Cacciola 1986

Applied Energy 25 (1986) 315-337
Chemical Processes for Energy Storage and

Transmission
G. Cacciola a n d N. G i o r d a n o
Istituto CRN/TAE, Via Salita S. Lucia sopra Contesse, 39,

98013 Pistunina, Messina (Italy)
SUMMARY
Chemical reaction, adsorption of a gas in a solid, or adsorption of gas

in a liquid solvent can be used to solve problems in conservation, storage
and transmission of energy. Possible applications of such processes are
chemical heat pumps, cooling systems, heat transformers, chemical heat
pipes, separation, storage and transmission of hydrogen. In the present
paper, the principal chemical processes are described with their applica-
tions, advantages and drawbacks.
INTRODUCTION
All types of primary fuels, whether renewable or not, need trans-

formations for their utilization, depending upon the characteristics of
the users; among others, the location (far from or close to the source)
and the time at which the energy is requested must be taken into account.
If the primary energy source is located far from the users or if there is
a time mismatch with the load request, it would be difficult for this
primary energy to be economic even if its cost at source were very cheap.
This is particularly true if the transmission or storage of the primary
energy is expensive or not very efficient.
In present energy production systems, the principal primary energies
are hydropower, nuclear and chemical fuel (i.e. oil, coal, gas), their
transformations depending on the type of energy required (Fig. 1). In
315
Applied Energy 0306-2619/86/$03-50 © Elsevier Applied Science Publishers Ltd,
England, 1986. Printed in Great Britain
316 G. Cacciola, N. Giordano
/ \
tSTORAGE)
~x~_~// MECHANICAL I
HYDROPOWER [ ~ . ,I ].i~.l ELECTRICITYI__
I ENERGY [ I I X \ TRANSMI.SSIOWLINE
FUEL 1'~ Tr~nsm,ss,o.'- .." ~ I I

I
("N RGY( / E,'ERGY I l JU
<ZZ]" .I,, THERMAL ENERGY )

FUEL USER
Fig. 1. Existing energy systems.
the first case (hydropower), the primary energy is stored by dams and
then transformed into electricity which is transmitted to the users; in
the second case (nuclear), fuel is transported to power stations and
stored before being transformed into electricity; in the third case, the
chemical fuel is transmitted to the users and then stored and transformed
into heat, as requested.
In these three energy systems, storage is accomplished by means of
reservoirs, fuel bunkering, and batteries and hot water tanks, respec-
tively. These types of storage systems have completely different charac-
teristics and, obviously, different energy densities, as shown in Table 1.
Energy transportation is accomplished by electricity transmission
TABLE 1
Approximate Energy Densities of Storage Systems
Energy density
Jm - 3 Jkg- 1
Chemical fuel 101o_1011 10 6

Lead accumulators 108-109 l0 s
Hot water (AT= 20 K) 10a l0 s
Water fall (elevation 100 m) 106 I0a
Chemical processes for energy storage and transmission 317
lines, gas and liquid pipelines, tank trucks and barges and, in a few
cases, by pumping fluids at higher temperatures with respect to the
environment: this latter transportation system, however, can be adopted
only for short distances.
By means of these relatively simple storage and transmission methods,
the actual energy system makes the above-mentioned primary sources
technically and economically exploitable. On the other hand, this energy
system is not optimized; in fact, when various energy transformations
are needed it would be preferable to store or transmit energy in the
form requested by the users, especially if the required transformations
were not very efficient. In this way the a m o u n t of energy to be stored
or transmitted would be the least possible with respect to the unitary
energy obtainable with the present systems. This is because in this way
energy losses which eventually accompany the transformations following
storage or transmission do not take part in the energy to be stored or
transmitted. Thus the influence of storage and transmission plants on
the total cost of the energy would be less, provided that the efficiency
of the storage and the transmission system is high. Therefore, because
energy is requested in the form of heat or electricity, it would be better
to find new processes which render feasible the direct storage of electricity
and the storage/transmission of thermal energy. Besides, owing to their
low temperature differences from ambient, large amounts of thermal
energy are not utilized: this waste heat, generally available in industrial
sectors, could be recovered by storing, upgrading and utilization in the
same or other similar operations.
Chemical processes could solve many of the above-mentioned prob-
lems, enabling the storage and transmission of energy in order both to
optimize the actual energy system and to render feasible a different
energy system in which new sources would play an important role.
Moreover, chemical processes could contribute, in the near future, to
the recovery of industrial waste heat, which could be considered as an
important alternative energy source.
T H E R M O C H E M I C A L S T O R A G E OF HEAT
The thermochemical storage concept is quite old, but the first reports
on the screening of chemical reactions for the storage of thermal
energy l - 3 started to appear in specialized magazines only about ten
CCH CCH
Fig. 2. Simple scheme o f t h e r m o c h e m i c a l energy storage system: E = t h e r m a l energy,

