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SPRINGER BRIEFS IN
APPLIED SCIENCES AND TECHNOLOGY

Alessio Sapienza
Andrea Frazzica
Angelo Freni
Yuri Aristov

Dynamics of
Adsorptive
Systems for Heat
Transformation
Optimization of
Adsorber, Adsorbent
and Cycle
SpringerBriefs in Applied Sciences
and Technology

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Alessio Sapienza Andrea Frazzica
•

Angelo Freni Yuri Aristov

•

Dynamics of Adsorptive
Systems for Heat
Transformation
Optimization of Adsorber, Adsorbent
and Cycle

123
Alessio Sapienza Angelo Freni
Consiglio Nazionale delle Ricerche Consiglio Nazionale delle Ricerche
Messina Messina
Italy Italy

Andrea Frazzica Yuri Aristov

Consiglio Nazionale delle Ricerche Boreskov Institute of Catalysis
Messina Novosibirsk
Italy Russia

ISSN 2191-530X ISSN 2191-5318 (electronic)

SpringerBriefs in Applied Sciences and Technology
ISBN 978-3-319-51285-3 ISBN 978-3-319-51287-7 (eBook)
https://doi.org/10.1007/978-3-319-51287-7
Library of Congress Control Number: 2018933011

© The Author(s) 2018

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Acknowledgements

One of the authors (Prof. Yuri Aristov) thanks the Russian Science Foundation
for financial support of the study on the pressure-driven HeCol cycle (grant
N 16-19-10259).

v
Contents

1 Adsorptive Heat Transformation and Storage: Thermodynamic

and Kinetic Aspects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1 Thermodynamic Cycles for AHT . . . . . . . . . . . . . . . . . . . . . . . . 3
1.1.1 Temperature-Driven Cycles . . . . . . . . . . . . . . . . . . . . . . 4
1.1.2 Pressure-Driven Cycles . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.1.3 Other Presentations of the AHT Cycles . . . . . . . . . . . . . . 7
1.2 The AHT Efficiency . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
1.2.1 The First Law Efficiency . . . . . . . . . . . . . . . . . . . . . . . . 8
1.2.2 The Second Law Efficiency . . . . . . . . . . . . . . . . . . . . . . 9
1.3 Dynamics of AHT Cycles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
1.4 Adsorbents Optimal for AHT . . . . . . . . . . . . . . . . . . . . . . . . . . 12
1.4.1 The First Law Efficiency . . . . . . . . . . . . . . . . . . . . . . . . 13
1.4.2 The Second Law Efficiency . . . . . . . . . . . . . . . . . . . . . . 13
1.4.3 Adsorbent Optimal from the Dynamic Point of View . . . . 14
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
2 Measurement of Adsorption Dynamics: An Overview . . . . . . . . . . . 19
2.1 Differential Step (IDS) Method . . . . . . . . . . . . . . . . . . . . . . . . . 21
2.2 Large Pressure Jump (LPJ) Method . . . . . . . . . . . . . . . . . . . . . . 22
2.3 Large Temperature Jump (LTJ) Method . . . . . . . . . . . . . . . . . . . 24
2.3.1 Volumetric Large Temperature Jump Method (V-LTJ) . . . . 25
2.3.2 Gravimetric Large Temperature Jump Method (G-LTJ) . . . . 27
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
3 Experimental Findings: Main Factors Affecting the Adsorptive
Temperature-Driven Cycle Dynamics . . . . . . . . . . . . . . . . . . . . . . . 31
3.1 Adsorbate and Adsorbent Nature . . . . . . . . . . . . . . . . . . . . . . . . 32
3.1.1 Water Sorption Dynamics . . . . . . . . . . . . . . . . . . . . . . . . 33
3.1.2 Methanol Sorption Dynamics . . . . . . . . . . . . . . . . . . . . . 34
3.2 Adsorbent Grain Size . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35

vii
viii Contents

3.2.1 Water Sorption Dynamics . . . . . . . . . . . . . . . . . . . . . . . . 36

3.2.2 Methanol Sorption Dynamics . . . . . . . . . . . . . . . . . . . . . 41
3.2.3 Ethanol Sorption Dynamics . . . . . . . . . . . . . . . . . . . . . . 44
3.3 Geometry of the Adsorber . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
3.3.1 Water Sorption Dynamics . . . . . . . . . . . . . . . . . . . . . . . . 49
3.3.2 Methanol Sorption Dynamics . . . . . . . . . . . . . . . . . . . . . 49
3.3.3 Ethanol Sorption Dynamics . . . . . . . . . . . . . . . . . . . . . . 52
3.4 Cycle Boundary Conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
3.4.1 Methanol Sorption Dynamics . . . . . . . . . . . . . . . . . . . . . 57
3.4.2 Ethanol Sorption Dynamics . . . . . . . . . . . . . . . . . . . . . . 60
3.5 Residual Gases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
3.5.1 Water Sorption Dynamics . . . . . . . . . . . . . . . . . . . . . . . . 62
3.6 Flux of Cooling/Heating Heat Carrier Fluid . . . . . . . . . . . . . . . . 65
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
4 Optimization of an “Adsorbent/Heat Exchanger” Unit . . . . . . . . . . 69
4.1 Optimization of the “Adsorbent–Heat Exchanger” Unit . . . . . . . . 71
4.1.1 Adsorbent Grain Size . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
4.1.2 The Ratio “Heat Transfer Surface”/“Adsorbent Mass” . . . . . 74
4.1.3 The Effect of the Flow Rate of External Heat Carrier . . . . 76
4.1.4 Comparison of the Model Configurations
with Full-Scale AHT Units . . . . . . . . . . . . . . . . . . . . ... 78
4.2 Compact Layer Versus Loose Grains . . . . . . . . . . . . . . . . . . ... 79
4.3 The Effect of Residual Gases . . . . . . . . . . . . . . . . . . . . . . . . ... 81
4.4 Reallocation of Adsorption and Desorption Times
in the AHT Cycle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... 84
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... 85
Chapter 1
Adsorptive Heat Transformation
and Storage: Thermodynamic
and Kinetic Aspects

