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Kinetic Feasibility of A Chemical Heat Pump For Heat Utilization of High Temperature
Kinetic Feasibility of A Chemical Heat Pump For Heat Utilization of High Temperature
Kinetic Feasibility of A Chemical Heat Pump For Heat Utilization of High Temperature
Abstract
To utilize heat generated from high-temperature processes, the kinetic feasibility of a calcium oxide/
lead oxide/carbon dioxide chemical heat pump was examined experimentally by kinetic studies of CaO/
CO2 and PbO/CO2 reaction systems, which constitute the heat pump's reaction. In order to determine
the optimal reaction conditions that still allow practical operation of the heat pump, both reaction
systems were examined with respect to thermal drivability and reaction material durability. The heat
pump was able to store heat of about 8608C and transform it to a heat of above 8808C under sub-
atmospheric pressure without mechanical work. An applied system that combined the heat pump with a
high-temperature process was proposed for high-eciency heat utilization. The scale of the heat pump
in the combined system was estimated from the experimental results. # 1998 Elsevier Science Ltd. All
rights reserved.
Nomenclature
1359-4311/99/$ - see front matter # 1998 Elsevier Science Ltd. All rights reserved.
PII: S 1 3 5 9 - 4 3 1 1 ( 9 8 ) 0 0 0 4 9 - 0
240 Y. Kato et al. / Applied Thermal Engineering 19 (1999) 239±254
Subscripts
1 CaO/CO2 reaction system
2 PbO/CO2 reaction system
a output from high temperature gas reactor for a common system
b output from high temperature gas reactor for an applied system
c carbonation
d decarbonation
r output of a high temperature gas reactor
1. Introduction
based on comprehensive kinetic studies of both reaction systems needed to be determined for
heat pump realization. Thus, in the present study, the kinetics were studied with respect to
thermal drivability and reaction material durability. Thermal drivability is preferable for a
practical heat pump because the lack of mechanical work associated with the drivability allows
simple, safe and low-cost development. This point is particularly important at such high-
temperatures because of the diculty of designing a mechanical work system in that
temperature range. Both reaction systems are repeated cyclic systems under heat pump
operation. Reaction material durability in the repetitive cycle reaction was also examined.
Based on the results of the kinetic studies, an applied system that combines a heat pump with
a high-temperature process was proposed, and the scale of the applied system was discussed.
The following CaO/CO2 and PbO/CO2 reaction systems were used in the CaO/PbO/CO2
chemical heat pump.
CaO
s CO2
g CaCO3
s; DH1 ÿ178:321kJ=mol;
1
The equilibrium relationship of the heat pump operation is shown in Fig. 2. The solid and
broken sloping lines indicate the reaction equilibrium of CaO/CO2 [5] and PbO/CO2. PbO/CO2
equilibrium consists of three equilibriums as follows [6]:
Step A : 2PbCO3 Pb PbCO3 CO2 ;
3
242 Y. Kato et al. / Applied Thermal Engineering 19 (1999) 239±254
Fig. 1. Principle of CaO/PbO/CO2 chemical heat pump of heat transformation type operation; (a) heat storage
mode, and (b) heat output mode.
Preferably, as shown in Fig. 1 and mentioned in Section 1, the heat pump should be
thermally driven without any mechanical work. To successfully realize the thermal drive
operation, the choice of reaction pressure is important, as it ensures the reactivity of each
reaction and the safety of the reactor design. In a previous study, the basic kinetics of each
reaction was measured over a wide range of reaction pressures [7]. The four gray areas in Fig. 2
show the optimal reaction condition areas for thermal drive operation derived from that study.
The number of each operation in Fig. 2 corresponds to the same numbered operations in
Fig. 1. According to these operations, about 0.4 atm of reaction pressure is optimal for the
heat storage mode [(1)±(2) in Figs. 1 and 2], and 1.0 atm or more reaction pressure is suitable
for the heat output mode [(4)±(3) in Figs. 1 and 2]. However, the reactivity of each reaction is
244 Y. Kato et al. / Applied Thermal Engineering 19 (1999) 239±254
required to be high enough for practical operation of the heat pump and is aected by the
reaction temperature. Thus, comprehensive kinetic studies of the reaction areas shown in Fig. 2
were required to determine the reaction conditions which would realize practical heat pump
operation.
