Oxido de Zinc

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 0
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Solar thermochemical ZnO/ZnSO4 water splitting

cycle for hydrogen production
Rahul Bhosale a,*, Anand Kumar a, Fares AlMomani a, Ram B. Gupta b

a
Department of Chemical Engineering, College of Engineering, Qatar University, P.O. Box e 2713, Doha, Qatar
b
Department of Chemical and Life Science Engineering, Virginia Commonwealth University, Richmond, VA 23284,
United States
article info abstract
Article history: In this paper, solar reactor efficiency analysis of the solar thermochemical two-step zinc
Received 16 December 2016 oxideezinc sulfate (ZnOeZnSO4) water splitting cycle. In step-1, the ZnSO4 is thermally
Received in revised form decomposed into ZnO, SO2, and O2 using solar energy input. In step-2, the ZnO is re-
24 February 2017 oxidized into ZnSO4 via water splitting reaction producing H2. The ZnSO4 is recycled
Accepted 25 February 2017 back to the solar reactor and hence can be re-used in multiple cycles. The equilibrium
Available online xxx compositions associated with the thermal reduction and water-splitting steps are identi-
fied by performing HSC simulations. The effect of Ar towards decreasing the required
Keywords: thermal reduction temperature is also explored. The total solar energy input and the re-
Solar fuels radiation losses from the ZnOeZnSO4 water splitting cycle are estimated. Likewise, the
Solar reactor amount of heat energy released by different coolers and water splitting reactor is also
Thermodynamics determined. Thermodynamic calculations indicate that the cycle (hcycle) and solar-to-fuel
Hydrogen energy conversion efficiency (hsolar-to-fuel) of the ZnOeZnSO4 water splitting cycle are
Water splitting equal to 40.6% and 48.9% (without heat recuperation). These efficiency values are higher
Zinc oxide than previously investigated thermochemical water splitting cycles and can be increased
further by employing heat recuperation.
© 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
operating temperatures, the most challenging part is the

Introduction decomposition of SO3. The reduction of SO3 into SO2 and O2
requires high operating temperatures and it is possible only
The sulfureiodine cycle [1,2] and its variation the hybrid sul- under catalytic conditions. In past, various transition metal
fur cycle [3] are considered as more promising towards H2 based catalysts such as nickel, manganese, etc. were tested
production via water splitting reaction as the temperatures towards the SO3 decomposition reaction. However, it was
required to run these cycles are considerably lower than other observed that at higher temperatures these metal catalysts get
thermochemical water splitting cycles i.e. zinc oxide cycle, converted into metal sulfates and their catalytic activity is
iron oxide cycle, tin oxide cycle, ceria cycle, ferrite cycle, and hindered due to the sulfation poisoning [27]. Noble metal
perovskite based cycle [4e24] and comparable to hybrid based catalysts (supported on different metal oxides) were
photo-thermal sulfureammonia water splitting cycle [25,26]. also tested and observed to be attractive in terms of their
Although these cycles are advantageous in terms of lower catalytic activity towards decomposition of SO3. However, the
* Corresponding author. Fax: þ974 4403 4131.

