Adsorption

Applied Thermal Engineering 21 (2001) 14891519
www.elsevier.com/locate/apthermeng
Review
A review of chemical heat pump technology and applications

W. Wongsuwan a, S. Kumar a,*, P. Neveu b, F. Meunier b
a
b
Energy Program, School of Environment Resources and Development (SERD), Asian Institute of Technology,
P.O. Box 4, Klong Luang, Pathumthani 12120, Thailand
Institut Francais du Froid Industriel et du G
enie Climatique, Conservatoire National des Arts et M
etiers, Paris,
75141, France
Received 26 July 2000; accepted 5 February 2001
Abstract
Chemical heat pumps (CHPs) provide high storage capacity and high heat of reaction as compared to
sensible heat generated by absorption. Investigation of material properties and their operation have led to
their heat pumps exploitation for commercial and industrial applications. Integration of solar thermal
system to the CHPs would assist in expanding the utilization of CHPs and also for many applications in the
tropical region. The research done in CHP regarding to status of technology, current applications and their
future prospect has been reviewed, with special reference to their utilization with solar thermal energy for
cold production and upgrading/storage of heat. 2001 Elsevier Science Ltd. All rights reserved.
Keywords: Chemical heat pump; Working pairs; Performance; Metal-hydride chemical heat pump; Chemical reaction
chemical heat pump; Solid adsorption; Solar assisted chemical heat pump
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1490
1.1. Principle of operation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1493
2. Technology status . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1. Working pairs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2. Performance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.1. General theoretical studies on CHP performance. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.1.1. Solidgas CHP . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.1.2. Liquidgas system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.1.3. Solid-adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Corresponding author. Tel.: +66-2-524-5410; fax: +66-2-524-5439.

E-mail address: kumar@ait.ac.th (S. Kumar).
1359-4311/01/$ - see front matter 2001 Elsevier Science Ltd. All rights reserved.
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W. Wongsuwan et al. / Applied Thermal Engineering 21 (2001) 14891519

2.2.2. Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1505
3. Areas of further research . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1512

Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1515
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1516
1. Introduction
Low temperature sources coupled to a suitable heat pump upgrade heat to a higher temperature. This is achieved by the consumption of electricity (vapor compression heat pumps) or by
thermal means (vapor absorption and solidgas sorption heat pumps). Vapor absorption heat
pumps commonly use lithium bromide/water and water/ammonia as the working uids. Though
vapor compression and vapor absorption heat pumps are common, research in the other category
of heat pumps, namely chemical heat pumps (CHPs) has gained momentum in recent years [17].
CHP are those systems that utilize the reversible chemical reaction to change the temperature level
of the thermal energy, which is stored by chemical substances [8]. These chemical substances play
an important role in absorbing and releasing heat [9]. The advantages of thermochemical energy
storage [10], such as high storage capacity, long term storage of both reactants and products,
lower of heat loss, etc., suggests that CHP could be an option for energy upgrading of low
temperature heat as well as storage. Sources of low temperature heat could be from waste heat in
industries and/or solar thermal collectors.
Fig. 1 shows the general classication of CHP. Systems involving chemical reaction and requiring only one state variable (e.g. pressure) to be specied (e.g. metal hydrides reacting with
chlorine or ammoniametal chloride systems) are mono variant systems, and these induce volume
changes, while those that require both the temperature and pressure to be specied are di variant
systems (e.g. solid adsorption).
The general reaction taking place in the CHP reactor is of the form
AB$C
where, the forward and backward reactions occur at two dierent temperatures, thus allowing the
upgrading of heat from low to higher temperature. For example, the hydrogenation/dehydrogenation of a 2-propanolacetone system (liquidgas) is given by,
CH3 2 COg H2 g $ CH3 2 CHOH
During the backward reaction, 2-propanol is decomposed into acetone and hydrogen by dehydrogenation reaction (endothermic). For this reaction to occur (at lower temperature), heat could
be supplied from a low temperature source e.g. solar collector. The hydrogenation reaction is
exothermic and heat is liberated at a higher temperature, thus causing upgrading of heat [11] for
any suitable application.
Various chemical substances could be used in CHP involving chemical reaction. For example,
as shown in Fig. 1, water system (hydroxide/oxide, salt hydrate/salt or salt hydrate), ammonia
system (ammoniate/ammoniate or salt, amine complex with salt), sulfur dioxide system (sulphite/
1491
Nomenclature
COA
coecient of amplication (heat

