Energy Conversion and Management 157 (2018) 600–618

Contents lists available at ScienceDirect

Energy Conversion and Management

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

Analysis and assessment of a hydrogen production plant consisting of coal T

gasification, thermochemical water decomposition and hydrogen
compression systems
⁎
Maan Al-Zareer , Ibrahim Dincer, Marc A. Rosen
Clean Energy Research Laboratory, Faculty of Engineering and Applied Science, University of Ontario Institute of Technology, 2000 Simcoe Street North, Oshawa, Ontario
L1H 7K4, Canada

A R T I C L E I N F O A B S T R A C T

Keywords: A novel hydrogen production plant is proposed, including a thermochemical water decomposition cycle, a
Coal gasification pressurized entrained flow gasifier, a water gas shift membrane reactor, a cryogenic air separation unit, a hy-
Syngas drogen-fueled combined cycle for power production and a hydrogen compression system. The syngas produced
Hydrogen production by the pressurized entrained flow gasifier undergoes the shift reaction in the water gas shift membrane reactor.
Copper-chlorine cycle
The stripping of hydrogen is done simultaneously with the shift reaction in the water gas shift membrane reactor
Exergy
to capture more hydrogen and increase the shift reaction conversion percentage. The remaining syngas is
Efficiency
combusted in the Brayton cycle and power is produced through Brayton cycle gas turbine. The hot exhausts
exiting the Brayton cycle gas turbine goes to the heat recovery steam generation unit where steam is produced.
The generated steam goes to the copper-chlorine cycle to produce hydrogen. Part of the power generated by the
Brayton cycle is used for the electrolysis reactor in the copper-chlorine cycle. Then, a small part of the hydrogen
produced passes to the combined cycle to overcome the needed work rate by the components in the plant. The
remaining larger portion of the hydrogen produced goes to the compression system to compress hydrogen to
700 bar for storage. The hydrogen production plant is developed and modeled in the Aspen Plus software
package. Energy and exergy analyses are performed on the hydrogen production integrated system. The overall
energy and exergy efficiencies of the proposed hydrogen production plant are found to be 51.3% and 47.6%
respectively.

1. Introduction
People are gradually depleting the world’s fossil fuels resources,
forcing humanity to find alternative sources of energy to meet the
continuously rising demands for energy. Recent reports by the
International Energy Agency predict an increase in global energy de-
mand of 50% by 2030 [1]. Concerns about the limited nature of the
fossil fuels have resulted in extensive research and development on
alternative sources of energy and on how to use currently available
fossil fuels more efficiently. Many methods are used today to increase
the efficiency of energy production from fossil fuels; one of these
methods is to run the power plants at a constant rate and at full capacity
all the time, another approach is the integration of power systems.
Running power plants at full capacity is not possible due to the fluc-
tuating nature of the energy demands during night and day, summer
and winter. However, the successful use of energy storage systems can
make that possible. Hydrogen has the advantage of being both energy
storage medium and an energy carrier [2], meaning that running power
plants at full capacity and storing the excess energy in hydrogen will
result in more efficient use of the available fossil fuels. Muradov and
Veziroglu [3] analyzed the main methods for hydrogen production from
fossil fuels as a green path for fossil-based hydrogen production, one of
these methods is water electrolysis, and another promising hydrogen
production process is the thermochemical copper-chlorine cycle. An
advantage of the thermochemical hydrogen production cycle is that it
directly produces hydrogen from heat without the intermediate step of
heat to electricity, which is vital for water electrolysis.
A number of researchers have proposed various integrations of ga-
sification of coal with other systems, such as [4,5] where they have
utilized an IGCC system integrated with a Cu-Cl cycle, which provides
the oxygen to the coal gasifier. Other researchers looked into replacing
the oxygen blown gasifier with an air blown gasifier, and they have
investigated the IGCC system performance under each [7]. They have
found out that the air blown gasifier perform better than the oxygen

⁎
Corresponding author.
E-mail addresses: maan.al-zareer@uoit.ca (M. Al-Zareer), ibrahim.dincer@uoit.ca (I. Dincer), marc.rosen@uoit.ca (M.A. Rosen).

https://doi.org/10.1016/j.enconman.2017.11.047
Received 30 June 2017; Received in revised form 14 November 2017; Accepted 17 November 2017
Available online 19 December 2017
0196-8904/ © 2017 Elsevier Ltd. All rights reserved.
M. Al-Zareer et al. Energy Conversion and Management 157 (2018) 600–618

Nomenclature in input (flowing into the system boundary)

i state point named i
COP coefficient of performance j constituent name in the flow
Eẋ exergy rate (kW) net net result
ex specific exergy (kJ/kg) ov overall
h specific enthalpy (kJ/kg) out output (flowing out of the system boundary)
HHV higher heating value (kJ/kg) o at standard conditions
HV heating value (kJ/kg) Q̇ heat flow rate
LHV lower heating value (kJ/kg) RC Rankine cycle
ṁ mass flow rate (kg/s) ST steam turbine
P pressure (kPa) s the boundary where heat transfer takes
Q̇ heat rate (kW) W work
R universal gas constant (kJ/mol.K) WGSMR water gas shift membrane reactor
s specific entropy (kJ/kg.K)
S sulfur content in coal (see Eq. (37)) Superscripts
T temperature (°C)
Ẇ work rate (kW) coal coal
x Mole fraction of constituent j in the flow (moles of J/moles o at standard conditions
of the total flow)
Acronyms
Greek letters
BrC Brayton cycle
β Coal parameter calculated using Eq. (38) CASU cryogenic air separation unit
η energy efficiency Cu-Cl copper-chlorine cycle
ψ exergy efficiency GFEMA Gibbs free energy minimization approach
ω moisture content in coal HRSG heat recovery steam generator
HFCC hydrogen fueled combined cycle
Subscripts HCS hydrogen compression system
IGCC integrated gasification combined cycle
BrC Brayton cycle O/C oxygen content in the coal divided by the carbon content
CASU cryogenic air separation unit in the coal
ch chemical RC Rankin cycle
Cu-Cl copper-chlorine cycle WGSMR water gas shift membrane reactor
coal coal
d destruction Aspen Plus terms
e electrical
fg phase change between liquid and gas Rstoic Stoichiometric reactor
gen generation Cisolid for homogeneous solids that have a defined molecular
GT gas turbine weight, with the option of entering the particle size dis-
G&U gasifier and utilities tribution
HFCC hydrogen fueled combined cycle NC nonconventional solid (for heterogeneous solids that have
H2 hydrogen no defined molecular weight) with the option of entering
HCS hydrogen compression system the particle size distribution
is isentropic

blown gasifier, however the results were specific for the specific air
separation technology considered. The performance of an IGCC system
was compared for two different cases of output product in Ref. [8]. The
first case, the IGCC system was producing only electrical power, while
the second case the IGCC system was producing only hydrogen. The
results presented by Gnanapragasam et al. [8] indicated that the hy-
drogen production system appears to be advantageous over the IGCC
system based on their selected analysis method. Rather than having an
IGCC system with a single product, Seyitoglu et al. [9] proposed and
analyzed the performance of a trigeneration IGCC system, and they
proposed system is proposed to produce hydrogen, power and Fischer-
Tropsch synthesis products. The research outcomes of Refs. [8,9] con-
cluded that multigenerational IGCC systems were able to achieve higher
energy and exergy efficiency compared to single generation systems.
Further research was focused on optimizing the gasification process
through the introducing the thermal energy for renewable energy
sources, where solar energy was utilized in a coal gasification based
multi-generational system [10]. However, other investigated the per-
formance of an IGCC system where a dual chemical looping occurred
simultaneously with gasification, where the effect of several factors
were investigated such as oxygen, steam and CaO flow to coal ratios
[11]. The performance of an IGCC system for three different types of
fuel feed, which are coal, biomass and a combination of both [12].
However, the combinations introduced in [12] were limited to couple
of combined flows, which resulted in a very limited results that derived
from specific combinations. In order to have a more flexible models to
investigate the effect of wide range of fuel compositions, Cohce et al.
[13] proposed an ideal gasification model in Aspen Plus, which was
able to predict the syngas composition with an acceptable accuracy
based on the authors.
Researchers have proposed various integrations of gasification of
coal [5–12,16], biomass [13], or the combination of coal and biomass
[12] with other systems such as a solar power tower [10], or with a
Fischer-Tropsch unit [9]. Others have integrated the gasification system
with a dual chemical looping process, namely chemical looping air
separation and water gas shift with calcium looping CO2 absorption
[11]. The production of hydrogen from coals is primarily achieved
through gasification, which produces syngas. Syngas is further treated