E-mail addresses: rahul.bhosale@qu.edu.qa, solar.chemical.engineering@gmail.com (R. Bhosale).
http://dx.doi.org/10.1016/j.ijhydene.2017.02.190
0360-3199/© 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Please cite this article in press as: Bhosale R, et al., Solar thermochemical ZnO/ZnSO4 water splitting cycle for hydrogen production,
International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.02.190
2 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 0
extremely high cost of the noble metals pose limitations to- ZnSO4 /ZnO þ SO2 ðgÞ þ 1 2O2 ðgÞ =
(3)
wards utilization of such catalysts for commercial scale
application. ZnO þ SO2 ðgÞ þ H2 OðgÞ/ZnSO4 þ H2 ðgÞ (4)
Converting the sulfureiodine and the hybrid sulfur cycle
into solar driven metal oxideemetal sulfate (MOeMS) ther- The equilibrium compositions of the thermal reduction
mochemical water splitting can be considered as an alterna- and water splitting steps are determined by performing HSC
tive for the production of H2 at lower operating temperatures. simulations and by assuming the continuous operation of the
It is a two-step process in which the first step belongs to the solar reactor with molar feed rate of ZnSO4 equal to 1 mol/s.
solar thermal decomposition of metal sulfate (MSO4) into HSC simulations are performed to study the effects of various
metal oxide (MO), sulfur dioxide (SO2) and oxygen (O2). The operating parameters towards variations in the equilibrium
metal oxide and sulfur dioxide produced in step-1 can be re- compositions and solar reactor efficiency parameters.
oxidized into metal sulfate in step-2 with the help of water At first, the feasibility of the thermal reduction and water
splitting reaction which further yields into H2 production. The splitting reactions is analyzed by calculating the change in the
reaction chemistry associated with the MOeMS water split- Gibbs free energy (DG) as a function of thermal reduction
ting cycle is shown below. temperature (TH) and water splitting temperature (TL) in
absence of inert Ar. The results reported in Fig. 2a and b
MSO4 /MO þ SO2 þ 1 2O2
=
(1) indicate that the DG in case of thermal reduction of ZnSO4
decreases with the increase in the TH, whereas the DG in case
MO þ SO2 þ H2 O/MSO4 þ H2 (2) of water splitting reaction increases with the increase in the
TL. For instance, in case of thermal reduction of ZnSO4, DG
In one of our recent studies [28], the iron oxideeiron sulfate
decreases from 194.3 to 97.6 kJ/mol as the TH increases from
(IOeIS) water splitting cycle has been thermodynamically
500 to 1700 K. The DG associated with the water splitting re-
investigated. The results obtained in this study indicate that
action increases from 21.5 to 110.2 kJ/mol as the TL increases
the solar-to-fuel energy conversion efficiency in case of iron
from 300 to 900 K. The obtained results show that the com-
oxideeiron sulfate cycle is significantly higher than the pre-
plete thermal reduction of ZnSO4 is feasible above 1270 K (in
viously studied metal oxide based water splitting cycles. In
past, several metal oxides were examined towards water
splitting reaction and in addition to the iron oxide, zinc oxide
is also considered as one of the promising one. Therefore, in
this paper, the thermodynamic analysis of the zinc oxi-
deezinc sulfate (ZnOeZnSO4) water splitting cycle is carried
out by using HSC Chemistry software and its thermodynamic
database. The results obtained are compared with the previ-
ously studied thermochemical water splitting cycles. The
typical two-step solar thermochemical ZnOeZnSO4 water
splitting cycle is depicted in Fig. 1.
Thermodynamics equilibrium compositions
The specific reaction chemistry associated with the

ZnOeZnSO4 water splitting cycle is as follows:
Fig. 2 e Effect of (a) TH and (b) TL on DG associated with the

thermal reduction and water splitting step associated to
Fig. 1 e Typical two-step solar thermochemical the solar thermochemical ZnOeZnSO4 water splitting
ZnOeZnSO4 water splitting cycle. cycle.
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 0 3
absence of Ar) and the complete re-oxidation of ZnO into

ZnSO4 with the help of water splitting reaction is possible
below 395 K. The equilibrium compositions associated with
the water splitting and thermal reduction steps (in absence of
Ar) are presented in Figs. 3a,b and 4, respectively.
Effect of inclusion of Ar as an inert carrier gas during the
thermal reduction of ZnSO4 is studied and the HSC simulation
results are shown in Fig. 5. As per the reported results, with
the increase in the molar flow rate of Ar, the temperature
required for complete thermal reduction of ZnSO4 decreases.
At Ar ¼ 0 mol/s, the TH required for the complete thermal
reduction of ZnSO4 is equal to 1650 K. As the Ar molar flow rate
increases to 5, 10, 20, and 30 mol/s, the TH decreases to 1520,
1445, 1405, and 1395 K, respectively (Fig. 6). As the inert gas is
introduced in the solar reactor during the thermal reduction of
ZnSO4, the entropy associated with the product of thermal Fig. 4 e Equilibrium compositions associated with the
reduction step decreases and hence the thermodynamic thermal reduction step of ZnOeZnSO4 cycle in absence of
equilibrium shifts towards the lower temperature. Ar.
Solar reactor efficiency analysis

