2011 Third International Conference on Measuring Technology and Mechatronics Automation
Adsorption and Refrigeration Performance of
Ammonia-Composite Adsorbent Working Pair
Wan Yi, Zheng Kai, Sheng Lili, Cui Qun*, Chen Haijun, Wang Haiyan, Yao Huqing
College of Chemistry and Chemical Engineering, Nanjing University of Technology ,Nanjing, China
wanyi301805@163.com; cuiqun@njut.edu.cn
Abstract—Composite absorbent (CAds-AC-15) mainly used
activated carbon and CaCl2 as the resources for adsorption
refrigeration were prepared by the mixed method, and the
content of activated carbon in CAds-AC-15 was 15%.
Adsorption isotherms of ammonia on CAds-AC-15 were
determined by positive gravimetric method. Adsorption -
desorption cycle performance and cooling characteristics of
CAds-AC-15- ammonia working pair was evaluated by self-
made adsorption - desorption measuring device. Experimental
results show that the equilibrium capacity of ammonia on the
CAds-AC-15 is up to 1.136kg/kgads at 30 , which is 5% lower
than that of CaCl2. With the conditions of adsorption
temperature 30 , ammonia evaporation pressure 0.25 MPa,
desorption temperature 300 , the performance of CAds-AC-
15- ammonia working pair is stable after repetitious
adsorption-desorption cycles, adsorption capacity of ammonia
on the CAds-AC-15 and its cyclic adsorption capacity is
0.55~0.65 kg/kg and 0.2~0.25 kg/kg, respectively. The cooling
capacity is up to 328.38kJ/kgads, which is twice as high as CaCl2
- ammonia working pair.
Keywords-adsorption refrigeration; ammonia; composite
absorbent; adsorption capacity; cooling capacity
I. INTRODUCTION
Solid adsorption refrigeration is green refrigeration
technology, which makes use of refrigerant adsorbed in
porous solid adsorbent to achieve refrigeration [1]. Adsorption
refrigeration technologies could be driven by industrial waste
heat or solar power, what’s more, and can use environmental
friendly refrigerant such as ammonia, methanol or water [1, 2].
Therefore, there are two major advantages of energy saving
and environmental protection for the solid adsorption
refrigeration technology. So, adsorption refrigeration has
been attracting attention and research efforts [3] at home and
broad.
In the process of solid adsorption refrigeration, the role of
adsorption refrigeration working pairs equivalent to the
compressor in the process of compression refrigeration. So
the performance of refrigeration working pairs determines
the efficiency of absorption refrigeration system.
Ammonia, as a refrigerant, has advantages of large
vaporization heat of and positive pressure operation. Usually,
ammonia together with SrCl2, MgCl2 or CaCl2, composed
adsorption working pairs [4, 5]. Although, ammonia has large
adsorption capacity on CaCl2, it is easy expansion in
adsorption, especially after repetitious adsorption-desorption
cycles, lead to the adsorption and desorption performance
978-0-7695-4296-6/11 $26.00 © 2011 IEEE
DOI 10.1109/ICMTMA.2011.87
gradually weakened [6]. Activated carbon has abundant
microspores and quick mass transference, but cyclic
adsorption capacity of ammonia is poor [7, 8]. Therefore,
many researchers and scholars had been studies on activated
carbon / CaCl2 composite adsorbent. Such as, Wang
Zhihua[9] used activated carbon and CaCl2 mixture to prepare
composite adsorbent, its maximum cyclic adsorption
capacity of ammonia was up to 0.4kg/kg. Wang Liwei [10] et
al. considered that addition activated carbon may inhibit CaCl2
powder. Wang Ruzhu[11] et al. studied activated carbon /
CaCl2 composite adsorbent (mass ratio 1: 4) had effective to
restrain the degradation phenomena of CaCl2 on the
adsorption refrigeration prototype.
In this paper, activated carbon / CaCl2 composite
adsorbent was prepared. A positive pressure gravimetric
method was built up for measuring adsorption performance
of ammonia. The influence of temperature on the adsorption
isotherms was investigated. The adsorption-desorption cycle
and refrigeration performance of composite adsorbent-
ammonia working pair were evaluated under typical