601
M. Al-Zareer et al.
and the formed hydrogen is captured by a separation technology for
further processing and utilization. Not all researchers considered the
second law of thermodynamics in their analyses, where [6–13] per-
formed the first law analysis only for their proposed integrated gasifi-
cation systems, but only Refs.[8–13] performed the second law analysis
(particularly exergy analysis). The energy and exergy efficiencies of the
proposed integrated gasification system are listed in [6–13], and some
exhibited an energy efficiency more than 60%, which is very promising.
Although there are many different ways of producing hydrogen, the
thermochemical copper-chlorine cycle is of particular importance since
it decomposes water using relatively low temperature heat when
compared thermal decomposition of water. Al-Zareer et al. [16] pro-
posed hydrogen and power production integrated system where the
water gas shift reaction was carried out in a membrane reactor, where
energy and exergy analyses were performed on the proposed system
when different types of coal fed to the system. Other studies focused on
specific parameters of the gasification process such as the work done by
Ozbilen et al. [17] studied the effect of the nitrogen, which is sent from
the air separation unit to the combustion chamber of the gas turbine, on
the system overall performance. Ozbilen et al. [17] found that the ni-
trogen supply enhances the system performance. Another example on
the studies that focused on a specific component in the gasification
system is the work done by Kariznovi et al. [18] performed a simulation
study on the gasification of the underground coal in Alberta and pro-
vided estimations of the reactions kinetics. Others studied the effect of
the main operating conditions on the gasification process, Al-Zareer
et al. [19,20] investigated the effect of various gasification parameters
and operating conditions on the syngas chemical composition and their
effect on the energy efficiency of the gasification process. However, in
Al-Zareer et al. [20] they studied the effect of the main gasification
parameters on the overall system performance. Al-Zareer et al. [20]
found that gasifying low-grade coals has higher energy efficiency than
gasifying high-grade coal, the study considered three types of coals.
An integrated gasification combined cycle (IGCC) system based on
Texaco gasification power plant with the thermochemical copper-
chlorine cycle was proposed by Aghahosseini et al. [5]. The purpouse of
the integrated system in [5] is for trigeneration of hydrogen, steam, and
electricity. In the integrated system in [5] the only interaction between
the IGCC and the thermochemical copper-chlorine cycle is in terms of
heat and oxygen interactions; the copper-chlorine cycle receives heat
from two sources, where one is from the IGCC which produces oxygen
for the coal gasifier in the IGCC. The performance measure presented in
[5] is the overall efficiencies of the IGCC compared to Texaco IGCC
system, which are 43% and 45% respectively. Also in [5] they proposed
an integration of coal gasification combined cycle with the thermo-
chemical copper-chlorine cycle. The copper-chlorine cycle in their
proposed integration of coal gasification system was not completely
dependent on the heat received from the IGCC system rather it received
extra heat from other sources, and no exergy analysis was performed on
their proposed system. Ratlamwala and Dincer [21] proposed an in-
tegrated system of the thermochemical copper-chlorine cycle with Ka-
lina cycle and electrolyzer. The integrated system proposed in [16] is
mainly for hydrogen production. After the energy and exergy analysis
of the integrated system is carried out, a new copper-chlorine design
layout is presented with a heat exchanger network for heat recovery
within the copper-chlorine cycle to increase the overall efficiency. The
copper-chlorine cycle has also been integrated with other thermal en-
ergy production system, which was proposed by [22].
The aim of this paper is to integrate coal gasifier that receives its
gasification oxidant from a cryogenic air separation unit (CASU), with a
water gas shift membrane reactor, a Brayton cycle and a the thermo-
chemical copper-chlorine cycle for thermochemical water decomposi-
tion to produce hydrogen and a hydrogen compression system that is
novel and will be able to overcome the hydrogen production limits
introduced by the coal compostion and hydrogen seperation from the
syngas. The proposed hydrogen production plant produces highly
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Energy Conversion and Management 157 (2018) 600–618
compressed hydrogen (700 bar) with only one input, which is the coal
flow rate. One of the key reasons behind proposing, such an integrated
hydrogen production plant is to provide an alternative replacement for
an integrated Rankine cycle and electrolyser system which is employed
by numerous researchers, such as [10]. In their study it was aimed to
fully produce power first by combusting syngas and later hydrogen
through electrolyser. There were several other studies on coal gasifi-
cation [6–9,11–15] as combined with the steam power plant for elec-
tricity production only. As a novel approach, the gasification subsystem
is integrated with a Cu-Cl based thermochemical cycle for hydrogen
production in addition to the combined cycle (including Rankine and
Brayton cycles) for power production in a more efficient and effective
manner. The additional reason is that the proposed plant can operate at
a constant rate throughout the day, which produces hydrogen that is
compressed and ready for storage. The successful results of the pro-
posed full hydrogen production plant will promote the usage of the
thermochemical water decomposition cycle using the copper-chlorine
cycle for converting heat to hydrogen in many of power production
plants. These include power production plants such as coal-fired power
plants, nuclear power stations, and any power plants that burns fossil
fuels.
The thermochemical copper-chlorine cycle is simulated in Aspen
Plus software using its advantage over other chemical simulating soft-
ware like Aspen Hysys such as its capability for simulating solids. Since
the thermochemical copper-chlorine cycle contains materials in solid,
liquid and gaseous states, Aspen Plus is a better tool for simulating the
proposed hydrogen production plant and its main components, which
are a copper-chlorine cycle and a coal gasifier. In the proposed hy-
drogen production plant, the copper-chlorine cycle receives the re-
quired heat from the Brayton cycle gas turbine hot exhausts. However,
for the necessary electricity, it receives it from the gas turbines and the
generator in the cycle. The coal gasifier is based on an idealized model
using the Gibbs free energy minimization approach. The model is va-
lidated with experimental results from Wen et al. [23]. Then after the
gasification model is validated and the hydrogen production plant is
simulated on Aspen Plus, energy and exergy analysis is performed on
the proposed hydrogen production plant.
2. System description
Fig. 1 shows an overall view of the proposed integrated system, and
how the subsystems interact with each other. First air enters the CASU
where oxygen is separated. The CASU receives work rate for its com-
pressors and with the help of the cryogenic separation unit, the CASU
can separate oxygen from air in the distillation column. The coal ga-
sification system consisting of the pressurized entrained flow gasifier in
which oxygen is the gasification oxidant, and the gasification agent is
steam. The operating pressure of the gasifier is 24 atm. Illinois No. 6
coal is fed to the gasifier, chemical analysis (including approximate and
ultimate analysis), lower heating value (LHV). The higher heating value
(HHV) and specific exergy of the Illinois No.6 coal are provided in
Table 1. The gasifier receives oxygen from the CASU, and steam from
multiple steam generators spread throughout the system that utilizes
the recovered heat at different locations within the system (as shown in
Fig. 1). The syngas exiting the gasifier goes to a gas turbine where its
pressure is reduced to the optimum operating pressure of the water gas
shift membrane reactor based on the work of Augustine et al. [24].
Augustine et al. [24] reported that the optimum operating pressure and
temperature for the water gas shift membrane reactor (WGSMR) to
achieve 98.2% carbon monoxide conversion and 81.2% hydrogen re-
covery, are 14.4 bar and 450 °C, respectively. Also, the pressure of the
captured hydrogen (the retentate) is around 1 bar, with purity of
99.999% [24]. After the syngas pressure reduction in the gas turbine,
the syngas is sent to a heat exchanger to cool the syngas to the optimum
operating temperature of the WGSMR of 450 °C [18]. On the other side
of the heat exchanger, steam is produced. The cooled syngas is mixed
M. Al-Zareer et al. Energy Conversion and Management 157 (2018) 600–618

O2(g)
Entrained flow gasifier
(oxygen blown gasifier)
H2O Cu2OCl2
Electrical Molten CuCl
decomposition CuCl2
Refrigeration unit generator
reactor
(condenser)
Steam Hydrolysis H2O
R Gas turbine reactor CuCl(s)
Air Air compressor H2O
filter Steam H2O
Mixer HCl(g)
Dryer
Cu2OCl2
Pump
Molten
Coal CuCl
Heat Combustion Molten
recover Electrical
chamber CuCl
Syngas system generator
Hydrogen
CuCl 2(aq)
production
reactor Cu
Treated syngas Gas turbine Electrolysis H2O
WGSMR compressor H2O reactor
N2
Hydrogen
Hydrogen
distillation collector
compressor
column Pump
N2
Combustion Gas Electrical
N2 turbine Four stage compression of hydrogen chamber turbine generator

Air O2
compressor compressor Air compressor
Air
Hydrogen tank
Pump
O2 Intercoolers

Reboiler

Electrical
generator Cooling tower
Steam Steam Steam Steam
turbine turbine turbine turbine

Pump

Fig. 1. The overall system and its main components of coal gasifier, Brayton cycle, WGSMR, HRSG, CASU, and copper-chlorine five steps cycle.

with saturated steam then enters the WGSMR. The treated syngas ex- the discussion of the model development of each of these subsystems.
iting the WGSMR enters a compressor where its pressure increased to
the operating pressure of the 2300 kPa. Air is also compressed to pro-
vide the required oxygen to the combustion reaction. Both the com- 2.1. Gasification process
pressed air and the compressed treated syngas enters the combustion
chamber. The pressure of the combustion chamber is 2300 kPa and with There are two common types of gasifiers which use either air or
the assumption that no heat losses occur in the combustion chamber. oxygen only as an oxidation agent. In this paper, as mentioned earlier
The combustion products exiting the combustion chamber are sent to a an oxygen entrained flow gasifier is employed in the gasification
gas turbine then to the heat recovery steam generator (Hx-P1). The system. The Gibbs free energy minimization approach based model
produced steam is used to provide the necessary heat to the copper- (GFEMA based model) consist of two reactors when it is modeled in
chlorine cycle. The copper-chlorine cycle is five steps thermochemical Aspen Plus software as seen in Fig. 2a (Aspen Plus flow sheet of GFEMA
cycle for water decomposition with maximum temperature around based mode). Before building the model, coal has to be defined to Aspen
530 °C [25]. The copper-chlorine cycle has a step that requires elec- Plus as nonconventional solid (NC) based on its chemical composition
tricity and it is provided to it by the gas turbines in the plant generators. (see Table 1).
The full proposed hydrogen production plant is simulated on Aspen The GFEMA based model consist of two Aspen Plus reactors. The
Plus software, each subsystem simulation flowsheet is provided through first reactor in the GFEMA based model is a yield reactor (the mole or
mass fraction of the product should be specified). In the GFEMA based
model, the yield reactor decomposes the coal to its primary elements,
Table 1
Properties and chemical analysis of Illinois #6 coal used in this paper. which are based on the coal ultimate wet chemical analysis, which is
presented in Table 1 for Illinois No. 6 (converting NC material to con-
Illinois #6 [23] ventional material). The second reactor in the GFEMA based model is a
Gibbs reactor (carry out the reaction based on Gibbs free energy
Wet basis Dry basis Dry and ash free
(wt.%) (wt.%) basis (wt.%)
minimization approach), where the reaction that takes place in that
reactor depends on minimizing Gibbs free energy. To validate the
Proximate Moisture 0.20 0.00 0.00 GFEMA based model, the syngas molar fraction of its main chemical
analysis Fixed carbon 58.01 58.01 68.68 species is compared with experimental data from literature [23]. The
Volatile 26.46 26.46 31.32
matter
syngas exiting the GFEMA based model and the experimental data for
Ash 15.53 15.53 0.00 the Illinois No.6 coal are presented in Table 2. In Table 2, the molar
fraction of the main chemical species in the raw syngas, which are CO,
Ultimate analysis C 73.90 74.05 87.66
H 6.24 6.25 7.40 H2, and CO2 are compared between GFEMA based model results, and
N 0.71 0.71 0.84 the experimental data of the gasification process from literature [23],
Cl 0.37 0.37 0.44 and this is for Illinois No.6 coal. The difference in the carbon monoxide
S 1.77 1.77 2.10
mole fraction in the syngas exiting the gasifier between the GFEMA
O 1.32 1.32 1.56
Ash 15.53 15.53 0.00
based model and the experimental results [23] was 4.1%, for hydrogen
is 6.5%, and for carbon dioxide is 5.1%. Since the GFEMA based model
Sulfur analysis Pyritic 0.59 0.59 0.70
Sulfate 0.59 0.59 0.70
exhibited a highest difference of 6.5% with experimental values it can
Organic 0.59 0.59 0.70 be used with reasonable accuracy to simulate coals for which experi-
mental data are lacking. From here on, the GFEMA based model is used
HV HHV (MJ/kg) 25.35 29.14 33.35
LHV (MJ/kg) 24.12 27.10 32.50 due to its flexibility and good accuracy. Presented next are the main
chemical reactions that occur in the gasification process.
Exergy Exergy (MJ/ 29.00 34.50
kg) The gasification starts with the coal pyrolysis. In the pyrolysis re-
action, coal is broken into char and volatile matter. Volatile matter

603
M. Al-Zareer et al. Energy Conversion and Management 157 (2018) 600–618

Fig. 2. An Aspen Plus flow sheet for modeling and simulation of (a) the gasifier (GFEMA model), CASU, Brayton cycle, WGSMR and heat exchangers plus other utilities, (b) the copper-
chlorine cycle for thermochemical decomposition of water for large-scale hydrogen production, (c) the hydrogen compression system, compression hydrogen from 1 bar to 700 bar for
pressurized gas storage, (d) the hydrogen combustion combined cycle, combustion chamber operating pressure is 36 bar and a Rankine cycle with maximum pressure of 200 bar. (Note
that simple heating blocks presents a multi-stream heat exchanger, however they are presented in the following from to provide a clearer view of the modeled proposed system) (Cyclic
units are connected through a calculation block).

