with solar energy are vapour absorption refrigeration system, vapour
ejector refrigeration system and vapour adsorption refrigeration system. LiBr-
water and aqua–ammonia absorption systems are commercially available.
However, they generally suffer from disadvantages like crystallization, inability
to realize sub-zero evaporator temperature as in case of LiBr-water system and
while, corrosion and toxicity problems encountered in aqua– ammonia absorption
system and further, they demand specialized skill for construction and
maintenance. A vapour ejector refrigeration system requires a sophisticated and
accurately designed ejector to run the system effectively and efficiently. However,
a vapour adsorption refrigeration system is found to be more attractive for the
reasons, that it is simple in construction and involves negligible operation and
 4

maintenance costs besides, this system requires no skilled-man power and can be
installed in any hilly areas or isolated lands.
 5

CHAPTER 2
LITERATURE REVIEW
The main objective of the literature review is to provide an appraisal of the new
state of the art in the field of solar refrigeration techniques. In this context,
literature on importance of solar cooling and sorption techniques involved in the
cooling systems are emphasized. One of the most important applications of
refrigeration is the preservation of perishable food products, precious and vital
medicines, by storing them at low temperature. In earlier days, the technique of
cooling was started with utilization of ice derived through natural sources and
processes, but the requirement of ice in large quantity and a suitable method to
protect the cooling ice from melting have pushed the technocrats to develop an
artificial technology for producing ice in large quantity. Thus, the history of
artificial refrigeration began with the birth of laboratory-scale refrigerating
machine invented by the Scottish Professor William Cullen from University of
Edinburgh in 1755. Various research papers have been studied to understand
concept properly and to study present work done in the field of vapour adsorption
for refrigeration and air conditioning applications. Solid vapour adsorption is
similar to liquid vapour absorption system, except that the refrigerant is adsorbed
on the surface of another solid known as adsorbent.

2.1 SOLAR COOLING TECHNIQUES

The solar cooling techniques are to diminish the environmental ramification and
provide economic solution to the energy consumption issues raised by traditional
cooling methods. The use of sorption processes to produce refrigeration has been
extensively studied from the first half of the last century. Heat operated thermally
driven sorption cooling cycles are existing from 1909. Miller and Walter (1929)
listed a number of systems that utilized silica-gel and sulphur dioxide as the solid
sorbent -refrigerant pairs. Later research in this area were sedate the concept of
solar operated refrigerator was appeared about half a century back with the first
model using a liquid-based sorption cycle as discussed by Sumathy and
Zhongfu(1999a). The four-core heat operated solar energy assisted cooling
systems available are absorption, ejector, desiccant and adsorption cooling
systems.

2.2 SORPTION TECHNIQUES

Sorption technology is used in thermal cooling mechanisms wherein the
refrigerant outcome is achieved from the physical or chemical variations
(concentration difference) between the adsorbent and adsorbate. Thermal-
operated sorption cooling has been considered as an efficient economic energy
saving technique(s). Sorption cooling technology can generate useful cooling
effect for the beneficiary, based on nonconventional sources or waste heat
recovery systems. Perhaps these cooling systems are especially simple in
 6

operation and are dependable, flexible and they are widely applied. Figure 2.2
shows the various types of sorption cooling techniques. Heat operated absorption
and adsorption systems with sorption cooling models wherein the work operated
mechanical compressor of the common vapour compression cycle is substituted
by a heat operated compressor and sorbent. In the adsorption cooling system, the
sorbent is in the solid phase and whereas liquid phase in case of absorption
systems. On heating the solid/liquid sorbent, desorbs the refrigerant at the
pressure of condenser. The vapour refrigerant is condensed to the liquid state in
the condenser, and then passed through throttling valve to enter the evaporator at
low pressure. The cooled refrigerant in the evaporator engrosses heat from the
cooled space and evaporates. Thus, it produces the required cooling. Refrigeration
using adsorption system can be used continuously, if multiple sorption beds are
used. Refrigeration using solid sorption systems requires large surface area to
transfer heat to the adsorbent materials that cost high.

FIG.2.1 SORPTION TECHNIQUES USED FOR REFRIGERATION

2.3 PERFORMANCE PREDICTION OF VAdRS

“Sarbu et al (2015) in the presented work demonstrated that Solar sorption
systems are more suitable than conventional refrigeration systems because
pollution-free working fluids (instead of chlorofluorocarbons) are used as
refrigerants. The review indicates that much research has recently been performed
on continuous operation absorption systems that use NH3/H2O and H2O/LiBr as
the working fluid. For solar sorption systems, considerable reduction in unit cost
or significant improvements in its performances at present costs are still required
to increase their competitiveness and commercialization potential.
 7

“Fernandes et al (2014) gives that experimental solar COP is still considerably

low (typically, between10% and 20%), seeming unlikely of further increase.
Despite all, the efforts made and numerous studies conducted all over the world
regarding the improvement of solar adsorption refrigeration systems. An overview
of the hybrid adsorption systems operating with the basic cycle has also been
conducted in this paper, to understand its present status and future trends.
Performance of solar cooler was analysed by Li and Wang (2003). This paper
dealt with effects of the adsorbent finned tube heat transfer, solar energy collector,
coating of the collector tubes, number of glasses used in the collector, thermal
resistance of contact materials used, thermal conductivity of the solid-sorbent
materials, and packing solidity of the solid-sorbent on the overall performance of
the system. Solar assisted sorption refrigerator utilising an evacuated tube for
thermal insulation was numerically studied by Li et. al (2003) with zeolite–water
pair. They computed relationships between the diameter of evacuated tube
collector and its performance with respect to distance among two adjacent tube
centres. The study concluded for evacuated tube diameter of 70 mm, both the
COP and cooling capacity reached their highest possible values of 0.25 and 4377
kJ/ m2.

