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Activated Carbon, Silica-gel and Calcium Chloride Composite Adsorbents

for Energy Efficient Adsorption Cooling Systems

BY

TSO Chi Yan

A Thesis Submitted to
The Hong Kong University of Science and Technology
in Partial Fulfillment of the Requirements for
the Degree of Master of Philosophy
in the Environmental Engineering Program

August 2012, Hong Kong


i

HKUST Library
Reproduction is prohibited without the authors prior written consent

Acknowledgements

During the past two years doing the research work, I received countless help from many
people. I want to thank everyone who helped me here. Firstly, I would like to take this
opportunity to express my sincere appreciation to my respectful supervisor, Prof. Christopher
Y. H. Chao. I thank him for offering me a valuable opportunity for me to pursue an MPhil
degree in HKUST. It would not have been possible for me to finish my research work without
his academic and financial support. His advice is always critical and helped me overcome the
difficulties. He shared many different experiences with me, not only about study and research
but also how to work in the real world.

Besides, very special thanks should be given to the technicians and staff from the Department
of Mechanical Engineering (MECH), Environmental Engineering Program (EVNG), Material
Characterization and Preparation Facilities (MCPF) and Advanced Engineering Materials
Facility (AEMF). They were so helpful and patient, listening to my problems and solving
them with specialized knowledge. In particular, Mr. S. W. Woo, Mr. Matthew K K Lai, Mr. C
S Seto and Mr. C. K. Kam from MECH, Ms. Connie M F Tsang from EVNG, Dr. Fanny L Y
Shek, Mr. Nick K C Ho and Mr. T K Cheung from MCPF, and Ms. Marjorie M L Liu from
AEMF for their kind help.

Last but not least, I would like to express my gratitude to my family and to Mr. Cao Jiakang
and Ms Yeung So Fan, for their care and support in my life. Thanks for their persistent
contribution to my family. Finally, I would like to thank my girlfriend, Ms. Crystal W K Fung,
for her endless support and encouragement for my study. She picks me up when I lose my
motivation and is just the perfect one for me.

iv

Table of Contents

Title Page..................................................................................................................................... i
Authorization Page ..................................................................................................................... ii
Signature Page...........................................................................................................................iii
Acknowledgements ................................................................................................................... iv
Table of Contents ....................................................................................................................... v
List of Tables ........................................................................................................................... viii
List of Figures ............................................................................................................................ x
Nomenclature ........................................................................................................................... xv
Abstract ................................................................................................................................... xix
Chapter 1

Introduction .......................................................................................................... 1

1.1 Background ....................................................................................................................... 1


1.2 Literature Review ........................................................................................................... 12
Chapter 2

Objectives ........................................................................................................... 17

Chapter 3

Activated Carbon/Silica-gel/CaCl2 Composite Adsorbent Development .......... 19

3.1 Conceptual Design .......................................................................................................... 19


3.2 Material Synthesis .......................................................................................................... 21
3.3 Experimental Setup and Methodology ........................................................................... 29
3.3.1 X-ray photoelectron spectroscopy (XPS) ................................................................ 29
3.3.2 BET specific surface area and total pore volume .................................................... 29
3.3.3 Thermogravimetric analysis (TGA) ......................................................................... 33
3.3.4 Adsorption rate test unit ........................................................................................... 36
3.4 Result and Discussion ..................................................................................................... 39
3.4.1 Elemental composition............................................................................................. 39
3.4.2 Specific surface area and total pore volume ............................................................ 41
v

3.4.3 TGA ......................................................................................................................... 42


3.4.4 Pore structure ........................................................................................................... 44
3.4.5 Equilibrium water uptake ......................................................................................... 46
3.4.6 Adsorption rate......................................................................................................... 49
3.4.7 Ideal COP and average SCP analysis ....................................................................... 54
3.5 Summary......................................................................................................................... 56
Chapter 4

Waste Heat Driven Adsorption Chiller Simulation............................................ 58

4.1 Background ..................................................................................................................... 58


4.2 Working principle of a waste heat driven double bed composite adsorbent based + water
adsorption chiller .................................................................................................................. 62
4.3 Mathematical modeling .................................................................................................. 65
4.3.1Assumptions .............................................................................................................. 65
4.3.2 Equilibrium water uptake ......................................................................................... 66
4.3.3 Adsorption rate......................................................................................................... 68
4.3.4 Heat of adsorption .................................................................................................... 69
4.3.5 Adsorption energy balance ...................................................................................... 72
4.3.6 Desorption energy balance ....................................................................................... 73
4.3.7 Energy balance for the condenser ............................................................................ 74
4.3.8 Energy balance for the evaporator ........................................................................... 74
4.3.9 Mass balance in the evaporator ................................................................................ 75
4.3.10 Measure of system performance ............................................................................ 76
4.4 Result and discussion...................................................................................................... 78
4.4.1 Temperature profile of the heat transfer fluids ........................................................ 79
4.4.2. The time variation of water content ........................................................................ 80
4.4.3 The COP & SCP performance ................................................................................. 81
4.4.4 Hot water temperature influence .............................................................................. 84
vi

4.4.5 Cool water temperature influence ............................................................................ 87


4.4.6 Chilled water inlet temperature influence ................................................................ 90
4.5 Summary......................................................................................................................... 92
Chapter 5 Conclusion and Future Work ................................................................................... 94
5.1 Conclusion ...................................................................................................................... 94
5.2 Future Work .................................................................................................................... 96
5.2.1 Build a prototype of the adsorption air conditioner ................................................. 96
5.2.2 Upgrade the prototype of the adsorption air conditioner ....................................... 100
5.2.3 Capillary-assisted evaporator in adsorption cooling systems ................................ 102
5.2.4 Development of a nanofluid enhanced adsorption cooling systems ...................... 104
Chapter 6 Reference ............................................................................................................... 106

vii

List of Tables

Table 1.1:

Monthly Air Temperature Recorded at the Observatory between 1971 and


2000

Table 1.2:

Properties of selected adsorbents

Table 1.3:

Properties of selected adsorbate

Table 3.1:

Variable parameters of the composite adsorbents for the experiments

Table 3.2:

Results of x-ray photoelectron spectroscopy of the samples

Table 3.3:

Specific surface areas and total pore volumes of the samples

Table 3.4:

The difference in equilibrium water uptake between 25C and 115C, , and
the percentage improvement compared with raw activated carbon at
atmospheric pressure

Table 3.5:

Pore volume of the best five samples

Table 3.6:

The adsorption capacity and the percentage improvement compared with raw
activated carbon at various pressures.

Table 3.7:

The adsorption rate coefficients of the 5 best samples at 300K

viii

Table 3.8:

The average SCP and ideal COP of the 5 best samples at 900 Pa

Table 4.1:

Summary of adsorbent adsorbate pair for adsorption cooling systems

Table 4.2:

Equilibrium water uptake against relative pressure

Table 4.3:

Result of the constant A and B in equation (4.1)

Table 4.4:

Equilibrium water uptake against relative pressure under 297K

Table 4.5:

Equilibrium water uptake against relative pressure under 307K

Table 4.6:

Numerical values of ai & bi (i=0, 1, 2, 3) constants, which appear in the


equilibrium equation of adsorbent - adsorbate pair (silica activated
carbon/CaCl2 composite adsorbents)

Table 4.7:

Values of parameters adopted in the simulation

Table 4.8:

Nominal operating condition for the 2-bed adsorption chiller

Table 4.9:

Comparison of the different adsorbents

Table 4.10:

Comparisons of the simulation results between this study and some improved
design

ix

List of Figures

Figure 1.1:

Basic components of a refrigeration system and typical operating conditions

Figure 1.2:

Typical process of vapor compression system

Figure 1.3:

Schematic diagram of a solar adsorption cooling system during adsorption


phase

Figure 1.4:

Schematic diagram of a solar adsorption cooling system during desorption


phase

Figure 1.5:

Pressure - Temperature diagram of the adsorption cooling cycle

Figure 1.6:

Energy flow in the adsorption cooling cycle

Figure 1.7:

Schematic diagram of a double-bed adsorption cooling system

Figure 3.1:

Scheme for impregnating hydrophilic silica

Figure 3.2:

CaCl2 impregnation process

Figure 3.3:

SEM images of the activated carbon before penetration

Figure 3.4:

SEM images of the activated carbon before penetration

Figure 3.5:

SEM images of the activated carbon before penetration

Figure 3.6:

SEM images of the activated carbon before penetration

Figure 3.7:

SEM images of typical activated carbon samples after penetration

Figure 3.8:

SEM images of typical activated carbon samples after penetration

Figure 3.9:

SEM images of typical activated carbon samples after penetration

Figure 3.10: SEM images of typical activated carbon samples after penetration

Figure 3.11: BET surface area analyzer: Coulter SA 3100

Figure 3.12: Inside the SA 3100, left hand side: outgas ports, right hand side: sample port
and saturation port in liquid nitrogen bath

Figure 3.13: Control panel of SA 3100

Figure 3.14: Thermogravimetric analyzer TA Q5000 IR

Figure 3.15: Schematic diagram of the adsorption rate test unit

Figure 3.16: The adsorption rate test unit

xi

Figure 3.17: TGA results of the different composite adsorbent samples at atmospheric
pressure

Figure 3.18: An overall view of differences in equilibrium water uptake () with different
impregnation times and CaCl2 solution concentrations

Figure 3.19: Pore size distribution of activated carbon before and after impregnation

Figure 3.20: A three dimensional view of the adsorption capacity at different water vapor
pressures and CaCl2 concentrations in the impregnating solution

Figure 3.21: Water adsorption isotherms of the AC01, AC03, AC07, AC10 and AC12
samples at 300K

Figure 3.22: Water adsorption rates of AC01, AC03, AC07, AC10 and AC12 300K and
750 Pa

Figure 3.23: Water adsorption rates of AC01, AC03, AC07, AC10 and AC12 300K and
900 Pa

Figure 3.24: Water adsorption rates of AC01, AC03, AC07, AC10 and AC12 300K and
1000 Pa

Figure 3.25: Water adsorption rates of AC01, AC03, AC07, AC10 and AC12 300K and
1100 Pa

xii

Figure 4.1:

Schematic diagram of the double-bed waste heat driven adsorption chiller

Figure 4.2 (a):

Mode A operation of the waste heat driven double bed composite


adsorbent based + water adsorption chiller

Figure 4.2 (b):

Mode B operation of the waste heat driven double bed composite


adsorbent based + water adsorption chiller

Figure 4.3:

Overall outlet temperature profile of heat transfer fluid for 2-bed adsorption
chiller

Figure 4.4:

The time variation of water content in two adsorbers

Figure 4.5:

Effect of COP against the adsorption-desorption cycle time

Figure 4.6:

Effect of SCP against the adsorption-desorption cycle time

Figure 4.7:

Effect of SCP on hot water inlet temperature

Figure 4.8:

Effect of chilled water outlet temperature on hot water inlet temperature

Figure 4.9:

Effect of COP on hot water inlet temperature

Figure 4.10: Effect of COP on cooling water inlet temperature

Figure 4.11: Effect of SCP on cooling water inlet temperature


xiii

Figure 4.12: Effect of chilled water outlet temperature on cooling water inlet temperature

Figure 4.13: Effect of COP on chilled water inlet tempearture

Figure 4.14: Effect of SCP on chilled water inlet temperature

Figure 4.15: The relationship between chilled water outlet temperature and inlet
temperature

Figure 5.1:

Schematic diagram of the dual-adsorber adsorption air conditioner

Figure 5.2:

The prototype of a silica-gel + water adsorption air conditioner

Figure 5.3:

The temperature profile of the heat transfer fluid in adsorption air conditioner

Figure 5.4:

An inner component of the adsorber

Figure 5.5:

A whole adsorber assembly design drawing

Figure 5.6:

Schematic diagram of the capillary-assisted evaporator

xiv

Nomenclature

Alphabet
ai (i = 0 - 3)

Numerical constants for Equation (4.12)

[dimensionless]

area

[m2]

Langmuir constant

[Pa-1]

bi (i = 0 - 3)

Numerical constants for Equation (4.13)

[dimensionless]

BET constant

[dimensionless]

Cac

specific heat capacity of the activated carbon

[J kg-1 K-1]

Cad

specific heat capacity of the adsorbate (water vapor)

[J kg-1 K-1]

Dso

pre-exponent constant of surface diffusivity

[m2 s-1]

Ea

activation energy of surface diffusion

[J]

had/H

heat of adsorption

[J kg-1]

hfg/Lw

latent heat of vaporization of water

[J kg-1]

Kads

adsorption rate coefficient

[s-1]

Kdes

desorption rate coefficient

[s-1]

k1

empirical constant in linear driving force model

[s-1]

k2

empirical constant in linear driving force model

[s]

mass of adsorbent at current stage

[kg]

mass flow rate

[kg s-1]

mdry

dry mass of the composite adsorbent

[kg]

NA

Avogadros number

[mol-1]

P0/Ps

saturation pressure

[Pa]

Pr

relative pressure

[Pa]

Qchill

cooling capacity

[KW]

xv

Qhot

driving heat

[KW]

Individual/universal gas constant

[J kg-1 K-1]

Rp

average radius of the adsorbent

[nm]

adsorbate cross section area

[nm2]

SBET

BET surface area

[m2 g-1]

temperature

[K]

Tc

composite adsorbent temperature

[K]

time

[s]

time interval

[s]

overall heat transfer coefficient

[W m-2 K-1]

Volume

[cm3]

mass

[kg]

AC

activated carbon

[dimensionless]

BET

Brunauer-Emmett-Teller

[dimensionless]

CaCl2

calcium chloride

[dimensionless]

CFC

chlorofluorocarbon

[dimensionless]

HCFC

hydrochlorofluorocarbons

[dimensionless]

COP

coefficient of performance

[dimensionless]

EER

energy efficiency ratio

[dimensionless]

LDFM

linear driving force model

[dimensionless]

MCM-41

mobile composite material

[dimensionless]

SCP

average specific cooling power

[W kg-1]

SCP

specific cooling power

[W kg-1]

SEM

scanning electron microscope

[dimensionless]

Abbreviation

xvi

TGA

thermogravimetric analysis

[dimensionless]

VC

vapor compression

[dimensionless]

VOC

violate organic compound

[dimensionless]

XPS

X-ray photoelectron spectroscope

[dimensionless]

the adsorbed gas quantity

[kg kg-1]

the monolayer adsorbed gas quantity

[kg kg-1]

the difference between uptake and off-take during

Greek symbol

[kg kg-1]

adsorption/desorption process

eq

amount adsorbed (mass of water vapor per mass of dry


adsorbent )

[kg kg -1]

equilibrium amount adsorbed

[kg kg-1]

Subscripts
ad

adsorber

ads

adsorption

al

aluminum

chw

chilled water

com

composite adsorbent

cond

condenser

cu

copper heat transfer tube

cwa

cooling water in adsorber/desorber

cwc

cooling water in condenser

de

desorber

des

desorption
xvii

eva

evaporator

eq

equilibrium state

fin

aluminum fin

hw

hot water

macro

macropores

meso

mesopores

micro

micropores

in

inlet

initial

out

outlet

water vapor

water

xviii

Abstract

In recent years, global warming and energy shortage have become more and more serious as
economies develop rapidly all over the world. Adsorption cooling systems powered by solar
energy or waste heat have drawn increasing attention, as such systems need neither CFCs nor
HCFCs as the working fluid and neither fossil fuel nor electricity to drive them.

