Accepted Manuscript

Adsorptive heat storage and amplification: new cycles and adsorbents

L.G. Gordeeva, Yu.I. Aristov

PII: S0360-5442(18)32128-5

DOI: 10.1016/j.energy.2018.10.132

Reference: EGY 14029

To appear in: Energy

Received Date: 14 July 2018

Accepted Date: 22 October 2018

Please cite this article as: L.G. Gordeeva, Yu.I. Aristov, Adsorptive heat storage and amplification:
new cycles and adsorbents, Energy (2018), doi: 10.1016/j.energy.2018.10.132

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 ACCEPTED MANUSCRIPT
ADSORPTIVE HEAT STORAGE AND AMPLIFICATION:
NEW CYCLES AND ADSORBENTS

L.G. Gordeeva1, 2*, Yu.I. Aristov1, 2

1 Boreskov Institute of Catalysis, Novosibirsk, Russia
2 Novosibirsk State University, Novosibirsk, Russia
* Corresponding author, e-mail: Gordeeva@catalysis.ru

Abstract. The increasing demands for cooling/heating, depletion of fossil fuels, and
greenhouse gases emissions promote the development of adsorption heat transformation and storage
(AHTS). This emerging technology is especially promising for converting low-temperature heat, like
environmental, solar, and waste heat. Among the known AHTS applications (cooling, heat pumping,
amplification, and storage), the adsorption heat storage and amplification are less developed, thus
gaining an increasing attention of the scientific community. The researchers are mainly focused on
the developing new cycles for heat storage/amplification and advanced adsorbents specialized for
these cycles. In this paper, we review the state-of-the-art in the fields of adsorption heat
storage/amplification. The new, recently suggested, cycles (e.g. a "Heat from Cold" cycle for
upgrading the ambient heat) will be described and analyzed from both thermodynamic and dynamic
points of view. New adsorbents developed for adsorption heat storage/amplification will be presented.
Special attention will be paid to the problem how to harmonize the adsorbent with the AHTS cycle
under various climatic conditions. The lab-scale units constructed for verification of the cycle
feasibility and adsorbent efficiency also are briefly described and analyzed. Finally, the problems and
outlooks of adsorption heat storage/amplification will be discussed.

KEYWORDS: Adsorptive heat storage, upgrading the heat temperature, cycle dynamics, cycle
thermodynamics, adsorbents, target-oriented design

CONTENTS
1. Introduction
2. Principles
2.1. Adsorptive heat amplification
2.2. Adsorptive heat storage

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3. Pressure- and temperature-driven cycles for adsorptive transformation of low temperature
heat
3.1. The cycles description
3.2. Thermodynamic considerations
3.3. Dynamic considerations
3.4. Summary
4. New adsorbents
4.1. Intent designing
4.2. Promising materials
4.2.1. AHA
4.2.2. AHS
5. Conclussions

1. INTRODUCTION
According to [1], global energy needs will rise by 30% between today and 2040, the equivalent of
adding another China and India to today’s global demand. Owing to growing living standards
heating and cooling (H/C) have become one of the biggest energy sectors, and it is forecasted to
remain so. The H/C consume nearly half of global final energy demand – more than either
electricity or transport [2]. Although the H/C sector is moving to clean low carbon energy, 75% of
the fuel it uses still comes from fossil fuels (nearly half from gas) [3]. However, according to the
Sustainable Development Scenario [1], low-carbon sources double their share in the energy mix to
40% in 2040.
Renewable H/C technologies have been recently compared to “sleeping giants”, because
demand for such services is substantial, yet historically renewable energy policies have been
focused primarily on renewable electricity or transport, thereby missing an opportunity to target the
largest energy demand sector [2]. The main barriers for the use of renewable heat sources for H/C
are: (i) low temperature potential of the available heat, which is not sufficient for direct heating of
dwellings, (ii) temporal and geographic mismatch between the periods of the generation of and
demands for the energy, (iii) cost and difficulty of evaluating the suitability of individual
installation sites.
Adsorption heat transformation and storage (AHTS) is gaining more and more attention in
the scientific community as an emerging technology, which makes it possible to surmount these
barriers and to effectively utilize low-temperature renewable heat sources for H/C. The working
principle of AHTS is based on the reversible exothermal adsorption (heat generation/rejection) and

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endothermic desorption (heat absorption/storage) processes. There are four basic AHTS
applications, namely the cooling, heating (or heat pumping), heat storage (AHS) and amplification
(AHA). The adsorption cooling and heat pumping have attracted a lot of researches during last
decades. A number of pilot units have been investigated for refrigeration and air conditioning [4, 5,
6], ice-making [7], desiccant cooling [8, 9], portable climate control [10], tri-generation systems for
combined cooling, heating and power supply [11, 12] etc. and nowadays several chillers and heat
pumps are commercially available [13]. On the contrary, to the best of our knowledge AHA and
AHS are still being at the laboratory or pilot research scale. Here we discuss the state-of-the-art in
the fields of adsorption heat storage/ amplification. The main challenges and advances are
considered with a special focus on novel cycles, advanced adsorbent materials prepared for these
cycles and lab-scale verification of their feasibility.

2. PRINCIPLES
2.1. Adsorptive heat amplification
The idea of utilization of the reverse absorption heat pump for upgrading the temperature level of a
heat source was suggested about 100 years ago [14, 15] and latter was adapted for adsorption
systems [16].A simplest three temperature (3T) AHTS unit exchanges heat between three thermostats
at high (ТH), middle (ТM) and low (ТL) temperatures and transforms heat at four modes: (1) cooling,
(2) heating, (3) upgrading the temperature potential, and (4) storage. In AHA cycle during desorption
stage (adsorbent regeneration) the heat is consumed at middle temperature TM from the external heat
source, which is used to drive the cycle (Fig. 1 a). That forces the vapor to desorb from the adsorbent,
and to collect in the condenser. The condensation heat is dissipated to the ambient, which is used as
heat sink at low temperature TL. Then the adsorption stage is carried out, during which the heat is
released at high temperature TH and transferred to a consumer (Fig. 1 b). The evaporation heat is
consumed from the driving heat source at temperature TM. Thus, the heat of the source at middle
temperature is partially upgraded to higher temperature level suitable for heating, by means of
rejecting the remaining fraction to a lower temperature level (Fig. 1) [16].

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Fig. 1. The principle scheme of AHA cycle: (a) adsorption/heat release stage; (b)
desorption/adsorbent regeneration stage.

The research efforts in the field are focused on the development of advanced adsorption
cycles to increase the efficiency and temperature lift. The most part of the researches analyse the
utilization of industry waste heat at TM = 80-150o C as heat source to produce useful heat at TH =
150-250oC, which can be returned to the industry process that enhances its efficiency [16, 17].

Recently a novel cycle for amplification of the ambient heat, the so called "Heat from Cold"
or HeCol, has been suggested in [18]. In the HeCol cycle the heat of natural water basin or domestic
waste heat at temperature TM = 2-20C is used as a heat source and the ambient air with ultra-low
temperature TL= -40  -20C is used as a heat sink to produce the useful heat at TH = 35-50C.