Anyanwu (2004) conducted transient study and performance forecasting of single

solar sorption bed refrigerator with AC - methanol pair incorporated in a tubular
solar FPC. They observed developments on COP and condensate yield ranging
from 29 to 38% and 26 to 35% respectively. This was arrived based on tubes
spacing, packing density of the adsorbent and selection of the collector plate tube
material.

Anyanwu and Ogueke (2005) reviewed the core concepts and theories of solar
adsorption refrigerator; the thermodynamic design and process development for
solar adsorption using three different pairs such as activated carbon (AC)-
ammonia, AC- methanol and zeolite - water. It was concluded in their study AC-
ammonia is preferred for providing cooling effect below freezing point of ice (for
preserving food and medicine) and zeolite – water is preferred for air
conditioning. They also concluded that in all the above three cases, the systems
were dependent heavily on adsorber and condenser temperature and lightly on
evaporator temperature. The best COP’s (Solar) were about 0.19, 0.16 and 0.3
respectively for AC-ammonia, AC-methanol and zeolitewater with FPC.

Hamdeh and Muhtaseb (2010) designed prototype of a solar solid-sorption

refrigeration unit suitable for air-conditioning and refrigeration unit in remote
areas. This device used the AC-methanol pair. A minimum refrigerator
temperature of 90C was obtained for an ambient temperature of 260C and gross
cycle COP of 0.688 was obtained.

Tashtoush et. al. (2011) utilised a multi-dimensional curve-fitting formula to fit

the experimental and theoretical data by correlating the COP value to one of the
three temperatures of generator, condenser, and evaporator. Many cylindrical
 8

tubes were used in their study on solar radiation exposed sorption bed filled with
AC-ammonia pair.

Solmus et. al. (2012) investigated a numerical model for mass and heat transfer
of silica gel - water pair based on local volume averaging technique. A local
thermal non equilibrium one-dimensional model was developed to account both
external and internal resistance of mass transfer. The model simplifies along with
assumptions on solid-sorbent particle size, permeability, ideal gas radiation
behavior of vapour refrigerant and viscous dissipation. Neglected work done due
to pressure changes. The surface penetrability was deemed to be equal to the total
penetrability. Adsorption bed thermo-physical properties like thermal
conductivity, specific heat and viscosity are considered to be independent of
temperature. They established that, in order to increase the performance of the
sorption bed, it is essential to reduce the heat transfer resistance.

2.4 SUMMARY OF LITERATURE

S.N. Author Name YEAR Summary of Work

1 Ioan Sarbu, Calin 2015 - Solar VAdRS more suitable than

Sebarchievici VCC - next several years will be
decisive

2 Fernandes et al 2014 - intermittent Solar VAdRS -

Working Pair: AC-Methanol -
Solar COP 10% and 20%
3

3 Solmus et. al. 2012 - internal mass transfer resistances

are focused

4 Tashtoush et. al. 2011 - many cylindrical tubes were used -

COP=0.616

5 Hamdeh and 2010 - Minimum Te= 9°C & Tamb=26°C

AlMuhtaseb - COP is found to be 0.688

6 Anyanwu and 2005 - Performance Analysis of VAdRS -

Ogueke best COP’s (Solar) 0.16-0.3.

7 Rifat Ara Rouf 2013 - Performance of an adsorption

et. al. chiller with Heat Stored in reserve
tank - Maximum COP=0.65 for
direct solar coupling while it is 0.6
for the heat storage

TABLE 2.1 SUMMARY OF LITERATURE

 9

CHAPTER 3
METHODOLOGY
3.1 PRINCIPLE OF ADSORPTION REFRIGERATION
Adsorption refers to the binding of molecules (sorbate) to the surface of a material
(sorbent) without any chemical change. Adsorption occurs because the atoms,
molecules or ions at the surface of the sorbent are extremely reactive with
unfulfilled valence requirements as compared to their counterparts in the interior,
which have valence requirements satisfied. The unused bonding capacity of
surface atoms may be utilized to bond molecules of the sorbate to the surface of
sorbent. It uses clathrate material: a clathrate is an organic compound that has 3-
dimentional lattices that make up a network of micro pores or individual sites for
the sorbate to reside. The sorbate, while attached to the sorbent surface, gets
trapped in cavities of the sorbents’ cage like crystals. The material, which adsorbs
gases, is known as adsorbent and the gases which are adsorbed are the
refrigerants. The adsorption capacity is a function of physical and chemical
properties of sorbate and sorbent such as; sorbent porosity, sorbate boiling point,
the operating temperature and pressure. The adsorption capacity is enhanced
when the sorbent material is activated as it increases the available surface area
necessary for adsorption. Activated carbon is an example of sorbent material. The
adsorption refrigeration technology is based on the ability of sorbent material to
adsorb a relatively large quantity of refrigerant vapour (adsorbate) at low
temperature and pressure and desorbs the refrigerant at a higher temperature and
pressure. The compressor effect is generated by heating and cooling the sorbent
material and refrigerant. This result in high pressure outward flow as the
refrigerant is released during the hot desorption phase, and inward flow or low-
pressure suction during the cold adsorption phase.

