Energy Conversion and Management 50 (2009) 1295–1303

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Energy Conversion and Management

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Mathematical model of the sorption phenomenon of methanol in activated coal

Farid B. Cortés, Farid Chejne *, Juan M. Mejía, Carlos A. Londoño
Grupo de Termodinámica Aplicada y Energías Alternativas – Instituto de Energía, Facultad de Minas, Universidad Nacional de Colombia, sede Medellín, Colombia

a r t i c l e i n f o a b s t r a c t

Article history: A transient model of a sorption refrigerator using activated carbon/methanol pair is presented. It is a non-
Received 13 September 2007 uniform pressure model conformed by the mass, energy and momentum balance equations in cylindrical
Received in revised form 18 November 2008 coordinates, for the activated coal bed contained in the adsorber. The results obtained from the simula-
Accepted 18 January 2009
tion were suitably validated by the experimental information obtained from field test data and from data
Available online 23 February 2009
reported in the literature, presenting errors below 1.6% for each cycle step. The model allows to get data
of temperature, pressure, density and gas velocity profiles in radial direction, as well as the solid temper-
Keywords:
ature and the quantity of adsorbed methanol in the activated carbon bed in adsorption/evaporation and
Refrigeration
Adsorption
desorption/condensation steps.
Desorption Ó 2009 Elsevier Ltd. All rights reserved.
Mathematical modeling

1. Introduction to understanding the system behavior during cool-down and

Refrigeration systems have been developed since 1798 for the
preparation and preservation of foods such as meats, beverages
and jams; for food storage and distribution; for its use in industrial
processes such as the separation and condensation of gases, air
drying, and medicine and ice production; for industrial air condi-
tioning in laboratories, the mechanics of precision and textile fac-
tories. In order to provide for the refrigeration needs in non-
interconnected zones, a clean-based technology is proposed based
on the use of solar energy and of substances with no environmen-
tal impact. We are talking about systems of adsorption refrigera-
tion, which allow us to take advantage of non-conventional
thermal sources and residual heat wastes generated by the indus-
trial process. High electrical consumption equipments such as
compressors are not used in these systems; they were replaced
by ‘‘adsorbers” that perform the same function within the process
of cold generation. The key point to continue advancing in these
studies is the modeling of the adsorber, because of the complex
coupled heat and mass transfer and transport phenomena that oc-
cur during the cycle.
Many mathematical models are listed in the literature to de-
scribe the behavior of adsorption phenomena, where the mass
and/or energy balances are considered, neglecting the pressure
effects. Those works include the model of Anyanwu et al. [1] on
the transient analysis and performance prediction of a solid
adsorption solar refrigerator, using a uniform pressure model for
activated carbon/methanol adsorbent/adsorbate pair with a view
* Corresponding author. Tel.: +57 4 4255333; fax: +57 4 2341002.
E-mail address: fchejne@unalmed.edu.co (F. Chejne).
refrigeration phases. The errors between theoretical and experi-
mental data were less 4%. Cortes et al. [2] on a transient analysis
of the adsorption methanol on actived carbon with a pressure uni-
form model to understanding the complex transient behavior of
the desorption process. However, it fails to account for the complex
behavior observed in desorption, and gives large quantitative devi-
ations (up to 20%) for the average temperature. Li and Wang [3]
presented a pressure uniform model for the description of the
regeneration step. This transient model is conformed by the energy
balance, where the diffusive effect is considered. The errors be-
tween the calculated and measured results are less than 4%. Luo
and Tondeur [4] present an adsorption transient model conformed
by the mass balance, where the mass transport is due a pressure
gradient. It is connected by the energy balance, where the Fourieŕs
law is assumed. The errors between the experimental and theoret-
ical data are close to 23% and 50% for the adsorption and desorp-
tion steps, respectively. The authors attribute this error, probably
to the calculation of the mass coefficient ‘‘D”, the thermal inertial
of the metal and insulation has not been considered. Leite and
Daguenet [5] present a pressure uniform model conformed by
the energy balance in the bed, absorber plate, condenser and evap-
orator. The bed’s radial temperature distribution is determined by
means of a one-dimensional numerical method based on a finite
difference technique. The theoretical results have the same trend
to those concerning the experimental study in Tunisia. Wang
et al. [6] present a heat transfer model between the fluid and bed
is established to investigate the thermal wave. This is a pressure
uniform model and the energy transport is due Fourieŕs law with
view to understanding of this process type. Dai and Sumathy [7]
present a pressure non-uniform model for the description of the

