13 Vasiliev Lyah Rabinovich 2011

VIII Minsk International Seminar Heat Pipes, Heat Pumps, Refrigerators, Power Sources,
Minsk, Belarus, 12-15 September, 2011

PROGRAM TOOLKIT FOR MODELING AND OPTIMIZATION
OF ADSORPTION AND CHEMICAL HEAT PUMPS
AND REFRIGERATORS

Vasiliev L.L., Lyah M.Yu., Rabinovich O.S.
A.V. Luikov Heat and Mass Transfer Institute, NAS of Belarus
15 P.Brovka St., Minsk, 220072, Belarus
Tel/fax: 375 (17) 2842133; E-mail: lvasil@hmti.ac.by

Abstract
A set of programs for numerical modeling and optimization of adsorption and chemical heat pumps and
refrigerators has been developed. The modeling is based on one-dimensional (in the radial direction) consideration of
dynamic adsorption or chemical reversible reactions in a cylindrical reactor filled with adsorbent. The program toolkit
allows investigation of various heat-conversion devices designed as a combination of one or several reactors with
condensers and evaporators. The programs have options for varying reactor parameters, thermal reservoir temperatures,
resistance of control valves connecting the reactors and time of their opening and closing. The graphical representation
of time history for mean temperature and sorbate content in the reactors is shown in the program screen as well as the
effective Clausius-Clapeyron-diagram dynamics of working medium. As a result of modeling, the programs calculate
main characteristics of thermal energy conversion such as COP, SHP (SCP), and the maximal temperature difference
between the heat carrier and adsorbent during the process. The program tool has also an option for optimizing
characteristics of heat conversion for a chosen set of parameters. Optimizing part of the code is based on the simplex-
method algorithm. The developed approach and algorithms were validated by comparison of numerical results with
experimental data.

KEYWORDS
Adsorption, chemical reaction, heat pump, refrigerator, modeling.

INTRODUCTION
Thermal energy conversion by the use of the heat of physical or chemical adsorption has rather long
history with partaking of such great names as Faraday and Einstein [1, 2]. In spite of this, the attention to this
problem given by investigators and engineers does not reduce, that is caused by general energy demands as
well as due to emergence of new materials and compounds for adsorption and suggesting new heat
conversion schemes [316]. Needs for further improvements of adsorption and chemical heat pumps and
refrigerators make of current importance the development of programming tools for numerical modeling of
most commonly used schemes and methods of heat conversion with adsorbers having different fillings,
kinetics and transport properties, dimensions. The present work is aimed at development such a toolkit with
rather diverse options, working as meccano and helpful for engineers, designers and students specializing
in the related fields of engineering science. The idea lying in the base of the work is to use a simple (one-
dimensional) model of an adsorber unit and to provide means for modeling of heat conversion in an
apparatus comprised of different combinations of such units with heat sources, condensers and evaporators,
connected trough control valves.

MODEL OF ADSORPTION-CHEMICAL THERMAL ENERGY CONVERTER
Description of the adsorber unit
The sketch of the adsorber unit is shown in Fig. 1. The reactor represents a cylinder filled with a porous
adsorbent of arbitrary composition (it can be a monotype matter or a complex compound of adsorbents
having different nature, capacity and kinetic properties). The adsorbent has an effective porosity c and
thermal conductivity . There are external jacket and central tube in the reactor. If the sorbate is supplied
trough the central tube, the wall of the tube has perforations and the impermeable external jacket serves for

the forced circulation of the heat carrier (with the temperature T
f
). In the opposite case, the heat carrier can
be supplied through the central tube (which should be impermeable in this situation) and gas-sorbate is fed
trough the external jacket having perforated internal wall. In further description of the numerical model we
will suppose the first of above described possibilities. The tube for gas-sorbate supply is equipped with a
control valve having the hydraulic resistance Kv.

Fig. 1. The sketch of adsorber unit. 1 is the channel for sorbate supply; 2, the sorbent; 3, the heat carrier
jacket.