En R = e n d o t h e r m i c reactor, Ex R = exothermic reactor, T = storage tank, C C H =
c o u n t e r c u r r e n t heat exchanger.
years ago, i.e. after the energy crisis of 1973. In the simplest scheme (see
Fig. 2), the thermochemical storage system is made up of two reactors,
the endothermic (En R) and the exothermic (Ex R), two tanks (T) and
two heat exchangers (CCH). The generic reaction is
heat out
(reagents) (products)
where the energy to be stored drives the reaction to the right, while the
heat is re-obtained by allowing the products (P~) to react and thus to
reform the reagents (RI).
Originally the basic idea was to allow, by these means, the storage of
solar energy at a high temperature, and for a long period. Moreover,
as the adaptation of the latent or sensible heat of salts or other materials
would have required large volumes, thermochemical reactions appeared
immediately as the best solution to these problems. In fact they allow
the storage of heat at high temperatures, with high densities and without
time-dependent losses. But after detailed analysis more problems have
emerged. A m o n g these, the most important are:
(1) The sensible and the latent heats to be supplied to the reagents
entering the reactor are very high, so that a countercurrent heat
exchanger system would be needed to recover the same heat from
the products exiting from the reactor.'* Lacking the recovery of
this large a m o u n t of energy, the efficiency of the whole system
is drastically reduced, and therefore it is important that the

countercurrent heat exchanger be efficient, which means large
exchangers and high investment costs.
(2) Simulation studies on solar-energy applications have shown that
the annual amount of energy coming from a storage system and
furnished to the user depends on the energy-storage capacity, as
shown by the function in Fig. 3. 5.6 Thus 9h storage capacity (1 h
storage capacity being the amount of energy that must be stored
to supply the load for 1 h, during the discharge phase) is sufficient
to obtain good performance. Beyond this, the performance
increase per hour of storage added diminishes. Even though the
curve shown in Fig. 3 refers to a specific location (Albuquerque,
New Mexico, USA) and to a constant load, a general result is
that a hybrid plant (i.e. a solar-energy system with storage and
with a conventional energy source) would be better than an
autonomous plant with seasonal storage. But this would render
useless one of the principal advantages of thermochemical
storage.
(3) The cost of a storage plant could be divided into two parts:
(A) cost of the power-dependent equipment;

(B) cost of the capacity-dependent equipment.
In this way the general formula of the cost per unit of installed
power is
C=A+Bh
where h represents the hours of storage. Coefficient A is very
high for thermochemical energy storage because the cost of
reactors, heat exchangers, pumps, compressors, etc., must be
taken into account, whereas coefficient B is low because only the
cost of the non-insulated tanks is considered. The opposite
situation ensues with storage systems using latent or sensible
heats. Therefore, as shown in Fig.4, thermochemical energy
storage becomes competitive only for storage periods exceeding
30 h, but, as mentioned in (2) above, storage of solar energy for
a long period is useless, especially if the load is constant. 5'6
Thus, not considering chemical and physical problems such as corrosion,
reversibility, catalysis, kinetics, etc., which could be solved or have been
_J
tY,¢
to >_
v--
tt~ >- 5000
<
{~0
eet--
taJZ 3~0
Z<
W..a
la
1000
O
"I"
' 2; ' ~b ' 5b ' 8'0 ' ,00

HOURS OF STORAGE
Fig. 3. Annual energy from storage versus storage capacity for Albuquerque, New
Mexico, USA.
SENSIBLE PHASE
/ HEA, / CHANGE
/ //" .1 "
~T~ERMOCHEMICAL
/ jJ
/2---'"
/
o ,o o 30 ~o s 60 70 o ~oo
HOURS OF STORAGE
Fig. 4. Storage investment costs (in arbitrary units) versus storage capacity for three
storage systems.
solved on a laboratory scale, the thermochemical storage of energy has

not yet given the expected answer to the problem of thermal storage.
On the other hand, this analysis has indicated two other important
applications which will later be described.
Chemical heat pumps
The general scheme of a chemical heat-storage system (Fig. 5) using one

