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Concept of adsorbent optimal for adsorptive

cooling/heating
Article in Applied Thermal Engineering November 2014
DOI: 10.1016/j.applthermaleng.2014.04.077

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Applied Thermal Engineering xxx (2014) 1e10

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Applied Thermal Engineering

journal homepage: www.elsevier.com/locate/apthermeng

Concept of adsorbent optimal for adsorptive cooling/heating

Yuri Aristov a, b, *
b

Boreskov Institute of Catalysis, Lavrentiev Av. 5, Novosibirsk 630090, Russia

Novosibirsk State University, Pirogova str. 2, Novosibirsk 630090, Russia

h i g h l i g h t s

Concept of the adsorbent optimal for
specic adsorptive cooling/heating
(ACH) cycle.

Testing of known adsorbents and
tailoring of new adsorbents for
various ACH cycles.

Modication of aluminophosphates,
metal-organic
frameworks
and
composites.

Harmony of the optimal adsorbent
with
other
components,
cycle
boundaries and duration.

g r a p h i c a l a b s t r a c t
1

Water uptake, g/g

0.3

Zeolites
3

0.2

0.1

0.0
0

10

15

20

25

Adsorption potential, kJ/mol

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 2 December 2013
Received in revised form
16 April 2014
Accepted 22 April 2014
Available online xxx

In this paper, we consider the role of adsorbents in adsorptive cooling/heating (ACH) and analyse which
are optimal for specic ACH cycles. The conclusions are formulated in terms of the optimum isobar
shape, the Dubinin adsorption potential being used as a universal measure of the afnity between the
adsorbent and the adsorptive. Selection/tailoring of the optimum adsorbents, creation of database of
their properties as well as harmonization of the adsorbent and other components of ACH unit, cycle
boundary conditions, and cycle management strategy are briey discussed. New efcient adsorbents
harmonized with particular ACH cycles are a prerequisite to achieving a major breakthrough in ACH, and
therefore, are pivotal for this challenging application.
2014 Elsevier Ltd. All rights reserved.

Keywords:
Adsorption cooling/heating
Optimal adsorbent
Adsorption dynamics
Heat- and mass-transfer
Nano-tailoring
Database of adsorbent properties
Sigmoid isobar shape
Limiting efciency and power

1. Introduction
Adsorptive cooling and heating (ACH) is an emerging technology that offers both economic and ecological advantages [1,2]. It
uses benign working uids which reduce the direct emissions of

* Boreskov Institute of Catalysis, Lavrentiev Av. 5, Novosibirsk 630090, Russia.

Tel.: 7 3833309673.
E-mail address: aristov@catalysis.ru.

greenhouse gases. Moreover, waste heat can be utilised to drive the

process reducing the consumption of fossil fuel and, therefore, indirect emissions [1].
The ACH development was initiated by the 1973 oil crises, and
the rst, quite large (50e1000 kW), adsorptive chillers appeared on
the market as early as in 1986 from two Japanese companies,
Nishiyodo Kuchouki Co. Ltd [3]. and Mycom [4]. Various small
adsorption chillers (5e22 kW) were developed in the 21st century,
and some of them have passed over from the prototype stage to
small serial production (SorTech, InvenSor) [5]. Also, small capacity

http://dx.doi.org/10.1016/j.applthermaleng.2014.04.077
1359-4311/ 2014 Elsevier Ltd. All rights reserved.

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Y. Aristov / Applied Thermal Engineering xxx (2014) 1e10

(up to 15 kW) gas red adsorption heat pumps have recently been
developed by Vaillant and Viessmann [6].
Despite signicant progress, the ACH technology as yet remains
unnished and expensive, so that there is still a big room for its
improvement [7]. Therefore, further R&D is necessary to realize the
potential economic and ecological advantages of ACH technology
[8]. In this paper we consider the role of adsorbent in ACH technology, analyse which adsorbent is optimal for a specic ACH cycle,
and discuss which COP and SCHP can be obtained if they are limited
only by properties of the adsorbent. Since the adsorbent is just one,
although important, constituent of real ACH unit, it must be in
harmony with all other elements and the cycle strategy, which is
briey considered as well.
2. Presentations of ACH cycle
A three temperature (3T) ACH cycle consists of two isosters and
two isobars and is commonly presented on the Clapeyron diagram
ln(P) vs. (1/T) (Fig. 1a). Three temperatures (those of evaporator Te,
condenser Tc T1, and external heat source Tg) uniquely dene the
cycle. Other usable ways to present this cycle are w(T) and T(S)
diagrams, where S is the entropy change. Here, we mainly consider
the ACH cycle on the diagram w(DF) that is rarely used yet [9].
The Dubinin adsorption potential DF RT ln(P/Po) was introduced as a universal measure of the adsorbent afnity to the
adsorptive [10] (here Po is the saturated vapour pressure at temperature T). Fortunately, for the majority of adsorbents that are
promising for ACH, there is a one-to-one correspondence between
the equilibrium uptake w and the DF-value [11]. In particular, it is
valid for adsorbenteadsorbate pairs described by the DubininAstakhov or DubinineRadushkevich equations.
The ACH cycle in the w(DF) presentation is very simple: it is just
one line which represents both isobaric adsorption and desorption
stages of a 3T ACH cycle (Fig. 1b). If hysteresis is present, two
different curves describe the ad/desorption runs. Point A in Fig. 1b
represents the boundary conditions at the end of the adsorption
stage (point 1 on Fig. 1a). It corresponds to the adsorption potential
DFmin RT1 ln[Pe/Po(T1)] that characterizes the minimal adsorbent afnity necessary to bind an adsorptive at temperature T1 Tc
and pressure P(Te). This potential depends on the adsorptive nature
as seen from Table 1 that displays the DFmin-values for several ACH
cycles selected as reference cycles in the key review [12]. Five basic
applications, such as air-conditioning (AC2), heat pumping (HP1,
HP2), and deep freezing (DF1, DF2), were suggested. We have added
one more air-conditioning cycle with Te 15  C (AC1) that is also
commonly in demand. Two options were suggested for the external
cooling: Tc 40  C for water-cooled units and Tc 50  C for aircooled units (55  C for heat pumping) [12]. We offer here two
realistic changes in those boundary conditions: Te 5  C instead of
3  C for AC2, and Tc 35  C instead of 40  C for water-cooled units.

