Energy Com'ers. Mgmt Vol. 23. No. 1, pp. 55-63. 1983 0196-8904/83/010055-09503.

00/0
Printed in Great Britain. All rights reserved Copyright ,C 1983 Pergamon Press Ltd

INDUSTRIAL SCALE MODELLING OF THE

THERMOCHEMICAL ENERGY STORAGE SYSTEM
BASED ON CO2 + 2NH3 ~ NH2COONH4
EQUILIBRIUM
A. A. KOUTINAS j, P. YIANOULIS 2 and A. LYCOURGHIOTIS3
~Chemical Technology Laboratory, 2Physics Laboratory II and 3PhysicalChemistry Laboratory, Univer-
sity of Patras, Patras, Greece

(Receit, ed 5 March 1982)

Abstract--The thermochemical storage of energy by the system carbon dioxide, ammonia and ammonium
carbamate is studied in detail. In particular, the kinetics and the thermodynamics of the reversiblereaction
is studied. We give two industrial models for the operation of this system. In the first, the separation of
the gases NH 3 and CO2 is achieved by compression and liquefaction of NH 3. In the second, a method
of separation of the gases is proposed which is based on the solubility of NH 3 in ethanol while CO2 is
practically insoluble. The operation of this system is examined both in closed form and in the case in which
CO, is rejected in the atmosphere, and it is taken from alcoholic fermentation or from the combustion
gases of power plants burning lignite. The mass and energy balance is given, for each case, and the amount
of energy losses by the use of this storage system is calculated. Finally, we give some estimates for the
area of solar collectors and the amount of chemicals which are required in order to cover the energy needs
of a community.

Energy storage Thermal storage Chemicalstorage Carbamate

INTRODUCTION which satisfy this requirement and are chosen in such

a way that they cover a broad area of temperatures.
The reaction between dry carbon dioxide and dry
ammonia has been studied in the past. The two dry For relatively high temperatures, the system of SO2
gases react vigorously and exothermally under nor- and 02 has been proposed [4]. These gases react at
mal temperature and pressure of one atmosphere 500°C, releasing 24 kcal/mol and forming SO3 which
according to the scheme is consequently decomposed thermally, in a reactor-
heat exchanger, to SO2 and 02. For the area of lower
CO: + 2NH 3 ~ NH2COONH4 + 34.17 kcal. (a) temperatures, 100-130°C, the system ethylene-
sulfuric acid has been proposed [5]. Ethylene and
The thermodynamics of this reaction has been sulfuric acid react exothermally (220 kcal/kg H2SO4)
studied during the first half of the 20th century by forming monoethyl sulphate which is decomposed
Briggs et al. [1, 2]. Under high pressures, and tem- thermally to ethylene and sulfuric acid. Another
peratures greater than 140°C, the reaction is directed system with inexpensive raw materials used for inter-
to the formation of urea. Under these conditions, mediate temperatures, is the physical-chemical sys-
urea has been produced on an industrial scale for tem of sulfuric acid and water [6]. The high heat of
many years now. dissolution of sulfuric acid is used in this system. Of
Lately, in a patent [3] assigned to Honeywell Inc., interest is also the system of carbon monoxide and
Lefrois proposed a system for the storage of solar hydrogen [7]. These gases react exothermally, under
thermal energy. According to this system, urea reacts suitable conditions, and form CO2 and CH4, which
with water to form ammonium carbamate, which react endothermally to form CO and H2, using the
is consequently decomposed to carbon dioxide heat from a nuclear plant, for example. In the
and ammonia. The gases are separated after the temperature area of 400-500°C, storage of thermal
liquefaction of NH 3 by compression; carbon dioxide energy can be achieved by the reversible reaction of
is stored under pressure. The gases, carbon dioxide dissociation of COCI2 to CO and C%. The thermal
and ammonia, react exothermally under such condi- energy is recovered by the exothermal reaction of CO
tions that the reaction products are ammonium car- and CIE [8].
bamate and urea. In this paper, we present a detailed study of the
Many chemical systems have been proposed for the system of carbon dioxide, ammonia and ammonium
thermochemical storage of energy. Some of them are carbamate under dry conditions. This is a variation
interesting from the point of view of availability of of the system which has been proposed already [3],
raw materials. We give some example of such systems and in our opinion, it has many advantages from the
55
56 KOUTINAS et al.: THERMOCHEMICAL STORAGE SYSTEM