604
M. Al-Zareer et al. Energy Conversion and Management 157 (2018) 600–618

Table 2 the gasifier and for capturing and separating the hydrogen produced in
Results comparison between the Gibbs-based model with experimental data concerning the shift reaction is the WGSMR. The optimum operating parameters of
the mole fraction of CO, H2, and CO2 species.
the WGSMR are adopted from the work of Augustine et al. [24]. The
Components Mole fraction (dry Mole fraction (dry Gibbs-based model parameters of the WGSMR are presented in Table 4c. The water gas
basis) basis) % difference shift reaction follows:
Gibbs free energy Experiment [17]
model CO(g) + H2 O(g) → CO2 (g) + H2 (g) (15)

CO 0.552 0.576 −4.1 Since the water gas shift reaction is an exothermic reaction, continuous
H2 0.366 0.391 −6.5 removal of heat is required to maintain the WGSMR operating at the
CO2 0.028 0.030 −5.1 optimum temperature. Water is used to absorbs the WGSMR heat and
maintain it at the optimum operating temperature. The water used to
absorb the WGSMR heat is then heated and mixed with the syngas
includes moisture and tar, it is presented by C6 H6. The pyrolysis reac- exiting the gasifier. The shifted syngas exiting the WGSMR is com-
tion is written as follows: pressed and combusted in a Gibbs free energy minimization approach
Coal → Char + (CO + H2 + H2 O+ CO2 + CH 4 + H2 S+ N2 + C6 H6) reactor COMB (see Fig. 2a). The hot combustion gases leaving the
(1) combustion chamber (COMB in Fig. 2a) enter the gas turbine (GT). The
gas turbine GT hot exhausts go to the heat recovery steam generator
After the pyrolysis reaction, the volatile matter combust as follows:
that produces steam that will be used to provide the needed heat to the
C6 H6 + 7.5O2 → 6CO2 + 3H2 O (2) copper-chlorine cycle. The modeling and the working principle of the
new copper-chlorine five steps cycle configuration are provided next.
H2 + 0.5O2 → H2 O (3)

CO + 0.5O2 → CO2 (4) 2.3. Copper-chlorine thermochemical cycle (thermochemical water

decomposition cycle)
CH 4 + 2O2 → CO2 + 2H2 O (5)
The char element composition can be presented as follows: The copper-chlorine thermochemical cycle decomposes water
through a thermochemical process to hydrogen and oxygen by low-
Char → C+ H2 + O2 + N2 + S+ ASH (6)
temperature heat relative to the required temperature of thermal de-
The results of char decomposition reaction (Eq. (6)), the results of the composition of water. There are many copper-chlorine cycle config-
volatile combustion reactions, gasification oxidant, and the gasification urations [26]. The copper-chlorine cycle configuration chosen in this
agent react based on the following equations: article is the five steps copper-chlorine cycle, and its main interactions
C+ O2 → CO2 (7) are shown in Table 3 [25]. Presented next is the description of Table 3
reactions, which are the reactions of the five steps copper-chlorine
C+ 0.5O2 → CO (8) cycle. The modeling and simulation of the process is performed in
Aspen Plus which is described in detail in the following section.
C+ H2O→ CO + H2 (9)

C+ CO2 → 2CO (10) 2.3.1. Hydrolysis reaction

C+ 2H2 → CH 4
S+ H2 → H2 S
CO + H2O→ CO2 + H2
CH 4 + H2O→ CO2 + 3H2
The results of Eqs. (7)–(14) is the raw syngas exiting the gasifier, where
the syngas is presented in stream Product in Fig. 2a.
2.2. Cryogenic air separation unit and water gas shift membrane reactor
The system that provides the gasifier with the oxygen is the CASU.
Shown in Fig. 2a is the Aspen Plus flow sheet of CASU. The CASU
produces O2 with purity more than 95%. First air is compressed in
compressor B1 (see Fig. 2a) to 8 atm. Then it goes to the heat exchanger
B11 where the compressed air exchanges heat with the separated O2
and N2 to a very low temperature of −146 °C. Then cooled compressed
air is throttled to a pressure of 5 atm and sent to the distillation column
B4 (see Fig. 2a). The operating pressure of the distillation column is
5 atm. The gas separated at the condenser of the distillation column is
N2, and that at the boiler is O2. Since the condenser operating tem-
perature is −179 °C, a refrigerator unit is used to keep the required cold
temperature for the condensation to take place. Then both of the se-
parated O2 and N2 are sent to the heat exchanger B11 to cool the
compressed air. The N2 takes most of the heat from the compressed air
and then the hot compressed N2 gas is sent to a turbine B12. The N2
exiting B12 turbine is used to preheat water before going to the steam
generators.
The unit responsible for both the shift reaction of the syngas exiting
The first reaction in the five steps copper-chlorine cycle is the hy-
(11)
drolysis reaction, which is the first reaction in Table 3. In the hydrolysis
(12) reactor were superheated steam combines with cupric chloride (CuCl2)
to form copper oxychloride (Cu2OCl2) and hydrochloric acid (HCl)
(13) [25]. The hydrolysis reaction must take place at a temperature between
(14) 325 and 375 °C [25], and since the reaction is an endothermic reaction,
heat must be supplied to maintain the reactants at a temperature be-
tween 325 and 375 °C [25]. Wang et al. [27] suggested conducting the
endothermic hydrolysis reaction by providing the reactor with super-
heated steam at 400 °C with excess steam than that required by the
balanced reaction. The excess steam will drive the chemical reaction in
the direction of the product due to the increase in the concentration of
one of the reactants and also it will supply the required reaction heat.
2.3.2. Copper oxychloride thermal decomposition reaction
The second reaction in the five steps copper-chlorine cycle is the
thermal decomposition of copper oxychloride to oxygen gas and a
molten salt of cuprous chloride (CuCl) as shown in the second step in
Table 3
The five steps in the copper-chlorine cycle with their corresponding reactions and oper-
ating conditions [25,31].
Step Chemical reaction Temperature range (°C)
1 H2 O(g) + 2CuCl2 (s) → Cu2 OCl2 (s) + 2HCl(g) 375–400
2 1
Cu2 OCl2 (s) → O2 (g) + 2CuCl(l) 500–530
2
3 4CuCl(aq) → 2Cu(s) + 2CuCl2 (aq) 30–80
4 CuCl2 (aq) → CuCl2 (s) > 100
5 2Cu(s) + 2HCl(g) → 2CuCl(l) + H2 (g) 430–475

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M. Al-Zareer et al.
Table 3. The thermal decomposition of Cu2OCl2 is an endothermic
process, and the reaction temperature must be maintained at 530 °C. A
method for supplying the reaction heat to retain the temperature of the
reaction at 530 °C was suggested by Naterer et al. [28]. Naterer et al.
[28] suggested the reaction heat can be supplied by a loop of molten
salt that is heated by steam in a direct contact heat exchanger and then
its re-introduced into the chemical reactor. In the chemical reactor the
molten salt gives the heat to the reaction which results in producing
oxygen gas and additional molten CuCl. During the decomposition
there is an intermediate step where copper oxychloride decomposes to
form a crystalline structure of cupric oxide and cupric chloride
(CuO × CuCl2) . the decomposition of Cu2OCl2 into (CuO × CuCl2) oc-
curs at 500 °C and then (CuO × CuCl2) decomposes into O2 gas and
CuCl molten salt at 530 °C [25].
2.3.3. Electrolysis step
The third step in the five steps copper-chlorine cycle is the elec-
trolysis step where cupric chloride (CuCl2) is reproduced electro-
chemically as shown in Table 3. In the electrolysis reactor, cupric
chloride and solid copper are extracted electrochemically from solid
cuprous chloride (CuCl). The produced cupric chloride from the elec-
trolysis reactor is in an aqueous form (CuCl2 × 2H2 O) , which is dried to
reproduce the solid cupric chloride (CuCl2). Reported in Zamfirescu
et al. [25] that the electrolysis step requires nearly 63 kJ/mol H2 of
electrical power. In the drying step all of the water in the aqueous
material CuCl2 × 2H2 O is removed, and the solid CuCl2 is returned to
step 1 to complete the half of the cycle where the other half is with the
solid copper and the hydrochloric acid (HCl).
2.3.4. Hydrogen production reactor
The second reactor where cuprous chloride (CuCl) is produced is in
the hydrogen production reactor. In the hydrogen production reactor,
copper from the electrolysis reactor is combined with the hydrochloric
acid (HCl) to produce cuprous chloride (CuCl) and hydrogen. After
providing a description of the reactions of the five step copper-chlorine
cycle, the next section will discuss the building of the copper-chlorine
cycle model on Aspen Plus.
2.3.5. Copper-chlorine cycle Aspen Plus model
The first step in modeling the five steps copper-chlorine in Aspen
Plus is entering the solid phase properties of the materials in the copper-
chlorine cycle. The second thing that must be taken care of is the phase
changes from the solid phase to either liquid or gas phase or the other
way around of a conventional solid components that are defined by the
user. These phase changes must be done manually through any reactor,
but the product must be limited to the same material but in the re-
sulting phase (phase change reactor). In this model stoichiometric re-
actor is used to change the phase from solid to liquid or from liquid to
solid. Properties and correlations of copper oxychloride (Cu2OCl2),
cupric oxide (CuO), cupric chloride (CuCl2) and cuprous chloride
(CuCl) that were entered in the Aspen Plus model are adapted from
[25,37–41]. For copper oxychloride properties and correlations only for
the solid phase since the Cu2OCl2 is present only in the solid phase
throughout the copper-chlorine cycle.
Shown in Fig. 2b is the Aspen Plus model of the copper-chlorine
cycle for thermochemical water decomposition for large-scale hydrogen
production. The novelty of the developed model of the copper-chlorine
cycle in this article lies in the more practical system configuration than
other copper-chlorine cycle models that were published. The practi-
cality of the proposed model over those proposed in the literature is due
to the fact that it considers the recent development and findings for
each of the individual reacts [25,27,28,37]. Based on the work of Wang
et al. [27] as mentioned in Section 2.3.1 and based on the Gibbs free
energy minimization approach eight times more superheated steam
than required for the hydrolysis reaction balanced chemical equation is
provided through stream S2 (see Fig. 2b) for the hydrolysis reactor B3
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Energy Conversion and Management 157 (2018) 600–618
in Fig. 2b. The part that goes to the copper-chlorine cycle of the steam
produced by the HRSG is not directly used rather it is used to provide
the required heat only. The water in stream S2 (see Fig. 2b) enter the
system at ambient conditions and then preheated by the excess steam
exiting the hydrolysis reactor S23 and the produced O2 S11 from the
Cu2OCl2 thermal decomposition reactor B6, the heat exchange is done
through heat exchanger B15 in Fig. 2b. Stream S2 exits the heat ex-
changer B15 through stream S17. Stream S17 is then heated to the
required input temperature of 400 °C by the steam from the HRSG.
Steam from the HRSG is also used to heat the CuCl2 from 347 °C for S1
(which is the same as S37 but they are disconnected in the Aspen Plus to
avoid long computational time) to 350 °C for S3. Streams S3 and S4
enters the hydrolysis reactor B3, which is an isothermal reactor oper-
ating at a constant temperature of 325 °C. The extra heat required by
reactor B3 is provided by the steam produced from the HRSG. The re-
sults of the hydrolysis reaction exit reactor B3 in stream S5 as shown in
Fig. 2b.
Separator B4 separates the results of the hydrolysis reactor (stream
S5). Separator B4 separates the products of the hydrolysis reactor,
Cu2OCl2 from HCl and excess H2O (stream S5 to S6 and S7). Separator
B16 separates S7 to S24 (HCl) and S23 (excess H2O at 325 °C). The
produced CuCl S10 heats stream S6 carrying Cu2OCl2 from the copper
oxychloride decomposition reactor B6 in the heat exchanger B21. Note
that CuCl (stream S36) exits the heat exchanger B21 at 437 °C, which is
higher than the melting/solidification temperature 436 °C of the CuCl
since the heat exchanger B21 is a liquid-liquid heat exchanger. Stream
S6 exits the heat exchanger B21 through stream S31. S31 is heated by
the steam produced by the HRSG in the heat exchanger B5 to 530 °C,
which is stream S8. Cu2OCl2 enters the copper oxychloride decom-
position reactor B6, which is an isothermal reactor kept at 530 °C. Since
the copper oxychloride decomposition reaction is an endothermic re-
action, which means a continuous supply of heat to the reactor B6 is
required to maintain the reactor temperature at 530 °C. The products of
the copper oxychloride decomposition reactor are oxygen gas and
molten CuCl. The molten CuCl is separated from the oxygen gas
through a liquid gas separator B7. Stream S11 exiting the B7 separator
carries the oxygen gas and stream S10 carries the molten CuCl. The
molten CuCl is sent to the phase change reactor B8 to conduct the phase
change from liquid to solid since as mentioned earlier the phase change
between solid and liquid must be done manually in Aspen Plus V8.8.
The solid CuCl exiting the phase change reactor B8 (stream S30) enters
the heat exchanger B22 to heat up the dried CuCl2 (stream S21).
The solid CuCl (streams S39 and S35) is mixed with water to form
an aqueous solution that is sent to the electrolysis reactor B10. The
electrolysis reactor is modeled as a stoichiometric reactor (RStoic), and
it occurs at constant temperature. The required heat duty reported by
the model is discarded for the electrolysis reactor and the electrical
power needed for the electrolysis reaction is taken from the literature as
discussed in Section 2.3.3, which is later considered in the energy and
exergy analysis. Both Cu and CuCl2 (stream S15) exiting the electrolysis
reactor enter the separator B13. Separator B13 separate Cu from CuCl2,
where Cu (stream S19) goes to the hydrogen production reactor after
passing into two heat exchangers B20 and B18. In heat exchanger B20
Cu exchanges heat with molten CuCl produced by the hydrogen pro-
duction reactor. However, in heat exchanger B18 Cu exchange heat
with steam generated by the HRSG. The resulting heated Cu exiting
heat exchanger B18 (stream S25) enters the hydrogen production re-
actor, where it reacts with HCl at an isothermal reactor operating at a
constant temperature of 450 °C. As mentioned in Section 2.3.4 heat is
required to maintain the reactor constant temperature and it is pro-
vided for the reactor from steam generated from the HRSG. The product
of the hydrogen production reactor (stream S27) are sent to the gas-
liquid separator B23 to separate the hydrogen gas from the molten
CuCl. The separated hydrogen exits the separator B23 in stream S33.
The molten CuCl (stream S32) goes to heat exchanger B20 to a tem-
perature slightly higher than the melting/solidification temperature,
M. Al-Zareer et al. Energy Conversion and Management 157 (2018) 600–618