of the three processes shown in Table 2 7 points out that, during the
charge (endothermic) phase, the liquid solvent or the solid remains in
the 'reactor', R, while the freed gas product, to be cooled by heat
exchanger Ex l, is stored inside tank C. Due to the particular configura-
tion of the storage system, the heat recovered in cooling the gas and
made available during the charge step must be considered as a loss,
whilst during the discharge phase the liquid has to be heated before
entering R. For these two reasons, the efficiency of the system is expected
to be very low. On the contrary, the efficiency could improve if the
system were allowed to work in a closed loop, and if it were possible
to recover the condensation heat of the fluid. To do so, operative
conditions as in a heat pump system must be realized: more particularly,
three different temperature levels are needed, high (T1), medium (T2)
Ex 1
I
E
oo ---:--.-.-._-
Ex 2
Fig. 5. Simple scheme of a chemical heat-storage system using gas-solid reactions:
Ex l and Ex 2 -- heat exchangers,C = tank for condensedfluid, R = reactor.
TABLE 2
Chemical Processes to be Used in Chemical Heat Pump Systems
Endo
(a) Liquid absorption Solvent, xG . • Solvent, yG + ( x - y ) G
liquid Exo liquid gas
Endo
(b) Solid adsorption Adsorbant, zG . • Adsorbant, nG + (z -- n)G
solid Exo solid gas
Endo
(c) Decomposition of defined Salt, n G . ~ Salt, mG + (n - rn)G
chemical compound solid Exo solid gas
and low (T3). During the charge phase, the endothermic reaction (which
evolves by the heat furnished by an external source at T~) takes place
at pressure PI and temperature T~, and the desorbed gas is cooled at
the medium temperature T2 (T2 < T~), releasing heat to the user. During
the discharge step, because the solid or liquid adsorbant is maintained
at temperature T2, the vapour pressure becomes lower (P2) with respect
to the charge phase, so that it is possible to evaporate the gas in Ex 2
at a very low temperature, T3 (i.e. near ambient). Finally, with such a
system it is possible to release heat at a medium temperature (T2) during
both the charge and discharge phases, while the heat is furnished to the
system at temperatures TI and T3.
Because the latter temperature is referred to ambient, the corre-
sponding heat is generally not taken into account in the evaluation of
the system efficiency, which in this case is called the coefficient of
performance (COP):
COP=.Q2 + Q4
Q1
where Q2 = condensation heat, Q4 = adsorption heat, and Q1 = desorp-
tion heat. Since Q~ = Q4 and Q2 = Q3 and not taking into account the
heat Qa coming from the cold source T3, the theoretical COP is greater
than unity.
As mentioned above, processes which can be used accordingly belong
to the three different schemes reported in Table 2, where the first two
are bivariant while the third is monovariant. In the bivariant systems,
the equilibrium is controlled by two variables among temperature,
pressure and percentage by weight of gas in the adsorbant or in the
solvent. For such cases, the chemical heat p u m p thermodynamic cycle
LOG(P) [turn Hg ]
3.13
2.6
2.2 ..... \ °,__ .,so,

1.8
l ~ T"N- (co.cE.rR.r,o.
tzJ
r,- 1.4
u3 J ",,,LO~ N_03
,,i 1.0
n- I j - i-
o_ 0.15 I
n-
0.2 ' \
oo_._ I .
I
< -0.2 I
-0.6 '
I
I
)
-I .01 I I I ' l I I I I il
1.5 2.0 2.5 39 3,5 4.0 lfl 3

L 1 [ T,K,
Ti : 245.I'C T2 :Tt : 61,4°C T3:l 2.7"C
Fig. 6. Chemical heat pump thermodynamic cycle referred to the H2SOJH20 system.
as shown in Figs 6 and 7, referred to a sulphuric acid solution 8 and a

zeolite-water adsorption process, respectively. 9"1°
In the monovariant process, the control of only one variable of the
system (temperature or pressure) is required, the other variable being
fixed when the reaction is taking place. In this process, if one maintains
the decomposition pressure at P1, the temperature remains at 7"1 as long
as the decomposition is incomplete, while in the bivariant process,
during desorption at pressure P~, the temperature requested increases
with the decrease of the percentage of gas in the adsorbant or in the
solvent.
A thermodynamic cycle of the monovariant process type:
CaC12 . 2 C H 3 O H . , ~ CaC12 + 2CHaOH
solid solid gas
is shown in Fig. 8.11"~2
LOGOP [n r. Hg]
2.#- °' ~ l Q2 D
2.2- i
I
1.8, I
I
1.4 II
I
1.0 I
0.6.
0.2
-0.2
-0.1
-1.10
1.5 ~ 2.0 2.5 [ 3.0 3.5[ 4.0 10'
T(K)
Tl : 298.4"C T2 : T¢:83.5 °C T3:3.2

Fig. 7. Chemicalheat pump thermodynamiccyclereferredto the zeolite-watersystem.
The processes described could also work with two solids; that is,
instead of gas condensation, another gas-adsorption process is added.
By this means, the thermodynamic cycle of the process is limited by the
equilibrium lines of the two reactions.
A possible example of this application is furnished by the following
reactions: 9
397K
Feel2" 6NHa "a47K FeC12" 2NHa + 4NHa
267K
CaC12 "4NH3 + 4NH3 "3o5K CaCl2" 8NHa
Other energy cycles with liquid absorption and gas-solid reactions
The three processes described above could also be utilized in two

other energy systems, cooling systems and heat transformers. The
LOG( P)[mmHg ]
02
3.0
2.6
2.2
1.8
Q4 ~t ~_ 03
1.l,
1.0
O.G
0.2
-0.2
-o.61
-1.0 I I I I I I ~'~ I I It
1.5 2.0 2.5 3.0 3.5 4.0 10 3

t t t
T~:125.4"C T2:T~:80.3"C T3:53"C
Fig. 8. Chemical heat pump thermodynamic cycle referred to the CaCIz/CH3OH
system.
t h e r m o d y n a m i c cycle o f a cooling system using gas-solid reactions or