Nomenclature
A Adsorber
Ad-HEx Adsorbent–heat exchanger
AHP Adsorption heat pump
AHT Adsorptive heat transformer
C Condenser, thermal capacity J K−1
COP Coefficient of performance
d Thickness, m
ΔF Adsorption potential, J mol−1
E Evaporator
LTJ Large Temperature Jump method
LPJ Large Pressure Jump method
h Convective heat transfer coefficient, W m−2 K−1
HEx Heat exchanger
HMT Heat and mass transfer
m Dry adsorbent mass, kg
P Pressure, Pa
PD Pressure driven
Q Thermal energy, J
R Universal gas constant, J mol−1 K−1
S Solid, entropy J kg−1, heat transfer surface area, m2
SP Specific power, W kg−1
T Temperature, K
TD Temperature driven
U Overall heat transfer coefficient, W m−2 K−1
V Vapour
w Water uptake, g g-1
W Work, J

© The Author(s) 2018 1

A. Sapienza et al., Dynamics of Adsorptive Systems for Heat Transformation,
SpringerBriefs in Applied Sciences and Technology,
https://doi.org/10.1007/978-3-319-51287-7_1
2 1 Adsorptive Heat Transformation and Storage …

Greek Symbols
D Differential operator
k Thermal conductivity, W m−1 K−1

Subscripts
0 Initial stage, saturation vapour
ads Adsorbent/adsorption
c Cooling
con Condensation
des Desorption
ef Effective
ev Evaporation
f Fluid
h Heating
H High
L Low
M Medium
met Metal
us Useful
w Wall/solid side

At present, the majority of thermodynamic cycles of heat engines are

high-temperature cycles that are realized by internal combustion engines, steam and
gas turbines, etc. [1]. Traditional heat engine cycles are mainly based on burning of
organic fuel that may result in dramatic increase of CO2 emissions and global
warming. The world community has realized the gravity of these problems and
taken initiatives to alleviate or reverse this situation. Fulfilment of these initiatives
requires, first of all, the replacement of fossil fuels with renewable energy sources
(e.g. the sun, wind, ambient heat, natural water basins, soil, air). These new heat
sources have significantly lower temperature potential than that achieved by
burning of fossil fuels which opens a niche for applying adsorption technologies for
heat transformation and storage [2].
A classical heat engine consumes heat Q1 from a heat source with high tem-
perature TM, discharges heat Q2 to a heat sink with lower temperature TL and
produces the maximal work W = Q1 − Q2 = Q1 (1 − TL/TM) [3] (the left part of
Fig. 1.1). The produced work can be used to drive a heat pumping cycle (the right
part of Fig. 1.1). An adsorptive heat transformer (AHT) operates between three
thermostats (TL, TM, TH) (Fig. 1.2) and consumes/produces only thermal energy. In
this chapter, we shortly survey the fundamentals of the heat transformation via
adsorption processes:
1 Adsorptive Heat Transformation and Storage … 3

Fig. 1.1 Three temperature Q4

(3T) diagram of the heat Q1
transformation TH
TM

WORK PRODUCTION HEAT PUMPING

TL TM
Q2 Q3

Fig. 1.2 Operation principle

of an AHT: 1—cooling mode, TH
2—heating mode, 3–
temperature upgrading mode
TM C

TL E

(a) various heat transformers and thermodynamic cycles;

(b) their first and second law efficiencies;
(c) dynamic peculiarities of the AHT cycles.
Finally, the question “What adsorbent is optimal for particular AHT cycle?” is
analysed to make appropriate practical recommendations.

1.1 Thermodynamic Cycles for AHT

An AHT exchanges heat fluxes between three thermostats (I, II and III) maintained
at high (TH), middle (TM) and low (TL) temperatures (Fig. 1.2). The AHT trans-
forms heat at three modes: (1) cooling, (2) heating and (3) upgrading temperature
potential (heat amplification). Such a three temperature (3T) AHT consists of an
evaporator, E, at temperature TL, a condenser, C, at temperature, TM, and an
adsorber, A, among which a vapour, V, of the working fluid is exchanged and
which consumes/supplies heat from/to the appropriate thermostats (Fig. 1.2).
The interaction between a non-volatile solid S (adsorbent) and a volatile V
(adsorptive) compound
4 1 Adsorptive Heat Transformation and Storage …

V þ S , VS ð1:1Þ

leads to transition of the vapour V into an adsorbed state VS (adsorbate) with

releasing the heat of adsorption Qads (discharging or heat release stage). The inverse
process of VS decomposition (or vapour desorption) requires supply of thermal
energy which is converted to chemical (charging or heat storage stage). The
evaporator, E, is a source of the vapour at the adsorption stage, which is concen-
trated in the condenser, C, during the desorption stage.
Two types of the cycles suggested for AHT essentially differ by the way of
adsorbent regeneration:
• by adsorbent heating up to the temperature sufficient for the adsorbate removal;
• by reducing the adsorptive pressure over adsorbent at constant temperature.
The first, temperature-driven (TD), cycles are very common and widely used to
realize cooling and heating modes (1 and 2 on Fig. 1.2) [2, 4]. The second,
pressure-driven (PD), cycles are much less spread and suggested mainly for the
temperature upgrading mode (3 on Fig. 1.2) [5, 6]. In this book, generally TD
cycles are considered as the most prevalent. However, the examination of PD
cycles, even if preliminary, is very important as this way of desorption initiation can
be different from the TD one [7].