Kinetics of physical and chemical adsorption
The program toolkit is adapted for the usage of two types of sorbent, i.e. with physical and chemical
adsorption. The activated carbon fibers in the form of Busofit [5, 6] is used as a prototype for the adsorbent
with physical adsorption, while chemical reversible adsorption is meant on metal salts like BaCl
2
, CaCl
2
,
NiCl
2
, etc [4]. There is also an option for the use of composite adsorbent which combines properties of both
physical and chemical adsorption. In this case, the composite adsorbent is treated as simple (independent)
superposition of two or more adsorbents with different properties. Studies of heat converters with composite
adsorbents are also widespread [5, 6, 11, 15].
The Dubinin-Astahov equation [17] is used for description an equilibrium physical adsorption of gases :
|
|
|
.
|
\
|
(
(
(
|
|
.
|
\
|
|
|
.
|
\
|
|
=
2
2
2
2
0
P
P
T
T
ln
T
B exp
b
W
a
cr
cr
eq
, (1)
where aeq is the equilibrium capacity of sorbent, and other constants are defined conventionally: T
cr
and P
cr

are critical temperature and pressure for sorbate, W
0
is the limiting volume of adsorption space, B is the
structure constant related to the size and distribution of micro pores, b is Van-der-Waals constant, is
affinity coefficient, T and P are the current temperature and pressure.
The equations for the kinetics of physical adsorption have the following form [18] (the adsorption rate):
( a a
RT
E
K W
dt
da
eq s ad
|
.
|
\
|
= = exp
0
)
e
, (2)
where E is the activation energy, K
s0
is the preexponential factor, a is the current value of adsorption and t
is the tim
For the kinetics of chemical adsorption the following equation were used, correspondingly for the
reactions of synthesis and decomposition [9] (the synthesis and decomposition rates):
|
|
.
|
\
|
=
t
=
P
P
x Aa
d
dx
a W
eq
b
syn
1 ) 1 (
0 0
;
|
|
.
|
\
|
= =
P
P
x Aa
d
dx
a W
eq b
dec
1
0 0
t
, (3)
where x is the degree of reaction completion,
0
a a x = .

L
1 2 3
T T f
in
f
out
R
2
R

The equilibrium pressure for the chemical adsorption is given by Clausius-Clapeyron equation (4):
S T H P R
eq
A + A = ln . (4)
Generally, chemical adsorption of a gas-sorbate can proceed in different reaction paths by forming
different chemical compounds of gaseous and solid reactants. The equilibrium for each type of reactions
obeys to separate equation (4) with different sets of parameters. The developed program can be adapted to
multi-reaction sorption as well.
Main assumptions for the model of heat and mass transfer in the adsorber unit
To describe the transport processes in the adsorber the following simplifying assumption were used:
the gas in the reactor is the pure sorbate, so the diffusion limitations are absent and the pressure in
the reactor is distributed homogeneously;
the temperatures of solid and gaseous phases are equal in the same point due to high interphase
heat transfer coefficient;
the gas in the reactor obeys the ideal gas law;
the heat evolved/consumed due to compression/expansion of the gas in pores is negligible.
Mass balance equation
Accordingly to the described assumption the local mass balance in the cylindrical adsorber is expressed
by the mass conservation equation:
( )
s ad g
g
W v r
r r

t
c =
c
c
+
c
c
1
. (5)
Variations of the pressure in the adsorber caused by changes of temperature and gas content can be
found by accounting integral mass balance:
(
0
P P K w
d
dm
v
g
=
t
), (6)
where
}
=
V
g
dV m c and . (7)
}
=
V
s ad
dV W w
The gas density is given by the ideal gas law:
RT
P
g

= ,. (8)
is the molar mass of sorbate.
Energy equation
Conservation of energy into within the cylindrical reactor is expressed by Eq. 9:
( ) ( )
t c
c
+ |
.
|
\
|
c
c
c
c
=
c
c
+
t c
c
+ + c
a
q
r
T
r
r r r
T
vc
T
ac c c
s eff g g a s s s g g
1
. (9)
It is worth noting the absence of axial convection in the porous sorbent.