2.2. Adsorptive heat storage

AHS cycle includes two stages, namely the heat storage (charging), and the heat release
(discharging), which contrary to common adsorption heat transformation cycles are separated in time
[19]. During warm period the exceess heat to be stored is used to carry out endothermic desorption of
the working fluid from an adsorbent. The desorbed vapor is condensed and the heat is dissipated to
the ambient. On the heating demand, during cold period the stored energy is released when the
exothermic adsorption occurs. A heat source for evaporation is also needed to carry out the
adsorption stage.
The operating conditions of the AHS are determined by 4 temperatures (4T cycle): the
desorption temperature TH of the stored heat, and the condensation temperature equal to the ambient
temperature TM where the condensation heat is dissipated during the heat storage stage, the
adsorption temperature equal to the temperature Tuh of useful heat needed to a consumer, and the
evaporation temperature equal to the temperature TL of the heat source needed for evaporation (or the
ambient temperature during the heat release stage) (Fig. 2). It is worth noting, that during the storage
period (3-4*) the adsorber is cooled down to the temperature TUH, or below, therefor, for AHS the
combine cycle with isobaric desorption stage (2-3) and isothermal adsorption stage (4*-1) is more
appropriarte, instead of common isobaric adsorption cooling (heating) cycle (1-2-3-4) (see details in
section 3.1).
Among four ways suggested for thermal energy storage, namely as sensible, latent, sorption and
chemical heat [20], AHS offers the important benefits: 1) larger Heat Storage Capacity (HSC); 2)
possibility to vary the temperature potential of released heat [21]; and 3) negligible heat losses during

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the storage phase [22]. However, contrary to the latent and, particularly, sensible heat storage, which are
presently in an advanced stage of development and has already been applied at large scale in solar
thermal plant applications [23, 24], the AHS technology is attracting an increasing research interest.
Further progress in AHA and AHS technologies can be related to two main factors: (i) the
development of new adsorbents, whose properties are adapted for the specific cycle, and (ii)
optimization of the cycles [19].

Fig. 2. 4T AHTS isobaric (1-2-3-4) and combined isobaric – isothermal (1-2-3-4*) cycles.

3. PRESSURE- AND TEMPERATURE-DRIVEN CYCLES FOR ADSORPTIVE

TRANSFORMATION OF LOW TEMPERATURE HEAT
Adsorptive cycles suggested for storage/amplification of low-temperature heat from various sources
(renewable heat, thermal wastes, geothermal heat, etc), can be also classified according to the way
of the desorption initiation, namely, as temperature-initiated and pressure-initiated cycles. This
Section addresses a preliminary analysis and comparison of these cycles from both thermodynamic
and dynamic points of view.

3.1. The cycles description

These two types of AHTS cycles can essentially differ by the way of adsorbent regeneration: (i)
adsorbent heating up to the temperature sufficient for the adsorbate removal (temperature- initiated,
TI cycles, Fig. 3a), (ii) reducing the adsorptive pressure over the adsorbent (pressure-initiated, PI
cycles, Fig. 3b). In a more wide sense, a single adsorption stage can also be either TI (cycle a in
Figs. 3 and 4) or PI (cycle b in Figs. 3 and 4).

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Fig. 3. P-T diagrams of various 3T AHTS cycles: a – TI cycle (cooling/heating), b – PI cycle (heat
amplification) [18]. Reprinted from Applied Thermal Engineering, Vol 124, Yuri I. Aristov.,
Adsorptive transformation of ambient heat: A new cycle, Pages 521-524, Copyright (2018), with
permission from Elsevier.

The TI cycles are very common and widely used to realize cooling and heating modes [25,
26]. The PI cycles are much less spread and suggested so far mainly for temperature upgrading
mode [16, 18]. In this work, we endeavor to make a preliminary comparison of the TI and PI cycles
from both thermodynamic and dynamic points of view. We take into account literature data which
are plentifully available for TI cycles and rarely accessible for PI cycles as well as our own
experimental data on the new HeCol cycle recently suggested for upgrading the ambient heat in [18]
and studied in [27, 28, 29, 30]. Moreover, combined TI/PI cycles which have both TI and PI stages
(Fig. 4) are also briefly considered. For instance, cycle a (route 12341 in Fig. 3)
represents a non-isothermal HeCol cycle for heat amplification [27-29]. It can also operate as an
adsorptive cycle for short-term heat storage (route 14321), whereas cycle b can be applied
for long-term heat storage [31].

a b
Fig. 4. P-T diagrams of combined TI/PI AHTS cycles.

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3.2. Thermodynamic considerations

3.2.1. The first law efficiency. The first law efficiency of the two basic TI and PI cycles (a and b in
Fig. 3) depends only on the ratio of heats [25]. If neglect inert masses in the system, for cycle a, the
cooling and heating efficiencies are COPc = Qev/Qdes < 1 and COPh = (Qcon + Qads)/Qdes > 1,
respectively. The efficiency of heat amplification for cycle b is COPa = Qads/(Qev + Qdes)  0.5. For
the HeCol cycle, the latter value, however, has no practical meaning because the heats Qdes and Qev
are taken for free from an inexhaustible natural heat reservoir, such as river, lake, sea, at low
temperature TM = 0-20oC [18]. On the contrary, the useful heat Qads may have a commercial value
and be used for heating.
For basic 3T cycles a and b, accounting for the heat capacity of inert masses reduces the
above ultimate COPs. In this case, the first law efficiency also depends on the adsorbate mass ∆w
exchanged in the cycle

COPc(∆w) = Qev ∆w/[Qdes ∆w + C(TH – TM)] = COPcid [∆w/(∆w + B)], (1)

where B = C(TH – TM)/Qdes is the ratio of the sensible heat of all inert masses to the latent heat
necessary for desorption. Therefore, to increase the first law efficiency, the exchanged mass ∆w =
wmax - wmin has to be maximized [32], whereas the inert masses should be minimized [33]. For
“adsorbent – adsorbate” pairs the cooling COP approaches its maximum value (Qev/Qdes) already at
∆w  (0.1- 0.15) g/g and (0.2-0.3) g/g for the exchange of water and methanol (ammonia),
respectively [32, 34]. However for real Adsorber – HeatExchenger (AdHEx) units it should be
larger due to inert thermal mass of the HEx.
Much more important is the effect of inert masses on the efficiency of adsorptive cycles for
AHS (Fig. 4). For instance, for short-term (daily) AHS by using the working pair "AQSOA FAM-
Z01 – water" studied in [35], the sensible heat of the AdHEx unit (including Heat Transfer Fluid
HTF, tubes, fins and adsorbent) gives ca. 40% contribution to the useful heat transferred by the HTF
to a consumer. This heat has been accumulated in the inert masses during the heat storage phase
(123 in Fig. 4b or 432 in Fig. 4a). The major thermal masses are the HTF (water) (40%)
and the adsorbent itself (27%). The heat released directly in the adsorption process contributes only
60%. For long-term (seasonal) AHS, this sensible contribution is completely lost as the AHS unit is
cooled down to ambient temperature (isostere 21 in Fig. 4a or 34 in Fig. 4b). Moreover, in this
case, a part of the potentially useful adsorption heat is spent for sensible heating of inert masses
from ambient temperature Tam to TM, thus additionally reducing the net useful heat. This part
depends on the particular design of the AdHEx heat storage unit, the cycle boundary conditions and

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the HTF flow rate. Therefore, more attention should be paid to all these issues for optimization of
heat storage performance.