pump eect)
COP coecient of performance (refrigeration eect)
DEGDME dimethyl ether of diethylene
glycol
E
heat of formation of hydride per unit
volume, J/m3 (Eq. (9))
h
heat transfer coecient, W/m2 K
DH
change of enthalpy, J/mol
standard reaction enthalpy, kJ/mol
DH0
(Eq. (12))
K
eective thermal conductivity in metal hydride, W/m K (Eq. (9))
L
latent heat of vaporization, kJ/kg
m
mass of working uid per kg of sorbent, kg
M
molecular weight, kg/mol
P
pressure, Pa
Q
quantity of heat exchange, J
current radius at hydration front (Eq.
rf
(9))
R
reactor bed, perfect gas constant, J/
mol K
internal radius of reaction bed, m
R1
external radius of reaction bed, m
R2
DS
entropy, J/mol K
SCP cooling rate, W/kg of pure adsorbent
t
cycle time, m
T
temperature, C or K
q
g
h
k
density, kg/m3
eciency
Carnot eciency
thermal conductivity
Subscripts
abs
absorption
ads
adsorption
amb ambient
b
value at bed boundary
chem chemical
cond condensation
des
desorption
eq
equilibrium
ev
evaporation
ex
exergetic, eective
ext
external
f
hydration front
h
high, high temperature process
hydrogen
H2
i
element of
l
low
m
medium, moderate, metal hydride
max maximum value
o
initial value, ambient, sink
reg
regeneration
s
source temperature
w
wall, heat transfer medium owing
through the inner tube of a reactor
module
Greeks
r
permeability
oxide, pyrosulphate/sulfate) [12], carbon dioxide system (carbonate/oxide, barium oxide/barium
carbonate) [13], hydrogen system (hydride/hydride or metal, hydrogenation/dehydrogenation)
[14], etc. have been proposed as the working media.
The solid constituents used in the CHP can be categorized in many ways (Fig. 1). This could be
in terms of adsorbents (e.g. zeolite and activated carbon (AC) with water and methanol), metal
hydrides (e.g. porous metallic foam of Ni and Cu, Al-foam metrics) and compounds with chemical reaction (i.e. reaction with ammonia derivatives such as monomethylamine or dimethylamine
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Fig. 1. Classication of CHP.
by alkaline, alkaline-earth or metallic halides, double or mixed halides, sulphates, nitrates and
phosphates). Another classication could be based on organic and inorganic substances. For
example, an inorganic reaction system could be calcium chloride/methylamine, calcium oxide/
water/calcium hydroxide, sodium carbonate dehydration/hydration and magnesium oxide/water,
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Fig. 2. A simple CHP.
which normally operate with batch process involving solidgas or solidliquid reaction [8]. The
organic reaction system includes hydrocarbon and hydrocarbon derivatives, for example, 2propanol/acetone, isobutene/water/tert-butanol, cyclohexane/benzene and paraldehyde/acetaldehyde (Pa/A) systems. CHP employing organic reaction have advantages of high energy density
and possibility of continuous cycle because of the liquidliquid or gasliquid reaction. Generally,
the gas is condensed and stored as a liquid (e.g. ammoniated salts), condensed and adsorbed (e.g.
zeolite), or reabsorbed (e.g. metal hydrides). In the two later cases, the gas could be stored in
zeolite or in metal hydrides [5].
Depending on the phase of working substance, CHP could be categorized into two types, solid
gas and liquidgas. Solidgas CHPs basically consist of reactor(s) (or adsorber), condenser and
evaporator (Fig. 2) [15]. Liquidgas systems consist of at least two reactors: endothermic and
exothermic reactors. Besides, other components such as condensers, separators and heat exchanger are also usually required.
This paper presents a review of the work done in the recent years on the various types of CHPs
and discusses their applications. For this review, the classication of CHP considered are the
solidgas system, solid-adsorption and liquidgas system with focus on the status of technology,
current applications and the areas and activities for further research.
1.1. Principle of operation
The general working of a CHP occurs in two stages: adsorption/synthesis/production and
desorption/ regeneration/decomposition. The synthesis stage is the cold production stage, and this
is followed by the regeneration stage, where decomposition takes place. This can take place in the
same or dierent reactors depending on the system design (Fig. 2). Basic solidgas CHPs are not
suitable for continuous production as they are based on two successive phases: synthesis (cold
production stage), which is followed by regeneration (decomposition) [16]. This can be explained
with reference to ammoniachloride salt system.
During the production phase, the liquidgas transformation of ammonia produces cold at low
temperature in the evaporator. At the same time, chemical reaction between the gaseous ammonia
and solid would release heat of reaction at higher temperature. In the regeneration phase, the
system is regenerated by heating the reactor and leads to an increase of temperature of solid. This
causes the decomposition of the solid and allows the refrigerant to condense in the evaporator.
When complete decomposition is achieved, the device is ready for a new production phase.
On the other hand, the liquidgas system is more amenable to be run as a continuous process.
The reactants and products could be fed or removed continuously. Reaction could also take place
1494
Fig. 3. Clapeyrons diagram showing the heat pump mode of operation.
by passing the reactants through the catalyst bed. Production and regeneration could also be done
in dierent reactors [14,17].
Fig. 3 shows the cycle represented in the Clapeyrons diagram [18]:
LnPeq
DH DS
RT
R
For an analysis of the cycle and the design of systems, the working conditions of the CHP cycle
could be plotted in a Clapeyron diagram, from which the various characteristics could be obtained. Chemical reaction will take place when the salt is in a state outside the equilibrium line.
The dierence of the state in equilibrium and outside of equilibrium is known as ``equilibrium
drop''. Eq. (3) also relates the equilibrium pressure and the temperature. By plotting the systems
cycle along the equilibrium lines of the Clapeyron diagram, the operating pressure, the range of
temperature upgrade, mass of the working pairs required, amount of power consumed and heat
released, etc. could be predicted. Goetz et al. [19] have given a graphical representation of the
temperature levels required to ensure cold production and refrigeration for dierent chlorides
reacting with ammonia, the variation of coecient of performance (COP) and exergetic eciency
as function of cold production temperature.
The working of an intermittent solid adsorption cycle can be also represented in a Clapeyron
diagram by knowing the relation between vapor pressure of working uid (e.g. water) and the
adsorbent (e.g. NaX zeolite) temperature in equilibrium [20].
CHP could operate in two modes depending on the required output: ``heat pump'' (cold production at low temperature and heat generation at medium temperature) and ``heat transformer''
(heat supplied at the medium temperature and heat utilization at higher temperature) [21]. In the
heat pump mode (Fig. 3) [19], in the rst stage, heat is supplied to the reactor at high temperature
(Th ) to regenerate ammonia which will then be condensed in the condenser at medium temperature
(Tm ). The heat required at evaporator at low temperature (Tl ) is supplied to vaporize ammonia, which reacts with the chloride salt and releases heat at medium temperature (Tm ). In heat
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transformer mode, the consumption of heat is at medium temperature, while the heat rejection is at
high temperature (Th ) and also at low temperature.
2. Technology status
The technology status of the CHP is described in terms of the working pairs used, the performance of the system and its application, and recent developments promoting energy upgrading.
2.1. Working pairs
Working pairs for absorption/adsorption systems are substances or chemicals used, which
without changing their properties (mechanical or chemical) induce consumption or production of
heat. For example, chloride saltsammonia [18], zeolitewater [20], ACmethanol [22], and carbonammonia [23] are some of the common working pairs used, and a discussion on the common
adsorbents and adsorbates used in solidvapor adsorption heat pump systems has been presented
in Ref. [24]. The amount of heat consumed or released due to the thermochemical process is
utilized for production of heating and cooling eect.
The major requirements of working pairs properties are their high storage capacity, thermal
stability within the working conditions (temperature and pressure range), high thermal conductivity, high external heat transfer coecient, high specic power output, transportability (easy to
handle), small specic volume, non-corrosive and non-toxic (environmental friendly), low viscosity and surface tension, etc. [25]. Lebrun and Neveu [21] suggest the following criteria be
considered in the selection of an appropriate working pair: economic criteria (cost of working pair
itself or cost of equipment), performance criteria (temperature rise, specic power production,
mass of working pair), and cost and performance criteria (specic power per unit mass and unit
area of exchange surface or temperature rise by unit mass or unit area of exchange surface). Neveu
and Castaing [18] note that the selection of working pairs needs the understanding of the machines characteristics as a function of target temperature required. For instance, the nal selection of the ideal working pair requires information of the machines characteristics as a function
of refrigeration temperature for all the possible combinations of the considered working pairs.
A detailed experimental procedure for the estimation of thermal conductivity, permeability,
porosity and specic heat of two types of monolithic carbon as adsorbents has been presented by
Tamainot-Telto and Critoph [23]. The heat transfer coecient for the carbon block of coarse
powder has been measured to be 350 W/m2 K, while for ne powder, it is about 800 W/m2 K. The
permeability of the coarse powder in both the arial and radial direction is signicantly higher than
that of ne powder. The specic heat of both samples was found to be very close.
The varying properties of working pairs lead to dierent designs and development of processes,
covering a large temperature range. Table 1 shows the possible systems and their application
(depending on the temperature) to cooling. The chemical reaction system could be utilized in a
larger cold temperature range ( 40C to 10C). However, in a narrower range, adsorption systems could be used ( 20C to 10C), while metal hydrides seem to be suitable in the range 30C
to 0C.
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Table 1
Possible solidgas systems possible for cold production applications [3]
Applications/temperature level
System possible
Air-conditioning/chilled water 2C to 10C
Adsorption
Chemical reaction
Chemical reaction
Adsorption
Metal hydrides
Chemical reaction
Metal hydrides
Refrigeration ( 20C to 0C)

Freezing ( 40C to
30C)
Heat and mass transfer characteristics of dierent types of reaction beds are also important
considerations inuencing the performance of systems and are given in Table 2. To improve heat
transfer characteristics, limitations due to mass transfer needed to be considered by modication
type and properties of material used (e.g. graphite or binder), applying new assembling or mixing
techniques, varying combination of material (percent in use), etc. For example, using consolidated
zeolite and activated graphite adsorbents as compared with granular beds could improve the
eective thermal conductances of zeolitewater system [2,5].
2.2. Performance
CHP performance can be characterized by dierent parameters, such as, actual upgrading
temperature, specic power production (either cooling or heating), COP, coecient of amplication (COA) and exergetic eciency.
Actual temperature upgrade gives the temperature gain obtained from the lower temperature to
the higher level, while the specic power production gives the amount of heat generated or extracted by the CHP to the amount of working substance used (e.g. salts, adsorbents). COP is
dened as the eciency in cold production (enthalpy of evaporation divided by heat supplied for
regeneration), while COA represents the ratio of hot production to the quantity supplied for
regeneration. Exergetic eciency is dened as the ratio of output exergy and the input. These
eciencies could be mathematically represented [18] as:
COP Qev =Qreg
For systems operating between three temperature levels (and considering the rst laws and
second laws of thermodynamics) the COP could be expressed [26] as:
0
1
1
1
Qev Tm Th @
Di S

A
1
5
COP
1
Qreg T1l T1m
Qreg 1
Tm
COA Qcond Qabs =Qreg
Th
Goetz et al. [19] expressed the equation for exergetic eciency for thermo-transformer system
as:
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Table 2
Heat and mass transfer characteristics of reaction beds of CHPs [2,5]
1
2
3
4
5
6
7
8
Reaction beds
Specic power output
Eective thermal conductances (keff in W/

m K) and wall heat
transfer coecient (hw
in W/m2 K)
Anisotropic heat conduction porous graphite matrices,

thermal contact resistance upto 1000 W/m2 K
Consolidated AC and zeolite (NaX, 4A) beds forming
porous block, including highly porous metallic foams
(Ni, Cu) as heat transfer matrices
Metallic matrices (highly porous metallic foams, internal n-like structures): carbon methanol
Generation of compacts made by mixing metal (hydride) power with aluminum powder and cold compression to pellets, with or without subsequent sintering
Lanthanum-rich mischmetal alloy LmNi(5) in a 94%
porous Al-foam matrix
Thermal energy storage with 1020 wt.% graphite and
8090 wt.% MnCl2 , reaction time 512 h, R 315 cm,
DT 2050 K
High power system TES, 2550 wt.% graphite, 7550
wt.% MnCl2 , reaction time for each phase 0.51.0 h
D 28 cm, DT 43 K
Consolidated zeolite or activated graphite adsorbents
Upto 1 kW/kg
530 W/m K (radial) <1

W/m K (axial)
29 W/m K
PMH-compacts and equivalent high-conductance

structures
10
Chlorides-type reactants (alkaline, alkaline-earth or

metallic)
"
gex COA
1
1
T0
Th
T0
Ts
23 W/m K for 31 wt.%
7.5 W/m K
200 kW/m3 , 360
Wh/kg of salts
800 kW/m3
Cold output of 0.51.0
kW/kg adsorbent
Continuous specic
power output >1 kW/
kg of heat pump >0.5
kW/kg for refrigerator
515 W/m K (radial) <1

W/m K (axial) 400600
W/m2 K
1530 W/m K (radial)
<1 W/m K (axial)
>6001000 W/m2 K
510 W/m K 500100
W/m2 K
0.10.4 W/m K <40 W/

m2 K
#
7
where 1 T0 =Ti is the Carnot temperature.

