International Journal of Refrigeration 27 (2004) 401408

www.elsevier.com/locate/ijrefrig

Compound adsorbent for adsorption ice maker on

shing boats
L.W. Wang, R.Z. Wang*, J.Y. Wu, K. Wang
Institute of Refrigeration and Cryogenics, Shanghai Jiao Tong University, Shanghai, 200030, China
Received 2 September 2003; received in revised form 28 November 2003; accepted 28 November 2003

Abstract
Adsorption performances of three types of adsorbents, CaCl2 with dierent expansion space, simple compound
adsorbent and solidied compound adsorbent made by CaCl2 and activated carbon, are tested, in which ammonia is
used as refrigerant. The solidied compound adsorbent shows the best performance for adsorption ice makers on
shing boats for the larger lling quantity of adsorbent in adsorber. The mass transfer performance is improved by the
additive of activated carbon in solidied compound adsorbent at the condition of low evaporating temperature. The
volume cooling density of solidied compound adsorbent is about 35% improved at least in comparison with the
optimal results of CaCl2 at the evaporating temperature of
15  C.
# 2003 Elsevier Ltd and IIR. All rights reserved.
Keywords: Adsorption system; Fishing boat; Ice maker; Adsorbent

Un compose adsorbant dans une machine a` glace a`

adsorption utilisee a` bord de chalutiers
Mots cles : Syste`me a` adsorption ; Chalutier ; Machine a` glace ; Adsorbant

1. Introduction
Adsorption refrigeration and heat pump have been
thought as environment benign and cost eective in
waste heat recovery systems [1]. Adsorption working
pair of calcium chloride-ammonia, has been proposed
and developed for cooling and heat pumping [24]. The
principles and operating cycle of a chemical adsorption
refrigeration are illustrated in Fig. 1a, b and c [5]. A
cycle comprises four steps: decomposition reaction,

* Corresponding author. Tel.: +86-21-629-33838; fax: +8621-629-33250.

E-mail address: rzwang@sjtu.edu.cn (R.Z. Wang).
0140-7007/$35.00 # 2003 Elsevier Ltd and IIR. All rights reserved.
doi:10.1016/j.ijrefrig.2003.11.010

condensation, evaporation and synthesis reaction represented, respectively, by points 14 in Fig.1a and b. The
basic operation system is shown in Fig. 1c. In the rst
phase, reactor coupled to the condenser by the gas
phase, is heated to temperature TH. Decomposition
reaction carries out. The gas produced is condensed.
Theoretically, this phase terminates when the decomposition reaction in reactor is complete. At the beginning of the second phase, the valve between the reactor
and the condenser is closed. Reactor is cooled by a heat
transfer uid at Tm. Reactor goes into the synthesis
condition, causing a drop in the pressure. When the
pressure in reactor reaches the evaporation pressure,
the gas valve connecting to the evaporator is opened. The
synthesis reaction carries out. The gas consumed by

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L.W. Wang et al. / International Journal of Refrigeration 27 (2004) 401408

Nomenclature
hT
m
ma
mc
n
n1
P
Pc
Pe
Q1
Q2
Q3
Q4
Qs
ras
T
T1

latent heat of vaporization at a constant

saturated temperature (kJ kg
1)
mass of adsorbent (kg)
mass of activated carbon in solidied
compound adsorbent (kg)
mass of solidied compound adsorbent (kg)
number of ammonia in ammoniate calcium
chloride (2,4,6,8)
number of ammonia decompose from
ammoniate calcium chloride (2,4,6,8)
adsorption pressure (Pa)
condensing pressure (Pa)
evaporating pressure (Pa)
heat of decomposition reaction (J)
heat of condensation (J)
heat of evaporation (J)
heat of sythesis reaction (J)
volume cooling density (kJm
3)
ratio between expansion space for
adsorbent and adsorbent volume
adsorption temperature ( C)
decomposition temperature (K)

the reaction is supplied by the evaporator, which produces cold at TL. Theoretically, this phase terminates
when the synthesis in reactor is complete.
The stoichiometric equation for the synthesis and
decomposition reactions between CaCl2 and NH3 is
CaCl2  nNH3 n1 DHr

! CaCl2  n
n1 NH3

n1 NH3

The reaction process is monovariant which means

that by specifying the pressure, the temperature will also
be specied. The condensation and evaporation processes are based on the vapourliquid equilibrium as
shown in the following equation and are also monovariant [6]:
n1 NH3 gas

! n1 NH3 liq n1 DHce

The compound adsorbent made by CaCl2 and activated carbon we tested is mainly for the adsorption ice
makers on shing boats. There are two challenges for
the design of adsorption ice makers using calcium chloride as adsorbent on shing boats, one is to assure
safety because ammonia is used as refrigerant, the second is to improve the lling quantity of adsorbent in
adsorbers which will decrease the volume of adsorber
eciently because the space on shing boats is limited.

