Energy Conversion and Management 242 (2021) 114318

Contents lists available at ScienceDirect

Energy Conversion and Management

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

Thermodynamic investigation of a novel hydrogen liquefaction process

using thermo-electrochemical water splitting cycle and solar collectors
Armin Ebrahimi a, Mohammad Hossein Monajati Saharkhiz b, Bahram Ghorbani c, *
a
Faculty of Mechanical Engineering, K. N. Toosi University of Technology, Tehran, Iran
b
Faculty of Mechanical Engineering, Tarbiat Modares University, Tehran, Iran
c
Faculty of Engineering Modern Technologies, Amol University of Special Modern Technologies, Amol, Iran

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

Keywords: Hydrogen production and liquefaction using solar thermo-electrochemical water splitting systems can as an
Process integration effective method for long-term renewable energy source storage are suggested. In this paper, a novel integrated
Thermo-electrochemical water splitting cycle configuration for the cogeneration of liquid hydrogen and oxygen by magnesium-chlorine thermo-electro­
Hydrogen liquefaction cycle
chemical water splitting cycle, hydrogen liquefaction unit, and solar dish collectors is developed. The novel
Solar parabolic dish collector
Pinch analysis
integrated structure produces 7116 kg/h liquid hydrogen and 57597 kg/h oxygen. Through the magnesium-
chlorine cycle, pure hydrogen is produced and the required energy is supplied through solar renewable en­
ergy based on the climatic conditions of Isfahan city in Iran. Then the produced hydrogen enters the liquefaction
process to generate liquid hydrogen. The heat and power consumption of the whole system for the cogeneration
of liquid hydrogen and oxygen are 207.9 MW and 373.9 MW, respectively. The heat waste of the integrated
structure is used to produce hot water as a by-product. The specific power consumption of the liquefaction cycle
is 7.6 kWh/kg LH2 and also the total thermal efficiency of the whole integrated system is 71.4%. Through the
pinch method, heat exchanger networks related to multi-stream heat exchangers of the present system are
extracted. Sensitivity analysis is used to investigate the effects of changes in major parameters including oper­
ating conditions of the thermo-electrochemical cycle as well as changes in the solar dish collector main pa­
rameters and the results are reported.

to produce hydrogen. Steam methane reforming (SMR) is currently the

most common method of hydrogen production and is highly dependent
1. Introduction
on fossil fuels because it uses natural gas as a fuel. Partial oxidation,
along with gasification, is another common method of hydrogen pro­
The increase of the world population, energy demand, declining
duction, which also uses fossil fuels such as petroleum and coal. Water
fossil fuels, and environmental pollution lead researchers around the
electrolysis is another way of generating hydrogen [4]. In addition to the
world to concentrate on new energy alternatives [1]. In this regard,
conventional methods, new methods of hydrogen production have also
hydrogen as one of the energy carriers has attracted much attention due
been considered. One of the developing methods of hydrogen produc­
to its numerous advantages, especially to the environment [2].
tion is thermochemical. This method consists of the decomposition of
Hydrogen is a clean fuel that can burn in the presence of air and produce
water into hydrogen and oxygen through an intermediate substance to
little pollution. In addition to direct combustion with air, it can be used
reduce the decomposition temperature [5]. Water splitting at high
in fuel cells that convert chemical energy into electrical energy.
temperature (thermolysis) requires a temperature of more than 2000 K
Hydrogen is the most abundant element on Earth, often in combination
to produce pure hydrogen. This temperature leads to a lot of process
with other substances. These compounds include hydrogen with oxygen
considerations, including temperature supply and limitations on the
in the water and with carbon in hydrocarbons and organic compounds.
choice of the structure material. Therefore, by different thermochemical
Hydrogen is a chemically highly active element with a high heat value
cycles, the required maximum temperature for decomposition can be
[3]. Hydrogen, in particular, can be generated from any substance that
reduced. Hydrogen decomposition by thermochemical cycles at tem­
contains its constituent atoms, such as hydrocarbons, water, and organic
peratures below 2000 K (even up to 700 K) can overcome these
compounds. There are different technologies and methods in the world

* Corresponding author.
E-mail address: [email protected] (B. Ghorbani).