3.2.2. The second law efficiency. The second law analysis of a 3T adsorptive cycle (Fig. 3) is well
known and presented e.g. in [36, 37]. The Carnot efficiency COPC was calculated for cooling,
heating and temperature amplification modes as

COPCc = (1/TM – 1/TH) / (1/TL – 1/TM), (2)

COPCh = (1/TL – 1/TH) / (1/TL – 1/TM), (3)

COPCamp = (1/TL – 1/TM) / (1/TL – 1/TH). (4)

In fact, eqs. (2-4) give the limiting efficiencies which are fully determined by the three cycle
temperature and do not take into account the particular way of the cycle initiation (TI or PI).
It is well known from the previous broad experience, that the maximum COPc for real
adsorptive cycles initiated by a T-change is significantly lower than predicted for a reversible
Carnot cycle (eqs. (2-4)) with the same boundary temperatures [37, 38]. The main reason of this
distinction is the thermal entropy production caused by the external thermal coupling ∆T = TH – T2
(for desorption) and ∆T = T4 – TM (for adsorption), which is responsible for about 95% of the total
entropy production [37]. Here T2 and T4 are the initial desorption and adsorption temperatures (Fig.
3a). Indeed, the process of heat transfer during the adsorber heating (stages 1-2 and 2-3) and cooling
(3-4 and 4-1) is highly irreversible. The thermal entropy generated due to the thermal coupling at

desorption stage (2-3) can be calculated as STI = A ( 1

T  T1H )dq , where T is the internal temperature at

which the heat dq is effectively transferred during the desorption stage. If the whole desorption heat
is transferred at T = TH, no entropy is generated [32]. If the whole heat is transferred at T = T2, the
maximal entropy is generated SmaxTI = Qdes ( T12  T1H ) . The latter value can be estimated for the typical

TI cooling cycle (Tev = 10oC, Tcon = 30oC, TH = 90oC) with the working pair "carbon ACM-35.4 –
methanol" for which T2 = 56oC and QTI = ΔHdes Δw = (1.23 kJ/gmethanol) [0.21 gmethanol/gads] = 290
J/gads [39], thus, giving SmaxTI = 0.08 J/(Kgads). Similar entropy is generated in the adsorber during
the adsorption phase of the cycle. Much less entropy is generated during the isosteric stages of the
TI cycle (1-3 and 3-4 in Fig. 3a).
In ref. [30], the entropy balance was calculated at each stage of the pressure-initiated HeCol
cycle and in each converter element under conditions of an ideal heat transfer. The entropy is
generated in
a) the condenser, because the vapor temperature TM differs from the condenser temperature
TL;

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b) the evaporator, because the liquid adsorptive is moved from the condenser at TL and
heated irreversibly to TM;
c) the adsorber, because the vapor temperature TM differs from the adsorber temperature TH
as well as due to isosteric heating (1-2) and cooling (3-4) of the adsorbent;
d) the adsorber, due to vapor drop from P4 to P1 at desorption stage (4-1) and to vapor jump
from P2 to P3 at adsorption stage (2-3).
All these processes of entropy generation are inevitable due to the intrinsic irreversibility of
the system. Processes (a)-(c) that involve sensible heat are similar to those in a common 3T TI cycle
and lead to a similar entropy generation. Process (d) concerns the entropy produced in the adsorber
during ad-/desorption stages. This entropy is lower than for TI ad-/desorption, because both these PI
stages are isothermal, so that there is a zero thermal coupling. The isothermal vapor drop/jump is
irreversible, however, results in a small entropy generation in the adsorber, because the mass ∆wg of
gaseous adsorptive compressed/expanded during the pressure equalization is very low as compared
to the difference of adsorbate mass ∆w exchanged between isosteres (1-2) and (3-4) of the cycle
[30].
The entropy generated in the adsorber during the adsorbent regeneration, caused by the
pressure drop from P4 to P1, can be evaluated as follows: SPI = N R ln(P4/P1), where N is the
number of moles of gas in the system "adsorber – evaporator", and R is the universal gas constant.
For ideal gas, the N-value can be calculated as N = (P4 Vad) / (RT), where Vad is the adsorber "dead"
volume. The latter volume is minimized in well-designed adsorbers. Let's consider that the
adsorbent volume is 0.5 dm3 and the adsorber "dead" volume around the adsorbent is 2 dm3 = 210-3
m3. At P4 = 8.2 mbar = 820 Pa and T = 2C = 275 K, N = (870 Pa  210-3 m3)/(8.3 J/(molK)  275
K) = 810-4 mol of methanol. Then, SPI = NRln(P4/P1) = (810-4 mol)(8.3 J/(molK))0.56 = 0.036
J/K. To make a brief comparison of this value with that estimated above for TI desorption (0.01 –
0.1 J/(Kgads), it has to be related to the adsorbent (carbon ACM-35.4) mass that is mad  300 g.
Hence, SPI/mad = 0.00012 J/(Kgads) << STI/mad = 0.01 J/(Kgads). This confirms a small entropy
generation in the isothermal adsorption of a PI process.
As a result, the second law efficiency of PI HeCol cycles is expected to be higher as
compared to the common TI AHTS cycle and even close to the Carnot efficiency, if consider only
processes in the adsorber. For the common TI cycle, the Carnot efficiency in the adsorber can be
reached only, if the weak and rich isosters of the cycle coincide, i.e. for a mono-variant equilibrium
[40]. This encouraging thermodynamic finding may be extended to any AHTS cycle initiated by a
drop of the adsorptive pressure.

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3.3. Dynamic considerations

3.3.1. The effect of non-zero power. Strictly speaking, the above statement is true for quasi-
equilibrium PI cycles that are usually not a case in actual practice. Indeed, apart from the efficiency,
a high specific power is another target parameter which is important to develop compact AHTS
units. Since this power is exchanged between an adsorbent bed and a heat transfer fluid (HTF), a
certain temperature difference ΔT between them is necessary to reach a reasonable specific power
Wsp (in kW/(kg adsorbent)), according to the following heat balance equation

Wsp = U (S/m) T, (5)

where U is the heat transfer coefficient, S is the heat transfer surface area, and m is the adsorbent
mass. The minimal "obligatory" temperature difference can be briefly estimated as T = 10K, if
assume the typical values of Wsp = 1 kW/(kg ads), U = 100 W/(m2 K), and (S/m) = 1 m2/(kg ads)
[39]. This thermal coupling appears in real PI AHTS units and leads to appropriate entropy
generation and reduction of the actual second law efficiency below the high theoretical value
predicted above. However, the estimated coupling (10K) is still much smaller than the typical
external thermal coupling in TI cycles (30-50K). Moreover, the "obligatory" coupling for PI cycles
can be further reduced if utilize advanced heat exchangers with (S/m) = 2-4 m2/kg [41, 42, 43, 44,
45]. Thus, the above conclusion about the higher second law efficiency of PI cycles still remains
valid even for real non-equilibrium PI cycles with the average power of about 1 kW/kg that can be
promising for practical use.

a b

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Fig. 5. a - The experimental (––––) and theoretical (-----) lnP – (-1/T) diagrams of real HeCol cycle
as reported in [27]. Boundary temperatures TL/TM/TH = -20/20/28С, the HTF flux f = 1.1 L/min.
The CaClBr/SiO2 sorbent. b - the maximum outlet HTF temperature Tmax vs. the HTF rate f.
TL/TM/TH = -20/20/28C.  - LiCl/silica,  - CaClBr/silica [28]. Reprinted from Applied Energy,
Vol 211, M. M. Tokarev, L. G. Gordeeva, A. D. Grekova, Yuri I. Aristov., Adsorption cycle “heat
from cold” for upgrading the ambient heat: The testing a lab-scale prototype with the composite
sorbent CaClBr/silica, Pages 136-145, Copyright (2018), with permission from Elsevier (a).