0196-8904/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.enconman.2009.01.017
1296 F.B. Cortés et al. / Energy Conversion and Management 50 (2009) 1295–1303
Nomenclature
A transversal area
Cg gas density (kg/m3)
Cgevap gas density at the evaporator conditions (kg/m3)
Ccon gas density at the condenser conditions (kg/m3)
Cpliq calorific capacity of condensed methanol (kJ/kg K)
Cpgas calorific capacity of methanol in the gaseous phase (kJ/
kg K)
Cpc calorific capacity of coal (kJ/kg K)
h convective coefficient of heat transference (kW/m2 K)
ha heat transference coefficient between the two phases
(kW/m3 K)
hg gas enthalpy (kJ/kg)
hr coefficient of the transference of gas (kW/m2 K)
K1 thermal conductivity of the gaseous phase (kW/m2 K)
K2 thermal conductivity of the solid phase (kW/m2 K)
M molecular weight of the adsorbate (kg/kmol)
P gas pressure (Pa)
Pevap gas pressure at the evaporator conditions (Pa)
Psat saturation pressure (Pa)
Qads heat sorption (kJ/mol)
process of adsorption conformed by the mass balance in the tran-
sitional state, three-dimensional and governed by the convective
phenomenon. It is connected to the energy balance in the transi-
tory state, in three dimensions, where the diffusive and convective
effects are considered, neglecting the pressure effects. Darcy’s law
for porous beds is used as momentum balance. In the author’s for-
mulation of the model, problems with the energy balance are pre-
sented because it includes the generation/required energy of
adsorption/desorption process by duplicated.
In this article, a non-uniform pressure mathematical model of a
phenomenological character in radial direction was performed, in
which the equations for the mass, energy and momentum balances
in cylindrical coordinates, varying the pressure in the activated
carbon bed contained in the adsorber, are compiled. Apart from
satisfactorily validating the theoretical results obtained from the
mathematical model in regards to the experimental data on
adsorption [4] and desorption [8]; presenting errors of below
1.6% in every step of the cycle. The main objective is to analyze,
explaining and predicting the transient heat and mass transfer
and transport process in the adsorber of the sorption refrigeration.
2. Mathematical model
The model developed to predict the adsorption and desorption
behavior of methanol in an activated coal bed was performed in
a concentric tube configuration ‘‘adsorber” (Fig. 1). The inner tube
is the methanol distributor, with a diameter of 0.02 m and a longi-
Fig. 1. Diagram of the annular adsorber [4].
Qvap latent heat of methanol vaporization (kJ/mol)
r radial position of the bed (m)
R universal constant of the gases (kJ/mol K)
t time (s)
Tg gaseous phase temperature (K)
Tgevap gas temperature at the evaporator conditions (K)
Tc solid phase temperature (K)
q quantity of adsorbed gas (kg/kg)
ug internal energy of gas (kJ/kg)
Ug coefficient of the transference of energy from the gas-
eous phase to the amb. (kW/m2 K)
Uc coefficient of transference of energy from the solid
phase to the amb. (kW/m2 K)
v velocity of the gas (m/s)
Greek letters
a coefficient of the thermal expansion of liquid methanol
e porosity (m3/m3)
qs density of the solid (kg/m3)
l viscosity of the adsorbate (kg/ms)
tude of 0.95 m (made of stainless steel), which is connected to the
rest of the refrigerator’s components [4]; according to the step of
the refrigeration cycle at which it is operating (for adsorption it
operates with the evaporator and for desorption with the con-
denser). The activated coal is located between the distributor and
the external cylinder, this is where the mass and energy transfer-
ence, and transport phenomena (methanol adsorption and desorp-
tion on actived carbon) take place.
For the formulation of the mathematical model a differential
element was used, with a thickness of ‘‘dr” (Fig. 2), and the follow-
ing assumptions were taken into consideration:
 Convection causes the mass transportation in the vapor phase.
 The temperature and concentration in the adsorber are assumed
axially homogeneous (but dependent on radial position) [4].
 The adsorbate presents an ideal behavior in the gaseous phase.
 All adsorbed particles remain fixed, migration radial position is
non-existent.
 The thermal conductivity of the adsorbate and adsorbent are
constants in the interval of operational temperatures.
 Thermal equilibrium is assumed between the adsorbed and
adsorbent phases (there is no heat transfer resistance between
the two phases) ‘‘this phase is called the solid phase”.
 The kinetic and potential energy are negligible.
 The adsorbent has a defined and uniform particle size for the
bed.
Fig. 2. Radial differential in the adsorber.
 F.B. Cortés et al. / Energy Conversion and Management 50 (2009) 1295–1303 1297