The specic cooling power (SCP), which is another important indicator of the CHP performance, is given by [4] as:
SCP Lm=t
The performance of systems could be obtained from experimental results and/or theoretical
studies. The results of the experimental observations are expressed graphically, for example, in
terms of COP or exergetic eciency as function of cold production temperature, or by developing
nomograms for the specications of the reactor by providing the system characteristics. For example, the relation between the theoretical COP as function of refrigeration temperature for
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MnCl2 /2NH3 salt has been given [18]. Parametric studies such as the COP-specic power production function for cycle time, etc. are other methods of representing experimental data [20].
These relations could be used to nd the optimum operating condition considering COP and
specic power, which are inversely related.
2.2.1. General theoretical studies on CHP performance
A CHP consists of reactors (where adsorption or chemical reaction takes place) and an
evaporator and condenser to supply or reject heat respectively. The condenser and evaporator
is characterized by temperature and pressure of the vapor and liquid used and their specications (e.g. power, dimensions, and material properties) are usually provided by manufacturers.
Therefore, the performance of evaporator and condenser are not discussed here except where they
are also integrated to the adsorbers [27,28]. Details of the performance of the reactor are discussed
below.
The most critical component of CHPs is the reactor, where heat and mass transfer, chemical
reaction, adsorption and absorption occur. Many researchers have developed models to simulate
the dynamic behavior of the reactor [7,2933]. The reactor performance predicted by these theoretical models generally provides information on the progress of the reaction (% conversion), instantaneous power and mean power per volume of reactive salts, heat exchange area per
volume of salt, progressive of moles of gas adsorbed in salt, temperature and pressure proles,
etc.
Stitou and Crozat [34] classify models into three categories: local, global and analytical models.
Local models consider mass and heat transfer, and kinetics of small volume that result in partial
derivatives equations, which are numerically solved. Global models consider variables and average values of reactor features such as permeability, thermal conductivity, heat capacity, etc. for
simulation. Numerical solutions for these global models give sets of dierential equations. Analytical models consider average values of the variables during reaction time and these dierential
equations are related to the space variable only.
The local and global models could be solved by the grainpellet model presented by Goetz [35]
and Goetz and Marty [29], and by shrinking-core models (coupled heat and mass transfer with
chemical reaction) of Lu et al. [36]. This helps to dene the parameters; e.g. hydraulic radius of
pores, internal porosity of the grain, kinetic absorption/desorption parameters and radius of
grain. These models calculate the reaction progress in relation to three variables (P ; T ; X ).
Therefore, this helps to simulate:
the instantaneous rate of desorption and absorption as a function of pressure and temperature,
temperature proles in desorption as a function of radial position,
degree of advancement (% conversion) proles for desorption as a function of radial position
and isokinetic lines, and
global and local advancement under dierent operation pressures, permeability, etc.
Lu et al. [36] have given the chemical kinetic equations at grain level. The solution to the
coupled heat and mass equations has been done at the pellet (macroscopic) level. The unreactedcore model (shrinking core model) has been formulated for the reversible solidgas reaction and
1499
has been used to interpret the experimental results. This general model was later simplied by
considering the progressive reactive fronts as sharp reactive fronts [37]. Mauran et al. [38] adopted
a simplied approach to demonstrate the reactive fronts, and showed that two sharp fronts of
reaction, mass front and heat front exists. They noted that there are similarities between the results of these simplied models and the general model on the global advancement of the reactive
front and local temperature and pressure proles in the reactor.
Mass transfer inuences the heat transfer rate due to low permeability of the reaction bed at
very low pressure. Moreover, the overall heat and mass transfer process is controlled by the
chemical kinetics, especially at the grain (microscopic) level. Experimental studies have shown
that heat transfer also strongly inuence the performance of reactor, as compared to diusion or
mass transfer and chemical reaction [39]. To solve the general coupling heat and mass model
numerically, source-based method (xed grid enthalpy approach) has been developed, where each
parameter is determined independently. A control volume approach has been used for each
special node to solve the partial dierential equation. The global conversion was then calculated
by integrating the local conversion overall material volume at each time step. This algorithm helps
to simulate with various geometries in one-, two- and three-dimensional systems and was found to
give good agreement with the experimental results [39].
In the case of temperature (or power) production at a constant level, dimensioning studies give
the characteristics of the installation to enable performance prediction. The analytical heat
transfer model developed by Stitou and Crozat [34] leads to the single dierential equation (neglecting mass transfer) and is useful for dimensioning purposes. The dimensioning nomograms
developed by Stitou et al. [33] consider the average functional characteristics of a thermochemical
reactor over a given time step. Nomograms give the relationship between the average thermal
power of the reactor and its geometry, thermal characteristics of the reactive medium and working
conditions for various types of heat exchanger structures. They have also demonstrated how these
nomograms could be used to dimension/size a system and illustrated this by examples.
The simplied dynamic numerical models have been used to simulate thermal comfort (heating
and air-conditioning) in electrical vehicles and storage by solidgas system for persons wearing
insulated garment [15,40]. The model results indicate that the high exibility of thermochemical
transformers at dierent working constraints (cold and heat production) make it suitable for such
applications.
Recently, Meunier et al. [41] have carried out a study on the second-law analysis of adsorptive refrigeration cycles considering the role of thermal coupling and entropy production. For nadsorber uniform temperature cycles, internal thermal entropy production (due to heat recovery
between adsorbers) may reach 50% of the external thermal entropy production. The COP and the
thermal coupling entropy production can be calculated if the thermodynamic properties of the
given pair and the isostere equilibrium chart, are known.
Critoph [42] has described a convection thermal wave adsorption cycle where higher heat
transfer rates between the adsorbent grains and the refrigerant are obtained by forced convection
and higher external surface area of the grains. Theoretical simulation studies for ammoniacarbon
working pair have been done for various evaporating and condensing temperatures, and the
maximum operating temperature would be about 200C. A simplied diagram of dQ=dT versus T
(eective specic heat along an isotere) has been shown, which helps also to visualize the heat
rejection and heat input.
1500
2.2.1.1. Solidgas CHP. There have been signicant developments in solidgas CHPs in recent
years and several are presently in stages of commercialization [2]. For example, thermochemical
system ELF (STELF) includes industrial refrigeration and air-conditioning, hot and cold storage
in transported container, refrigerators, etc. Eorts are also underway to improve their operational
reliability and scale up from laboratory to commercial scale.
Metal hydrides system: Exothermic reaction takes place when hydrogen is absorbed by a hydride and heat is liberated, while cooling is provided due to desorption of hydrogen gas from
hydride. Metal hydride absorbs large amounts of hydrogen gas and could also be used for hydrogen storage.
Kim et al. [43] have developed a compressor-driven hydrogen metal-hydride heat pump system
utilizing hydride reactors. This achieves higher eciency and appears to have competitive lifecycle costs as compared to conventional refrigeration system. Testing this system with 500 full
cycle operation shows that the performance does not degrade and the specic cooling power
obtained could reach 1.5 kW/kg of LaNi5 . Enhanced internal heat transfer in the hydride reactor
both within the hydride bed and between the hydride bed and the external heat exchanger is
required. To improve the heat transfer in reactor, the hydride-forming metal particles are coated
with a thin layer of copper (around 1 lm thickness) and then compressed and sintered into a
porous powder of metal hydride (PMH) compact. The hydride reactors containing PMH compact
are sintered into lightweight nned tubes, and air is forced over the exterior to transfer heat to
surroundings.
Kang and Yabe [44] report a continuous metal-hydride heat transformer, which contains two
pairs of reactors of metal hydrides (LaNi5 at lower temperature and LaNi4:5 Al0:5 at higher temperature). The reactors are made of bundles of tubes and are fabricated as cylindrical tubes. Heat
transfer medium ows through the inner tube to supply and extract heat to and from the reactors.
The reactors are packed by hydride material, of inner diameter R1 and outer diameter R2 . This
hydride material is surrounded by a ne net to allow hydrogen to pass through. The performance
of this heat transformer system is predicted based on heat and mass balances and thermodynamic
properties of hydride material and hydrogen. To determine the reaction progress during the
adsorption phase, the current radius is expressed as a function of temperature front for hydration
(Tf ) as:
rf
K
hTf Tw