FIG.3.1 PRINCIPLE OF ADSORPTION REFRIGERATION

 10

CHAPTER 4
SOLAR VAPOUR ADSORPTION REFRIGERATION SYSTEM
4.1 BASIC SOLAR VAdRS

Solar energy is the energy source of most adsorption devices operating with the
basic cycle. In the remaining cases the components are kept unchanged, the main
difference being the heat collection method. A solar adsorption refrigerator based
on the basic adsorption refrigeration cycle does not require any mechanical or
electrical energy, just thermal energy, and it operates intermittently according to
the daily cycle. Like a simple vapor compression system, these adsorption
systems are closed systems, comprising a compressor, a condenser and an
evaporator. However, in this case, the compressor is an adsorber powered by the
thermal energy, and the cooling effect is achieved by the evaporation of a
refrigerant while the vapor produced is adsorbed by the adsorbent layer in the
adsorber. The adsorbed content of refrigerant varies cyclically, depending on the
adsorbent temperature and system pressure, which varies between a maximum
limit set by the condensation pressure and a minimum limit imposed by the
evaporation pressure. In its simplest form, a solar refrigerator is a closed system
consisting of a solar collector containing the adsorbent bed (hermetically sealed
and painted in black, to optimize the solar radiation absorption), a condenser, a
receiver equipped with a 2-way valve and a cold box with the evaporator inside.
The basic adsorption cycle consists of four stages (two isobar and two isosteric
lines.)

(A) (B)

FIG.4.1 SIMPLE SOLAR ADSORPTION REFRIGERATION SYSTEM

(A) SCHEMATIC, INTERMITTENT CYCLE

(B) CONSTRUCTIVE, CONTINUOUS CYCLE

 11

Figure 4.2 describes the thermodynamic processes involved in the operation of the
adsorption refrigeration system.

b Isobaric
P c
desorption
c
o
Isoste
n
ric
d
Isosteric
desor
ption adsorpti
on
a
P d
e Isobaric
v
adsorption
a T T
FIG.4.2 THERMODYNAMIC
p a CYCLE OF ADSORPTION
d REFRIGERATION
d e

1. Process (a-b) (isosteric desorption) At states a, cool canister, or adsorber,

s

contains adsorbent saturated with a large fraction of refrigerant at pressure

slightly below Pevap. Cool adsorber is heated and desorbs refrigerant
vapour isosterically (i.e. at constant total mass in the adsorber), to state b
slightly above Pcond. At this point, vapour starts being forced out of the
hot adsorber through a check valve to the condenser.
2. Process (b-c) (isobaric desorption) Isobaric heating desorbs more
refrigerant, forcing it into the condenser until state c attained, where the
adsorber is nearly devoid of refrigerant.
3. Process (c-d) (isosteric adsorption) The hot adsorber is then cooled
isosterically (at constant total mass), causing adsorption and
depressurization, until the pressure drops below Pevap (state d), opening
another check valve to allow vapour to enter the adsorber from the
evaporator.
4. Process (d-a) (isobaric adsorption) Isobaric cooling to state a, the
refrigerant saturates the adsorbent and thus completing the cycle. [4]

As the adsorber releases heat, cooling takes place. Consequently, the adsorbent
temperature falls down; the vapour pressure is dropped down to the evaporation
pressure. Thus, on receipt of latent heat from the space of cooling, the refrigerant
is evaporated and subsequently adsorbed by the solid sorbent in the adsorber.
Typical Solar refrigerator with parabolic collector is shown below
 12

FIG. 4.3 SOLAR REFRIGERATORS WITH PARABOLIC COLLECTOR

4.2 COMPONENTS OF VAdRS

4.2.1 ADSORBER
Adsorber is the main element of the adsorption refrigeration system. The adsorber
provides the necessary compression effect required for refrigeration in an
adsorption refrigeration system by absorbing and rejecting heat of adsorption and
desorption. It works like generator as well as absorber both in an AR system. It is
designed as a tube in tube heat. Perorated tubes are placed inside the bed.
Activated carbon granules are filled in the space between the adsorber tubes and
perforated tubes. Aluminum chips are proposed to be mixed with activated carbon
to enhance heat transfer in adsorber bed.

4.2.2 CONDENSER
The condenser is a tubular heat exchanger where vapour refrigerant is chilled and
condensed at high pressure and temperature. The refrigerant vapour while passing
through the condensing coil, dissipates the latent heat into atmospheric air. The
tubes are normally constructed with plate type fins almost in all cases to increase
the heat transfer surface area. The weight-less material of aluminium is used for
the fins. The space between the fins is wider in order strengthen and to reduce
dust clogging.

4.2.3 CONDENSATE RECEIVER TANK

The condensate receiver tank (CRT) is an insulated vessel that stores liquid
refrigerant received from the condenser at a lower temperature. This receiving
 13

tank is placed between condenser and evaporator. The receiving tank and
connecting copper pipes are usually insulated to avoid heat gain to refrigerant.

4.2.4 EXPANSION DEVICE

Liquid refrigerant from the condensate receiver is passed through a throttling
device to bring down the pressure suitable for optimum heat recovery in the
evaporator. It sustains the required pressure difference between the maximum and
minimum pressure side of the system. Hence the liquid refrigerant is vapourised
at the predetermined pressure in the evaporator. Therefore, the flow of refrigerant
was controlled based on the load on the evaporator. The throttling device usually
used is capillary tube. The selection is made on the basis of its simplicity,
adaptability and cost. The capillary tube is usually made up of copper tube of
small diameter with varying length based on the application.