point of view of conditions of operation and avail- From equations (2) and (3), a relationship between
ability of raw materials. The working temperature of K~ and P is easily obtained
this system is 80-120°C, under dry conditions. Under
4
these conditions, we avoid the formation of urea or Kv = . e3. (4)
a m m o n i u m carbonate, which are formed when there
is water in the system, and the reactions of storage Experimental measurements carried out by Briggs et
and recovery of thermal energy are al. [1, 2] allow a determination to be made of P and
then Kv at various temperatures within the range of
CO2 + 2NH3-* NH2COONH4 + 34.17 kcal/gmol
10-45°C. On the basis of these data, we found that
NH2COONH 4 + 34.17 kcal/gmol--*CO2 + 2NH3. both lie and P are related with temperature by the
This system can be combined with appropriate solar following, Van't Hoff type, equations
thermal collectors and with a Rankine cycle engine, 1
using an organic working fluid, for the production of In K e = - 18946.659.- + 75.1028 (5)
T
mechanical power and electricity. The principle of
layered solar collectors [9] can be used in connection In P = -6321.7225. T + 25.6891 (6)
with this system.
Our goal is to give an industrial diagram of oper- from equations (5) and (6), one can calculate values
ation in which the energy losses are minimized. For of Ke and P at a given temperature.
this purpose, we investigate the thermodynamics of
Kinetics
the reaction and we give the mass and energy balance
for every case we propose. As far as in the system under consideration, the
rate of energy production is proportional to the rate
of carbamate formation, a kinetic study of combina-
THERMODYNAMIC AND KINETIC tion of CO2 with N H 3 seems to be quite needful. The
CONSIDERATIONS following considerations are basically supported by
Thermodynamics the Pinset et al. [10a] kinetic experiments.
The dissociation of the solid carbamate at tem- On the basis of Faurholt's [10b] and Pinset studies,
peratures lower than 130°C can be represented by it seems to us plausible to assume that in the gas
equation (1) phase the formation of NH2COONH 4 follows the
mechanism
k I
NH2COONH4(S ) . " 2NH3(g ) + CO2(g ) (1)
kj
CO2 + NH3---~NH2COO- + H + (7)
The above equilibrium is described by equation (2)
H ÷ + NH3~NH4 ~ (8)
PzH3 "Pco2 = Kp (2)
N H : + N H 2 C O O - ~ N H 2 C O O N H a. (9)
where PNH3 and Pco2 denote the partial pressures of
N H 3 and CO2, respectively; Kp symbolizes the equi- Since the reactions (8) and (9) are extremely rapid, the
librium constant. Provided that the carbamate va- overall rate is governed by the speed of (7), thus we
pour is completely dissociated into a m m o n i a and can write
carbon dioxide, the partial pressures mentioned are -- d [C02]
related to the pressure of equilibrium (P) by d~ = k' CNH 3 ' C c o 2. (10)

2P P The second order specific rate k, reduced to zero ionic

PNH3 = ~ - , Pco2 = ~" (3)
strength was found to be related with temperature by

Table 1. Various thermodynamic and kinetic parameters calculated for the synthesis of NH2COONH 4
-d[COz] k
k dt vl kl (RT) 2

t P K ( 1 ) (molCO2) + (kcal) ( mo,

("C) (mmHg) (mm~'Hg) \] ~ k, l's ] \l's] \i-s-mmm2Hg/
80 2406.6 2059714622 8.85 X 10 3 23.6 806 1.84 x 10-5
85 3099.1 4394851763 11.13 x 103 47.8 1633 2.23 x 10-5
90 3940.6 9028686035 14.00 × 103 94.6 3233 2.73 x 10-5
95 5010.6 18548332440 17.40 × 10 3 184.5 6304 3.31 × 10-5
100 6291.1 36689405800 21.60 × 10 3 351.8 12021 4.00× 10-5
105 7849.1 71209134810 26.60 × 103 656.2 22416 4.80 × 10-5
110 9792.9 138207222800 32.5 × 103 1217.1 41588 5.86 x 10-5
tThe rates of formation near the point of equilibrium are the same as the decomposition rates of carbamate.
 KOUTINAS et aL: THERMOCHEMICAL STORAGE SYSTEM 57