E rf h ln rf K
R1
R1
Therefore, the temperature front and reaction progress is calculated when the thermodynamic
properties of material (e.g. conductivity and heat transfer coecient) and reactor geometries are
known.
The performance analysis shows that the COP is inuenced strongly by the cycle period at
higher ratio of internal to external radius R1 =R2 0:5, but not much at lower ratios
R1 =R2 0:25. The optimum cycle period becomes longer at smaller radius ratios.
Compounds with chemical reaction (ammonia-based): For ammonia-based system utilizing
chloride salts (alkaline, alkaline-earth or metallic), the heat of reaction are of the same order of
magnitude, typically DHR 50 15 kJ/mol. However, the enthalpy of evaporation or condensation of the ammonia gas is only about half of this. The reaction in chloride salts bed of
1501
Table 3
Upgraded temperature of dierent working pairs used in ammonia-based reacting system of CHPs [18]
Couple of chloride saltsa
Upgraded temperature (low temperature (Tl ) to high

temperature (Th ))
CaCl2 (4/2) and MnCl2 (6/2)

BaCl2 (8/0) and CaCl2 (4/2)
CaCl2 (8/4) and MnCl2 (6/2)
CaCl2 (8/4) and FeCl2 (6/2)
MnCl2 (6/2) and NiCl2 (6/2)
CaCl2 (4/2) and MgCl2 (6/4)
90125C
95120C
100135C
120185C
130195C
145215C
155220C
155235C
The low temperature heat sink is 15C except for the last couple, which is 35C.
ammoniated system takes place within the operating pressure range up to 50 bar, temperature
range of 50C to 300C, and depends on the number of moles of gas reacting per mole of salt
compound [1]. Table 3 illustrates the upgraded temperature in heat transformer system of various
working pairs of two connected reactors system, in the pressure range between 0.1 and 50 bar and
temperature lifts (temperature dierence between the heat transfer uid of two reactors) of at least
40C. When the heat source temperature is lower than 100C the possible reactive salts are CaCl2
MnCl2 , BaCl2 CaCl2 and CaCl2 MnCl2 . Reactor(s) containing chloride salts of Mn and Ni give
the highest output temperature (maximum of 235C), but the temperature source must be greater
than 100C.
The temperature lifts are classied in two ranges: 4055C and 6680C. Eight chloride couples
reacting with ammonia include six alkaline, earth alkaline or metal cations, i.e. Ca, Ba, Sr and Fe,
Mn, Zn, that could be used for refrigeration (with COP of 0.40.7, exergetic eciency of 0.02
0.3). Five chlorides salts of Ca, Mn, Mg, Fe and Ni could be used to upgrade heat from 105C to
200C [19].
Lebrun and Spinner [45] developed a dimensioning method using a dynamic numerical model
and an optimization algorithm to calculate the instantaneous or average performances over a
xed time period for solidgas CHP operation. The power to be extracted from the reactor was
between 5 and 20 kW in a time period of 1 h. The salt quantity required in the system was about
500 mol corresponding to 30 kW h of energy storage. Lebrun and Neveu [21] fabricated a 2050
kW (68,000170,000 Btu/h) prototype of ammonia based CHP using CaCl2 /CH3 NH2 pair. This
system used a reactive having 10 m2 (100 ft2 ) exchanger area and 8.5 mm (0.33 in.) thickness for
reactive layers. The experimental results by testing this system with several dierent cycles, i.e.
phase sequences showed good agreement with the simulated performances (power output, COP
and COA).
2.2.1.2. Liquidgas system. The useful heat is obtained from the exothermic reaction, while the
heat supplied (at lower temperature) is used for endothermic reaction. The reactant with the
catalyst is normally in the liquid phase. The vapor thus released from endothermic reaction induces the backward reaction in another reactor, where the exothermic reaction takes place and
temperature upgrading is thus achieved.
1502
Heat pumps based on acetone/hydrogen/2-propanol have been studied by many researchers

[14,4650]. Mathematical models to simulate the performance of this working pair have been
developed [49]. Studies on a suitable catalyst have been investigated for both endothermic and
exothermic reactions. Kim et al. [50] has studied the use of Raney nickel as a catalyst for both the
reactions, while Doi et al. [47] have studied the dehydrogenation reaction, namely the eect of
heat supplied, reux ratio and speed of stirrer on the distillate ow when using carbon supported
ruthenium palladium as catalyst. The use of Ni particles as a catalyst for the dehydrogenation
reaction and the inuence of reaction temperature and catalyst concentration have been studied
[48]. Taneda et al. [46] have presented preliminary data on a pilot plant, which shows that the
acetone2-propanol system could be used to produce steam and note that the system operation
was stable during the 18 h of test.
Magnesium oxide/water CHP has been developed by Kato et al. [9] where the endothermic
reaction takes place at 100150C and 12.347.4 kPa. The reaction involved is:
MgOs H2 Og () MgOH2 s;
DH
81:02 kJ=mol
10
The CHP enhances the thermal energy to temperatures higher than 297C. For this system,
exhaust heat from industrial processes or other heat sources could be utilized.
For cooling purpose, a CHP with Pa/A has been developed [8]. This has high energy density
and the possibility of the continuous cycle due to the liquidliquid or gasliquid reaction. This
organic CHP consists of four parts: an endothermic reactor, an exothermic reactor, a compressor
and an expansion valve. The reaction is as follows:
Paraldehyde2; 4; 6-trimethyl-trioxane () 3 acetaldehydel () 3 acetaldehydeg
0
110:3 kJmol-Pa
DH298
and 26:4 kJmol-A :
11
The working uid of Pa/A system shows the possibilities of energy storage for cooling. Paradehyde (2,4,6-trimethyl-trioxane) is depolymerized to acetaldehyde with an acid catalyst. The
depolymerization is endothermic and reversible. Hence, the depolymerization is promoted by
the vaporization of acetaldehyde (endothermic reaction). A comparison of Pa/A system with the
conventional compression heat pump at 13C heat source and 40C heat release temperature
shows that although the COP obtained is 6.9 which is similar to that of HFC-134a, the output of
the Pa/A system is larger than that of uorocarbons and require less driving energy.
For high-temperatures, a calcium oxide/lead oxide and PbO/CO2 reaction system has been
recently investigated [6]. The reaction involved is:
CaOs CO2 g () CaCO3 s;
DH10
178:32 kJ=mol
PbOs CO2 g () PbCO3 s;
DH20
88:27 kJ=mol
12
The system consists of CaO and PbO reactors. Two modes are encountered: heat storage and
heat supply mode. In the storage mode, CaO reactor receives heat from heat source to form CaO
and CO2 . This is followed by decarbonation that produces CaCO3 . Carbon dioxide also reacts
with PbO in PbO reactor yielding PbCO3 and exothermic heat of carbonation is released. During
the heat supply mode, decarbonation of PbCO3 takes place in the PbO reactor. The carbon dioxide produced is led to the CaO reactor. Carbonation of CaO then proceeds and heat is generated in the reactor (exothermic reaction).
1503
Fig. 4. Flow diagram of the catalyst-assisted chemical heat pump system of the storage type [14].
In the case of continuous type liquidgas CHP, the exothermic reaction heat is produced at
high temperature, whereas the endothermic reaction heat and the evaporation heat are supplied at
low temperature for the decomposition of metal hydride [14]. The maximum COP obtained is
0.36, at a condition of high temperature production of about 200C, rate of reaction of 0.98 and
ratio of hydrogen to acetone is 5. However, when compact storage of hydrogen is not possible to
accommodate the large variation of heat duty or long timelag between heat supply and demand,
the storage shown in Fig. 4 is more useful as compared to the continuous type.
2.2.1.3. Solid-adsorption. An adsorption cycle consists of one or several adsorbers with a condenser and an evaporator, which are connected to either a heat source or heat sink at high, intermediate or low temperature. An experimental prototype of AC/methanol pair is one of the
most ecient solar icemakers with a COP of 0.14. The adsorptive solar powered icemakers tested
in Agidir gave a net solar COP of 0.080.12. The nominal production of 5.2 kg of ice a day was
obtained for 40% of operation days and the temperature of produced ice was between 15C and
5C [27,51].
A comparison of the working pair for absorption and adsorption cycles given in Table 4 shows
that the zeolite/water pairs give the highest performance (COP of up to 0.75). The applications are
for ice making, cold storage, refrigeration and air-conditioning. Applications in ice making and
cold store have been studied by coupling the solid-adsorption system to the solar collectors
[22,27,51]. However, the maximum COP that could be obtained from the coupled of zeolite/water
and AC/methanol system [52] is 1.06.
A summary of the performance of dierent working pairs utilized in adsorption systems given
in Table 4 shows that solar/solid adsorption system for cold production using water and calcium
oxide gives COP between 0.10 and 0.40 at specied conditions [53]. Experiments done by Tather
and Erdem-Senatalar [54] shows that the average value of 65 and 61 kJ/mol are the heat of
adsorption of water in zeolite 4A and 13X. In comparison, the use of zeolite 13X results in less
optimum mass of zeolite required in an adsorption heat pump than that of zeolite 4A. However,
the eciency of solar adsorption heat pump is higher when zeolite 13X in used. The adsorber
characteristic is improved by directly coating the zeolitewater pair onto the stainless steel wire
gauzes, which are placed vertically in the collector. As a result, the presence of thermal gradient
22C/42C 60C/200Ca
Icemaker
Icemaker
Cold storage
Air-conditioning
Icemaker
Zeolite (NaX)/water
CaCl2 NH3 (Worsoe-Schmidt)
Tev /Tcd and Tads /Tdes .
0.75
25C/35C 105C/220C for