1.1.1 Temperature-Driven Cycles

A typical cycle driven by jump of the adsorbent temperature consists of two iso-
steres and two isobars as presented on the Clapeyron diagram ln(P) versus (−1/T)
(Fig. 1.3). The heat supplied from external heat source at temperature TH is used for
isosteric heating of adsorbent (stage 1–2) and removing adsorbed vapour (regen-
eration stage 2–3) at constant vapour pressure PM. Commonly, the regeneration
temperature has to be at least 50–60°C [8]. The heat Qdes is supplied for desorption.
During desorption process 2–3, the valve between the adsorber and condenser is
opened, and the desorbed vapour is collected in the condenser where the heat of
condensation Qcon is released. The regenerated adsorbent is cooled by a heat carrier
(cooling fluid) at temperature TM. The cooling is first performed at constant uptake
w1 (isostere 3–4) and then at constant pressure PL (isobar 4–1). During adsorption
process 4–1, the valve between the adsorber and the evaporator is opened. The heat
of adsorption Qads transfers to the cooling fluid and can be supplied to a consumer.
During isosteric stages, the valve between the adsorber and condenser/evaporator is
closed.
Five basic TD cycles, such as air conditioning, heat pumping (two cycles) and
deep freezing (two cycles), were selected as reference cycles in the key review [2].
These basic cycles differ by the three boundary temperatures TL, TM and TH [2].
Small changes of this cycle classification have been recently suggested in [9, 10].
1.1 Thermodynamic Cycles for AHT 5

-Qc LG +Qd
ln (P) SL
ln(Pc)
2 3

1 4

-Qa - 1/T

1/Te 1/Tc 1/T2 1/Tg

Fig. 1.3 P-T diagram of the TD adsorptive cycle

There are many modifications of this basic cycle suggested to improve its perfor-
mance, the most important of which are heat [11] and mass recovery [12], cascaded
sorption refrigeration [13] and thermal wave [14] cycles. Recently, reallocation of
the duration of the adsorption and desorption phases of AHT cycle has been sug-
gested in order to further improve both the cycle COP and specific power [15, 16].
This new approach will be considered in Chap. 4. Further cycle modification was
suggested for a three-bed adsorption chiller in order to make possible a combination
of the “time reallocation” concept with the “mass recovery” approach [17].

1.1.2 Pressure-Driven Cycles

A typical PD cycle consists of two isosteres and two isotherms (Fig. 1.4). The
regeneration of adsorbent is performed at constant temperature TM by dropping the
vapour pressure over the adsorbent (stage 4–1). It is somewhat similar to the
pressure swing adsorption process used for gas drying and separation [18].
The initial adsorbent state (point 1 on Fig. 1.4) corresponds to temperature TM
and pressure of the adsorptive vapour PL = P0(TL), where P0(TL) is the saturation
vapour pressure at temperature TL. The weak isostere is characterized by the
equilibrium adsorbate content w1 = w(TM, PL). Then, the adsorbent is heated up to
temperature TH (stage 1–2) at constant uptake w1. At point 2, the adsorber is
connected with the evaporator maintained at TM that is the temperature of the
external heat source which temperature level to be upgraded. The evaporator
6 1 Adsorptive Heat Transformation and Storage …

Fig. 1.4 P-T diagram of the PD adsorptive cycle

generates the constant pressure PM = P0(TM) of adsorptive. This pressure jump P2

! PM causes the vapour adsorption that leads to an increase in the equilibrium
adsorbate content up to w2 = w (TH, PM) (point 3 on Fig. 1.4). The heat of
adsorbate evaporation Qev is absorbed in the evaporator at T = TM, and the useful
adsorption heat Qads is released at constant temperature TH (isotherm 2–3) in the
heating circuit of a consumer. Then, the adsorber is disconnected from the evap-
orator and cooled down to the intermediate temperature TM (isostere 3–4) at con-
stant uptake w2. At point 4, the adsorber is connected with the condenser
maintained at temperature TL and pressure PL = P0(TL). This pressure drop P4 !
PL results in the adsorbate desorption to restore the initial uptake w1 = w(TM, PL)
(point 1). The heat Qdes needed for adsorbate desorption is supplied to the adsorbent
at temperature TM from the external heat source (isotherm 4–1). The excess of
adsorbate is collected in the condenser releasing the heat Qcon to the ambient, and
the cycle is closed. The work is required to pump the liquid adsorbate from the low
pressure level in the condenser to the high pressure level in the evaporator.
This cycle was considered in [5, 19] for upgrading industrial waste heat and
suggested in [6] for increasing the temperature potential of the ambient heat to the
level sufficient for heating dwellings. The main feature of the latter cycle is that
regeneration of adsorbent is performed by dropping the vapour pressure and this
drop is ensured by low ambient air temperature (e.g. TL = (−20)–(−60)oC). In this
case, the adsorbent regeneration does not need supply of energy that has com-
mercial value, and it is easier at colder ambient. Since the useful heat that gains
commercial value is obtained by means a low ambient temperature, the new
approach is called “Heat from Cold” (HeCol). It can be interesting for countries
with cold climate, especially for the Arctic zone [6].
1.1 Thermodynamic Cycles for AHT 7