adsorption ice making conditions. It would provide the basic
parameters for application development of adsorption
refrigeration technology.
II. EXPERIMENTAL
A. Preparation composite adsorbent sample
Activated carbon / CaCl2 composite adsorbent was
prepared by the mixing method. Dissolving CaCl2(AR, pro-
vided by Nanjing Middle East Glass Instrument Co., Ltd ) in
the distilled water, adding activated carbon(powder, pro-
vided by SanQing Activated Carbon Plant) and additive,
mixing, shaping, drying, roasting, the composite adsorbent
with containing 15% (mass fraction)activated carbon was
gained. The composite adsorbent (CAds) was named CAds-
AC-15 (“CAds” means Composite Adsorbent, “AC” means
Activated Carbon, “15” is the content of activated carbon in
the composite adsorbent).
B. Measuring adsorption isotherms of ammonia on the
composite adsorbent
A positive pressure gravimetric method was built up for
composite adsorbent-ammonia adsorption isotherm [12, 13], as
is shown in the Fig. 1. The bottom of measuring tube was
made by quartz glass, the rest was made of stainless steel.
The quartz spring and the sample basket were hung in the
measuring tube. In the adsorption process, spring elongation
was read by altimeter for obtaining the adsorption
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parameters. The resolution of altimeter was 0.02mm, the
pressure of system was determined by pressure transmitter,
and adsorpt- ion temperature was controlled by constant
temperature water bath.
C. Investigating adsorption–desorption and refrigeration
performance
The adsorption-desorption performance for ammonia on
the composite adsorbent was measured in the device shown
Figure 2[14]. The experimental equipment system was made
up of adsorption column, ammonia cylinder, vacuum pump
and thermostatic device. Firstly adsorbent was pretreated
through heating the adsorption column and vacuuming. Then
cooling to adsorption temperature, opening ammonia
cylinder, and ammonia was adsorbed in the adsorption
column with certain pressure. When adsorption was over, the
quality of adsorption column (M1) was weighed. And
ammonia desorption with certain temperature, the quality of
adsorption column (M2) was weighed. The ammonia from
desorption was cooled down and collecting in a reservoir
tank. Then the process turned to the next cycle of adsorption.
According to the weight variation of adsorption column after
adsorption or desorption, cyclic adsorption capacity of
ammonia would be got to calculate cooling capacity of
composite adsorbent-ammonia working pair.
III. RESULTS AND DISCUSSIONS
A. Adsorption isotherms of ammonia on the composite
adsorbent
Adsorption isotherms of ammonia on CAds-AC-15 and
CaCl2 were determined, as is shown in Figure 3. From
Figure 3, the shape of adsorption isotherms of ammonia on
the composite adsorbent was basically same to the calcium
chloride, which mainly presented adsorption characteristics
of the CaCl2 for ammonia. Ammonia adsorbed on CaCl2 was
mainly chemical adsorption [15]. Its adsorption isotherm can
not be classified by Brunauer types.
From Figure 3, when adsorption pressure less than
0.05MPa, equilibrium adsorption capacity of CAds-AC-15
was higher than that of CaCl2 at 30℃. For adsorption of
activated carbon was mainly physical adsorption, the type of
ad-sorption isotherm was Brunauer I. In the lower pressure,
adsorption capacity of activated carbon for ammonia was
relatively large. When the adsorption pressure above
0.1MPa, equilibrium adsorption capacity of CAds-AC-15 for
ammo-nia had little change and reached to
1.074~1.136kg/kgads, which was lower than that of CaCl2
(1.195 kg/kgads). As is shown that addition of appropriate
activated carbon, it could enhance the absorption capacity of
ammonia at low pressure, while equilibrium adsorption
capacity of ammonia decreased about 5% at high pressure.
The adsorption temperature had significant effect on
adsorption isotherms of ammonia on CAds-AC-15.With the
increase of adsorption temperature, equilibrium pressure