T2
T3
T4
TH
TL
Tm
Tk
Tks
V
x
xc
xa

condensing temperature (K)

evaporating temperature (K)
temperature of synthesis reaction (K)
temperature of energy source (K)
temperature of cold production (K)
ambient temperature (K)
adsorption temperature(K)
saturated adsorption temperature(K)
the volume for the adsorbent and the
expansion space (m3)
adsorption quantity of CaCl2 and simple
compound adsorbent (kg kg
1)
adsorption quantity of solidied compound
adsorbent (kg kg
1)
adsorption quantity of activated carbon in
solidied compound adsorbent (kg kg
1)

Greek letters
enthalpy of transformation for reaction
Hr
(J mol
1)
Hce
enthalpy of transformation for
condensation (J mol
1)
x
cycle adsorption quantity

The safety, rst challenge of design, can be assured by

the reasonable installation, that is to put all the parts in
which ammonia ows on the deck, and antifreezing uid
is used as the cooling medium that will ow in the part
in the cabin. The lling quantity, second challenge of
design, is mainly limited by the mass transfer performance that is caused by the phenomenon of agglomeration of CaCl2 [7] at the time of adsorption and the
low evaporating pressure at the condition of ice making.
Many researches are performed on the compound
adsorbents and results show that compound adsorbents
can improve the mass transfer performance of chemical
adsorbents in vacuum system and can avoid the
agglomeration phenomenon. Mikhail Tokarev conned
CaCl2 to mesoporous host matrix MCM-41 to improve
the mass transfer that caused by agglomeration [8]. T.
Dellero has studied three mixtures of carbon bers with
MnCl2, the sample of GFIC (intercalation of MnCl2
into ex-pitch graphitized carbon bers P120) not only
provide a very fast reaction but also give a complete
reaction by avoiding the agglomeration phenomenon
[9,10].
Two types of compound adsorbents, granular adsorbent and solidied compound adsorbent, are studied in
this paper for their performances of adsorption on
ammonia, and the results are compared with the
adsorption performance of CaCl2. The aim of this work
is to nd the best way to improve the lling quantity of

L.W. Wang et al. / International Journal of Refrigeration 27 (2004) 401408

adsorbent in adsorbers and avoid the mass transfer

performance deterioration at the same time.

2. Adsorbent-ammonia adsorption test unit

The adsorption test unit (shown in Fig. 2) is designed
in order to test the adsorption on ammonia of the
granular adsorbents and solidied adsorbents. The system consists mainly two parts, adsorber /generator
(reactor) and condenser (evaporator), which are respectively put in oil tank and ethanol jacket considering
the operation modes of desorption and adsorption. The
adsorber is cooled by water circuit heat exchanger at
the time of adsorption and heated by electric heater at the
time of desorption. The temperature of evaporator/
condenser is controlled by the thermostatic bath that

403

could control temperature from
40  C to 90  C with

an accuracy of 0.1  C. Adsorption quantity and desorption quantity are measured by magneto strictive displacement sensor inserted into the ammonia container,
whose measuring error is 0.05%.
Two adsorbers (Fig. 3) are designed for the test unit.
The adsorber with edge fold is designed for the granular
chemical and composite adsorbent, and the adsorber
without edge fold is designed for the solidied composite adsorbent. Each adsorber is divided into two halfparts which are connected by ange seals. The spaces
are separated by ns and the void between two ns is 12
mm high. Various samples are tested in order to nd the
optimal lling quantity. Because the adsorbent will swell
at the time of adsorption, expansion space for adsorbent
that is dened as the void between adsorbent and n is
provided. The ratio between expansion space for adsorbent and adsorbent volume is dened as ras. In this
research, the thickness of 2 mm CaCl2 with ras of 5:1 is
named as sample 1, thickness of 3 mm CaCl2 with ras of
3:1 is named as sample 2, thickness of 4 mm CaCl2 with
ras of 2:1 is named as sample 3, and the thickness of 5
mm CaCl2 with ras of 1.4:1 is named as sample 4,
thickness of 6 mm simple composite adsorbent which is
combined by CaCl2 and activated carbon is named as
sample 5, thickness of 9 mm solidied adsorbent which
is also combined by CaCl2 and activated carbon is
named as sample 6.