2.1. Mass balance The energy balances for the vapor and solid phases, respec-
tively, are:
In order to perform the mass balance in an activated coal bed, a
@ 1 @ e @ @T g
differential ‘‘dr” was used for the activated coal bed (Fig. 2); to e ðC g ug Þ þ ðrC g v hg Þ ¼ ðK 1 r Þ
@t r @r r @r @r
which the law of mass conservation was applied [9].
v @ðrPÞ
In the adsorption and desorption steps, the transport of metha- þ ð1  eÞhaðT c  T g Þ þ ð4Þ
r @r
nol occurs as a consequence of the differential pressure found
@ðuc þ quga Þ ð1  eÞ @ @T c
throughout the activated coal bed, provoking convective move- ð1  eÞqs ¼ ðK 2 r Þ  ð1  eÞhaðT c  T g Þ
ments of gas: @t r @r @r
ð5Þ
@C @q 1 @
e g þ ð1  eÞqs þ ðC g v rÞ ¼ 0 ð1Þ
@t @t r @r
2.3. Momentum balance
In Eq. (1), the balance of methanol in the activated coal bed is
established. It predicts the transient behavior of the radial direc- The gas transport inside the bed is originated by pressure gradi-
tion of the gas density, for the adsorption and desorption phenom- ents [16] during the steps of adsorption and desorption. Therefore,
enon. The first two terms on the left side of the Eq. (1), represent this convective transport can be described by Darcy’s law. The acti-
the accumulation of gas for the porous spaces in the activated coal vated coal bed is a porous medium of low-porosity, for which
bed as well as for the adsorbed phase, and the third term repre- Darcy’s law is applicable:
sents the convective net flow of gas through the porous space.  
Given that in the mass balance the uptake adsorbed or desorbed
K D dP
V ¼  qg ð6Þ
for every ‘‘q” instance of sorption, the dynamic for this adsorbate/ l dr
adsorbent pair must be involved. For this, a kinetic adsorption gov- where KD is the permeability constant of the bed and is defined by
erned by a impulsory force within the adsorbed quantity in the means of a relation between the porosity and the medium diameter
equilibrium (Dubinin–Asthakov equation), at temperature, system of the pores, for which it is necessary to employ empirical equations
pressure and absorbed quantity, is proposed [10] or equations based on the simple structural models for porous
dq   mediums, such as the Carman–Koseny equation [17]; deduced for
¼ ð15D0 =r 2 Þ expðEa =RTÞ ðC geq  qÞ ð2Þ porous environments with spherical particles of a uniform diame-
dt
ter. Permeability is given by the following expression, taken from
The parameters that appear in Eq. (2) (15D0/r2, Ea/RT) are ob- Ref. [7]:
tained through experimental validation [11]. The existing relation
at a temperature, pressure and quantity of gas adsorbed in equilib- e2 d2p
rium C geq is the adsorbate quantity. The quantity of gas adsorbed in KD ¼ ð7Þ
equilibrium is obtained by means of the Dubinin–Asthakov (D–A) 150ð1  eÞ2
equation [12].
By neglecting the gravitational field in Eq. (6), in regards to the
The phenomenon of physical adsorption of vapors in micropo-
fall of differential pressure in the bed, the following expression is
rous solids was described by Dubinin and Asthakov [12], who led
obtained:
their investigations on the problem of physical adsorption on por-  
ous materials and resulted in the Dubinin–Polanyi theory of micro- K D dP
V ¼ ð8Þ
pore filling (also known as the theory of volume filling of l dr
micropores (TVFM)). This theory is based on the postulate that
the mechanism for adsorption in micropores is that of pore filling The negative sign of Darcy’s law is compensated by the fall of
rather than a layer-by-layer formation of a film on the walls of the differential pressure in the bed, since this term is negative.
pores [12]. Also, that there is no interaction within the adsorbed
molecules, and that the adsorption heat is the same all throughout 2.4. Boundary conditions
independently of the fraction of the surface covered [13–15]. The
formulation of this ‘‘theory of volume filling of the micropore” is 2.4.1. Boundary conditions applicable to adsorption
expressed by the Dubinin and Astakhov equation [12], which is de- The concentration and pressure of methanol during feeding are
fined as follows: constant, and are given by the conditions in which the evaporator
is found:
  a 
Tc
C geq ¼ C g max  exp b1 1 ð3Þ C g jr¼ra ¼ C gev ap ð9Þ
T sat
T g jr¼ra ¼ T gev ap ð10Þ
where C g max is the maximum amount adsorbed by coal under cer- 
@T c 
tain conditions of pressure and temperature in the system, ‘‘b1”  K2 ¼ hr ðT c jr¼ra  T gev ap Þ ð11Þ
@r r¼ra
and ‘‘a” are parameters provided by the intrinsic properties of coal
called structural constants of activated coal, along with its adsorp- Pjr¼ra ¼ Pev ap ð12Þ
tive partner.
The boundary conditions for the surface r = rb, are as follows:
2.2. Energy balances
C g mjr¼rb ¼ 0 ð13Þ