Point B in Fig. 1b represents the boundary conditions at the end

of the desorption stage (point 3, Fig. 1a) and corresponds to the
adsorption potential DFmax RT3 ln[Pc/Po(T3)] that is dened by
the conditions of heat rejection (Tc) and adsorbent regeneration
(Tg). Adsorbate molecules that are bound to the adsorbent with an
afnity lower than DFmax RTg ln[Pc/Po(Tg)] can be desorbed
during the regeneration stage 2e3. Those bound more strongly
remain adsorbed and are not involved in the heat transformation
cycle. The DFmaxevalues associated with the regeneration conditions (Pc, Tg) are collected for Tc 35 and 50  C, and Tg 60, 80,
100  C in Table 2.
If the two boundary temperatures Te and Tc are xed, the minimal desorption temperature Tmin can be estimated by equating the
DF-values for the rich and weak isosters

RTc lnPe =Po Tc  RTmin lnPc =Po Tmin :

(1)

Eq. (1) can be solved graphically to get Tmin(Te, Tc). Interestingly, this
value is equal to that calculated by simple Trutoun's rule [13,14]

.
Tmin Tc 2 Te

(2)

within an accuracy of 1  C [11]. Evidently, if the temperature of the

external heat source Tg is lower than Tmin, the cycle cannot be
realized at all. Although both right and left parts of Eq. (1) depend
on the adsorbate nature, the minimal desorption temperature does
not (Table 3).
Eq. (2) also denes the minimal temperature, Te (Tc)2/Tg that
can be reached in the evaporator if the adsorbent was regenerated
at temperature Tg and pressure Pc Po(Tc). A large temperature lift

. i
h

 
Tc  Te Tc eTc 2 Tg Tc 1eTc Tg

(3)

can be obtained only if the adsorbent has high regeneration temperature Tg and, hence, a strong afnity to adsorptive, which is
typical e.g. for classical zeolites.
The easiest conditions for air conditioning are Te 15  C and
Tc 35  C which corresponds to DFmin 3.05, 2.66, and 1.58 kJ/mol
for water, methanol and ammonia, respectively. The most severe AC
conditions are Te 5  C and Tc 50  C which corresponds to
DFmin 7.10, 6.21, and 3.70 kJ/mol (Table 1). Thus, adsorbents
promising for AC should have a moderate afnity to a working uid
lying between these limits. For the strongest adsorbent, the minimal regeneration temperature is determined as Tmin 102  C, and
56  C for the weakest one, regardless of the nature of adsorbate
(Table 3). These upper and lower boundary adsorbents are quite
different, and all others adsorbents suitable for AC should lie between these two. Similar analysis can be done for heat pumping
and deep freezing.

Fig. 1. Common Clapeyron diagram of 3T AHT cycle (left) and the same cycle presented in the w vs. DF co-ordinates (right).

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Y. Aristov / Applied Thermal Engineering xxx (2014) 1e10

Table 1
DFmin-value for the reference ACH cycles.
Cycle

AC1
AC2
HP1
HP2
DF1
DF2

Te,  C

15
5
5
15
18
50

Table 3
Minimal desorption temperature Tmin and the Carnot efciency COPCarnot. The latter
is calculated for the reference cycles assuming that Tg Tmin 20 K.

DFmin, kJ/mol

Tc,  C

35e50
35e50
35e55
35e55
35e50
35e50

H2O

CH3OH

NH3

3.05e5.30
4.76e7.10
4.76e7.85
9.02e12.4
9.73e12.3
18.6e21.6

2.66e4.64
4.15e6.21
4.15e6.90
7.53e10.4
8.09e10.3
15.2e17.8

1.58e2.78
2.46e3.70
2.46e4.10
4.43e6.20
4.74e6.12
8.90e10.5

Table 1 and Fig. 2 show that various ACH applications need quite
different adsorbents. AC2 asks for a moderate afnity and requires
adsorbents very similar to HP1. The same is true for HP2 and DF1
but at higher afnity level than for AC. Adsorbents for DF2 application require much greater afnity than those for the other applications. AC1, 2 and HP1 are the most commonly used ACH
applications. They require an adsorbent with afnity to water,
methanol and ammonia that should be in the range 3.0e7.9,
2.6e6.9, 1.5e4.1 kJ/mol, respectively (see Table 1).
3. Concept of the optimum adsorbent
Here we analyse which adsorbent is optimum for a particular
ACH cycle. The answer evidently depends on how one evaluates the
cycle efciency.
3.1. The rst law efciency
For an ideal 3T cycle (with zero thermal masses) the energy
balance is given as

