Renewable Energy 29 (2004) 22352244

www.elsevier.com/locate/renene

Experimental study on adsorbent of activated

carbon with refrigerant of methanol
and ethanol for solar ice maker
M. Li a,
, H.B. Huang b, R.Z. Wang c, L.L. Wang a, W.D. Cai a,
W.M. Yang a
a

School of Physics and Electronic Information, Yunnan Normal University, Kunming 650092, PR China
b
Physics Department, NingXia University, Yinchuan 750105, PR China
c
Institute of Refrigeration and Cryogenics, Shanghai Jiao Tong University, Shanghai 20030, PR China
Received 17 March 2003; accepted 23 April 2004

Abstract
Two dierent working pairs, one of them activated carbonmethanol and the other activated carbonethanol, are used in a solar ice maker to determine ice production and
refrigerant criteria in desorption and adsorption processes under similar radiation energy
and environmental conditions. Experimental results show that ice can be produced with activated carbonmethanol, however, ice could not be obtained with the use of activated carbonethanol using the same solar ice maker with similar environments and radiation
intensities. Further experiments have shown that the adsorbing and desorbing refrigerant
amounts of the two working pairs gave quite dierent results, the activated carbonmethanol has proven to be the superior one of the two working pairs in ice production of solar
adsorption refrigeration.
# 2004 Elsevier Ltd. All rights reserved.
Keywords: Solar energy; Adsorption refrigeration; Two working pairs; Experiments

1. Introduction
The intermittent solid adsorption cycle provides a promising alternative for solar
refrigeration due to its simple operation. Most research methods have used

Corresponding author. Tel.: +86-871-551-7093; fax: +86-871-551-6058.

E-mail address: lmdocyn@public.km.yn.cn (M. Li).

0960-1481/$ - see front matter # 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.renene.2004.04.006

2236

M. Li et al. / Renewable Energy 29 (2004) 22352244

activated carbonmethanol for working pairs, and this has been considered as the
most suitable working pair for solar solid adsorption ice maker [16]. However,
recent research has shown that the thermal decomposition of methanol occurs in
normal solar powered adsorption refrigeration, while the maximum temperature of
v
methanol keeping stable in solid adsorption cycle process is about 120 C [7]. Some
research work from simulation and simple experimental results also shows that the
activated carbonethanol possesses good characteristics for a solar ice maker, and
that methanol can be replaced by ethanol in the solar adsorption refrigeration
cycle [8,9]. Generally speaking, methanol is non-toxic, but on contact it is harmful
to skin and eyes. Therefore, another suitable working pair would be preferred.
Recently, more attention has been paid to solid adsorption techniques in our
research group. Many solar refrigerator devices have been designed and improved,
and the characteristics of solar ice maker have been analyzed according to experimental works and simulated results [1014]. Based on prior studies, this study
focuses on an experimental study of the adsorbing and desorbing characteristics as
well as the ice mass produced by the solar ice maker when activated carbonmethanol and carbonethanol working pairs are used in the same solar ice maker under
similar experimental conditions.

2. Introduction of experimental device and experimental procedure

In order to be sure that the experimental results between the activated carbon
methanol and the activated carbonethanol working pair could be practically
related to solar adsorption refrigeration elds, a valveless solar ice maker was used
for carrying out the experiments. This valveless solar ice maker was developed in
September 2001 following our prior experimental work. This valveless solar ice
maker could produce 4.06.0 kg of ice under the condition of accepting radiation
energy 1722 MJ/m2 both inside the door with quartz lamps and outside with real
solar radiation. The COP of this solar ice maker is about 0.100.12. Fig. 1 shows a
schematic layout of the valveless solar at plate ice maker. The working principle
can be described as follows:
On a sunny day, adsorbent bed 2 absorbs solar radiation energy and causes the
temperature of the adsorbent to rise, causing a rise also in the pressure of refrigerant in the adsorbent bed. When the temperature of the adsorbent inside the
adsorbent bed reaches the desorption temperature, the adsorbent begins to desorb
the refrigerant. The desorbed refrigerant vapor will be condensed into liquid in
condenser 5, and will ow directly into evaporator 7. This process continues until
the temperature of the adsorbent reaches the maximum desorption temperature.
After the maximum desorption temperature of the adsorbent is reached, the
adsorbent will adsorb the refrigerant from evaporator 7. The adsorption process
lasts until the next cycle. During the adsorption process, the cooling eect is
obtained from refrigerant evaporation, and the ice is formed in water tank 8 placed
inside thermally insulated container 9.

M. Li et al. / Renewable Energy 29 (2004) 22352244

2237

Fig. 1. A sketch of the structure of the valveless solar ice maker: (1) cover plate, (2) adsorbent bed,
(3) insulation materials, (4) ice maker frame, (5) condenser, (6) connecting pipe, (7) evaporator, (8)
water tank, (9) insulation box.