Thus, the current state of adsorber, determined by internal pressure, P, and radial distributions of the
temperature, T(r), and sorbate content, a(r), can be found as the solution of the system of equation (1)(9)
supplemented by initial and boundary conditions.
Initial and boundary conditions
In the beginning of operation of any adsorber its temperature is set equal to the initial temperature, T
ini
,
and the pressure within the adsorber is given as P
0
.
The conditions for heat exchange at the internal (R
1
) and external (R
2
) boundaries of sorbent are
regulated by the convective heat exchange law with the coefficients o
1
and o
2
:

( )
1
1
0 1
R r
eff R r
r
T
T T
=
=
c
c
= o , ( )
2
2
2
R r
eff in , f R r
r
T
T T
=
=
c
c
= o . (10)
Interaction of adsorber with others elements of heat converter
The adsorber unit described in the previous sections should be connected to others elements of a
modeled heat transformer, such as another adsorber, evaporator and condensers. All these connections are
performed with the use of control valves; each of them is characterized by a respective hydraulic resistance
Kv. Each condenser or evaporator is maintained at a given temperature T
ev/cond
and pressure P
ev/cond
, which
satisfy the equation of liquid/vapor phase equilibrium, similar to Eq. (4).
Also, the inlet temperature of a heat carrier, Tf,in, is equal always to the temperature of respective heat
reservoir. The outlet temperature of a heat carrier is determined from the heat exchange balance
( ) ( )
in , f out , f f , p f in , f R r
T T c G T T = o
=
2
2
. (11)
The program provides the options of choosing if the heat transfer between a heat carrier and adsorber is
completed, or the outlet heat carrier and sorbent surface have different temperatures.

CAPABILITIES AND OPTIONS OF COMPUTER PROGRAM
Available heat converter models
The set of programs for modeling adsorption-chemical heat converters provides a choice of model from
the list presented below (Table 1).

Table 1. Heat converter models
1
One absorber with condenser and evaporator

2
Two similar absorbers with condenser and
evaporator

3
Two similar absorbers with condenser and
evaporator, and with mass recovery

4
Two absorbers with different sorbents

5
Two absorbers with different sorbents and
with condenser and evaporator

6
Thermal wave in two-channels with high-and
low-temperature adsorbers


These models allow investigating the most of classical designs represented in scientific publications.
For example, the model #6 relates to the study of idea of successive amplification of the heat-upgrading
thermal wave in the channel with high-temperature adsorbers. This design provides mark improvement of
SHP and the temperature of heat upgrading.
A light modification of program codes is needed to adapt the tool for modeling heat conversion systems
with other configurations.
Examples of program results and output screen
The programs have options for varying reactor parameters, thermal reservoir temperatures, resistance of
control valves connecting the reactors and time of their opening and closing. There is also a possibility to
optimize the main characteristics of heat conversion for a chosen set of parameters. Optimizing part of the
code is based on the simplex-method algorithm.
The first example of program output screen is shown in Fig. 2. Modeling was performed for the two-
adsorber heat converter represented by the scheme #2 of Table 1. Chemical adsorption of ammonia on the
calcium chlorate salt was considered in this modeling. This output contains the plots of reaction degree,
pressure and temperature in both adsorbers vs. the time. The bottom graph represents Clausius-Clapeyron
diagram. Quantitative data on ideal (Carnot) COP for refrigeration(COP
ideal
), heating COP (COP
_heat
),
refregiration COP (COP
_ref
), specific cool and heat production (SCP and SHP), and the cycle time (dt) are
presented also in the bottom par of the screen.
As a second example of numerical modeling on the base of developed codes we present here the results
for heat upgrading in the two-channel chemical-adsorption system which corresponds to the model #6 in
Table 1. The considered system includes high-temperature adsorbers of ammonia filled with MnCl
2
and low-
temperature adsorbers with CaCl
2
. The heat carrier at the inlet of high-temperature channel is fed from a
middle-temperature reservoir with the constant temperature T
M
. The temperature of the heat carrier in the
low-temperature channel is switched from low-temperature T
L
at the beginning of the process to T
M
, and
then again to T
L
. The thermal wave in the high-temperature channel is amplified while the wave passes the
series of adsorber pairs. Table 2 shows that addition a new pair of adsorbers into the system leads to the
increase of main heat conversion characteristics though the rate of this increase gradually drops.