Qc eQe eQd Qa 0

(4)

Cycle

Te,  C

Tc,  C

Tmin,  C

COPCarnot

AC 1
AC 2
HP 1
HP 2
DF 1
DF 2

15
5
5
15
18
50

35e50
35e50
35e55
35e55
35e50
35e50

56e89
68e102
68e112
95e144
99e136
152e195

1.73e1.28
1.37e1.12
2.37e2.06
2.07e1.92
1.04e0.93
e

Dw, the rst law efciency attains the maximum value (Qe/Qd) for
single effect AC cycles and is no longer dependant on Dw. Hence,
to achieve the maximum rst law efciency it is sufcient to use an
adsorbent that exchanges the mentioned amount of a working uid
(or more) between the rich and weak isosters. Such an adsorbent
may be considered as harmonized with a particular cycle. Well
enough adsorbents of water, methanol and ammonia adequately
satisfy this condition for AC1, 2 and HP1 cycles.
It is important to highlight that:
a) searching for adsorbents with very large Dw values (>0.5 g/g) is
the ultimate priority for heat storage rather than for cooling/
heating;
b) for any cooling application, the efciency increases at lower
heats of desorption. E.g. for small-pore aluminophosphates the
heat of water desorption is Qd 55e60 kJ/mol [15,16], therefore,
the cooling COPc can not exceed 0.65e0.75. For silica gels, that
have lower afnity for water vapour, the COPc can reach z0.9;
c) the maximum COPc (0.7e0.9) for single effect AC cycles, is
signicantly lower than predicted for a reversible Carnot cycle
with the same boundary temperatures [17] (Table 3 and Section
3.2).

(see denition of heats on Fig. 1a). The rst law efciency or the
Coefcient Of Performance (COP) is then dened as

3.2. The second law efciency

COPid
c Qe =Qd
COPid
h Qc Qa =Qd 1 COPc

For an ideal 3T system, the energy balance (the rst law) of Eq.
(4) should be supplemented with the entropy balance (the second
law) and given as;

(5)

for cooling and heating, respectively. For real systems, heating of

inert masses is also important, and the COP-value is also dependent
on the adsorbate mass Dw exchanged in the cycle


eQc = Qe = e Qd g eQa = a DS  0:




COPc Dw Qe Dw Qd Dw C Tg  Tc
6

COPid
c Dw=Dw B;

(6)

AC 1

AC 2

Methanol

HP 1

where B C(TgTc)/Qd which is the ratio of the sensible heat of all

inert masses to the latent heat necessary for desorption. To increase
the
rst
law
efciency,
the
exchanged
mass
Dw wmaxwmin w(DFmin)w(DFmax) must be maximized.
For well-designed ACH units, the COP approaches its maximum
value (Qe/Qd) already at Dw  (0.1e0.15) g/g and (0.2e0.3) g/g for
exchange of water and methanol (ammonia), respectively. At larger

(7)

HP 2
DF 2

DF 1

Table 2
DFmax-value for the reference boundary conditions and selected values of Tg.
Tc,  C

35

Tg ,  C

60

80

100

60

80

100

Water
Methanol
Ammonia

3.50
3.05
1.85

6.25
5.50
3.35

8.90
7.90
4.83

1.32
1.15
0.71

3.95
3.45
2.12

6.47
5.75
3.55

50

10

15

20

Free adsorption energy, kJ/mol

Fig. 2. Classication of methanol adsorbents: the afnity at adsorption stage for

various ACH applications.

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Y. Aristov / Applied Thermal Engineering xxx (2014) 1e10

If all the processes are completely reversible, the entropy generation is equal to zero (DS 0), and the Carnot COP can be
calculated for cooling and heating [13,18]


 
COPCarnot
1=Tc e1 Tg =1=Te e1=Tc ;
c

(8)


 
COPCarnot
1=Te e1 Tg =1=Te e1=Tc :
h

(9)

If the heat for regeneration is supplied directly at the minimal

desorption temperature (Tg Tmin), no entropy is generated. As a
result, the COP-values calculated from the rst and second laws are
equal, so that the maximum (Carnot) efciency is reached [19]. This
imposes an appropriate requirement on the shape of the sorption
isobar for an optimum adsorbent: the rich and weak isosters must
coincide, so that the cycle becomes degenerated, and the isobaric
adsorption 4e1 and desorption 2e3 (Fig. 1a) occur immediately and
completely at the temperatures Tc and Tg (Fig. 3a), respectively [11].
The degenerated cycle can be realized only with an adsorbent
characterized by a mono-variant equilibrium. The adsorbent has to
sorb a large amount of adsorbate in a stepwise manner directly at Tc
and Pe and completely desorb it at Tg and Pc (Fig. 3b). Hence, in
theory, the adsorbent optimum for ACH should have a step-wise
adsorption isobar. Real adsorbents, however, display S-shaped
adsorption isobars (Fig. 3c) instead of strictly step-wise ones. Such
adsorption equilibrium corresponds to isotherms of types V and VI
in the IUPAC classication. The second law harmonization of the
adsorbent and the cycle means that the position of the step must
coincide with the boundary temperatures Tc T4 at P Pe and
T2 Tg at P Pc as shown in Fig. 3b).
If the adsorbent is not optimal so that the adsorbate is removed
at Tg > Tmin, the efciency becomes lower than the Carnot efciency
due to the thermal entropy production caused by the external
thermal coupling DT TgTmin [17]. The Carnot values calculated
for the reference cycles at a moderate coupling of 20 K are displayed
in Table 3. A key difference is found for AC1 at the boundary con C,
 C,
 C):
ditions
(Te,
Tc,
Tg)