For this valveless solar ice maker, the eective solar collector area was approximately 0.94 m2, and the adsorbent was activated carbon produced in Hainan Province, China. Stainless steel is used as a heat transfer metal. With the above
mentioned solar ice maker, experiments were carried out using both activated carbonmethanol and activated carbonethanol working pairs. The experimental
methods and contents follow the four procedures given below:
1. Measure the ice mass produced by the solar ice maker with the activated carbonmethanol working pair under the condition of accepting radiation intensity
generated by quartz lamps.
2. Evacuate the methanol refrigerant from the solar ice maker, and add the ethanol refrigerant instead of methanol, then measure the ice mass produced by the
solar ice maker under the condition of accepting similar radiation intensity and
environment as in procedure 1. One would expect to compare the ice mass production from each of the two working pairs.
3. Substitute the evaporator of the solar ice maker by a graduated glass ask, then
measure the adsorbing and desorbing characteristics of the activated carbon
ethanol under the condition of accepting radiation intensity generated by the
quartz lamps.
4. Evacuate the ethanol refrigerant from the experimental device, and then add
methanol as refrigerant, then measure the adsorbing and desorbing characteristics of the activated carbonmethanol under the condition of accepting similar
radiation intensity and experimental environments mentioned as in procedure 3.
Then, compare the desorbing and adsorbing characteristics of these two working pairs.

2238

M. Li et al. / Renewable Energy 29 (2004) 22352244

3. Experiment on two dierent refrigeration working pairs

3.1. Experiment on ice mass
According to the rst procedure and the second procedure mentioned in Section
2, experiments of the ice mass produced by the solar ice maker with activated carbonmethanol and activated carbonethanol working pairs were carried out. The
experimental results were shown in Table 1. It can be seen from Table 1 that
3.45 kg of ice mass can be produced from the solar ice maker with the activated
carbonmethanol working pair under the condition of accepting radiation energy
of 15.2 MJ. However, no ice can be obtained from the same solar ice maker with
the activated carbonethanol working pair under the condition of accepting similar
radiation energy and the experimental environments. When the solar radiation
energy accepted by the adsorbent bed collector increased from 15.2 to 18.2 MJ,
4.4 kg of ice mass were produced by the solar ice maker with the activated carbon
methanol working pair, but no ice could be obtained in the solar ice maker with
the activated carbonethanol working pair. The refrigeration eect of the solar ice
maker with the activated carbonethanol working pair was to cool the water in the
v
ice box to 24 C. The COP of the solar ice maker with the activated carbon
methanol working pair is about four times higher than that of the solar ice maker
with the activated carbonethanol working pair from experimental results. Other
experiments under the condition of dierent radiation energy input were carried
out and similar experimental results as shown in Table 1 were obtained. This
Table 1
Ice mass production with activated carbonmethanol and activated carbonethanol working pairs
Working
pairs

Desorbing Accepting Water

time (h)
radiation mass in
energy
ice box
(MJ)
(kg)

Adsorp- Refrigeration eects

Initial
tempera- tion time
Ice mass Water
COP
ture of (h)
(kg)
ice box
Mass Temperav
v
( C)
(kg)
ture ( C)

Activated
carbon
and methanol
Activated
carbon
and ethanol
Activated
carbon
and methanol
Activated
carbon
and ethanol

15.2

25

18

3.45

2.55

0.113

15.2

25

18

0.034

18.2

16

18

4.4

2.6

0.105

18.2

17

18

0.029

M. Li et al. / Renewable Energy 29 (2004) 22352244

2239

indicated that the activated carbonethanol working pair was not a suitable one
for application in the solar ice maker.
3.2. Experiments on desorbing and adsorbing characteristics of refrigerant
In order to further analyze the characteristics of activated carbonmethanol and
activated carbonethanol working pairs for the solar ice maker, it was necessary
to measure the desorbing and adsorbing characteristics of the two refrigeration
working pairs. According to the third and the fourth procedures mentioned in
Section 2, experiments were carried out, and the experimental results are shown in
Table 2. Variations with time in the desorbing and adsorbing refrigerant amounts
are illustrated in Figs. 27, and provide us with a vivid demonstration of the dierence between the two refrigeration working pairs.
It can be seen in Table 2 that the amount of desorbed and adsorbed refrigerant
is stable under the desorbing and adsorbing conditions for the activated carbon
methanol working pair. The desorbed and adsorbed refrigerant is directly
dependent on the energy of adsorbent it accepts. The more the adsorbent accepted
radiation energy, the more the adsorbent desorbed the refrigerant in the desorbing
process, and also the more the adsorbent adsorbed the refrigerant in the adsorbing
process. But this did not take place for the activated carbonethanol working pair,
the amount of the desorbed and adsorbed refrigerant uctuated greatly.
It can be seen in Fig. 2 curve B1 that the activated carbon may desorb 2750 ml
of methanol with 19.44 MJ of energy input. Also the activated carbon may adsorb
2550 ml methanol after 18 h of adsorption as seen in Fig. 3 curve D1. The same
activated carbon may desorb 2450 ml of ethanol in the rst desorbing process with
19.44 MJ of radiation energy as seen Fig. 2 curve A1. However, the activated carbon only adsorbs 950 ml of ethanol after 18 h of adsorption time as seen in Fig. 3
curve C1. The adsorption amount of methanol by the activated carbon is three
Table 2
Desorbing and adsorbing characteristics for activated carbon with methanol and ethanol working pairs
Contrast experi- Working pair
ments