the following, Arrhenius type, equation collected in the reservoir (3). The slurry is then
transferred into the reactor (4).
k(mol I . l ' s I ) = 1 0 1 H 3 ( m o l - I " l ' s -I) (b) The dissociation of the ammonium carbamate:
exp[-5837.947/T]. (11) this takes place in the reactor (4). The remainder,
after dissociation, small amount of petroleum is
Equation (11) can be used to extrapolate k values, collected in the reservoir (5). The energy necessary for
experimentally found in the region of 0-40°C, to any the dissociation is taken from the system of solar
desirable temperature. In order to apply the extrapo- collectors (6). The transfer of solar heat from the
lated k values to the gas phase reaction, a trans- collectors to the reactor is obtained using a con-
formation of equation (10) is necessary. tinuous stream of water or silicon oil and a heat
-d[CO2] k exchanger situated inside the reactor.
d~ - k' CNH 3" Cco 2 = (RT) 2 "PNH3"Pco2 (c) The separation and storage of the NH3 and
CO2: this is performed in the system (7) and includes
= k l ' PNH3" PC02 (12) a liquefaction of the NH 3 by applying on it a
Assuming that the second order rate constant kl does sufficient pressure. The so-produced liquid ammonia
not considerably vary with the partial pressures, the is collected in the reservoir (8). The liquefaction of
calculated k values from equation (11) can be inserted CO2 then follows. The reservoir (9) is used for the
into (12) to determine the rate of the carbamate storage of the liquid CO2.
formation. PNH3and Pco2 can be calculated by equa-
tions (6) and (3) at any temperature. From the rate The reservoirs (8) and (9) feed the reactor (1) with
of the carbamate formation, the velocity (v) of energy the necessary amount of NH 3 and CO2, respectively.
production near to the equilibrium is easily calcu- The liquid CO2 is evaporated and cooled in the heat
lated. Table 1 compiles values of K e, P, k, k,, exchanger (10) before it is inserted in the reactor (1).
-d[CO2]/dt and vl calculated by us at various tem- The above described storage system is a closed one
peratures. in the sense that a continuous circulation of an almost
The estimation of the rate of energy absorption by constant amount of CO2 and NH3 is sufficient for its
the system demands the determination of the rate of function. Alternatively, the system can work without
the ammonium carbamate decomposition. Un- circulation of CO2. The necessary amounts of CO2
fortunately, to the extent of our knowledge, experi- can be taken from alcoholic fermentation or thermal
mental results close to our system requirements are power plants. Obviously, in such cases, the storage
not reported in the literature. However, one can system must be constructed near these units.
estimate v ~ at partial pressures near to the equi- The CO2 produced from the alcoholic fermentation
librium, using equation (13) contains small quantities of water vapour. Therefore,
a drying of it is needed. This is obtained using a
vl = v 1. (13)
cooling machine (11) which maintains the tem-
Therefore, the v~ values compiled in Table 1 are perature at 10C. The restoration of the dry CO2 at
numerically equal to the corresponding values of v_,. the ambient temperature takes place in the heat
exchanger (12) connected with the exit of the cooling
machine. The transport of CO2 into the reactor (1) is
PROCESS DESIGN performed with the aid of the pressure feed system
(13).
Process description The gas mixture produced from the combustion of
For the thermochemical storage of solar energy the solid and fuels in the thermal power plants usually
based on the title system, two methods are proposed contains CO2 and SO2, N2, H20 and 02. The latter
in the present work. can cause some difficulties in the function of the
Block diagram 1 reactor (1), namely production of NH4OH,
(NH4)2CO3 and (NH4)2SO 3 as well as an undesirable
The first process is performed in the experimental
decrease of the NH3 and CO2 partial pressures. To
set-up illustrated in Fig. 1. This includes the following
avoid these problems, the carbon dioxide must be
steps:
purified. For such a purification, the well known
(a) The reaction of CO 2 with NH3: this is carried method used in the industries of hydrogen production
out in the reactor (1) which contains petroleum must be followed: the mixture of gases under the
(b.p.: = 150°C). The pumping of the heat produced is pressure of 30atm is passed through the cleaning
obtained using water at a temperature of about tower (15) following a down-up direction, whereas at
90-100°C as well as a heat exchanger located inside the same time, water flows in the opposite direction.
the reactor. The separation of the solvent from the Due to their low solubilities, the 02 and N 2 escape
product is performed in a Laval separator (2). The from the up outlet of the tower. As far as CO2 and
petroleum is restored continuously into the reactor, SO2 are quite soluble in the water, they are collected
whereas the product, which is a slurry consisting of in the hollow of the tower. A decrease of pressure
NH2COONH4 and small amounts of petroleum, is from 30 brings about the evaporation of CO2. Then