NaX/water 25C/35C 35C/
100C for AC35/methanola
5C/25C 25C/110Ca
10C/170C 10C/170C
10C/170C 10C/170C
Air-conditioning
Zeolite NaX/water
and AC AC35/methanol
Zeolite (NaX)/water
Zeolite (NaX)/water
Zeolite (NaX)/water
0.30
0.44/0.21 0.48/0.11
0.10 (solar COP)
5C/25C 25C/110Ca
5C/20C 30C/80Ca
Icemaker
Air-conditioning
AC/methanol
AC/methanol
6C/28C
24.5C/87Ca
0.10 (solar COP)
1.06
0.12 (net solar COP)

0.35
0.080.12 (solar COP)
0.15 (net COP)
Icemaker
10C/110C
AC/methanol
25C/130C
Icemaker
COP/exergetic eciency
AC/methanol
Temperature range (low/high

temperature source)
Application
Working pair
Table 4
Performance of dierent working pairs used in solid-adsorption and absorption systems
Absorption machine
12 m3 of cold stored, average daily gross production
of ice of 7 kg/m2
Two adsorbers, SPC 19.6
kg ads., cooling output 1
kW
No rectifying column, initial temperature of water is
0C
Collector equipped with

boosters
Ice production of 5.2 kg in
isolation between 18 and 28
MJ/m2
6 kg of ice/m2 of collector
Two adsorbers, mass recovery (isothermal), SPC
89 W/kg ads., cooling output 3.5 kW
Three adsorbers, cascading
cycle with two dierent
heat recovery phases
Remark
[81]
[52]
[22]
[76]
[22]
[77]
[51]
[82]
[27]
[51]
References
1504
1505
becomes more eective, and the eciency of the system decreases as the amount of zeolite employed increases.
Experiments were conducted by Poyelle et al. [20] by introducing heat and mass recovery cycle
using a zeolitewater pair to a new consolidated adsorbent composite. The adsorptive material is
made up of NaX zeolite (5.0 kg), binder (1.3 kg) and expanded natural graphite (ENG) (1.8 kg).
Each adsorber consists of four rows of four tubes comprising of adsorbent composites distributed
in the form of rod around tubes. A heat and mass recovery cycle of zeolitewater pair gave an
experimental SCP of 97 W/kg at an evaporation temperature of 4C. However, the authors note
that at higher evaporating temperature (2530C), a COP of 0.68 and a SCP of 135 W/kg could be
obtained.
For moderate low temperature source ( 1010C) and high temperature source (170C),
zeolitewater system gives relatively high COP values (>0.40), as well as the higher exergetic
eciency (up to 0.21). However, with higher temperature of low temperature source and lower
temperature of high temperature source, ammoniawater system shows highest performance in
term of COP and exergetic eciency.
Meunier et al. [41] have proposed an entropy production concept to analyze the quality of heat
management inside the adsorption cycle as well as between the cycle and the heat sources. Internal
entropy production (due to heat recovery) and external entropy production (due to coupling
between heat reservoirs and adsorbers) for n-adsorber uniform temperature cycles and thermal
wave cycles have been determined. They have suggested a design of novel regenerative process
that leads to reduction of the entropy production.
Critoph [55] has evaluated the performance of new refrigerantadsorbent pairs, namely, butane, R32 and ammonia with monolithic carbon. The cycle COPs were calculated for one bed
cycle and a two bed cycle. Of the studied pairs, ammonia has about three times the COP of R32,
while those of butane were found signicantly lower.
Another study by Critoph [56] using ammoniacarbon in a forced convection adsorption cycle
using inert bed for air-conditioning applications was found to give a COP of 0.56 and a cooling
power of about 300 W/kg. The inuence of COP due to design parameters such as bed length, ow
rate, gas exit temperature and initial isothermal temperature indicates that increasing bed length
or decreasing ow rate improves COP, but decreases the cooling power. However, signicant
improvements were observed if the heat transfer is increased. A 10 kW demonstration cooling
system is expected to give a COP of 0.95 and a cooling density of about 400 W/kg.
2.2.2. Applications
Among industrial processes, certain unit operations such as drying, distillation, evaporation
and condensation deal with large amount of enthalpy changes where CHP can be eectively
utilized. However, the COP of the basic cycle of CHP might be limited because of the sensible heat
consumed during the temperature swings. Using thermochemical substances, designing new reactors or new systems could possibly lead to improving the heat rate and thus reduce the size of
units.
The current applications of CHP and related systems can be broadly categorized into areas
such as, refrigeration, heat production (heat pump), combined heat and cold production, lifting
temperature of heat source (thermotransformer), thermal energy storage and the integration of
solar thermal collectors for applications to heating and cooling.
1506
Table 5 summarizes the information on working pairs, their applications, and range of operation or working conditions of adsorption system, solidgas system, liquidgas system, metalhydrides, absorption system and solar assisted CHP system.
In zeolite/water systems the heat of adsorption could reach 61 kJ/mol of water adsorbed [54].
Poyelle et al.s [20] experimental work obtained a specic cooling power of 97 W/kg of adsorbent.
In solar assisted solid-adsorption system, the solar powered adsorption cold store utilizing NaX
water pair gave a COP of about 0.10. By enhancing the conductivity of the zeolite bed, COP could
be as high as 0.15 [28]. A solar adsorption heat pump [54] utilizing the zeolitewater pair using a
continuous coating of the zeolite on stainless steel wire gauzes has been developed. They are
placed vertically in the collector to ensure a rm contact between the absorber plate and the wire
gauzes. The solar collector consists of two separate regions, namely, the glass cover and the
adsorbent metal integrated system. The variation of solar COP with respect to the thermal gradient possible to be found in a conventional solar collector (030C) was between 0.06 and 0.13
for the system using 23.3 kg of zeolite 4A.
Zeolite/methanol pair cannot be used at around 100C because zeolite is a catalyst of the
reaction methanol ) water dimethylether. As AC has a signicant volume of micropores, AC
methanol pair is suitable for solar adsorption icemaker with at-plate collectors [51]. A comparison of two collectorcondenser units (solar collector merged with condenser) of adsorptive
solar powered icemakers has been done by Boubakri et al. [57], equipped with a radiation shield.
This shield leads to 40% reduction of heat transfer coecient inside condenser. Wang et al. [58]
have presented simulation results for ACmethanol working pair for producing hot water and ice.
This was done by coupling a solar water heater and an adsorber, which is connected to the cold
storage. The results indicate that solar refrigeration COP of about 0.150.23 and a heating eciency of about 0.350.38 could be obtained. Preliminary tests using an electric heater to simulate
a vacuum solar collector was found to produce about 10.5 kg of ice at 2C.
In solidgas CHP system, dierent chloride salts reacting with ammonia have been studied, and
Lebrun and Neveu [21] have tested 2050 kW solidgas (plate reactor) prototype.
In liquidgas system, both organic and inorganic reactants are in use. Many studies have been
carried out for dierent catalyst enhancing the endothermic/exothermic reaction of 2-propanol/
acetone with hydrogen [14,17,5961]. Low-grade heat from solar thermal collectors could supply
heat to an endothermic reactor of a liquidgas system. Taneda et al. [17] noted that heat at 80C
could be upgraded by liquidgas CHP to 150200C. The endothermic liquid-phase dehydrogenation of 2-propanol release acetone and hydrogen at 80C with appropriate catalysts (e.g. Ru/C,
RuPt/C and RuPd/C) [59]. In the following phase, exothermic gas-phase hydrogenation of
acetone into 2-propanol takes place at high temperature (200C) with another catalyst (e.g.
NiCu/alumina [16]). Experiments on 2-propanol dehydrogenation conducted by Mooksuwan
[62] shows that the 10 wt.% and 1.3 g l 1 of RuPt/AC catalyst used could achieve the maximum
heat utilization of 4.5% when oil bath temperature is about 100o C. For hydrogenation of acetone
using 10 wt.% NiCu/c-Al2 O3 catalyst, at the catalyst bed temperature about 110150C, the
maximum acetone conversion of 25% was obtained at reactors inlet temperature of 120C.
In calcium oxide/lead oxide reaction system, the operating decarbonation/carbonation temperature ranges from 300C to 880C.
In refrigeration process, new applications for CHP has been discussed by Spinner [2] including air-conditioning for automobiles (electrical vehicles), individual air-conditioning
Solidgas
system
Zeolitemethanol
Adsorption
system
Flat plate selective collectors, desorption