solar reactor efficiency analysis is carried out by employing
To estimate the cycle and solar-to-fuel energy conversion ef- similar assumptions and methodology used in our previous
ficiency of the ZnOeZnSO4 water splitting cycle, the process study related to iron oxideeiron sulfate water splitting cycle
flow configuration is developed and it is reported in Fig. 7. The [28]. The thermodynamic property database of HSC Chemistry
software is used to perform these calculations. The solar
reactor is assumed as a continuously operated system and
energy required for the separation of SO2 from O2 and Ar is not
taken under consideration during the thermodynamic calcu-
lations. The entire thermodynamic analysis is normalized to
the molar flow rate of ZnSO4 equal to 1 mol/s.
The process flow configuration of ZnOeZnSO4 water
splitting cycle involves four solar heated sections, namely,
solar reactor, heater 1, heater 2, and heater 3. All these units
are assumed as perfectly insulated cavity apparatus in which
heating of the material is achieved by the use of concentrated
solar radiations. The solar energy absorption efficiency of
each unit is determined as per following equation.
4
sT
habsorption ¼ 1 (5)
IC
where,
I ¼ direct-normal solar irradiance ¼ 1000 (W/m2)

C ¼ solar flux concentration ratio ¼ 5000 suns
T ¼ temperature up to which the heating is desired (in K),
TH in case of solar reactor and TL in case of all heaters
s ¼ StefaneBoltzmann constant ¼ 5.6705 108 (W/m2$K4)
The habsorption of heater 1, heater 2, and heater 3 is observed

to be constant (99.97%) as all the heaters are used to heat Ar,
H2O, and SO2 from 298 to 393 K. In case of solar reactor though,
the habsorption is increasing in order with the decrease in the TH.
For instance, at TH ¼ 1650 K, the habsorption is equal to 91.6%. The
habsorption increases upto 93.9, 95.0, 95.6, and 95.7% as the TH
decrease to 1520, 1445, 1405, and 1395 K, respectively.
The net heat energy required to run the ZnOeZnSO4 water
Fig. 3 e Equilibrium compositions associated with the splitting cycle can be estimated by calculating the energy
water splitting step of ZnOeZnSO4 cycle at 1 bar, (a) solid needed for 1) heating of Ar, 2) reduction of ZnSO4, 3) heating of
components and (b) gaseous components. SO2, and 4) heating of H2O.
Fig. 5 e Effect of n_ Ar on equilibrium compositions associated with the thermal reduction of ZnSO4, (a) solid components, (b)
gaseous components.
Q_ cyclenet ¼ Q_ Arheating þ Q_ ZnSO4 reduction þ Q_ SO2 heating þ Q_ H2 Oheating (6)
The energy needed to heat the Ar, SO2, and H2O is deter-
mined as:
Q_ Arheating ¼ n_Ar DHjArðgÞ@298K/ArðgÞ@TL (7)
Q_ SO2 heating ¼ n_SO2 DHjso2 ðgÞ@298K/so2 ðgÞ@TL (8)
Q_ H2 Oheating ¼ n_H2 O DHjH2 OðlÞ@298K/H2 OðgÞ@TL (9)
The molar flow rate of SO2 and H2O used in the ZnOeZnSO4
cycle is constant (1 mol/s). Therefore, amount of energy
needed to heat SO2 and H2O remain constant at all TH. 4.0 and
Fig. 6 e Effect of n_ Ar on (a) TH of ZnSO4, and (b) Q_ Arheating . 47.2 kW of energy is needed to heat SO2 and H2O from 298 to
393 K, respectively. However, the molar flow rate of Ar varies
Fig. 7 e Process flow configuration of solar thermochemical ZnOeZnSO4 water splitting cycle.
as the TH differs and hence variable amount of energy is the TH decrease to 1395 K. As expected, the reason for the
needed to heat Ar from 298 to 393 K. Deviation in Q_ Arheating as a higher amount of heat energy required at lower operating
function of TH is presented in Fig. 6 and it is observed that the temperatures is due to the heating of inert Ar.
Q_ Arheating increases as the molar flow rate of Ar increases due The total amount of solar energy required to run the
to the reduction in the TH. At n_Ar ¼ 5 mol=s, the Q_ Arheating is ZnOeZnSO4 water splitting cycle can be estimated as:
equal to 9.9 kW and as the n_Ar increases up to 30 mol/s, the
Q_ Arheating also upsurges up to 59.3 kW. Q_ solarcycle ¼ Q_ heater 1 þ Q_ solar reactor þ Q_ heater 2 þ Q_ heater 3 (11)
The ZnSO4 enters the solar reactor at TL and it is heated up where,
to TH to achieve complete thermal reduction. The heat energy
Q_ Arheating
needed for the thermal reduction of ZnSO4 is estimated as per Q_ heater 1 ¼ (12)
habsorptionheater
Eq. (10) and variation in the Q_ ZnSO4 reduction with respect to in-
1
crease in the TH is shown in Fig. 8.
Q_ ZnSO4 reduction ¼ n_ZnSO4 DHjZnSO4 þn_Ar ArðgÞ@TL /ZnOþSO2 ðgÞþ 1