shifted to the high-pressure. In the same adsorption pressure,
as the adsorption temperature increasing, equilibrium
adsorption capacity of ammonia on CAds-AC-15 (before
adsorption equilibrium) significantly decreased. It was
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advantageous to adsorption refrigeration cycle using swing
temperature adsorption.
B. Adsorption-desorption performance of CAds-AC-15-
ammonia
Referring to adsorption ice making conditions, adsorption
temperature 30℃,adsorption pressure 0.25MPa, desorption
temperature 300℃, and cycle time 30min, relationship cycle
adsorption capacity variation of ammonia on CAds-AC-15
and repetitious adsorption and desorption cycles were
measured, shown in Fig.4.
As was shown in Fig.4, the adsorption and desorption
process of CAds-AC-15-ammonia derived to stability after
three or five adsorption and desorption cycles. Fluctuant data
points were caused mainly by intermittent testing process.
Adsorption capacity and cyclic adsorption capacity of
ammonia were 0.55~0.65kg/kg, 0.2~0.25kg/kg respectively.
Addition of 15 % carbon, the composite adsorbent presented
nicer adsorption-desorption stability.
C. Adsorption refrigeration performance of CAds-AC-15-
ammonia
The adsorption capacity and cyclic adsorption capacity of
CAds-AC-15-ammonia was measured by the above mention.
When the evaporation pressure 0.25 MPa, adsorption
temperature 30℃, desorption temperature 300℃, desorption
pressure 1.35MPa and cycle time 30min, by equation (1) and
(2), the cooling capacity (Qref)and SCP of CAds-AC-15-
ammonia were 328.38kJ/kgads and 429.25W/kg,
respectively. Under the same conditions, the results in the
paper were 2.05 times and 1.83 times higher than Qref(159.83
kJ /kgads) and SCP (234.10 W/kgads) of CaCl2-ammonia,
respectively.
Qref =γam﹒△q (1)
SCP = Qref / △t (2)
In the equation (1), Qref was cooling capacity, kJ/kgads.
γam was vaporization heat of ammonia, kJ/kg. △q was cyclic
adsorption capacity of ammonia, kg/kgads. In the equation
(2), △t was cyclic absorption time, s; SCP was specific
cooling power W/kg.
IV. CONCLUSIONS
Through studying the refrigeration performance of
ammonia-carbon- CaCl2 composite adsorbents, we can get
main conclusions as follows:
The adsorption isotherm shape of composite adsorbent
with adding 15% activated carbon was the same as the
CaCl2’s; by increasing the adsorption temperature,
equilibrium adsorption capacity of CAds-AC-15-ammonia
de-creased significantly before reaching to the adsorption
platform. Equilibrium adsorption capacity of CAds-AC-15
was 1.074~1.136kg/kgads at 30℃, which was 5% lower than
that of CaCl2.
Stability of CAds-AC-15 was preferable. When the
conditions of the adsorption temperature 30℃, evaporation
pressure 0.25 MPa, desorption temperature 300 ℃, cyclic
adsorption capacity of Cads-AC-15-ammonia were
0.2~0.25kg/kg. The cooling capacity and SCP of Cads-AC-
15-ammonia working pair were 2.05 times and 1.83 times as
high as that of CaCl2-ammonia working pair, respectively.
ACKNOWLEDGMENT
Financial support for this work, supported by the
National Natural Science Foundation of China (Project
20876074), is gratefully acknowledged.
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1-ammonia cylinder；2-vacuum pump；3-Altimeter；4-quartz spring；5- sample basket
Figure 1. Schematic diagram of adsorption isotherm device
P
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P P
 Figure 2. Diagram of menstruated device of adsorption performance

1.2

1.0

0.8

q, kg/kgads
0.6 30℃ ( CaCl2)
30℃ ( CAds-AC-15 )
0.4 45℃ ( CAds-AC-15 )
62℃ ( CAds-AC-15 )
0.2

0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6

P, MPa

Figure 3. Adsorption isotherms of NH3 on composite adsorbents at 30℃

0 .8
adsorption capacity
0 .7 adsorption capacity after desorption
cycle adsorption capacity
0 .6

0 .5
q, kg/kg

0 .4

0 .3

0 .2

0 .1

0 .0
0 5 10 15 20 25 30 35 40 45 50 55
t c , num ber of cycle

Figure 4. Capacity of ammonia in the adsorption and desorption cycle on CAds-AC-15 composite adsorbent

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