temperature (100C)
Ammonia based system

in general
Alkaline and earth
alkaline coupled with
ammonia (Ca, Ba, Sr,
Fe, Mn, Zn)
For example; ve chloride salts (Ca, Mn, Mb,
Fe and Ni)
Zeolitewater with
HMR (with new consolidated adsorbent
composite)
Activated carbon
methanol
Zeolitewater (4A and

13X)
Heat of reaction about 50 15

kJ/mol
For refrigeration, COP ranges
from 0.4 to 0.7, exergetic eciency from 0.02 to 0.3
COP 0:14 Net solar

COP 0:08 0:12, 5.2 kg/day
of ice production ( 15 to 5C)
SCP 97 W/kg SCP 135 W/kg
Reactive area 10 m2 , thickness of reactive 2050 kW prototype 68,000

layers 8.5 mm, Tc 65C, Tev 18C,
170,000 Btu/h
COP 0:53
Operating pressure 50 bar, temperature

range 50C to 300C;
Heat sources from 105C to 200C and
temperature lift from 105120C (low
pressure steam network) to 155170C
(medium pressure network)
Maximum temperature of
adsorption 110C
minimum Tamb 20C,

Tcd Tev 18C Tcd 20C, Tev 2C
or Tcd Tev 33C Tcd 35C,
Tev 2C
Evaporating temperature of 4C, Condensing temperature 2530C
Latent heat of evaporation 19.8

MJ, mass of ice produced 14.7
kJ, incident radiation 120 MJ (6
m2 ), cycle COP 0.43, net solar
COP 0.12
Heat storage capacity 13 GJ/
m3 , heat released 2257 kJ/kg of
water absorbed (9.73 kcal/mol)
Cold production during evaporation 1.93 MJ/m2 , net cold production 1.88 MJ/m2 , incident
radiation 17.8 MJ/m2 , cycle COP
0.38, net solar COP 0.105
Heat of adsorption of water in
zeolite 4A: 65 kJ/mol 13X: 61
kJ/mol
Range of operation or working condition Heat of reaction or adsorption

and application
and system performance
Calcium oxide xed bed Adsorption of 0.012 g/g s of water vapor

in 1 kg of xed bed calcium oxide, store
temperature of 180C
Zeolitewater
15 kg/cm2 of zeolite
Working pairs
Category
Table 5
Selected characteristics of some CHP systems
(continued on next page)
Lebrun and Neveu [21]
Spinner [1]
Spinner [1]
Pons and Guilleminot,

[51]; Boubakri et al. [27]
and Grenier et al., [28]
Poyelle et al. [20]
Tather and ErdemSenatalar, [54]
Grenier et al. [28]
Darkwa and OCallaghan [53]
Pons and Guilliminot

[51]
Author(s)

1507
Metal
hydrides
Reaction temperature 373423 K, vapor

pressure 12.347.4 kPa; upgrade temperature from 370440 K to 373570 K
Thermal comfort (heating and air-conditioning) in electrical vehicles and insulation of garment
High temperature metal

(LaNi4:5 Al0:5 ) and low
temperature metal
(LaNi5 )
Useful heat temperature 423 K, waste

heat temperature 383 K, cooling water
temperature 303 K, cycle period 600 s,
R1 /R2 0.325, optimum cycle period is
longer when radius ratio (internal to
external radius) is smaller
Author(s)
Kang and Yabe [44]
Chung et al. [60]; Mears

and Boudart [59]; Taneda et al. [17]; Mooksuwan and Kumar [61]
Achieve maximum heat utilization of 4.5% (oil bath temperature of 100C); maximum
acetone conversion of 25% at
inlet temperature of 120C
Heating output is 4045 W/kg

COP 0.450.5
Saito et al. [14]
Kato et al. [6]
Kawasaki et al. [8]
Kato et al. [9]
Maximum COP is 0.36, 200C
Heat of hydration 79.9 kJ/mol

water, heat of adsorption 49 kJ/
mol water, heat of condensation
37.4 kJ/mol water
COP is 6.9
Specic heat and cold production Goetz et al. [40], Gardie

is 90 Wh/kg and 45 Wh/kg of salt and Goetz [15]
used

and application
Possible for cooling; 286 K and heat

release of 313 K
Calcium oxide/lead
PbO CO2 ) PbCO3 (2); decarbonaoxide and PbO/CO2
tion: Pdc 1.0 atm, optimum
Tdc 440450C; carbonation: Pcb 0:01
reaction system
atm, Tcb 300C CaO CO2 ) CaCO3
(1); decarbonation: Pdc 0:4 atm,
optimum Tdc 860C; carbonation:
Pcb 1:0 atm, Tcb 880C
Continuous type liquid Exothermic reaction heat is produced at
gas CHP
high temperature; endothermic reaction
heat and evaporation heat supplied at low
temperature; rate of reaction of 0.98 and
ratio of hydrogen to acetone is 5
Upgrading solar thermal energy by endoLiquidgas system
thermic/exothermic reaction (dehydro(2-propanol/acetone/
genation/hydrogenation); using
hydrogen)
appropriate catalyst: Ru/C, RuPt/C, Ru
Pd/C, NiCu/cAl2 O3 (endothermic); Ni
Cu/alumina, RuPt/AC (exothermic; take
place at high temperature of 200C)
Magnesium oxide
water
Liquidgas
system
Pa/A
Working pairs
Category
Table 5 (continued)
1508
Solarassisted
CHP
Solar/
absorption
system or
energy
storage
Solar collector-chemical
reactor as receiver/reactor
Gas/solar-driven heat
pumps
Solar-assisted heat
pump (SAHP)
PCM (calcium chloride

hexahydrate) integrated
to solar collector
Solar-aided R22DEGDE
LiBrH2 O and
NH3 H2 O
Solar collector of 20 m2 paraboloidal dish Capacity 15 kWchem

solar concentrator and U-shaped tubular
chemical reactor
Used as coolers or heat pumps; maximum Maximum theoretical