Composite adsorbents were synthesized from activated carbon, silica-gel and CaCl2. The
optimized condition for adsorption cooling systems was obtained when raw activated carbon
was impregnated by soaking in 10 wt.% sodium silicate solution for 48 hours and then in 30
wt.% CaCl2 solution for 48 hours. A 0.805kg kg-1 of difference in equilibrium water uptake
between 25C and 115C was recorded at atmospheric pressure. Besides, an adsorption rate
test unit was built to study the adsorption isotherms and adsorption rates in which 0.23kg kg-1
of adsorption capacity was recorded at 27C with a water vapor pressure of 900 Pa.

The performance of a waste heat driven adsorption chiller by applying the novel composite
adsorbent (silica activated carbon/CaCl2) was also studied. Modeling was performed to
analyze the influence of the hot water inlet temperature, cooling water inlet temperature,
chilled water inlet temperatures, and adsorption/desorption cycle time on the SCP and COP of
the chiller system with the composite adsorbent. The simulation calculation indicates a COP
value of 0.65 with a driving source temperature of 85C in combination with coolant inlet and
chilled water inlet temperature of 30C and 14C, respectively. The most optimum
adsorption-desorption cycle time is approximately 360s based on the performance from COP
and SCP. The delivered chilled water temperature is about 9C under these operating
conditions, achieving an SCP of 380W kg-1.

xix

Chapter 1

Introduction

1.1 Background
It is well known that cooling systems have become a necessity in our daily life. In the
developed and most of the developing countries, almost every indoor area has air conditioning
systems installed. Temperature and relative humidity are two major factors that can directly
affect thermal comfort for humans. Air conditioning systems can control both temperature
and humidity at the same time. However, using air conditioning systems requires
consumption of a large amount of electricity. In the past decades, as the demand of cooling
systems keeps on increasing in commercial areas and in residential areas, the energy
consumption of air conditioning has become one of the largest proportions of energy used in
the world. Cooling systems contribute to a significant amount of electricity consumption in
buildings, contributing to 40 - 50% of the total building electricity consumption.

In Hong

Kong, buildings themselves contribute to about 90% of total electricity consumption (EMSD,
2010). The high concentration of energy consumption in air conditioning systems is due to a
very high mean daily maximum temperature in Hong Kong, approximately 30C during the
summer time as shown in Table 1.1 (HKO, 2010). And, Hong Kong has many high-rise
buildings which are the result of very high occupancy density formed simultaneously by the
limited land area and the large amount of population.

Table 1.1: Monthly air temperature recorded at the observatory between 1971 and 2000
Month

Mean Daily

Mean (C)

Maximum (C)

Mean Daily
Minimum (C)

January

18.6

16.1

14.1

February

18.6

16.3

14.4

March

21.5

18.9

16.9

April

25.1

22.5

20.6

May

28.4

25.8

23.9

June

30.4

27.9

26.1

July

31.3

28.7

26.7

August

31.1

28.4

26.4

September

30.2

27.6

25.6

October

27.7

25.3

23.4

November

24.0

21.4

19.4

December

20.3

17.8

15.7

Year

25.6

23.1

21.1

Although air conditioning systems have improved the indoor environment, they not only
consume a huge amount of electricity, but also pollute the outdoor environment. The heat
from indoor environment is transferred to outdoor by the air conditioning systems. The global
ambient temperature is increased due to the waste heat from electricity generation and air
conditioning systems. Thus, the use of air conditioning systems has worsened the situation.
Energy crisis, air pollution, acid rain and other fossil burning related problems will also be
aggravate the situation. In the long term, if society continues using traditional air conditioners,
more and more problems will occur in the future.

Existing cooling systems include vapor compression (VC) systems, absorption systems,
adsorption systems, thermoelectric elements, Stirling refrigeration, thermo-acoustic
refrigeration and magnetic cooling. The VC system is the most common type of cooling
system due to a high coefficient of performance (COP), about 3 to 4, and common availability
2

in a variety of sizes. In VC systems, a compressor is used to increase the pressure of the


refrigerant to complete the VC cycle. The basic components of a VC system are shown in
Figure 1.1 and the typical processes of operation are shown in Figure 1.2 ( engel Y.A. and
Boles M.A., 2006). The operation of the compressor in VC systems causes the system to
consume a large amount of electricity. Moreover, VC systems utilize HCFCs or HFCs as
refrigerants. The refrigerants are VOC in nature which can directly affect peoples health, and
many of them have strong ozone depletion potential (Derwent R.G. et al., 2007) and global
warming power (Johnson E., 1998). Thus, the environmental problems are worsening.

Figure 1.1: Basic components of a refrigeration system and typical operating conditions

Figure 1.2: Typical process of vapor compression system

To ease those environmental problems, the most effective method is to cut down the energy
consumption and use less electricity in cooling systems. One of the approaches is to use the
adsorption cooling systems which are energy-efficient and environmentally friendly machines
for cooling and refrigeration. Adsorption cooling systems offer a number of distinctive
advantages as they do not require a compressor which consumes a major part of the electricity,
and the solid adsorbents and their corresponding refrigerants (e.g. water) used in these
systems are more environmentally friendly and easy to handle in operation and maintenance.
Besides, adsorption cooling systems require a low grade heat source with little electricity
requirement. Integrating adsorption thermal systems with renewable heat sources, such as
solar thermal, geothermal, earth residue heat (Zhang J. and Haghighat F., 2009) or waste heat
can substantially reduce electricity consumption and thus reduce the dependence on fossil
fuels making them potential candidates for net zero energy building operation. Chiller is one
of the major applications for the adsorption cooling systems in many industrial buildings (Xu
T., 2005).

During an adsorption phase, the adsorbate (e.g. water vapor) becomes physically attached to
the surface of the adsorbent. Basically, there are two phases which include solid phase and
gas phase materials. The vapor phase material, called adsorbate, is adsorbed on the surface of
the solid phase material, called adsorbent. Van Der Waals forces and hydrogen bonding act
between the molecules, binding them together. The attachment force between the adsorbent
and adsorbate depends on the binding energy between the two. The binding energy varies
with the amount of adsorbate uptake and equilibrium is reached when the binding energy is
equal to the kinetic energy of the free adsorbate. The equilibrium adsorbate uptake varies for
each adsorbent - adsorbate pair and is a function of adsorbate vapor pressure and temperature
(Golubovic M.N. et al., 2006). Most of the adsorbent can adsorb more adsorbate under lower
temperature and higher pressure conditions because the adsorbate has lower kinetic energy
and the energy in free state is higher. More adsorbate with lower kinetic energy can be
captured under the higher potential boundary. Therefore, the adsorbent - adsorbate pair is a
core element for consideration in the design of the adsorption cooling systems.

The working principle of the adsorption cooling system is the evaporation of adsorbate at a
low pressure condition. For example, the boiling point of water is 5oC under 870 Pa. If the
adsorbate is placed in an evacuated container, it will evaporate and the temperature of the
adsorbate will decrease. The schematic diagram of the cycle is given in Figures 1.3 and 1.4.
The Pressure - Temperature diagram of the cycle is also given in Figure 1.5. The adsorption
phase is shown in Figure 1.3 while the desorption phase of the solar adsorption cooling
system is shown in Figure 1.4. The adsorber containing porous adsorbent adsorbs the
evaporated adsorbate and maintains a low pressure in the evaporator. The adsorbate in the
evaporator vaporizes under the low pressure. The temperature of the adsorbate decreases until
equilibrium between evaporation and adsorption is reached. If water is the adsorbate, heat
transfer during adsorption will generate chilled water which can be used to remove the
5

cooling load from the process air. Because heat from adsorption is released when the
adsorbate is adsorbed on the adsorbent, a heat exchanger is used to take away the heat
produced during the adsorption process. The adsorbent will be saturated with the adsorbate
(water vapor) after a few minutes, meaning the adsorption phase is stopped. Thus, the
adsorbate has to be desorbed from the adsorbent. The desorption process can be achieved by
increasing the temperature of the adsorbent. Energy should be applied to increase the kinetic
energy of the adsorbate to overcome the potential boundary between the molecules to desorb
the adsorbate. A renewable low grade heat source, such as solar energy or waste heat, can be
utilized. The heat is transferred to the absorber through a heat transfer fluid. The adsorbate
will then be desorbed from the adsorbent when the temperature of the adsorbent increases.
The desorbed adsorbate will then go to the condenser. Adsorbate condenses in the condenser
and while the heat of condensation is rejected. The condensed water returns to the evaporator
and completes the whole thermodynamic cycle. In short, the adsorption cooling system
utilizes the temperature dependence of the equilibrium adsorbate uptake of adsorbents. The
adsorbent can adsorb more adsorbate under lower temperature. Cooling effect is produced by
adsorption under a lower temperature and saturated adsorbent is regenerated under a higher
temperature.

Figure 1.3: Schematic diagram of a solar adsorption cooling system during adsorption phase

Figure 1.4: Schematic diagram of a solar adsorption cooling system during desorption phase
7

Figure 1.5: Pressure - Temperature diagram of the adsorption cooling cycle

The energy flow of the system is given in Figure 1.6. The heat-to-cool efficiency, which
refers to the COP of the system, is

heatcool

Qe
Qg Wel

(1.1)

where Qe is the heat transferred from cooling place, Qg is the heat rejected to the ambient
environment and Wel is the electricity supplied to the system. The ideal Carnot efficiency
between high source temperature, TH, and ambient temperature, TM, is

id
heat
mid

TH TM
TH

(1.2)

Also, the ideal Carnot efficiency between ambient temperature, TM, and cooling place
temperature, TL, is

id
mid
cool

TL
TM TL

(1.3)

Hence, the ideal overall efficiency is

id
id
id
heat
cool heat mid mid cool

TL
TH

TH TM

TM TL

(1.4)

Apart from the COP of the system, energy efficiency ratio (EER) is also frequently discussed
recently which can be used and represented for the efficiency of the adsorption cooling
system. This is because EER can truly show the efficiency of the adsorption cooling system
while the COP is just for a fair comparison with the traditional air conditioning system. EER
is defined as

EER

Qe
Wel

(1.5)

It is reasonable that EER is the true parameter to represent the efficiency of the adsorption
cooling systems. As the heat required for the energy input is from the solar or waste heat. In

another word, it is totally free from the environment. It is not suggested to be count into the
calculation of the efficiency of the solar adsorption systems.

Figure 1.6: Energy flow in the adsorption cooling cycle

It can be seen that the working principle of the adsorption cooling system is quite similar to
an absorption system. Both can utilize solar energy and other renewable heat sources to
operate the systems. The main difference is the sorbent. Solid sorbent called adsorbent is used
in adsorption cooling systems and the adsorbate is adsorbed on the surface and internal voids
10

of adsorbent by physical reaction. In absorption cooling systems, liquid sorbent called


absorbent is used and the sorbate is absorbed in the absorbent by chemical reaction (Jain S. et
al., 2000). The sorption capacity of liquid absorbent is higher than solid adsorbent, giving the
absorption cooling system a higher specific cooling power (SCP) than an adsorption cooling
system. For example, the SCP of a commercial adsorption cooling system is around 13W kg-1
while an absorption system is about 60W kg-1 (Kim D.S. and Ferreira C.A.I., 2008). The COP
of the absorption system is also generally higher than the adsorption system (Hwang Y. et al.,
2008). The absorbates used in absorption cooling systems are toxic, are a hazard if leakage
occurs and they are corrosive, causing damage to the system. Ammonia and lithium bromide
are two most common absorbates (Restuccia G. and Cacciola G., 1999). Ammonia vapor is
severely irritating to the eyes and the respiratory tract (Griffiths R.F. and Megson L.C., 1984).
Ammonia solution is highly toxic to aquatic animals even at low concentration (Knoph M.B.
and Thorud K., 1996). Lithium bromide is psychoactive. Taking as low as 225mg day-1 of
lithium bromide can result in Bromism, causing a neurotoxic effect on the brain (Mangurten
H.H. and Ban R., 1974). The high concentration absorbent solution will crystallize inside the
duct of the system and damage the pump and other system components. Compared with liquid
absorption systems, adsorption systems can be powered by a larger range of heat source
temperatures (Wang R.Z. and Oliveira R.G., 2006) and the adsorbent can be replaced more
easily than absorbents in some designs (Chua K.J. and Chou S.K., 2003). Adsorbent adsorbate pairs used in adsorption cooling systems are usually chemical inert and have little
environmental impact. Few moving parts are required, alleviating the problem of noise and
wear, because the adsorbent does not need to flow by gravitational force as in absorption
system. In other words, the adsorption cooling system depends less on orientation. Lastly, in
order to generate a continuous cooling effect from the adsorption cooling system, more than
one adsorber has to be installed. A double-bed adsorption cooling system is shown in Figure
1.7. When one adsorber is doing adsorption, another one is doing desorption by supplying
11

heat to it. So, it can continuously produce a cooling effect from the adsorption cooling
systems. All in all, adsorption cooling systems are proposed as a solution to solve energy
problems, emission problems and pollution problems without sacrificing peoples comfort
and they are relatively better than absorption cooling systems.

Figure 1.7: Schematic diagram of a double-bed adsorption cooling system

1.2 Literature Review


Adsorption cooling systems are energy efficient and environmentally friendly, but some
difficulties need to be overcome. Until now, adsorption cooling systems have not been
12

commercialized since the size of the system is very large and inefficient. For small or
medium-size cooling systems, such as for households and vehicles, the adsorption cooling
system is relatively bulky and expensive (Wang R.Z. et al., 2001). A vapor compression (VC)
system is generally more compact since an adsorption cooling system has lower SCP than a
VC system. The COP of adsorption cooling systems is also low (Wang R.Z. et al., 2009). In
order to fully utilize adsorption technology, the SCP and COP of adsorption systems need to
be improved. Studies have been focusing to overcome the limitations. Adsorbent
improvement, better adsorber design and adsorption cycle management can allow higher SCP
and COP, and are discussed below.