For energy balance, it is assumed that energy is transferred by @T g 
 K1 ¼ U g ðT g jr¼rb  T 1 Þ ð14Þ
conduction in the solid phase and by conduction and convection @r r¼rb

in the vapor phase; apart from taking into consideration the suppo- @T c 
 K2 ¼ U c ðT c jr¼rb  T 1 Þ ð15Þ
sitions proposed for the balances. This way, and by conducting a @r r¼rb
procedure similar to that developed for the mass balance, the fol-
lowing balances are formulated. Vjr¼rb ¼ 0 ð16Þ
1298 F.B. Cortés et al. / Energy Conversion and Management 50 (2009) 1295–1303

2.4.2. Boundary conditions applicable to desorption 0.07

The concentration and pressure of methanol in the condenser
are constant, and are given by the conditions in which the evapo- 0.06 Density (r = 29 mm)
rator is found:
0.05 Density (r = 11 mm)
in r = ra

Density (kg/m3)
C g jr¼ra ¼ C con ð17Þ 0.04

@T g 
 K1 ¼0 ð18Þ 0.03
@r r¼ra

@T c  0.02
 K2 ¼0 ð19Þ
@r r¼ra
0.01
The ‘‘r = rb” surface is isolated for the mass transport and is
found in contact with the thermal oil, which delivers energy to 0
the system in order to allow the methanol desorption, 0 5 10 15 20
Time (s)
C g mjr¼rb ¼ 0 ð20Þ
 Fig. 3a. Evolution of the gas density.
@T g 
 K1 ¼ U g ðT a  T g jr¼rb Þ ð21Þ
@r r¼rb

@T c  0.03 t = 20 s
 K2 ¼ U c ðT a  T c jr¼rb Þ ð22Þ
@r r¼rb t = 1000 s
0.025 t = 5000 s

3. Results obtained from the mathematical model Density (kg/m3) 0.02

0.015
The mathematical model for the adsorption and desorption of
methanol in activated coal was discretized in space by the finite
0.01
volume method [18], using the approximation of a central differen-
tial scheme to represent the thermal conduction of the gas and the 0.005
solid. For convective terms, a first order upwind scheme was used
in order to compute the values for each of the analyzed sides of the 0
control volume. 11 13 15 17 19 21 23 25 27 29
By discretizing the mass and energy balances in space, a system Radial Distance (mm)
of highly non-linear ordinary differential equations is created.
Fig. 3b. Gas density profile.
These set of differential equations were solved using the Fortran
DIVPAG subroutine [19]. This subroutine uses either the Adams–
Moulton method or the Gear method in order to solve initial value capacity and therefore the gas density of the bed increases until the
problems (Visual Numeric IMSL). value reaches the conditions of the evaporator.
In order to have a totally defined system, a series of comple- In Fig. 3b, the density profile of methanol within the adsorber is
mentary equations are used for calculating the physical properties illustrated. After the process has initiated, it is observed that for
of the adsorbent and adsorbate material, isothermal adsorption, relatively short periods of time the adsorption process the gas den-
among others. sity in the radial position nearest to the methanol distributor
(11 mm) is much greater than those of the radial positions that
3.1. Results during adsorption are farther away from the distributor; with density presenting a
decreasing tendency in function of the radius. For times over
In Table 1, the parameters used to simulate adsorption are pre- 5000 s, the difference in densities between node 1 (radius of
sented [4].
In Fig. 3, the evolution and profile of the density of gas, the pres-
sure in the system, the temperatures for both phases and the up-
5000
take are observed. The gas density in the bed rapidly decreases
due to the velocity of adsorption being much greater than that of 4500
Pressure (r = 29 mm)
the flow of methanol which enters into the activated coal bed from 4000
the evaporator (Fig. 3a). As time goes by, coal looses its adsorption
3500 Pressure (r = 11 mm)
Pressure (Pa)