1.1.3 Other Presentations of the AHT Cycles

Both types of the AHT cycles can be presented in many different ways, e.g. plotted
as P(T) [20], T(S) [21] and w(ΔF) [9, 22] diagrams, where S is the entropy change,
which sometimes can be more convenient than the Clapeyron chart. For instance,
both TD and PD cycles in the w(ΔF) presentation are very simple. If there is no
hysteresis, they are just one line that describes both isobaric adsorption and des-
orption stages (Fig. 1.5). In this case, only two parameters (ΔFmin and ΔFmax) are
necessary to describe the cycle; therefore, it is convenient to plot the cycle ΔF-
windows as made in [9, 23, 24].
Point A in Fig. 1.5 represents the boundary conditions at the end of the
adsorption stage (point 1 on Fig. 1.3). It corresponds to the adsorption potential
ΔFmin = −RT1 ln[Pe/Po(T1)] that characterizes the minimal adsorbent affinity nec-
essary to bind an adsorptive at temperature T1 = Tc and pressure P(Te). Point B in
Fig. 1.5 represents the boundary conditions at the end of the desorption stage (point
3 in Fig. 1.3) and corresponds to the adsorption potential ΔFmax = −RT3 ln[Pc/
Po(T3)] that is defined by the conditions of heat rejection P(Tc) and adsorbent
regeneration (TH). Adsorbate molecules that are bound to the adsorbent with an
affinity lower than ΔFmax = −RTH ln[Pc/Po(TH)] can be desorbed during the
regeneration stage 2–3. Those bound more strongly remain adsorbed and are not
involved in the heat transformation cycle.
If the two boundary temperatures TL and TM are fixed, the minimal desorption
temperature Tmin = T2 can be estimated by equating the ΔF-values for the rich and
weak isosteres:

RTM In½PL =Po ðTM Þ ¼ RTmin In½PM =Po ðTmin Þ: ð1:2Þ

Equation (1.2) can be solved graphically to get Tmin(TL, TM). Interestingly, this
value is equal to that calculated by simple Trouton’s rule [8, 25]:

Fig. 1.5 w(ΔF) presentation w

of AHT cycle
A
wmax

wmin
B

∆Fmax
∆F
∆Fmin
8 1 Adsorptive Heat Transformation and Storage …

Tmin ¼ ðTM Þ2 =TL ð1:3Þ

within an accuracy of ±1°C [26]. Evidently, if the temperature of the external heat
source TH is lower than Tmin, the cycle cannot be realized at all. Although both right
and left parts of Eq. (1.2) depend on the adsorbate nature, the minimal desorption
temperature does not.
The w(ΔF)-presentation is very convenient because the ΔF-value can be used to
define the AHT cycle borders, on the one hand, and is a universal measure of the
adsorbent affinity to the adsorptive, on the other hand [9, 27]. Fortunately, for the
majority of adsorbents promising for AHT, this presentation can be correctly
applied, because there is a one-to-one correspondence between the equilibrium
uptake w and the ΔF-value [26].
Although this and other cycle presentations listed above can be very useful for
particular cases, in whole, they are much less spreading than the common
Clapeyron diagram.

1.2 The AHT Efficiency

Here, the efficiency of AHT cycles is considered based on the first and second laws
of thermodynamics. This analysis made is invariant with the cycle type (TD or PD),
and the efficiencies are determined only by the heats exchanged and the cycle
boundary temperatures.

1.2.1 The First Law Efficiency

For an ideal 3T cycle (with zero thermal masses), the energy balance is given as

Qcon Qev Qdes þ Qads ¼ 0 ð1:4Þ

(see definition of the heats on Figs. 1.2 and 1.3). The first law efficiency of AHT
unit or its coefficient of performance (COP) is then defined as

COPc ¼ Qev =Qdes ð1:5Þ

COPh ¼ ðQcon þ Qads Þ=Qdes ¼ 1 þ COPc ð1:6Þ

for cooling and heating, respectively. For real systems, heating of inert masses
(adsorbent, metal, etc.) is also important, and the COP value depends on the
adsorbate mass Δw exchanged in the cycle
1.2 The AHT Efficiency 9

COPc ðDwÞ ¼ Qev Dw=½Qdes Dw þ CðTH TM Þ ¼ COPc ½Dw=ðDw þ BÞ; ð1:7Þ

where B = C(TH–TM)/Qdes which is the ratio of the sensible heat of all inert masses
to the latent heat necessary for desorption. Equation (1.7) suggests that to increase
the first law efficiency, the exchanged mass Δw = w2–w1 must be maximized and
the contribution B of inert masses minimized (see more detailed analysis in [20] and
in Sect. 1.4.1).