(15
35
76
COPCarnotCOPc 1.73e0.90 0.83. This difference rapidly increases at larger DT therefore to enhance the second law efciency
the thermal coupling should be minimized. This suggests that a
high second law efciency may be attained by a proper choice of
adsorbent without using efcient, but sophisticated methods of
heat recovery in multi-bed [20] and thermal wave [21] systems, or
multi-effect cycles in which waste heat from an upper cycle is
used to drive a lower cycle [2,13].

3.3. The dynamic efciency

As opposed to the thermodynamic efciencies considered
above, the adsorbent dynamic efciency depends less on adsorbent
inherent properties and more on a number of external factors [8].
Among these are the design of the adsorber e heat exchanger,
efciency of heat supply/rejection, pressure and temperature
levels, etc. The nal aim of the dynamic analysis is to maximize the
specic ACH power which can be dened for cooling as

SCP Qe =m t;

Fig. 3. Degenerated AHT cycle characterized by a single ad-/desorption isoster (a);

corresponding step-like (b, d) and S-shaped (c) isobars of adsorption (at P Pe) and
desorption (at P Pc) optimum from the thermodynamic (b, c) and dynamic (d) points
of view [8,61].

(10)

where m is the adsorbent mass and t is the cycle time.

A Large Temperature Jump (LTJ) method appears to be very
useful for making the dynamic analysis. Its Volumetric version (VLTJ) was suggested to study ad/desorption dynamics under conditions that are close to those at isobaric stages of ACH cycles [22]: ad/
desorption are initiated by a large drop/jump of temperature of HEx
wall that is in thermal contact with the adsorbent.

The dynamic analysis may be simplied if the adsorption rate is

controlled by the heat transfer between the adsorbent and the HEx
n. For loose grains conguration, it is a case for methanol and
ammonia adsorption [23] because it occurs at a relatively high
pressure of 0.1e10 bar. It is also often valid for water adsorption
[23]. Under the heat transfer control, the dynamic harmonization
means that the most advantageous adsorption isobar is step-like

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Y. Aristov / Applied Thermal Engineering xxx (2014) 1e10

with the largest possible DT between the step temperature and the
HEx n temperature (Fig. 3d).
Thus, step-like (sigmoid) adsorption isobars are advantageous
from both thermodynamic and dynamic points of view. The dynamic requirement to maximize the average temperature difference between the adsorbent and the n is in direct contradiction
with the thermodynamic requirement to minimize this difference
[11,17]. Thus, proper choice of the isobar step position greatly depends on which output parameter is to be maximized e COP or SCP.
If both parameters are important, a reasonable compromise must
be reached by intelligent design of Ad-HEx unit (see Section 7).

b) For zeolites with low (Si/Al) ratio, the afnity for water is very
high, and they reach maximum adsorption uptake (c.a.
0.25e0.35 g/g) at large DF-values (see the data for zeolites 13X
and 4A in Figs. 4 and 5). This high afnity is protable for gas
drying or deep freezing but not for AC and HP because of too
high temperature required for regeneration.
c) Post synthetic ion exchange presents another tool for tuning
zeolite sorption properties: e.g. a linear increase of the adsorbed
amount of water with the Mg ion exchange degree is found for
zeolite NaA (from 0.28 to 0.36 g/g) and NaX (from 0.34 to 0.41 g/
g) [29].

4. Screening of adsorbents developed for other applications

To reduce the afnity for water and better t with ACH demands, a zeolite DDZ-70 was developed by UOP. It is a high silica
content Y zeolite (Si/Al > 10) that is exchanged with cerium as
described in Ref. [30]. It is available as a ne powder, pellets and
paper-like foil glued to a HEx surface. This material adsorbs water at
lower DF-values (Fig. 5) and, thus, can be used for AC1, 2 and HP1.
The heat of water adsorption on DDZ-70 is 2335 J/g [30] which is
advantageous for adsorptive cooling.
Zeolites 4A, 13X and particularly DDZ-70 can thus be considered
as water adsorbents suitable for ACH [12,31]. The temperature lift
using classical zeolites can exceed 50e70  C. These materials could
be mainly interesting for deep freezing (Fig. 5) or double effect
ACH cycles rather than for single effect ones.