The earliest research found on adsorption cooling systems was conducted in the late 1970s to
1980s (Tchernev D.I., 1978; Shigeishi R.A. et al., 1979; Sakoda A. and Suzuki M., 1984).
Activated carbon-methanol or -ammonia (Pons M. and Guilleminot J.J., 1986), zeolite-water
(Tchernev D.I., 1978; Shigeishi R.A. et al., 1979) and silica gel-water (Grenier P. et al., 1988;
Saha B.B. et al., 2009; Thu K. et al., 2011) were the most common adsorbent-adsorbate pairs
used for cooling system studies. When choosing an adsorbent, some criteria have to be
fulfilled. Low cost of the adsorbent, high adsorption capacity, high thermal conductivity, low
specific heat capacity, suitable temperature range for adsorption and desorption and high rate
of adsorption/desorption. Potential adsorbents include zeolite 13X, silica gel and activated
carbon. Their properties are summarized in Table 1.2. Similar to adsorbent, adsorbate should
be low cost, widely available, non-toxic, environmentally friendly and high specific
evaporative latent heat. The potential adsorbates are water, methanol and ammonia and their
properties are summarized in Table 1.3.

Table 1.2: Properties of selected adsorbents

13

Zeolite 13X

Silica-gel

Activated carbon

Cost (HKD kg-1)

11.5

78.43

211

Adsorption capacity (kg kg-1)

0.3

0.37

0.4

Thermal conductivity

0.2

0.196

0.28

(W m-1 K-1)

(Zhang L.Z.,

(Gurgel J.M. and

(Kuwagaki H. et al.,

2000)

Klppel R.P.,

2003)

1996)
Specific heat capacity

0.921

0.88

1.09

(kJ kg-1)

Table 1.3: Properties of selected adsorbate


Water

Methanol

Ammonia

Cost (HKD kg-1)

0.0042

2.17

1.86

Widely available

Yes

No

No

Toxic

No

10ml: blindness,

toxic in high

100ml: death

concentration

1100

1369

Latent Heat

2257

(kg kg-1)

From Table 1.2 & 1.3, it is not difficult to observe that activated carbon water is one of the
most suitable adsorbent adsorbate pair for use in an adsorption cooling system. However,
the adsorption capacity could be further improved by developing a composite adsorbent as
well as enhancing the thermal conductivity.

Heat and mass transfer performance of adsorption cooling systems play another very
14

important role, having a large effect on the COP and SCP of the system. During adsorption,
adsorbate molecules have to diffuse into the adsorbent's micropores/mesopores and heat is
generated due to the loss of freedom of the adsorbate molecules. Although activated carbon
has the highest value in terms of thermal conductivity among all the potential adsorbents, it is
still very low when utilized in adsorption cooling systems (Jakubinek M.B. et al., 2007).
Following, are some suggested solutions from literature focused on improving the heat and
mass transfer performance. Using extended surfaces like plate-fin heat exchangers (HIJC
USA, Boer R.D. et al., 2005), adsorbent-coated heat exchangers (Wojcik A.M.W. et al., 2001)
and consolidated composite adsorbents (Tamainot-Telto Z. and Critoph R.E., 1997) are some
recommended methods to improve the overall thermal conductivity in adsorbers. In detail, an
extended surface can increase the surface area for heat transfer and is useful for operation in
normal cases, but is not applicable for low pressure operation for zeolite-water, silica
gel-water or activated carbonwater due to Knudsen effect. Coating adsorbents on the surface
of a heat exchanger can decrease the thermal contact resistance between the adsorbent and the
wall, but the thin layer of coated adsorbent, about 1mm (Restuccia G. and Cacciola G., 1999),
limits the COP and SCP of the system. A large metal surface is required to coat the required
amount of adsorbent and make the ratio of metal mass to adsorbent mass very high. It seems
that the best solution may be the development of a consolidated composite adsorbent.
Consolidating adsorbents with high thermal conductivity material can largely increase the
thermal conductivity of the adsorbent bed. Studies on consolidating metal foam and zeolite,
show improvement in thermal conductivity exceeding 20 times that of raw adsorbent material
(Tamainot-Telto Z. and Critoph R.E., 1997).

Adsorption/desorption cycle time can significantly affect the COP and SCP of the cooling
systems and the adsorption cooling system is an intermittent process so that the temperature
and pressure of the components have to be changed for the adsorbers to adsorb/desorb the
15

adsorbate (Wang R.Z. et al., 2001). The cycle time determines the duration of each
temperature and pressure stage. The longer adsorption/desorption cycle time might not
generate a higher COP and SCP. At the same time, the shorter adsorption/desorption cycle
time might not be good as well. So, there is an optimized adsorption/desorption cycle time
which has to be studied by the simulation analysis. Usually, the adsorption/desorption cycle
time is about 500 seconds. Besides, heat and mass recovery are the processes that can
improve system performance (Wang R.Z. and Oliveira R.G., 2006). During heat recovery, the
stored regenerative heat in the desorbed adsorber is transferred to the saturated adsorber after
adsorption by circulating the heat transfer fluid between them. This increases the system COP
because the heat left in the desorbed adsorber is transferred to the adsorber that needs to be
desorbed, allowing the desorbed adsorber to cool faster (Wang R.Z., 2001). Thus, it saves
some re-generating power. In the mass recovery process, adsorbate is transferred between two
adsorbers. This balances the pressure between them and increases the difference in adsorbate
content between the adsorption and desorption stages. It is reported that mass recovery can
increase the SCP by up to 20% and COP by up to 100% (Wang R.Z., 2001). Certainly, the
heat and mass recovery time is always within 30 seconds since no cooling effect can be
produced during these periods. Most of the heat and mass recovery process can finish within
30 seconds, explaining why the heat and mass recovery are always very short compared to the
adsorption/desorption cycle time.

16

Chapter 2

Objectives

To make the adsorption cooling systems practicable with an acceptable size and power
requires the following research work to be conducted:

1. Development of a novel composite adsorbent material having more favorable adsorption


properties, such as adsorption capacities and adsorption rate, than the traditional
adsorbents (activated carbon, silica-gel, zeolite, etc.).

2. System performance prediction and optimization under different operation conditions for
the waste heat driven composite adsorbent material based and water adsorption chillers.

This research work carried out a series of studies from basic material investigation, through
mathematical analysis, to overall system performance prediction conducted both theoretically
and experimentally. The aim of this study was to develop a novel composite adsorbent made
by impregnating silica-gel and CaCl2 into the pores of activated carbon. Ultimately, the
composite adsorbent should have a high adsorption capacity, high adsorption rate, high
thermal conductivity and low heat of adsorption, resulting in more compact design, lower
chilled water outlet temperature and lower exhaust air temperature. These properties allow
higher COP and SCP of the systems. Experiments were performed to characterize the
properties of the new novel composite adsorbents and make comparison to other existing
adsorbents, such as activated carbon, silica-gel and zeolite 13X. In short, this research
revealed the impact of composite adsorbents on adsorption systems and the potential of
adsorption cooling systems in small scale usage.

Objectives in point form:


17

1.

To develop a novel silica activated carbon/CaCl2 composite adsorbent and characterize


the properties which should have better adsorption properties than traditional adsorbents
for both adsorption dehumidification and cooling systems;

2.

To construct mathematical models and numerical simulation for waste heat driven
adsorption chiller analysis. The models will be used for operation cycle analysis, system
performance prediction and design optimization of the adsorption cooling systems to
increase the COP and SCP of the system.

18

Chapter 3

Activated Carbon/Silica-gel/CaCl2 Composite Adsorbent


Development

3.1 Conceptual Design


Silica-gel, activated carbon and zeolite 13X are three common adsorbents used in adsorption
cooling systems, each having their own strengths and weaknesses in terms of adsorption
capacity. Zeolite 13X has excellent adsorption capacity at low pressures, but requires heating
to more than 100C to desorb the adsorbate (Shigeishi R.A. et al., 1979) and it cannot adsorb
and desorb large quantities of adsorbate within a narrow humidity/pressure range (Wang L.W.
et al., 2009). Silica-gel can adsorb average amounts of water vapor at any pressure because of
its hydrophilic properties (Kakiuchi H. et al., 2004). Activated carbon has a large internal
surface area (commonly in the range of 1000-1500m2/g) because of high porosity, high
surface reactivity, and hence a large capacity for adsorbing chemicals from liquids or gases
(Swiatkowski A. et al., 1999). In adsorption cooling systems, an adsorbent which can adsorb a
large amount of gas (such as water vapor) is preferred. Much of the literature (Mowla D. et al.,
2003; Edwin O.W. and Juhola, A.J. 1949; Kim M.B. et al., 2005; Sullivan P.D. et al., 2007)
reported that activated carbon is a good adsorbent for water vapor. Foley N.J. et al. (1997)
studied the adsorption of water vapor on highly microporous activated carbon. The adsorption
and desorption characteristics of water vapor on the activated carbon were investigated over
the pressure range 0 2.41 KPa in a static water vapor system. The results showed that the
microporous activated carbon had strong adsorption ability on water vapor. Besides, Qi S. et
al. (1998) developed a simple isotherm model for the adsorption systems. The water vapor
adsorption capacities of four activated carbon adsorbents for relative vapor pressure from 0 to
0.95 and temperature between 288 and 308K were investigated. The modeling results
correlated well to the experimental data. Therefore, activated carbon is a good choice for
adsorbing water vapor and is suitable for use in adsorption cooling systems.
19

Apart from that, for an adsorption cooling system, a desirable adsorbent should have an
S-shape adsorption isotherm with huge adsorption capacity at pressures from 750 Pa to 1100
Pa (Kakiuchi H. et al., 2004). Basically, activated carbon can form an S-shape adsorption
isotherm, but the adsorption capacity of activated carbon within that pressure range is quite
low (Shigeishi R.A. et al., 1979). A combination of activated carbon and silica-gel might be
able to solve the problem because the adsorption capacity of silica-gel at the lower pressure
condition is relatively higher than activated carbon (Shigeishi R.A. et al., 1979). At the same
time, it can retain an S-shape isotherm since activated carbon is the host matrix. However, the
overall adsorption capacity still has room for further improvement. It could be further
enhanced by impregnating the micropores of silica activated carbon with an inorganic salt
such as CaCl2. Experiments have shown that CaCl2 could adsorb approximately 0.9g of water
vapor per gram of CaCl2 at room temperature and pressure, which is why CaCl2 is one of the
adsorbents used widely in dehumidifier boxes.

Moreover, thermal conductivity of the activated carbon itself is the best among all common
adsorbents (zeolite 13X and silica-gel) being about 0.5 W m-1 K-1 (Menard D. et al., 2005).
Higher thermal conductivity will result in a higher performance of heat and mass transfer in
the adsorber during adsorption/desorption process. The COP of the adsorption cooling system
can be improved a lot. After further impregnation with silica-gel and CaCl2, the thermal
conductivity of the composite adsorbent can be enhanced more since CaCl2 and silica-gel fill
in the space between the activated carbon molecules, which create paths for heat transfer. So
activated carbon is not just a structure for the composite adsorbent but is indeed playing a
very important role.

20

Therefore, the possibility to develop a high density composite adsorbent by impregnating the
pores of activated carbon with silica-gel and CaCl2, might not only improve the adsorption
capacity at low pressures, but also enhance the overall adsorption capacity and adsorption rate,
improving both the COP and the SCP of an adsorption cooling system.

3.2 Material Synthesis


Huang et al. reported that impregnating with a 10 wt.% sodium silicate solution for 48 hours
was the optimum for preparing a composite absorbent based on silica-gel and activated
carbon (Huang H. et al., 2010). This study followed that sample preparation procedure.

To incorporate CaCl2, the raw materials used were 30 mesh activated carbon pellets
(Sigma-Aldrich), sodium silicate solution (Sigma-Aldrich, 11 wt.% of Na2O and 27 wt.% of
SiO2) and anhydrous CaCl2 powder (Sigma-Aldrich, 96 wt.%). 10g of activated carbon was
dried at 110C for 24 hours, then impregnated using 150ml of the sodium silicate solution for
different soaking times (24 hours, 48 hours and 72 hours) at room temperature with stirring.
After filtration, the samples were dried at 110C for a further 24 hours. The dried samples
were then mixed with 75ml of 3.9 mole L-1 concentration of H2SO4 solution for 24 hours at
room temperature with stirring. After another filtration they were dried at 110C for 24 hours.
The dried samples were washed with deionized water to remove any Na2SO4 which had
formed, and then dried again at 150C for 24 hours. By doing so, it can naturally form dry
pellets of adsorbent.

Another process of impregnating the pellets with CaCl2 was then necessary. The dried silica
activated carbon was mixed with different concentrations of CaCl2 solution (10 wt.%, 30
wt.% and 46 wt.%) at a mass ratio 1 : 9 with stirring for different soaking times (24 hours, 48
hours and 72 hours respectively). After that, filtration was required again. Finally, the
21

adsorbent was dried at 150C for 24 hours. The initial impregnation sequence is shown in
Figure 3.1. The final CaCl2 impregnation process is shown in Figure 3.2. The silica
impregnation time was fixed at 48 hours, and 10 wt.% sodium silicate solution was used in all
cases, so the two parameters studied were the concentration of the CaCl2 aqueous solution and
the impregnation time. The different values tested are tabulated in Table 3.1. Including the
untreated activated carbon, there were 13 samples. AC02, AC03 and AC04 involved only
silica impregnated with different impregnation times. They were included for purposes of
comparison with AC05 AC13.

A scanning electron microscope (SEM, JEOL JSM 6300) was used to analyse the surface
structure of the composite adsorbent. An accelerating voltage of 15-20kV was selected as this
gave the brightest image without ionizing the zeolite. Images with magnification of 85, 400,
600, 650, 700, 950, 1300 and 4000 were taken for each sample.

Scanning electron microscope (SEM) images of the samples are presented in Figures 3.3 to
3.10.

22

Activated carbon (10g)

Heating for evacuation (383K, 24 hrs)


1st Penetration (150ml Na2O 3.3 SiO2 solution)

Filtration
Drying (383K, 24 hrs)
2nd Penetration (75ml 3.9 N H2SO4 solution, 24 hrs)
Filtration
Drying (383K, 24 hrs)
Washing with De-ionized water to remove Na2SO4

Drying (423K, 24 hrs)

Silica Activated Carbon Produced


Figure 3.1: Scheme for impregnating hydrophilic silica

Silica Activated Carbon (10g) + CaCl2 solution (100ml)

Filtration
Drying at 423K for 24 hrs

Composite Adsorbent (Silica Activated Carbon/CaCl2)


Produced
Figure 3.2: CaCl2 impregnation process

23

Table 3.1: Variable parameters of the composite adsorbents for the experiments
Sample

sodium silicate

sodium silicate

CaCl2 in

CaCl2 solution

number

solution

solution

solution

impregnation

impregnation

concentration

concentration

time

time
AC01 (raw)

N.A.