theoretical heat gain factor is 210%
COP 0:9, cooling power of 355
W/m2 , useful thermal power 344
W/m2 , COP decrease with increasing ambient temperature
(88% at 20C to 75% at 40C),
linear reduction of cooling capacity with increasing ambient
temperature (1196 kJ/kg NH3 at
20C to 1144 kJ/kg NH3 at 40C)
Two stage vapor absorption system (heat Flat plate collector 13 m2 , average refrigerating eect 420 W
transformer and refrigerating machine)
lower hot source temperature (thermal
euents or at plate collectors)
Minimum allowable levels of requirement Cooling capacity 100 kW; solar
energy supplies 38% and 91%
is 20C in winter and over 80C in
summer; 400 m2 of high eciency collec- demand in winter and summer
respectively
tor s(4 m2 /kW cooling)
PCM 1500 kg with collector area of 30 m2 Storage eciency 4060%; mean
for laboratory building of 75 m2 oor area collector eciency, heat pump
COP, system COP and storage
eciency are 70%, 4.5%, 4.0%
and 60% respectively
For sea water purication, refrigeration
COP of 0.75 and thermal eand power generation
ciency of 16%
Simulation of two serial SAHP compared Saving of 21% or 41% of annual
total costs; operating with R134a
with conventional heat pump and solar
increase COP by 50% and 4% of
air heater
heat pump and collector eciency; reduction of collector
area by 25% and 50%
Solar driven NH3

LiNO3 and NH3
NaSCN
(continued on next page)
Meirovitch et al. [69]
Abou-Ziyan et al. [68]
Nguyen et al. [75]
Comakli et al. [7880]
Ileri [66]
Ahachad et al. [74]
Antonopoulos and
Rogdakis [67]
Specic cooling power is 1.5 kW/ Kim et al. [43]

kg
With fast reactors, 500 full cycle testing
Compressor-driven
hydrogen metal-hydride

1509
Category
Ammonia based using directly irradiated
catalyst lled tubes (receiver/reactor)
Adsorbent metal integrated system
Solar energy storage

and transport system
Solar/adsorption heat
pump (zeolite-water
pair)
Maximum power level per reactor tube pair is 390 W at mass

ow of 0.12 g/s for 750C, 680 W
at 0.21 g/s at 800C
COP between 0.06 and 0.13 using
23.3 kg of zeolite 4A

and application
Working pairs
Table 5 (continued)
Tather and ErdemSenatalar [54]
Lovegrove and Luzzi

[70]
Author(s)
1510
1511
(with built-in cold storage), rapid cold generation and product freezing, continuous cold generation in a chamber and self-contained cold generation and storage, cooling for electronic devices
and calculators, and instant ice cubes for household use.
Two applications showing the advantage of storage function allows the design of appropriate
CHP congurations [40]. For thermal comfort in electrical vehicle application, specic energy dened as the ratio of energy extracted to evaporator or energy released by reactor and/
or condenser to the amount of ammonia used is about 93 and 46 Wh/kg of hot and cold production.
For applications of air-conditioning in automobiles, a solidgas accumulator (MnCl2 (6/2)/
NH3 ) in electric vehicles which provides heating and cooling (for dierent seasons) has been
evaluated by Gardie and Goetz [15]. This system uses MnCl2 of 2.3 kg in a reactor for 1 kW h of
heat storage. During production phase, cold is produced by evaporation to cool in summer and
heat is produced by the reaction to heat in winter. Regeneration takes place when the automobile
is stopped or during the charging of batteries. On the other hand, for individual air-conditioning,
during the production phase, cold is provided by the decomposition of BaCl2 (8NH3 ). Then in
regeneration phase, decomposition of MnCl2 (6NH3 ) takes place. The two solidgas reactors are
closed and are then ready for cold production. This enables cold production at 1020C, which is
sucient for direct air-conditioning [40].
Adsorption chiller developed by NAK [63] using silica gel/water as working pair is rated at 50
430 kW and has a COP varying between 0.46 and 0.65. Heat at 85C is used to produce chilled
water at 9C. This single-eect machine could use waste heat for commercial air-conditioning
applications.
The scale up from laboratory scale or experimental unit (prototype) necessitates the development of an operating method to control the CHPs cycling. Studies to predict the performance and
comparison with pilot scale units have been described [21,45,64].
Suda [65] notes that commercialization of metal hydride systems (for heat pumps and refrigerating purposes) should take into account the limitation to actual power generated by the design.
For instance, some of the factors to be considered are overall mass of the reactor system, reactor
conguration, and operating temperatures of the heat source, heat sink, heat or cold to be generated, and a combination of the hydriding materials selected.
Solar assisted absorption systems with R22-DEGDME [66] and NH3 LiNO3 , and NH3
NaSCN [67] have been studied. Performance of solar assisted heat pump using R22, R404a and
R134a as working uids was compared with conventional heat pump and solar air heater by
Abou-Ziyan et al. [68].
Chung et al. [60] show that the CHPs, where heat is stored in chemical substances do not have
losses due to temperature dierences. In addition, low-temperature source such as solar thermal
energy could be upgraded to satisfy the requirements at higher level by exothermic reaction. Solar
collector (20 m2 paraboloidal dish solar concentrator) directly integrated to a U-shaped tubular
chemical reactor as receiver/reactor (15 kWchem ) was developed for reforming of methane [69]. By
this way, thermochemical conversion of solar energy into chemical energy and sensible heat could
be integrated into a self-regulatory system.
A design of ammonia based thermochemical solar energy storage and transport system has
been developed by Lovegrove and Luzzi [70] using directly irradiated catalyst lled tubes
(receiver/reactor). The study shows the technical feasibility for a 20-m2 paraboloidal dish
1512
concentrator with Ni catalyst. Experimental studies have also shown that simple tube and tube
counter ow heat exchanger are adequate for obtaining higher storage eciencies.
Tamainot-Telto and Critoph have presented preliminary results of concentrating (CPC) solar
energy collector with absorber containing carbon and ammonia at the focus [71]. The experimental setup is designed to produce a cooling power of up to 120 W.
Ito et al. [72] have investigated a solar assisted heat pump system using hybrid photovoltaic (PV) and thermal panels as an evaporator for heat pump. Evaporator with multiple ns
(convective-type evaporator) is placed in parallel with the at-plate collectors (radiative-type
evaporator) over a total area of 3.24 m2 . Polycrystalline silicon PV is bonded to the surface of
the collector plates, which are made of copper. Electricity produced by PV is supplied to compressor of heat pump, while a part of waste heat produced is used for raising evaporation
temperature. COP of six obtained is higher than that of a conventional heat pump during daytime.
Hu [73] has developed a mathematical model for simulating a non-valve solar powered carbon/
methanol adsorption refrigeration system and studied the phases of temperature change and
methanol migration. The results of the study compared well with experimental observations and
the model is a useful tool to analyze the eect of daily operations in a non-valve system.
3. Areas of further research
Being an environmental friendly technology, CHPs for various applications need to be investigated as they could oer a viable solution for ecient thermal energy use. They could help to
utilize renewable energy (e.g. solar energy, biomass, etc.) and waste heat over a wide range of
temperatures.
The potential research areas for development of CHP are summarized in Table 6. The domains
for CHP application in industries include pulp and paper, chemicals, textiles, and food and drink
[7]. Meunier [4] noted two areas for CHP development: low eciency applications with simple
technology (e.g. domestic appliance, short-term storage, waste heat assisted air-conditioning) and
high ecient applications (industrial). Solar-assisted CHP could be used for small (residential)
and large (i.e. industry, building, commercial, agriculture) scale applications. The possible activities (experimental and theoretical studies) in building and industrial sector and techniques
(new or those which have been already successfully applied) have been noted.
Besides the improvement of technology for solidgas or liquidgas CHP itself, integration with
other system requires further research. Both theoretical (modeling, simulation, evaluation/verication techniques) and experimental (laboratory scale, scale transposition to prototype and pilot)
studies are required to improve the overall performance (e.g. eciencies, given power/work) to
suit particular applications. Scale transposition from laboratory scale (experimental unit and
prototype) to practical application is also an area of work, which could result in the development
of general design procedures.
At present research on upgrading of solar energy by liquidgas CHP are being done [60,72]. A
CHP component (e.g. reactor, adsorber, condenser, and evaporator) might be coupled directly to
solar collector as well as an integral evaporator/condenser to the storage unit of solar system for
optimizing the system size.
The simulation tools could be TRNSYS, MATLAB