~(~ 23,1 v
58 KOUTINAS et al.: THERMOCHEMICAL STORAGE SYSTEM

13
12
!- [j,, II
I
I

t
I 15
I
L- - - m J
I

9
(106C"
C02

COz
SOz
N2
,a
/ Oz
H20

~" ] ~,(11800) T
C02 14
:

I
, 2 0 *C Po
r~
0
0
?1 ,° : 90* C

NH2 COONH4

h
4 5
Fig. 1. Process mass flow (kg/h of total stream). Block diagram 1 for thermochemical energy storage by
the system CO2, NH3 and NH2COONH 4. The separation of NH 3 is performed by liquefaction.

it follows the route which has been described above to 24.5 g NHa per 100 g CHaCH2OH; namely, equal
for CO2 produced by alcoholic fermentation. to the solubility of the ammonia in ethanol at t = 0°C
and P = 1 atm. A heat exchanger located inside the
Block Diagram 2 reactor, as well as water of temperature 95°C, are
The second process takes place in the experimental used for the pumping of the heat produced.
set-up illustrated in Fig. 2. This exploits the fact (b) The dissociation of carbamate: this also takes
that the solubility of CO2 in alcohols is low, while place in the reactor (2). The system of solar collectors
NH3 is quite soluble in inexpensive alcohols, such as (3) provides the energy necessary for the dissociation.
ethanol (24.5gNH3/100gC2HsOH) and methanol A stream of water heated by the collectors at 95°C is
(41.4 g NHa/100 g CH3OH) [11]. The following steps used for the transport of solar energy into the reactor.
are included. The gases produced, as well as the ethanol evapo-
(a) The reaction of carbon dioxide with ammonia rated, are cooled by water at room temperature using
in the reactor (2). Carbon dioxide [from the tank (1)] the heat exchanger (4). Of them, the ethanol is
is introduced through the heat exchanger (10) of 0°C liquefied and then is restored into,,the reactor (2). A
in an ethanolic solution of ammonia, being in the gas mixture consisting of CO2 and NH3 escapes from
reactor (2). The concentration of the solution is equal the up-outlet of the heat exchanger (4). The sepa-
 KOUTINAS et al.: THERMOCHEMICAL STORAGE SYSTEM 59

co~, NH3 8 ,,.-x B

C02"A~ I1~
"~ C02 18020
I I I - t I 6

H20 H20 " 20"C

4 xlO6 Kcal
•- 9 5 " C

Fig. 2. Process mass flow (kg/h of total stream). Block diagram 2 is a schematic diagram for
thermochemical energy storage by the system CO2, NH 3 and NH2COONH4. The separation of NH3 is
performed by solution of NH 3 in C2HsOH.