N.A.

N.A.

N.A.

AC02

24 hr

10 wt.%

N.A.

N.A.

AC03

48 hr

10 wt.%

N.A.

N.A.

AC04

72 hr

10 wt.%

N.A.

N.A.

AC05

48 hr

10 wt.%

46 wt.%

24 hr

(saturation)
AC06

48 hr

10 wt.%

46 wt.%

48 hr

(saturation)
AC07

48 hr

10 wt.%

46 wt.%

72 hr

(saturation)
AC08

48 hr

10 wt.%

10 wt.%

24 hr

AC09

48 hr

10 wt.%

10 wt.%

48 hr

AC10

48 hr

10 wt.%

10 wt.%

72 hr

AC11

48 hr

10 wt.%

30 wt.%

24 hr

AC12

48 hr

10 wt.%

30 wt.%

48 hr

AC13

48 hr

10 wt.%

30 wt.%

72 hr

24

Figure 3.3: SEM images of the activated carbon before penetration

Figure 3.4: SEM images of the activated carbon before penetration

25

Figure 3.5: SEM images of the activated carbon before penetration

Figure 3.6: SEM images of the activated carbon before penetration

26

Figure 3.7: SEM images of typical activated carbon samples after penetration

Figure 3.8: SEM images of typical activated carbon samples after penetration

27

Figure 3.9: SEM images of typical activated carbon samples after penetration

Figure 3.10: SEM images of typical activated carbon samples after penetration
28

3.3 Experimental Setup and Methodology


3.3.1 X-ray photoelectron spectroscopy (XPS)
The elemental composition of the composite adsorbent materials was first analyzed using
X-ray photoelectron spectroscopy (XPS). The XPS spectra confirmed that all the pores of the
activated carbon were impregnated with the silica-gel and CaCl2 and also revealed the weight
percentage of each compound.

3.3.2 BET specific surface area and total pore volume


BET surface area, total pore volume and pore size distribution were measured using the
Coulter SA310 physical-adsorption apparatus as shown in Figure 3.11 to 3.13. Before
measurement, a sample port was evacuated to remove any adsorbed substances, a process
called outgas. The outgas time and temperature were 90 minutes and 250C respectively.
After outgas, the sample port was placed inside a bath of liquid nitrogen where the
temperature was maintained at -196C. A saturation port was also placed inside the liquid
nitrogen bath as a reference and nitrogen was used as the adsorbate. BET models were used to
calculate the specific surface area, SBET, which was found from the adsorption isotherm of
nitrogen. The BET model was developed to address the issue of multilayer adsorption and
was given by (Brunauer S. et al., 1938):

P
c 1 P 1

vP0 P vm c P0 vm c

(3.1)

where P is the present pressure, P0 is the saturation pressure of adsorbate, is the adsorbed
gas quantity, m is the monolayer adsorbed gas quantity, c is the BET constant. By plotting P/
(P0-P) against P/P0, m and c can be found. The SBET of the adsorbent can be found by:
29

S BET

vm N A s
VM

(3.2)

where NA is Avogadros number, s is the adsorbate cross section area, V is the molar volume
of adsorbate gas, M is the molar mass of the adsorbate gas. The simplest model describing
adsorption on surface is the Langmuir model (Ruthven D.M., 2008):

eq
BPeq

m 1 BPeq

(3.3)

where m is the maximum adsorbate uptake, B is the Langmuir constant, Peq is equilibrium
pressure. Langmuir model provides a useful qualitative representation of the equilibrium
behavior, but can be quantitatively unreliable at high loadings (Ruthven D.M., 2008). The
SBET is useful in describing the level of porosity of the material. Total pore volume was found
from direct measurement of the volume of nitrogen adsorbed. Adsorption pore size
distribution was also characterized according to the BJH model proposed by Barrett E.P.,
Joyner L.G. and Halenda P.P (Barrett E.P. et al., 1951). This technique characterizes pore size
distribution independent of the external area due to particle size of the sample. If the majority
of pore volume is contributed by pores with very large pore size, a bulk calcium chloride
accumulation will be formed after impregnation. This will affect the mass diffusion into the
pore and decrease the rate of adsorption. If the majority is contributed by pores with very
small pore size, it is difficult for calcium chloride to diffuse in it during impregnation. Thus,
the most suitable activated carbon is that the pore size is within the middle pore size range
which is mesopores or micropores.

30

Figure 3.11: BET surface area analyzer: Coulter SA 3100

31

Figure 3.12: Inside the SA 3100, left hand side: outgas ports, right hand side: sample port and
saturation port in liquid nitrogen bath

32

Figure 3.13: Control panel of SA 3100

3.3.3 Thermogravimetric analysis (TGA)


Thermogravimetric analysis (TGA, TA Q5000 IR) was used to track the samples changes in
weight with temperature as shown in Figure 3.14. Thus the equilibrium adsorption capacities
of the composites at different temperatures were estimated. These results were generated at
atmospheric pressure. The thirteen adsorbent samples were initially saturated with water
vapor under 95% relative humidity conditions for 24 hours before performing the TGA tests.
TGA was then performed in 15C temperature steps from 25C to 205C with an
equilibration time of 10 minutes at each step. Afterwards, the temperature was increased to
400C to get the dry mass of the composite adsorbent, mdry. Finally, the water uptake, (kg
kg-1), could be calculated as

33

m mdry
mdry

(3.4)

where m is the total mass of the adsorbent including the mass of the adsorbed water vapor.

The TGA temperatures used were based on the operating conditions of typical adsorption
cooling systems. The adsorption temperatures in the adsorber were in the range from 25C to
50C, and any temperature increase attributed to the heat of adsorption released in the
adsorbent. At the same time, the desorption temperature in the desorber was never higher than
200C, not only because most of the water vapor in the adsorbent is desorbed at around 200C,
but also regeneration using solar thermal energy or waste heat is generally below 200C.

34

Figure 3.14: Thermogravimetric analyzer TA Q5000 IR

The adsorption (desorption) rate at that particular temperature was also calculated using the
linear driving force model which is given here: (Sakoda A. and Suzuki M., 1984)

35

E
d 15
2 Ds 0 exp a eq
dt R p
RT z

(3.5)

which can be simplified to (Wang D.C. et al., 2006):

k
d
k1 exp 2 eq K eq ,
dt
Tc

k
K k1 exp 2
Tc

(3.6)

where eq is the equilibrium water uptake, Rp is the average radius of the adsorbent, Ds0 is a
pre-exponent constant of surface diffusivity, Ea is the activation energy of surface diffusion, R
is the universal gas constant, Tc is the composite adsorbent temperature, k1 and k2 are
empirical constants to be determined experimentally and K is the adsorption rate coefficient
which is a function of temperature only. Under the linear driving force model, the adsorption
and desorption rate, as well as the equilibrium water uptake, are both governed by the
equation (3.6) shown above. The empirical constants, k1 and k2, are the same for adsorption
and desorption by assuming no hysteresis effect.

3.3.4 Adsorption rate test unit


An adsorption rate test unit (Figures 3.15 and 3.16) was constructed in order to test the
adsorption capacity and adsorption rate of the composite adsorbent materials. The system had
two main components, a water bath evaporator and a test vacuum chamber. The sample
adsorbents inside the vacuum chamber were kept at a constant temperature by a digital
temperature controller (9600 series refrigerating/heating circulator, Poly-Science) so that the
adsorption isotherms and adsorption rate curves were recorded at a constant temperature. A
K-type thermocouple was used to record the temperature of the adsorbent. The weight of
water vapor adsorbed material was tracked using an electronic balance (precise to 0.001g).
36

The pressure in the vacuum chamber was measured by a pressure gauge and controlled using
vacuum valves. A humidity and temperature transmitter (HMT330, VAISALA) recorded the
water vapor pressure, relative humidity and temperature continuously. The temperature of the
working fluid (water) was controlled by another 9600 series refrigerating/heating circulator
(Poly-Science). The K-type thermocouple used here was for measuring the temperature of the
water when it evaporated under the low pressure condition. Four vacuum valves controlled
the amount of water vapor evaporated in the vacuum chamber.

Figure 3.15: Schematic diagram of the adsorption rate test unit

37

1: vacuum pump, 2: digital temperature controller, 3: pressure gauge, 4: water tank, 5:


pressure gauge, 6: vacuum test chamber, 7: weight balance and composite adsorbents, 8:
digital temperature controller, 9: thermocouple, 10: control system, 11: vacuum valves
Figure 3.16: The adsorption rate test unit

First, the samples were carefully put in the test chamber. Next, the temperature inside the
chamber was increased in order to perform the desorption process for the samples and ensure
that all the water vapor in the composite adsorbent was desorbed before performing the
adsorption test. After that, the adsorption test began by closing valves 1 and 2 while valves 3
and 4 were opened to purge any air and water vapor in the vacuum chamber. When the
pressure gauge indicated about 40 Pa, valve 3 was closed and valve 2 was opened
immediately, while valve 1 was kept closed and valve 4 opened for pumping. After 1 minute,
38

water vapor formed over the water bath. With valve 1 still closed, the pressure in the vacuum
chamber remained almost unchanged at 40 Pa, as shown on the pressure gauge. Valve 2 was
then closed and valve 1 opened slowly to allow the water vapor to flow into the vacuum
chamber. The humidity and temperature transmitter showed the water vapor level increasing
slowly. Valve 1 was then closed as soon as the water vapor pressure reached the target value.
The total amount of water adsorbed by the sample could then be read directly from the
electronic balance. After about 1.5 hours, the test was stopped since the composite adsorbent
almost achieved the equilibrium stage, at the same time recording the data.

Although the experiment results were not obtained by the repeated adsorption/desorption
cycles described above, it was found that the results were almost the same no matter doing
one cycle, two cycles or even more than three cycles. However, if the test was performed for a
few thousand times following the adsorption/desorption cycles, the performance would
decline. Therefore, the experiment was only performed once for each sample for each
working condition.

The precision of the time measurements was 0.5%. The temperature measurements using a
K-type thermocouple were precise to less than 1C. The error of the pressure measurements
by the humidity and temperature transmitter was 1%. The weight of the adsorbent was
precise within 5%. The total precision of the adsorption capacity and adsorption rate
measurements was estimated to be 8%.

3.4 Result and Discussion


3.4.1 Elemental composition
Originally, the activated carbon contained no silica, calcium or chlorine. It was just pure
carbon. After being impregnated with sodium silicate solution and calcium chloride solution,
39

silica-gel and CaCl2 co-existed inside the pores, as shown in Table 3.2. In AC07, for example,
the weight percentages of activated carbon, silica and CaCl2 were around 30%~35%,
5%~10%, and 55%~65% respectively. The XPS spectra confirmed that the impregnation
process was generally successful, as most of the silica and CaCl2 had been taken into the
pores of the activated carbon.

Table 3.2: Results of x-ray photoelectron spectroscopy of the samples


Sample No.

XPS
wt.% of Activated Carbon wt.% of Silica wt.% of CaCl2

AC01 (raw)

100

AC02

84

16

N.A.

AC03

74

26

N.A.

AC04

81

19

N.A.

AC05

30

68

AC06

39

57

AC07

33

64

AC08

69

20

11

AC09

63

24

13

AC10

74

22

AC11

73

22

AC12

66

13

21

AC13

75

10

15

40

3.4.2 Specific surface area and total pore volume


The BET specific surface areas and total pore volumes of the thirteen samples are shown in
Table 3.3. The particle sizes of these thirteen samples were almost the same, around 2040
mesh. The impregnation time clearly did not significantly affect the specific surface area or
total pore volume, because comparing AC02AC04, AC05AC07, AC08AC10 and AC11
AC13, the specific surface areas and total pore volumes were quite similar. However, there
was a significant difference among these groups. Certainly, AC01 showed the largest surface
area and pore volume, since there were many micropores/mesopores in the raw activated
carbon as shown in the Table 3.5 below. However, the smallest surface area and pore volume
was in the series AC05AC07, derived from saturated CaCl2 solution.

Table 3.3: Specific surface areas and total pore volumes of the samples
Sample No. SBET (m2 g-1) Total Pore Volume (cm3 g-1)
AC01

1117

0.5329

AC02

610

0.2934

AC03

664

0.3121

AC04

682

0.3242

AC05

118

0.0740

AC06

82

0.0449

AC07

83

0.0589

AC08

602

0.2895

AC09

626

0.2975

AC10

680

0.3270

AC11

156

0.0812

AC12

160

0.0882
41

AC13

188

0.0958

3.4.3 TGA
Figure 3.17 shows the TGA results for the different composite adsorbent samples. All had a
higher equilibrium water uptake than raw activated carbon at temperatures below 100C, and
95% of the water vapor was desorbed when the temperature reached about 100C. Table 3.4
illustrates the differences in equilibrium water uptake () between 25C and 115C. It is
clear that AC07 showed the greatest difference in equilibrium water uptake (0.805kg kg-1)
which was a 324% improvement over AC01. Figure 3.18 presents a three dimensional view of
the differences in equilibrium water uptake () with different CaCl2 solution concentrations
and impregnation times. It again shows that the higher the concentration of the CaCl2 solution
and the longer the impregnation time, better the . ACO7 therefore appears to be the best
among the adsorbents tested for open systems such as dehumidification systems.

However, it was also necessary to perform the test at lower pressure, since the TGA
determination was performed at atmospheric pressure. In adsorption cooling systems, the
adsorbent works at lower pressure conditions. The TGA and BET results suggest that the
different impregnation times in the same group did not greatly affect adsorption performance,
so the best sample in each group was chosen for low pressure comparison testing. AC01, the
raw material, was of course tested. AC02AC04 were all samples very close in their TGA and
BET results, so AC03 was chosen because its impregnation time was 48 hours, the overall
average. AC07 was another choice since it performed the best in its group, and AC10 and
AC12 were chosen for the same reason. So, AC01, AC03, AC07, AC10 and AC12 were the
best samples in their groups and were sent for further adsorption rate test at lower pressure
condition. The results are shown in the following sections.

42

Figure 3.17: TGA results of the different composite adsorbent samples at atmospheric
pressure

Table 3.4: The difference in equilibrium water uptake between 25C and 115C, , and the
percentage improvement compared with raw activated carbon at atmospheric pressure.
Sample

% Improvement

Sample

(kg kg-1)

% Improvement

(kg kg-1)

AC02

0.244

28%

AC08

0.243

28%

AC03

0.246

29%

AC09

0.236

24%

AC04

0.250

32%

AC10

0.264

39%

AC05

0.410

116%

AC11

0.412

117%

AC06

0.699

268%

AC12

0.433

128%

AC07

0.805

324%

AC13

0.332

69%

43

AC01

0.19

N.A.