3. Experiments and results

3.1. Adsorption performance for CaCl2NH3
In order to test the adsorption performance at a
stable condition, the repeated experiments are performed rst when the temperature of oil bath is controlled at 30  C, the adsorption temperature is
controlled at 40  C and evaporating temperature is controlled at 0  C. Results shown in Fig. 4, where x is the
adsorption quantity of CaCl2 (kg kg
1). The adsorption
time for sample 1, sample 2, sample 3 and sample 4 are
respectively 30 min, 45 min, 60 min and 75 min con-

Fig. 1. (a) Basic principles; (b) [ln(P),
1/Tk] diagram for the

basic chemical reaction system. L/G: Liquid/Gas phase. S/G:
Solid/Gas reaction. (c) Basic system.

Fig. 2. Adsorption test unit.

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L.W. Wang et al. / International Journal of Refrigeration 27 (2004) 401408

Fig. 3. (a) Bed for granular adsorbent, (b) Bed for solidied adsorbent.

sidering the adsorption heat is proportional to the mass

of adsorbent. The repeated tests wont be ended until
the dierence of adsorption quantities between ve
times or more than ve times are less than 0.2 kg kg
1,
and that means the condition of adsorbent becomes
stable. Because the adsorption time is xed and the
adsorption isnt saturated in the rst several experiments, the adsorption quantities shown in Fig. 4 is
increasing in the rst 34 tests. Adsorption performance
of sample 2 is similar with that of sample 1, and they are
much dierent from that of sample 3 and sample 4.
The performance of sample 3 and sample 4 becomes
stable after the second or third experiment, and the
performance of sample 1 and sample 2 begin to deteriorate after the fourth test, and didnt became stable
until the test number is larger than 10.
The volume cooling density (Qs, kJ m
3) is dened
as
Qs

Dx
m
hT
V

Fig. 4. Adsorption performance in the repeated experiments.

The saturated liquid temperature is 0  C, and adsorption
temperature is 40  C.

Where x (kg kg
1) is the cycle adsorption quantity

at the xed saturated temperature, m is the mass of
adsorbent(kg); hT (kJ kg
1) is the latent heat of vaporization at that saturated temperature and V (m3) is the
volume for the adsorbent and the expansion space (the
volume of ns and casing isnt involved). The adsorption quantity of ammonia to CaCl2 (x, kg kg
1) and Qs
for sample 1, sample 3 and sample 4 are tested and
computed at the evaporating temperature of
15  C,
condensing temperature of 25  C and highest desorption
temperature for adsorbent of 140  C after the repeated
experiments, results are shown in Fig. 5. The adsorbents
for sample 1 and sample 3 are checked after adsorption,
photos are shown in Fig. 6. Sample 3 gives the best
adsorption quantity and the best Qs although its phenomenon of agglomeration (shown in Fig. 6) is serious.
The performance of sample 1 is worse than other two
samples although it has enough expansion space and
there is no phenomenon of agglomeration (Fig. 6). The
performance of sample 4 at saturated temperature of

15  C is much worse than that of sample 3 and the

Fig. 5. Comparison of x and Qs for sample 1, sample 3 and

sample 4 at the evaporating temperature of
15  C; condensing
temperature is 25  C and the highest desorption temperature of
adsorbent is 140  C.

L.W. Wang et al. / International Journal of Refrigeration 27 (2004) 401408

reason of it should be the bad mass transfer performance which caused by narrow expansion space. A
conclusion is obtained from the experiments: the
agglomeration is benecial to the adsorption but there is
a limit; serious agglomeration will lead to bad mass
transfer performance and it will inuence the adsorption
performance at low evaporating temperature.
One possible explanation for the dierent adsorption
performances of dierent samples is the shielded factor
(the ratio of repulsive force to attractive force for each
anion) of complex compound that is increasing with the
number of ammonia in ammoniate. For example, the
shielded factor is 0.96 for tetra-ammoniate while it is
1.66 for hexad-ammoniate. The NH3 is easier to be lled
around Ca2+ for sample 1 than sample 3 at the time of
adsorption because sample 1 is looser than sample 3,
then the inuence of shield factor on sample 1 will be
larger because it has larger concentration of NH3
around Ca2+, and then octo-ammoniate will be more
dicult to be formed in sample 1 than sample 3.
3.2. Adsorption performance of granular compound
adsorbent-ammonia