then it enters the phase change reactor B28 and then it cools down by
heat exchanger B11. The resulting solid CuCl (stream S35) goes to the
electrolysis reactor. However the aqueous CuCl2 exiting the separator
B13 (stream S18) goes to reactor B14 where the solid CuCl2 is converted
from Aspen stream type; mixed to stream type; cisolid so that the drying
process can take place since the dryer requires solid in the form of ci-
solid. The dryer requires heat to evaporate the water from the aqueous
solution (CuCl2(aq)). The dried CuCl2 (stream S21) goes to the heat
exchanger B22 then to the hydrolysis reactor, but it gets heated first as
mentioned above. The produced hydrogen from the thermochemical
water decomposition copper-chlorine cycle is in stream S33 in Fig. 2b.
2.4. Hydrogen compression system (HCS)
Compressing hydrogen is treated as a crucial step for adequate
storage [29,30]. The pressure of the storage tanks can vary between 350
and 700 bar based on the size requirements of the storage tank [29,30].
A four-stage compression system is developed and simulated on Aspen
Plus as shown in Fig. 2c. The four-stage compression system compresses
hydrogen from the pressure of 1 bar to a pressure of 700 bars. Four
simple Rankine cycles are integrated with compression system to re-
duce the required compression power. As shown in Fig. 2c, hydrogen
produced by the system (stream 1) enters the first compression stage,
compressor C1. The first compression stage has a pressure ratio of 5.
The compressed hydrogen (stream 2) exits compressor C1 and enters
the heat exchanger HX1. In heat exchanger HX1 high temperature
compressed hydrogen exchange heat with pressurized water at 20 bar
(stream R2). Compressed hydrogen exits heat exchanger HX1 through
stream 3, while the pressurized water exits heat exchanger HX1 through
stream R3 as pressurized superheated steam. The steam turbine ST1
extract the thermal energy of pressurized superheated steam and pro-
duce work rate. Then what exits the steam turbine ST1 goes to the
condenser, and pump P1 pumps the saturated liquid to a pressure of
20 bar. For the remaining three compression stages with intercooling,
they use a Rankine cycle to benefit from the heat rejected by the
compressed hydrogen at each stage to produce a work rate to reduce
the required work rate for compressing the hydrogen.
complete combustion in the combustion chamber G1. G1 is a Gibbs free
energy minimization reactor. Then combustion gases E5 exiting the
combustion chamber G1 are expanded in the gas turbine GAST (see
Fig. 2d). The exhaust gases E6 exiting the gas turbine produces steam in
the heat exchanger HX5. The produced pressurized steam enters the
steam turbine ST5 and it goes to the condenser where P5 pumps the
liquid water exiting the condenser and then sent to the heat exchanger
HX5. The produced net work rate of this cycle is used to cover the needs
of the hydrogen production plant of work rate. After the hydrogen is
compressed it is stored in hydrogen pressurized tanks for commercial,
industrial and transportation purposes. Before presenting the analysis
methodology, it is important to mention that heating jackets are used to
deliver or absorb the thermal energy required or released by the reac-
tions, where other reactors are set to operate as an adiabatic reactor
(see Fig. 1).
3. Analysis
Some general assumptions are made for the analyses of the system
components as follows:
• The hydrogen production plant operates at steady state conditions
• The hydrogen production plant starting up period is not considered
• The kinetic and gravitational potential energies changes are ne-
glected throughout the plant
• All gases in the system are treated as real gases (exception for this
assumption is for the gases in the chemical exergy equation, they are
treated as ideal gases)
• The electrical generator thermal efficiency is ηgen = 95%
The property sources used in Aspen Plus simulation are given in
Table 4a, and the assumptions made for specific components in the
developed system are presented in Table 4b. The gasification system
consisting of gasifier GFEMA model for the gasifier, CASU, WGSMR and
Brayton cycle plus another system utilizes main input parameters are
presented in Table 4c.
3.1. Energy analysis

2.5. Hydrogen-fueled combined cycle (HFCC) General steady-state thermodynamic rate balance equations for
mass and energy, for open systems and with kinetic and gravitational
To provide the needed work to compress the produced hydrogen potential energies neglected follow:
and for other work consuming devices, a combined cycle that burns
part of the hydrogen generated by the plant to provide the needed work ∑ ṁ in = ∑ ṁ out (16)
rate. Shown in Fig. 2d is the Aspen Plus model of the HFCC. The re-
quired amount of the produced hydrogen is compressed by compressor Q̇ in + Ẇin + ∑ mḣ = Q̇out + Ẇout + ∑ mḣ
in out (17)
C5, which has a compression ratio of 36 [10]. Air is compressed by
compressor C6 to provide the needed hydrogen with oxygen for where ṁ is the mass flow rate, Q̇ is the heat rate, Ẇ is the work rate, h is

Table 4a
The Aspen Plus property methods used in modeling and simulating the proposed integrated system.

Material The property sources used in Aspen Plus simulation

H2O The 1984 NBS/NRC: Steam table correlations for thermodynamic properties are used for H2O
The International Association for Properties of Steam (IAPS) correlations for transport properties for H2O (Aspen Plus
property method: STEAMNBS for the temperature range of 273.15 K to 2000 K at a maximum pressure of over 10,000 bar)
are used
For all of the remaining fluids in the hydrogen The general model for real components (Aspen Plus property method: RK-SOAVE)
production plant As a second choice, the Redlich-Kwong-Soave (RKS) cubic equation of state with the Boston-Mathias alpha function
Coal ASTM Standard D5865-07a for measuring the gross calorific value of coal
The Boie correlation for calculating the heat of combustion
The Kirov correlation for calculating coal’s heat capacity (Aspen Plus option: HCOALGEN)
The coal density is evaluated based on equations from [42] (Aspen Plus option: DCOALIGT)

o Input data to Aspen Plus for each type of coal are as follows:
• Proximate analysis (wet, mass basis)
• Ultimate analysis (dry, mass basis)
• Sulfuric analysis (wet, mass basis)

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M. Al-Zareer et al. Energy Conversion and Management 157 (2018) 600–618

Table 4b
Specific assumptions made for the different parts of the integrated system.

Subsystem or component Assumptions that applies only to the mentioned subsystem or component

Gasifier All gas and solid mixtures in the system are homogenous
Pressure drops are negligible in the gasifier components
The main syngas products can be taken to be CO, H2, and CO2 for the model validation

Combustion chambers and the heat Pressure drops are neglected

exchangers The combustion is based on Gibbs free energy minimization approach
The heat loss in the HRSG is 10% of the total exchanged heat
The heat loss is 10% of the total exchanged heat in the in other heat exchangers in the system (unless otherwise stated)

Gas turbines The gas turbines are adiabatic (i.e., to incur no heat losses)
The isentropic efficiency of all gas turbines are ηis,GT = 0.72 [43]

CASU The condensing fluid in the distillation column occur at a temperature of −179 °C
In the distillation column, the condenser operating temperature is very low which requires a refrigerator system to maintain that
low temperature for the fluid to condense. The refrigerator system has a COP = 2. COP = 2 was selected based on the results of
the parametric study shown in Fig. 6. Fig. 6 indicates that the value of COP that the energy and exergy of the system stay nearly
constant at 2

Copper-chlorine cycle No heat losses occur in the copper-chlorine cycle heat exchangers
Electrical power requirement by the electrolysis reactor is 63 kJ/mol H2 [25]
Electrical power generator efficiency is 95%

Hydrogen compression system The isentropic efficiency of all steam turbines can be taken to be ηis,ST = 0.72 [43]
The steam turbines can be considered adiabatic (i.e., to incur no heat losses)
The hydrogen compressors can be regarded as adiabatic (i.e., to incur no heat losses)
The isentropic efficiency for all hydrogen compressors can be taken to be ηis,GT = 0.72 [43]

Hydrogen-fueled combined cycle
The isentropic efficiency of all steam turbines can be taken to be ηis,ST = 0.72 [43]
The steam turbines can be considered adiabatic (i.e., to incur no heat losses)
The hydrogen compressors can be regarded as adiabatic (i.e., to incur no heat losses)
The isentropic efficiency for all hydrogen compressors can be taken to be ηis,GT = 0.72 [43]
The combustion chamber oxidant is air
The combustion is carried out based on Gibbs free energy minimization approach (Gibbs reactor)
Hydrogen compressor has a compression ratio of 36 [10]
Air compressor has a compression ratio of 36 [10]
The Rankine cycle has a maximum pressure of 200 bar

the specific enthalpy, and the subscripts in and out denote input and ṁ AS17 hAs17
ηCASU =
output. The energy and exergy balance equations for each component ẆB1 + ṁ AS1hAS1 + Q̇RB(B4) + ẆRC (20)
in the system are presented in Tables 5–7 for each of the components in
Fig. 2a–d respectively. where the subscripts refer to the component name or the stream name
shown in Fig. 2a except for RC, which denotes to the refrigerator re-
moving the heat from the distillation column condenser.
3.1.1. Energy efficiencies of the hydrogen production plant The WGSMR energy efficiency is as follows:
In the following section the energy efficiencies of the subsystems in
ṁ S10 LHVH2 + ṁ S24 LHVS24
the hydrogen production plant that produce hydrogen from coal by ηWGSMR =
utilizing the thermochemical water decomposition cycle, and the ṁ S6 LHVS6 (21)
WGSMR. Here, the subscripts refer to the stream name shown in Fig. 2a.
The gasifier and utilities energy efficiency is as follows: The copper-chlorine thermochemical water decomposition cycle is
ṁ syngas LHVsyngas as follows:
ηG&U =
ṁ coal LHVcoal + Ẇpump −w + Ẇpump − W2 + Ẇcompres2 + Q̇STMG1 ṁ H2 LHVH2 ṁ S33LHVS33
ηCu − Cl = =
+ Q̇ STGM2 + Q̇QO Q̇ in + Ẇe (ṁ S2−ṁ s23)hS2 + Q̇ in + Ẇe (22)

(18)
Q̇ in = Q̇B2 + Q̇B3 + Q̇B1 + Q̇B3 + Q̇B17 + Q̇B19 + Q̇B18 + Q̇B5 + Q̇B6 + Q̇B8
where the syngas in the numerator of the gasifier energy equation (Eq. + Q̇B24 + Q̇B26 + Q̇B11 + Q̇B10 + Q̇B14 + Q̇B12 (23)
(18)), referring to stream S1 in Fig. 2a. Note that the subscripts are
referring to components names in Fig. 2a except for syngas (stream S1) where the subscripts refer to the component name or the stream name
and coal (stream 1coal in Fig. 2a). The gasifier and utilities (G&U) refer shown in Fig. 2b. In Eq. (23) the sign convention for the heat transfer
to the gasifier (GFEMA model), oxygen compressor, the two in-cycle rate is, positive for heat flowing into the system and negative for heat
heat recovery systems and the two water pumps. The coal LHV used in flowing out of the system.
Eq. (18) is on a dry basis (see Table 1). The HCS energy efficiency is as follows:
The Brayton cycle energy efficiency is defined as follows:
ṁ 9 h9
ηHCS =
Ẇ −Ẇ −ẆTFCOMP ẆC1 + ẆC2 + ẆC3 + ẆC4−ẆST1−ẆST2−ẆST3−ẆST4 + ẆP1
ηBrC = GT COMPR1
ṁ S24 LHVS24 (19) + ẆP2 + ẆP3 + ẆP4 (24)

where the subscripts refer to the component name or the stream name where the subscripts refer to the component name or the stream name
shown in Fig. 2a. shown in Fig.2c. In Eq. (24), the sign convention for the work transfer
The CASU energy efficiency is as follows: rate is positive for all work interactions.