https://doi.org/10.1016/j.enconman.2021.114318
Received 19 February 2021; Accepted 20 May 2021
Available online 2 June 2021
0196-8904/© 2021 Elsevier Ltd. All rights reserved.
A. Ebrahimi et al. Energy Conversion and Management 242 (2021) 114318

Nomenclatures s0 Specific enthalpy at reference state (kJ/kg.K)

T Temperature
Acronyms/Abbreviations T0 Temperature of the dead state (K)
LHV Lower heating value Ta Ambient temperature (◦ C)
LMTD Logarithmic mean temperature difference Ts Temperature of the Sun (5777 K)
LNG Liquefied natural gas Tw Receiver temperature (◦ C)
ORC Organic Rankine cycle U Overall heat transfer coefficient
SOFC Solid oxide fuel cell s Entropy
SPC Specific power consumption W Shell weight (lb)
Ẇ Work rate
Equipment names
xi Mole fraction of component i
Ci Compressor i
HXi Heat exchanger i Greek letters/symbols
Ti Turbine i η Efficiency
Si Splitter Σ Summation sign
∫
Pi Pump Integration sign
Vi Valve i Δ Difference operator
ρ Reflectance
Variables/parameters
λ Land factor of un-shading
A Surface area
τ Transmittance
Aa Surface area of the concentrator (m2)
α Absorptance
Ac Surface area of the receiver aperture (m2)
γ Intercept factor
Aw Cavity internal area of receiver (m2)
η Efficiency (%)
c Geometrical concentration ratio (-)
φ1 Tilt angle of cavity (Radian)
D Diameter
β Coefficient of thermal expansion (1/◦ C)
g Gravitational acceleration (9.806 m/s2)
v Kinematic viscosity (m2/s)
Grl Grashof number
δ Declination
Gon Extraterrestrial radiation incident
∅ Latitude
Gsc Solar constant (1367 W/m2)
ωs Sunset hour angle
G Gibbs free energy
εeff Effective infrared emittance of cavity
h Enthalpy
εc Cavity surface emittance
hc Convection heat transfer coefficient
σ Stefan–Boltzmann constant (5.67 × 10-8 W/m2 K4)
Hd Daily diffuse solar radiation
ω Hour angle
h0 Specific enthalpy at reference state (kJ/kg)
H0 Extraterrestrial solar radiation Superscripts and Subscripts
Id Hourly diffuse solar radiation Ab absorber
Is Beam solar radiation reached to concentrator surface c Cold, Collector
It Hourly global solar radiation e exit
K Thermal conductivity, W/m K gen generated
Kt Clearness index of a day h hot
L Length Id ideal
Llog Local geographical longitude in inlet
ṁ Mass flow rate (kg/s) m material
ṅi Mole rate of the ith stream (mol/kg) min minimum
Nul Nusselt number (-) mix mixing
P Pressure 0 standard condition
Q Volumetric flow rate o Optical
Q̇ Heat transfer rate out outlet
Ql Power lost in the receiver p pressure
Qlc Power lost from receiver through convection Qin input heat
Qlk Power lost from receiver through conduction Qout output heat
Qlr Power lost from receiver through radiation (W) r Receiver
Qr Power reached to the receiver (W) real real state
Qs Power reached on the surface of the dish (W) s isentropic
Qu Useful thermal power reached to the receiver (W) tot total
R Universal gas constant (8.314 J/ mol. K)

limitations [6]. Researches on thermochemical cycles began in the 1960 declined sharply and continued into late 1990 s [7]. Studies on these
s, and there were many proposed theoretical cycles. During the 1970 s cycles have flourished again in recent years due to the significant
and early 1980 s, studies on proposed cycles based on thermodynamic reduction in non-renewable energy sources; the main reason is to
criteria and perspectives, theoretical efficiency along cost analysis were consider hydrogen as an energy carrier without producing greenhouse
performed, in which the best cycles that met the examined criteria were gases. In addition to the thermochemical method, a variety of other
identified. In the late 1980 s, researches on thermochemical cycles methods are developed, including electrochemical, photochemical,