ration of the CO2 and NH 3 is obtained by passing the For the winter months, the above mentioned en-
gas mixture through the reactor (5) which contains ergy demands are about 27,500 kcal per family for
ethanol at 0'C. Ammonia is diluted almost quan- one day. Therefore, 27,500 × 500 x 15 ~21 x
titatively. The insoluble CO2 is collected in the reser- 10vkcal are required. Taking in mind that the heat
voir (6) using the pressure pump (B). produced from CO2 + 2NH3-~NH2COONH4 is equal
The so described process is now repeated starting to 34.17 kcal. mol ~ (or 1005kcal. kg-~ NH3,
with the reaction between NH3 and CO2. [The reser- 777 kcal. kg ~COO, we calculate the amounts of the
voir (6) provides the necessary CO2 in the reactor (5)]. NH 3 and CO2 required for the production of the
The energy necessary is now transferred from the 21 x 107kcal. They are found to be equal to:
system of solar collectors (7). 27× 104kgCO: and 209× 103kgNH3. Provided
The small reservoirs (8) and (9) are used to trap that the unit works for 17 h per day, a mass flow of
small amounts of NH 3 which eventually escape from 820kg NH 3 and 1060 kg CO 2 per hour is required.
the reactors (5) and (2), respectively. The ammonia The reaction of these amounts produces heat which
collected in this reservoir is restored in the corre- can raise the temperature of 11,800 kg H20 from 20
sponding reactors, after NH2COONH 4 dissociation, to 90°C. The reaction takes place at 105°C in the
or before the reaction leads to NH2COONH4 for- reactor (1). The volume of the reactor (1) is 5 m 3. This
mation. contains 3.220 kg petroleum of b.p. equal to 150°C.
When it is estimated economically convenient, CO2 The quantity of the petroleum and the volume of the
can be rejected after each cycle. In such cases, the reactor corresponds to a reaction time equal to 1 h.
purification of the CO2, provided from the industries After the separation in the Laval separator, a quan-
mentioned, is performed using the processes de- tity of petroleum equal to 3200 kg per hour returns
scribed in the block diagram 1. to the reactor (1); whereas an amount of a slurry
containing NH2COONH4 and petroleum, equal to
4000 kg, flows per hour to the tank 3. The fact that
MASS FLOW
the process takes place continuously in conjunction
Block diagram 1 with the relatively high speed of the reaction (see
The mass flow calculations carried out concern an Table 1) permits the use of a reactor with quite small
installation which can store energy necessary for dimensions.
space and water heating for a Greek settlement For the dissociation of the NH2COONH4 in the
including 500 families for a period of 15 winter days. reactor (4), the energy necessary can be drawn from
60 KOUTINAS et al.: THERMOCHEMICAL STORAGE SYSTEM

solar collectors having a total area equal to Table 2. Specific volume of CO2 calculated from van der
11,400 m 2. The fact that the rate of the NH2COONH 4 Waals equation for various temperatures and pressure
dissociation [taking place in the reactor (4)] is quite P = 1 atm
high in the region of 80-110°C (see Table 1) allows Temperature (K) 300 305 320
us to use a reactor of similar dimensions to that of Specific volume (cm3/gmol) 24480 24910 26160
reactor (1).
Block diagram 2
Using equation (15) and Table 2 we calculate E for
To cover the energy demands of the above men- three initial temperatures; the results are given in
tioned settlement, a solution containing Table 3. We should note that the temperature of
13,940 kg NH3 and 57,000 kg C2HsOH is initially pre- 320 K is such that no cooling is required. In practice,
pared at t = 0°C and P = 1 atm in a batch reactor (2) the liquefaction takes place in the usual cycle (com-
(see Fig. 2). The volume of the reactor is equal to pression, aftercooling expansion through a throttle
90 m 3, the same volume as reactor (5). The amount of valve), taking advantage of the Joule Thomson
CO2 used for the reaction is equal to 18,020 kg per effect. There are two requirements which must be
day. The heat produced for the same period is equal
met:
to 14 × 106kcal. The amount of water used for the
pumping of the heat produced is equal to (i) The gas must be cooled below the critical
187 × 103 kg, namely 1100 lit/h. temperature.
(ii) The gas temperature before the throttling pro-
cess must be below the maximum inversion tem-
ENERGY BALANCE perature (T/max) of the gas, so that cooling can be
Block diagram 1 obtained from the Joule-Thomson expansion.
In order to give the energy balance for the system, From Table 4, it follows that these requirements
we should calculate the amount of energy which are easily satisfied for CO2 and NH3. T,max for most
should be supplied at the various stages of operation. gases, except H 2 and He, is well above room tem-
Of interest to us is the net thermal energy which can perature [12]. From Table 3, we conclude that a
be recovered by this storage system. The energy reasonable estimate for the energy which is required
requirements for the closed form (Fig. 1) include: for the liquefaction of CO2 is approximately
3 kcal/gmol.
(i) energy for the compression of CO2 in order to
liquefy and store it at 9, Energy requirements for the separation of ammonia
(ii) energy for the compression of the mixture of The energy which is required for isothermal com-
CO2 and NH 3 in order to liquefy NH 3 at 7 by pression of NH 3 to final U = Uc is calculated from
expansion, equation (14) with the help of Table 4, and the results
(iii) energy for mass transfer. are given in Table 5. This is approximately the energy
Energy required for the liquefaction of COz required for the liquefaction of NH 3.
For a mixture of 2 gmol of NH 3 and 1 gmol CO2 it
The critical constants for CO2 are [12],
is calculated that we need approximately 7.5 kcal in
T, =304.5 K, P, = 72.9 atm and U, = 94 (cm3/gmol).
order to liquefy NH 3 and separate it from CO2 which
The van der Waals constants are,
will be in the gaseous state under pressure. This is
a = 3.61 × 104[atm(cm3/gmol)2], done by isothermal compression at a temperature
b = 42.8(cm3/gmol). slightly above ambient, that is 305-320 K. The final
pressure of CO2 will be 50-57atm at these tem-
From van der Waals equation peratures and has been determined from the van der
Waals equation at the limit of its validity (saturated
(P + ~52)(U - b) = RT (14) vapour line) for NH 3. At these temperatures and
pressures, from CO2 data, we find that the specific
we find U = U ( T , P ) . For P = l a t m and various volume is U2 = 370--340 cm3/gmol. The energy for the
temperatures the corresponding values of U are given isothermal compression of CO2 is 2.4 kcal/gmol for
in Table 2. An estimate for the energy which is T = 305 K and 2.6 kcal/gmol for T = 320 K. These
required for liquefaction can be obtained from the
energy for isothermal compression from U1 to
Table 3. Energy (E) required for isothermal
/-/2 = Uc, where U1 is the specific volume under the
compression of CO 2 from Pt = l atm to
initial conditions. We have P2 = 1°, for various temperatures
u2 E T
(kcal/gmol) (K)
E = fPdU
UI
(, l) .
=RTInx, u~Z-~_b]+a ~ - ~ (15)
2.75
2.82
3.04
300
305
320
 KOUTINAS et al.: THERMOCHEMICAL STORAGE SYSTEM 61