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M. Al-Zareer et al. Energy Conversion and Management 157 (2018) 600–618

Table 4c Ẇe = ẆCu − Cl/ηgen (29)

The main input parameters for the gasification system consisting of gasifier GFEMA model
for the gasifier, CASU, WGSMR and Brayton cycle plus other system utilizations.
ẆCASU = ẆB1 + ẆRC (30)
Unit Main parameters
Here, subscripts refers to system component in Fig. 2a–d.
Gasifier • Operating pressure is 24.0 atm
• Gasification agent is steam which is at 420 °C
ṁ H2 = ṁ S10 (see Fig. 2a) + ṁ S33 (see Fig. 2b)−ṁ E1 (see Fig. 2d)
• Gasification oxidant is oxygen which is at 490 °C = ṁ 1 (see Fig. 2c) (31)
• Steam to fuel ratio (mass basis) = 0.893
• Oxygen to fuel ratio (mass basis) = 0.241 Subscripts in Eq. (31) refers to the stream number in Fig. 2a–d.
The syngas exiting the • Temperature of the syngas is 1215 °C
gasifier (stream
product in Fig.2a
• Chemical composition (mole basis):
o 0.000 for O 2
3.2. Exergy analysis
o 0.550 for CO
o 0.367 for H2 General steady-state thermodynamic rate balance equations for
o 0.024 for CO2 exergy, for open systems and with kinetic and gravitational potential
o 0.043 for H2O energies neglected, is given in the following equation:
o 0.004 for H2S
o 0.012 for N2 Eẋ Q̇netin + ∑ ṁ in exin = Eẋ ẇ netout + ∑ ṁ out ex out + Eẋ d
o 0.002 for CH4 in out (32)
Syngas cooling unit • Cooling water is at pressure of 14.4 bar and
temperature 260 °C
where ṁ is the mass flow rate, Q̇ is the heat rate, Ẇ is the work rate, ex

• Direct mixing chamber

is the specific exergy and the subscripts in and out denote input and
• Cooling
to 0.730
water to syngas ratio (mass basis) is equal output. The exergy rate balance in Eq. (31) can be used to determine the
exergy destruction rate Eẋ d , i.e., the irreversibility rate, for the system
CASU • Air at ambient condition is fed to CASU and each of its components, as well as overall and component exergy
• Maximum pressure in CASU is 8.0 atm (exiting O
in compressed to gasifier operating pressure)
2 efficiencies.
The exergy rate due to heat transfer Eẋ Q̇ in Eq. (32), for Ts is the
• Separation method: distillation column temperature of the boundary where heat transfer takes place, and a
• Gas turbine reduces pressure of exiting N
• Condenser
2
dead state temperature To , is as follows:
refrigerator COP is 2.0 (to remove heat
so condensing fluid can condense at a very low
T
temperature of −179 °C) Eẋ Q̇ = Q̇ ⎛1− 0 ⎞
⎜ ⎟

⎝ Ts ⎠
• Operating
(33)
WGSMR pressure is equal to 14.4 bar [24]
• Operating temperature is equal to 450 °C [24] where Q̇ is the heat transfer rate.
• CO conversion percentage is equal to 98.2% [24]
• HH capture
The exergy rate of work (mechanical shaft work or electrical work)
percentage is equal to 81.2% [24]
• recovered pressure is equal to 1 bar [24] Eẋw is the same as the work rate:
2

Brayton cycle • Syngas

2300 kPa
combustion chamber operating pressure: Eẋ ẇ = Ẇ (34)

• Discharge pressure = 1.2 atm In Eq. (32), the specific exergy ex of a flowing fluid can be expressed for
HSC • Compression
stages is 5
ratio of the first three compression
state i in the system as follows:

• Hydrogen
exi = (hi−h 0)−T0 (s i−s 0) + ex ch (35)
final pressure is 700 bar [31]
• Compressed hydrogen final temperature is 25 °C,
cooled down after the last compression stage.
where hi and s i are the specific enthalpy and specific entropy of the flow
respectively at the state i, and h 0 and s 0 are the specific enthalpy and
HFCC • Compression ratio of the hydrogen and the air
compressors is 36
specific entropy of the flow respectively at the dead state. Also,ex ch
denotes the specific chemical exergy of the flow and can be expressed as
• Combustion chamber operating pressure is 36 atm
• Maximum pressure in the Rankine cycle is 200 bar follows:
Cu-Cl • For copper-chlorine cycle, check Table 3. ex ch = ∑ xjex 0ch + RT0 ∑ xjln(xj) (36)

where xj denotes the mole fraction of constituent j in the flow, ex 0ch is

Ẇ + ẆST5−ẆC5−ẆC6−ẆP5 the standard specific chemical exergy of the constituent j in kJ/mol
ηHFCC = GAST
ṁ E1LHVH2 + ṁ E3hE3 (25) units, and R is the universal gas constant in kJ/mol·K units. The specific
chemical exergy of coal is calculated as follows:
In Eq. (25), the subscripts refer to the component name or the stream
name shown in Fig. 2d. In Eq. (25), the sign convention for the work ex coal
ch = [β × (LHV + ωhfg) + 9.417S] (37)
transfer rate is positive for all work interactions
The hydrogen production plant overall energy efficiency is as fol- which is used to calculate the specific exergy of any type of coal. Here,
lows: LHV is the lower heating value of the coal, hfg is the latent heat of water
at T0 , ω is the moisture content in the coal and S is the mass fraction of
ṁ H2 LHVH2 + Ẇnet sulfur in the coal. In Eq. (36), LHV is based on dry and ash free coal
ηov =
ṁ coal LHVcoal (26) Finally β in Eq. (37) is expressed based on the dry analysis of the coal
used as the following [11].
For Ẇnet , ẆHCS , ẆCASU , and Ẇe they are calculated as follows:
H O N
Ẇnet = ẆCOMPRES2 + ẆCOMPR1 + ẆTFCOMP + ẆPUMP − W2 + ẆPUMP −W−ẆGT β = 0.1882 + 0.061 + 0.0404 + 1.0437
C C C (38)
−ẆGT2 + ẆHCS + Ẇe (27)
Here, H, O, C, and N denote respectively the mass fractions of hy-
drogen, oxygen, carbon, and nitrogen in the coal used on a dry basis.
ẆHCS = ẆC1 + ẆC2 + ẆC3 + ẆC4−ẆST1−ẆST2−ẆST3−ẆST4 + ẆP1 + ẆP2
Eq. (38) can is valid only when the parameter O/C is less than 0.667,
+ ẆP3 + ẆP4 (28) which is the case for the coals considered in this article.

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Table 5
Energy and exergy balance equation for the components of the system shown in Fig. 2a, the subscripts refer to the component name, and stream names in Fig. 2a.

Component Energy balance equation Exergy balance equation

B1(compressor) ṁ AS1hAS1 + Ẇin = ṁ AS2 hAS2 ṁ AS1exAS1 + Ẇin = ṁ AS2 exAS2 + Eẋ d
B11(heat exchanger) ṁ AS3hAS3−ṁ AS3hAS3 = (ṁ AS10 hAS10−ṁ AS16 hAS16) + (ṁ AS7 hAS7−ṁ AS17 hAS17) ṁ AS3exAS3−ṁ AS3exAS3 = (ṁ AS10 exAS10−ṁ AS16 exAS16) + (ṁ AS7 exAS7−ṁ AS17 exAS17) + Eẋ d
B3(pressure valve) ṁ AS3hAS3 = ṁ AS4 hAS4 ṁ AS3exAS3 = ṁ AS4 exAS4 + Eẋ d
B4(distillation column) ṁ AS4 hAS4 + Q̇RB = ṁ AS5hAS5 + ṁ AS6 hAS6 + Q̇RC ṁ AS4 exAS4 + Eẋ Q̇RB = ṁ AS5exAS5 + ṁ AS6 exAS6 + Eẋ Q̇RC + Eẋ d
RCa Q̇Rc + ẆRC = Q̇out Eẋ Q̇Rc + ẆRC = Eẋ Q̇out + Eẋ d
B5(pressure valve) ṁ AS5hAS5 = ṁ AS10 hAS10 ṁ AS5exAS5 = ṁ AS10 exAS10 + Eẋ d
B6(pressure valve) ṁ AS6 hAs6 = ṁ AS7 hAS7 ṁ AS6 exAs6 = ṁ AS7 exAS7 + Eẋ d
B12(N2 turbine) ṁ AS16 hAS16−ṁ AS18 hAS18 = ẆB12 ṁ AS16 exAS16−ṁ AS18 exAS18 = ẆB12 + Eẋ d
QQ(heat exchanger) ṁ AS18hAS18−ṁ AS18hAS18 = Q̇QQ ṁ AS18exAS18−ṁ AS18exAS18 = Eẋ Q̇QQ + Eẋ d
Pump-W ṁ Z2 hZ2 + Ẇin = ṁ z3hZ3 ṁ Z2 exZ2 + Ẇin = ṁ z3exZ3 + Eẋ d
STMG1(heat exchanger) ṁ Z3hZ3 + Q̇in = ṁ ttsteam httsteam ṁ Z3exZ3 + Eẋ Q̇in = ṁ ttsteam exttsteam + Eẋ d
Compres2(O2 compressor) ṁ AS17 hAS17 + Ẇin = ṁ oxygen hoxygen ṁ AS17 exAS17 + Ẇin = ṁ oxygen ex oxygen + Eẋ d
Ryield(Yield reactor) ṁ coal LHVcoal + Q̇DECOMP1 = ṁ pyrprd LHVpyrprd ṁ coal ex coal = Eẋ Q̇DECOMP1 + ṁ pyrprd expyrprd + Eẋ d
Gasifica(Gibbs free energy minimization reactor) ṁ ttsteam httsteam + ṁ oxygen h oxygen + ṁ pyrprd LHVpyrprd−Q̇ DECOMP1 = ṁ product hproduct ṁ ttsteam exttsteam + ṁ oxygen ex oxygen + ṁ pyrprd expyrprd−Eẋ Q̇DECOMP1