=
2O2 ðgÞþn_Ar ArðgÞ@TH
(10)
As per the values reported in Fig. 8, with the increase in the

TH, the Q_ ZnSO4 reduction decreases significantly. At TH ¼ 1650 K, the
amount of heat energy required for the thermal reduction of
ZnSO4 is equal to 488.3 kW. As the TH decreases to 1395 K, the
Q_ ZnSO4 reduction increases up to 1079.3 kW. The thermal reduction
of ZnSO4 is possible at lower TH with high molar flow rate of
inert Ar. Therefore, at lower values of TH, most of heat energy
is used to heat the inert Ar from 393 K to TH and hence the total
Q_ ZnSO4 reduction is higher at these conditions.
The net amount of heat energy needed to run the
ZnOeZnSO4 water splitting cycle is calculated as per Eq. (6)
and the values are plotted in Fig. 8. As TH ¼ 1650 K, the Fig. 8 e Effect of TH on Q_ SO2 heating , Q_ H2 Oheating , Q_ ZnSO4 reduction ,
Q_ cyclenet is equal to 539.5 kW and it increases by 650.2 kW as Q_ cyclenet at constant TL.
Q_ SO2 heating Data points reported in Table 1 indicate steady re-radiation

Q_ heater 2 ¼ (13)
habsorptionheater 2
losses in case of heater 2 and heater 3 as both SO2 and H2O
molar flow rates are constant. For heater 1, as the molar flow
Q_ H2 Oheating rate of Ar increases due to the decrease in the TH, the re-
Q_ heater 3 ¼ (14) radiation losses raise from 0 to 0.06 kW. Moreover, in case of
habsorptionheater
solar reactor, at TH ¼ 1650 K, the Q_ radsolar reactor is equal to
3
44.8 kW. As the TH decreases to 1520 and 1445 K, the re-