For PI stages (4-1) and (2-3), which are theoretically isothermal (Fig. 4b), the mentioned
"obligatory" coupling T is caused by cooling/heating of the adsorbent bed due to the heat of
desorption/adsorption. Indeed, the desorption process starts at point 4 and is initiated by the
pressure drop from the initial desorption pressure P4 to the final pressure P1 = P0(TL) at constant
temperature TM. At t = 0, right after this pressure drop, the driving force for heat transfer equals
zero because the system is isothermal and there is no temperature gradient. At the same time, the
driving force for mass transfer is maximal because the pressure difference ΔP(t) = [Pgr(t) - PL]
between the vapor pressure inside (Pgr(t) ) and outside (PL) the grain/bed is maximal and equals
ΔP(0) = P4 – P1. This pressure gradient causes the diffusion of adsorptive, occupied the pores, out
of the grain. The pressure Pgr inside the grain reduces that, in its turn, initiates desorption of the
adsorbate from the grain surface. This process needs a heat consumption that leads to the grain
cooling which creates a temperature difference ΔT between the grain/bed and the external heat
source (HTF) at TM. As a result, the driving force for heat transfer appears so that the intensive
vapor flux causes appropriate heat flux [46] to generate the significant power Wsp (see eq. (5)). This
increases the first law efficiency. On the other hand, this induced thermal coupling can somewhat
reduce the second law efficiency as discussed above.
The predicted cooling of adsorbent bed during PI desorption was experimentally revealed in
[27] where a first lab-scale HeCol prototype loaded with the grains of CaClBr/SiO2 composite
sorbent in flat finned tube HEx was tested. A thermocouple located at the adsorber outlet detected
the HTF cooling by T  6 oC (Fig. 5a). Hence, the real process of PI methanol desorption occurs in
the non-isothermal mode, different from the theoretically assumed for the ideal HeCol cycle. The
deviation of the real cycle from the ideal one strongly depends on the HTF flux f [27-29]: the
cycles approach each other at f   (see Fig. 5b and the explanation right below).
The same was found for the methanol adsorption stage: a significant HTF heating (by 15-
20oC) was detected ((2-2') in Fig. 5a). For the HeCol cycle, it is the useful effect as the released heat
has the temperature potential sufficient for heating (e.g. in warm floor systems) and, hence, gains

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the commercial value [18, 27]. Fig. 5b shows that the maximum outlet HTF temperature gradually
approaches the set (equilibrium) temperature T2 = 28oC when the HTF flux increases [28].
3.3.2. Adsorbent optimal for TI and PI cycles from the dynamic point of view. Here we only briefly
survey the results of our previous analysis of adsorbents dynamically optimal for TI [47] and PI [48]
cycles. The main findings can be generalized as follows:
(i) the dynamically optimal (ideal) adsorbent should have a step-like adsorption
isotherm (for PI process)/isobar (for TI process) with the step positioned at the initial pressure (PI)/
temperature (TI) of appropriate isothermal (PI)/isobaric (TI) stage. For instance, for PI cycle in Fig.
3b, the step should be at P4 for desorption and at P2 for adsorption [48];
(ii) the adsorbent, which is the best for desorption stage, is the worst for adsorption stage
and vice versa. To compromise between reasonable rates of both adsorption and desorption, the step
should be at an intermediate point between the rich and weak isosteres. The position of this point
provides an efficient tool to manage rates of the HeCol stages;
(iii) the real adsorbent optimal for desorption/adsorption stages of both TI and PI cycles
should have concave/convex segment of the adsorption isobar (TI)/isotherm (PI) between the
boundary pressures/temperatures of the cycle.
We believe that these general findings can be a lodestar for reliable selection of adsorbents,
proper for particular TI and PI cycles, among those already known or for tailoring new adsorbents
specialized for the given cycles.

3.3.3. Direct comparison of TI and PI dynamics. Even if the adsorptive is exchanged between the
same weak and rich isosteres, the initial driving forces for TI and PI processes are different. At the
beginning of TI processes (t = 0), the driving force is the temperature drop/jump so that the heat
transfer rate is maximum, whereas the mass transfer rate is zero [47]. On the contrary, for PI
processes, at t = 0 the driving force is the pressure drop/jump so that the mass transfer rate is
maximum, whereas the heat transfer rate is zero [48]. Hence, one can expect different dynamics of
the TI and PI processes [46].
The first direct comparison of the TI and PI dynamics has recently been performed in [49] in
the frame of studying the new HeCol cycle. The aim was to investigate the methanol desorption
dynamics initiated by the pressure drop (4-1) as well as by the temperature jump (4*-1) between the
same isosteres of the tested cycle (Fig. 6a). For the two versions of the adsorbent regeneration stage,
the heat for methanol desorption was taken at a quite low temperature TM = 2oC, so that both
versions can be used for upgrading the ambient heat in cold countries [49]. A commercial activated
carbon ACM-35.4 was used as methanol adsorbent according to [39].The boundary conditions for

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the regeneration were as follows: for the PI stage (4-1) - TM = 2oC, P4 = 8.2 mbar and PL = 4.7 mbar;
for the TI stage (4*-1) - PL = 4.7 mbar, TM* = -6oC and TM = 2oC.

(a) (b)

Fig. 6. (a) P-T diagram of the studied cycles with isothermal (4-1 and 2-3) and isobaric (4*-1 and
2*-3) transitions between rich (3-4) and weak (1-2) isosteres of the HeCol cycle; and (b) methanol
release curves as a function of time for PI (4-1) (●) and TI (4*-1) (■) stages. Solid line –
exponential fitting [49].

The main finding of this study is that the kinetic curves for both PI and TI desorption stages
are identical (Fig. 6b). Hence, the regeneration dynamics does not depend on the regeneration path,
either isothermal (4-1) or isobaric (4*-1). The release curves can be well approximated by the
exponential function
w( g / g )  0.08  (1  e  t /  ) (6 )
with a single characteristic time τ = 104  6 s regardless the way of the desorption initiation. The
same trend is found for the adsorption dynamics which does not depend on whether the path is
isobaric (2*-3) or isothermal (2-3) (not presented) [49]. Again, both uptake curves are exponential
with τ = 78  4 s that is shorter than for the desorption run. The adsorption boundary conditions
were: for the PI stage (2-3) – TH = 30oC, P2 = 26.2 mbar and PM = 45.1 mbar; for the TI stage (2*-3)
- PL = 45.1 mbar, TH* = 39oC and TH = 30oC (Fig. 6a).
The revealed invariance of ad-/desorption dynamics is somewhat unexpected because
isothermal and isobaric processes are initiated by quite different driving forces as considered above.
The invariance is likely to indicate that heat and mass transfer processes are strongly coupled so that
after a short transient period a steady state regime is established in the adsorbent bed, and this regime is
similar, regardless the initial driving force (P or T) applied. The formation of this steady-state

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regime for TI adsorption cycle was numerically studied in [50], and the time interval for setting the
stationary mode was found to be ca. 5 s. No similar study has been done yet for PI adsorption cycles.