2
A. Ebrahimi et al. Energy Conversion and Management 242 (2021) 114318

radiochemical, biochemical, and hybrid. In the thermo-electrochemical pyrolysis, and thermochemical water splitting methods were examined
method, which is a thermochemical hybrid method, electricity is used to and compared in various aspects. An integrated structure including a
help the hydrogen decomposition process at least in one stage of the solar copper-chlorine (Cu-Cl) thermochemical hydrogen production
system. process was presented by Sayyaadi et al. [19]. Through optimization of
The various methods of hydrogen production through thermo­ the proposed system, thermal and exergy efficiencies increased to 49.8%
chemical water splitting cycles were reviewed by Mehrpooya et al. [8]. and 58.2%, respectively. Sadeghi et al. [20] investigated the exer­
These cycles included Sulfur-Iodine, Copper-Chlorine, Magnesium- goeconomic analysis and multi-objective optimization of a solar ther­
Chlorine, Iron-Chlorine, Vanadium-Chlorine, and Zinc-Sulfur-Iodine. mochemical hydrogen production plant. The hybrid structure included a
These cycles were compared thermodynamically and economically, pressurized solar power tower, gas turbine cycle, phase change material
and the hydrogen production cost of each was calculated. Mao et al. [9] (PCM) for thermal energy storage system (TES), Cu-Cl unit, regenerative
investigated hydrogen production via a two-step thermochemical unit steam Rankine process, and a heat recovery plant. The proposed system
based on metal oxide. Heat source and chemical reactors for reaction had an exergy efficiency of 50.1%. The results of exergoeconomic
were investigated and studied in detail. Cui et al. [10] introduced low- analysis showed that the product cost per unit of exergy of the system
temperature electro-thermochemical water splitting cycle to produce was 11.9 $/GJ. Roeb et al. [21] developed a two-step thermochemical
hydrogen. This cycle, which was based on the redox pair LiFeO2/Fe, cycle process for solar hydrogen production from water. The system
operated at 773 K and both electrochemical and thermochemical phases used a ferrite-based redox system at moderate temperature. The system
proceed isothermally. The five-step ZnSI thermochemical cycle oxidation and reduction steps operated at 1073 K and 1473 K, respec­
hydrogen production process was presented by Ahangar et al. [11]. tively. Galvez et al. [22] performed thermodynamic and kinetic analyzes
Thermal efficiency increased to 61.0% by applying heat integration for on a solar hydrogen production process via magnesium oxide/ magne­
the system. Also, the required hot and cold utilities of the system were sium (MgO/Mg) redox reactions. A continuous hydrogen production
reduced to 51.9% and 65.5%, respectively. Myagmarjav et al. [12] system based on the SI thermochemical cycle was proposed by Cump­
worked on the iodine–sulfur (IS) thermochemical water splitting unit to ston et al. [23]. The whole system was powered by solar energy. Heat to
apply silica membrane reactor for hydrogen iodide (HI) decomposition hydrogen efficiency of the system was 38.0% and the results of economic
process. The results showed that the system performance was improved. analysis of the system showed that the levelized cost of hydrogen was
The system is investigated in a wide range of operating conditions and 10.4 $/kgH2. Brendeberger et al. [24] developed a solar thermochemical
the relationship between HI conversion and the number of membrane hydrogen production plant system based on performance analysis and
tubes was evaluated. Naguchi et al. [13] reported on the latest research operational strategies for its receiver-reactor arrays. Corgnale et al. [25]
and development (R&D) status in the iodine–sulfur thermochemical developed a direct solar receiver reactor for the decomposition of sul­
water splitting hydrogen production process at Japan Atomic Energy furic acid in thermochemical hydrogen production units. The maximum
Agency (JAEA). Xu et al. [14] conducted an extensive study on the obtainable temperature of the reactor body was 1152 K. Fu et al. [26]
catalyst used in the HI decomposition in the iodine–sulfur thermo­ developed a solar thermochemical cycle based on thermal reduction of
chemical water splitting process. The IS process had three reactions tin oxide (SnO2) for the production of H2 and carbon monoxide (CO).
called Bunsen reaction, sulfuric acid (H2SO4) decomposition, and HI The proposed system oxidation and reduction steps operated at tem­
decomposition, among which, HI decomposition reaction has the lowest peratures of 600 K and 1400 K, respectively. The solar to fuel efficiency
reaction rate and thermodynamic equilibrium conversion (about 23% at of the system was calculated to be 46.1%. Hoskins et al. [27] developed