1.2.2 The Second Law Efficiency

For an ideal TD system, the energy balance (the first law) of Eq. (1.4) should be
supplemented with the entropy balance and given as

Qcon =TM þ Qev =TL þ Qdes =TM  Qads =TH ¼ DS  0: ð1:8Þ

If all the processes are completely reversible, the entropy generation is equal to
zero (DS = 0). Figure 1.1 can be used for better physical interpretation of the
second law analysis. It illustrates that a 3T AHT cycle can be conditionally divided
into two Carnot cycles, namely the bottom cycle between temperatures TL and TM
and the top cycle between temperatures TM and TH. For instance, for the heat
amplification (mode 3 on Fig. 1.2), the bottom cycle works as a heat engine cycle
and the top one as a heat pump cycle. Both the cycles are coupled and run
simultaneously. The bottom cycle produces the work W = Q1(1 − TL/TM) which is
used to upgrade the heat Q3 to higher temperature level TH in the top cycle
(Fig. 1.1). The Carnot efficiency of the heat engine working at very unusual con-
ditions is shown in Fig. 1.6 left: the heat is consumed at TM = 2°C = 275 K and
rejected at TL between 275 and 100 K. The thermostat at 2°C can be a natural
non-freezing water reservoir, such as ocean, sea, river, lake, underground water. If

(a) (b)

Fig. 1.6 The second law efficiency for two (a) and three (b) temperature cycles as a function of
the ambient air temperature TL (left—TM = constant = 275 K; right—the TM values are indicated
near appropriate curves (in K) and (TH−TM) = 30 K) [6])
10 1 Adsorptive Heat Transformation and Storage …

the other natural thermostat, e.g. the ambient air, has temperature TL = −30°C
(243 K) and −50°C (223 K), the efficiency of the Carnot heat engine equals 0.116
and 0.189, respectively (Fig. 1.6a). It seems quite encouraging, especially if keep in
mind that the heat at TM is consumed for free. Afterwards, this work can be used to
upgrade the temperature of heat taken from the water basin up to a higher level (TH)
sufficient for heating, thus gaining commercial value [6].
The Carnot efficiency of the whole 3T heat transformer was calculated for
cooling, heating and temperature upgrading modes in [28, 29]:

COPCc ¼ ð1=TM 1=TH Þ=ð1=TL 1=TM Þ; ð1:9Þ

COPCh ¼ ð1=TL 1=TH Þ=ð1=TL 1=TM Þ; ð1:10Þ

COPCT ¼ ð1=TL 1=TM Þ=ð1=TL  1=TH Þ: ð1:11Þ

The function COPCT (TL) is calculated from Eq. (1.11) for various TM and the
constant temperature lift (TH − TM) = 30 K (Fig. 1.6b). At ambient temperature
TL = −40°C, the Carnot efficiency is higher than 0.6 and further increases if more
warm natural water is available (e.g. underground water at TM = 30°C).
Equations (1.5) and (1.6) express the first law AHT efficiency through the
enthalpies of evaporation and desorption which are characteristics of the adsorbent–
adsorbate pair. The second law efficiency in Eqs. (1.9)–(1.11) depends only on the
three temperatures that determine the AHT cycle, but not on properties of the
working pair in an explicit form. The link between these two COP definitions was
considered in [29] (see also Sect. 1.4.2).

1.3 Dynamics of AHT Cycles

Another important figure of merit that is used to characterize the AHT performance
is the specific power (SP) which can be defined as

SP ¼ Qus =ðmads tÞ; ð1:12Þ

where Qus is the useful heat (e.g. Qev for cooling cycles), mads is the dry adsorbent
mass, and t is the cycle time. The power can also be related to a unit volume of the
adsorbent or the whole AHT device. This parameter defines the quantity of
adsorbent or the size of AHT unit necessary to obtain a given power.
The target to develop compact and efficient AHT units asks for a high rate of
adsorption/desorption process at the isobaric stages of AHT cycle (Fig. 1.3). The
interaction of vapour molecules with a solid surface is itself very fast, and the
overall rate is usually determined by the intensity of heat and mass transfer
(HMT) in the unit “adsorbent–heat exchanger” (Ad-HEx). Namely, poor HMT is
considered to be a crucial factor for heat transformers based on solid sorption
1.3 Dynamics of AHT Cycles 11

technology [30] and its improvement is a key point. The heat transfer is deemed to
limit the sorption processes if the adsorbent bed is composed of loose grains. The
mass transfer is crucial for compact adsorbent beds/layers consolidated with a
binder.
The heat transfer in AHT systems is characterized by the overall heat transfer
coefficient U given by the well-known relation:

1 1 1 def
¼ þ þ ; ð1:13Þ
USf hf Sf hw Sef kef Sef

where Sf and Sef are the heat transfer surfaces on the fluid and solid sides, hf and hw
are the heat transfer coefficients on these sides, and def and kef are the effective
thickness and thermal conductivity of the adsorbent bed.
It is convenient to use Eq. (1.13) for analysing the main heat transfer resistances
(Fig. 1.7):
• The first term in the right side describes the heat transfer between the heat carrier
fluid and the HEx fin; the heat transfer coefficient hf is high (> 500−1,000 W/
(m2 K)) except for the special case of thermal wave process for which a laminar
flow is required [14]. The heat transfer surface Sf has to be maximized; there-
fore, advanced HEx modules are highly desirable as discussed in Chap. 4;
• Slow heat transfer in AHT units is deemed to be due to the high thermal contact
resistance between the adsorbent bed and the HEx wall (the second term in
Eq. (1.13)) and the low effective thermal conductivity of the bed (the third
term). This is especially crucial for AHT utilizing loosed adsorbent grains. The
high wall contact resistance is mainly due to (a) increasing porosity of the
adsorbent bed adjacent to the HEx wall and (b) the absence of gas convection in
the voids near the wall. In the majority of mathematical models, the heat transfer