3.4. Summary
Both temperature- and pressure-initiated adsorptive cycles for heat transformation/storage allow
an efficient heat conversion process to be realized. The PI cycles can ensure the higher second law
efficiency due to smaller (or zero) temperature coupling of the adsorber and external heat
source/sink. This is true for quasi-equilibrium PI cycles, however, the real PI process can occur in
the non-isothermal mode due to significant adsorbent cooling/heating during the desorption/
adsorption modes. The preliminary direct comparison of the TI and PI dynamics for particular
HeCol cycle revealed that the kinetic curves do not depend on the process path, either isothermal or
isobaric. Further experimental and numerical study of the TI and PI dynamics is necessary to answer a
question what is the true driving for AHTS cycles – pressure drop P, temperature jump T, variation
of the uptake w or of the adsorption potential F. More attention should be also paid to dynamic
studying PI cycles for heat amplification as well as combined TI/PI cycles for heat storage.
More general comments are as follows: All issues considered in Section 3 are valid for any
solid sorption cycle based on bi-variant sorption equilibrium. Such a 3T sorption cycle consists of
two isosters (rich and weak) and either two isobars (TI cycle) or two isotherms (PI cycle), therefore
two ways of initiation are possible. For thermochemical cycles based on chemical reactions with
mono-variant equilibrium (e.g. formation of salt hydrates), the gas-solid equilibrium is described by
a single isoster instead of two for bi-variant process. Theoretically, the transformation from a salt
towards its hydrate is initiated by either an infinitely small reduction of temperature (TI) at constant
vapour pressure or an infinitely small increase of vapour pressure (PI) at constant temperature. Both
transitions are reversible and results in zero entropy generation. Therefore, no difference can be
expected between TI and PI thermochemical processes from the thermodynamic point of view. The
kinetic analysis of TI and PI cycles is a subject of special analysis.

4. NEW ADSORBENTS
4.1. Intent designing the adsorbents adapted for the specific AHTS cycles
The adsorbent is a key component of both AHA and AHS systems. In our opinion, a harmonization
of adsorbent properties with operating conditions of the specific cycles is a corner-stone for the
enhancement of the system performance [32]. The recent progress in material science results in the
development of new classes of adsorbent materials, such as crystalline aluminophosphates (AlPO)
and silicon- or metal- substituted aluminophosphates (SAPO and MeAPO) [51], composite sorbents

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containing a salt placed inside porous matrix (CSPMs) [52], Metal-Organic Frameworks (MOFs) or
porous coordination polymers [53,54], mesophase mesoporous materials (MCM, SBA, FSM, etc.)
[55], pillared clays [56], carbon nanotubes [57], activated carbon fibers (ACF) [58], etc. Wide
variability (or even chemical tailorability) of these materials provides large avenue for a target-
oriented design of novel adsorbents adapted to a particular adsorption cycle [59].
The main idea of this approach is that for each AHTS cycle there is an optimal adsorbent, the
properties of which allow perfect performance of this cycle. The practical realization of this approach
consists of two tasks: at first, one has to understand which adsorbent is optimal to the specific AHTS
cycle, in other words, to formulate the demands for the properties of an adsorbent optimal for this
cycle, and then to synthesize (or select among already existing materials) the real adsorbent, which
properties precisely or nearly fit these demands.
The general qualitative demands (first task) for the optimal adsorbent adapted to the specific
AHTS cycle were discussed from thermodynamic (the first and second law efficiencies) and dynamic
points of view in sections 3.2 and 3.3. In sum, the real adsorbent optimal for the AHTS cycles should
possess a step-wise or S-shaped adsorption isobar (for TI cycles)/isotherm (for PI cycles) with a large
uptake variation. The step position is dictated by boundary pressures/temperatures of the selected
cycle.
The quantitative reqirements for the adsorbent properties can be formulated in terms of the
Polanyi-Dubinin adsorption potential ΔF(Р,Т) = RT ln[P0(T)/P] [60]. It was shown [60, 61, 62] that
for many adsorbents, both meso- and microporous, there is one-to-one correspondence between the
equilibrium uptake w and the adsorption potential, w = f(F) (Fig. 7 a). This correspondence allows
the optimal characteristic curve of adsorption, which matches the specific AHTS cycle, to be plotted,
based on the analysis of operating conditions of this cycle. In other words, the values of adsorption
potential ΔFad(Р,Т) corresponding to the adsorption stage and ΔFdes(Р,Т) corresponding to the
regeneration stage, in which the adsorbent has to exchange a large amount w = w(Fad) - w(Fdes)
of the working fluid vapor in S-shaped manner, can be defined (Fig. 7 b).

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Fig. 7. Сommon (a) and optimal S-shaped (b) characteristic curves of adsorption for the AHA and
AHS cycles.

For the 3T AHA cycles, the operating conditions are determined by the three temperatures,
namely, ТH of the useful heat, ТM of the heat source, and ТL of the heat sink (section 2.1). The
optimal adsorbent is characterized by an S-shaped adsorption characteristic curve w = f(F) with a
large uptake variation w = w(Fad) - w(Fdes) = w[RTHln(PH/PM)] - w[RTMln(PM/PL)] between the
boundary isosters (Fig. 7 b) [28].
The operating conditions of a typical AHS cycle are determined by the following four
temperatures (4T cycle): TH of the driving heat source, TM of the heat sink (ambient) during the
regeneration, and Tuh of the useful heat, and TL of the heat source for the evaporation during
adsorption stage (section 2.2, Fig. 2). Consequently, the optimal adsorption isotherm for AHS
cycles is an S-shaped curve with a large uptake variation w = w(Fad) - w(Fdes) =
w[RTuhln(Puh/PL)] - w[RTHln(PH/PM)] between the boundary isosters [28].
It is worth noting that the adsorbents with the step-wise adsorption isotherms are poorer
adaptable for changing operating conditions, or, in other words, for variable temperatures of the
heat sink (the ambient) and heat source (solar thermal energy). However, commonly the AHTS
units are water cooled and heated, and the temperatures of the cooling and heating water tanks are
much less variable, and consequently their effect on the uptake variation and the cycle efficiency is
expected to be not drammatic. Furthermore, to avoid a reduction of the uptake variation and the
cycle efficiency at changing operating temperatures the operating F -range (Fad and Fdes) has to
be defined considering the most severe climatic conditions (high ambient and low heat source
temperatures). That allows avoiding the negative effect of the variable operating temperatures on
the cycle efficiency.

4.2. Promising adsorbents

Let’s briefly screen the adsorbents suggested for AHA and AHS keeping in mind the above mentioned
considerations.
The adsorptions suggested for AHT can be divided by three groups according to sorption
mechanism: physi-sorbents (zeolites, silica gels, aluminophosphates AlPO and SAPO, metal-
organic frameworks, etc.), chemi-sorbents (inorganic salts, metal oxides, metal hydrides), and
composite materials, which combine the chemi- and physi-sorbents in the same structure (so-called
Composites Salt/Porous Matrix (CSPMs)).