VALIDATION OF THE MODEL
The developed programs were tested in two aspects; first, with respect to sensitivity of numerical results
to the choice of space and time meshes, and, second, by comparison with known experimental
measurements.
Comparison with two-adsorber heat upgrading experiment
Results of modeled heat upgrading in the system of two different adsorbers (with MnCl
2
and CaCl
2

salts) were compared with the experimental data presented in [16] (Fig. 3). As can be seen from the figure,
the durations of heat converter operation cycle for modeling and experiment are very close. There is a mark
difference between modeling and experiment for the initial phase of the process that can be explained by
discrepancy of initial conditions for compared cases. There is also discrepancy between calculated and
experimental results for low-pressure stage of the process, when the temperature in the adsorber with low-
temperature salt sharply drops to the temperature of heat carrier, whereas the behavior of similar temperature
in the experiment much smoother. These disagreements can be related to limitations of 1D model of an
adsorber, which does not take into account longitudinal thermal conductivity in the reactor. Nevertheless, the
stated disagreements are not high, and one can conclude that the developed model has sufficiently acceptable
level of adequacy.
Comparison with the experimental data for the system of two adsorbers filled with different composite
sorbents
Another validation of the developed program was performed by comparison with experimental data from
the paper [19], more specifically, with the cooling stage for two-adsorber system. In the experiment the

adsorbers were filled by composite sorbents: Busofit + MnCl
2
for high-temperature adsorber and Busofit
+ BaCl
2
for low-temperature one. Figure 4 illustrates the results of the comparison, which again looks
acceptably good.



Fig. 2. Fragments of output screen for modeling chemical heat converter in the system with two similar
adsorbers (NH
3
chemo-sorption on CaCl
2
).

Table 2. Modeling of heat upgrading with the use of thermal wave
Characteristics of heat
ungrading
One pair of
adsorbers
Two pairs of
adsorbers
Three pairs of
adsorbers
COP ideal 0.54 0.54 0.54
COP 0.35 0.42 0.44
SHP, Wt/kg 11.9 22.9 32.7
dT
max
, 8 13.8 18

0 10000 20000
300
320
340
360
380
400
420
0 10000 20000
T, K
t, c
t, c
- - - - -

T
M
= 120
0
C
T
L
= 30
0
C
e
experiment
numerical simulation
s
s
0 10000 20000
300
320
340
360
380
400
420
0 10000 20000
T, K
t, c
t, c
- - - - -

T
M
= 120
0
C
T
L
= 30
0
C
e
experiment
0 10000 20000
300
320
340
360
380
400
420
0 10000 20000
T, K
t, c
t, c
- - - - -

T
M
= 120
0
C
T
L
= 30
0
C
e
experiment
s
s

Fig. 3. Comparison of temperature vs. time evolution in the modeled two-adsorber system with the
experimental results from [16]


0 2000 4000 6000 8000
0
10
20
30
40
50
T,
o
C
t,s
- - - - - - numerical results
_____

experimental results
1
2
3
0 2000 4000 6000 8000
0
10
20
30
40
50
T,
o
C
t,s
- - - - - - numerical results
_____

experimental results
1
2
3

Fig. 4. Comparison of numerical results with the experiment [19] on cooling stage in the heat converter
containing two adsorbers with composite sorbents. 1 is the temperature of heat carrier at the outlet of
low-temperature adsorber; 2, the mean calculated temperature within the low-temperature adsorber; 3,
the experimental temperature at the external surface of low-temperature adsorber.

CONCLUSION
The program toolkit for numerical modeling of adsorption-chemical heat conversion has been developed.
The modeling is based on one-dimensional (in the radial direction) consideration of dynamic adsorption or
chemical reversible reactions in a cylindrical reactor filled with adsorbent. The program toolkit allows
investigation of various heat-conversion devices designed as a combination of one or several reactors with
condensers and evaporators. The programs have options for varying reactor parameters, thermal reservoir
temperatures, and resistance of control valves connecting the reactors and time of their opening and closing.
The program tool has also an option for optimizing characteristics of heat conversion for a chosen set of
parameters. The developed approach and algorithms were validated by comparison of numerical results with
experimental data. The comparison showed some marked but not high roughness of used 1D model for the
heat and mass transfer in an adsorber. Enhancement of the model by their extension for 2D and 3D cases and
by more precise description of elementary processes in an adsorber can be considered as the next step of the
work.