liquid absorption processes is the same as that o f the heat pump, if one
considers that the useful effect is the cooling o f the low temperature
source, which allows evaporation o f the gas. Thus, using the previous
symbols, the efficiency of the system in this case is
03
-- eZ
where Q3 = evaporation heat.
The heat transformer is a system which upgrades heat to a higher
temperature without the use o f other mechanical or highly valued
thermal energy. In this case, the discharging operation occurs at a
pressure higher than that of the charge phase, as shown in Fig. 9. The
energy is furnished to the system at temperature T, and is composed of
two quantities: the desorption heat (Q~) and the heat necessary to
LOG( P)[rn m t-i:j]
15% 22.3%
3,0
Q2
2.6
2,2
H20
1.8
1.4
Q3
1,0
0.6
0,2
-0.2
-0.6
-1,0
1.5 2.0 215 3'.0 3.5 ,~.0 103
It :121.4"13 I1:T2=90.6"C T3:15.1"C

Fig. 9. Heat-transformer thermodynamic cycle referred to the zeolite-water system.
evaporate the gas (Q2). Useful heat is the adsorption heat (Q4), which
is released at the highest temperature of the cycle (T4). Thus the efficiency
of a heat-transformer system is given by
Q,
t/= Q1 + Q2
Many chemical 'reactions' among processes (a), (b) and (c) of Table 2
have been studied and their principal properties as well as their
thermodynamic and kinetic characteristics have been related to the
above applications. Also pilot-plants have been built in order to optimize
the efficiencies and to evaluate the economics of such systems. A few of
the principal parameters which show the expected performances of these
reactions are reported in Table 3.
The actual problems related to these types of systems are:

(1) optimization of the design of the heat exchanger;
(2) identification of the sectors (industrial or civil) where these
systems can be utilized.
For both, many answers have been given in relation to the geometries
and the materials of the heat exchangers, as well as to the fields of
application. Nevertheless, more detailed work will have to be done,
TABLE 3
Thermodynamic Comparisons of Two Chemical Processes for CHP, Cooling and
Heat-transformer Systems
System Process TI(K) T2(K) Ta(K) COP Energy densiO"

(kJkg- 1)
CHP Zeolite/H20 552 353 278 1"7 624

H2SO4/H20 397 313"5 272 !.57 535
Cooling Zeolite/H20 485 313 278 0.80 334
H2SO4/H20 394 300 277"4 0-72 245
Tt(K) T,(K) T3(K)
Heat- Zeolite/H20 363 393 293 0.55 102

transformer H2SOJH20a 377 422 283 0"3 114
a Experimental results.t 3
especially in the industrial sectors, to identify the optimal boost

temperature (AT) to recover large amounts of waste heat through a
heat transformer. Besides, both in Germany and in France the use of
the combined heat and power (CHP) system has been proposed in civil
sectors in order to store electrical energy for household heating. This is
possible because, in both countries, low-priced electricity is available
during the night so that it would become convenient to transform this
night-time electricity into heat and feed it into the system in order to
complete the desorption phase (i.e. the endothermic step). During the
daytime, the system discharges itself, giving heat by means of the
chemical heat p u m p effect. ~
C H E M I C A L HEAT PIPE
The concept of the chemical heat pipe was first proposed in West
Germany for transporting heat from a high-temperature gas-cooled
nuclear reactor to a district-heating system. Thereafter other companies
and research institutions made economic and technical studies, for both
low- and high-temperature chemical reactions, to be used in a chemical
heat pipe system. 14']5 In its simplest form (Fig. 10), heat to be
transported in the chemical heat pipe is absorbed during the endothermic
THERMAL
ENERGY THERMAL
INPUT ENERGY
OUTPUT
I
TRANSMISSION / STORAGE
Fig. 10. Chemical heat pipe scheme.
reaction and chemical reagents are transformed into high-energy chemi-

cal products; the latter are then cooled to ambient temperature by heat
exchange with the incoming reagents, providing the necessary specific
heat to bring the reagents to an elevated temperature. The products of
the endothermic step are then transported by pipeline at ambient
temperature to the user site; at this end, the reverse exothermic reaction
is carried out, so releasing the stored energy. As in the endothermic
step, also in this case the reagents are heated to the proper temperature
by heat exchange with the products. The latter are then transported
back to the site of the primary energy source to serve as reagents in the
endothermic reaction, thereby completing a closed-loop cycle.
The system described above presents many advantages, the most
important being:
(1) the possibility of transporting high-grade heat over large distances
without the use of thermally-insulated pipes;
(2) the possibility of storing energy also in the form of liquid and
gaseous products;
(3) no net consumption of chemical raw materials, the only exchange