Fig. 1.7 Schematics of various heat transfer resistances in the Ad-HEx unit
12 1 Adsorptive Heat Transformation and Storage …

coefficient hw on the solid side is taken as 15–50 W/(m2 K) [31, 32]. It can be
enhanced by (a) increasing the bed density near the wall due to grain gluing
(binding) [33] or by the bed filling with multi-sized grains [34]. The “wall–bed”
heat transfer can also be enhanced by simply extending the heat transfer surface
Sef as typical for well-designed Ad-HExes [35]. In this case, the term (hw Sef)
can reach high values even if hw is small, provided Sef be high enough [30];
• High heat transfer resistance is caused by the low effective conductivity kef of
the granular bed itself (about 0.1 W/(m K) for zeolite and 0.2–0.3 W/(m K)
active carbon). This conductivity can be increased by developing either con-
solidated adsorbent beds or coated HEx surfaces [30, 33, 36] with advanced kef -
values. However, in consolidated beds/coatings the mass transfer problems can
arise. The extensive, yet efficient, trick is reduction of the bed thickness that is
readily reached in modern HExs with extended surface area (see Chap. 4). As
shown in [35], for the loose grains configuration, practically interesting SP
values can be obtained only for thick enough beds of 2–4 mm.
It is worthy to mention that the above-discussed low values of the bed heat
transfer parameters (hf and keff) were measured under quasi-equilibrium conditions,
means, at small deviation of the system from the equilibrium. Typical examples are
the IDS method (see [37] and Sect. 2.1) suggested for measuring the gas diffusivity
under isothermal and isobaric conditions, or a hot wire method [38] widely applied
for determination of the thermal conductivity by analysing the system response after
a small deviation from adsorption or thermal equilibrium. For real AHT units, the
essential temperature difference (20–40°C) between the HEx fin and the adsorbent
bed is typical. This may result in significant intensification of heat and mass transfer
(see [7, 39] and Chap. 4).

1.4 Adsorbents Optimal for AHT

Future progress in the AHT field is essentially related to the development of

innovative adsorbents suitable of efficient AHT performance. Two complementary
strategies are used [40]: (a) systematic testing for AHT aims various adsorbents
initially developed for other targets (gas drying, separation, etc.) and (b) tailoring of
new specific adsorbents adapted to variety of AHT cycles under different climatic
and boundary conditions. The first step of both strategies is the formulation of
requirements to an adsorbent which is, in theory, optimal for the particular AHT
cycle [40]. The requirements evidently depend on what criterion is used to evaluate
the optimal performance: the first or second law efficiency. More difficult is the
assessment of the dynamic optimality, which depends less on adsorbent inherent
properties and more on a number of external factors, such as design of heat
exchanger, configuration of adsorbent bed, efficiency of heat supply/rejection,
pressure and temperature levels. [7, 9, 39]. The requirements to adsorbents optimal
1.4 Adsorbents Optimal for AHT 13

for common TD cycles are discussed below. Those for PD cycles have recently
been formulated elsewhere [41, 42].

1.4.1 The First Law Efficiency

According to Eqs. (1.5) and (1.6), the ideal cooling and heating COP approaches to
1 and 2, respectively, when Qev ! Qdes. For instance, this COP for silica gels is
larger than for zeolites as less heat is used for regeneration (45–55 kJ/mol vs. 60–
80 kJ/mol). If carefully account for the inert masses M (Eq. (1.7)), the COP can
significantly decrease, when these masses are 2–3 times larger than the mass of
adsorbent mads [20]. This is more pronounced for the “Fuji silica RD—water”
system than for “Mitsubishi AQSOA Z02—water” one, because for the latter
system the exchanged mass Δw is 3–4 times larger, which accords with Eq. (1.7).
For well-designed AHT units (mmet/mads  1), the COP approaches its maximum
value (Qev/Qdes) already at Δw  (0.1–0.15) and (0.2–0.3) g/g for water and
methanol/ammonia, respectively. Hence, to achieve the maximum first law effi-
ciency it is sufficient to use an adsorbent that exchanges the mentioned amount of a
working fluid (or more) between the rich and weak isosteres. Such an adsorbent
may be considered as harmonized with the particular cycle. Well-enough adsor-
bents of water, methanol and ammonia adequately satisfy this condition for air
conditioning and heat pumping cycles.
It is important to highlight that:
(a) searching for adsorbents with very large Δw values (> 0.5 g/g), such as SWSs
[43], MOFs [44], is the ultimate priority for heat storage rather than for cooling/
heating applications;
(b) the maximum COPc (0.7–0.9) for real AHT cycles is significantly lower than
predicted (Eq. (1.9)) for a reversible Carnot cycle with the same boundary
temperatures [45, 46]. Very special case when the first and second law effi-
ciencies are equal is considered right below;
(c) the question “What is the well-designed Ad-HEx unit?” is considered in
Sect. 1.4.

1.4.2 The Second Law Efficiency

As stated just above, the experimental COP of typical adsorptive and absorptive
chillers is significantly lower than predicted by Eq. (1.9) [46]. This difference is
only slightly compensated by various modifications of the basic 3T cycle, e.g. by
using “double-effect” cycles in which waste heat from an upper cycle is used to
drive a lower cycle [13, 25]. The main reason of this huge distinction is the thermal
entropy production caused by the external thermal coupling ΔT = TH – TM [45].
14 1 Adsorptive Heat Transformation and Storage …