405

Fig. 7. Performance deterioration; the saturated liquid temperature is 0  C, and adsorption temperature is 40  C. 1
Adsorption quantity for CaCl2 in composite adsorbent; 2
Adsorption quantity of composite adsorbent.

for the deterioration. The adsorbent after adsorption is

shown in Fig. 8.
Sample 5 after adsorption is much dierent from
sample 3 although its mass of CaCl2 is equal to sample
3. There is no phenomenon of agglomeration in sample
5. The reason for it should be the additive of activated
carbon. The thickness of adsorbent on ns should be
increased in order to get the phenomena of agglomeration. Considering the thickness of granular adsorbent
on ns cant be higher than 6 mm because the edge fold
of n (Fig. 3a) is 6 mm high, the compound adsorbent is
solidied and adsorber with ns without fold edge
(Fig. 3b) is used.

In order to improve the lling quantity and at the

same time to ensure the mass transfer performance of
CaCl2 at low evaporating temperature, the compound
adsorbents are studied.
Simple compound adsorbent (sample 5) are mixed by
the ratio of 4:1 between the mass of CaCl2 and mass of
activated carbon. The mass of CaCl2 of sample 5 in
adsorber is equal with the mass of sample 3 in adsorber,
and the thickness of compound adsorbent on ns is
about 6 mm. Repeated experiments at the condition of
40  C adsorption temperature and 0  C evaporating
temperature are performed and results are shown in
Fig. 7.
There is great performance deterioration for the sample 5; the adsorption quantity of the seventh time is
about 20.4% less than the adsorption quantity of rst
time. The adsorber is checked in order to nd the reason

Sample 6 is made by CaCl2, activated carbon and

cement. The ratio between the mass of CaCl2 and activated carbon is also 4:1, and cement and water are used
to bind these two types of adsorbent. The solidied
adsorbent is shown in Fig. 9. The thickness of sample 6
is about 9 mm, and the lling quantity of CaCl2 in
adsorber is about 16% more in comparison with sample 4.

Fig. 6. (a) Expansion and agglomeration phenomena of sample

1 after adsorption. (b) Expansion and agglomeration phenomena of sample 3 after adsorption.

Fig. 8. Granular compound adsorbent after adsorption.

3.3. Adsorption performance of solidied compound

adsorbent-ammonia

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L.W. Wang et al. / International Journal of Refrigeration 27 (2004) 401408

There is no phenomenon of performance deterioration in the repeated experiments. It is shown that the
adsorption quantity becomes stable after the second
repeated test, which is about 0.796 kg kg
1.
Adsorption isobars at saturated temperature
20  C,

15  C,
10  C, 0  C, 9  C and desorption isobars at
saturated temperature 25  C, 35  C are shown in Fig. 10.
Where xc is the adsorption quantity of solidied compound adsorbent (kg kg
1).
The adsorption quantity of CaCl2 in sample 6 is
computed by the adsorption quantity of compound
adsorbent (Fig. 10) and the DR equation of activated
carbon. The performance of activated carbon is tested,
and the DR equation obtained is
"


1:38 #
Tk
xa 0:2856
exp
3:5671

1
4
Tks
In Eq. (4), xa (kg kg
1) is the adsorption quantity of
activated carbon, Tk is the adsorption temperature (K),
and Tks is the saturated temperature corresponding to
the adsorption pressure (K).
Then the adsorption quantity of CaCl2 in sample 6 is
mc
xc
ma
xa
5
x
mc
ma
Where x (kg kg
1) is the adsorption quantity of
CaCl2 in sample 6, mc (kg) is the mass of compound

adsorbent, xc (kg kg
1) is the adsorption quantity of

compound adsorbent, ma (kg) is the mass of activated
carbon.
The adsorption quantity of CaCl2 in sample 6 is
compared with the adsorption quantity of sample 3, and
the results are shown in Fig. 11. The adsorption quantity of CaCl2 in sample 6 is a little worse that that of
sample 3. The reason for this phenomenon is analyzed;
it should be the uncertain adsorption quantity of activated carbon, which is inuenced by the agglomeration
of adsorbent and should be less than the values computed by DR equation. Compare the adsorption
quantity of CaCl2 in sample 6 at the evaporating temperature of
15  C (Fig. 11) with that of sample 4 in
Fig. 5, the maximum adsorption quantity is improved
about 0.15 kg kg
1 although the lling quantity of
CaCl2 is increased in sample 6. This means that the mass
transfer performance is improved for sample 6 by the
additive of activated carbon.
Volume cooling density Qs for sample 3, sample 4 and
sample 6 are compared. Results are respectively shown
in Figs. 12 and 13. The condensing temperature for
experiments is 25  C which is similar with the temperature of seawater in summer, and the highest desorption
temperature of adsorbent is 140  C. In comparison with
sample 3 (Fig. 12), Qs of sample 6 is improved about
39% when the evaporating temperatures are higher
than
15  C, and it is improved about 35% when the

Fig. 9. Solidied compound adsorbent (sample 6).