610
= ṁ product exproduct + Eẋ d
GT2(gas turbine) ṁ product hproduct = ṁ Z6 hZ6 + Ẇout ṁ product exproduct = ṁ Z6 exZ6 + Ẇout + Eẋ d
Coolingm(mixer) ṁ steam2 h steam2 + ṁ Z6 hZ6 = ṁ S1hS1 ṁ steam2 ex steam2 + ṁ Z6 exZ6 = ṁ S1exS1 + Eẋ d
QO and STMG2(heat exchanger) ṁ klp hklp = Q̇out + ṁ steam2 h steam2 ṁ klp exklp = Eẋ Q̇out + ṁ steam2 ex steam2 + Eẋ d
HX10(heat exchanger) ṁ s1h s1−ṁ s6 hs6 = ṁ klp hklp−ṁ z5hz5 ṁ s1ex s1−ṁ s6 ex s6 = ṁ klp exklp−ṁ z5exz5 + Eẋ d
Pump-W2 ṁ z4 hz4 + Ẇin = ṁ z5hz5 ṁ z4 exz4 + Ẇin = ṁ z5exz5
Hwgmrp1(stoichiometric reactorb) ṁ s6 h s6 = Q̇out + ṁ s7 h s7 ṁ s6 ex s6 = Eẋ Q̇out + ṁ s7 ex s7 + Eẋ d
Hwgmrp2(separator) ṁ s7 h s7 = ṁ s24 h s24 + ṁ s9 h s9 ṁ s7 ex s7 = ṁ s24 ex s24 + ṁ s9 ex s9 + Eẋ d
MRP3 (pressure valve) ṁ s9 h s9 = ṁ s10 h s10 ṁ s9 ex s9 = ṁ s10 ex s10 + Eẋ d
Compr1(air compressor) ṁ s12 h s12 + Ẇin = ṁ s13h s13 ṁ s12 ex s12 + Ẇin = ṁ s13ex s13 + Eẋ d
Tfcomp (treated syngas compressor) ṁ s24 h s24 + Ẇin = ṁ s14 h s14 ṁ s24 ex s24 + Ẇin = ṁ s14 ex s14 + Eẋ d
Comb(Gibbs free energy minimization reactor) ṁ s13h s13 + ṁ s14 h s14 = ṁ s16 h s16 + Q̇out ṁ s13ex s13 + ṁ s14 ex s14 = ṁ s16 ex s16 + Eẋ Q̇out + Eẋ d
GT(gas turbine) ṁ s16 h s16 = ṁ s18h s18 + Ẇout ṁ s16 ex s16 = ṁ s18ex s18 + Ẇout + Eẋ d
Hx-P1(heat exchanger) ṁ s18h s18 = ṁ s19 h s19 + Q̇out ṁ s18ex s18 = ṁ s19 ex s19 + Eẋ Q̇out + Eẋ d
STMGG(heat exchanger) ṁ s19 h s19 = ṁ exhu h exhu + Q̇out ṁ s19 ex s19 = ṁ exhu ex exhu + Eẋ Q̇out + Eẋ d

a
The refrigerator system used to remove the heat from the condensing fluid in the distillation column in the condenser is not simulated in the Aspen Plus model, however it is considered in the energy analysis.
b
Stoichiometric reactor is a reactor that carries the reaction based on the conversion percentage of one of the reactants set by the user, with mass and energy balance.
Energy Conversion and Management 157 (2018) 600–618
M. Al-Zareer et al. Energy Conversion and Management 157 (2018) 600–618

Table 6
Energy and exergy balance equation for the components of the system shown in Fig. 2b, the subscripts refer to the component name, and stream names in Fig. 2b.

Component Energy balance equation Exergy balance equation

B1(heat exchanger) ṁ s1h s1 = ṁ s3h s3 + Q̇out ṁ s1ex s1 = ṁ s3ex s3 + Eẋ Q̇out + Eẋ d
B2(heat exchanger) ṁ s17 h s17 = ṁ s4 h s4 + Q̇out ṁ s17 ex s17 = ṁ s4 ex s4 + Eẋ Q̇out + Eẋ d
B3(stoichiometric reactora) ṁ s3h s3 + ṁ s4 h s4 + Q̇ in = ṁ s5h s5 ṁ s3ex s3 + ṁ s4 ex s4 + Eẋ Q̇in = ṁ s5ex s5 + Eẋ d
B4(separator) ṁ s5h s5 = ṁ s6 h s6 + ṁ s7 h s7 ṁ s5ex s5 = ṁ s6 ex s6 + ṁ s7 ex s7 + Eẋ d
B5(heat exchanger) ṁ s31h s31 + Q̇ in = ṁ s8h s8 ṁ s31ex s31 + Eẋ Q̇in = ṁ s8ex s8 + Eẋ d
B6(stoichiometric reactora) ṁ s8h s8 + Q̇ in = ṁ s9 h s9 ṁ s8ex s8 + Eẋ Q̇in = ṁ s9 ex s9 + Eẋ d
B7(separator) ṁ s9 h s9 = ṁ s11hs11 + ṁ s10 h s10 ṁ s9 ex s9 = ṁ s11ex s11 + ṁ s10 ex s10 + Eẋ d
B8(stoichiometric reactora, used for ṁ s36 h s36 = Q̇out + ṁ s30 h s30 ṁ s36 ex s36 = Eẋ Q̇out + ṁ s30 ex s30 + Eẋ d
phase change)
B9(mixer) ṁ s39 h s39 + ṁ s35h s35 + ṁ s13h s13 = ṁ s14 h s14 ṁ s39 ex s39 + ṁ s35ex s35 + ṁ s13ex s13 = ṁ s14 ex s14 + Eẋ d
B10(stoichiometric reactora) ṁ s14 h s14 + Ẇe = ṁ s15h s15 ṁ s14 ex s14 + Ẇe = ṁ s15ex s15 + Eẋ d
B11(heat exchanger) ṁ s34 h s34 = ṁ s41h s41 + Q̇out ṁ s34 ex s34 = ṁ s41ex s41 + Eẋ Q̇out + Eẋ d
B12(Dryer) ṁ s20 h s20 + Q̇ in = ṁ s22 h s22 + ṁ s21h s21 ṁ s20 ex s20 + Eẋ Q̇in = ṁ s22 ex s22 + ṁ s21ex s21 + Ėx d
B13(separator) ṁ s15h s15 = ṁ s18h s18 + ṁ s19 hs19 ṁ s15ex s15 = ṁ s18ex s18 + ṁ s19 ex s19 + Eẋ d
B14(stoichiometric reactora) ṁ s18h s18 = ṁ s20 h s20 ṁ s18ex s18 = ṁ s20 ex s20 + Eẋ d
B15(heat exchanger) ṁ s2 h s2−ṁ s17 hs17 = (ṁ s23hs23−ṁ s16 hs16) + (ṁ s11h s11−ṁ s28h s28) ṁ s2 ex s2−ṁ s17 ex s17 = (ṁ s23ex s23−ṁ s16 ex s16) + (ṁ s11ex s11−ṁ s28ex s28) + Eẋ d
B16(separator) ṁ s7 h s7 = ṁ s24 h s24 + ṁ s23h s23 ṁ s7 ex s7 = ṁ s24 ex s24 + ṁ s23ex s23 + Eẋ d
B17(heat exchanger) ṁ s24 h s24 + Q̇ in = ṁ s26 h s26 ṁ s24 ex s24 + Eẋ Q̇in = ṁ s26 ex s26 + Eẋ d
B18(heat exchanger) ṁ s40 h s40 + Q̇ in = ṁ s25h s25 ṁ s40 ex s40 + Eẋ Q̇in = ṁ s25ex s25 + Eẋ d
B19(stoichiometric reactora) ṁ s25h s25 + ṁ s26 h s26 + Q̇ in = ṁ s27 hs27 ṁ s25ex s25 + ṁ s26 ex s26 + Eẋ Q̇in = ṁ s27 ex s27 + Eẋ d
B20(heat exchanger) ṁ s32 h s32−ṁ s29 h s29 = ṁ s40 hs40−ṁ s19 hs19 ṁ s32 ex s32−ṁ s29 ex s29 = ṁ s40 ex s40−ṁ s19 ex s19 + Eẋ d
B21(heat exchanger) ṁ s10 h s10−ṁ s36 h s36 = ṁ s31h s31−ṁ s6 h s6 ṁ s10 ex s10−ṁ s36 ex s36 = ṁ s31ex s31−ṁ s6 ex s6 + Eẋ d
B22(heat exchanger) ṁ s30 h s30−ṁ s38h s38 = ṁ s37 h s37−ṁ s21h s21 ṁ s30 ex s30−ṁ s38ex s38 = ṁ s37 ex s37−ṁ s21ex s21 + Eẋ d
B23(separator) ṁ s27 h s27 = ṁ s32 h s32 + ṁ s33hs33 ṁ s27 ex s27 = ṁ s32 ex s32 + ṁ s33ex s33 + Eẋ d
B24(heat exchanger) ṁ s38h s38 = ṁ s39 h s39 + Q̇out ṁ s38ex s38 = ṁ s39 ex s39 + Eẋ Q̇out + Eẋ d
B28(stoichiometric reactora, used ṁ s29 h s29 = Q̇out + ṁ s34 h s34 ṁ s29 ex s29 = Eẋ Q̇out + ṁ s34 ex s34 + Eẋ d
for phase change)

a
Stoichiometric reactor is a reactor that carries the reaction based on the conversion percentage of one of the reactants set by the user, with mass and energy balance.

Table 7
Energy and exergy balance equation for the components of the system shown in Figs. 2c and 6, the subscripts refer to the component name, and stream names in Figs. 2c and 6.

Component Energy balance equation Exergy balance equation

C1(compressor) ṁ 1h1 + Ẇin = ṁ 2 h2 ṁ 1ex1 + Ẇin = ṁ 2 ex2 + Eẋ d

C2(compressor) ṁ 3h3 + Ẇin = ṁ 4 h 4 ṁ 3ex3 + Ẇin = ṁ 4 ex 4 + Eẋ d
C3(compressor) ṁ 5h5 + Ẇin = ṁ 6 h6 ṁ 5ex5 + Ẇin = ṁ 6 ex 6 + Eẋ d
C4(compressor) ṁ 7 h7 + Ẇin = ṁ 8h8 ṁ 7 ex7 + Ẇin = ṁ 8ex 8 + Eẋ d
C5(compressor) ṁ E1hE1 + Ẇin = ṁ E2 hE2 ṁ E1exE1 + Ẇin = ṁ E2 exE2 + Eẋ d
C6(compressor) ṁ E3hE3 + Ẇin = ṁ E4 hE4 ṁ E3exE3 + Ẇin = ṁ E4 exE4 + Eẋ d
HX1(heat exchanger) ṁ 2 h2−ṁ 3h3 = ṁ R3hR3−ṁ R2 hR2 ṁ 2 ex2−ṁ 3ex3 = ṁ R3exR3−ṁ R2 exR2 + Eẋ d
HX2(heat exchanger) ṁ 4 h 4−ṁ 5h5 = ṁ x3hx3−ṁ x2 hx2 ṁ 4 ex 4−ṁ 5ex5 = ṁ x3exx3−ṁ x2 exx2 + Eẋ d
HX3(heat exchanger) ṁ 6 h6−ṁ 7 h7 = ṁ Y3hY3−ṁ Y2 hY2 ṁ 6 ex 6−ṁ 7 ex7 = ṁ Y3exY3−ṁ Y2 exY2 + Eẋ d
HX4(heat exchanger) ṁ 8h8−ṁ 9 h9 = ṁ z3hz3−ṁ z2 hz2 ṁ 8ex 8−ṁ 9 ex 9 = ṁ z3exz3−ṁ z2 exz2 + Eẋ d
HX5(heat exchanger) ṁ E6 hE6−ṁ E7 hE7 = ṁ k3hk3−ṁ k2 hk2 ṁ E6 exE6−ṁ E7 exE7 = ṁ k3exk3−ṁ k2 exk2 + Eẋ d
ST1(steam turbine) ṁ R3hR3 = Ẇout + ṁ R4 hR4 ṁ R3exR3 = Ẇout + ṁ R4 exR4 + Eẋ d
ST2(steam turbine) ṁ x3hx3 = Ẇout + ṁ x4 hx4 ṁ x3exx3 = Ẇout + ṁ x4 exx4 + Eẋ d
ST3(steam turbine) ṁ Y3hY3 = Ẇout + ṁ Y4 hY4 ṁ Y3exY3 = Ẇout + ṁ Y4 exY4 + Eẋ d
ST4(steam turbine) ṁ z3hz3 = Ẇout + ṁ z4 hz4 ṁ z3exz3 = Ẇout + ṁ z4 exz4 + Eẋ d
ST5(steam turbine) ṁ k3hk3 = Ẇout + ṁ k4 hk4 ṁ k3exk3 = Ẇout + ṁ k4 exk4 + Eẋ d
COND1(condenser and a heat exchanger) ṁ R4 hR4 = Q̇out + ṁ R1hR1 ṁ R4 exR4 = Eẋ Q̇out + ṁ R1exR1 + Eẋ d
COND2(condenser and a heat exchanger) ṁ X4 hX4 = Q̇out + ṁ X1hX1 ṁ X4 exX4 = Eẋ Q̇out + ṁ X1exX1 + Eẋ d
COND3(condenser and a heat exchanger) ṁ Y4 hY4 = Q̇out + ṁ Y1hY1 ṁ Y4 exY4 = Eẋ Q̇out + ṁ Y1exY1 + Eẋ d
COND4(condenser and a heat exchanger) ṁ Z4 hZ4 = Q̇out + ṁ Z1hZ1 ṁ Z4 exZ4 = Eẋ Q̇out + ṁ Z1exZ1 + Eẋ d
COND5(condenser and a heat exchanger) ṁ K4 hK4 = Q̇out + ṁ K1hK1 ṁ K4 exK4 = Eẋ Q̇out + ṁ K1exK1 + Eẋ d
P1(pump) ṁ R1 −C hR1 −C + Ẇin = ṁ R2 hR2 ṁ R1 −C exR1 −C + Ẇin = ṁ R2 exR2 + Eẋ d
P2(pump) ṁ X1 −C hX1 −C + Ẇin = ṁ X2 hX2 ṁ X1 −C exX1 −C + Ẇin = ṁ X2 exX2 + Eẋ d
P3(pump) ṁ Y1 −C hY1 −C + Ẇin = ṁ Y2 hY2 ṁ Y1 −C exY1 −C + Ẇin = ṁ Y2 exY2 + Eẋ d
P4(pump) ṁ Z1 −C hZ1 −C + Ẇin = ṁ Z2 hZ2 ṁ Z1 −C exZ1 −C + Ẇin = ṁ Z2 exZ2 + Eẋ d
P5(pump) ṁ K1 −C hK1 −C + Ẇin = ṁ K2 hK2 ṁ K1 −C exK1 −C + Ẇin = ṁ K2 exK2 + Eẋ d
G1(Gibbs free energy minimization reactor) ṁ E2 hE2 + ṁ E4 hE4 = ṁ E5hE5 ṁ E2 exE2 + ṁ E4 exE4 = ṁ E5exE5 + Eẋ d
GAST(gas turbine) ṁ E5hE5 = Ẇout + ṁ E6 hE6 ṁ E5exE5 = Ẇout + ṁ E6 exE6 + Eẋ d