3000

2500
Table 1 2000
Parameters for the simulation of adsorption.
1500
Parameter Value Parameter Value
1000
ra (m) 0.01 rb (m) 0.03
l (kg/m s) 1.0E4 Tevap (K) 265 500
Tamb (K) 300 M (g/mol) 32 0
qmax (kg/kg) 0.238 K1 (W/m K) 0.0164 0 5 10 15 20
ha (W/m3 K) 20,000 R (J/mol K) 8314
b1 (k  2) 13.289 hr (W/m2 K) 0.5
Time (s)
a 1.33 e 0.72
Fig. 3c. Evolution of the pressure in the bed.
 F.B. Cortés et al. / Energy Conversion and Management 50 (2009) 1295–1303 1299

11 mm) and node 10 (radius of 29 mm) are not very marked,
reducing the negative slope that can be observed for times under
5000 s.
In Fig. 3c, the pressure evolution is observed. Pressure decreases
rapidly at the beginning of the process (for times under 15 s), this
occurs because the methanol adsorption phenomenon takes place
within the activated coal bed, it is more relevant than the transport
of material through the same. For times over 15 s, the methanol
transport within the process becomes relevant, because the
adsorption capacity of the adsorbent is progressively affected by
the lack of free surface for the methanol adsorption; pressure
slightly increases until it reaches the pressure value of the
evaporator.
In Fig. 3d, the pressure profile in radial direction is illustrated. A
tendency very similar to that of the gas density can be observed,
because pressure is a function of density. In addition, as shown
in Fig. 3d, the pressure of the last node of the adsorber (radius of
29 mm) is lowest; due to the tortuosity and restrictions presented
by the porous material for transportation.
In Fig. 3e, a comparison is made between the temperatures of
the two phases that coexist within the bed evaluated at the same
radial position. The initial node (radius of 11 mm) for the gaseous
phase presents a lower temperature because this position is in di-
rect contact with the vapor of methanol that comes out from the
evaporator; which is found at a temperature far below that of
ambient temperature (saturation temperature at the pressure of
the evaporator).
Aside from initially presenting an increase in temperature,
caused by the velocity of adsorption being greater than that of heat
transference or loss of energy in the system, as time goes by the
mechanisms involved in the energy transport and transference
for each phase start to take on an important role; because activated
coal gradually looses its capacity of adsorption. For this reason,
temperature decreases.
The solid phase temperature is always higher when compared
to that of the vapor phase, both evaluated at a same radial position
within the bed. This is clear given that the adsorption heat is gen-
erated in the coal by adsorption and from there energy is trans-
ferred to the vapor phase.
The gas temperature of the radius function (Fig. 3f) presents a
maximum local temperature in the adsorber at any time. The ini-
tial node (11 mm) coming into contact with the feeding of metha-
nol feeding from the evaporator and the final node (29 mm) is
always in contact with the environment transferring energy. Addi-
tionally, when the adsorption process has recently initiated, for
times under 160 s, the temperature within the adsorber is almost
homogenous and does not show the previously described
tendencies.
Fig. 3g shows how the quantity of methanol adsorbed by the
activated coal varies in the function of time. It is evident that the
activated coal adsorbed a greater amount of methanol by the initial
node (radius of 11 mm) than those defined by the final node (ra-
dius of 29 mm), given that for the radial position of 11 mm temper-
ature is lowest.
Fig. 3h shows how the adsorbed quantity is a decreasing func-
tion in regards to the radial position. In addition, it can be thought
that as time goes by, the adsorbed quantity increases in an attempt
to reach the maximum adsorbed quantity given the physical prop-
erties of the activated coal.

335
2500 t = 20 s
330
t = 1000 s
325
Temperature (K)

2000 t = 5000 s
320
Pressure (Pa)

1500 315

310
1000
305 t = 160 s
t = 1000 s
500 300
t = 5000 s
295
0 11 13 15 17 19 21 23 25 27 29
11 13 15 17 19 21 23 25 27 29 Radial Distance (mm)
Radial Distance (mm)
Fig. 3f. Gas temperature profile.
Fig. 3d. Bed pressure profile.

