Applied Thermal Engineering 71 (2014) 445e449

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Applied Thermal Engineering

journal homepage: www.elsevier.com/locate/apthermeng

Design of an isopropanoleacetoneehydrogen chemical heat pump

with exothermic reactors in series
Min Xu a, Yanjun Duan a, b, Fang Xin a, b, Xiulan Huai a, *, Xunfeng Li a
a
Institute of Engineering Thermophysics, Chinese Academy of Sciences, Beijing 100190, China
b
University of Chinese Academy of Sciences, Beijing 100049, China

h i g h l i g h t s

We propose the IAH-CHP system with exothermic reactors in series.

The COP and exergy efficiency of the system increase by 7.6% and 10.3% respectively.

The work input of the system is reduced notably at the same quantity of heat released.

a r t i c l e i n f o a b s t r a c t

Article history: The isopropanoleacetoneehydrogen chemical heat pump system with a series of exothermic reactors in
Received 4 May 2014 which the reaction temperatures decrease successively is proposed. This system shows the better energy
Accepted 20 June 2014 performances as compared with the traditional system with a single exothermic reactor, especially when
Available online 27 June 2014
the higher upgraded temperature is need. At the same amounts of the heat released, the work input of
the compressor and the heater are both reduced notably. The results indicate that the advantages of the
Keywords:
IAH-CHP system with exothermic reactors in series are obvious.
Chemical heat pump
© 2014 Elsevier Ltd. All rights reserved.
Acetone hydrogenation
Exothermic reactor
Energy performance

1. Introduction drive the reaction and subsequently to separate of acetone and

It is important for saving energy to reuse the low-temperature
waste heat which is usually released to the environment in in-
dustrial processes. The waste heat can be utilized more easily by
upgrading its quality. Mechanical heat pumps have been widely
used in various process industries, but many shortcomings of me-
chanical heat pump such as high operation cost, low efficiency and
low upgrading temperature are still present [1,2]. In recent years,
Many researchers [3e9] are putting more focus on chemical heat
pump, which converts the low-level heat to high-quality thermal
energy through a reversible chemical reaction, because of its ad-
vantages such as high upgrading temperature, possibility of energy
storage, and low hazard. The schematic diagram of an iso-
propanoleacetoneehydrogen (IAH-CHP) system is shown in Fig. 1.
In this system, the dehydrogenation of isopropanol takes place at
the temperature TL in the endothermic reactor (reboiler in Fig. 1) to
yield acetone and hydrogen. The low-level heat QL is introduced to
* Corresponding author. Tel./fax: þ86 10 82543108.
E-mail addresses: hxl@iet.cn, hxl@mail.etp.ac.cn (X. Huai).
isopropanol in the distillation column. The acetone and hydrogen
as the distillate are compressed by the compressor, and then are
heated in the recuperator. Subsequently, the acetone and hydrogen
are introduced to the exothermic reactor after being heated up to
the reaction temperature in the heater. Acetone hydrogenation
occurs at the temperature TH in the exothermic reactor and the
high-temperature heat QH is produced and released. The effluent is
cooled in the recuperator and subsequently gets back to the
distillation column to close a cycle.
In recent decades, many researchers put focus on catalyst design
[10e12] and performance evaluation [7e9] for the IAH-CHP sys-
tem. But little literature investigated this system from the view of
chemical reactor engineering. Our previous works [13,14] proposed
an IAH-CHP system with a reactive distillation column to couple the
endothermic reactor and distillation column, and experimentally
verified its superiority. The optimal design of the exothermic fixed-
bed reactor for high-temperature acetone hydrogenation was also
carried out [15,16]. However, a contradiction is present for
exothermic reaction of the IAH-CHP system. From the view of waste
heat recovery, the higher upgraded temperature is more inter-
esting. Accordingly, when the upgraded thermal energy with a