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In sum, the equilibrium of the chemi-sorption systems is monovariant, consequently, it is
described by step-wise characteristic curves that can be profitable for AHA from thermo-dynamic
point of view (see section 3.2.2.). Actually, the salts with water and ammonia as working fluid
suggest the largest heat storage capacity of 1-5 MJ/kg or 1000 - 10000 MJ/m3 [22]. However, the
practical implementation of the thermo-chemical heat storage systems is hampered by: (i) poor
mass transport, which leads to slow sorption dynamics and incomplete conversion, (ii)
adsorption/desorption hysteresis which results in smaller temperature lift, (iii) salt swelling,
mechanical destruction and dust formation [ 19, 63].
The common adsorbent of “old” generation (e.g. microporous silica gel RD, classical
alumino-silicate zeolites of type 4A and 13X) can hardly be utilized for AHA and AHS applications
due to smooth shape of the adsorption isotherm. During last decades several “new” classes of
adsorbents were developed, whose adsorption equilibrium with the common working fluids (water,
methanol, ethanol) can be described by the S-shaped curves, advantageous for AHTA systems.
Among these “new” adsorbents the following materials inspire high hopes for AHA and AHS [64]:
1) Crystalline aluminophosphates (AlPO) and silicon- or metal- substituted aluminophosphates
(SAPO and MeAPO) are zeolite-like microporous crystalline solids, composed of Al–O and
P–O tetrahedrons [51, 65]. Contrary to common zeolites, they possess electrically neutral
network and, as a consequence, moderate variable hydrophilicity [66].
2) Y-type zeolites DDZ-70, CBV-901 with enhanced Si content were invented for AHTS
applications by UOP Llc. and by Zeolyst Int., respectively. Owing to partially hydrophobic
behavior they can be applied as water and methanol adsorbents and require a moderate
regeneration temperature of nearly 150C [67, 68].
3) Composite sorbents SCPMs were first suggested for AHS in ref. [69] and now are widely
being studied and used for sorptive transformation and storage of low temperature heat [52].
Water, methanol, ethanol, and ammonia sorption on CSPMs combines the three process:
adsorption on the active surface centers of the matrix; reaction between a salt S and a
sorptive V resulting in the formation of solid complex SnV; and the formation of a “salt -
sorbate” solution inside the matrix pores and absorption of the vapor by the solution. The
formation/ decomposition of the SnV complex is described by monovariant equilibrium, so
that the isotherms (isobars) of water, methanol, ethanol, and ammonia sorption on the
CSPMs can be the S-shaped curves, profitable for the AHTS systems.
4) Metal Organic Frameworks belong to a novel family of porous crystalline solids, which
consist of the metal-oxygen units bonded through multydentat organic linkers with each
other forming continuous porous structures [53, 54]. Their extra-large surface area and

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porosity, unique adsorption properties provide promising avenues for AHT applications [70,
71]. To date, thousands MOFs have been synthesized with 0-, 1-, 2-, and 3- dimensional
frameworks, micro- and meso- porous structure. A wide variability of both metal-oxide
clusters and organic linkers, and additional chemical functionalization of the linkers afford
tailored adsorption behavior of MOFs [53, 72]. Particularly, owing to presence of both
hydrophilic and hydrophobic surface centers, as well as of flexible “breathing” structure of
certain MOFs, some of them possess the S-shaped adsorption isotherms. Large adsorption
capacity, tunable sorption behavior, and steep adsorption isotherms provide promising
avenues for AHTs applications. To date, several MOFs have been studied as water and
methanol adsorbents for AHTs [73], such as MIL-101 [74, 75], MIL-100 [76], p-AF or
Basolite™ A520 [77], NH2-MIL-125 [78, 79, 80], UiO-66 [78], MOF-801 [81], etc.

4.2.1. Adsorbents for AHA

The most part of researches in the heat amplification relate to thermo-chemical systems.
Comprehensive reviews on the thermo-chemical heat amplification (thermodynamic cycles,
working pairs, system performance, etc.) has been presented in [19, 20]. Here we only briefly
summarize the main features revealed. Several types of working pairs have been suggested and
studied for heat amplification cycles: “inorganic salt – water” [82, 83], “inorganic salts – ammonia”,
“inorganic salts – methanol”, and metal hydrides (see [19,20] and Ref. listed there).
Mainly, the utilization of industry waste heat at TM = 80-150oC as heat source to produce
useful heat at TH = 150 – 250oC, which can be returned to the industry process to enhance its
efficiency, is analysed.
To the best of our knowledge, there are only a few reports on properly adsorption heat
amplification systems. Chandra and Patwrdhan [16] suggested 1-2-3 and 4 beds system employing
“zeolite – water” working pair. They showed that the AHA unit can provide the temperature lift as
high as 50°C with a fairly good COP value. The 4-tank system gives a much improved COP value
as compared to the 2-tank and 3-tank systems for the same operating conditions. It is also found that
the effect of temperature driving force for heat transfer on the COP value is quite pronounced.
Frazzica et all. analyzed the applicability of two pairs, namely, the "aluminophosphate
AQSOA Z02 – water” and the “activated carbon – ammonia” for AHA [84]. They demonstrated
that the shape of the equilibrium curves highly affected the achievable COPs. The "AQSOA Z02 –
water" working pair with the S-shaped equilibrium curve was able of high performance: at the heat
sink temperature TL = 5C and the heart source temperature TM = 65-85C, the temperature lift T =

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TH-TM = 40-60C can be achieved with the COP equal to 0.4. The AHA based on the "AQSOA Z02
– water" working pair could be employed when the temperature difference between the waste and
ambient heat is in the range of 50°C. This makes it more interesting for industrial rather than for
domestic applications. The AC208C - ammonia working pair provided lower both COP and specic
storage capacity.
An open adsorption heat amplifier based on the “zeolite 13X – water” working pair for
steam generation was suggested [85] and examined experimentally [86]. Superheated steam (200C,
0.1 MPa) is generated from hot water (70-80C) and dry air (100-130C).
Recently, the mentioned above concept of target-oriented designing the sorbents adapted to
the specific AHT cycle, was realized in practice for the HeCol cycle aimed at amplification of the
ambient heat [27, 28]. It is worth noting that the adsorbent for the HeCol cycle should be very
specific. On the one hand, its affinity to working fluid (methanol) must not be too high in order it
can be easily regenerated at point 1 (Fig. 2 b) at the relatively low temperature of heat source TM =
0-20оС. On the other hand, this affinity has to be high enough to bind methanol effectively at point
3 (Fig. 2 b), releasing the useful heat at temperature TH sufficient for heating. At first, the operating
conditions of several HeCol cycles were analyzed and the requirements for the optimal adsorbent
were formulated. Then, the composite sorbents, based on LiCl [28], CaCl2, CaBr2 and binary salt
system CaClBr [27] inside the silica gel pores adapted to HeCol cycles with various operating
conditions were selected and their applicability was analyzed.
It was shown that owing to the S-shaped adsorption isotherms and the harmonization of the
sorbent properties with the operating conditions of the cycles the composites ensure the uptake
variation of 0.25-0.73 g/g under operating conditions of the studied HeCol cycles, which is superior
to conventional activated carbons. The large amount of methanol cycled on the LiCl/silica
composite leads to high values of the useful heat Qad generated during adsorption of 700-100 kJ/g
as compared to Qad = 150-250 kJ/g for activated carbon ACM-35.4 [87]. Among the studied
sorbents the LiCl/silica composite possesses strong affinity to methanol vapor and is promising for
the HeCol cycles with the temperature lift T = 20 - 27C (e.g. TL/TM/TH = -20/20/45С or TL/TM/
TH = -35/3/30С). The CaClBr/SiO2 composite is characterized by a weaker affinity and can be
regenerated at a higher heat sink (the ambient air) temperature TL at the expense of smaller
temperature lift of 15C (e.g. TL/TM/TH = -10/20/35С).
Testing a lab-scale HeCol prototype (Fig. 8) loaded with the LiCl/silica [28] and
CaClBr/silica [27] composites demonstrated the practical feasibility of the HeCol cycle. At the heat
sink temperature TL = -20С and the heat source temperature TM varied from 10 to 25С, a maximal
temperature of the released heat of 32-49C was obtained with the CaClBr/silica composite that is

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suitable for warm floor systems (Table 1). The LiCl/silica allows the higher maximal temperature
34-53C, but requires the higher heat source temperature TM = 20 - 28С as well. The maximum
Specific Heating Power SHP = 1.4-3.6 and 6.0-10.8 kW/kg was reached with the CaClBr/silica and
the LiCl/silica, respectively, that is the excellent base for designing compact HeCol units for
upgrading the ambient heat temperature in cold countries. Both temperature lift and SHP of the
HeCol unit employing the LiCl/silica and CaClBr/silica composites far exceed the appropriate
values for activated carbon ACM-35.4 based unit [29] due to the harmonization of the adsorbent
properties with the operating conditions of the HeCol cycle.