A vast number of new adsorbents with diverse structures and

properties are synthesized every year. A survey of the main classes
of adsorbents and their feasibility for ACH cycles can be found in
very recent reviews [24,25]. It has been concluded that among new
materials pure and substituted aluminophosphates and metalorganic frameworks can be considered as potentially interesting
for ACH application. In the following sections data relating to the
main adsorbent classes for ACH are analysed taking into account
their afnity to water in terms of the adsorption potential DF.
4.1. Preliminary selection
In Section 3 we considered which adsorbent is optimal for a
particular ACH cycle. The reported ndings on the boundary DFminvalues, minimal desorption temperature Tmin and optimal isobar
shape may signicantly simplify a practical selection of adsorbent
for a particular ACH cycle.
4.2. Silica gels
Silica gels were considered in detail in Ref. [24], and here we just
briey summarize their main features for ACH:
a) RD silica gels exchange just Dw 0.03e0.12 g/g within a typical
ACH cycle [9,24e26]: e.g. a Fuji silica RD exchanges 0.11 g/g and
0.07 g/g in typical AC1 and AC2 cycles, respectively (Fig. 4). Similar
Dw-values were reported for an RD silica gel Grace 127B [26]. This
results in large silica mass required and thus, big ACH units.
b) The temperature lift is typically low, 15e25  C, because the
majority of water is removed at 50e70  C.
c) Despite these obstacles, RD silica gels are the only adsorbents
currently used in large commercial adsorptive chillers [3,4].
Silica gel Grace 127B has been applied in a small commercial
adsorption chiller [27]. This is because the RD silica gels are
commercially available, stable and cheap. They can be regenerated with very low temperature heat (down to 45e50  C) [14].

4.4. Aluminophosphates
Pure and substituted aluminophosphates (APs) are found to be
promising for ACH applications because they have quite steep and
properly positioned adsorption isobars and relatively low desorption temperature (60e90  C) [15,16,24,26,29]. The main AP disadvantages are high heat of desorption (55e60 kJ/mol [15,16]) and
moderate pore volume (0.05e0.35 cm3/g) (both may restrict the
cooling COPc), possible ad/desorption hysteresis (see FAM-Z02 on
Fig. 6), and relatively high cost.
The Mitsubishi Chemical Ltd. developed three AP based adsorbents specialized for ACH, namely, FAM-Z01, Z02, and Z05 [16,32].
All are commercially available from the Mitsubishi Plastics Ltd. as
coated heat exchangers. They are likely to be used in small
adsorption chillers recently appeared in the market [5].

Other porous silicates e LD silica gels, aerogels, ordered mesoporous silicates (SBA, MCM, etc) e can not be used for ACH as they
adsorb water and methanol at P/Po too high (or DF too low) for ACH
applications [24].
4.3. Classical zeolites
Application of classical zeolites (aluminosilicates) for ACH can
be summarized as follows [24]:
a) Water adsorption properties of classical zeolites can be adjusted
by changing the framework composition; the Si/Al ratio [28]:
the lower the ratio of Si to Al, the more hydrophilic the zeolite
structure (e.g. type A).

Fig. 4. Characteristic curves for water sorption on zeolite 13, ads/des ( ) [74], SWS1L, ads/des ( ) [60]; FAM-Z02, ads (o); FAM-Z02, des (C) [32]; Fuji silica RD, ads/des
( ). The selected areas represent DFmin-windows for typical AC1 (1), (AC2/HP1) (2) and
HP2 (3) cycles.

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Y. Aristov / Applied Thermal Engineering xxx (2014) 1e10

MIL-100 (Fe, Al, Cr) [38,39], MIL-101 (Cr, Fe) [26,36], MIL-125 (Ti)
[40], UiO-65, and UiO-66 [40], etc.
The main advantages of MOFs are steep adsorption isobars and
large capacity, e.g. 0.8e1.2 g H2O/g for MIL-100 and MIL-101. MIL100 has larger afnity to water vapour probably because of its
smaller cages (2.5 nm) in comparison with those for MIL-101
(3.4 nm). Commonly, the afnity to water is hardly sufcient even
for the AC1 cycle. Therefore, chemical modication to enhance the
MOFs afnity to water is strictly necessary (see Section 5.3).
Other obstacles to using MOF's are signicant ad/desorption
hysteresis and low hydrothermal stability. E.g. HKUST-1 and DUT-4
are not enough stable towards water, however, MIL-100 (Fe) displays no reduction in adsorption capacity after 2000 ad/desorption
tests [38].
In general, the potential of MOFs for ACH has not been fully unveiled, and it is quite possible that a target-oriented modication/
screening of MOFs may reveal novel highly efcient working pairs.

1
2

Water uptake, g/g

0.3

3
0.2

0.1

0.0
0

10

15

20

25

Adsorption potential, kJ/mol

Fig. 5. Characteristic curves for water adsorption on zeolite NaX, ads/des ( ) [74], 4A,
ads/des ( ) [75], and DDZ70 ads/des ( ). DFmin-windows for AC1 - 1, AC2/HP1 e 2,
HP2/DF1 e 3, DF2 e 4.