0.14
320 Uptake (r = 11 mm)
0.12
315
Uptake (r = 29 mm)
Solid (r = 11 mm)
0.1
Gas (r=11 mm)
Uptake (kg/kg)

310
Temperature (K)

0.08
305
0.06
300
0.04
295

0.02
290

0
285
0 5000 10000 15000 20000 -1000 4000 9000 14000 19000 24000
Time (s) Time (s)

Fig. 3e. Temperature evolution for the two phases. Fig. 3g. Uptake evolution.
1300 F.B. Cortés et al. / Energy Conversion and Management 50 (2009) 1295–1303

0.045 The entry data required by the simulator comes directly from
0.04
t = 160 s those reported by the authors [4], although the information is lim-
t = 1000 s ited. In order for the simulation to be effective, the physical prop-
0.035
t = 5000 s erties of activated coal and pure methanol were employed; aside
Uptake (kg/kg)

0.03
from the information obtained by Ceballos and Velez [20] on the
0.025 parameters of the Dubinnin–Ashtakov isothermal. As in Fig. 5,
0.02 the average theoretical temperature obtained through the mathe-
0.015 matical model adjusts fairly well to the experimental data.
0.01
3.2. Results during desorption
0.005
0 In Table 2, the parameters used to simulate the desorption phe-
11 13 15 17 19 21 23 25 27 29
nomenon in the device shown in Fig. 1 are presented.
Radial Distance (mm)
The mathematical model was formulated using the geometry
Fig. 3h. Profile of the uptake.
proposed by Ceballos and Velez [20]. It consists of three concentric
cylinders organized in the following way: an internal tube of r = ra
radius, through which the circulation of methanol is going to take
In Fig. 4, the evolution of the velocity of methanol within the place in order to be distributed to the activated coal bed. An inter-
activated coal bed is presented. According to Fig. 4, the initial mediate tube, where the activated coal is confined; and which is
velocity increases because the pressure gradient is very high the object of interest in this study. rb < r < ra and an external tube:
(impulsory force for the transport of material). As time goes by thermal oil flows in the ring formed between the intermediate and
within the process of adsorption the gradients of pressure gradu- external tube, which provides the necessary energy for desorption.
ally decrease; for which the transportation or velocity within the In Fig. 6 the evolution in time and profile of the gas density, the
bed is affected. pressure in the system, the temperature for both phases and the
In Fig. 5, a comparison between the temperature data obtained desorbed quantity during the desorption step are observed.
theoretically by means of the mathematical model developed for Fig. 6a shows how the gas density in the two nodes closest
the process of adsorption and the experimental and theoretically (11.08 and 10.25 mm) to the energy source (thermal oil), at the
data reported by Luo and Tondeur [4] are illustrated. beginning of the process of desorption (for times under 50 s), pres-
ent a greater density than the rest of the activated coal bed; since
these points are found at a higher temperature and hence the
velocity of desorption of methanol is favored, thus increasing the
0.0035
gas density for said position.
As time goes by, gas density in these points decreases given that
0.003
the activated coal located there has desorbed a great quantity of
0.0025
Velocity (m/s)

Velocity (r = 11 mm)
0.002 Table 2
Velocity (r = 29 mm) Parameters for the simulation of desorption.
0.0015
Parameter Value Parameter Value

0.001 ra (m) 0.003175 rb (m) 0.0115

l (kg/m s) 1.0E4 Tcon (K) 295
Lv (J/kg) 1,135,937 Cpgas (kJ/kg K) 1430
0.0005 qmax 0.238 Cpliq (kJ/kg K) 2632
ha (W/m3 K) 20,000 M (g/mol) 32
0 b1 (k  2) 13.289 K1 (W/m K) 0.0164
0 5000 10000 15000 20000 a 1.33 Tamb (K) 300
Time (s) e 0.4 R (J/mol K) 8314
hr (W/m2 K) 0.5 Ta (K) 343
Fig. 4. Evolution of the velocity of gas in time during the adsorption phase.