Figure 3.18: An overall view of differences in equilibrium water uptake () with


different impregnation times and CaCl2 solution concentrations

3.4.4 Pore structure


The pore size distribution curve of raw activated carbon and the activated carbon after
impregnation are shown in Figure 3.19. The range of the pore size shown in Figure 3.19 is
between 3nm and 150nm. This range mainly covered the pores from meso to macro scales. It
showed that the slope of the activated carbon after impregnation reduced a lot compared to
that of raw activated carbon at the range between 3nm and 50nm, meaning the mesopores
were filled with silica-gel and CaCl2, which led to a decrease in the slope at this pore size
range.

44

Figure 3.19: Pore size distribution of activated carbon before and after impregnation

Moreover, the microporous, mesoporous & macroporous volume for all the best samples
(AC01, AC03, AC07, AC10 and AC12) are presented in Table 3.5. It was observed that the
raw activated carbon was a highly microporous material, which showed a volume percentage
of nearly 75% being concentrated within small pores with a size below 2nm. At the same time,
the value of micropores volume for composite adsorbents (AC03, AC07, AC10 and AC12)
decreased a lot, for example, the value of micropores volume for AC07 reduced about 95%. It
proved that almost all the micropores in the raw activated carbon were filled with silica-gel
and CaCl2. The weight percentage of each chemical is presented in Table 3.2 above.

Table 3.5: Pore volume of the best five samples


Samples Vmicro Vmeso+macro ( > 2nm)

Vtotal

AC01

0.400

0.133

0.533

AC03

0.220

0.092

0.312

45

AC07

0.022

0.037

0.059

AC10

0.244

0.083

0.327

AC12

0.043

0.045

0.088

All in all, from the pore size distribution curves and the pore volume values, it is known that
the micropores dominated almost 75% of the raw activated carbon, which played a very
important role in the impregnation process of silica-gel and CaCl2. Next was the mesopores,
which were partially filled with silica-gel and CaCl2. Small amounts of silica-gel and CaCl2
were inside the macropores since the volume percentage of macropores existing in raw
activated carbon was the least. Lastly, due to the fact that silica-gel and CaCl2 could be
impregnated into the micropores and mesopores of the raw activated carbon, the adsorption
capacity of the composite adsorbent was significantly improved by the role of silica-gel and
CaCl2, making micro/mesoporous activated carbon the host matrix.

3.4.5 Equilibrium water uptake


Figure 3.20 presents a three dimensional view of the adsorption isotherms. Adsorption
capacity clearly increased with the concentration of CaCl2 solution and with pressure. Figure
3.21 shows the adsorption isotherms of the individual adsorbents at 300K. The adsorption
capacity of AC01 was lower over the pressure range from 200 to 1400 Pa, but after 1600 Pa
its adsorption capacity increased slightly.

The performance of AC03 was quite close to that of AC10 in that both achieved the value of
0.13kg kg-1 at 900 Pa, but the compositions of AC03 and AC10 were completely different, as
AC03 was not soaked in CaCl2 solution. It could be concluded that 10 wt.% CaCl2 solution
was too weak to improve the water uptake performance. AC03 and AC10 were therefore
inappropriate adsorbents for adsorption cooling systems.
46

AC07 and AC12 showed the best adsorption, much better than AC01, AC03 and AC10.
AC07 exhibited the highest adsorption capacity of 0.25kg kg-1, a 992% improvement over
raw activated carbon at 900 Pa, as shown in Table 3.6. AC12 also gave a reasonable
adsorption capacity at 0.23kg kg-1, which was slightly lower than AC07. However, the
adsorption rate of AC12 was much higher than AC07, and in the lower pressure region (200
Pa750 Pa) its adsorption capacity was also higher. This was probably because AC12
contained more silica than AC07. This result again demonstrates that silica-gel could help
improve the adsorption capacity in the lower pressure region while CaCl2 enhanced it at
higher pressures. Furthermore, during the desorption process; AC12 only took around 15
minutes to desorb 90% of the water vapor at 115C. The desorption rate of AC07 was much
slower, requiring more than 30 minutes. Figure 3.21 also shows an S-shaped isotherm for
AC12, and this further reinforces the idea that AC12 is the best composite adsorbent for
adsorption cooling systems among those tested.

47

Figure 3.20: A three dimensional view of the adsorption capacity at different water vapor
pressures and CaCl2 concentrations in the impregnating solution

Figure 3.21: Water adsorption isotherms of the AC01, AC03, AC07, AC10 and AC12
samples at 300K

Table 3.6: The adsorption capacity and the percentage improvement compared with raw
activated carbon at various pressures
Water Vapor Pressure at 750 Pa
Sample

Water Vapor Pressure at 900 Pa

% Improvement

Sample

(kg kg-1)
AC01

0.0339

% Improvement

(kg kg-1)
N.A.

AC01
48

0.0226

N.A.

AC03

0.1097

234%

AC03

0.1319

484%

AC07

0.1971

481%

AC07

0.2468

992%

AC10

0.1012

199%

AC10

0.1281

467%

AC12

0.1948

475%

AC12

0.2335

933%

Water Vapor Pressure at 1000 Pa


Sample

Water Vapor Pressure at 1100 Pa

% Improvement

Sample

(kg kg-1)

% Improvement

(kg kg-1)

AC01

0.0547

N.A.

AC01

0.0495

N.A.

AC03

0.1506

175%

AC03

0.1804

264%

AC07

0.2965

442%

AC07

0.3289

564%

AC10

0.1413

158%

AC10

0.1664

236%

AC12

0.2485

354%

AC12

0.2634

432%

3.4.6 Adsorption rate


The Linear Driving Force (LDF) Model generally describes the kinetics of the adsorption
process in which the driving force is the difference between the average current and the
equilibrium concentration of an adsorbate (water vapor). For most of the fast runs, the shape
of the kinetic curves is near-exponential (Figures 3.22 3.25), which fits well with an LDF
model. Table 3.7 shows the adsorption rate coefficients (K) of the best five samples at
different low pressure levels (750 Pa1100 Pa). The adsorption rate performance of AC12 is
clearly better than that of AC07 in any pressure region because its specific surface area and
total pore volume are much larger, as shown in Table 3.3. In other words, the adsorbate (water
vapor) can be adsorbed quickly due to its fast diffusion process. This phenomenon is the same
for AC01 of which the adsorption rate coefficients at 750 Pa and 900 Pa are higher than AC12
at the same working condition. However, the adsorption rate coefficient of AC01 reduces
49

significantly when the pressure level increases because AC01 starts to adsorb more water
vapor at the higher pressure level, taking some time to saturate. Thus, the adsorption rate
coefficient of AC01 decreases significantly at the higher pressure level. Although the
adsorption rate coefficients of AC01 at 750 Pa and 900 Pa are the highest, its adsorption
capacity is the poorest. Therefore, AC01 was not considered.

However, from Figure 3.22 3.25, it seems that all samples reached the equilibrium stage,
except AC07. Actually, AC07 just achieved the equilibrium stage at 3000s. Based on the
experiment results; the final equilibrium adsorption capacity recorded at 5000s for AC07 was
0.2107g g-1 at 750 Pa; 0.2616g g-1 at 900 Pa; 0.3128g g-1 at 1000 Pa and 0.3453g g-1 at 1100
Pa. It was calculated that the adsorption capacities recorded at 3000s for AC07 shown in
Table 3.6 and in Figure 3.15 above were, on average, 6% lower than the adsorption capacities
recorded at 5000s, indicating that the error when presenting the data at 3000s was very small
(approximately 6%). So, it is reasonable to present the data for AC07 at 3000s in terms of the
equilibrium adsorption capacity and 3000s can be treated as the saturated time.

To conclude, no matter what the amount of adsorption or adsorption rate performance is,
AC12 is the best composite adsorbent for adsorption cooling systems.

50

Figure 3.22: Water adsorption rates of AC01, AC03, AC07, AC10 and AC12 at 300K
and 750 Pa

51

Figure 3.23: Water vapor adsorption rates of AC01, AC03, AC07, AC10 and AC12 at
300K and 900 Pa

Figure 3.24: Water vapor adsorption rates of AC01, AC03, AC07, AC10 and AC12 at
300K and 1000 Pa

52

Figure 3.25: Water vapor adsorption rates of AC01, AC03, AC07, AC10 and AC12 at
300K and 1100 Pa

Table 3.7: The adsorption rate coefficients of the 5 best samples at 300K.
Sample Number

AC01 AC03 AC07 AC10 AC12

Adsorption Rate Coefficient (K) x103

4.1

0.9

0.9

1.2

1.2

2.3

1.0

1.0

1.0

1.3

1.0

0.9

0.9

1.0

1.1

0.9

1.0

1.0

1.0

1.2

at water vapor pressure 750 Pa [s-1]


Adsorption Rate Coefficient (K) x103
at water vapor pressure 900 Pa [s-1]
Adsorption Rate Coefficient (K) x103
at water vapor pressure 1000 Pa [s-1]
Adsorption Rate Coefficient (K) x103
at water vapor pressure 1100 Pa [s-1]

53

3.4.7 Ideal COP and average SCP analysis


The ideal COP is equivalent to the cooling energy divided by the supplied energy, which is
shown in equation (3.7) (Chan K.C. et al., 2012). This equation shows that the difference in
equilibrium water uptake has a positive effect on the performance of adsorption cooling
systems. A larger results in a greater ideal COP. The adsorption isotherms give at the
adsorption temperature (27C) and the desorption temperature (115C). Thus the ideal COP
can be calculated as

COP

Ecooling
Esupplied

mz h fg ,adsorbate
mz [Cac Cad ](TH TL ) mz had

COP

h fg , adsorbate
[ cac Cad ](TH TL ) had

(3.7)

where is the difference in equilibrium water uptake between the adsorption and desorption
phases; mz is the mass of composite adsorbent used in the adsorption cooling system;
hfg,adsorbate is the latent heat of vaporization of water (2489kJ kg-1 at 5C); Cac and Cad are the
specific heat capacities of the composite adsorbent and the adsorbate (1.09kJ kg-1 K-1 and
4.186kJ kg-1 K-1, respectively); TH-TL is the temperature difference of the composite adsorbent
between the adsorption and desorption phases (approximately 88K) and had is the adsorption
heat of the composite adsorbent, calculated from the equilibrium between the chemical
potential for the gas and the adsorbent (Ruthven D.M., 2008). Clausius-Clapeyron equation
is used to develop the equilibrium of chemical potential (Ko D. et al., 2002). On average, the
value of the adsorption heat of the composite adsorbent is about 2885kJ kg-1. According to
equation (3.7), the ideal COP of raw activated carbon adsorbent (AC01) is about 0.37, while

54

composite adsorbent AC07 can achieve 0.71, a 92% improvement. The details are shown in
Table 3.8.

The adsorption rate is proportional to the specific cooling power (SCP), which is defined as
the cooling load divided by the mass of adsorbent. The cooling load is given by (Chan K.C. et
al., 2012)

Q m ad mz h fg ,adsorbate

(3.8)

where Q is the cooling load in Watts; m ad is the unit adsorption rate in kilograms of
.

adsorbate per kilogram of adsorbent in one second and the value of m ad is calculated by
Equation (3.6) based on the experimental result of adsorption rate coefficient (K) as shown in
Table 3.7.; mz is the mass of adsorbent in kg and hfg,adsorbate is the latent heat of vaporization of
water vapor (2489kJ kg-1 at 5oC). The SCP is given by (Chan K.C. et al., 2012):

SCP mad h fg ,adsorbate

(3.9)

The average SCP can also be calculated as:

weq

SCP

ad

h fg .water dw

0
weq

dw
0

55

(3.10)

Therefore, the higher the adsorption rate, the higher the SCP that can be obtained in an
adsorption cooling system. The results are shown in Table 3.8. AC12 has the highest SCP of
378W kg-1, a 482% improvement over AC01.

Table 3.8: The average SCP and ideal COP of the 5 best samples at 900 Pa
Sample No.

AC01 AC03 AC07 AC10 AC12

Avg. SCP (W kg-1)

65

% Improvement

N.A.

152% 372% 145% 482%

Ideal COP

0.37

0.65

0.71

0.65

0.70

% Improvement

N.A.

76%

92%

76%

89%

164

307

159

378

3.5 Summary
An adsorption rate test unit was built to study adsorption dynamics under conditions typical
for adsorption cooling systems. It provides an appropriate methodology for obtaining the
adsorption isotherm, adsorption rate, ideal COP and average SCP for an adsorbent. A
composite adsorbent (AC12) was prepared which was able to absorb up to 0.23grams of H2O
per gram of the dry adsorbent at 900 Pa, which was a 933% improvement over raw activated
carbon. The adsorption rate data were well fitted by an LDF Model. Due to its high
adsorptivity, AC12 demonstrated an average SCP of 378W kg-1 and an ideal COP of 0.7.

Overall, the results of this study demonstrate that silica activated carbon/CaCl 2 can
outperform commonly used single adsorbents such as zeolites, activated carbon and silica-gel.
AC07 can be used as an effective adsorbent in desiccant wheel dehumidification systems due
to its high difference in equilibrium water uptake () at atmospheric pressure. AC12 showed
the best adsorption performance including adsorption capacity and adsorption rate at low
56

pressure among the adsorbents tested. It has great potential as an adsorbent in adsorption
cooling systems.

57

Chapter 4

Waste Heat Driven Adsorption Chiller Simulation

4.1 Background
Waste heat and solar energy can both be used in adsorption cooling systems to reduce reliance
on fossil fuel energy. Both are economical, clean and green sources of energy. However, solar
energy is rather unsteady and cannot be used during night time. The investment in solar
collectors is also high. However, waste heat can be obtained cheaply in power stations,
chemical plants and diesel engines, and is much more stable than solar energy (Wang D.C. et
al. 2006a; Akahira A. et al. 2004 and Saha B.B. et al. 2003a). In view of this, the usage of
waste heat in a cooling system is a valuable and significant green energy approach.
Absorption cooling systems (liquid-gas) and adsorption cooling systems (solid-gas) are two
types of cooling systems that can utilize waste heat. By comparing the materials involved,
adsorption cooling systems have certain advantages, e.g., simple structure, non-corroding, no
crystallizing problem, non-toxic adsorbate and are easily adapted for a mobile setup (Zhang
L.Z. and Wang L., 1997; Wang R.Z., 2001; Wang R.Z. and Oliveira R.G., 2006). Adsorption
cooling systems are environmentally benign (Meunier F., 1993) and have good energy saving
potential for buildings, particularly in commercial buildings or hospitals with waste heat
easily obtained from sources such as commercial kitchens and boiler exhaust.