Several other materials from this class (AlPO-5, AlPO-11, APOTric, AlPO-17, AlPO-18, etc.) have been evaluated with promising
results [15,26]. The APO-Tric material synthesized in a uoride
containing medium was discussed in Ref. [15] for use in solar energy storage. It exchanges z0.25 g H2O/g in an extremely narrow
range of the relative pressure P/Po 0.12-0.15 or DF 4.93e5.51 kJ/
mol (Fig. 6) that makes this material challenging for AC2/HP1. Only
a small reduction in its adsorption capacity was detected after 50
ad/desorption cycles. The preparation method of APO-Tric shows
the importance of the uoride route for AP synthesis. It was
assumed that the frameworks containing double-six or double-four
rings would provide steep isobars because Al in this case can readily
change its coordination between 4 and 6 [15,33].
Further progress may be expected if new AP, including zinc, iron
or nickel phosphates, will be tested for ACH eld.
4.5. Metal-organic frameworks
Metal organic frameworks (MOFs) present a new family of
supra-molecular materials potentially interesting for ACH [34,35].
Many MOFs exhibit S-shaped isotherms of water sorption that are
true for ACH: DUT-4, HKUST-1 (Cu-BTC) [36], MIL-53(Cr) [37],

Water uptake, g/g

0.3

1
2

0.2

0.1

0.0

10

12

Adsorption potential, kJ/mol

Fig. 6. Characteristic curves for water sorption on FAM-Z02, ads(O)/des(C) [32]; APOTric, ads ( ) [15]; AlPO-18, ads( ) [15], FAM-Z01, ads( )/des( ) [32]; FAM-Z05, ads( )
[32]. DFmin e windows for AC1 e 1, (AC2/HP1) e 2.

4.6. Porous carbons

Many Activated Carbons (ACs) were suggested and analysed as
adsorbents of methanol and ammonia in ACH systems [12,41e43]
among which the most tested was AC-35 [44]. The inuence of
the carbons physical characteristics on the ACH performance was
theoretically studied in Ref. [41]. The authors showed that, for given
cycle boundary temperatures, there is an AC optimal to obtain the
best cycle performance.
A comprehensive thermophysical characterisation of 6 commercial ACs with particular focus on ACH applications was reported
in Ref. [43]. The typical methanol exchange was 0.25 g/g, whereas
the maximal one reaches 0.38 g/g, the latter corresponds to a
specic cooling enthalpy of 244 kJ/kg. Much larger exchange was
found for Tsurumi activated charcoal (0.39 g/g) and AC Maxsorb III
(0.65 g/g) at Tg 90  C [45]. The authors of [42] analysed the
performance of 26 ACeammonia pairs under typical conditions of
three ACH cycles: Te 5  C and Tc 35  C (ice making); Te 10  C
and Tc 35  C (between AC1 and 2); and Te 5  C and Tc 40  C
(HP1). These AC absorbents were mainly coconut shell and coal
based types in various shapes and sizes (monolithic, granular,
compacted granular, bre, compacted bre, cloth, compacted cloth
and powder). Quite good performance was found at Tg 200  C.
Thus, ACs are available and relatively cheap. Since ACs are microporous and have large afnity to methanol and ammonia, a high
regeneration temperature is necessary.
High attraction for ACH has Activated Carbon Fibres (ACFs). An
ACF Busot, pure and impregnated with metal chlorides, was rst
applied for ACH in Refs. [46,47]. After this, various pure ACFs were
comprehensively tested for ACH cycles as adsorbents of methanol
[48,49] and ethanol [50]. Numerous experiments and results on the
application of ACFs in ACH are summarized in Ref. [51]. The ACF type
A-20 was concluded to be the best adsorbent due to its large surface
area and pore volume. Practical shortcomings due to the low density
and thermal conductivity of ACFs are also addressed [51].
On the whole, because of the huge variety of porous carbons and
their excellent adsorption characteristics these adsorbents of
methanol, ethanol and ammonia remain very attractive for ACH
applications driven by heat with a temperature potential higher
than 100e150  C.
5. Nanotailoring and intent modifying
5.1. Substituted aluminophosphates
Efcient tuning of the AP pore structure and adsorption properties can be made by isomorphous substitution of various metals

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Y. Aristov / Applied Thermal Engineering xxx (2014) 1e10

into the AP framework [52]. The most famous family of substituted

APs is presented by SAPO materials (Si inserted instead of P): e.g.
FAM-Z02 is a kind of SAPO-34. FAM-Z01 and -Z05 also belong to
substituted aluminophosphates (FAPO-5 and FAPO-34) with Fe
instead of Al and P. Despite expectation that displacement of
substituting cations from the framework sites may result in the
structural degradation in ad/desorption cycles, both FAM-Z01 and
Z02 have high durability of 200,000 and 60,000 cycles, respectively
[32].
The substitution approach still has great potential as the
isotherm shape is very sensitive to such substitution. The shape was
shown to be controlled mainly by the amount of the substituted
metal rather than the type of the metal, as revealed for MAPO-5,
MAPO-11 and APO-31 [52]. Applying isomorphous substitution
for synthesizing novel MAPOs which have S-shaped isotherms of
methanol and ammonia sorption could be important for ACH applications. Another important progress may be by increasing the
total micropore volume of both pure and substituted APs.
5.2. Modied MOFs
Chemical modication aiming to enhance MOFs afnity to water
can be performed by changing MOF structural components such as
organic ligands, metal cations, and counter anions.
The adsorption of water vapour on three MIL-100s with Cr3,
Fe3 and Al3 as metal cations was studied in Refs. [38,39]. All the
materials displayed equal adsorption increases at P/Po < 0.20-0.25
(up to 0.15 g/g) that is due to water adsorption on the active metal
sites. Two adsorption steps are then observed, caused by consecutive capillary condensation in the mesoporous cages of 2.5 nm and
2.9 nm. The step positions for all the adsorbents are only slightly
shifted, however signicant difference in the nal water uptake
was observed between MIL-100(Al) (0.65 g/g) and MIL-100(Cr or
Fe) (0.8e0.9 g/g).
Three MIL-100(Cr) adsorbents are synthesized using different
types of counter anions (F, Cl, SO2
4 ) for better adaptation to ACH
cycles [38]. Indeed, the pressure of water adsorption was found to
depend on the anion nature: for SO2
4 both adsorption steps moved
to lower P/Po-values, while for (Cl) shifted to higher P/Po. The
authors assumed that this can be attributed to appropriate variation in the hydration energy of these counter anions.
Finally, the effect of the functional group in the organic ligand of
MIL-101(Cr) on water adsorption was evaluated by varying
different substituents (eH, eNO2, eNH2, eSO3H) [53,54]. The isotherms of MIL-101-NH2 and MIL-101-SO3H moved to lower P/Po as
compared to that of common MIL-101 due to a high hydrophilicity
of these functional groups. The step position for MIL-101-NO2 was
almost the same as for MIL-101. The amino-modied UiO-66 and
MIL-125 exhibit very promising water adsorption isotherms: e.g.
for NH2-MIL-125 a steep uptake rise was observed at 0.1 < P/
P0 < 0.2 [40].
Thus, the MOF adsorption properties can be intentionally tuned
by changing organic ligands, metal cations, and counter anions.
These can lead to the development of new MOFs adapted for ACH
cycles.