0.144
Density (r = 3.6 mm)
60
Theoretical Data - Luo et al.[4] 0.142 Density (r = 10.25 mm)
55 Density (r = 11.08 mm)
Density (kg/m3)

Theoretical Data
Temperature (°C)

50 0.14
Experiemental data - Luo et al. [4]
45 0.138
40
0.136
35

30 0.134

25
0 4000 8000 12000 16000 20000 24000 0.132
0 50 100 150 200
Time (s)
Time (s)
Fig. 5. Validation of the theoretical model with experimental and theoretical
results during the adsorption step. Data adapted from Ref. [4]. Fig. 6a. Evolution density of gas.
 F.B. Cortés et al. / Energy Conversion and Management 50 (2009) 1295–1303 1301

0.145 11060
t = 500 s t = 30 s
11040
0.14
11020
t = 2500 s
Density (kg/m3)

Pressure (Pa)
0.135
11000
0.13 10980

10960
0.125
t = 500 s t = 10 s 10940
0.12
t = 2500 s 10920
0.115 10900
3.61 4.44 5.27 6.1 6.93 7.76 8.59 9.42 10.25 11.08 3.61 4.44 5.27 6.1 6.93 7.76 8.59 9.42 10.25 11.08
Nodos Nodos

Fig. 6b. Gas density profile. Fig. 6d. Bed pressure profile.

material that was adhered to it, and the desorbed material begins
to transport itself towards the condenser. The gas density reaches a 345
quasi stationary state at approximately 3500 s, in an attempt to 340
reach the density of the gas at the conditions of the condenser. 335
In Fig. 6b, the transient behavior of the density of the gas in the

Temperature (K)
330
parametrized space is reported. At the beginning of the process of
325
desorption, the density in space obeys to an increasing monoto-
320
nous function in the bed thickness function. At the end (times un-
der 170 s), the behavior of the gas density is inversely 315
Solid (r = 3.6 mm)
proportionate to that of the radius, because the desorption capacity 310
of methanol for coal located in the last nodes (which are in direct 305 Gas (r = 11.08 mm)
contact with the source of heat) decreases and the transport of 300 Solid (r = 11.08)
material takes on an important role within the process. 295
In Fig. 6c, the behavior of pressure within the activated coal bed 0 500 1000 1500 2000 2500 3000
for desorption is illustrated. The pressure within the bed for the Time (s)
last nodes notably increases because the material is desorbed
due to the high temperatures present, increasing gas density and Fig. 6e. Temperature evolution for the two phases.
hence pressure. For the initial nodes (3.6 and 4.4 mm) that are clo-
ser to the methanol distributor, a slight increase of pressure ap-
pears caused by an increase in temperature. But as time goes by, In Fig. 6e, the transient behavior of temperature for both the so-
pressure starts to decrease with a tendency to that of the pressure lid and gaseous phases is evidenced. By comparing the tempera-
of the condenser; given that the transport gains importance. ture of the two coexisting phases within the bed (11.08 mm), a
In Fig. 6d, an increasing monotonous function of pressure in the tendency similar to that of the curves can clearly be seen;
bed thickness function is evidenced, even though it is much more although, it is important to clarify that the solid phase temperature
marked for relatively short periods of time after the initiation of is slightly superior that the gaseous phase. This fact comes to show
the process of desorption (times under 50 s). For times substan- that the resistance to the transference of heat between the solid
tially over 170 s, the slope of pressure decreases, given that the and the gaseous phases is negligible; therefore it is possible to de-
transport of material is more important than the velocity of velop a phenomenological model by proposing just one energy bal-
desorption. For times over 2500 s, it is observed that pressure ance without any separation between the phases.
reaches a quasi stationary state with a tendency to a pressure dic- The marked difference in temperatures among radial positions
tated by the conditions of the condenser. (radius = 11.08 mm and radius = 3.6 mm) is evidenced by the low
thermal conductivity of the activated coal.
The slope for the hottest nodes is much (11.08 mm) at the
11079
beginning of desorption (times under 300 s). After a time of
Pressure (r = 3.6 mm) 2000 s, they begin to show a decline in the rapidity of heating, gi-
11059 ven that the quantity of energy supplied is practically used for
Pressure (r = 4.4 mm)
11039 heating in the gaseous and solid phases.
Pressure (r = 11.08 mm)
Pressure (Pa)