http://dx.doi.org/10.1016/j.applthermaleng.2014.06.041
1359-4311/© 2014 Elsevier Ltd. All rights reserved.
446 M. Xu et al. / Applied Thermal Engineering 71 (2014) 445e449
Fig. 1. Schematic diagram of the isopropanoleacetoneehydrogen chemical heat pump
with a single exothermic reactor.
higher temperature is need, we must increase the reaction tem-
perature in the exothermic reactor. Nevertheless, the higher tem-
perature in the exothermic reactor reduces the equilibrium
conversion of acetone from the view of the thermodynamic aspect
and ends the reaction when the equilibrium composition is reached
(18% at 483 K [17]). Thus the amounts of the heat released from the
system are also decreased. Moreover, the lower conversion results
in the invalid cycle of hydrogen and acetone in the system and
hence increases the power consumption of the compressor and the
energy cost during the separation process. Unfortunately, to our
best knowledge, how high-temperature heat recovery and chemi-
cal equilibrium limitation can be balanced is still not clear in the
literature.
To address the above issues, we propose the IAH-CHP system
with exothermic reactors in series as shown in Figs. 2 and 3 to
replace the conventional one with a single high-temperature
equilibrium reactor. The first one of a series of reactors in the
modified system is equal with the high-temperature equilibrium
reactor of the conventional IAH-CHP, but the temperatures in the
other reactors are lower than that in the first reactor. Figs. 2 and 3
show the IAH-CHP system with two and three exothermic reactors
in series, respectively. Take the former for example, the acetone and
hydrogen are fed into the first exothermic reactor and reach equi-
librium at the highest temperature TH,1. The heat of the effluent is
released in the first recuperator, and then the equilibrium products
are introduced to the second exothermic reactor and reach the
Fig. 2. Schematic diagram of the isopropanoleacetoneehydrogen chemical heat pump
with two in-series exothermic reactors.
Fig. 3. Schematic diagram of the isopropanoleacetoneehydrogen chemical heat pump
with three in-series exothermic reactors.
other equilibrium at a lower temperature TH,2. The effluent is cooled
in the second recuperator and goes back to close the cycle.
Following this method, the conversion of acetone increases and the
amounts of the heat released grows while the high upgraded
temperature is maintained in this system.
In our previous work [13,14], a rigorous mathematic model is
established to simulate the IAH-CHP system with reactive distilla-
tion. In this work, we establish a mathematical model for an IAH-
CHP system with a reactive distillation column and exothermic
reactors in series, and the superiority of the IAH-CHP system using
in-series exothermic reactors is expounded.
2. Mathematical model
In this section, the mathematical models of the IAH-CHP system
with a single exothermic reactor and the system with two and three
exothermic reactors in series are established. All calculations are
carried out in the commercial simulation software Aspen Plus. The
rigorous equilibrium stage model RadFrac is used to simulate the
distillation column. The user kinetics subroutine (FORTRAN code) is
used to depict the experimentally-determined reaction kinetic
model in our previous work [13], and then compiled and linked
with the simulation model in ASPEN PLUS by using the Aspen Plus
Simulation Engine. The Compr module with isentropic type is used
to model the compressor, and a simple model called HeatX is used
for the recuperator. For the exothermic reactor, the RGIBBS module
with specified temperatures and pressures is used. Based on our
previous work, the reactive distillation column substitutes the
conventional distillation column for the IAH-CHP system in this
paper.
The optimized specifications and operating conditions of the
IAH-CHP system with a single exothermic reactor are list in Table 1
and elaborated in details in our previous work [13]. For the IAH-
CHP system with two and three in-series exothermic reactors, the
optimized specifications and operating conditions are also list in
Table 1. The various temperatures of the in-series exothermic re-
actors are specified and the temperature difference between the
two adjacent reactors is set to more than 20 K. The feed stage of the
distillation column is also changed to obtain the optimized energy
performance. The amount of catalyst loading in the reactive
distillation column increases due to the increase of acetone con-
version in the in-series exothermic reactors(it is more than two-
 M. Xu et al. / Applied Thermal Engineering 71 (2014) 445e449 447

Table 1
The optimized specifications and operation conditions of the IAH chemical heat pump in our simulations.