Much work (Suzuki M., 1993; Zhang L.Z. and Wang L., 1997; Zhang L.Z., 2000; Wang R.Z.,
2001; Wu J.Y., et al. 2002; Saha B.B., et al. 2003b; Khedari J., et al. 2003; Miltkau T. and
Dawoud B., 2002; Khan M.Z.I., et al. 2006) has been conducted in the study of adsorption
cooling systems driven by waste heat. A review of literature reveals that numerous
investigations were reported on various adsorption system configurations, experimental
investigations and mathematical modeling of the steady state and transient behavior of
adsorption cycles (Critoph R.Z. and Zhong Y., 2005; Yong L. and Sumathy K., 2002;
58

Srivastava N.C. and Eames I.W., 1998). It should be noted that the performance of adsorption
chillers depends hugely on the adsorption isotherms, kinetics and the isosteric heat of
adsorption of the adsorbent adsorbate pair (Wang R.Z. and Oliveira R.G., 2006). A number
of adsorbent adsorbate pairs have been studied theoretically and experimentally by different
researchers for use in adsorption chillers and their performance is summarized in Table 4.1.
Among them, silica gel, zeolite 13X, activated carbon and CaCl2 are the popular ingredients
for constructing composite adsorbents. A number of recent achievements related to low
temperature driven adsorption cooling systems were reported. Xia Z.Z., et al. (2009)
developed a novel adsorption chiller employing silica gel-water pair with a methanol
evaporator to produce the cooling effect. They obtained a coefficient of performance (COP)
of 0.39 with the heat source temperature of 82.5C, cooling water temperature of 30.4C, and
the chilled water outlet temperature of 12C. Saha B.B., et al. (2009) investigated a two-bed
adsorption chiller using a composite adsorbent called the SWS-1L (CaCl2 confined to KSK
silica gel). The SWS-1L has a high water adsorption capacity (Aristov Y.I., 2007), which
shows a favorable characteristic as an adsorbent for adsorption chillers. Further, described in
Chapter 3 above, a new composite adsorbent material (silica activated carbon/CaCl2) was
developed which was synthesized from activated carbon, silica-gel and CaCl2. The optimized
condition for adsorption cooling systems was obtained when raw activated carbon was
impregnated by soaking in 10 wt.% sodium silicate solution for 48 hours and then in 30 wt.%
CaCl2 solution for 48 hours. The adsorption isotherms of the composite adsorbent were
studied showing it was able to adsorb up to 0.23grams of H2O per gram of the dry adsorbent
at 27C and a water vapor pressure of 900 Pa. This was a 933% improvement over raw
activated carbon. The adsorption rate data were well fitted by a linear driving force model.
Due to its high adsorptivity, the composite adsorbent (silica activated carbon/CaCl2)
demonstrated an ideal COP of 0.7 and an average SCP of 378W kg-1. However, the ideal COP
and average SCP were only based on the adsorption capacity and adsorption rate instead of
59

the whole adsorption/desorption cooling cycle. It is not known whether such high values can
still be reached in an actual adsorption/desorption cycle. In order to investigate the possibility
of implementing this material to an adsorption cooling system, in this chapter, the
performance of a waste heat driven adsorption chiller using the silica activated carbon/CaCl2
composite adsorbent were analyzed by the modeling approach. The results were compared
with those of silica-gel + water based or activated carbon + water based adsorption chillers.
The heat and mass transfer characteristics of the adsorption heat exchangers, and the energy
balance in the evaporator and condensers were taken into account in the model. In this chapter,
the effects of the total cycle time on the system performance including the COP and SCP are
also addressed.

Table 4.1: Summary of adsorbent adsorbate pair for adsorption cooling systems
Adsorbent Adsorbate Pair

Adsorption characteristics & System

Reference

performance
Silica gel (type RD) + Water

Silica gel (type RD) + Water

Electro-Adsorption chiller

Ng K.C., et al.,

eq = 0.45Kg Kg-1

2006.

COP = 0.8

[Experiment]

Two bed / four bed adsorption chiller

Chua H.T., et al.,

eq = 0.45Kg Kg-1

2004

Optimum COP = 0.35 for cooling

[Calculation]

capacity of 10KW
Zeolite + Water

Evaporating temperature at 5C.

Lai H.M., 2000

Intermittent convective thermal wave

[Calculation]

cycle
COP = 0.9

60

SCP = 250W Kg-1


Zeolite 13X/CaCl2 + Water

COP = 0.76

Chan K.C., et al.,

SCP = 18W Kg-1

2012
[Calculation]

Activated carbon + Ammonia

Evaporating temperature at 3C.

Critoph R.E., 1999

Convective thermal wave cycle.

[Calculation]

COP = 0.67
SCP = 557W Kg-1
Activated carbon/CaCl2 +

Evaporating temperature at -15C

Wang L.W., et al,

Ammonia

COP = 0.41

2006b

SCP = 731W Kg-1

[Experiment]

Evaporating temperature at -15C

Oliveira R.G., et

COP=0.3

al., 2007

SCP=1000W Kg-1

[Calculation]

Activated

eq = 0.23Kg Kg-1 (900 Pa)

Tso C.Y. and

carbon/Silica-gel/CaCl2 +

COP = 0.7

Chao C.Y.H.,

Water

SCP = 378W Kg-1

2011

Graphite/CaCl2 + Ammonia

[Calculation]
SrCl2/NiCl2 + NH3

Metal hydride + Hydrogen

Evaporating temperature at -10C

Pons M., et al.,

COP = 0.32

1999

SCP 230W Kg-1

[Experiment]

Evaporating temperature at -10C

Willers E. and

COP = 0.43

Groll M., 1999

SCP = 50W Kg-1

[Experiment]

61

Calculation: data calculated from the adsorption performance of working pairs or from the
simulation of an adsorption refrigeration cycle.
Experiment: data obtained experimentally.
Remark: eq, COP and SCP were obtained under various conditions and adsorption system
configurations; the values shown are for reference only.

4.2 Working principle of a waste heat driven, double bed, composite adsorbent based +
water adsorption chiller
The adsorption cooling system can be compared to conventional cooling systems of air
conditioners, chillers or refrigerators in which the electric powered mechanical compressor is
replaced by an adsorber. The system can be powered by a rather low temperature, e.g. waste
heat, which makes it attractive for electric energy savers (Saha B.B., et al., 2001; Wang D.C.,
et al., 2005). Further, adsorption chillers can be operated without moving parts, except where
solenoid vacuum valves are used. This results in low vibration, mechanically simple device,
high reliability and very long life time. A schematic diagram of a double-bed waste heat
driven adsorption chiller is shown in Figure 4.1, which is the most fundamental design for
building a double-bed adsorption chiller. The chiller mainly comprises four heat exchangers
(namely, an evaporator, a condenser, and two adsorber/desorber heat exchangers), four
solenoid vacuum valves, eight solenoid valves, four water pumps and three water tanks. There
is

47Kg composite

adsorbent

(Silica

Activated Carbon/CaCl2) packed in

each

adsorber/desorber heat exchanger. The cycle basically has two modes; mode A and B run
alternately. In this Chapter, simulations will be carried out based on this two-mode cycle
design to analyze the performance of a typical adsorption chiller with the implementation of
the composite adsorbent.

62

Figure 4.1: Schematic diagram of the double-bed waste heat driven adsorption chiller

In mode A, as shown in Figure 4.2 (a), valves V1, V4, V5, V8, V10 and V11 are open, while
valves V2, V3, V6, V7, V9 and V12 are closed. In this mode, adsorber A adsorbs while
adsorber B desorbs. In the adsorption-evaporation process, refrigerant (water) in the
evaporator is evaporated at evaporation temperature, Teva, and seized heat, Qeva is removed
from the chilled water. Typically, Teva is at about 5C. The evaporated vapor is adsorbed by
the composite adsorbent (silica activated carbon/CaCl2) in adsorber A, where cooling water
removes the adsorption heat, Qads. The desorption-condensation process takes place at
pressure Pcond. The desorber (adsorber B) is heated to the temperature (Tdes) by Qdes, provided
by the waste heat from hot water tank. The resulting refrigerant vapor is cooled to temperature
63

(Tcond) in the condenser by the cooling water, which removes the heat, Qcond. The condensed
refrigerant returns to the evaporator via the capillary U-tube connecting the condenser and
evaporator to complete the cycle. Use of the same cooling water tank for the condenser and
adsorber A results in similar temperature levels at the condenser (Tcond) and adsorber A (Tads).
After running in Mode A for a period of time (to be determined later), the cycle is continued
by changing into mode B.

Figure 4.2 (a): Mode A operation of the waste heat driven double bed composite
adsorbent based + water adsorption chiller

In mode B, as shown in Figure 4.2 (b), valves V2, V3, V6, V7, V9 and V12 are open while
V1, V4, V5, V8, V10 and V11 are closed. In this mode, adsorber B adsorbs while adsorber A
64

desorbs. After running in Mode B for a period of time (to be determined later) the cycle
returns to mode A.

Figure 4.2 (b): Mode B operation of the waste heat driven double bed composite
adsorbent based + water adsorption chiller

4.3 Mathematical modeling


4.3.1Assumptions
1) The temperature, pressure and the amount of water vapor adsorbed are uniform
throughout the adsorber beds.
2) There is no external heat loss to the environment as all the beds are well-insulated.
3) The condensate can flow into the evaporator easily.

65

4) All desorbed water vapor from the desorber will flow into the condenser immediately
and the condensate will flow into the evaporator directly.
5) The condensate from the condenser will evaporate instantaneously in the evaporator
and will be adsorbed by the adsorbent in the adsorber immediately.
6) The adsorbed phase is considered as a liquid and the adsorbate gas is assumed to be an
ideal gas.
7) The thermal resistance between the metal tube and the adsorbent bed is neglected.
8) Flow resistance arising from the water flowing in the pipeline is neglected.
9) The properties of the fluid, the metal tube and adsorbate vapor are constant.

According to these assumptions, the dynamic behavior of heat and mass transfer inside the
different components of the adsorption chiller can be written as shown below.

4.3.2 Equilibrium water uptake


The adsorption equilibrium for composite adsorbent/water vapor can be expressed by the
following correlation

eq A[ Pr ]

1
B

(4.1)

Where Pr refers to relative pressure and the value of equilibrium of water uptake was taken
under the constant temperature at 297K as shown in Table 4.2.

Table 4.2: Equilibrium water uptake against relative pressure


Pr

eq (kg kg-1) Temperature (k)

66

0.1

0.1065

297

0.2

0.1286

297

0.3

0.1517

297

0.375

0.1948

297

0.45

0.2335

297

0.5

0.2485

297

0.55

0.2634

297

0.625

0.276

297

0.7

0.2973

297

0.8

0.3292

297

0.9

0.3526

297

1.0

0.4241

297

Using the values above, the constant A and B in equation (4.1) can be determined and is
shown in Table 4.3.

Table 4.3: Result of the constant A and B in equation (4.1)


Constant A in equation (4.1) 0.375
Constant B in equation (4.1)

1
1.6

eq 0.375[ Pr ]

where Pr is equal to

67

1.6

(4.2)

Pr

Ps (Tw )
Ps (Ts )

(4.3)

From equation (4.3), the different values of equilibrium water uptake at different saturation
vapor pressure at temperature Tw (water vapor) and Ts (composite adsorbent) were determined.
By applying the Antoines Equation:

Ps (T ) exp(C

D
)
T E

(4.4)

where constant C is equal to 23.4776, constant D is equal to 3984.9228 and constant E is


equal to -39.724. Combining Equations (4.1) to (4.4), after calculating the saturation vapor
pressure at temperature Tw (water vapor) and Ts (composite adsorbent), the value of
equilibrium water uptake could also be calculated.

4.3.3 Adsorption rate


The adsorption process in an adsorbent bed considered to be controlled by macroscopic
diffusion. Using a linear driving force equation, the adsorption rate is proportional to the
difference between the concentrations of equilibrium and present state. Therefore, it is
expressed as

dads
kads (adseq ads )
dt

ads adseq (adseq adso ) exp Kadst


68

(4.5)

(4.6)

dads
(adseq adso ) K ads exp K adst
dt

dd e s
kd es d e s
dt

des des eq (des eq des o ) exp K dest


ddes
(des eq des o )kdes exp K dest
dt

(4.7)

(4.8)

(4.9)

(4.10)

where ads is defined as the amount of water vapor in the adsorbent during adsorption, ads
eq

is defined as the equilibrium amount of water vapor in the adsorbent during adsorption

while the subscript des represents the desorption process. The subscript o represents the
initial condition, i.e. starting condition for each mode (Mode A or B). The adsorption and
desorption rate coefficient is obtained from the experiments described in Chapter 3.

4.3.4 Heat of adsorption


When the refrigerant was adsorbed by the adsorbent, the refrigerant in gas state was caught by
the energy field and changed to adsorbed state. The adsorbed state has physical properties
similar to liquid state. The degree of freedom in the adsorbed state is much lower than the gas
state. Hence, heat from adsorption was released during adsorption in the same magnitude as
latent heat of vaporization. The adsorption heat for a specific amount of adsorbent adsorbed
can be calculated from the equilibrium between the chemical potential for the gas and the
69

adsorbent (Ruthven D.M., 2008). Clausius-Clapeyron equation was used to develop the
equilibrium of chemical potential (Ko D., et al, 2002) which is given by

ln( P) A(eq )

B(eq )

(4.11)

where the unit of P is in mbar and A(eq) and B(eq) are shown in equation (4.12) & (4.13):

A(eq ) ao a1eq a2eq a3eq

B(eq ) bo b1eq b2eq b3eq

H RB(eq )

(4.12)

(4.13)

(4.14)

where R is the real gas constant which is equal to 286.9 J Kg-1 K-1 and Hs is the heat of
adsorption. The values listed in Table 4.4 and Table 4.5 were used to get the numerical
constants in Equation (4.11) and the results are listed in Table 4.6. Therefore, according to
Equation (4.14), the adsorption heat is calculated with the value 2.3X106 J Kg-1.