At the end of the 3500 s, it can be said that the system reaches a
11019
quasi stationary state. The temperature for all nodes in which the
10999 partition of the control volume was carried out tend to the temper-
10979 ature of the thermal oil.
In Fig. 6f, the temperature profiles for activated coal can be ob-
10959
served. As was expected, the temperature of coal increases with an
10939 increase in radial distance; moreover, for greater times (times
3500 s) the temperature in the bed tends to the temperature of
10919
0 50 100 150 200 the heat source (thermal oil).
Time (s) For times less than 200 s, marked gradient temperatures in ra-
dial direction can be observed, and as time goes by it decreases
Fig. 6c. Evolution of the pressure in the bed. (time 2000). It is also observed that once the desorption process
1302 F.B. Cortés et al. / Energy Conversion and Management 50 (2009) 1295–1303

340 Experimental average (Ta = 70 °C)

330
335 Theoretical average (Ta = 70 °C)
325
330
Temperature (K)

Temperatura (K)
t = 500 s t = 10 s
325 320
t = 2500 s
320 315
315
310
310
305
305

300 300
0 200 400 600 800 1000 1200 1400
3.61 4.44 5.27 6.1 6.93 7.76 8.59 9.42 10.25 11.08
Nodos Tiempo (s)

Fig. 8. Validation of the theoretical model with experimental data results during
Fig. 6f. Temperature profile.
the desorption step.

has initiated, the heat transfer in the nodes farther away from the
heat source are null (3.6 and 4.44 mm); due to the high thermal the pressure profile within the bed. Initially, the velocity increases
resistivity of coal. because the pressure gradient is very elevated (impulsory force for
Fig. 6g shows how the quantity of desorbed methanol in the the transport material). As time goes by within the process of
time function varies. It is evident that there is a greater adsorbed adsorption the pressure gradients for all nodes begin to decrease,
quantity of methanol in the initial node (radius 3.6 mm) than in and hence the transport or velocity within the bed is affected.
the final node (radius 11.08 mm), because the final node is closer The negative velocity values are representative for this process of
to the heat source. desorption since the desorbed methanol within the activated coal
The adsorbed quantity in coal tends to reach a quasi stationary bed is taken to the condenser, hence it is an output for the analyzed
state at around 3500 s, and it tends to a quantity defined by the control volume; and according to the sign convention for the law of
pressure conditions of the condenser and by the thermal oil conservation, the output terms must be negative.
temperature. Fig. 8 illustrates the behavior of the theoretical average temper-
According to Fig. 7, the velocity of the gas within the bed de- ature and the experimental average temperature obtained from
creases as the radial position advances; given the dependency of the thesis written by Ochoa and Reyes [8]. A very similar tendency
between the behavior described in the experimental data and that
obtained from the results provided by the mathematical model for
0.19
the desorption of methanol in an activated coal bed are clearly ob-
served. Although the experimentation time employed for the vali-
Uptake (r = 11.08 mm)
0.17 dation was a bit short, it is known that the desorption process
Uptake (r = 3.6 mm) reaches a quasi stationary state in a relatively short period of time
0.15
Uptake (kg/kg)

(3500 s).
0.13

0.11
4. Conclusions
0.09
One-dimensional, non-stationary mathematical model in cylin-
0.07
drical coordinates for the activated coal bed contained in the ad-
0.05 sorber, by using the methanol/activated coal pair, has been
0 500 1000 1500 2000 2500 3000 developed. The results data obtained during the simulation of
Time (s) adsorption step were validated by the experimental information
reported in the literature. As for the desorption step, it was vali-
Fig. 6g. Uptake evolution. dated with the experimental results obtained from a device de-
signed to generate adsorption and desorption curves at National
University of Colombia.
This model can be used to design and construction of refrigera-
Time (s) tors by adsorption, due to it allows predicting adsorber’s behavior
0
0 500 1000 1500 2000 2500 3000 and it can determine cycle times and optimal methanol loads for
-0.0002
any given cooling needs. One important contribution of this model
-0.0004 is that it has showed the influence of pressure differential profile as
Velocity (m/s)

-0.0006 it can be seen on the radial gas velocity which decreased taken into
account this term on the momentum equation.
-0.0008
-0.001 Velocity (r = 4.4 mm)
Acknowledgements
-0.0012
Velocity (r = 11.08 mm)
-0.0014 The authors thank to Professor Antonio Pralon Ferreira, UFPB,
-0.0016
Brazil, for their friendship and fruitful collaboration, COLCIENCIAS
and the Universidad Nacional de Colombia for their logistical and
Fig. 7. Evolution of the velocity of gas during the adsorption phase. economical support.
 F.B. Cortés et al. / Energy Conversion and Management 50 (2009) 1295–1303 1303

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