Contents Single-stage Two-stage Three-stage

RadFrac (reactive distillation column)

Total stages 15 15 15
Rectification zone 1e7 1e7 1e7
Reactive zone 8e15 8e15 8e15
Feed stage 4 7 7
Column pressure (MPa) 0.11 0.11 0.11
Distillate flow rate (mol s1) 0.3 0.3 0.3
Catalyst loading in reboiler (kg) 1.3/1/0.75 2 2
Catalyst loading on plate (kg/stage) 0.4/0.3/0.24 0.6 0.6
Isopropanol mole fraction in distillate 0.03 0.03 0.03
RGibbs (exothermic reactor)
Temperature (K) 453/473/493 453e413/473e413/493e413 453e433e413/473e443e413/493e453e413
Pressure (MPa) 0.12 0.12 0.12
Hydrogen to acetone mole ratio 1 1 1
HeatX (recuperator)
Feed temperature of the distillation column, Tfeed (K) 345 345 345
Compr (compressor)
Outlet pressure 0.12 0.12 0.12
Isentropic efficiency 0.72 0.72 0.72
Mechanical efficiency 1 1 1

fold of the conversion in the single exothermic reactor). Three cases Likewise, as seen in Fig. 5, the COP also increases when the
are calculated at the varying the highest exothermic temperature number of exothermic reactor changes from one to two. Especially
TH,1 (493 K, 473 K and 453 K, respectively). The predictive UNIFAC for the case that TH,1 is 493 K, the COP increases by 7.6%. The reason
model is used to account for liquid-phase non-idealities in the may be clear if we explore the variation tendency of the numerator
mixture during the whole process. and denominator of the Eq. (1). As the increase of the acetone
conversion and the amounts of heat released from the exothermic
3. Results and discussions reactors, the heat input to drive the endothermic reaction increase
in the same proportion, but the heat duty in reboiler remains un-
Two thermodynamic parameters are used to evaluate the per- changed through varying the feed stage of the distillation column.
formance of the IAH-CHP system with in-series exothermic re- Therefore, the total heat input increases in the lower proportion
actors. First, the coefficient of performance (COP) or enthalpy with the amounts of heat released, and hence the COP increases
efficiency is defined as follows: according to Eq. (1).
As seen in Fig. 6, the exergy efficiency increases significantly by
QH;tot the growth of the amount of exothermic reactor. When the highest
COP ¼ (1)
QL exothermic temperature (TH,1) is higher, the increasing tendency of
exergy efficiency is more obvious. For the case that TH,1 is 493 K, the
where QH,tot is the total amounts of the heat released from the exergy efficiency increases by 10.3% when the number of
exothermic reactor(s). exothermic reactor changes from one to three. The increase of the
Another parameter is exergy efficiency h which is defined as conversion of acetone and the amounts of heat released should
follows [9]: attribute to this improvement of the modified system, and another



reason is due to the decrease of the exergy loss of the recuperator
QH;1 1  T0 TH;1 þ QH;2 1  T0 TH;2 þ QH;3 1  T0 TH;3 through the multiple heat exchange. In addition, when the number
h¼
QL ð1  T0 =TL Þ þ Win
(2)

where T0 is the environmental temperature (298 K in our work),

QH,1, QH,2, and QH,3 is the amounts of the heat released from the first,
5
second and third exothermic reactor, and Win is the work supplied
to the compressor and the heater.
Figs. 4e6 show the effect of the number of exothermic reactors
on the amount of the heat released, COP and exergy efficiency of the 4
QH,tot(kW)

IAH-CHP system. As shown in Fig. 4, the total amounts of heat

released increases remarkably when the amount of exothermic
reactor changes from one to two. Especially for the case that the 3 TH,1=453K
high exothermic temperature (TH,1) is equal to 493 K, the total TH,1=473K
amounts of heat released increases by about three times. It is due to
TH,1=493K
the fact that the reaction temperature in the second exothermic
2
reactor is lower and the equilibrium conversion increases from
19.6% to 56.3% at 493 K. However, when the amount of exothermic
reactor changes from two to three the total amounts of heat 1.0 1.5 2.0 2.5 3.0
released remains unchanged for the reason that the lowest reaction Reactor number
temperature and equilibrium conversion in the exothermic reactor
is invariant. Fig. 4. Effect of the number of the exothermic reactor on the heat released.
448 M. Xu et al. / Applied Thermal Engineering 71 (2014) 445e449

Table 2
Comparison of the operating performances of the IAH chemical heat pump with
multi-stage exothermic reactor at the similar heat release QH,tot.
0.183
Contents One stage Two stage Three stage