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; therefore, to enhance the AHT
efficiency the thermal coupling should be minimized.
The most of entropy is produced during isobaric adsorption (4–1) and desorption
(2–3) stages. If the heat for regeneration is supplied directly at the minimal des-
orption temperature (TH = Tmin = T2), there is no thermal coupling at stage 2–3;
therefore, no entropy is generated during desorption process. As a result, the COP
values calculated from the first and second laws are equal, so that the maximum
(Carnot) efficiency is reached as shown in [29].
This imposes appropriate requirements on the shape of the sorption isobar for an
adsorbent optimal for TD AHT cycles: The rich and weak isosteres must coincide,
so that the cycle becomes degenerated, and the isobaric adsorption 4–1 and des-
orption 2–3 (Fig. 1.3) occur immediately and completely at temperatures TM and
TH (Fig. 1.8a), respectively [26]. The degenerated cycle can be realized only with
an adsorbent characterized by a mono-variant equilibrium. The optimal adsorbent
has to sorb a large amount of adsorbate in a stepwise manner directly at TM and PL
and completely desorb it at TH and PM (Fig. 1.8b). Hence, in theory, the adsorbent
optimum for AHT should have a stepwise adsorption isobar [26, 47]. Real adsor-
bents, however, exhibit S-shaped adsorption isobars (Fig. 1.8c) instead of strictly
stepwise ones. Such adsorption equilibrium corresponds to isotherms of types V
and VI in the IUPAC classification [48]. The second law harmonization of the
adsorbent and the cycle means that the position of the step must coincide with the
boundary temperatures TM = T4 at P = PL and T2 = TH at P = PM as shown in
Fig. 1.8b. If the adsorbent is not optimal so that the adsorbate is removed at
TH > Tmin, the efficiency becomes lower than the Carnot one.
Hence, a high second law efficiency may be attained by a proper choice of
adsorbent without using efficient, but sophisticated methods of heat recovery in
multi-bed [49] and thermal wave [14] systems, or “multi-effect” cycles [13, 25].

1.4.3 Adsorbent Optimal from the Dynamic Point of View

As mentioned above, it is more difficult to formulate the dynamic requirements to

the optimal adsorbent because the whole unit “adsorbent + heat exchanger” has to
be considered [7, 9, 39]. A simplified dynamic analysis can be performed for the
common case when the adsorption rate, at least, initial, is controlled by the heat
transfer between the adsorbent and heat exchanger (HEx) fin [50].
This analysis reveals that for the process intensification and reduction of the
cycle time the most profitable is to supply the majority of heat to or reject it from
the adsorbent bed at maximal possible temperature difference between the HEx and
the adsorbent. At desorption stage, the position of the isobar step should be close to
the minimum desorption temperature T2, while the regeneration temperature TH
should be higher to create sufficient driving force to supply heat for desorption. At
adsorption stage, the step should be positioned at temperature Tads that is higher
1.4 Adsorbents Optimal for AHT 15

Fig. 1.8 Degenerated AHT

cycle characterized by a
single adsorption/desorption
isostere (a); corresponding
step-like (b, d) and S-shaped
(c) isobars of adsorption (at
P = PL) and desorption (at
P = PM) optimum from the
thermodynamic (b, c) and
dynamic (d) points of view
[9]

than the temperature TM of cooling fluid to create sufficient driving force for
rejecting heat of adsorption. It is worthy to mention that this dynamic requirement
to maximize the temperature difference DT = TH – Tdes (or Tads – TM) is in a dis-
tinct contradiction with the thermodynamic requirements which suggest to mini-
mize DT to reduce the entropy generation. Thus, proper choice of the isobar step
16 1 Adsorptive Heat Transformation and Storage …

position greatly depends on which output parameter is to be maximized—the

efficiency or the power. If both parameters are important, a reasonable compromise
must be reached by intelligent design of the “adsorbent—heat exchanger”
(Ad-HEx) unit (see Chap. 2). This situation is very typical since the highest COP is
always obtained at low power [30], means, at slow dynamics. In any case, the most
advantageous adsorption isobar is step-like with the largest acceptable ΔT between
the step temperature and the HEx fin temperature (Fig. 1.8d).
The two types of adsorptive cycles for heat transformation, namely temperature
and pressure driven, dictate two different methodologies for studying the cycle
dynamics. A Large Temperature Jump (LTJ) method [51] imitates non-isothermal
conditions of the isobaric stages of TD AHT cycles (2–3 and 4–1 on Fig. 1.3).
A Large Pressure Jump (LPJ) method can be used to simulate isothermal
adsorption/desorption dynamics caused by the vapour pressure jump/drop at
appropriate stages of PD AHT cycles (2–3 and 4–1 on Fig. 1.4) [52]. The latter
method is known since many years [53]; however, until recently, it has been used in
a way that the pressure jump/drop was not linked with the particular AHP cycle (see
e.g. [54]) as discussed in [7]. Both these methods are comprehensively introduced
in Chap. 2, and appropriate results obtained are considered in Chap. 4.

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Chapter 2
Measurement of Adsorption Dynamics:
An Overview

Nomenclature
Ad-HEx Adsorbent–heat exchanger
COP Coefficient of performance
LTJ Large Temperature Jump method
V-LTJ Volumetric version of the Large Temperature Jump method
G-LTJ Gravimetric version of the Large Temperature Jump method
LPJ Large Pressure Jump method
HEx Heat exchanger
IDS Isothermal Differential Step
P Pressure, Pa
PD Pressure driven
SCP Specific cooling power, W kg−1
T Temperature, K
TD Temperature driven

Subscripts
ads Adsorbent/adsorption
c Condensation
e Evaporation
H High

Analysis of the Ad-HEx dynamic behaviour is of pivotal importance in develop-

ment of advanced adsorber concepts, enabling reduction of weight and volume of
the real adsorption heat pump/chiller unit, as well as its energy density enhance-
ment. In general, the experimental methodologies for adsorber performance eval-
uation can be distinguished considering different scales of the tested adsorber:
(1) Investigation of adsorption kinetics of the adsorbent itself, allowing to obtain
detailed experimental data, that are useful for estimating the heat and mass
transfer characteristics.