(a) (b)
Fig. 8. View of the lab-scale HeCol unit (a): 1 – adsorber, 2 – condenser/evaporator, 3, –
thermocryostats, 4 – vacuum pump, F1-F3 – flowmeters, V0 – vacuum valve, V1-V8 – valves, Р –
pressure gauge, and the fragment of HEx loaded with the sorbent (b). Reprinted from Applied
Energy, Vol 211, M. M. Tokarev, L. G. Gordeeva, A. D. Grekova, Yuri I. Aristov., Adsorption cycle
“heat from cold” for upgrading the ambient heat: The testing a lab-scale prototype with the
composite sorbent CaClBr/silica, Pages 136-145, Copyright (2018), with permission from Elsevier.

4.2.2. Adsorbents for AHS

Currently, the AHS researches are focused mainly on the development of novel working pairs with
enhanced heat storage density. A number of reviews have been published during the last decade [19, 88,
89, 90]. Water is mainly considered as a sorbate due to its environmentally friendly properties and the
large heat of sorption. Methanol and ammonia can also be used, especially if the environment
temperature is below 0C. Here we analyze the applicability of various adsorbents for two practically
important AHS cycles as the reference. The former is Daily heat Storage (DS) in winter in regions,
where the solar thermal energy during day time is intense enough to be stored, and then used for heating

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at night, when the ambient temperature falls below the comfortable level. The latter cycle is Seasonal
heat Storage (SS) in regions with moderately cold winter, so that the heating demands can be, at least,
partially, compensated by the excess of solar heat stored in summer. The operating conditions of the SS
and DS AHS cycles are collected from the climatic data in regions, where these cycles can be realized,
and analyzed to determine the boundary values of the Polanyi-Dubinin potential Fad and Fdes during
the adsorption and desorption stages (Table 2) [91]. The amount of water (methanol) exchanged under
conditions of SS and DS AHS cycles and the heat storage capacity HSC are evaluated based on the
analysis of the literature data on water/methanol adsorption equilibrium and heat.

Table 2. Operating conditions of the SS and DS cycles.

Cycle Tuh,C TL,C TH,C TM,C Fad,kJ/mol Fdes, kJ/mol
75 6.4
SS 35 10 30 3.9
85 7.7
75 9.0
DS 35 5 15 4.8
85 10.1

Traditional silica gel RD and zeolites seem to be not optimal adsorbents for the considered
cycles. The silica gel adsorbs small amount of water at these cycles because its affinity to water is weak.
Contrary, the affinity of zeolites is too high and they cannot be regenerated by low temperature heat.
According to [92, 93, 94] their total HSC = 670 – 1290 kJ/kg (490-830 MJ/m3) at the charge
temperature TH = 180-230C. However, the uptake variation under conditions of the SS and DS cycles is
0.03-0.08 g/g, and HSC = 100-200 kJ/kg. Actually, testing a lab-scale AHS unit loaded with zeolites
4A, 13X, and 13XFB demonstrated a good performance with HSC = 280-960 kJ/kg at rather high
regeneration temperature TH = 170-300C (Table 3) [95, 96, 97]. Therefore, AHS systems based on
these zeolites are more suitable for storage of industrial waste heat.
Among zeotypes, several materials, namely AlPO-18, SAPO-18, APO-Tric, FAPO-34 (or FAM
Z05), and FAPO-6 (or FAM Z01) are characterized by S-shaped adsorption isotherms with the uptake
rise positioned within the range of the adsorption potential Fad and Fdes (Fig. 9a). The water uptake
variation under conditions of the DS and SS cycles changes from 0.15-0.16 g/g to 0.21-0.30 g/g for
FAPO-34 and AlPO-18, respectively [98, 99, 100, 101, 102]. The HSC of these zeotypes under
conditions of the SS and DS cycles equals 350 - 660 kJ/kg. Testing the AHS units loaded with FAM
Z01 [35] and AQSOA FAM Z02 [111] illustrated the feasibility of the AHS cycles at low regeneration
temperature TH =70 - 90C with good HSC 520-1000 kJ/kg.

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Several mesoporous MOFs possess the huge pore volume, e.g. Vp=1.1-2.4 cm3/g for MIL-
101(Cr) and Cr-Soc-801, respectively, and adsorb as much water as 1.1-1.95 cm3/g [103, 104].
However, the capillary condensation in mesopores occurs at F < Fads for the SS and DS cycles (Fig.
9b) and cannot be employed for them. Despite the total HSC (adsorption at relative humidity 85-90%)
of these mesoporous MOFs is very large (1500-2600 kJ/kg), due to the weak affinity to water vapor they
can provide only small temperature lift at the adsorption (heat generation) stage. The amount of water
cycled under the considered conditions does not exceed 0.1 g/g. Contrary, some microporous MOFs
(HKUST, CPO-27(Mg)) possess the high affinity to water and adsorb about 0.5-0.6 g/g under
conditions of the considered AHS cycles; however they cannot be regenerated at Fdes of the cycles
[105]. Several microporous MOFs (NH2-MIL-125 [106, 79], NO2-UIO-66 [78, 105], CAU-10 [107],
and MOF-801 [108, 81] are characterized by the S-shaped characteristic adsorption curve with the steep
rise in adsorption at Fads < F < Fdes (Fig 9 b). The water uptake variation on these MOFs under
condition of the SS and DS cycles changes from 0.25 to 0.30 g/g that corresponds to HSC = 600-830
kJ/kg.

Table 3. Characteristics of lab-scale AHS units tested.

Adsorbent o Efficiencies Ref.
Operating T, C
Silica gel HSC = 250- 690* kJ/g [109]
Zeolites 4A, TL = 25, Tad=40-47 HSC = 280-960 kJ/kg [95, 96]
13X, open syst. TH=170-185 SP = 3-30 W/kg
Zeolite 13XFB TL = 20, Tad =25-45 HSD = 570-670 kJ/kg [97]
TH=180 SP = 3-30 W/kg
NaX zeolite-copper Tad=40, TH=300 SP = 49-65 W/kg [110]
foam
FAM Z01, TM = TL= 30, HSC = 805 kJ/kg [35]
fin-coated HEx Tad=40-60, TH=70
FAM-Z02, fin-flat TL = 5-15, Tad=35-40 HSC = 520-1008 kJ/kg [111]
tube, grain TM=15-20, TH=75-90 SP = 46-151 W/kg
SWS-8L TL=15-20, Tad=30 HSC =1440 kJ/kg
(CaNO ) /silica TM =30, TH =90
3 2

SrBr /ENG TL = 15, Tad=35 HSC =1152 kJ/kg [112]

2
TH =80
* HSC was calculated considering the packing density of silica RD equal to 650-700 kg/m3

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(a) (b)

(c) (d)
Fig. 9. The characteristic curves of water adsorption on (a) zeotypes: AlPO-18 (1), SAPO-18 (2),
SAPO-34 (FAM-Z02) (3), APO-TRIC (4), FAPO-5 (FAM-Z01) (5), and FAPO-34 (FAM-Z05) (6); (b)
MOFs: MIL-101(Cr) (1), MIL-100 (Cr) (2), CPO-27(Mg) (3), NH2-MIL-125 (4), MOF-841 (5), UIO-66
(6), CAU-10 (7), and MOF-801 (8); (c, d) CSPMs: LiCl/silica (1), MgSO4/silica (2), LiBr/silica (3),
LiNO3/silica (4), Ca(NO3)2/silica (5), LiCl/MWCNT (6) and LiCl/ExVer (7).