3. Experimental procedure
The kinetics of the CaO/CO2 and PbO/CO2 reaction systems were studied using a
thermobalance system under a closed system. Based on our previous study, 0.4 atm of reaction
pressure for the heat storage mode [(1)±(2) in Fig. 2] and 1.0 atm for the heat output mode
[(3)±(4) in Fig. 2] were appropriate reaction conditions. Reaction reactivity of both the CaO/
CO2 and PbO/CO2 systems under these conditions and under repetitive reaction were
measured. Reaction samples were set in a sample cell placed on a balance. During each
reaction, sample weight was monitored continuously and the reacted fraction was calculated
based on the change in weight. Temperature was measured directly at the bottom of the cell
using a thermocouple. This temperature was considered to be the reaction temperature and was
maintained using an electric heater. After residual inert gas in the apparatus was removed
using a vacuum pump at the beginning of each experiment, reaction pressure was controlled by
introducing CO2 gas, and was measured using a manometer. The experiments were carried out
at a reaction temperature between 300 and 9008C and under sub-atmospheric reaction
pressure. The starting reactants were 45 mg of lead carbonate (PbCO3) and 18 mg of calcium
carbonate (CaCO3) in 99.9% grade powder form (Kojundo Chemical Laboratory Co, Ltd).
The dierent sample weights employed ensured identical sample volumes. Experimental
analysis of the carbonation and decarbonation of PbO and the repetitive reaction was
performed under the following process.
PbCO3
ÿÿÿÿ4 PbO ÿÿÿÿ4 PbCO3 ÿÿÿÿ4 PbO . . .
6
Precursor Decarbonation
Exp:
Carbonation
Exp:
Repetition
Exp:
The reactivity of the carbonation and decarbonation of CaO was analyzed in a similar manner
as the PbO/CO2 system.
4. Experimental results
1.0 atm is shown in Fig. 3. The sample was heated at 508C/min to the target decarbonation
temperatures and was held at the temperature after 0 min in Fig. 3. Each reaction proceeds via
step A and B during initial heating until about 4008C. This is con®rmed by the initial change
in reacted fraction being about 67%, which is equal to the sum of 50 and 16.7 mol% for steps
A and B, before 0 min in Fig. 3 and by our previous study. The reaction then attains step C.
At 4208C, step C does not proceed because the reaction equilibrium temperature is higher than
4208C. The higher the reaction temperature was raised above 4308C, the faster the reaction
rate increased. The reactions at 4408C and 4508C were complete at about 60 and 30 min,
respectively, which indicates that decarbonation temperatures of 4408C or 4508C are optimal
for the carbonation of a practical heat pump operation with respect to reaction rate.
reactivity has a maximal eect on the reaction temperature. This result shows that a reaction
temperature of 3008C is optimal for the carbonation.
Fig. 5. Repetitive reaction of PbO/CO2 reaction system under derived optimal reaction conditions.
Fig. 7. Reactivity change in the carbonation of CaO in response to change in reaction temperature.
Y. Kato et al. / Applied Thermal Engineering 19 (1999) 239±254 249
Fig. 8. Repetitive reaction of CaO/CO2 reaction system under derived optimal reaction conditions.
in reaction amount during repetition was observed in contrast with the repetition result of the
PbO/CO2 system (Fig. 5). The CaO sample is expected to lose reactivity in further repetitive
cycles. A similar reduction in reactivity upon repetition was measured in a magnesium oxide/
water chemical heat pump, however, this reduction has already been overcome using a newly
designed reaction material [8]. Thus, development of a highly-durable material for the CaO/
CO2 reaction is a realistic possibility.
5. Discussion
The optimal reaction conditions for heat pump operation derived from the discussion in
Section 4 are shown as four black dots in Fig. 2. The results show that the reaction systems
can realize a heat transformation type operation, which means that the output temperature
(Tc1) is higher than the input temperature (Td1), under thermal driving conditions without
mechanical work. With respect to practical operation, the pressure gradient between reactors at
(1) and (2), and between (3) and (4) in the ®gure are required to ensure the mobility of CO2
reactant between reactors. Thus, some adjustment of the reaction conditions would be required
according to the heat pump design. Lower temperature input [process (1) in Figs. 1 and 2] and
higher output [process (3)] are preferred for this type of heat pump. Higher temperature output
is realized by higher temperature carbonation of CaO [process (3)] which is induced by the
high pressure CO2 generated by the higher temperature decarbonation of PbCO3 [process (4)].
250 Y. Kato et al. / Applied Thermal Engineering 19 (1999) 239±254
Although these high temperature experiments, which were performed above 1.0 atm, were not
examined with respect to restrictions of experimental apparatus, higher temperature reactions
and output would be possible, because the reaction rates will be accelerated with the rise in the
reaction temperature.