between the system and the surroundings being the heat and the
mechanical work required for compressors and pumps;
(4) varying the general scheme, by working at different pressures in
the endothermic and exothermic steps or by using an excess of
chemical c o m p o u n d , it is possible to release the heat at a higher
temperature than that required in the charging step, thus allowing
a chemical heat p u m p to be realized. 16.1~
The chemical heat pipe concept has been the object of theoretical and
experimental studies, la'19 and the general conclusion is that the system
is economically and technically feasible, at least for distances of between
80 and 300 kin.14 More efforts are needed, in both the engineering and
the chemical fields (with regard to heat exchanger, catalytic and kinetic
problems), but since the energy crisis our energy system has not changed
as much as one might have expected and so the above-mentioned efforts
have never been realized.
Moreover, the use of the chemical heat pipe is particularly suited to
the creation of a heat network with nuclear plant or coal as the principal
sources, to deliver process steam to small-scale industrial users. Therefore
if these conditions are met with, the selected reactions for the chemical
heat pipe system would be used. A m o n g these, the most important are:
(1) The methane-steam reforming reaction for high temperatures
(> 875 K):
CH 4 + H 2 0 - ~ CO + 3H 2
A H = 206 k J m o l - l T*= 1059K
where T* -- AH/AS is the temperature for which the equilibrium

constant is unity (i.e. AG = A H - TAS with AG = 0).
(2) The (de)hydrogenation of cyclohexane/benzene for low tempera-
tures (550-~ 850 K):
C6H16 - • C6H6 + 3H 2
A H = 260 kJ m o l - 1 T * = 563 K
(3) As an alternative to (2), the (de)hydrogenation of methylcyclo-

hexane/toluene:
C7H12 - - C7H8 + 3H 2
A H = 205 kJ m o l - 1 T * = 549 K
which uses the less-toxic toluene c o m p o u n d instead of benzene.

Notice that for all these reactions, the levels of technological development
and industrial know-how for both directions are very high.
HYDROGEN STORAGE AND TRANSPORTATION
The use of hydrogen as an energy vector could represent one o f the

most promising solutions to energy problems. In fact, by using this gas,
it could be possible to store or to transmit high-quality energy (i.e.
energy with a high exergy ratio). A m o n g the possible methods for
storing or transmitting hydrogen, chemical processes have recently
become very important, owing to their proven technical and economic
feasibilities.
Adsorption on metal hydrides
Metal hydrides have the capacity to adsorb and desorb hydrogen by a

slight change in temperature or pressure, their absolute values depending
upon the type o f metal. Metal hydride could be a single-component
metal system, such as Mg, V or Nb, or binary intermetallic compounds,
such as Mg2Ni, FeTi or LaNi 5.
The leading candidate for hydride storage is the i r o n - t i t a n i u m alloy
FeTi, whose theoretical weight per cent, expressed by grams o f H 2 per
gram of saturated compound, is 1"8%, and whose density, expressed by
grams o f H 2 per litre, is 45"5. 20
TABLE 4
Performances of Metal Hydride Heat Pumps
Metal hydride System Operation performance
MmNi4qsFeo.s5 Heat pump T1 = 383 K

LaNi4.~Alo.3 T2 = 313-323 K
T3 = 283 + 10K
Tio.gZroqCrMn Cooling Tl = 423 K
LaNi5 T2 = 323 K
T3 = 248 K
LaNis Heat-transformer T~ = 338-348 K
LaNi4.TAIo.3 T4 = 363 K
T3 = 288-298 K
(COP 0.34-0.39)
During the desorption step, heat is required (14kcalkg -1 of FeTi),

the same quantity of energy being released during the adsorption. This
latter characteristic (i.e. two separate reactions, the one exothermic and
the other endothermic) renders the metal hydride a candidate also for
heat storage or for use in chemical heat pump systems. As in gas-solid
adsorption with two solids, the use of metal hydrides in a chemical heat
pump system requires two metal hydrides to complete the charge and the
discharge phase, with a cycle similar to that described above. 21.22 Trends
in developments in using metal hydrides in different processes are
outlined in Table 4.
Open-loop chemical process
This process involves the use of ammonia or methanol, as a liquid

carrier of hydrogen, taking into account the following reactions:
N2 + 3H 2 ~ 2NH 3
CO + 2H 2 ~ CHaOH
These systems should not really be considered as a hydrogen storage/
transmission method. In fact, the hydrogen is transformed into another
compound which is stored or transmitted and finally directly used either
as a fertilizer or as a fuel, without re-transformation into the original
hydrogen. Besides, in order to transport or store energy in the form of
hydrogen with this system, there must be on-site availability of nitrogen
or CO, together with hydrogen. 23
Closed-loop chemical process
This process, although similar to the one above, is a real means

for storing or transmitting hydrogen; this scheme involves a double
transformation through which hydrogen initially stored is finally released
as an output from the system. In particular, as schematically shown in
Fig. 11, 24 the hydrogen to be stored or transmitted is made to react
with a liquid compound B in a catalytic reactor wherein hydrogenation
of the latter occurs to give another liquid compound A:
B+H 2 =A
At the end of this phase, the liquid product A can be stored easily or
transported readily over long distances and, at the time and place
LIQUIDS TRANSMISSION
AND/OR STORAGI~
Fig. 11. Hydrogen storage and transmission by chemical closed-loop cycle: Rd =