TH (K) 493 493e413 493e453e413

0.180 Flow rate (kg/h) 101.281 32.452 32.452
Catalyst loading in reboiler (kg) 3 2 2
Catalyst loading on plate (kg/stage) 0.9 0.6 0.6
COP

0.177 Heat duty (kW)

Reboiler 30.623 28.925 28.925
TH,1=453K Compressor 0.302 0.091 0.091
0.174 TH,1=453K Heater 1.435 0.464 0.283
Performances
TH,1=453K
QH (kW) 5.386 5.315 5.315
COP 0.174 0.184 0.184
0.171 h 0.325 0.331 0.353
Overall heat transfer area 0.138 0.133 0.175
1.0 1.5 2.0 2.5 3.0 of recuperator (m2)

Reactor number

Fig. 5. Effect of the number of the exothermic reactor on the COP. efficiency of the IAH-CHP system with exothermic reactors in series
is superior. At the same time, the overall heat exchanger area of
recuperator changes a little. These results indicate the advantages
of exothermic reactor increases from two to three, the temperature
of the IAH-CHP system with exothermic reactors in series are
difference of the adjacent exothermic reactors is reduced, and the
obvious.
quality of the heat released is improved and hence the exergy ef-
One disadvantage of the IAH-CHP system with a series of
ficiency increases. In general, for the IAH-CHP system with single
exothermic reactors is that the quality of the heat released is lower
exothermic reactor, the exergy efficiency decrease as the
than that from the one with a single high-temperature exothermic
exothermic reaction temperature increases [13,18]. However, the
reactor, which is in the form of the highest level thermal energy, at
exergy efficiency of the IAH-CHP system with three exothermic
the same amounts of heat released. It can be improved by
reactors when TH,1 is 493 K is higher than that when TH,1 is 453 K. It
increasing the number of the exothermic reactors in series and
also indicates that the IAH-CHP system with exothermic reactors in
narrowing the temperature difference of the two adjacent reactors.
series is notably superior to that with a single exothermic reactor
The heat with various quality released from the different
when the high upgraded temperature is need.
exothermic reactors can be conveyed to the separate heat user to
Moreover, one more case has been calculated to compare the
achieve the cascaded utilization of the thermal energy.
performances of the IAH-CHP system with a single exothermic
reactor and the exothermic reactors in series at the similar amounts
4. Conclusion
of heat released. Some operating conditions and the results are list
in Table 2. The catalyst loading in reactive distillation column of the
In this work, we proposed the IAH-CHP system with the
IAH-CHP system with a single exothermic reactor and the flow rate
exothermic reactors in series, replacing the conventional one with
of the reactants in the system are varied to meet the change of the
one high-temperature equilibrium reactor. The first one of the re-
amounts of heat released. As shown in Table 2, the flow rate of the
actors in series of the modified system is equal to the single high-
reactants in the IAH-CHP system with a single exothermic reactor is
temperature equilibrium reactor of the conventional IAH-CHP, but
higher than three-fold of that in the IAH-CHP system with in-series
the temperature in the other reactors decline. Compared with the
exothermic reactors at the similar amounts of heat released.
conventional IAH-CHP system with a single exothermic reactor, the
Therefore, the heat duty of the compressor and the heater of the
COP and exergy efficiency increased. When the highest exothermic
former are also larger dramatically, while the COP and exergy
temperature is 493 K, the COP and exergy efficiency increased by
7.6% and 10.3%, respectively. At the same amounts of heat released,
the input work of the compressor and the heater was notably
reduced. The results indicated that the advantages of the IAH-CHP
system with exothermic reactors in series were obvious.
The construction of a prototype is being performed in our lab-
oratory to verify experimentally the superiority of the IAH-CHP
system with exothermic reactors in series.

Acknowledgements

This research is supported by the National Basic Research Pro-

gram of China (2011CB710705) and the National Natural Science
Foundation of China (21306192 and 51276181).