Table 4.4: Equilibrium water uptake against relative pressure under 297K
Pressure (mbar) eq (kg kg-1) Temperature (k)
2

0.1065

297

0.1286

297

0.1517

297

70

7.5

0.1948

297

0.2335

297

10

0.2485

297

11

0.2634

297

12.5

0.276

297

14

0.2973

297

16

0.3292

297

18

0.3526

297

20

0.4241

297

Table 4.5: Equilibrium water uptake against relative pressure under 307K
Pressure (mbar) eq (kg kg-1) Temperature (k)
2

0.0852

307

0.1035

307

0.1263

307

7.5

0.1594

307

0.1899

307

10

0.2037

307

11

0.2344

307

12.5

0.2522

307

14

0.2711

307

16

0.2954

307

18

0.3299

307

20

0.3617

307

71

Table 4.6: Numerical values of ai & bi (i=0, 1, 2, 3) constants, which appear in the
equilibrium equation of adsorbent-adsorbate pair (silica activated carbon/CaCl2 composite
adsorbents)
Parameter

Value

Constant in equation (4.12) a0

-7.61921

Constant in equation (4.12) a1

405.3

Constant in equation (4.12) a2

-2328.3

Constant in equation (4.12) a3

3724

Constant in equation (4.13) b0

1716.9

Constant in equation (4.13) b1

-110153.3

Constant in equation (4.13) b2

664138.7

Constant in equation (4.13) b3 -1079240.2

4.3.5 Adsorption energy balance


The adsorption energy balance is described by

d
[(WcomC p com WcomC p wads C p alWal fin Wcu adsC p cu )Tads ]
dt
.
dads
d
HWcom
WcomC p v (Teva Tads ) ads mcwa C p w (Tcwa in Tcwa out )
dt
dt

(4.15)

The outlet temperature of cooling water can be expressed as

Tcwa out Tads (Tcwa in Tads ) exp(

U ad Aad
.

mcwa C p w

72

(4.16)

The left hand side of the adsorption energy balance equation (4.15) represents the rate of
sensible heat to cool the adsorption chamber including the composite adsorbent and the water
content inside. The first term on the right hand side of equation (4.15) represents the release
of adsorption heat, while the second term represents the sensible heat of the adsorbed vapor.
The last term on the right hand side of Equation (4.15) indicates the rate of heat transferred to
the cooling water upon adsorption. The outlet temperature of the cooling water can be
calculated by considering the heat transfer from the cooling water to the adsorber. Equation
(4.16) expresses the importance of heat transfer parameters, namely heat transfer area Aad and
heat transfer coefficient Uad.

4.3.6 Desorption energy balance


The desorption energy balance is described by

d
[(Wcom C p com Wcom C p w des C p alW fin al C p cu Wcu des )Tdes ]
dt
d des .
HWcom
m hot C p w (Thw in Thw out )
dt

(4.17)

The outlet temperature of the hot water can be expressed as

Thw out Tdes (Thw in Tdes ) exp(

U de Ade
.

(4.18)

m hot C p w

The left hand side of the adsorption energy balance equation (4.17) represents the rate of
sensible heat to heat the desorption chamber including the composite adsorbent and the water
content inside. The first term on the right hand side of equation (4.17) represents the heat
73

required in the desorption process, while the second term represents the rate of heat provided
by the waste heat hot water supply. Equation (4.18) expresses the importance of the heat
transfer parameters, namely the heat transfer area Ade and the heat transfer coefficient Ude.

4.3.7 Energy balance for the condenser


The condenser energy balance equation can be written as

dTcond
ddes
(C p cuWcu,cond WcwC p w ) LwWcom

dt
dt
ddes .
WcomC p w (Tdes Tcond )
mcwc C p w (Tcwc in Tcwc out )
dt

(4.19)

The outlet temperature of cooling water is given as

Tcwc out Tcond (Tcwc in Tcond ) exp(

U cond Acond
.

(4.20)

mcwc C p w

The left hand side of Equation (4.19) represents the rate of sensible heat required by the
metallic parts of the heat exchanger tubes due to the temperature variations in the condenser.
On the right hand side, the first term gives the latent heat of vaporization (Lw) for the rate of
refrigerant desorbed (

) and the second term shows the rate of sensible heat required to

cool the incoming vapor from the desorber at temperature Tdes to condenser at temperature
Tcond, and the last term represents the total rate of heat released to the cooling water.

4.3.8 Energy balance for the evaporator


The energy balance in the evaporator is expressed as:
74

d ads
d
[(Weva C p , w C p ,cu Wcu ,eva )Teva ] LwWcom

dt
dt
d des .
Wcom C p , w (Tcond Teva )
m ch C p ,c (Tchw,in Tchw,out )
dt

(4.21)

The outlet temperature of chilled water can be written as:

Tchw out Teva (Tchw in Teva ) exp(

U eva Aeva
.

mch C p c

(4.22)

The left hand side of equation (4.21) represents the rate of sensible heat required by the liquid
refrigerant and the metal of the heat exchanger tubes in the evaporator. On the right hand side,
the first term gives the latent heat of evaporation (Lw) for the rate of refrigerant adsorbed
(

) and the second term shows the sensible heat required to cool the incoming condensate

from the condensation temperature Tcond to evaporation temperature Teva, while the last term
represents the total rate of heat given away by the chilled water. Weva is the total mass in the
evaporator and will be found in the next section.

4.3.9 Mass balance in the evaporator


The mass balance of the refrigerant (water in liquid form inside the evaporator) is written as:

dWeva
d
d
Wcom des Wcom ads
dt
dt
dt

75

(4.23)

where Wcom is the weight of the composite adsorbent used in the adsorption chiller and Weva is
the weight of water in the evaporator.

4.3.10 Measure of system performance


The specific cooling power of the system is expressed by

t cycle

m ch C p c
SCP

(T

chw in

Tchw out )dt

Wcomtcycle

(4.24)

The COP value is defined by the following equation

t cycle

m ch C p c
COP
.

m hot C p w

(T

chw in

Tchw out )dt

0
t cycle

(T

hw in

Thw out )dt

(4.25)

The system of differential equations (4.1) (4.25) was solved simultaneously by numerical
integration using finite difference substitution in the derivatives. The values of physical
parameters used in the calculations are shown in Table 4.7. In reality, a chiller starts operation
with indeterminate conditions; however, after a few cycles, it reaches its cyclical steady state
condition. Similarly, iteration process is employed in the solution procedure. At the beginning
of the solution process, initial values are assumed and the energy equations are solved in the
sequence of desorption (Eq. 4.17), condenser (Eq. 4.19), evaporator (Eq. 4.21) and adsorption
(Eq. 4.15), followed by a heat and mass recovery, in which Tads and Tdes are reset, taking their
76

averaged value. Then the energy equations are solved again until the satisfactory convergence
criterion is achieved. The calculations were made with a time interval of 0.02s and the
iteration stops when the absolute difference between successive cycles is smaller than 10-3.
In the simulation, the adsorber A and B change their role of adsorption and desorption
alternatively; mode A is employed in every odd iteration while the system is operating in
mode B in each even iteration.

Table 4.7: Values of parameters adopted in the simulation


Symbol

Value

Unit

Aad (Heat transfer area in adsorber)

2.46

m2

Ade (Heat transfer area in desorber)

2.46

m2

Acond (Heat transfer area in condenser)

3.73

m2

Aeva (Heat transfer area in evaporator)

1.91

m2

Cp,cu (Specific heat of copper)

386

J Kg-1 K-1

Cp,al (Specific heat of aluminum)

905

J Kg-1 K-1

Cp,w (Specific heat of water in liquid phase)

4180

J Kg-1 K-1

Cp,v (Specific heat of water in vapor phase)

4190

J Kg-1 K-1

Cp,c (Specific heat of chilled water)

4200

J Kg-1 K-1

Cp,com (Specific heat of composite adsorbent)

930

J Kg-1 K-1

H (Heat of Adsorption)

2.30E+06

J Kg-1

Kads (Adsorption rate coefficient)

1.30E-03

s-1

Kdes (Desorption rate coefficient)

1.20E-03

s-1

Lw (Latent heat of vaporization)

2.5E+06

J Kg-1

Uad (Overall heat transfer coefficient of adsorber)

1602.56

W m-2 K-1

Ude (Overall heat transfer coefficient of desorber)

1724.14

W m-2 K-1

77

Ucond (Overall heat transfer coefficient of condenser)

4115.23

W m-2 K-1

Ueva (Overall heat transfer coefficient of evaporator)

2557.54

W m-2 K-1

Wal,ads/des (Weight of aluminum fin in adsorber/desorber)

51.2

Kg

Wcu,ads/des (Weight of copper in adsorber/desorber)

64.04

kg

Wcom (Weight of composite adsorbent)

47

kg

Wcu,eva (Weight of copper in evaporator)

12.45

kg

Wcu,cond (Weight of copper in condenser)

27.28

kg

Wcw (Weight of condenser cooling water)

15

Kg

4.4 Result and discussion


In order to analyze the performance of the new composite adsorbent, cyclic simulation runs
were performed. Since our main interest is to utilize low grade waste heat as the driving
source, the investigation was conducted for hot water between 50 and 95C. The base line
parameters and standard operating conditions for the chiller operation are listed in Table 4.7
and Table 4.8, respectively. The effect of operating temperature (hot and cooling water) was
calculated by the simulation runs.

Table 4.8: Nominal operating condition for the 2-bed adsorption chiller
Parameter

Symbol Value

Hot water inlet temperature


Hot water mass flow rate
Adsorber cooling water inlet temperature
Adsorber cooling water mass flow rate
Condenser cooling water inlet temperature

78

Thw in
.

m hot
Tcwa in
.

m cwa
Tcwc in

Unit

85

1.7

Kg s-1

30

1.7

Kg s-1

30

Condenser cooling water mass flow rate


Chilled water inlet temperature
Chilled water mass flow rate

mcwc
Tchw in
.

m ch

1.3

Kg s-1

14

0.7

Kg s-1

4.4.1 Temperature profile of the heat transfer fluids


Figure 4.3 shows the inlet and outlet temperature profiles of the hot, cooling and chilled water
obtained at the rated condition. After about 300s, the hot water outlet temperature approaches
the inlet temperature value (85C). Similarly, the cooling water outlet temperature from the
adsorber approaches its inlet temperature at 360s. From this time onward there is practically
no further consumption of driving heat. This led the authors to select the standard
adsorption/desorption cycle time as 360s or less, as further discussed in a later section. The
delivered chilled water temperature is kept below its inlet temperature in the whole cycle,
showing the continuation of cooling energy production, which is highly desirable as a cooling
system.

79

Figure 4.3: Overall outlet temperature profile of heat transfer fluid for 2-bed adsorption
chiller

4.4.2. The time variation of water content


The water content of the adsorbent beds at the nominal operating condition is depicted in
Figure 4.4. During the first 360s, the adsorbent in bed A was in adsorption (Mode A) and the
water content of the adsorbent was increased to about 0.2kg kg-1. At the same time, the
adsorbent in bed B was in desorption mode and the water content of the adsorbent was
decreased to about 0.1kg kg-1. The adsorbents exchange their roles in the next 360s (mode B)
and return to mode A in the third cycle.

80

Figure 4.4: The time variation of water content in two adsorbers

4.4.3 The COP & SCP performance


Simulated results of SCP and COP variations for activated carbon, silica-gel and silica
activated

carbon/CaCl2

(composite

adsorbent)

based

adsorption

chiller

with

adsorption/desorption cycle times are shown in Figure 4.5 and 4.6, respectively. It is clear that
the COP increases monotonically with the cycle time because, with a longer cycle time, the
consumption of driving heat is reduced at a faster rate than the reduction of useful energy
production in chilled water which leads to a favorable effect on the COP. The variation of
SCP is not monotonic. It increases steeply up to 100s, and it begins to decrease steadily for
cycle time over 100s. As SCP will keep decreasing after 360s as shown in Figure 4.6, a longer
adsorption/desorption cycle time would not deliver a higher performance in terms of the
cooling capacity.

By balancing the results between the SCP and COP (with values equal to

380W Kg-1 and 0.65, respectively), Figure 4.5 & 4.6 suggest a suitable cycle time around
360s. A comparison of different adsorbents at the same nominal operating condition is shown
in Table 4.9.
81

Table 4.9: Comparison of the different adsorbents


Activated Carbon Silica-gel Silica Activated Carbon/CaCl2
COP

0.41

0.49

0.65

SCP (W Kg-1)

189

245

380

Table 4.10 shows the comparison of the simulation results between this study and some
improved design at the same working condition with the hot water inlet and cooling water
inlet temperature, but the adsorption/desorption cycle time is selected at their optimum
cycling time. As shown in Table 4.10, the silica activated carbon/CaCl2 + water based
adsorption chiller is better than the Silica-gel/CaCl2 + Water based adsorption chiller (Saha
B.B., et al., 2009) in terms of COP while the SCP is comparable. It is Also better than an
improved (in structure) chiller (Miyazaki T., et al., 2010) for the SCP while the COP is only
slightly decreased. Therefore, this novel silica activated carbon/CaCl2 composite adsorbent +
water based adsorption chiller is another effective cooling machine compared to some
formerly developed adsorption chillers.

Table 4.10: Comparisons of the simulation results between this study and some
improved design

Adsorbent

Miyazaki et al., 2010

Saha et al., 2009

(Improved in

(Improved in

structure)

composite adsorbent)

Silica-gel

Silica-gel/CaCl2

Material
COP

This study

Silica Activated
Carbon/CaCl2

0.77

0.46
82

0.65

SCP (W Kg-1)

160

480

380

Figure 4.5: Effect of COP against the adsorption-desorption cycle time

83

Figure 4.6: Effect of SCP against the adsorption-desorption cycle time

4.4.4 Hot water temperature influence


As the driving force, the hot water inlet temperature is one of the key parameters for
adsorption chillers. A high hot water inlet temperature causes a large temperature increase for
the system with the same cooling water inlet temperature. The large temperature increase
results in a high cooling power and low chilled water output temperature, as shown in Figure
4.7 & 4.8. Because water vapor is desorbed faster at the higher desorption temperature it
causes more water vapor to be adsorbed during the next adsorption process. If the hot water
inlet temperature is higher than a certain value (e.g. 85C), the value of COP does not
continue to increase significantly as shown in Figure 4.9. After reaching 85C, the COP tends
to remain unchanged. Although the SCP increases continuously, it has already achieved a
sufficient value at 85C (Table 4.10). Besides, 85C is within the working temperature range
84

for low grade heat sources from waste heat. All in all, the composite adsorbent studied in this
chapter was suitable for use in waste heat driven adsorption chillers.

In Figure 4.7 & 4.9, the SCP and COP are compared with other adsorbents, silica-gel and
activated carbon. For silica-gel + water based adsorption chillers and activated carbon + water
based adsorption chillers, the COP reaches the maximum value of 0.49 and 0.43 at T = 80
95C, respectively. However, for a silica activated carbon/CaCl2 (AC12) + water based
adsorption chiller at this temperature range the COP is larger (0.61 - 0.65) at about 33%
improvement to the silica-gel and 51% improvement to the activated carbon. This much larger
COP shows the significant advantage of the new working pair as compared with the
conventional unit. Thus, from the present simulation results, it was found that the new silica
activated carbon/CaCl2 based adsorption chiller provides a promising unit for cooling
applications.