© The Author(s) 2018 19

A. Sapienza et al., Dynamics of Adsorptive Systems for Heat Transformation,
SpringerBriefs in Applied Sciences and Technology,
https://doi.org/10.1007/978-3-319-51287-7_2
20 2 Measurement of Adsorption Dynamics: An Overview

In case of water as adsorbate kinetics of adsorption in common porous media

(zeolite, silica gel, etc.) was a subject of numerous studies [1], demonstrating that
the adsorption kinetics is dictated by heat transfer and water transport through
adsorbent pores. In the following paragraph, we treat an Isothermal Differential
Step (IDS) method that is considered today the most adequate method to measure
the water adsorption kinetics on adsorbents.
(2) Study of adsorption dynamics of the adsorbent (Ad) and heat exchanger
(HEx) as an integrated unit (Ad-HEx).
This is an important aspect, as the overall adsorption rate depends on both heat
and mass transfer properties of the combination of the adsorbent itself and the heat
exchanger unit. Another important requirement is to study the adsorption dynamics
under operating conditions that are as close as possible to the real operating con-
ditions of an adsorption heat pump. To fit these requirements, two main different
approaches are used [2]:
(a) a Large Pressure Jump (LPJ) method, where adsorption is initiated by a pres-
sure jump imposed to the sample, continuously cooled by an external source. In
this method, the heat transfer properties of the samples still have major influ-
ence in the experiments due to the heat released during adsorption. The LPJ
method is adequate for pressure-driven AHT cycles (see Chap. 1, Fig. 1.4)
(b) a Large Temperature Jump (LTJ) method, where adsorption is enabled by a
temperature swing of a heat exchanger wall that is in thermal contact with the
adsorbent under an almost isobaric ad/desorption stage. The LTJ method is
practically implemented in two ways, depending on the measurement technique
for monitoring the temporal evolution of the adsorbed mass: indirect (volu-
metric) and direct (gravimetric). These LTJ methods are suitable for common
temperature-driven AHT cycles (see Chap. 1, Fig. 1.3)
In the following paragraph, the fundamentals and main apparatuses realized for
the LPJ and LTJ tests are introduced.
(3) Study of the dynamic behaviour of full-scale adsorbers, allowing to evaluate the
coefficient of performance (COP) and the Specific Cooling Power (SCP), that
are important figures of merit for adsorption heat pumping/cooling processes.
Normally, such experimental studies are carried out by dedicated test-rigs that
are designed to test the entire adsorber under realistic boundary conditions [3]. This
specific testing methodology will not be a subject of this book.
2.1 Differential Step (IDS) Method 21

2.1 Differential Step (IDS) Method

The Isothermal Differential Step (IDS) method is considered the simplest and most
effective method to investigate the adsorption kinetics of the adsorbent, allowing to
obtain important kinetic parameters like the diffusion constant, vapour diffusivity
and heat transfer parameters [1]. The uptake rate is determined by the analytical
solution of the differential mass balance equation. Normally, measurement of
kinetic curves is coupled with water adsorption equilibrium measurement, as the
knowledge of adsorption equilibrium parameters is required for the data analysis.
IDS method involves the following typical test procedure:
(i) setting of initial equilibrium between the adsorbent and adsorbate vapour at
given pressure P0 and temperature T0;
(ii) stepwise change of pressure by a small value ΔP (typically a few mbars)
under isothermal conditions;
(iii) direct measurement of the adsorbent weight evolution due to water sorption
(i.e. measurement of the kinetic curves).
Many papers on the IDS method are available in literature. Here, as an example,
we report application of the IDS method for studying the kinetics of water
adsorption on silica Fuji Davison RD and the composite sorbent SWS-1L “calcium
chloride in silica gel” [4, 5]. In such works, the IDS method was applied by using a
CAHN 2000 thermo-balance, which is a force-to-current converter (balance reso-
lution: 0.1 mg, reproducibility ± 0.2 mg, accuracy ± 0.1%). Figure 2.1 shows the
overall schematic of the closed-volume thermo-gravimetric system. The essential
components are the measuring cell (glass version) where the sample and balance are
contained, a vacuum pump for initial degassing operations, a thermostated water
reservoir, which acts as vapour dosing system, a thermal regulator that allows the
sample temperature control with accuracy ± 0.1 K.
Measurements are carried out using a small amount of sample (typically 10 mg)
in order to reduce thermal effects [1]. For further reduction of these effects, the
adsorbent grains are dispersed on the surface of aluminium pan and mixed with
small pieces of copper wire in order to increase the heat capacity of the measuring
cell and keep the sample as close as possible to the ideal isothermal condition.
Typical experimental run to obtain direct experimental data for the kinetics of water
adsorption is as follows: the sample under test is initially degassed at high temperature
for several hours and then cooled down to the required test temperature under vacuum
conditions (P = 1e−4 kPa). Afterwards, the measuring cell is connected to the ther-
mostated evaporator in order to establish fixed pressure and temperature conditions
until reaching equilibrium conditions over the sample. Subsequently, the connection
between evaporator and measurement chamber is closed and the temperature of
evaporator is slightly increased in order to obtain a correspondent water vapour pres-
sure increase (typically 2–3 mbar). Finally, the gate valve connecting the evaporator
and measurement chamber is suddenly opened, allowing a quasi-instantaneous pressure
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