4.2.5 EVAPORATOR
The evaporator consists of copper tube coiled inside a water bath. The liquid
refrigerant is at low pressure and temperature is passed through the coil and it is
converted into vapor on receiving heat from the surroundings. The latent heat gain
by refrigerant is from the surrounding medium (water) in the evaporator.

4.3 TYPES OF ADSORPTION PROCESSES AND ADSORBENTS

In adsorption process a solid adsorbent adsorb a gaseous adsorbate, which is a
refrigerant. This adsorption process can be a physical or chemical. The
adsorption based on the adsorption process is divided into three types,

a. Physical adsorption
b. Chemical adsorption and combination of both
c. Composite adsorptions.

These processes of adsorption are described below,

4.3.1 PHYSICAL ADSORPTION

It is caused by Vander Walls forces between the molecules of the adsorbent and
the adsorbate. Physical adsorbents with macro-pores can adsorb consecutives
layers of adsorbate, while those with micro-pores have the volume of the pores
filled with the adsorbate. Physical adsorbents develop the selectivity to the
adsorbate after the former undergo specific treatments, like react under a gas
stream or with certain agents. The kind of treatment will depend on the type of
sorbents. These adsorbents and their adsorption properties are discussed below.
 14

Physical adsorbents

The physical adsorbents are the porous materials which can reversibly adsorb a
large amount of vapour at their surface. This process is purely physical and there
is no chemical change in the adsorbent as well as adsorbate. Some of the most
commonly used physical adsorbents used in adsorption refrigeration are activated
carbon or activated carbon fiber, silica gel and zeolite. The main features of these
adsorbents and their properties are discussed as follows,

a. Activated carbon and activated carbon fiber

Activated carbon (AC) is made from material such as wood, peat, coal, fossil oil,
chark, bone, coconut shell and nut stone. The net structure of activated carbon
pores is composed of irregular channels, which have large pore area at the surface
of the grain and the narrow pore area within the grain. The specific area of carbon
is between 500 to 1500 m2/g. The surface of activated carbon is covered by an
oxide matrix and by some inorganic materials and therefore, it is non- polar or a
weak polarity. The adsorption heat of activated carbon pair is lower than that of
other physical adsorbents. Activated carbons are used as powdered form or in
granular form. Activated carbon fiber is generally used in the production of fabric
such as cloth, tissues etc. The carbon fiber has better mass transfer performance as
compared to activated carbon. The specific surface area of carbon fiber is larger
than that of activated carbon. The pores of activated carbon are more uniform and
it shows better heat transfer performance also. The disadvantage of activated
carbon fiber is its anisotropic thermal conductivity and the higher thermal
resistance at contact surfaces as compared to granular activated carbon.

b. Silica Gel

The silica gel is a type of amorphous synthetic silica. It can be realized as a rigid
continuous net of colloidal silica, connected to very small grains of hydrated
SiO4. The hydroxyl in the structure is the adsorption centre because it is polar and
can form hydrogen bonds with polar oxides such as water and alcohol. The
adsorption ability of silica gel increases when the polarity increases. One
molecule can adsorb one molecule of water. Each kind of silica gel has only one
type of pore, which usually is confined in narrow channels. The pore diameter of
silica gel is about 0.7 to 3 nm and the specific surface area is about 100 – 1000
m2/g. Silica gel is widely used for desiccation because of its adsorption capacity.
c. Zeolite Zeolite is a type of alumina-silicate crystal composed of alkali or alkali
soil. The chemical formula of zeolite is My/n[(AlO2)y SiO2)m]zH2O Where, y
and m are integers and m/y is equal or larger than 1, n is the chemical valence of
positive ion of M, z is the number of water molecules inside a crystal cell unit.
There are 40 types of natural zeolites and the main types for adsorption
refrigeration are chabazite, sodium chabazite, cowlesite and fauzisite. About 150
types of zeolite can be artificially synthesized and they are named by Type A,
Type X, Type Y, Type ZSM. The adsorption and desorption heat of zeolites are
 15

high, the desorption temperature required is also high. The zeolites can be used in
adsorption refrigeration for the temperature range of 200 to 3000C.

4.3.2 CHEMICAL ADSORPTION

It is caused by the reaction between sorbate and the surface molecules of sorbent.
Electron transfer, atom rearrangement and fracture or formation of chemical bond
always occurs in the process of chemical adsorption. Only one layer of adsorbate
reacts with the surface molecules of chemical adsorbent. The sorbate and sorbent
molecules after adsorption never keep their original state. Moreover, there are the
phenomena of salt swelling and agglomeration, which are critical for heat and
mass transfer performance. The commonly used Chemical adsorption working
pairs are Metal Chloride and ammonia Metal hydride and hydrogen Metal Oxide
and hydrogen. The most commonly used chemical adsorption pair is Calcium
Chloride and ammonia.