dehydrogenation reactor, Rh = hydrogenation reactor, H 2 = hydrogen tank, S 1= liquid
gas separator, Sc = counter-flow heat exchanger.
requested, made to react in the same catalytic reactor (if it is a storage

system) or in another (if it is a transmission system), thus giving the
initial c o m p o u n d B and hydrogen by means of a dehydrogenation
process:
A • B+H 2
The latter is then sent to the user, while c o m p o u n d B is stored or

transmitted by pipeline to the primary-source site.
To assess the energy balance of the system, the heat released during
the hydrogenation step and the energy needed for the dehydrogenation
step must be taken into account. Extensive studies have succeeded in
showing the expected performance of such a system, relying upon the
reversible (de)hydrogenation of the cyclohexane. 24- 26
The most important characteristics of this type o f process can be
summarized as follows:
-- high hydrogen density

-- high efficiency
-- low cost, especially for long-time storage
-- possibility of transmitting large amounts o f energy over very long
distances
Table 5 shows the most important characteristics o f the proposed

TABLE 5
Comparison of Characteristic Properties of Hydrogen Storage Systems
H 2 storage system Density Theoretical wt%

(g H 2 litre- 1) (g H2 g - 1 saturated compound)
Gaseous H 2
P = 1 bar 0'09 100
P = 200 bar 18 100
Liquid H 2 70 100
Cryogenic storage with 16.9 4.76
adsorbing material
Metal hydrides
Till 2 150 3"8
FeTiH 2 45.5 1-8
Reversible organic reactions
C6H 6 + 3H2 ~C6H12 56 7"19
CTH s + 3H2 ~ C 7 H 1 4 47'4 6-16
Call16 + H 2 ~ C8H18 12.4 1.76
CIoH a + 5HE,-~-CloHIa 65"3 7-29
Cu ( I kwh )
0.0~
LH
0.0
CA
0.0,
0.02
J I000' ' 2000 ' ]dO0 Jr

A(h )
Fig. lZ. Storage cost per unit of stored energy as a function of yearly hours of
utilization for alternative storage facility: L H = l i q u i d hydrogen storage, C A =
cryoadsorber storage, MH = metal hydride storage (FeTi), L P = low pressure storage
(12bar), CBI =cyclohexane/benzene processes, CB2=cyclohexane/benzene process
without recovering hydrogenation heat.
reaction in comparison with other hydrogen storage systems. The

hydrogen density in (de)hydrogenation reactions is very high with respect
to other systems except for liquid hydrogen. However, the system's
efficiency for the latter is approximately 79%, while the closed-loop
cycle using the cyclohexane reaction would have an efficiency equal to
98-8% if the heat produced during the hydrogenation step could
be recovered. Besides, this system is unique in making possible the
transportation of hydrogen very safely and with acceptable costs. This
latter aspect is illustrated in Figs 12 and 13, which show the costs for
Cte ~ I kwh)
0.10
O.OS
O.OB
007
O.OE
G
0.0 c.
0.0 / ~ C/B
0.0"
0.0~
0.01' I I = t i m ~ i = I
I000 2000 3000 /.000 5000
L(km )
Fig. 13. Cost of transmitted energy versus distance: E =electricity, O = hydrogen

transmitted by gas pipeline, C/B = hydrogen transmitted by cyclohexane/benzene
system.
storing hydrogen and transmitting energy over long distances 24.26 in a

closed-loop cycle (calculated for the cyclohexane reaction) compared
with other competitive systems. As can be seen, using the closed-loop
chemical cycle based upon the cyclohexane/benzene reaction, the cost
of stored energy is the cheapest of all (Fig. 12). Comparisons in terms
of energy transmission systems (Fig. 13) show that the proposed chemical
cycle is more convenient than a gaseous hydrogen pipeline for distances
exceeding 1200 km, whilst it is also cheaper than electricity for distances
greater than 2300 km.
CONCLUSIONS
During the last few years, some of the previous energy strategies have
changed following both the indications of feasibility studies on new
options and the latest directions in economic energy policy. Because
extensive exploitation of alternative energy sources (solar, wind, etc.)
has not become a reality, the chemical processes considered ten years
ago as most apt for storing alternative energy have to find new outlets.
This change of objectives has just been achieved.
The principal possible applications for each process can be summarized
as follows:
Gas-solid reactions and gas-liquid adsorption

In this group, the gas-solid reactions and the gas-liquid adsorption
processes are to be considered for applications in sectors such as:
- Industrial waste-heat recovery by chemical heat p u m p or heat-

-
transformer systems.
- - Chemical heat p u m p and cooling systems for civil applications.
Reversible chemical reactions (gas-liquid)

By exploitation of the reactions included in this group, it would become
possible to transmit heat at medium-high temperatures (>100°C),
offering the possibility of locating thermal power stations (coal, nuclear,
geothermic) far from the users.
Reversible (de)hydrogenation reactions

These processes allow the use of hydrogen as an energy vector. By these
reactions, it is possible to store and to transmit hydrogen. The general
fields of application for energy purposes are:
- Transmission of large amounts of energy located very far from

-
the users (hydropower, etc.).