On the other hand, lower temperature heat input [process (1)] is dicult because of the low
reactivity of PbO carbonation [process (2)]. Lower temperature heat input is realized by lower
temperature decarbonation of CaCO3, which is induced by CO2 consumption during
carbonation of PbO at lower pressure. However, the current PbO material has limited
reactivity under low pressure and temperature [7]. Thus, performing process (2) under lower
pressure and process (1) at lower temperature heat input are dicult to realize at present.
Fig. 9. Applied system that combines the heat pump with a high temperature gas reactor for a turbine generator.
252 Y. Kato et al. / Applied Thermal Engineering 19 (1999) 239±254
the thermal quality of Qc1 is higher than that of Qd2 since Tc1>Td2. The applied system will be
available for load leveling of the electricity supply and will contribute to the stable operation
of the HTGR. As the heat pump can be operated under thermal driving conditions without
mechanical work, the system design will be simple and cheap, and heat pump operation will be
safe and highly reliable.
5.2.2.1. Speci®c reaction amount to output. The amount of reactant CaO to obtain 1 MW out-
put is de®ned as the speci®c reaction amount to output. The speci®c amount is inversely pro-
portional to the heat density and is calculated from experimental results in order to estimate
the reactor size. Fig. 10 shows the dependency of the amount on output temperature (Tc1) and
number of repetitions. For an output of 1 MW for 60 min, that is 1 MWh, 1.25 and 1.76 t/
MW are required for output temperatures of 800 and 8808C, respectively. The seventh cycle of
8808C output has a 3.42 t/MW. Since the speci®c amount is appreciably aected by the rep-
etition cycle, enhancement of the reactivity upon repetition is important for the further devel-
opment of heat pumps. Although considerations of heat and material transfer resistance are
required for scaling up the reactor bed size for practical purposes as well as enhancement of re-
petitive reactivity, the speci®c amount values are appropriate for practical use.
Fig. 10. Relationship between the speci®c reaction amount to output and output temperature (=Tc1).
Y. Kato et al. / Applied Thermal Engineering 19 (1999) 239±254 253
Fig. 11. Eect of reaction operation time of CaO carbonation on the reaction amount ratio.
5.2.2.2. Reaction amount ratio. The reaction rate and reaction amount are quite dierent
between the carbonation of CaO and PbO (Figs. 4 and 7). PbO carbonation will control the
whole operation rate because of its low reactivity. Consequently, a larger amount of PbO than
CaO is required for practical heat pump operation. The eect of the reactivity dierence on the
heat pump scale was estimated. The reaction amount ratio Z [mol%/mol%], de®ned as the
ratio of the carbonation amount of PbO (xc2 [mol%]) to that of CaO (Xc1 [mol%]) is calculated
by:
Z Xc1 =xc2
7
The ratio Z indicates the amount of PbO required to complete a speci®c amount of CaO carbo-
nation. Fig. 11 shows the result of the calculation under CaO carbonation conditions of 8808C
and 1.0 atm, and PbO carbonation conditions of 3008C and 0.4 atm. The sixth cycle results of
both PbO and CaO carbonation are used as stable reaction conditions in the calculation. Car-
bonation times of 5±120 min for CaO were used as the variable parameter. The horizontal axis
in Fig. 11 shows the carbonation time of PbO, that is, the time required for the decarbonation
process of CaCO3. When the carbonation time of CaO is 1 h, the value of Z implies that 19.4
times PbO compared with CaO is required if PbO carbonation is to be completed within the
same time frame. Even if 120 min are allowed for the carbonation of PbO, 7.32 times PbO is
required. The decrease in the amount of PbO required allows for a more compact system and
simple operation, and would thus be eective for the design of a heat pump and the enhance-
ment of operability.
254 Y. Kato et al. / Applied Thermal Engineering 19 (1999) 239±254
6. Conclusions
The feasibility of a CaO/PbO/CO2 chemical heat pump was examined using kinetic studies
of CaO/CO2 and PbO/CO2 reaction systems. The following results were obtained:
1. Optimal reaction conditions for practical thermal drive operation were proposed.
2. Heat output by carbonation of CaO was con®rmed up to 8808C under sub-atmospheric
pressure. Higher output temperature is expected by a rise in the carbonation pressure of
CaO.
3. Enhancement of durability of reaction materials were required in repetitive reactions.
4. An applied system that combined the heat pump with a high temperature gas reactor was
proposed as a high-temperature heat utilization system.
5. The scale of the heat pump is expected to have practical value. A decrease in reaction
amount ratio would be eective for heat pump design and enhancement of operability.
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