Q_ ZnSO4 reduction
Q_ solar reactor ¼ (15) radiation losses from the solar reactor also reduce to 37.9
habsorptionsolar reactor
and 35.4 kW, respectively. Additional decrease in the TH to
The effect of decrease in TH on Q_ solarcycle is presented in 1405 and 1395 K yields into increase in the re-radiation losses
Fig. 9. Similar to Q_ ZnSO4 reduction , the total amount of solar energy as the molar flow rate of Ar used at these conditions is
desired to run the ZnOeZnSO4 water splitting cycles is also significantly higher.
lower at higher TH. At TH ¼ 1650 K, the Q_ solarcycle is equal to Multiple coolers are used in the ZnOeZnSO4 water splitting
584.3 kW and it increases by a factor of 2.1 as the TH decreases cycle for reducing the temperature of, 1) gaseous mixture of
by 255 K. SO2, O2, and Ar exiting the solar reactor from TH to 298 K, 2)
As the operation of the solar reactor and heaters is carried ZnO from TH to TL, and 3) H2 exiting the water splitting reactor
out at high temperatures, the re-radiation losses are inevi- from TL to 298 K. The heat energy released by each cooler is
table. Therefore, the total amount of re-radiation losses from determined as per following equations.
the ZnOeZnSO4 water splitting cycle is determined as:
Q_ cooler 1 ¼ n_ZnSO4 DHjSO2 ðgÞþ0:5O2 ðgÞþn_Ar ArðgÞ@TH /SO2 ðgÞþ0:5O2 ðgÞþn_Ar ArðgÞ@298K
Q_ radcycle ¼ Q_ radheater _
1 þ Q radsolar
_
reactor þ Q radheater
_
2 þ Q radheater 3 (21)
(16)
Q_ cooler 2 ¼ n_ZnSO4 DHjZnO@TH /ZnO@TL (22)
where,
Q_ radheater 1 ¼ Q_ heater 1 Q_ Arheating (17) Q_ cooler 3 ¼ n_ZnSO4 DHjH2 ðgÞ@TL /H2 ðgÞ@298K (23)
Similarly, the heat energy released during exothermic

Q_ radheater 2 ¼ Q_ heater 2 Q_ SO2 heating (18)
oxidation of ZnO into ZnSO4 via water splitting reaction can be
calculated as:
Q_ radheater 3 ¼ Q_ heater 3 Q_ H2 Oheating (19)
Q_ splitting reactor ¼ n_ZnSO4 DHjZnOþH2 OðgÞþSO2 ðgÞ@TL /ZnSO4 þH2 ðgÞ@TL (24)
Q_ radsolar reactor ¼ Q_ solar _
reactor Q ZnSO4 reduction (20) As the water splitting reaction is carried out at constant
TL ¼ 393 K, the heat energy emitted by the water splitting
reactor and cooler 3 remain constant (Table 2).
As reported in Fig. 10, in case of cooler 1 and cooler 2, the
heat energy dissipated varies as a function of TH. For cooler 1,
the heat energy released increases with the decrease in the TH.
As the TH decreases from 1650 to 1395 K, Q_ cooler 1 upsurges by a
factor of 8.0. The reason for the increase in the Q_ cooler 1 is the
usage of higher molar flow rate of Ar at lower TH values.
Opposite to this, the Q_ cooler 2 decreases by 21.9% as the TH re-
duces from 1650 to 1395 K. This drop in the heat energy
released by the cooler 2 is due to the fact that, as the value of
TH reduces, the difference between TH and TL decreases and
hence less amount of cooling is needed to decrease the tem-
perature of ZnO to TL.
Due to the irreversible transformation, the entropy pro-
duced across various units associated with the ZnOeZnSO4
water splitting cycle can be estimated as per following
equations.
Fig. 9 e Effect of TH on Q_ solarcycle .
Table 1 e Re-radiation losses from various heating units associated with the ZnOeZnSO4 water splitting cycle.
TH (K) Q_ radheater 1 (kW) Q_ radheater 2 (kW) Q_ radheater 3 (kW) Q_ radsolar reactor (kW) Q_ radcycle (kW)
1650 0.000 0.001 0.013 44.8 44.9
1520 0.010 0.001 0.013 37.9 37.9
1445 0.020 0.001 0.013 35.4 35.4
1405 0.039 0.001 0.013 40.5 40.6
1395 0.059 0.001 0.013 48.4 48.5
!
Table 2 e Unchanged parameters in case of ZnOeZnSO4 _ cooler Q_ cooler
Irr 3 ¼ 3
þ n_ZnSO4 DSjH2 ðgÞ@TL /H2 ðgÞ@298K (31)
water splitting cycle. 298
Parameter Value
!
Q_ cooler3 Q_ splitting
2.7 kW _ splitting
Irr reactor ¼
reactor
Q_ splitting reactor 90.5 kW TL
Q_ FCIdeal 48.7 kW
_ FCIdeal þ n_ZnSO4 DSjZnOþH2 OðgÞþSO2 ðgÞ@TL /ZnSO4 þH2 ðgÞ@TL (32)
W 237.2 kW
_ cooler 3
Irr 0.0012 kW/K The irreversibility's associated with the various units are
_ heater 2
Irr 0.0014 kW/K
_ heater 3
determined and reported in Tables 2 and 3. The irrever-
Irr 0.0080 kW/K
_ splitting reactor sibility's associated with cooler 3, water splitting reactor,
Irr 0.0009 kW/K
heater 2, and heater 3 are steady. However, irreversibility's
related to cooler 1, cooler 2, heater 1, and solar reactor varies
as a function of TH. With the drop in the TH from 1650 to
1395 K, irreversibilities linked to heater 1, cooler 1, and solar
reactor increases by 0.0203, 1.3, and 0.301 kW/K, respectively.
_ cooler 2 reduces by 29.8% with the similar
Opposite to this, the Irr
decreases in TH.
The maximum work output of the H2 produced via
ZnOeZnSO4 water splitting reactor is estimated by using an
ideal H2/O2 fuel cell. The work output and the amount heat
energy released by the ideal H2/O2 fuel cell are determined by
using below given equations and the values are reported in
Table 2.
W_ FCIdeal ¼ nDGj
_ (33)
H2 ðgÞþ0:5O2 ðgÞ@298K/H2 OðlÞ@298K
Fig. 10 e Effect of TH on Q_ cooler 1 and Q_ cooler 2 . Q_ FCIdeal ¼ ð298Þ nDSj