- - Storage of electricity in chemical form.
- Separation, storage and transmission of hydrogen as a chemical
-
raw material.
Even though no great changes have as yet occurred in the energy

network, chemical processes could contribute towards optimizing the
more intensive exploitation of alternative energy sources.
REFERENCES
1. W. E. Wentworth and E. Chen, Simple thermal decomposition reactions

for storage of solar thermal energy, Solar Energy, 18 (1976) 205-15.
2. Boeing Engineering and Constructions, Advanced thermal energy storage
(TES) systems, EPRI EM-256-SY, Project RP788, Interim Summary
Report, November 1976.
3. G. Cacciola, S. Freni, C. Giangiacomi, N. Giordano and F. Salghetti,
Esame e criteri di valutazione relativi a sistemi di accumulo di energia di tipo
chimico, Final Report, CISE-NT 81.064, March 1981.
4. C. Wyman, Thermal energy storage for solar applications: an overview,
Seri/TR-34-089 for US Department of Energy, Contract EG-77-C-01-4042,
March 1979.
5. J. J. Iannucci, The impacts of storage upon solar plants: general principles
and seasonal applications, Sand 80-8242 for US Department of Energy
under Contract DE-AC04-76DP00789, February 1981.
6. G. Cacciola, Valutazione economica dei sistemi solari provvisti di accumulo
termochimico, per la produzione di energia termica a media temperatura,
Internal Report, October 1981.
7. Commission of the European Communities, Joint Research Centre, Energy
Storage and Transport, workshop on chemical storage of thermal energy,
Ispra, 15-17 December 1982.
8. S. Freni, G. Restuccia, A. Parmaliana and N. Giordano, 1 Caloria a 210
da 4 a 60, Tecnologie Chimiche, No. 3 (March 1983) 64-8.
9. G. Restuccia and N. Giordano, Accumulo di energia e pompa di calore in
sistemi chimici in cui almeno uno dei componenti ~ un solido, Internal Report,
Gennaio, 1982.
10. G. Alefeid, H. C. Bauer, P. Maier Laxhuber and M. Rothmeher, A zeolite
heat pump, heat transformer and heat accumulator, Int. Conf. on Energy
Storage, Brighton, UK, April 1981, pp. 61-72.
11. P. O'D. Offenhartz, M. J. Turner, F. C. Brown, R. B. Warren, J. P. Pemsler
and S. B. Brummer, Methanol based heat pumps for storage of solar thermal
energy, Phase I, Sand 79-8188 for US Department of Energy under contract
DE-AC04-76 DP00789, September 1979.
12. P. Offenhartz, F. C. Brown, R. W. Mor and R. W. Carling, A heat pump
and thermal storage system for solar heating and cooling based on the
reaction of calcium chloride and methanol vapor, Sand 798512, August
1979.
13. Rocket Research Company, Sulfuric acid/water chemical heat pump/
chemical energy storage, BNL Contract 494588-S RRC-82-R-813, Final
Report, Vol. II, January 1982.
14. General Electric Company, Closed-loop chemical systems for energy storage
and transmission, for US Department of Energy, ERDA Contract EY
70-C-02 2676, Final Report, Washington, DC, February 1978.
15. G. Cacciola, Trasporteremo energia termica con reazioni chimiche, Tecno-
logie Chimiche, No. 6 (October 1981) 56-62.
Chemical processesfor energy storage and transmission 337
16. G. Cacciola, R. Restuccia and N. Giordano, The catalytic reversible