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M. Al-Zareer et al.
Table 8
Overall results of the hydrogen production plant from coal.
Hydrogen production plant parameters
Energy efficiency
Exergy efficiency
Coal feed rate for hydrogen production of 1 kg/s (coal type: Illinois
No. 6)
Contribution of the copper-chlorine cycle in the total hydrogen
production
Power produced by the system for each 1 kg/s of hydrogen
generated by the hydrogen production system
Pressure of the produced hydrogen
Temperature of the produced hydrogen
Exergy destruction rate
3.2.1. Exergy efficiencies of the hydrogen production plant
In the following section the exergy efficiencies of the subsystems in
the hydrogen production plant from coal by utilizing the thermo-
chemical water decomposition cycle, via the copper-chlorine cycle.
The gasifier and utilities exergy efficiency is as follows:
ṁ syngas ex syngas
ψG&U =
ṁ coal ex coal ̇ ̇ ̇ ̇
ch + Wpump −w + Wpump − W2 + Wcompres2 + Ex Q̇STMG1
+ Eẋ Q̇STGM2 + Eẋ Q̇QO
where the syngas in the numerator of the gasifier exergy equation (Eq.
(39)) is referring to stream S1 in Fig. 2a. Note that the subscripts are
referring to components names in Fig. 2a except for syngas (stream S1)
and coal (stream 1coal in Fig. 2a). The gasifier and utilities (G&U) refers
to the gasifier (GFEMA model), oxygen compressor, the two in-cycle
heat recovery systems and the two water pumps. The coal exergy used
in Eq. (39) is on dry basis (see Table 1).
The Brayton cycle exergy efficiency is as follows:
ẆGT−ẆCOMPR1−ẆTFCOMP
ψBrC =
ṁ S24 exS24
where the subscripts refer to the component name or the stream name
shown in Fig. 2a.
The CASU exergy efficiency is as follows:
ṁ AS17 exAs17
ψCASU =
ẆB1 + ṁ AS1exAS1 + Ėx Q̇RB(B4) + ẆRC
where the subscripts refer to the component name or the stream name
shown in Fig. 2a except for RC, which denotes to the refrigerator re-
moving the heat from the distillation column condenser.
The WGSMR exergy efficiency is as follows:
ṁ S10 ex H2 + ṁ S24 exS24
ψ WGSMR =
ṁ S6 exS6
where the subscripts refer to the stream name shown in Fig. 2a.
The copper-chlorine thermochemical water decomposition cycle is
as follows:
ṁ H2 ex H2 ṁ S33exS33
ψCu − Cl = =
Eẋ Q̇ + Ẇe (ṁ S2−ṁ s23)exS2 + Eẋ Q̇in + Ẇe
The Eẋ Q̇in is calculated by the following equation:
Eẋ Q̇in = Eẋ Q̇B2 + Eẋ Q̇B3 + Eẋ Q̇B1 + Eẋ Q̇B3 + Eẋ Q̇B17 + Eẋ Q̇B19 + Eẋ Q̇B18
+ Eẋ Q̇B5 + Eẋ Q̇B6 + Eẋ Q̇B8 + Eẋ Q̇B24 + Eẋ Q̇B26 + Eẋ Q̇B11 + Eẋ Q̇B10
+ Eẋ Q̇B14 + Eẋ Q̇B12
In Eqs. (43) and (44), the subscripts refer to the component name or the
stream name shown in Fig. 2b. In Eq. (44) the sign convention for the
heat transfer rate is, positive for heat flowing into the system and ne-
gative for heat flowing out of the system.
Energy Conversion and Management 157 (2018) 600–618
The HCS exergy efficiency is as follows:
ṁ 9 ex 9
ψHCS =
Value Unit ẆC1 + ẆC2 + ẆC3 + ẆC4−ẆST1−ẆST2−ẆST3−ẆST4 + ẆP1
51.3 % + ẆP2 + ẆP3 + ẆP4 (45)
47.6 %
8.95 kg/s where the subscripts refer to the component name or the stream name
shown in Fig. 2c. In Eq. (45), the sign convention for the work transfer
7.43 %
rate is positive for all work interactions.
4.64 MW
ẆGAST + ẆST5−ẆC5−ẆC6−ẆP5
ψCC =
700 bar ṁ E1ex H2 + ṁ E3exE3 (46)
25 °C
187.5 MW Here, the subscripts refer to the component name or the stream name
shown in Fig. 2d. In Eq. (46), the sign convention for the work transfer
rate is positive for all work interactions
The hydrogen production plant overall exergy efficiency is as fol-
lows:
ṁ H2 ex H2 + Ẇnet
ψov =
ṁ coal ex coal
ch (47)
4. Results and discussion
(39) In this section the Aspen Plus simulation results and the results of
the energy and the exergy analysis are reported for the hydrogen pro-
duction plant.
The proposed hydrogen production plant is analyzed energetically
and exergetically using Eqs. (18)–(47) and the equations in Tables 5–7.
All stream properties are calculated using Aspen Plus software, while
chemical exergies, efficiencies, and exergy destruction rates are calcu-
lated using a programed Excel sheet. The reference environment tem-
perature and pressure are 25 °C and 1 atm respectively.
4.1. Hydrogen production plant’s overall performance
(40)
This section reports the overall results of the performance of the
hydrogen production plant. The results contain energy efficiency, ex-
ergy efficiency and exergy destruction rate and the plant operational
requirements for large-scale hydrogen production. The plant opera-
tional requirements for large-scale hydrogen production plus the
(41) overall energy and exergy efficiencies are reported in Table 8. As given
in Table 8 for the proposed hydrogen production plant for every
8.95 kg/s of Illinois No. 6 coal is fed to the plant, 1 kg/s of compressed
hydrogen is produced. For hydrogen production plant where the re-
quired production capacity of the plant to be 500 kg/day of stored
hydrogen ready to be transported, combusted or to be used in fuel cells.
A production of 500 kg/day of hydrogen for a plant that is operating
(42) 24 h per day will require a flow rate of 4464 kg/day of coal. The pro-
duced hydrogen from the hydrogen production plant is compressed at
700 bars by the HCS. The overall energy efficiency of the proposed
hydrogen production plant is 51.3%. The overall exergy efficiency of
the proposed hydrogen production plant is 47.6%.
(43)
4.2. Hydrogen production plant’s subsystems performance
In this section the performance of the hydrogen production plant
subsystems is discussed. These subsystems include gasifier, CASU,
WGSMR, Brayton cycle, Cu-Cl cycle, HCS and HFCC. The energy, exergy
efficiencies and the exergy destruction rate of the hydrogen production
(44)
plant subsystems is shown in Fig. 3. The exergy destruction ratio of the
main subsystems of the hydrogen production plant is shown in Fig. 4.
As shown in Figs. 3 and 4 the Cu-Cl cycle has the lowest exergy de-
struction ratio of 1% of the total exergy destruction in the hydrogen
production plant.
612
M. Al-Zareer et al.
Fig. 3. The energy, exergy efficiencies, and the exergy destruction rate of the hydrogen production plant subsystems.
4.2.1. Copper-chlorine thermochemical cycle (thermochemical water
decomposition)
The energy and exergy efficiencies of the copper-chlorine cycle are
38.2% and 89.4%, which are very close to those reported by Orhan
et al. [31] for the five steps copper-chlorine cycle. The energy and ex-
ergy efficiencies of the five steps copper-chlorine cycle reported by
Orhan et al. [31] are 44.8% and 73.0%. The difference between the
energy and exergy efficiencies found in this article and those that were
reported by Orhan et al. [31] is because of the different cycle design. In
the proposed copper-chlorine cycle design (see Fig. 2b) the differences
were the following:
• In the proposed design of the copper-chlorine cycle the produced
hydrogen was not sent back to heat up the coming water, unlike
what Orhan et al. [31] did, which they recovered heat from the
produced hydrogen. The reason behind not recovering the hydrogen
heat before storing it, which is for safety reasons. This point results
in reduction in the energy efficiency.
• In the proposed design of the copper-chlorine cycle the water is first
preheated by the extra steam that was sent to the hydrolysis reactor
(see Section 2.3.1) and then the steam is superheated by heat
coming from the gasification cycle. However in Orhan et al. [31]
Fig. 4. The exergy destruction ratio of the main subsystems of the hydrogen production plant.
613
Energy Conversion and Management 157 (2018) 600–618
they did not consider the extra steam to shift the reaction to pro-
ducts side, so they directly heat the water from ambient conditions
to superheated steam at 400 °C. This point results in higher exergy
efficiency for the proposed design of the copper-chlorine cycle.
• In the proposed design of the copper-chlorine cycle special reactors
that recovered high quality heat during the phase changes of the
materials in the cycle resulting in higher exergy efficiency.
• In the proposed design of the copper-chlorine cycle, the turbines in
the plant provide the needed electricity through an electrical gen-
erator.
The heat interactions in the five step copper-chlorine cycle design
proposed here is shown in Fig. 5. The reactor in the Cu-Cl cycle with the
highest heat energy interaction is the Cu2OCl2 decomposition reactor
B6 (see Fig. 2b). Where also the Cu2OCl2 decomposition reactor B6 also
possesses the highest exergy interaction, since it requires heat at high
temperature of 530 °C. Reactors B8 and B28, which are both responsible
for phase change of CuCl from liquid state, releases the highest amount
of heat and exergy recovered in the cycle. The high exergy is due to the
high and constant temperature at which the heat release takes place.
Regarding the exergy destruction contribution of the copper-chlorine
cycle in that of the hydrogen production plant. Copper-chlorine cycle
M. Al-Zareer et al.
Fig. 5. The thermal energy and exergy heat interactions in the proposed design of the copper-chlorine cycle in this article.
has the least contribution as shown in Fig. 4. The low exergy destruc-
tion ratio (1%) of the copper-chlorine cycle is due to its high exergy
efficiency, which was increased by the differences made to the cycle
structure compared to that proposed in the literature. The second
reason for the low exergy destruction ratio of the copper-chlorine cycle
is the small hydrogen production contribution percentage in the pro-
posed hydrogen production plant, which is 7.43%. Note that all Cu-Cl
cycle streams along with the thermophysical properties are tabulated in
Table 9.
Regarding an experimental validation of the generated model, the
copper-chlorine cycle is still in the proof-of-principle and bench-scale
apparatus stage. Thus, there are a very limited number of studies on the
simulation and thermodynamic analysis of the Cu-Cl cycle to compare
with. Most work done on the copper-chlorine cycle regarding full cycle
simulation and integration was done by Orhan et al. [26,31–33] and
Ozbilen et al. [34,35].
Fig. 6. The variation of the overall energy and exergy efficiencies and the CASU energy and exergy efficiencies.
614
Energy Conversion and Management 157 (2018) 600–618
4.2.2. CASU
The CASU has the second highest exergy destruction of the sub-
systems in the hydrogen production plant after combined cycle (see
Fig. 3). It has the lowest exergy efficiency in all of the subsystems in the
hydrogen production plant. The low exergy efficiency and the high
exergy destruction rate for the CASU is because the system consumes
large amount of work for separation process. The results of the se-
paration process is O2 and at a low pressure of 152 kPa, which is not a
combustible gas. Having high quality and high amount of energy input
to the CASU plus low energy in both quality and quantity in the output
of the CASU, resulting in low exergy efficiency. Which also explain the
reason for having the lowest energy efficiency of all of the subsystems.
Regarding the contribution of the CASU in the total exergy destruction
rate of the system, it has the second highest contribution ratio of 19%
after the combine cycle as shown in Fig. 4.
M. Al-Zareer et al. Energy Conversion and Management 157 (2018) 600–618