Accepted
radiation
energy (MJ)

Desorbing
time (h)

Desorbing
Adsorbing
refrigerant
time (h)
amount (ml)

Adsorbing
refrigerant
amount (ml)

The rst contrast group

The rst contrast group
The second contrast group
The second contrast group
The third contrast group
The third contrast group

19.44

2750

18

2550

19.44

2450

18

950

14.58

4.5

2150

18

2050

14.58

4.5

800

18

400

19.44

2550

18

2550

19.44

600

18

600

Activated carbonmethanol
Activated carbonethanol
Activated carbonmethanol
Activated carbonethanol
Activated carbonmethanol
Activated carbonethanol

2240

M. Li et al. / Renewable Energy 29 (2004) 22352244

Fig. 2. Variation of desorbed refrigerant mass with time in the rst contrast group.

times that of ethanol with similar energy inputs and experimental environments. It
may be seen in Fig. 4 curve B2 that the activated carbon may desorb 2150 ml of
methanol with 14.58 MJ of radiation energy input, and also that the activated carbon may adsorb 2050 ml methanol after 18 h of adsorption time as seen in Fig. 5
curve D2. However, the activated carbon only desorbs 800 ml of ethanol when
accepting 14.58 MJ of radiation energy input as seen in Fig. 4 curve A2. The activated carbon may only adsorb 400 ml of ethanol after 18 h of adsorption time as
seen in Fig. 5 curve C2. The desorbed methanol refrigerant amount from the acti-

Fig. 3. Variation of adsorption refrigerant mass with time in the rst contrast group.

M. Li et al. / Renewable Energy 29 (2004) 22352244

2241

Fig. 4. Variation of desorbed refrigerant mass with time in the second comparison group.

vated carbon is twice that of the desorbed ethanol under similar experimental conditions. The adsorption amount of methanol by the activated carbon is four times
that of ethanol under similar experimental conditions. It can be seen in Fig. 6
curve B3 that the activated carbon may desorb 2550 ml of methanol when accepting 19.44 MJ of radiation energy, and also that the activated carbon may adsorb
2550 ml of methanol after 18 h of adsorption time as seen in Fig. 7 curve D3.
However, the activated carbon only desorbs 600 ml ethanol when accepting 19.44
MJ of energy input as seen in Fig. 6 curve A3, and may adsorb 600 ml of ethanol
after 18 h of adsorption time as seen in Fig. 7 curve C3. From these experimental

Fig. 5. Variation of adsorption refrigerant mass with time in the second contrast group.

2242

M. Li et al. / Renewable Energy 29 (2004) 22352244

Fig. 6. Variation of desorbed refrigerant mass with time in the third contrast group.

results, it can be seen that the adsorbing and desorbing characteristics of the
activated carbonmethanol are quite stable, while the desorbed refrigerant in the
desorbing process may almost completely be adsorbed in the adsorption process.
For the activated carbonethanol, the desorbed and adsorbed refrigerant amount
varies quite greatly in both the rst and second cycles, due to the non-equilibrium
desorbing and adsorbing processes. After the third cycle, the desorbed refrigerant
may be completely adsorbed, but the amounts of desorbed or adsorbed refrigerant

Fig. 7. Variation of adsorption refrigerant mass with time in the third contrast group.