Chemical Adsorbents

Chemical adsorbents are the adsorbents where the adsorption takes place because
of a reversible chemical reaction between sorbent and sorbate. The chemical
adsorbents used in chemical adsorption refrigeration mainly include metal
chlorides, metal hydrides and metal oxides.

a. Metal chlorides

The Metal Chlorides for adsorption refrigeration are mainly calcium chlorides
strontium chloride, magnesium chloride and barium chloride. Ammonia is the
usual adsorbate of metal chlorides. The adsorption reaction between metal
chlorides and refrigerant is a complexion reaction and the complex compound is
called coordinated compound. During adsorption process salt swelling and
agglomeration can occur and influence heat and mass transfer performance.

b. Salt and metal hydrides

Hydrogen can react with almost all elements and forms four types of hydrides.
Out of these four types salt hydrides and metal hydrides are the hydrides which
can be used in adsorption refrigeration. The salt hydrides have hexagonal crystal
lattice structure with large density. In the adsorption process H atoms become
proton when they enter the space between hexagonal crystal lattices. The electron
motion is similar to the electron motion of metal bonds. The density of salt
hydrides is larger than the density of simple metals, but the density of metal
hydrides is smaller than the density of simple metals because the mass and
volume of the former does not increase proportionally in the adsorption process.
 16

c. Metal oxides

When the metal oxides are used in adsorption refrigeration oxygen is used as
refrigerant. On the surface of the metal oxides the elements which influence
adsorption performance are the coordination number of the metal ion, the
unsaturated degree of coordination, the direction of the chemical bond on the
surface of the chemical material the symmetrical characteristic of the transition
metal field and the arrangement of the active centre. The swelling and
agglomeration occurs during adsorption in metal oxides.

4.3.3 COMPOSITE ADSORPTION

Composite adsorption started to be studied about 20 years ago, and they aimed to
improve the heat and mass transfer performance of the original chemical
adsorbents. This kind of adsorbent is usually obtained by the combination of a
chemical adsorbent and a porous medium, that can be or not a physical adsorbent,
such as activated carbon, graphite, carbon fibre, etc.

Composite Adsorbents

Composite adsorbents are mainly developed for improving the heat and mass
transfer of chemical adsorbents and for increasing the adsorption quantity of
physical adsorbents. The composite adsorbent has a porous structure and high
thermal conductivity to help avoiding the problem of swelling and agglomeration.
The composite adsorbent increases the adsorption capacity of physical adsorbent.
The composite adsorbents are made from a combination of a porous media and
chemical adsorbent. Generally used composite adsorbents are metal chlorides plus
activated carbon or activated carbon fiber or expanded graphite or silica gel or
zeolite.

4.4 WORKING PAIRS

The working pair is the crucial part of adsorption refrigeration system. The basic
properties which are required for adsorption refrigeration are large adsorption
capacity, large change in adsorption capacity with change in temperature and
compatibility with refrigerant and low adsorption heat. The basic properties a
refrigerant should possess are same as that required in a vapour compression
system. The adsorbent and refrigerant pair is selected depending on the
application and the source temperature. The commonly used refrigerant adsorbent
pairs are described below,

4.4.1 ACTIVATED CARBON(AC) FIBRE AND METHANOL

The adsorption process for the above mentioned pair comprises filling and
condensation of sorbate inside adsorbent pores. The adsorption mainly occurs in
micro-pores whose specific volume is generally about 0.15-0.5 cm3/g and the
surface area is about 95% of the whole activated carbon surface area. The
 17

function of middle pores and large pores is to mainly transport sorbate molecules
to micro-pores. Activated Carbon- methanol is one of the most commonly used
working pair due to the large adsorption quantity and lower adsorption heat is
about 1800-2000 KJ/kg. Lower adsorption heat is necessary for better values of
COP. Activated carbon- methanol is a working pair suitable with solar energy at
temperatures around 1000C. This pair is not suitable at temperatures greater than
1200C as decomposition of methanol occurs at this temperature. This pair has a
disadvantage of requirement of vacuum. The requirement of vacuum inside a
system increases manufacturing complexity and reduces reliability of system as a
small amount of air infiltration seriously affects the performance. The maximum
value of X = 0.45 i.e. it can adsorb up to 45% methanol by mass.

4.4.2 ACTIVATED CARBON(AC) FIBRE AND AMMONIA

Activated carbon ammonia is another common working pair. Activated carbon-
ammonia also has the same adsorption heat. The working pressure is higher, it is
around 15 bar at a condenser temperature of 400C. It has a better mass transfer
and shorter heating time. Activated carbon ammonia pair can be used at
temperature of 2000C or above. The disadvantage of this pair is toxicity and
pungent odor of ammonia, the incompatibility of ammonia with copper and
relatively smaller value of X. The highest adsorption quantity of activated carbon
with ammonia is 0.29 kg/kg. The smaller value of X is compensated by large
value of latent heat of ammonia.

4.4.3 SILICA GEL AND WATER

Silica gel and water is another working pair used in adsorption refrigeration where
the ability of water to act as a refrigerant at lower pressure is utilized. The
adsorption heat of this pair is about 2500 kJ/kg. The desorption temperature
required for this pair is very low it can be up to 500C. Desorption temperature for
this pair should not be more than 1200C and generally lower than 900C is used.
The disadvantage of silica gel water adsorption pair is low adsorption quantity, it
is limited to 0.2 kg/kg adsorbent. Another disadvantage of this pair is to operate
below 00C.

4.4.4 ZEOLITE AND WATER

The zeolite adsorption pair is utilized in dehumidification, cooling and adsorption
refrigeration systems. The adsorption heat of this pair is about 3300-4200 kJ/kg.
The zeolites are stable at high temperatures hence this pair can be used with heat
sources more than 2000C. As the desorption temperature is high and the
adsorption heat is also high the performance of this pair is worse than that of
activated carbon-ammonia system at temperature lower than 1500C. This pair can
have higher values of COP and specific cooling power at temperature above
2000C. The limitation of this pair is to work below 00C and as the working
pressure is low the mass transfer is also low. The heating time required for this
 18

working pair is more as compared to above mentioned other adsorbent refrigerant

pairs. The maximum amount of water that can be adsorbed in zeolite (X) =
0.261kg/kg.