Table 9
Thermophysical properties of all streams in the Cu-Cl cycle.

Stream From Aspen block To Aspen block T (°C) P (bar) Mass vapor fraction Mass liquid fraction Mass solid fraction h (kJ/kg)

S1 B1 347.0 1.0 0.0 0.0 1.0 −1440

S10 B7 B21 530.0 1.0 0.0 1.0 0.0 544
S11 B7 B15 530.0 1.0 1.0 0.0 0.0 498
S13 B9 25.0 1.0 0.0 1.0 0.0 −15900
S14 B9 B10 25.0 1.0 0.0 0.3 0.7 −5260
S15 B10 B13 25.0 1.0 0.0 0.3 0.7 −5040
S16 B15 35.0 1.0 0.0 1.0 0.0 −15800
S17 B15 B2 141.4 1.0 1.0 0.0 0.0 −13200
S18 B13 B14 25.0 1.0 0.0 0.3 0.7 −6590
S19 B13 B20 25.0 1.0 0.0 0.0 1.0 0.0
S2 B15 25.0 1.0 0.0 1.0 0.0 −15900
S20 B14 B12 25.0 1.0 0.0 0.3 0.7 −6590
S21 B12 B22 99.6 1.0 0.0 0.0 1.0 −1580
S22 B12 99.6 1.0 1.0 0.0 0.0 −13300
S23 B16 B15 325.0 1.0 1.0 0.0 0.0 −12800
S24 B16 B17 325.0 1.0 1.0 0.0 0.0 −2290
S25 B18 B19 500.0 1.0 0.0 0.0 1.0 195
S26 B17 B19 500.0 1.0 1.0 0.0 0.0 −2150
S27 B19 B23 450.0 1.0 0.0 1.0 0.0 564
S28 B15 35.0 1.0 1.0 0.0 0.0 9.20
S29 B20 B28 437.0 1.0 0.0 1.0 0.0 481
S3 B1 B3 350.0 1.0 0.0 0.0 1.0 −1440
S30 B8 B22 436.0 1.0 0.0 0.0 1.0 −1160
S31 B21 B5 417.2 1.0 0.0 0.0 1.0 −1560
S32 B23 B20 450.0 1.0 0.0 1.0 0.0 489
S33 B23 450.0 1.0 1.0 0.0 0.0 6170
S34 B28 B11 436.0 1.0 0.0 0.0 1.0 −1160
S35 B9 25.0 1.0 0.0 0.0 1.0 −1390
S36 B21 B8 437.0 1.0 0.0 1.0 0.0 481
S37 B22 347.2 1.0 0.0 0.0 1.0 −1440
S38 B22 B24 105.0 1.0 0.0 0.0 1.0 −1350
S39 B24 B9 25.0 1.0 0.0 0.0 1.0 −1390
S4 B2 B3 400.0 1.0 1.0 0.0 0.0 −12700
S40 B20 B18 60.3 1.0 0.0 0.0 1.0 13.7
S41 B11 25.0 1.0 0.0 0.0 1.0 −1390
S5 B3 B4 325.0 1.0 0.5 0.0 0.5 −5170
S6 B4 B21 325.0 1.0 0.0 0.0 1.0 −1620
S7 B4 B16 325.0 1.0 1.0 0.0 0.0 −8980
S8 B5 B6 530.0 1.0 0.0 0.0 1.0 −1490
S9 B6 B7 530.0 1.0 0.1 0.9 0.0 541

Fig. 7. Work producing and consuming devices, work rate produced and their energy efficiency.

615
M. Al-Zareer et al.
4.2.3. Gasifier and WGSMR
The gasifier and the WGSMR have the highest energy and exergy
efficiencies of all the subsystems of the hydrogen production plant.
However, the WGSMR and the gasifier have the third and the fourth
place in the most contributors in the total exergy destruction of the
plant. The exergy destruction ratio of the WGSMR and the gasifier are
15% and 13% respectively. The syngas compositions and the gasifier
operating conditions are given in Table 4c.
4.2.4. Brayton cycle, HCS and HFCC
The subsystem with the highest exergy destruction rate is the HFCC
as shown in Fig. 3. Having the highest exergy destruction rate in all the
proposed hydrogen production plant subsystems results in making the
HFCC the main contributor in the overall plant exergy destruction ratio
of 25% as shown in Fig. 4. As shown in Fig. 3, there is a large difference
between the energy and exergy efficiencies of the Cu-Cl cycle and HCS
cycle. The reason behind the HCS having a large difference between its
energy and exergy efficiencies is due that the energy efficiency defini-
tion. The energy efficiency definition was mainly based on the enthalpy
of compressed hydrogen compared to the electrical power expenses,
and since the compressed hydrogen is made sure that it exits the HCS at
an ambient temperature then its enthalpy is not much larger than the
inlet enthalpy of the hydrogen entering the HCS. For the case of the Cu-
Cl cycle, the definition of the exergy content of a heat rate transferred
through a boundary with a specified temperature results in having the
exergy efficiency larger than the energy efficiency of the cycle (see Eqs.
(22) and (43)). The main and the largest work consuming and produ-
cing devices in the proposed hydrogen production plant is the Brayton
cycle, HCS, HFCC and CASU. All of the work consuming and producing
devices in the proposed hydrogen production plant results are shown in
Figs. 7 and 8. Shown in Fig. 7 the work rate produced or consumed by
these devices for the case of hydrogen production rate of 500 kg/day. It
is also shown in Fig. 7 the energy efficiency of each of the work con-
suming and producing devices in the proposed hydrogen production
plant. The highest work rate producing device is the gas turbine in the
HFCC cycle (GAST see Fig. 2d) as shown in Fig. 7. The highest work rate
consuming device is the air compressor in the HFCC cycle (C5 see
Fig. 2d) as shown in Fig. 7. Shown in Fig. 8 the exergy destruction rate
Fig. 8. Work producing and consuming devices, exergy destruction rate and their exergy efficiency.
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Energy Conversion and Management 157 (2018) 600–618
plus the exergy efficiency of each of the work producing or consuming
devices. The work producing or consuming cycle or the device that has
the highest exergy destruction rate is the Rankine cycle part of the
HFCC (RC5 see Fig. 2d). However, the work producing or consuming
cycle or the device with the lowest exergy destruction rate is the heat
recovery from the hydrogen compression intercooler Rankine cycles
RC1, RC2, RC3 and RC4 (see Fig. 2c). The Rankine cycle part of the
HFCC has the highest exergy destruction rate is because it receives heat
at high temperature but since the steam turbines has a maximum steam
inlet temperature of 650 °C [36], resulting in losing a huge amount of
exergy when limiting the temperature of the steam exiting the heat
exchanger HX5 see Fig. 2d. The lowest exergy destruction rate of the
Rankine cycles RC1, RC2, RC3 and RC4 (see Fig. 2c) is because the
temperature of the compressed hydrogen exiting each stage in the HCS
is below the steam turbines maximum steam inlet temperature of 650 °C
[36], which results in less amount of exergy lost. Since the inlet tem-
perature of the compressed hydrogen entering heat exchanger is very
close to the steam temperature exiting the heat exchanger. Fig. 9 shows
a graphical comparison between the proposed system’s energy and
exergy efficiencies with other multigenerational systems. These systems
are coal based where one of the products is hydrogen. Fig. 9 serves for
two main purposes. One of the purposes is validation of the system
results by comparing them to similar systems that were proposed in the
literature [6–13]. The second purpose is more complex in the sense that
it presents the advantages and disadvantages the proposed system is
compared to others available in the literature, as well as how the pro-
posed system improves them. It is important to note all the systems that
were considered from the literature, as shown in Fig. 9, do not include
the compressing process for the produced hydrogen. Compressing the
hydrogen is considered significant for an effective storage. The second
advantage of the proposed system is that it can produce higher amount
of hydrogen produced per each kg of coal feed rate to the gasifier. One
of the reasons the proposed system can produce higher hydrogen flow
rate is the thermal energy recovered from the processed syngas is used
directly to produce hydrogen through the five-step Cu-Cl cycle, com-
pared to the [6–13] systems that the produced hydrogen rate is directly
limited to coal feed, i.e. the hydrogen content in the processed syngas.
M. Al-Zareer et al.
Fig. 9. The energy and exergy efficiencies comparisons of the integrated gasification systems proposed in [6–13] with the results of the proposed hydrogen production plant in this
research.
5. Conclusions
A novel hydrogen production plant with production rate of 500 kg
of hydrogen per day is proposed, including thermochemical five steps
copper-chlorine cycle, pressurized entrained flow gasifier, water gas
shift membrane reactor, cryogenic air separation unit, Brayton cycle for
hydrogen and power production and a hydrogen compression system.
The main findings of this paper are summarized as follows:
• Overall energy and exergy efficiencies of the proposed hydrogen
production plant are 51.3% and 47.6% respectively.
• proposed hydrogen production plant has the capacity to pro-
The
duce 1.00 kg/s of compressed hydrogen at 700 bar and 4.64 MW of
work rate per 8.95 kg/s of Illinois No.6 coal.
The exergy analysis demonstrated large exergy destruction in the
hydrogen fueled combined cycle used to provide the needed work rate
to the rest of the hydrogen production plant. The main reason behind
the combined cycle having the highest exergy destruction rate is that
the combined cycle combustion chamber receives hydrogen, which has
a specific chemical exergy content equivalent to its lower heating value.
However due to the limitation of the gas turbines and steam turbines of
the Brayton and Rankine cycles respectively, a small fraction of the
exergy content is recovered. A recommendation is to propose a different
system that will produce the needed work but with higher exergy ef-
ficiency. Finally, the energy and exergy efficiencies of the proposed
hydrogen production plant are compared with systems that were pro-
posed in the literature for similar purposes, which is hydrogen pro-
duction. It is recommended to use another cycle to produce the needed
work rate of the hydrogen production plant in the place of the HFCC
system, due to its large exergy destruction rate. Consequently, the
proposed system is able to produce hydrogen from coal in a more ef-
ficient and effective manner.
617
Energy Conversion and Management 157 (2018) 600–618
Acknowledgement
The authors acknowledge the support provided by the Natural
Sciences and Engineering Research Council of Canada.
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