_ H2 ðgÞþ0:5O2 ðgÞ/H2 OðlÞ@298K (34)
To compare the ZnOeZnSO4 water splitting cycle with the

previously investigated thermochemical cycles, the cycle and
solar-to-fuel energy conversion efficiencies are calculated as:
! !
_ heater Q_ Q_ radheater W_ FCIdeal
Irr 1 ¼ heater 1
þ 1
hcycle ¼ (35)
TL 298K Qsolarcycle
þ n_Ar DSjArðgÞ@298K/ArðgÞ@TL (25)
HHVH2 ðmoles of H2 producedÞ
! ! hsolartofuel ¼ (36)
Qsolarcycle
_ heater Q_ Q_ radheater
Irr 2 ¼ heater 2
þ 2
TL 298K The data reported in Fig. 11 confirms that both hcycle and
þ n_SO2 DSjso2 ðgÞ@298K/so2 ðgÞ@TL (26) hsolar-to-fuel increases with the increase in the TH. At TH ¼ 1395 K
(Ar ¼ 30 mol/s), the hcycle and hsolar-to-fuel are equal to 19.1 and
! ! 23.1, respectively. hcycle and hsolar-to-fuel increases up to 40.6 and
_ heater Q_ heater 3 Q_ radheater 3
Irr 3 ¼ þ 48.9% as the TH upsurges to 1650 K (Ar ¼ 0 mol/s). When
TL 298K
compared with the iron oxideeiron oxide cycle at similar
þ n_H2 O DSjH2 OðlÞ@298K/H2 OðgÞ@TL (27) conditions (Ar ¼ 0 mol/s), the hcycle and hsolar-to-fuel values in
case of ZnOeZnSO4 water splitting cycle are observed to be
! !
_ solar Q_ ZnSO4 reduction Q_ radsolar reactor
slightly higher. Also, in comparison to the previously studied
Irr reactor ¼ þ
TH TL metal oxide cycles such as zinc oxide cycle (29%), tin oxide
cycle (29.8%), ceria cycle (20.2%) and iron oxide cycle (30%), the
þ n_ZnSO4 DSjZnSO4 þn_Ar ArðgÞ@TL /ZnOþSO2 ðgÞþ 1
=
2O2 ðgÞþn_Ar ArðgÞ@TH
(28)
! Table 3 e Effect of TH on Irr _ heater 1 , Irr