4.4.5 CALCIUM CHLORIDE AND AMMONIA

This is one of the most widely used chemical adsorption working pair. The
adsorption capacity of this pair is large. One mole of calcium chloride can adsorb
8 moles of ammonia and the combination is CaCl2 (8NH3) and four six or eight
moles can be desorbed from this depending on the desorption temperature. The
advantage of calcium chloride ammonia system is its adsorption quantity which is
higher than 1 kg/kg of adsorbent. The disadvantages of this working pair are
problem of swelling and agglomeration during adsorption.
 19

CHAPTER 5
PERFORMANCE OF SOLAR VAdRS
Experimental setup used in the present study is shown in figure 5.1. It consists of
an evaporator, sorption bed, condenser, refrigerant receiver, capillary tube and
measuring equipment along with necessary valve systems. Typical photographic
view of experimental setup is shown in figure 5. Solar radiation transfers the heat
to the sorption material, namely, activated charcoal, for regeneration of refrigerant
vapour that has been adsorbed during earlier cycle. The activated charcoal in
powder form is packed in annular space of co-axial tubes, 6 in number. Inside this
tube placed the refrigerant tube coaxially.

FIG.5.1 PHOTOGRAPHIC FRONT VIEW OF VAPOR ADSORPTION

REFRIGERATION SYSTEM
 20

FIG.5.2 EXPERIMENTAL SETUP (SCHEMATIC)

 21

5.1 SYSTEM PRELIMINARY SETUP

Initially, VAdRS used for the current study is evacuated utilizing a vacuum pump.
By adopting triple vacuum technique, it was ensured that the non-condensable
gases present in the vapor adsorption refrigeration system were removed. R152a
was charged then to break the vacuum. Once again, the system was evacuated and
the vacuum was held for about 24 hours. Finally, R152a refrigerant liquid form
was charged into the system partially filled in the condenser and CRT.

5.2 EXPERIMENTAL PROCEDURE

5.2.1 HEATING AND DESORPTION
Experiments were carried out in a systematic way. To start with in the morning
BV1 and PRV is closed (figure 5.2), and the sorption bed is exposed to solar
irradiation. After a prolonged time period the system reaches the set pressure. The
PRV is used to maintain the possible pressure in the sorption bed by controlling
the generation temperature. The PRV is opened and the vapour is allowed to enter
the condenser. The air-cooled condenser condenses the desorbed vapour and the
liquid adsorbate kept stored in a CRT through BV2 kept open. The level gauge
reading indicates the amount of adsorbate desorbing from the sorption bed. This
process continuous till the mass concentration ratio of the sorption bed reaches its
minimum level.

5.2.2 COOLING AND ADSORPTION

Now the sorption bed should be cooled down to make it ready to adsorb vapour
from the evaporator. BV2 is being closed FCV is opened to allow the liquid
adsorbate in to evaporator through the capillary tube. FCV helps to regulate the
flow of adsorbate through the evaporator. A flow meter is used to read out the
flowrate through the evaporator. The vapour refrigerant from the evaporator is
adsorbed in the sorption bed with BV1 remains open. This process continuous till
the mass concentration ratio reaches its maximum. The refrigeration effect of the
system can be measured from the cooling observed in the water bath (evaporator).
The pressure and the temperature at different locations can be measured with the
help of suitable measuring equipment. Yet again sorption bed is heated for
complete desorption then follows the next cycle of the VAdRS.
 22

5.3 VAdRS PERFORMANCE ANALYSIS

FIG.5.3 FLOW CHART OF PERFORMANCE ANALYSIS

Coefficient of performance of single adsorbent bed can be estimated as the ratio

of total refrigeration capacity of the system to the total heat supplied to the
system. For theoretical analysis, the system performance is compared by two
parameters, namely, Carnot COP and theoretical COP. The Carnot COP can be
expressed as,

The theoretical COP is expressed as,

(5.1)
 23

(5.2)

The eq. (5.2) can be re-written as,

(5.3)

The specific cooling power is expressed as,

(5.4)

