Escolar Documentos
Profissional Documentos
Cultura Documentos
BY
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
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
Objectives ........................................................................................................... 17
Chapter 3
vii
List of Tables
Table 1.1:
Table 1.2:
Table 1.3:
Table 3.1:
Table 3.2:
Table 3.3:
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:
Table 3.6:
The adsorption capacity and the percentage improvement compared with raw
activated carbon at various pressures.
Table 3.7:
viii
Table 3.8:
The average SCP and ideal COP of the 5 best samples at 900 Pa
Table 4.1:
Table 4.2:
Table 4.3:
Table 4.4:
Table 4.5:
Table 4.6:
Table 4.7:
Table 4.8:
Table 4.9:
Table 4.10:
Comparisons of the simulation results between this study and some improved
design
ix
List of Figures
Figure 1.1:
Figure 1.2:
Figure 1.3:
Figure 1.4:
Figure 1.5:
Figure 1.6:
Figure 1.7:
Figure 3.1:
Figure 3.2:
Figure 3.3:
Figure 3.4:
Figure 3.5:
Figure 3.6:
Figure 3.7:
Figure 3.8:
Figure 3.9:
Figure 3.10: SEM images of typical activated carbon samples after penetration
Figure 3.12: Inside the SA 3100, left hand side: outgas ports, right hand side: sample port
and saturation port in liquid nitrogen bath
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:
Figure 4.3:
Overall outlet temperature profile of heat transfer fluid for 2-bed adsorption
chiller
Figure 4.4:
Figure 4.5:
Figure 4.6:
Figure 4.7:
Figure 4.8:
Figure 4.9:
Figure 4.12: Effect of chilled water outlet temperature on cooling water inlet temperature
Figure 4.15: The relationship between chilled water outlet temperature and inlet
temperature
Figure 5.1:
Figure 5.2:
Figure 5.3:
The temperature profile of the heat transfer fluid in adsorption air conditioner
Figure 5.4:
Figure 5.5:
Figure 5.6:
xiv
Nomenclature
Alphabet
ai (i = 0 - 3)
[dimensionless]
area
[m2]
Langmuir constant
[Pa-1]
bi (i = 0 - 3)
[dimensionless]
BET constant
[dimensionless]
Cac
[J kg-1 K-1]
Cad
[J kg-1 K-1]
Dso
[m2 s-1]
Ea
[J]
had/H
heat of adsorption
[J kg-1]
hfg/Lw
[J kg-1]
Kads
[s-1]
Kdes
[s-1]
k1
[s-1]
k2
[s]
[kg]
[kg s-1]
mdry
[kg]
NA
Avogadros number
[mol-1]
P0/Ps
saturation pressure
[Pa]
Pr
relative pressure
[Pa]
Qchill
cooling capacity
[KW]
xv
Qhot
driving heat
[KW]
[J kg-1 K-1]
Rp
[nm]
[nm2]
SBET
[m2 g-1]
temperature
[K]
Tc
[K]
time
[s]
time interval
[s]
[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
[dimensionless]
LDFM
[dimensionless]
MCM-41
[dimensionless]
SCP
[W kg-1]
SCP
[W kg-1]
SEM
[dimensionless]
Abbreviation
xvi
TGA
thermogravimetric analysis
[dimensionless]
VC
vapor compression
[dimensionless]
VOC
[dimensionless]
XPS
[dimensionless]
[kg kg-1]
[kg kg-1]
Greek symbol
[kg kg-1]
adsorption/desorption process
eq
[kg kg -1]
[kg kg-1]
Subscripts
ad
adsorber
ads
adsorption
al
aluminum
chw
chilled water
com
composite adsorbent
cond
condenser
cu
cwa
cwc
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
Figure 1.1: Basic components of a refrigeration system and typical operating conditions
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
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)
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.
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
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.
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.
13
Zeolite 13X
Silica-gel
Activated carbon
11.5
78.43
211
0.3
0.37
0.4
Thermal conductivity
0.2
0.196
0.28
(W m-1 K-1)
(Zhang L.Z.,
(Kuwagaki H. et al.,
2000)
Klppel R.P.,
2003)
1996)
Specific heat capacity
0.921
0.88
1.09
(kJ kg-1)
Methanol
Ammonia
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:
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.
1.
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
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.
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
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
Filtration
Drying at 423K for 24 hrs
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
25
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
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
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
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
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)
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.
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.
37
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%.
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.
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
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.
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.
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.
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
% 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%
% 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%
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
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
53
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):
(3.9)
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.
65
% Improvement
N.A.
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
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
Reference
performance
Silica gel (type RD) + Water
Electro-Adsorption chiller
Ng K.C., et al.,
eq = 0.45Kg Kg-1
2006.
COP = 0.8
[Experiment]
eq = 0.45Kg Kg-1
2004
[Calculation]
capacity of 10KW
Zeolite + Water
[Calculation]
cycle
COP = 0.9
60
COP = 0.76
2012
[Calculation]
[Calculation]
COP = 0.67
SCP = 557W Kg-1
Activated carbon/CaCl2 +
Ammonia
COP = 0.41
2006b
[Experiment]
Oliveira R.G., et
COP=0.3
al., 2007
SCP=1000W Kg-1
[Calculation]
Activated
carbon/Silica-gel/CaCl2 +
COP = 0.7
Chao C.Y.H.,
Water
2011
Graphite/CaCl2 + Ammonia
[Calculation]
SrCl2/NiCl2 + NH3
COP = 0.32
1999
[Experiment]
Willers E. and
COP = 0.43
[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
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
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.
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.
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.
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)
dads
kads (adseq ads )
dt
(4.5)
(4.6)
dads
(adseq adso ) K ads exp K adst
dt
dd e s
kd es d e s
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.
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):
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
-7.61921
405.3
-2328.3
3724
1716.9
-110153.3
664138.7
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)
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.
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)
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.
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)
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.
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)
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.
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.
t cycle
m ch C p c
SCP
(T
chw in
Wcomtcycle
(4.24)
t cycle
m ch C p c
COP
.
m hot C p w
(T
chw in
0
t cycle
(T
hw in
(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.
Value
Unit
2.46
m2
2.46
m2
3.73
m2
1.91
m2
386
J Kg-1 K-1
905
J Kg-1 K-1
4180
J Kg-1 K-1
4190
J Kg-1 K-1
4200
J Kg-1 K-1
930
J Kg-1 K-1
H (Heat of Adsorption)
2.30E+06
J Kg-1
1.30E-03
s-1
1.20E-03
s-1
2.5E+06
J Kg-1
1602.56
W m-2 K-1
1724.14
W m-2 K-1
77
4115.23
W m-2 K-1
2557.54
W m-2 K-1
51.2
Kg
64.04
kg
47
kg
12.45
kg
27.28
kg
15
Kg
Table 4.8: Nominal operating condition for the 2-bed adsorption chiller
Parameter
Symbol Value
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
mcwc
Tchw in
.
m ch
1.3
Kg s-1
14
0.7
Kg s-1
79
Figure 4.3: Overall outlet temperature profile of heat transfer fluid for 2-bed adsorption
chiller
80
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
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
(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
83
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 4.8: Effect of chilled water outlet temperature on hot water inlet temperature
86
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.
88
Figure 4.12: Effect of chilled water outlet temperature on cooling water inlet temperature
89
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.
90
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
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.
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.
98
99
Figure 5.3: The temperature profile of the heat transfer fluid in adsorption air conditioner
100
101
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
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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