_ cooler 1 , Irr
_ cooler 2 , and
_
_ cooler 1 ¼ Q cooler 1
Irr _ solar reactor .
Irr
298
TH (K) _ heater 1
Irr _ cooler 1
Irr _ cooler 2
Irr _ solar reactor
Irr
þ n_ZnSO4 DSjSO2 ðgÞþ0:5O2 ðgÞþn_Ar ArðgÞ@TH /SO2 ðgÞþ0:5O2 ðgÞþn_Ar ArðgÞ@298K (kW/K) (kW/K) (kW/K) (kW/K)
(29) 1650 0.0000 0.205 0.094 0.27
1520 0.0034 0.434 0.080 0.29
!
_ cooler Q_ cooler 1445 0.0068 0.634 0.071 0.32
Irr 2 ¼ 2
þ n_ZnSO4 DSjZnO@TH /ZnO@TL (30) 1405 0.0135 1.054 0.067 0.44
TL
1395 0.0203 1.484 0.066 0.57
the heat recuperation. By applying 50% heat recuperation at

TH ¼ 1650 K, the hcycle-HR and hsolar-to-fuel-HR increases up to 51.8
and 62.5%, respectively. Similar trend is observed in case of
other thermal reduction temperatures.
The solar reactor efficiency analysis performed in this
study is further verified by calculating W _ FCIdeal by using
following equation and comparing it with the W _ FCIdeal
determined as per Eq. (33).

W_ FCIdeal ¼ Q_ solarcycle Q_ reradcycle þ Q_ cooler 1 þ Q_ cooler 2 þ Q_ cooler 3

þ Q_ splitting reactor þ Q_ FCIdeal
(42)
At all TH values, the W_ FCIdeal calculated by Eqs. (33) and (42)

matches very well which further confirms that the thermo-
Fig. 11 e Effect of TH on hcycle and hsolar-to-fuel for ZnOeZnSO4
dynamic analysis performed here is precise.
water splitting cycle.
Summary and conclusions

efficiency values in case of ZnOeZnSO4 water splitting cycle
are realized to be considerably higher. By using the commercially available HSC Chemistry software
By employing heat recuperation, the efficiency values can and its thermodynamic database, the computational ther-
be further enhanced. The total amount of heat energy that can modynamic analysis of the zinc oxideezinc sulfate
be recuperated in ZnOeZnSO4 cycle is calculated as: (ZnOeZnSO4) water splitting cycle is performed. The equilib-
rium thermodynamic calculations confirm that the thermal
Q_ recup ¼ Q_ cooler 1 þ Q_ cooler 2 þ Q_ cooler 3 þ Q_ splitting reactor (37) reduction of ZnSO4 is feasible above 1270 K, whereas H2 pro-
duction via water splitting reaction is possible below 395 K. At
Due to the recuperation of the heat energy released by
n_Ar ¼ 0 mol=s, the complete thermal reduction of ZnSO4 can
cooler 1, cooler 2, cooler 3, and water splitting reactor, the
be achieved at 1650 K. The thermal reduction temperature
solar energy required decreases which results into consider-
decreases further to 1395 K by using n_Ar ¼ 30 mol=s. The hab-
able increase in the process efficiencies.
sorption of the solar reactor increases from 91.59 to 95.70% with
Q_ recupHR ¼ ð% HRÞ Q_ recup (38) the decrease in the TH from 1650 to 1395 K. The total solar
energy input required to run the ZnOeZnSO4 water spitting
cycle is amplifies from 584.3 to 1238.8 kW with the decrease in
Q_ solarcycleHR ¼ Q_ solarcycle ð% HRÞ Q_ recupHR (39)
the TH from 1650 to 1395 K. The reason for this increase in the
use of higher molar flow rates of Ar. The hcycle and hsolar-to-fuel
W _ FCIdeal
hcycleHR ¼ (40) are maximum at TH ¼ 1650 K as the required solar energy
Q_ solarcycleHR input is lower as compared to TH ¼ 1395 K. The results ob-
tained in this study indicate that the efficiency values ob-
HHVH2 ðmoles of H2 producedÞ tained in case of ZnOeZnSO4 water splitting cycles are
hsolartofuelHR ¼ (41)
Q_ solarcycleHR significantly higher as compared to previously studied ther-
mochemical cycles. Also, by applying 50% recuperation of the
As listed in Table 4, the hcycle-HR and hsolar-to-fuel-HR in case of
heat released by the coolers and water splitting reactor, higher
ZnOeZnSO4 water splitting cycle increases significantly due to
values of hcycle (51.8%) and hsolar-to-fuel (62.5%) can be achieved.
Table 4 e Effect of HR on hcycle-HR and hsolar-to-fuel-HR of Acknowledgements