Table 4. Useful physical constants for some gases. T, Pc and Uc are the critical temperature, pressure
and specific volume respectively. T/maxis the maximum inversion temperature, a and b are the van der
Waals constants
U, 6/ b
T,. Timax Pc (/cm3 ~ {"cm3 "~'~ (_cm3 ~
Gas (K) (K) (atm) \gmolJ atm~ol) \gmol/
CO2 304.5 1500 72.9 94 3.61 x 104 42.8
NH 3 405,5 22100 111.3 72 4.19 x 104 37.3
N2 126 620 33.5 90 1.35 × 1 0 4 38.6
SO, 430 2--2300 77.7 124 6.78 X 1 0 4 56.9
H,O 647 -~2000 218.2 56 5.46 × 1 0 4 30.5
02 154 -~700 49.8 74 1.36 x 104 31.6

two values are lower than the corresponding ones of of CO2 and NH 3 in order to separate NH 3 by
Table 3, as expected, because now we do not liquefy liquefaction (7.5 kcal/mol), and
CO 2. Therefore, for T---320 K we have that the (ii) energy for mass transfer (4.1 kcal/mol). The
energy which is required to liquefy and separate NH3 total energy needed is 11.6 kcal/mol and the useful
from a mixture of 2mol NH3 and 1 mol CO2 is ap- amount of stored energy is 22.6 kcal/mol CO2.
proximately 7.7kcal. For T = 305K the energy
Energy requirements when CO 2 & taken from com-
which is required is approximately 7.1 kcal.
bustion gases
Energy requirements Jor mass transfer When CO2 is taken from combustion gases, energy
The energy which is required for mass transfer is needed:
includes the energy for the operation of pumps A, B
(i) for compression of the mixture of combustion
and C (Fig. 1), and the electric energy which is needed
gases up to 30 atm in order to separate CO2,
for the operation of the Laval separator. We estimate
(ii) for compression of the mixture of CO2 and NH 3
that the power consumed by A is 4 HP, for C 15 HP,
in order to separate NH3, and
and for B 7 HP (i.e. 4 HP for transfer plus 3 HP in
(iii) for mass transfer.
order to overcome the 12 atm). The power consumed
by the Laval separator is less than 20 HP. Therefore, The energy needed for (i) is estimated as the energy
we should have a total power of about 46 HP or for isothermal compression of the mixture of gases
34.3 kW which corresponds to a thermal energy of from the initial pressure of I atm to the final pressure
about 98328 kcal/h. The energy required per mol of of 30 atm. At this final pressure CO2, N2 and 02 are
CO2 for mass transfer is calculated to be 4.1 kcal/mol. in the gaseous state with U _~ 870 cm3/gmol while
Total energy requirements H20 and SO, are liquefied earlier and are separated.
From equation (15) and Table 4, we calculate the
We conclude that the total amount of energy which
energy which is required to compress, isothermally,
is needed in the plant under the closed form of
these gases. The mixture consists of N2 (69.5~), SO2
operation, is 12.1 kcal/mol CO2 (3 + 5 +
(0.2~,~,), HzO (13.5°), CO2 (12.6~o) and 02 (4.4~). The
4.1 kcal/mol) leaving a useful amount of stored en-
calculated energies are given in Table 6. The energy
ergy which is 22.1 kcal/mol CO2.
required is E = 2.10 kcal/equivalent mol of this mix-
Energy requirementsJor the ease that C02 is a product ture or E = 16.7 kcal/mol CO 2. Therefore, the total
c?[ alcoholic fermentation energy consumption in this case is approximately
In this case, CO2 is not compressed to be liquefied 28.3 kcal/mol, where we have added the energy for
at 9, but it is rejected at 14. Therefore, energy is not the separation of NH3 and for mass transfer. In this
consumed for the liquefaction and storage of CO2. case, the energy consumption is so high that the
The amount of energy which is needed for the process is not economical. However, we can apply
operation of the unit in this case is: another method for the separation of CO2, removing
SO2 by water sprinkling and drying for removal of
(i) energy for compression of the gaseous mixture