M. Li et al. / Renewable Energy 29 (2004) 22352244

2243

appear to be only one-quarter to that of the activated carbonmethanol working

pair.
4. Refrigeration eect analysis
Based on the above desorbing and adsorbing characteristics for the activated
carbonmethanol and activated carbonethanol, we can compare the eects of the
solar ice maker with these two dierent working pairs. Usually, the characteristics
of solar ice maker are described by its refrigeration eects Qref (or ice mass collected in water tank), and the coecient of performance, that is COP. They may be
expressed as follows:
Qref DxMa Le

Dx xconc  xdil

where xconc is the adsorption capacity before desorption, xdil is the adsorption
capacity after desorption, Ma is the mass of adsorbent inside the adsorbent bed,
and Le is the latent heat of vaporization.
Qref  Qcc
COP
it dt

T
where Qcc Tec Ma DxCpl dT is assumed to cool the refrigerant liquid from con
densing temperature Tc to the evaporation temperature Te . it dt is the total
radiant energy absorbed by the collector during the whole day.
Under the above denition, assume the COP of solar ice maker with the
activated carbonethanol as COP1 , the COP of solar ice maker with the activated
carbonmethanol as COP2 . For ethanol, Le 842 kJ=kg, q 789 kg=m3 ; for
methanol, Le 1102 kJ=kg, q 791 kg=m3 . It may be known from Section 3
experimental results that the desorbed ethanol amount from the activated carbon is
about one-quarter to that of the desorbed methanol under the condition of accepting similar radiation energy and adsorbent mass. According to these experimental
data and the above formula, COP1 =COP2 0:2 0:3. This means that the performance of solar ice maker with the activated carbonethanol is below that of the solar
ice maker with the activated carbonmethanol. So it appears impossible to substitute methanol with ethanol as a refrigerant for the solar ice maker as shown by
these results.
5. Conclusions
Many of the experimental results with the solar ice maker, regarding ice mass
production and desorbing and adsorbing characteristics, show that the refrigeration eect with the activated carbonmethanol is obviously superior to that of
the refrigeration eect using the activated carbonethanol. The performance of the

2244

M. Li et al. / Renewable Energy 29 (2004) 22352244

current solar ice maker with the activated carbonmethanol working pair is about
34 times higher than that with the activated carbonethanol working pair under
the condition of accepting similar radiation intensity and environment. For the
solar ice maker, the best suitable working pair is still activated carbonmethanol at
present, although some faults remain. Further theoretical analysis combined with
the experimental data on the activated carbonethanol working pair will be carried
out. The testing process for the solar ice maker using dierent refrigerants with
activated carbon as working pairs is being carried out to nd better working pairs
in addition to the activated carbonmethanol. Such research will help us speeden
up the practical application of the solar ice maker.
Acknowledgements
This work was supported by the Natural Science Foundation of Ministry of
Education of Yunnan Province, P.R. China and the Ministry of Education, P.R.
China.
References
[1] Critoph RE, Vogel R. Possible adsorption pairs for use in solar cooling. International Journal of
Ambient Energy 1986;7(4):18390.
[2] Hu J, Exell RHB. Adsorptive characteristics of activated charcoal/methanol combination.
Renewable Energy 1993;3(6/7).
[3] Pons M, Guilleminot JJ. Design of an experimental solar-powered, solid-adsorption ice maker.
Transactions of the ASME, Journal of Solar Energy Engineering 1986;108(4):3327.
[4] Pons M, Grenier PH. Phenomenological adsorption equilibrium law extracted from experimental
and theoretical considerations applied to the activated carbon+methanol pair. Carbon
1986;24(5):61525.
[5] Boubakri JJ, Guilleminot, Meunier. Adsorptive solar powered ice-maker: experiments and model.
Solar Energy 2000;69:24963.
[6] Leite APF, Daguenet M. Performance of a new solid adsorption ice maker with solar energy
regeneration. Energy Conversion and Management 2000;41:162547.
[7] Hu EJ. A study of thermal decomposition of methanol in solar powered adsorption refrigeration
systems. Solar Energy 1998;62:3259.
[8] Lu Q, Su Y, Liu Z, et al. Performance forecast of refrigeration cycle for some adsorbent-refrigerant
pairs. Acta Energiae Solaris Sinica 1996;17(2):1848.
[9] Cheng J, Que X, Chen Z. Experimental study of adsorption refrigeration system using activated
carbonethanol pair. Acta Energiae Solaris Sinica 1996;17(3):2169.
[10] Wang RZ, Li M, Wu JY, et al. An energy ecient hybrid system of solar powerd water heater and
adsorption ice maker. Solar Energy 2000;68(2):18995.
[11] Li M, Wang RZ. Experimental of a solar at plate hybrid system with heating and cooling. Applied
Thermal Engineering 2002;22:144554.
[12] Li M, Wang RZ, Xu YX. Experimental study on dynamic performance analysis of a at-plate solar
solid-adsorption refrigeration for ice maker. Renewable Energy 2002;27:21121.
[13] Li M, Wang RZ. A study of the eects of collector and environment parameters on the
performance of a solar powered solid adsorption refrigerator. Renewable Energy 2002;27:36982.
[14] Li M, Wang RZ. Heat and mass transfer in a at plate solar solid adsorption. Renewable Energy
2003;28:6123.