ZnOeZnSO4 water splitting cycle at TH ¼ 1650 K.
HR(%) Q_ recupHR Q_ solarcycleHR hcycle-HR hsolar-to-fuel-HR This publication was made possible by the NPRP grant (NPRP8-
(kW) (kW) (%) (%) 370-2-154) from the Qatar National Research Fund (a member
5 12.6 571.7 41.5 50.0 of Qatar Foundation). The statements made herein are solely
10 25.4 559.0 42.4 51.1 the responsibility of author(s).
15 38.1 546.3 43.4 52.3
20 50.7 533.6 44.4 53.6 Nomenclature
25 63.4 520.9 45.5 54.9
30 76.1 508.2 46.7 56.2
C solar flux concentration ratio, suns
35 88.8 495.6 47.9 57.7
40 101.5 482.8 49.1 59.2 HHV higher heating value
45 114.2 470.2 50.4 60.8 I normal beam solar insolation, W/m2
50 126.8 457.5 51.8 62.5 n_ molar flow rate, mol/s
n_Ar molar flow rate of Ar, mol/s references

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i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 0

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

Solar thermochemical ZnO/ZnSO4 water splitting

Rahul Bhosale a,*, Anand Kumar a, Fares AlMomani a, Ram B. Gupta b

article info abstract

operating temperatures, the most challenging part is the

* Corresponding author. Fax: þ974 4403 4131.

Thermodynamics equilibrium compositions

The specific reaction chemistry associated with the

Fig. 2 e Effect of (a) TH and (b) TL on DG associated with the

absence of Ar) and the complete re-oxidation of ZnO into

Solar reactor efficiency analysis

I ¼ direct-normal solar irradiance ¼ 1000 (W/m2)

The habsorption of heater 1, heater 2, and heater 3 is observed

Q_ cyclenet ¼ Q_ Arheating þ Q_ ZnSO4 reduction þ Q_ SO2 heating þ Q_ H2 Oheating (6)

Q_ Arheating ¼ n_Ar DHjArðgÞ@298K/ArðgÞ@TL (7)

Q_ SO2 heating ¼ n_SO2 DHjso2 ðgÞ@298K/so2 ðgÞ@TL (8)

Q_ H2 Oheating ¼ n_H2 O DHjH2 OðlÞ@298K/H2 OðgÞ@TL (9)

crease in the TH is shown in Fig. 8.

Q_ ZnSO4 reduction ¼ n_ZnSO4 DHjZnSO4 þn_Ar ArðgÞ@TL /ZnOþSO2 ðgÞþ 1

As per the values reported in Fig. 8, with the increase in the

Q_ SO2 heating Data points reported in Table 1 indicate steady re-radiation

44.8 kW. As the TH decreases to 1520 and 1445 K, the re-

Similarly, the heat energy released during exothermic

Fig. 10 e Effect of TH on Q_ cooler 1 and Q_ cooler 2 . Q_ FCIdeal ¼ ð298Þ nDSj

To compare the ZnOeZnSO4 water splitting cycle with the

! Table 3 e Effect of TH on Irr _ heater 1 , Irr

the heat recuperation. By applying 50% heat recuperation at

At all TH values, the W_ FCIdeal calculated by Eqs. (33) and (42)

Summary and conclusions

Table 4 e Effect of HR on hcycle-HR and hsolar-to-fuel-HR of Acknowledgements

n_Ar molar flow rate of Ar, mol/s references

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