Table 6. Energy for isothermal compression from U~

Table 5. The energy (E) which is required to (P~ = I atm, T = 320 K) to U2 (P2 = 30 atm), for CO_,, N 2,
compress isothermally NH3, from initial pres- SO2, H20, 02
sure P = latin to such a pressure that
U = U,, for various temperatures T Ui U2 E
Gas (cm3/gmol) (cm3/gmol) (kcal/mol)
T E
(K) (kcal/gmol) CO2 26160 870 2.1
N2 26220 870 2.15
300 2.26 SO2 17480 124 2.0
305 2.33 H,O 17480 56 1.8
320 2.55 02 26220 870 2.15
62 KOUTINAS et al.: THERMOCHEMICAL STORAGE SYSTEM

H20 and reaction of the mixture with ammonia. lectors. If we assume system losses, a reasonable
These processes are not energy consuming, and the system performance for heat losses, excluding solar
total amount of energy which is required is consider- collectors, is about 80~/o and the collector area be-
ably smaller. comes 11,400 m 2.
During the summer period (1 May-31 October),
Block diagram 2
we have an average total solar radiation reaching
Energy consumption for plant operation, requiring earth's surface, in Athens, of about 4920kcal
separation of NH 3 by dissolution m-2/day. Therefore, assuming again a system thermal
performance for heat losses of 80~o, but a collection
Let us consider the closed mode of operation
efficiency 70~o because of higher ambient temperature
(Fig. 2). The energy consumption for plant operation
mainly, we have that the produced thermal energy by
is:
the 11,400 m 2 collectors is, on average,
(i) energy for compression and liquefaction of CO2, 31.3 x 106 kcal/day. This is 17.3 x 106 kcal/day more
which is 3 kcal/gmol, than the corresponding thermal energy collected dur-
(ii) energy for mass transfer (pump C), which is ing the winter period.
estimated to be less than 1.5 kcal/gmol CO2, It is obvious that, during the summer period, we
(iii) energy to cool ethanol from 20 ° to 0°C, have an energy surplus which can be converted to
0.2 kcal/gmol. electricity. For the temperature of 100°C, the con-
version efficiency is at least 5/o,°/ and it can be
Therefore, the total energy consumption is
arranged so that the rejected heat is in the form of hot
4.7kcal/gmol and the useful stored energy is
water of 50°C which is suitable for use as domestic
29.5 kcal/gmol CO2. hot water. During the summer period, we have no
Energy required when CO2 is released to the atmos- heating needs, and we can convert all the thermal
phere energy to electricity. We shall have 1815 kWh/day of
In this mode of operation, CO2 is taken from electrical energy and about 1000m 3 of hot water
alcoholic fermentation, and the consumption of (50°C), assuming an initial water temperature
energy is restricted only to the consumption of pump 20°C. This is about 50~ of the electrical energy needs
C, which is working for the transfer of water, or other of the community of 500 families,
suitable fluid, used for heat transfer from solar
collectors 3 to the reactor heat exchanger 2. This DISCUSSION
energy is estimated to be less than 1.5 kcal/gmol CO2,
and therefore, the useful stored energy is The thermochemical energy storage system pro-
posed in this study presents the following advantages.
32.5 kcal/gmol CO2 if we take into account also the
(a) The energy produced is extremely high, equal to
energy required for the cooling of ethanol
(0.2 kcal/gmol). 1005kcal/kgNH3 or 777kcal/kgC02. This means
that, in the cases where CO2 is rejected, the energy
When CO2 is a product of the exhaust gases at
produced by the reaction of 4 kg CO2 is equal to that
power plants burning coal, CO2 is separated from the
produced by the combustion of 1 kg lignite of good
rest of the gases as has been described previously, and
quality. Concerning the closed system described, the
after use, it is discharged to the atmosphere. There-