The amount of heat transported (a-b) to the sorption bed is given by, 𝑄𝑎𝑏=[𝑚(𝐶𝑝
𝑎𝑑+𝑀𝑚𝑎𝑥𝐶𝑝 𝑟𝑒𝑓)+𝑚𝑏𝑒𝑑𝐶𝑝 𝑏𝑒𝑑](𝑇𝑏−𝑇𝑎) (5.5) The heating is continued
during isobaric desorption process (b-c). The valve between sorption bed and
condenser is opened. Condensation process starts and refrigerant vapour is
liquefied in the condenser. In this period, the pressure almost remains constant.
This pressure is known as condenser pressure. Equation 5.6 gives the amount of
heat acquired by the system in this process. 𝑄𝑏𝑐=[𝑚(𝐶𝑝 𝑎𝑑+𝑀𝑚𝑖𝑛𝐶𝑝
𝑟𝑒𝑓)+𝑚𝑏𝑒𝑑𝐶𝑝 𝑏𝑒𝑑](𝑇𝑐−𝑇𝑏)+𝑚Δ𝐻𝑎(𝑀𝑚𝑎𝑥−𝑀𝑚𝑖𝑛) (5.6) Once valve is closed
isosteric cooling period (c-d) begins. During the process adsorbent pressure is
decreased to that of evaporator. Temperature of the bed is the maximum Tc that is
decreased to Td. Heat rejection in (c-d) is given by, 𝑄𝑐𝑑=[𝑚(𝐶𝑝 𝑎𝑑+𝑀𝑚𝑎𝑥𝐶𝑝
𝑟𝑒𝑓)+𝑚𝑏𝑒𝑑𝐶𝑝 𝑏𝑒𝑑](𝑇𝑐−𝑇𝑑) (5.7) Isobaric adsorption (d-a) begins when the
valve is opened and vaporization of adsorbate in the evaporator is started during
adsorbing of refrigerant in the adsorbent. Further, heat is liberated due to the heat
of adsorption. This generated heat is to be removed from the sorption bed and the
temperature of the pair is reduced to Ta. 𝑄𝑑𝑎=[𝑚(𝐶𝑝 𝑎𝑑+𝑀𝑚𝑎𝑥𝐶𝑝
𝑟𝑒𝑓)+𝑚𝑏𝑒𝑑𝐶𝑝 𝑏𝑒𝑑](𝑇𝑑−𝑇𝑎)+𝑚Δ𝐻𝑎(𝑀𝑚𝑎𝑥−𝑀𝑚𝑖𝑛) (5.8) Measured parameters
from experimentation are Time, Tamb, Gi, Tgen, Pcond, Tcond, Level, Tw, Flow,
Tevap, Tads, Pevap. After conducting the test following parameters are
calculated,

a) Cooling capacity (Qevap)

b) Global incident radiation on the collector (Qgi)
c) Heat required to desorb refrigerant in the sorption bed (Qg)
d) Heat rejected at the condenser (Qcond)
e) Coefficient of performance (COPCarnot and COPSolar)
 24

5.4 PERFORMANCE

5.4.1 EFFECT OF CONDENSER TEMPERATURE

Figure 5.4 shows the effect of condenser temperature on COP. It is observed that
COP decreases as the condenser temperature decreases. This decrease in COP
attributed to reduction on refrigerating effect at the given heat input. To maintain
the evaporating capacity, it is necessary to have additional mass of adsorbent in
the system. Also, it appears that the trend of the curve shows a non-linear
behavior of condenser temperature on COP of the system

FIG.5.4 PLOT OF COP VS TCOND, QEVAP=1000 KJ/HR

 25

FIG.5.5 PLOT OF COPCARNOT VS TCOND, QEVAP=1000 KJ/HR

From Figure 5.5 it is understood that Carnot COP remains constant or decrease
little with increase in condenser temperature. This is attributed by lower
generation or desorption temperatures.

5.4.2 EFFECT OF EVAPORATOR TEMPERATURE

Figure 5.6 illustrates the variation of COP with evaporator temperature. It is noted
that an increase in evaporator temperature at the given condenser temperature
helps to rise the refrigeration effect. Hence at a given heat input COP increases
with increase in evaporator temperature. It is further understood that a higher
condenser temperature reduces the refrigerating effect. This is the reason for drop
in COP at higher condenser temperature. Figure 5.7 shows the variation of Carnot
COP with evaporator temperature. But similar to the condenser temperature, the
evaporator temperature also has negligible effect on Carnot COP of the system.
This behavior is attributed to similar reasons stated for condenser temperature in
figure 5.5
 26

FIGURE 5.6 PLOT OF COP VS TEVAP, QEVAP=1000 KJ/HR

FIGURE 5.7 PLOT OF COPCARNOT VS TEVAP, QEVAP=1000

KJ/HR

5.4.3 EFFECT OF GENERATION TEMPERATURE

Figure 5.8 shows the effect of generation temperature on COP at different
condenser temperature. When desorption temperature increases, mass of vapour
desorbed increases therefore the refrigerating capacity increases and hence COP
of the system is increasing. However, after certain desorption temperature, the
drop-in concentration ratio plays a major role and affects the COP. When the
change in mass concentration increases, heat of generation also will increase
 27

therefore COP tends to decrease. It is further observed that higher is the condenser
temperature, results in lowering of the COP of the system. Figure 5.9 presents the
effect of generation temperature on the Carnot COP of the system. Carnot COP of
the system increases with increase in generation temperature of the system. A rise
in generation temperature leads to increase in refrigeration capacity of the system.
This causes the Carnot COP to increase with increase in generation temperature of
the system. It is also observed that condenser temperature has no significant effect
on Carnot COP.

FIG.5.8 PLOT OF COP VS TGEN, QEVAP=1000 KJ/HR

FIG.5.9 PLOT OF COPCARNOT VS TGEN, QEVAP=1000 KJ/HR

 28

CHAPTER 6
SUMMARY
The range of COP for the Solar VAdRS is 0.2 - 0.7. The development of
adsorption system for refrigeration is promising. An overall thermodynamics-
based comparison of sorption systems shows that the performance of adsorption
systems depends highly on both the adsorption pairs and processes. The
technology continues to develop and the cost of producing power with solar
thermal adsorption refrigeration is falling. If the costs of fossil fuels,
transportation, energy conversion, electricity transmission and system
maintenance are taken into account, the cost of energy produced by solar thermal
adsorption systems would be much lower than that for conventional refrigeration
systems.