The CSPMs are widely being studied and used for sorptive storage of low temperature heat [52,
59, 90, 94, 113, 114, 115, 116, 117]. The salt is the main sorbing component of the CSPMs and it
mainly influences the affinity of the composite to water vapor and the position of the step on the
adsorption isotherm. Large number of hygroscopic salts are suggested as an active component of the
CSPMs, namely CaCl2 [69, 114], Al2(SO4)3 [118], MgSO4 [114, 115], MgCl2 [114, 117], LiBr and
CaNO3 [114]. CSPMs are characterized by high maximum (adsorption at relative humidity 85-90%)
HSC of 700 – 4300 kg/kg, suitable temperature lift at moderate charging temperature, and wide

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variability of the sorption properties [52, 114]. Due to these benefits, CSPMs are shown to be
advantageous for SHS [19, 88, 90].
The characteristic curves of water adsorption on several CSPMs presented in Fig 9 c are S-
shaped curves with steep rise of uptake, which correspond to the formation of the complexes SnH2O.
The variation of salts allows the position of the step on the isotherm to be shifted in order to match the
conditions of the specific AHS cycle. Generally, nitrates possess low affinity, they can be applied for
cycles driven by as low as TH = 60C at the condensation temperature TM = 30C, but provide the low
temperature lift T = 20C during adsorption. Chlorides, and particularly bromides, possess a higher
affinity; consequently they provide a larger temperature lift at the expense of higher charging
temperature TH.
The matrix supports the salt and its pore volume determines the total adsorption capacity.
Consequently, matrices with large pore volume are preferable for AHS. The CSPMs, based on various
salts and expanded vermiculite with the extremely large pore volume 2.4-2.8 cm3/g are characterized by
the total HSC up to 4200 J/g [90, 114].
Two CSPMs have recently been synthesized intently for the SS and DS cycles, based on LiCl as
an active salt and two highly porous matrixes, namely, expanded vermiculite and MultiWall Carbon
NanoTubes (MWCNT) [91, 119, 120]. Testing the adsorption ability of these CSPMs shows that the
water adsorption capacity of these CSPMs exceeds 1.0 g/g, and the most part of water is exchanged
under conditions of the SS and DS cycles (Fig. 9 d). The uptake variation w reaches 0.60-0.85 and
0.30- 0.57 g/g for LiCl/ExVer and LiCl/MWCNT, respectively. The HSC in the considered cycles
varies from 0.9 to 2.3 kJ/g at Tdes = 75-85C that is superior to the appropriate value for other
adsorbents.
The large porosity of the expanded vermiculite and MWCNTs results in quite low packing
density of the CSPMs based on these matrixes, and consequently in the lowering of the volumetric heat
storage density HSD. The HSD of the LiCl/ExVer composite was estimated as 175-253 kWh/m3 for SS
and DS cycles at TH = 75-85C, which is still higher than the appropriate values for the other common
and innovative adsorbents (28 –124 mJ/m3) [120].
Testing a lab-scale AHS units employing a flat finned-tube aluminum HEx loaded with 900 g of
LiCl/ExVer grains demonstrated quite good performance [121].The specific heating power at 80%
conversion equaled 2.12 kW/kg and the heat storage capacity of LiCl/ExVer was 1.25 kJ/g of the
material. It is about 40% less than the value evaluated at material level based on the uptake variation,
which is caused by the inert thermal mass of the Hex.

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Thus, the intelligent selection of the salt and the matrix, as well as the salt content is a powerful
tool for tailoring the CSPMs, whose properties are adapted to the specific AHS cycle, and allow perfect
performance of this cycle.

Conclussions
In this paper, the state-of-the-art in the fields of adsorption heat storage/amplification is reviewed. The
researches in the AHA are mainly focused in the development of new cycles to increase the efficiency
and the temperature lift (e.g. the HeCol cycle), while those in AHS are concentrated on searching the
novel working pairs with enhanced heat storage capacity.
Both temperature- and pressure-initiated AHA and AHS cycles allow an efficient heat
conversion process to be realized. The PI cycles can ensure the higher second law efficiency due to
smaller (or zero) temperature coupling of adsorber and external heat source/sink. However, the real PI
process can occur in the non-isothermal mode due to significant adsorbent cooling/heating during the
desorption/ adsorption modes. The preliminary direct comparison of the TI and PI dynamics for
particular HeCol cycle revealed that the kinetic curves do not depend on the process path, either
isothermal or isobaric. Further experimental and numerical study of the TI and PI dynamics is necessary
to answer a question what is the true driving force for these cycles. More attention should be also paid to
dynamic studying PI cycles for heat amplification as well as combined TI/PI cycles for heat storage.
A harmonization of adsorbent properties with operating conditions of the specific cycles is a
corner-stone of the enhancement of the system performance. The recent progress in material science
results in the development of new classes of adsorbents with tunable adsorption behavior (zeotypes
AlPO, SAPO, MeAPO, MOFs, CSPMs, etc.). That allows a target-oriented design of novel adsorbents
adapted to a particular adsorption cycle. The thermodynamic and dynamic analysis of the AHS and
AHA cycles revials that the optimal adsorbent should possess the S-shaped adsorption isobar (for TI
cycles)/isotherm (for PI cycles) with large uptake variation. The realization of this approach in practice
allows enhancement of their performance (the HSC for AHS; the specific heating power and the
temperature lift for AHA). Both AHA and AHS processes are being tested with the lab-scale prototypes,
demonstrating large potential of these emerging technologies for effective using the renewable heat
sources and mitigating the primary energy resources.

ACKNOWLEDGEMENT
This work is partially supported by the Russian Science Foundation grant n. 16-19-10259 (analysis of
the AHA cycles) and Russian Foundation of Basic Resarches grant n. 18-29-04033 (analysis of the
water adsorption on the MOFs).

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 ACCEPTED MANUSCRIPT
The state-of-the-art in the field of adsorption heat storage/amplification is reviewed

The efficiency and dynamics of pressure- and temperature-initiated cycles are compared

New adsorbents developed for adsorption heat storage/amplification are described

The problem of harmonization of the adsorbent with the cycle conditions is discussed
 ACCEPTED MANUSCRIPT
Table 1. The middle cycle temperature TM, maximum cycle temperature Tmax, maximum heating
power Wmax, and maximum specific heating power Wmax.sp at TL/TH = -20/28 C and heat transfer
fluid rate f = 360 L/h.

LiCl/silica CaClBr/silica
TM, C 20 - 28 10 - 25
Tmax, C 46 - 53 32 - 49*
Wmax, kW 3.0 – 4.0 1.0 – 2.5
Wmax.sp, kW/kg 6.0 – 8.0 1.4 – 3.6
* the maximum temperature was measure at f = 66 L/h.