in ventilation systems [58], CO2 abatement [59], and adsorptive

cooling/heating [60].
The current state of the art and new trends in developing efcient CSPMs for various ACH cycles are surveyed in Ref. [61]. Several
CSPMs have been tested for ACH and demonstrated promising
performance, especially at low regeneration temperatures
(70e90  C) [29,61]. E.g., a composite sorbent of methanol LiCl/silica
exchanges 0.6 g/g within a temperature range of just 2e3  C [62].
New trends in developing and studying CSPMs such as using of
mono-sized host matrices [63], binary salt systems [64] and modern physical methods [65] are considered in Ref. [61].
Comprehensive CSPM examination has revealed many potential
obstacles that could impede the introduction of these composites
in practice. The most worrying could be a leakage of the salt solution formed during sorption from the matrix pores, which can
cause corrosion of metal parts of the ACH unit and emission of noncondensable gas. Several ways to avoid or at least to reduce this risk
are considered in Ref. [61]:
a) proper selection of the salt content in the CSPM;
b) an anchoring the salt cations to the matrix surface;
c) covering the external surface of the CSPM grains with a hydrophobic coating.
Solution leakage can also be avoided by proper organization of
the ACH hardware, i.e. the amount of adsorptive in an evaporator
should be restricted in such a way that the outow is not possible
even if the whole of uid from the evaporator is sorbed on CSPM.
To summarise, despite the signicant progress in CSPMs synthesis and application in various ACH cycles, there is still much
scope for further optimization and development of CSPMs with
pre-requested properties.
6. Database of promising adsorbents for ACH
Developing a database of adsorbents that are promising for ACH
is very timely [66]. This database would play an important role in
the unication and comparison of adsorbent properties, theoretical
analysis and modelling of ACH cycle performance. The ACH performance essentially depends on both thermodynamic and dynamic
properties of the working pair adsorptive e adsorbent. Thus,
every property that is essential for analysing or modelling ACH
cycles has to be tabulated in the database. The principles of creating
such a database, the adsorbent properties which should be
collected therein and a tentative list of adsorbents to be included
were discussed in Ref. [66].
7. Conformity of the optimum adsorbent with the ACH unit/
cycle
The adsorbent is an important part of any ACH unit, which has to
be in harmony with all other components, the cycle boundary
conditions, and the cycle management strategy. This would greatly
assist in implementation of advantages that the optimum adsorbent promises.

5.3. Composites salt in porous matrix

7.1. Conformity with the heat exchanger
Two-component composites salt in porous matrix (CSPMs)
offer wide opportunities for nanotailoring their sorption properties
by varying the salt chemical nature and content, porous structure of
the host matrix and synthesis conditions [55]. CSPMs have been
tested for various applications, such as gas drying [56], extraction of
water from the atmosphere [57], regeneration of heat and moisture

For Ad-HEx harmonization one has to understand:

- What is the optimum adsorbent mass per 1 m2 of a HEx?
- What are the optimum size of adsorbent grains and the bed
thickness?

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Y. Aristov / Applied Thermal Engineering xxx (2014) 1e10

0.006

a) 6.5

0.005

5.5

0.004

4.4

0.003

3.3

0.002

2.2

0.4

0.001

1.1

0.2

0.0
3.5

0.0

0.000
0.0

0.5

1.0

1.5

2.0

2.5

3.0

S/m, m /kg

b)

1.0
0.8
0.6

W0, kW/kg

R0, kg/(kg s)

200

t, s

400

600

Fig. 7. Methanol adsorption on AC-35.4 [69]: a - the initial rate as function of the ratio S/m, D 0.8e0.9 ( ), 1.0e1.25 ( ), 1.6e1.8 (:), 2.5e2.8 ( ), and 4.0e4.1 ( ) mm; b e kinetic
curves at (S/m) 1.56 m2/kg and the grain size 0.8e0.9 ( ) and 1.6e1.8 ( ).