The intermittent system has its simplicity and cost effectiveness. However, the
main disadvantages such as long adsorption/desorption time have become
obstacles for commercial production of the system. Hence, to compete with
conventional vapor compression technologies, more efforts should be made in
enhancing the COP and SCP. The environmental benefit of this technology and its
non-dependence on conventional energy sources makes it highly attractive for
further developments and a potential alternative to conventional systems in the
future. The future of solar refrigeration and air conditioning seems to be a very
good proposition and no doubt will find its place in future industrial applications.
The major limiting factor at present is the shape of energy so as to make it
available whenever it is required, for example at nights and extended cloudy days
when we cannot attain a high enough temperature.
 29

CHAPTER 7
FUTURE PROSPECTS
Vapour absorption refrigeration system is not widely used due to its limitations.
There is need for certain developments like 1) Cop of the system, we have to
improve the cop of the system. 2) Size of the Condenser, Evaporator and
Generator which is reduces the size of the system. 3) Cost of System. Adsorption
technology combined with other technologies for multi-purpose application seems
to be a new trend in the research. This will widen the area of applications of
adsorption technologies and make the adsorption refrigeration more cost effective.
Any method that improves the efficiency even marginally would improve the
economic viability of operating such devices. Thus, further studies need to be
carried out to validate the potential for possible application in household
refrigerators.

Other researches such as multistage and cascade cycles augers well for future for
this technology. Another possibility is combining of the adsorption refrigeration
cycle with other refrigeration cycles to improve the overall performance. For this
the use of thermal energy storage systems due to their long retention capacity of
thermal energy without losses may prove to be beneficial. Recent application of
nanotechnology in adsorbent material development is also very promising.
Fluidized bed technology if integrated with adsorption refrigeration system can
also help in addressing the characteristic weakness of poor heat and mass transfer
in fixed bed adsorption cooling systems.
 30

REFERENCES
1. Sumathy K. and Zhongfu Li, “Experiments with solar-powered adsorption
icemaker”, Renewable Energy, vol.16, no.1-4, pp.704-707, 1999a
2. Ioan Sarbu and Calin Sebarchievici, “General review of solar-powered
closed sorption refrigeration systems”, Energy Conversion and
Management 105 (2015) 403–422
3. M.S. Fernandes, G.J.V.N.Brites, J.J.Costa, A.R.Gaspar, V.A.F.Costa,
“Review and future trends of solar adsorption refrigeration systems”,
Renewable and Sustainable Energy Reviews 39 (2014) 102–123.
4. Li M. and Wang R. Z., “Heat and mass transfer in a flat plate solar solid
adsorption refrigeration ice maker”, Renewable Energy, Vol. 28, no.4, pp.
613, 2003.
5. Anyanwu E. E., “Review of solid adsorption solar refrigeration I: An
overview of refrigeration cycle”, Energy Conversion and Management,
vol.44, no.2, pp. 301312, 2003.
6. Anyanwu E. E., “Review of solid adsorption solar refrigeration II: An
overview of the principles and theory”, Energy Conversion and
Management, vol. 45, pp. 12791295, 2004.
7. Anyanwu, E. E., and Ogueke, N. V., “Thermodynamic design procedure
for solid adsorption solar refrigerator”, Renewable Energy, vol.30, no.1,
pp. 81-96, 2005.
8. Hamdeh N. H. A. and Al-Muhtaseb M. A., “Optimization of Solar
Adsorption Refrigeration System Using Experimental and Statistical
Techniques”, Energy Conversion and Management, vol.51, pp.1610-1615,
2010.
9. Tashtoush G.M., Al-Ata M., and Al-Khazali A., “Solar adsorption
refrigeration (SAR) system modelling”, Energy Efficiency, vol.4, no.2, pp.
247-56, 2011.
10. Solmus. I.‚ Rees D. A. S., Yamal C., Baker D. and Kaftanoglu B.,
“Numerical investigation of coupled heat and mass transfer inside the
adsorbent bed of an adsorption cooling unit”, International Journal of
Refrigeration, vol. 35, pp. 652662, 2012.
11. Buchter F., Dind P., Hilbrand C., and Pons M., “A new solar powered
adsorption refrigerator with high performance”, Solar Energy, vol.77, pp.
311-318. 2004.
12. Boubakri, A., Guillemiont, J. J., and Meunier, F., “Adsorptive solar
powered icemaker: experiments and model”, Solar Energy, vol.69, no.3,
pp. 249-263, 2000.
13. Boubakri A.,“Performance of an adsorptive solar ice maker operating with
a single double function heat exchanger (evaporator/condenser)”,
Renewable Energy, vol.31. pp 1799–812. 2006.
14. Buchter F., Dind P., Pons M., “An experimental solar-powered adsorptive
refrigerator tested in Burkina-Faso”, International Journal of Refrigeration,
vol.26, pp.79– 86, 2003
 31

15. Buchter F., Dind P., Hilbrand C., and Pons M., “A new solar powered
adsorption refrigerator with high performance”, Solar Energy, vol.77, pp.
311-318. 2004.
16. Parash Goyal, Prashant Baredar, Arvind Mittal, Ameenur. R. Siddiqui,
“Adsorption refrigeration technology – An overview of theory and its solar
energy applications”, Renewable and Sustainable Energy Reviews
53(2016) 1389–1410.
17. Ioan Sarbu, Calin Sebarchievici, “Review of solar refrigeration and cooling
systems”, Energy and Buildings 67 (2013) 286–297.
18. Rifat Ara Rouf, K. C. Amanul Alam, M. A. Hakim Khan, Bidyut Baran
Saha, F. Meunier, M. Abdul Alim, K. M. Ariful Kabir, “Advancement of
solar adsorption cooling by means of heat storage”, Procedia Engineering
90 (2014) 649 – 656.
19. ASHARE Hand book, 2008