and any other user-developed programs
Examine thermodynamical limits of performance
analytically and graphically
Develop second law analysis of the new design and
determination of the exergetic eciency
Develop nomograms to estimate the characteristics
and sizing of the designed system Develop the scale
transposition procedure for eective sizing of the
practical system for commercialization
Forecasting the performance of the solar-assisted
CHP under dierent climate conditions using neural
network
Energy and economic comparison of dierent congurations (arrangement)
Industry
Thermal energy storage by CHP from waste heat
Dehumidication
Drying of agricultural products Replacement of the
steam usage by medium temperature steam/water
production (150250C)
Refrigeration rooms by coupled solar/CHP/absorption chiller
High temperature process supplied by solar-metal
hydrides system
Carry out the experimentation for

whole year and verify with the predicted performance from simulation
based on available meteorological
data
Testing the prototype
Validate Start-stop control strategies for solar/CHPs system
Comparison of performance of
dierent coupled combination under
identical and dierent conditions
Verify the performance of new deImprovement of one component by modication of

signs of solar-CHP in laboratory and the existing conguration(s), for example, increase
then scale to prototype
the heat exchange area at heat exchanger
To achieve better heat transfer and kinetics
To reduce the limitation of mass transfer
To obtain better overall heat transfer coecient
Design the new coupling technique between solar
components and CHP components Modication of
solar collector to merge with the reactor or adsorber
directly as well as to merge the storage tank with
other CHP components (e.g. condensor, adsorber,
evaporator)
Develop general design procedure
Building
Hot water and steam production by heat recovery
from air-conditioning units, other sources, etc. for
in-house use (e.g. laundry)
Hot and cold production for specic purpose (e.g.
supplying hot and cold water)
Air-conditioning
Theoretical work
Experimental work
Application
Table 6
Possible research areas for solar assisted CHPs
1513
1514
Fig. 5. (a) Integrated solar and heat pump for temperature upgrading and storage, (b) integrated solar, heat pump and
upgrading of waste heat temperature, and (c) integrated solar, heat pump, and waste heat for storage and upgrading.
Research on solarheat pumpenergy storage system for specic applications depend on requirements. This could be for: (1) only one component such as reactor, evaporator, condenser,
heat exchanger of CHP module and energy storage unit; (2) more than one component considering either individually or considering their interrelationship among sub-system (sub-module);
(3) energy transportation network; (4) control system; and (5) the complete assembly. For
example, dierent combinations to integrate solar system, heat pumps and energy storage could
be considered:
1. Input is solar energy only; heat pumps act as thermal energy storage (TES) to upgrade energy
and storage purpose (Fig. 5a).
1515
Table 7
Summary of recent theoretical and experimental studies on heat pump and refrigeration
Author
Application
Poyelle et al. [20]
Air-conditioning
Pons et al. [83]
Heat pump
Ben Amar et al. [84]
Heat pump
Balat and Spinner [85]
Heat pump
Lai [86]
Pons and Szarzynski [87]
Ortel and Fisher [88]
Vasiliev et al. [89]
Refrigeration
Cooling
Cooling
Cooling
Specic power
(W/kg)
Theoretical/
experimental
System studied
135
600
34.5
Experimental
Theoretical
Experimental
Zeolitewater
150
170
654/759
125.6
100
10
300
330
Theoretical
Theoretical
Experimental
(synthesis/
decomposition)
Theoretical
Theoretical
Experimental
Experimental
Zeolite (graphite)
water
Na ZeoliteWater
ACammonia
CaCl2 /CH3 NH2
Zeolitewater
Zeolite NaXwater
Methanolsilica gel
``Busot'' (AC ber)NH3 ``Busot''
(AC ber)CaCl2 /
NH3
2. Input is both solar energy (at solar collector) and/or waste heat (for heat pump) to upgrade energy (Fig. 5b).
3. Input is solar energy (at solar collector). The TES of solar thermal system is also available (e.g.
water tank, PCM). Heat pump could be integrated with the solar collector for temperature upgrading of solar collector output. Waste heat and other alternate source (if needed) could supply heat to heat pump unit. Heat from alternate source could be also supplied to storage unit
(Fig. 5c).
Table 7 summarizes results of some recent theoretical and experimental studies on heat pump
and refrigeration giving information on the specic power produced (heating or cooling) by
various researchers. Srivastava and Eames [24] also note that though signicant strides have been
made during the 1990s especially in adsorbent bed technologies, improvements need to be made
in order to compete with conventional absorption and vapor compression technologies. For
example, a recent simulation study [23] using monolithic carbon and ammonia as working pair
has shown that a cooling power of up to 1 kW/kg is possible, and could be a target for applications.
Acknowledgements
W. Wongsuwan is grateful to the French Government, and the Postgraduate Technical Studies
Programme sponsored by the European Commission DG1/B of the European Union for their
nancial support in conducting this study.
1516
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Applied Thermal Engineering 21 (2001) 14891519

A review of chemical heat pump technology and applications

Corresponding author. Tel.: +66-2-524-5410; fax: +66-2-524-5439.

W. Wongsuwan et al. / Applied Thermal Engineering 21 (2001) 14891519

3. Areas of further research . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1512

W. Wongsuwan et al. / Applied Thermal Engineering 21 (2001) 14891519

coecient of amplication (heat

W. Wongsuwan et al. / Applied Thermal Engineering 21 (2001) 14891519

Fig. 1. Classication of CHP.

W. Wongsuwan et al. / Applied Thermal Engineering 21 (2001) 14891519

Fig. 2. A simple CHP.

W. Wongsuwan et al. / Applied Thermal Engineering 21 (2001) 14891519

Fig. 3. Clapeyrons diagram showing the heat pump mode of operation.

W. Wongsuwan et al. / Applied Thermal Engineering 21 (2001) 14891519

W. Wongsuwan et al. / Applied Thermal Engineering 21 (2001) 14891519

Air-conditioning/chilled water 2C to 10C

Refrigeration ( 20C to 0C)

COA Qcond Qabs =Qreg

W. Wongsuwan et al. / Applied Thermal Engineering 21 (2001) 14891519

Specic power output

Eective thermal conductances (keff in W/

Anisotropic heat conduction porous graphite matrices,

530 W/m K (radial) <1

PMH-compacts and equivalent high-conductance

Chlorides-type reactants (alkaline, alkaline-earth or

23 W/m K for 31 wt.%

515 W/m K (radial) <1

0.10.4 W/m K <40 W/

where 1 T0 =Ti is the Carnot temperature.

W. Wongsuwan et al. / Applied Thermal Engineering 21 (2001) 14891519

W. Wongsuwan et al. / Applied Thermal Engineering 21 (2001) 14891519

W. Wongsuwan et al. / Applied Thermal Engineering 21 (2001) 14891519

W. Wongsuwan et al. / Applied Thermal Engineering 21 (2001) 14891519

Upgraded temperature (low temperature (Tl ) to high

CaCl2 (4/2) and MnCl2 (6/2)

W. Wongsuwan et al. / Applied Thermal Engineering 21 (2001) 14891519

Heat pumps based on acetone/hydrogen/2-propanol have been studied by many researchers

and 26:4 kJmol-A :

PbOs CO2 g () PbCO3 s;

W. Wongsuwan et al. / Applied Thermal Engineering 21 (2001) 14891519

CaCl2 NH3 (Worsoe-Schmidt)

Tev /Tcd and Tads /Tdes .

25C/35C 105C/220C for

0.10 (solar COP)

0.12 (net solar COP)

0.080.12 (solar COP)

0.15 (net COP)

Temperature range (low/high

Collector equipped with

W. Wongsuwan et al. / Applied Thermal Engineering 21 (2001) 14891519

W. Wongsuwan et al. / Applied Thermal Engineering 21 (2001) 14891519

Flat plate selective collectors, desorption

Ammonia based system

Zeolitewater (4A and

Heat of reaction about 50  15

COP 0:14 Net solar

SCP 97 W/kg SCP 135 W/kg

Reactive area 10 m2 , thickness of reactive 2050 kW prototype 68,000

Operating pressure 50 bar, temperature

minimum Tamb 20C,

Latent heat of evaporation 19.8

Range of operation or working condition Heat of reaction or adsorption

Calcium oxide xed bed Adsorption of 0.012 g/g s of water vapor

Heat of reaction about 50 15