Fig. 11. Adsorption quantity of CaCl2 in sample 6 and sample 3.

Fig. 10. Adsorption and desorption isobars.

Fig. 12. Qs of sample 3 and sample 6; condensing temperature

is 25  C and the highest desorption temperature of adsorbent is
140  C.

L.W. Wang et al. / International Journal of Refrigeration 27 (2004) 401408

evaporating temperature is about
15  C and
20  C.

In comparison with sample 4 (Fig. 13), Qs of sample 6 is
improved about 9% at the evaporating temperature of
0  C, and it is improved about 45% at the evaporating
temperature of
15  C.
After adsorption, the adsorber for sample 6 is
checked, and the photo is shown in Fig. 14. The adsorbent swelled and stuck on the ns and cant be departed
from ns, which will be much benecial for the heat
transfer performance.
Assuming the ice productivity of 40 kg ice per hour
and the ice temperature of
10  C is required (the
needed evaporating temperature and the needed cooling
power should be
15  C and 5.2 kW respectively), the
lowest condensing and adsorption temperature is 25  C
(cooled by sea water), and the cycle time of adsorption
ice maker on shing boats is 60 min, then the volume of

Fig. 13. Qs of sample 4 and Sample 6; condensing temperature

is 25  C and the highest desorption temperature of adsorbent is
140  C.

Fig. 14. Adsorber for solidied compound adsorbent after

adsorption.

407

adsorbers of solidied adsorbent which is computed by

the value of Qs is only about 0.0773 m3 when the volume
of ns and casing isnt taken into to account, which is
about 24.2% reduced comparing with the adsorbers for
sample 3 which is 0.1021 m3.

4. Conclusions
The adsorption performances of CaCl2 with dierent
expansion space are tested before studying the performance of compound adsorbents, one conclusion
obtained is that the agglomeration is benecial for the
improvement of adsorption performance but there is a
limit; the serious agglomeration will inuence the
adsorption performance which is caused by the critical
mass transfer performance especially at the condition of
ice making. In order to improve the mass transfer performance at the condition of large lling quantity of
adsorbent in adsorber, granular compound adsorbent is
studied, and the results show that the additive of activated carbon in CaCl2 is much helpful to solve the
question of agglomeration. In order to test the inuence
of additive of activated carbon at the condition of large
lling quantity of CaCl2 in adsorber, the solidied
compound adsorbent is studied, and several conclusions
are achieved.
1. The performance of solidied compound
adsorbent is much stable than that of granular
compound adsorbent, and there is no phenomenon of performance deterioration after second
test at a constant condition of experiments.
2. In comparison with sample 4, the lling quantity
of CaCl2 in sample 6 in adsorber is increased
about 16%, and the adsorption quantity is
improved about 0.15 kg kg
1 at the evaporating
temperature of
15  C because the mass transfer
performance is improved by the additive of
activated carbon.
3. The volume cooling density is analyzed, the
solidied compound adsorbent gives the best
results which is at least 35% improved at the
evaporating temperature of
15  C if sample 3 is
in comparison.
4. Assuming the ice productivity and ice temperature on shing boats required respectively 40 kg
per h and
10  C, the lowest condensing and
adsorption temperature is 25  C, and the
cycle time of adsorption ice maker on shing
boats is 60 min, then the volume of adsorbers
of solidied adsorbent is about 0.0773 m3
when the volume of ns and casing isnt taken
into account, which is about 24.2% less than
the adsorbers volume of normal chemical
adsorbent.

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L.W. Wang et al. / International Journal of Refrigeration 27 (2004) 401408

Acknowledgements
This work was supported by the State Key Fundamental
Research Program under the contract No. G2000026309,
National Science Fund for Distinguished Young Scholars of China under the contract No. 50225621,Shanghai
Shuguang Training Program for the Talents, the
Teaching and Research Award Program for Outstanding
Young Teachers in Higher Education Institutions of
MOE, P.R.C. The authors thank Mr. Xu Y.X. and Mr.
Sun Y.K. for helps to install the experimental setup.

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