(de)hydrogenation of cyclohexane as a means for energy storage and
chemical heat pump, Int. Conf. on Energy Storage, Brighton, UK, April
1981, pp. 73-89.
17. D. F. Suciu, P. M. Wikoff, R. D. Sanders and W. J. Toth, Survey and
assessment of heat of reactions type chemical heat pumps, IDAHO National
Engineering Laboratory, EGC-PBS-6579, April 1984.
18. A. Parmaliana, C. Crisafulli, R. Maggiore, J. C. L. Bart and N. Giordano,
Catalytic activity of honeycomb catalysts. I. The benzene/cyclohexane
(de)hydrogenation reaction, Reaction Kinetics and Catalysis Letters, Vol. 5,
Budapest, 1981.
19. A. Parmaliana, A. Mezzapica, C. Crisafulli, S" Galvagno, R. Maggiore and
N. Giordano, Benzene dehydrogenation reaction on nickel/honeycomb,
Reaction Kinetics and Catalysis Letters, Vol. 1, Budapest, 1982.
20. C. E. Lundin, Metal hydride storage of hydrogen, Solar/Hydrogen Systems
Technologies, DOE/SPL 955492, Vol. 2, part 2, pp. IV-58, IV-79, 1980.
21. Y. Osumi, Trends in the development of metal hydrides at home and
abroad, Chemical Economy & Engineering Review, 16(5) (May 1984).
22. G. Wettermark, International Seminar on Thermochemical Energy Storage,
Document D25:1980, Stockholm, 7-9 January 1980.
23. L. Green, An ammonia energy vector for the hydrogen economy, Proc.
3rd Worm Hydrogen Energy Conf., Tokyo, 23-26 June 1980, pp. 1265-71.
24. G. Cacciola, N. Giordano and G. Restuccia, Cyclohexane as a liquid phase
carrier in hydrogen storage and transport, Int. J. Hydrogen Energy, 9(5)
(1984) 411-19.
25. N. Giordano, G. Cacciola and A. Parmaliana, Catalytic and reaction
engineering aspects in the storage of hydrogen through the reversible
(de)hydrogenation of cyclohexane, Indian J. Technology, 21(9) (1983)
398-403.
26. G. Cacciola and N. Giordano, Hydrogen transmission by a chemical
closed-loop cycle, an alternative option for long-distance transport of
energy, Proc. 5th Worm Hydrogen Energy Conf., Vol. III, Toronto, 15-20
July 1984, pp, 1232-51.

Cacciola 1986

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Applied Energy 25 (1986) 315-337

Chemical Processes for Energy Storage and

Istituto CRN/TAE, Via Salita S. Lucia sopra Contesse, 39,

Chemical reaction, adsorption of a gas in a solid, or adsorption of gas

All types of primary fuels, whether renewable or not, need trans-

FUEL 1'~ Tr~nsm,ss,o.'- .." ~ I I

<ZZ]" .I,, THERMAL ENERGY )

Fig. 1. Existing energy systems.

Chemical fuel 101o_1011 10 6

Fig. 2. Simple scheme o f t h e r m o c h e m i c a l energy storage system: E = t h e r m a l energy,

is drastically reduced, and therefore it is important that the

(A) cost of the power-dependent equipment;

' 2; ' ~b ' 5b ' 8'0 ' ,00

solved on a laboratory scale, the thermochemical storage of energy has

Chemical heat pumps

The general scheme of a chemical heat-storage system (Fig. 5) using one

2.2 ..... \ °,__ .,so,

1.5 2.0 2.5 39 3,5 4.0 lfl 3

as shown in Figs 6 and 7, referred to a sulphuric acid solution 8 and a

Tl : 298.4"C T2 : T¢:83.5 °C T3:3.2

Other energy cycles with liquid absorption and gas-solid reactions

The three processes described above could also be utilized in two

1.5 2.0 2.5 3.0 3.5 4.0 10 3

t h e r m o d y n a m i c cycle o f a cooling system using gas-solid reactions or

LOG( P)[rn m t-i:j]

It :121.4"13 I1:T2=90.6"C T3:15.1"C

The actual problems related to these types of systems are:

System Process TI(K) T2(K) Ta(K) COP Energy densiO"

CHP Zeolite/H20 552 353 278 1"7 624

Tt(K) T,(K) T3(K)

Heat- Zeolite/H20 363 393 293 0.55 102

especially in the industrial sectors, to identify the optimal boost

Fig. 10. Chemical heat pipe scheme.

reaction and chemical reagents are transformed into high-energy chemi-

(3) no net consumption of chemical raw materials, the only exchange

where T* -- AH/AS is the temperature for which the equilibrium

(3) As an alternative to (2), the (de)hydrogenation of methylcyclo-

which uses the less-toxic toluene c o m p o u n d instead of benzene.

HYDROGEN STORAGE AND TRANSPORTATION

The use of hydrogen as an energy vector could represent one o f the

Adsorption on metal hydrides

Metal hydrides have the capacity to adsorb and desorb hydrogen by a

Metal hydride System Operation performance

MmNi4qsFeo.s5 Heat pump T1 = 383 K

During the desorption step, heat is required (14kcalkg -1 of FeTi),

Open-loop chemical process

This process involves the use of ammonia or methanol, as a liquid

Closed-loop chemical process

This process, although similar to the one above, is a real means

Fig. 11. Hydrogen storage and transmission by chemical closed-loop cycle: Rd =

requested, made to react in the same catalytic reactor (if it is a storage

The latter is then sent to the user, while c o m p o u n d B is stored or

-- high hydrogen density

Table 5 shows the most important characteristics o f the proposed

H 2 storage system Density Theoretical wt%

J I000' ' 2000 ' ]dO0 Jr

reaction in comparison with other hydrogen storage systems. The

Fig. 13. Cost of transmitted energy versus distance: E =electricity, O = hydrogen

storing hydrogen and transmitting energy over long distances 24.26 in a

Gas-solid reactions and gas-liquid adsorption

- Industrial waste-heat recovery by chemical heat p u m p or heat-

Reversible chemical reactions (gas-liquid)

Reversible (de)hydrogenation reactions