85

Figure 4.7: Effect of SCP on hot water inlet temperature

Figure 4.8: Effect of chilled water outlet temperature on hot water inlet temperature

86

Figure 4.9: Effect of COP on hot water inlet temperature

4.4.5 Cool water temperature influence


The cooling water temperature is one of the decisive factors on the performance of the
adsorption chiller because it influences not only the condensation process but also the
adsorption process. A high cooling water temperature results in a high temperature in the
condenser and adsorption chamber. Consequently, both desorption and adsorption processes
deteriorate in performance, losing more refrigerating power. The lower the cooling water inlet
temperature, the higher COP, SCP and the lower chilled water outlet temperature as shown in
Figures 4.10, 4.11 & 4.12, because more water vapor is adsorbed by the composite adsorbent
at a lower temperature for a given cycle time. For energy saving, it is desirable to use room
temperature water as cooling water for removal of the adsorption heat. Due to the water pump
operation, the cooling water inlet temperature may rise, but even though the cooling water
87

inlet temperature reaches 30C, the COP can still maintain a high value, close to 0.67, only
3% drop when compared to the cooling water inlet temperature at 20C. Therefore, the
present composite adsorbent based adsorption chiller system can use room temperature water
as cooling water even if the inlet temperature rises to 30C.

Figure 4.10: Effect of COP on cooling water inlet temperature

88

Figure 4.11: Effect of SCP on cooling water inlet temperature

Figure 4.12: Effect of chilled water outlet temperature on cooling water inlet temperature

89

4.4.6 Chilled water inlet temperature influence


Figure 4.13 & 4.14, respectively show the COP and SCP variations with different chilled
water inlet temperature. It shows that an increase of 6C in the chilled water inlet temperature
only causes about 5% improvement of COP and about 4% that of SCP with the same hot
water

inlet

temperature,

the

same

cooling

water

temperature

and

the

same

adsorption/desorption cycle time. Based on those facts, increasing the chilled water inlet
temperature has only minor effects on the system performance. So, the chilled water inlet
temperature is not a major parameter for consideration when studying adsorption chillers.

Figure 4.13: Effect of COP on chilled water inlet tempearture

90

Figure 4.14: Effect of SCP on chilled water inlet temperature

91

Figure 4.15: The relationship between chilled water outlet temperature and inlet
temperature

4.5 Summary
In this Chapter, the performance of silica activated carbon/CaCl2 + water based adsorption
chiller using the modeling approach has been successfully modeled and predicted. It was
found that the performance of an adsorption chiller incorporating the composite adsorbent, in
terms of coefficient of performance (COP), specific cooling power (SCP) and chilled water
outlet temperature were better than those of the commercially available silica-gel + water
based or activated carbon + water based adsorption chillers and even better than some
improved adsorption chillers (Miyazaki T., et al., 2010; Saha B.B., et al., 2009). The
simulation results also show that high SCP and COP of the adsorption chiller can be obtained
(380W Kg-1 and 0.65, respectively), when the hot water temperature is 85C, cooling water
inlet temperature is 30C and chilled water inlet temperature is 14C. The heat source
92

temperature is well suited to waste heat and room temperature water can be utilized in the
cooling water tank. Therefore, this kind of adsorption chiller is potentially a highly effective
refrigerating machine and may offer an attractive possibility for improving energy efficiency.

93

Chapter 5 Conclusion and Future Work

5.1 Conclusion
In this study, the effect of composite adsorbent material, composed of silica-gel, activated
carbon and CaCl2, was studied with different synthesis parameters. It was shown that most of
the silica-gel and CaCl2 were impregnated into the micropores or mesopores of the activated
carbon. The chemical composition, equilibrium water uptake, adsorption rate, specific surface
area, total pore volume and pore size distribution of the silica activated carbon/CaCl2
composite adsorbent material were measured. A maximum of 0.805kg kg-1 difference in
equilibrium water uptake at temperature between 25C and 115C and at room pressure
condition was recorded. The optimized composition for this result consisted of activated
carbon soaked in a 10 wt. % sodium silicate solution for 48 hours and then soaked in a 46 wt.
% CaCl2 solution for 72 hours. This represented a 324% increase over the difference in
equilibrium water uptake of pure activated carbon. The specific surface areas and the total
pore volume of the silica activated carbon/CaCl2 were decreased. It was shown that the
impregnation process for both silica-gel and CaCl2 was successful. Also, based on the pore
size distribution curve, it indicated that the micropores and mesopores were the major pores
existing in the raw activated carbon material.

As the equilibrium water uptake was performed at room pressure condition, it cannot
represent its performance for adsorption cooling systems. An adsorption rate test unit was
built in order to test its adsorption capacity and adsorption rate at low pressure condition. A
high difference in equilibrium water uptake, 0.23kg kg-1, between 25C and 110C under 870
Pa was recorded for the composite adsorbent soaked in 10 wt. % sodium silicate solution for
48 hours and then soaked in 30 wt. % CaCl2 solution for 48 hours. This was 933%
improvement over raw activated carbon under the same condition. It was expected that the
94

silica activated carbon/CaCl2 composite adsorbent would show a much better performance
than the raw activated carbon. The ideal COP of the adsorption cooling systems using silica
activated carbon/CaCl2 composite adsorbent was increased to 0.7, an 89% improvement
compared to the raw activated carbon. Desorption for the silica activated carbon/CaCl2
composite adsorbent can also be completed at around 75oC to 100oC. So, low grade thermal
energy like solar energy or waste heat energy can be more easily utilized as an energy source
for this system. In addition, the average SCP was increased to 378W Kg-1, a 482%
improvement. This high average SCP value was entirely due to the high value of adsorption
rate of the silica activated carbon/CaCl2 composite adsorbent material, resulting in the ability
to make adsorption cooling systems much smaller than before.

As the ideal COP and average SCP calculation was based on the adsorption capacity and
adsorption rate described in Chapter 3, it was unknown whether the silica activated
carbon/CaCl2 composite adsorbent could be used in adsorption cooling systems in terms of the
real cycle performance. Thus, the cycle performance of a waste heat driven double-bed
composite adsorbent material based + water adsorption chiller was studied in numerical
simulation in Chapter 4. This simulation model successfully predicted all the adsorption
chiller system performances. The COP, SCP, chilled water outlet temperature and the
adsorption/desorption cycle time were found. From the simulation result, it was suggested that
high SCP and COP of the adsorption chiller could be obtained (380W Kg-1 and 0.65,
respectively), when the hot water inlet temperature was 85C, cooling water inlet temperature
was 30C and chilled water inlet temperature was 14C. 360 seconds was the most optimized
adsorption/desorption cycle time. Lastly, the simulation results also indicated that the COP
and SCP performance using composite adsorbent were much better than that of the traditional
adsorbent material, and even some results in this study were better than other composite
adsorbent materials developed by other research teams. Therefore, this kind of adsorption
95

chiller is potentially a highly effective refrigerating machine and may offer an attractive
possibility to improve energy efficiency. And, the adsorption cooling system using this silica
activated carbon/CaCl2 composite adsorbent has high potential in replacing vapor
compression chillers to produce chilled water for central air-conditioning systems. Electricity
consumption can be reduced and the pollution problem of using refrigerant can be solved.

5.2 Future Work


5.2.1 Build a prototype of the adsorption air conditioner
The development of the advanced composite adsorbent has been completed. The next step is
to build a prototype of the adsorption cooling system to verify the real performance of the
composite adsorbent. The design of the system will be aided by the simulation model. The
suggestions made in the simulation will be employed to test for improvements. The schematic
diagram of an adsorption air conditioner is shown in Figure 5.1. It is a double bed adsorber
design with heat and mass recovery process which can provide continuous cooling. There will
be flow meters (F), thermocouples (T) and pressure sensors (P) for monitoring the system
cycle performance. The system cycle will consist of four phases including I) Adsorber 1
adsorbs and Adsorber 2 desorbs, II) mass recovery of water vapor between the adsorbers, III)
heat recovery of heat transfer fluid between the adsorbers and IV) Adsorber 1 desorbs and
Adsorber 2 adsorbs. The 21 solenoid valves will be operated in 8 sets, allowing the four
phases to be performed in different sequences and duration. There will be four phase
sequences tested: A) IIVI, B) IIIIVIII, C) IIIIIIIIII and D)
IIIIIIIVIIIIII. The individual effect of heat recovery and mass recovery can be
fully investigated by operating different phase sequences. A LabVIEW program with data
acquisition and control devices will be used to record the signals from the sensors and control
the solenoid valves. The system SCP, COP and efficiency will be found. The results obtained
from simulation will be compared to the prototype to verify the accuracy of the simulation.
96

The simulation model can then be used to further study any other changes in the system
without building a new prototype every time.

Recently, a prototype of a silica-gel + water based adsorption air conditioner was built based
on the schematic diagram of the dual-adsorber adsorption air conditioner as shown in Figure
5.1. The temperature difference between the air in-take and out-take (T) was about 3C. The
lowest air out-take temperature achieved was around 18C. The COP was about 0.15 and the
cooling power was around 200W. Based on the results reported, the performance of this
prototype was not good, mainly because the adsorber size was so small that only a small
amount of adsorbent (only 2kg silica-gel adsorbent was used in this prototype) was used. It
could not adsorb a huge amount of water vapor evaporated from the chilled water tank. It was
also difficult to maintain a low pressure in the chilled water tank. As a result, the chilled water
outlet temperature could not be lowered, which caused high air out-take temperature. In
addition, the heat transfer piping between the adsorbers and condenser was too long, so that
most of the water vapor had already condensed in the copper transmitting tubes. The water
vapor evaporated from the chilled water tank had to pass through a very long channel, which
significantly affected the adsorption and desorption performance. Therefore, the overall
performance of the adsorption air conditioner has to be improved in the following months to
solve the problems mentioned above. After that, the cooling power and COP can be enhanced
and the air out-take temperature can be lowered.

Some preliminary result is obtained based on the prototype of the adsorption air conditioner
which is shown in the Figure 5.3. The temperature difference of the chilled water inlet and
outlet temperature is shown at about 3 C which is quite low. The target or the normal
temperature difference of an adsorption air conditioner should be at around 5-6 C. So, some
improvement is required for this prototype of the adsorption air conditioner.
97

EER of this adsorption air conditioner is calculated at about 4.2 which is higher than the COP
of the similar scale of the traditional vapor compression system. Again, these preliminary
results can confidently show that the adsorption air conditioner can be a good competitor to
the traditional vapor compression system, even it is better than the absorption cooling
systems.

Figure 5.1: Schematic diagram of the dual-adsorber adsorption air conditioner

98

Figure 5.2: The prototype of a silica-gel + water adsorption air conditioner

99

Figure 5.3: The temperature profile of the heat transfer fluid in adsorption air conditioner

5.2.2 Upgrade the prototype of the adsorption air conditioner


Due to the poor performance of the prototype adsorption air conditioner mentioned in Section
5.2.1, a larger adsorber must be built to accommodate more adsorbent. A new inner
component of the adsorber was assembled, shown in Figure 5.4. Each of the inner
components can carry about 4Kg adsorbent. There are 7 new inner components for the
adsorber. So, the adsorber can now hold 28Kg of adsorbent. The new adsorber design is
shown in Figure 5.5. As the amount of adsorbent is increased by 14 times, the cooling
performance of the adsorption air conditioner can be significantly improved. A higher COP
and SCP can be recorded. The air temperature difference (T) can also be increased
accordingly.

100

Figure 5.4: One unit of the adsorber

101

Figure 5.5: A whole adsorber assembly design drawing

5.2.3 Capillary-assisted evaporator in adsorption cooling systems


Besides upgrading the amount of adsorbent, it is also possible to study the evaporator. This
further research work should aim at developing a capillary-assisted evaporator for an
adsorption cooling system to enhance the performance. The concept is to make use of
capillary suction to increase the effective evaporation surface area, a process requiring zero
additional energy but could enhance the evaporation rate of the adsorbate. A schematic
diagram of the capillary-assisted evaporator is shown in Figure 5.6. A pack of heat transfer
tubes with external circumferential capillary-grooves are held horizontally and are partially
immersed into trays holding the liquid adsorbate. The trays are stacked and sandwiched with
space to make the overall evaporator more compact. By capillary suction, the liquid will flow
102

upward along the micro-grooves and form a liquid thin film to cover the heat transfer tube, as
shown in Figure 5.6. Process air will pass through the heat transfer tube and heat will be
transferred from the air to the evaporating liquid film, resulting in the process air being cooled.
The following design factors of the capillary-assisted evaporator will be studied in order to
optimize the performance: (i) shape and dimensions of capillary-grooves (triangular,
trapezoidal, sinusoidal or rectangular), (ii) diameter and material of the heat transfer tubes, (iii)
spacing between the grooves, (iv) immersion depth, and (v) working temperature and pressure.
Experiments to measure the evaporation rate of the adsorbate under each design will be
conducted. Numerical models will also be constructed. It is expected that the evaporation
coefficient of the capillary-assisted evaporator will be greatly enhanced by 30 - 40%. This
will also improve the heat transfer efficiency between the air and adsorbate, which improves
the coefficient of performance (COP) of the adsorption cooling system. The specific cooling
power (SCP) of the system will also be increased by 30 - 40% owing to the enhanced
evaporating mass flow rate and compact design. Additional advantages of such an evaporator
include structural simplicity and low cost.

103

Figure 5.6: Schematic diagram of the capillary-assisted evaporator

5.2.4 Development of nanofluid enhanced adsorption cooling systems


Research of nanoparticles on heat transfer and nanofluid on fuel droplet evaporation has
become a very hot topic. Nanofluids are solutions containing particles of sizes typically in the
range of 10 100 nm. They are known to exhibit different thermo-physical properties from
their base fluids such as thermal conductivity, surface tension, wettability, and
non-Newtonian viscosity (Wang X. et al., 1999; Sefiane, K. et al., 2008; Phuoc T.X. et al.,
2009) because they have a very high surface to volume ratio. For metal nanoparticles such as
zinc and silver, the percentage of atoms on the surface dramatically increases when the size is
below 10nm (Phuoc T.X. et al., 2009). Available results indicate that nanofluids made from
metal particles and water or engine oil can improve heat transfer by up to 40% (Wang X.,
1999); more than 250% improvement has been shown for multiwalled carbon nanotubes
(mean diameter and length of 25nm and 50nm, respectively) (Choi S.U.S. et al., 2001). Such
an enhancement could occur for particle concentrations lower than 1% and as low as 0.001%.
104

These phenomena could not be explained by conventional theories developed for pure fluids.
The effect nanoparticles have implications in liquid evaporation practice. In other words, if
the nanoparticles can help increase the evaporation rate of their base fluids, the cooling
performance of an adsorption cooling system could be improved accordingly and this will be
another way to improve the cooling performance of adsorption cooling systems.

105

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