The dynamic study of water, methanol and ammonia adsorption

on loose grains of various adsorbents has revealed that commonly
the sorption rate is proportional to the ratio (S/m) of the area of heat
transfer surface S between the adsorbent bed and the HEx ns to
the adsorbent mass m (Fig. 7a)) [23,67,68]. Surprisingly that the
methanol adsorption dynamics is the same for 1 layer of
1.6e1.8 mm carbon grains, and 2 layers of 0.8e0.9 mm grains
(Fig. 7b)). For all these congurations S/m const 1.56 m2/kg. For
practice, it means that it is not strictly necessary to precisely select
the adsorbent grain size, however, it must guarantee the grain size
insensitive regime. The latter was also revealed by mathematical
modelling of AC performance with zeolite 13X [69] and SWS-1L
[70] as water sorbents.
Hence, to maximize the SCP it is necessary to use Ad-Hexs with
high S/m ratios. This ratio is naturally limited from the upper side as
the thermal mass of the metal should not be too large with respect
to that of the adsorbent. The optimal S/m ratio is expected to be
between 2 and 5 m2/kg which gives an estimation of the optimum
adsorbent mass.
7.2. Conformity with the cycle boundary temperatures
As demonstrated in 3.2 and 3.3, it is thermodynamically profitable to supply heat right at the minimal desorption temperature
(Tg T2), whereas good dynamics asks for maximizing the difference (Tg e T2). Reasonable compromise is possible if one properly
chooses a shape of the adsorption isobar which affects the cycleaveraged temperature difference DTav between the adsorbent and
the HEx n [71]. Possible power enhancement due to optimizing
the isobar shape may reach 1.5e3.5 times that offers essential dynamics improvement [23]. For a well-designed Ad-HEx (e.g. with S/
m 4 m2/kg), the DTav-value of 2e3  C results in the cycle-averaged
power Wav ADTav (S/m) 0.8e1.2 kW/kg. This is much larger than
for common ACH units which use loose adsorbent grains
(0.1e0.4 kW/kg), thus giving a decent compromise option.
7.3. Conformity with the durations of the cycle isobaric stages
Proper cycle management strategy may also help in realizing
advantages which the optimum adsorbent offers. Results obtained
by the LTJ method have suggested that the equal duration of
adsorption and desorption phases is hardly an optimal case, and
proper reallocation is necessary to allow more time for adsorption
at the expense of desorption time reducing [72e74]. This reallocation realized in a single bed adsorption chiller [73] conrmed
that the optimum desorption duration should indeed be 1.5e2.5

times shorter that the adsorption one. For the optimum ratio
f tads/tdes, both the COP and the cooling power may signicantly
increase as compared with the common case tdes tads.
8. Conclusions
New materials are a prerequisite for major breakthrough applications inuencing our daily life, and therefore new efcient
adsorbents are pivotal for the adsorption heat transformation.
Despite signicant progress achieved, more R&D is still necessary
to push the ACH technology to be competitive with the current
state of the art.
In this review, we have considered the role of adsorbents in
adsorptive cooling/heating (ACH) and analysed which adsorbents
are optimal for specic ACH cycles. The conclusions are formulated
in terms of the optimum isobar shape, the Dubinin adsorption
potential being used as a universal measure of the afnity between
the adsorbent and the adsorptive. Two complementary lines to
select the optimum adsorbent are considered: a) testing of adsorbents initially developed for applications different from ACH, and b)
tailoring of new adsorbents adapted to a variety of ACH cycles.
An overview of original and collected data on several classes of
materials which are potentially promising for ACH application,
namely, silica gels, classical zeolites, aluminophosphates, metalorganic frameworks, porous carbons and composites salt in
porous matrix, is presented.
We briey consider several issues of harmonizing the optimal
adsorbent with other components of ACH unit, the cycle boundary
conditions, and the cycle management strategy. Recommendations
on how to choose the HEx design, the size of adsorbent grains, bed
thickness and so on are made. Although the above examples
concern adsorbents of water, methanol and ammonia this approach
can be also applied for sorbents of hydrogen [75], ethanol [76],
carbon dioxide [77], etc.
We hope that this review will provide a new impetus to targetoriented research on the novel adsorbents for AHT and may also
prove benecial for further consolidating international activities in
materials science and heat transformation applications.
Acknowledgements
The author thanks Drs. I.S. Glaznev, L.G. Gordeeva, M.M. Tokarev,
J.V. Veselovskaya, A. Freni, A.D. Grekova and Mr. I.S. Girnik for their
experimental contributions, Dr. B.N. Okunev for modelling of
coupled heat and mass transfer, Profs. L.I. Heifets, F. Meunier, L.
Bonaccorsi and R. Critoph for useful discussions, the Russian

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Y. Aristov / Applied Thermal Engineering xxx (2014) 1e10

Foundation for Basic Researches (grant 14-08-01186) and the Siberian Branch of the Russian Academy of Sciences (grants 120/2012
and 9/SB RAS-NASU) for partial nancial support.
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http://dx.doi.org/10.1016/j.applthermaleng.2014.04.077

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Please cite this article in press as: Y. Aristov, Concept of adsorbent optimal for adsorptive cooling/heating, Applied Thermal Engineering (2014),
http://dx.doi.org/10.1016/j.applthermaleng.2014.04.077