References
1. Faraday M. On the condensation of several gases into liquids // Philosophical transactions of the
Royal Society of London. 1823. Vol. 113. Pp. 189-198.
2. Patent 1,781,541. USA. Refrigeration / A. Einstein, L. Szilard. 1930.
3. Demir H., Mobedi M., Ulku S. A review on adsorption heat pump: Problems and solutions //
Renewable and Sustainable Energy Reviews. 2008. Vol. 12. P. 2381-2403.
4. Wang L.W., Wang R.Z., Oliveira R.G.. A review on adsorption working pairs for refrigeration //
Renewable and Sustainable Energy Reviews. 2009. Vol. 13. P. 518-534.
5. Vasiliev L.L., Mishkinis D.A., Antukh A.A., Vasiliev L.L. Jr. Solar-Gas Solid Sorption Refrigerator /
// Manufactured in The Netherlands. Adsorption. Kluwer Academic Publishers.2001. Vol. 7. Pp. 149
161.
6. Lu Z.S., Wang R.Z., Wang L.W., Chen C.J.. Performance analysis of an adsorption refrigerator using
activated carbon in a compound adsorbent / // Carbon. 2006. Vol. 44. Pp. 747752.

7. Basova YV., Edie D.D., Badheka P. Y., Hari-Chandana Bellam. The effect of precursor chemistry and
preparation conditions on the formation of pore structure in metal-containing carbon fibers // Carbon.
2005. Vol. 43. Pp. 15331545.
8. Tamainot-Telto Z., Metcalf S.J., Critoph R.E., Zhong Y., Thorpe R.. Carbonammonia pairs for
adsorption refrigeration applications: ice making, air conditioning and heat pumping // International
journal of refrigeration. 2009. Vol. 32. Pp. 12121229.
9. Wang C., Zhang P., Wang R.Z. Performance of solidgas reaction heat transformer system with gas
valve control // Chemical Engineering Science. 2010. Vol.65.,No.10. Pp. 2910-2920.
10. .., .., ..
/ // - .
2008. 81, 1. C. 19-48.
11. Li T.X., Wang R.Z., Wang L.W., Lu Z.S., Wu J.Y. Inuence of mass recovery on the performance of a
heat pipe type ammonia sorption refrigeration system using CaCl2/activated carbon as compound
adsorbent // Applied Thermal Engineering. 2008. Vol. 28. Pp. 16381646.
12. Taylan O., Baker D. K., Kaftanoglu B. COP trends for ideal thermal wave adsorption cooling cycles
with enhancements // International journal of refrigeration. 2010. Vol. 30. Pp. 1-9.
13. Li T.X., Wang R.Z., Kiplagat J.K., Wang L.W., Oliveira R.G. Thermodynamic study of a combined
double-way solidgas thermochemical sorption refrigeration cycle // International journal of
refrigeration. 2009. Vol. 32. Pp. 15701578.
14. Babenko V.A., Kanonchik L.E., Vasiliev L.L. Heat and mass transfer intensification in solid sorption
systems // Enhanced Heat Transfer. 1998. Vol. 5. Pp 111-125.
15. Han J.H., Lee K.H., Kim D.H., Han H.K. Transformation Analysis of Thermochemical Reactor Based
on Thermophysical Properties of Graphite-MnCl
2
Complex // Ind. Eng. Chem. Res. 2000. Vol. 39. Pp.
4127-4139.
16. Wang C., Zhang P., Wang R. Z.. Investigation of SolidGas Reaction Heat Transformer System with
the Consideration of Multistep Reactions // AIChE Journal. 2008. Vol. 54, 9. Pp. 2464-2478.
17. Dubinin, M.M., Astakhov, V.A. Description of adsorption equilibria of vapors on zeolites over wide
ranges of temperature and pressure // Advances in Chemistry Series. 1971. Vol. 102. Pp. 6985.
18. Babenko V.A., Kanonchik L.E. Mathematical Modeling of a Cylinder with a Sorbent and Natural Gas
// J. Eng. Phys.and Thermophys. 2000. Vol. 73. Pp. 516-529.
19. Antukh A.A., Tsitovich A.P., Vasiliev L.L., Alousef Y. Solid sorption cooler with composite sorbent
bed and heat pipe thermal control // Proc. of VIII Minsk International Seminar Heat Pipes, Heat
Pumps, Refrigerators, Power Sources, Minsk, Belarus, 2011.

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VIII Minsk International Seminar Heat Pipes, Heat Pumps, Refrigerators, Power Sources,

Minsk, Belarus, 12-15 September, 2011

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