above mentioned energy can be taken when four
fore, in this case, energy is consumed for compression
thermochemical cycles have been accomplished.
of the mixture of exhaust gases at 30atm and for
(b) The values of Ke (Table 1) show that the yield
mass transfer using pump C. The total energy con-
of the reaction responsible for the energy production
sumed is 18.6kcal/gmol CO2 and the useful stored
is quite high at moderate temperatures (80-110°C)
energy is 15.6 kcal/gmol.
and pressures (2407-9793 mmHg).
Available thermal energy from solar collectors
On the basis of existing meteorological data for the Table 7. Collector efficiency r/at various temperatures t and
years 1956-1974 from the National Observatory in energy collected per m 2 of collector in l h, assuming in-
Athens [13] we have calculated that, for the winter solation of 800 Wm -2. The amount of NH2COONH4 which
period (1 November-31 April) with an average total is needed for decomposition per h for 1 m 2 of solar collector
is also given
solar radiation of 2560kcal m 2/day, we need ap-
proximately 9090 m 2 of solar collectors to capture Energy Decomposition rate
14 × 106kcal/day. We have assumed that the final t r/ collected of NH2COONH4
(C) (%) (kcal.m 2.h i) (kg-m 2.h t)
temperature which is required is 100°C. At this . . . . . . . . . . . .
temperature, a suitable solar collector [9] with con- 80 67 460 1.05
85 63 433 0.99
centration of sunlight C = 2, and under average solar 90 60 412 0.94
radiation intensity has a collection efficiency of about 95 56 385 0.88
60~. The collector area is mixed: collectors plus 100 52 357 0.82
reflectors. The collector area has been calculated 105 47 323 0.74
110 42 289 0.66
assuming no losses in the system, besides the col-
 KOUTINAS et al.: THERMOCHEMICAL STORAGE SYSTEM 63

Table 8. Percentage of useful energy obtained by the various systems described in this
work
Open system
CO 2 from
alcoholic CO2 from
Closed system fermentation combustion gases
(%) (%) (%)
Block diagram 1 56 65 15
Block diagram2 86 95 46

(c) The velocities of the NH2COONH 4 production Although a system based on block diagram 2 and
in the range 80--110°C (Table 1) allow very high rates using CO2 from combustion gases presents relatively
of energy production to be obtained. Concerning the small efficiencies (46%) its construction will be, per-
block diagram 1, these rates permit the use of a haps, advantageous near thermoelectric units. In such
reactor with very small dimensions. For example, a cases, the dissociation of NH2COONH4 can be per-
reactor with v = 1 lit working at 80°C is sufficient for formed at the expense of the heat of the combustion
the taking of the energy recorded in Fig. 1. However, gases.
from the point of view of heat transfer, this volume In view of the relatively low cost of NH 3 and COz,
is too small. Thus, for the transport of the systems proposed in the present work are quite
823,620 kcal/h, a surface, heated, equal to 16.5 m 2 is beneficial. Furthermore, as already mentioned, the
necessary. Therefore, a realistic volume for a reactor CO2 can be rejected in some cases. An approximate
equipped with a heat exchanger is 3 m 3. calculation, taking into account the particular solar
(d) The high rates of the NH2COONH4 dis- conditions in Greece, demonstrates that 7 kg NH3,
sociation (Table 1) permit very rapid regeneration of 9 kg CO2 and 6 m 2 of collector area are necessary to
the system. Table 8 allows a comparison to be made fulfill the demands for space heating and domestic
of the efficiencies of the various processes proposed. hot water per individual.
An inspection of this table demonstrates that the
processes based on block diagram 2 are more efficient
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