Nomenclature and units

COP coefficient of performance

QH heat released from the exothermic reactor (kW)
QL heat consumed by the endothermic reactor (kW)
Fig. 6. Effect of the number of the exothermic reactor on the exergy efficiency. T temperature (K)
 M. Xu et al. / Applied Thermal Engineering 71 (2014) 445e449 449

T0 environment temperature (K) [7] Y. Chung, B.J. Kim, Y.K. Yeo, H.K. Song, Optimal design of a chemical heat
pump using the 2-propanol/acetone/hydrogen system, Energy 22 (1997)
Win energy input (kW)
525e536.
[8] L.M. Gandia, M. Montes, Effect of the design variables on the energy perfor-
Greek symbols mance and size parameters of a heat transformer based on the system
h exergy efficiency acetone/H2/2-propanol, Int. J. Energy Res. 16 (1992) 851e864.
[9] I. KlinSoda, P. Piumsomboon, Isopropanoleacetoneehydrogen chemical heat
pump: a demonstration unit, Energy Convers. Manag. 48 (2007) 1200e1207.
Subscripts [10] E. Ito, M. Yamashita, S. Hagiwara, Y. Saito, A composite RuePt catalyst for 2-
1, 2, 3 no. of exothermic reactors propanol dehydrogenation adoptable to the chemical heat pump system,
Chem. Lett. 20 (1991) 351e354.
H high temperature [11] L.M. Gandia, A. Diaz, M. Montes, Selectivity in the high-temperature hydro-
L low temperature genation of acetone with silica-supported nickel and cobalt catalysts, J. Catal.
tot total 157 (1995) 461e471.
[12] W. Mooksuwan, S. Kumar, Study on 2-propanol/acetone/hydrogen chemical
heat pump: endothermic dehydrogenation of 2-propanol, Int. J. Energy Res.
References 24 (2000) 1109e1122.
[13] M. Xu, F. Xin, X.F. Li, X.L. Huai, J.F. Guo, H. Liu, Equilibrium model and per-
[1] K.J. Chua, S.K. Chou, W.M. Yang, Advances in heat pump systems: a review, formances of an isopropanoleacetoneehydrogen chemical heat pump with a
Appl. Energy 87 (2010) 3611e3624. reactive distillation column, Ind. Eng. Chem. Res. 52 (2013) 4040e4048.
[2] M.B. Blarke, Towards an intermittency-friendly energy system: comparing [14] F. Xin, M. Xu, X.L. Huai, X.F. Li, Study on isopropanoleacetone-hydrogen
electric boilers and heat pumps in distributed cogeneration, Appl. Energy 91 chemical heat pump: liquid phase dehydrogenation of isopropanol using a
(2012) 349e365. reactive distillation column, Appl. Therm. Eng. 58 (2013) 369e373.
[3] A.N. Ajah, A. Mesbah, J. Grievink, P.M. Herder, P.W. Falcao, S. Wennekes, On [15] X.M. Zhou, Y.J. Duan, X.L. Huai, X.F. Li, 3D CFD modeling of acetone hydro-
the robustness, effectiveness and reliability of chemical and mechanical heat genation in fixed bed reactor with spherical particles, Particuology 11 (2013)
pumps for low-temperature heat source district heating: a comparative 715e722.
simulation-based analysis and evaluation, Energy 33 (2008) 908e929. [16] Y.J. Duan, M. Xu, X.M. Zhou, X.L. Huai, A structured packed-bed reactor
[4] S. Spoelstra, W.G. Haije, J.W. Dijkstra, Techno-economic feasibility of high- designed for exothermic hydrogenation of acetone, Particuology (2014),
temperature high-lift chemical heat pumps for upgrading industrial waste http://dx.doi.org/10.1016/j.partic.2013.07.010 in press.
heat, Appl. Therm. Eng. 22 (2002) 1619e1630. [17] W. Kitikiatsophon, P. Piumsomboon, Dynamic simulation and control of an
[5] T.G. Kim, Y.K. Yeo, H.K. Song, Chemical heat pump based on dehydrogenation isopropanoleacetoneehydrogen chemical heat pump, Sci. Asia 30 (2004)
and hydrogenation of i-propanol and acetone, Int. J. Energy Res. 16 (1992) 135e147.
897e916. [18] J.F. Guo, X.L. Huai, X.F. Li, M.T. Xu, Performance analysis of iso-
[6] M. Prevost, R. Bugarel, Chemical heat pump: system iso- propanoleacetoneehydrogen chemical heat pump, Appl. Energy 93 (2012)
propanoleacetoneehydrogen, in: Proceedings of the International Seminar on 261e267.
Thermochemical Energy Storage, Stockholm, 1980, pp. 95e111.