773 K). In the study, they attempted to increase the mentioned rate by isothermal on-sun hydrogen production via active iron aluminate par­
applying a catalyst. A four-step cycle based on the Iron-Chlorine (Fe-Cl) ticles. In the structure, a fluidized bed reactor was used to absorb solar
thermochemical water splitting unit for hydrogen production was energy. A solar hydrogen production system via the magnesium oxide-
considered by Safari et al. [15]. The 4 steps included the reverse Deacon magnesium sulfate thermochemical water splitting cycle was pre­
reaction, chlorination, thermal decomposition, and hydrolysis. The sented by Bhosale et al. [28]. The effect of inert gas argon as the carrier
whole system was simulated in ASPEN PLUS software. The effect of gas on the thermal reduction temperature was investigated on the per­
changing important parameters of the proposed system on its perfor­ formance of the proposed system. The results showed that by increasing
mance was investigated and reported. The thermochemical cycle based the argon rate from 1 to 50 mol/s, the thermal reduction temperature
on the trimanganese tetraoxide/ manganese oxide (Mn3O4/MnO) redox decreased from 1490 K to 1282 K, but on the other hand solar to fuel
pair is one of the methods of producing pure hydrogen which was energy conversion efficiency was also greatly affected and reduced from
investigated. The required maximum temperature to complete its de 47.7% to 18.1%.
reduction step is very high (1623–1723 K). By combining Mn3O4 with One of the two methods of converting to compressed gas or liquid
Co3O4, a metal oxide with a much lower reduction step temperature form must be used to store and transfer pure hydrogen, no matter which
(between 1048 and 1173 K) is obtained. Also, oxidation of the reduced method it is produced by. Liquid hydrogen has the highest energy
metal oxide with water to produce hydrogen (H2) is not thermody­ density among all energy sources. Many studies were performed on
namically possible and requires a higher operating temperature. For this various hydrogen liquefaction processes. The types of large-scale
purpose, a stronger oxidizing agent, as sodium hydroxide is required and hydrogen liquefaction processes were studied and compared from
it can reduce the maximum cycle temperature to 1373 K [16]. different aspects by Krasae-in et al. [29] and Aasadnia et al. [30]. Chang
Solar energy is not available at all hours of the day. Therefore, how to et al. [31] investigated a hydrogen liquefaction cycle applying liquefied
store and use this renewable resource is very important. One of the natural gas (LNG) cold energy in the Brayton refrigeration system. Two-
leading methods of storing energy for a long time is thermochemical stage expansion Brayton cycle with low-pressure LNG pre-cooling was
processes. One of the main goals of thermochemical water splitting cycle introduced as the best scenario. The optimization of a liquid hydrogen
development is the use of solar energy so that this type of renewable production system by geothermal absorption precooling refrigeration
energy can be stored as pure hydrogen. Numerous studies have been cycle was presented by Yilmaz et al. [32]. In the precooling cycle, the
performed on the supply of required heat (usually at very high tem­ temperature of the hydrogen dropped to 243 K. The modification of the
peratures) by thermochemical reactions through solar radiation energy. integrated structure reduced the exergetic cost of hydrogen to 20.1 $/GJ
Villafán-Vidales et al. [17] reviewed the various solar thermochemical (2.4 $/kg LH2). By changing the important parameters of the system, the
processes for hydrogen and syngas production in terms of reactor and optimized exergetic cost of the liquefied hydrogen was 4.9 $/GJ (1.3
facility specifications. In a similar work presented by Chuayboon et al. $/kg LH2). Ansarinasab et al. [33] performed a comprehensive analysis
[18], various methods of solar fuel production using different sources including exergy, exergoeconomic, and exergoenvironmental methods
including biomass and methane as well as water through gasification, on a liquid hydrogen production system. The hydrogen liquefaction

3
A. Ebrahimi et al. Energy Conversion and Management 242 (2021) 114318

Fig. 1. Block flow diagram of the present integrated system.

cycle in the study consisted of two separate mixed refrigerant cycles. 2. Materials and methods
Total exergy efficiency and specific energy consumption of the system
were 55.4% and 1.1 kWh/kg LH2, respectively. Yuksel et al. [34] pro­ The multi-step thermochemical cycles operate at lower maximum
vided an integrated system of hydrogen production and liquefaction temperatures. In fact, as the steps increase, the maximum required
cycles. This system consisted of the solar power unit, solid oxide steam temperature decreases in spite of the increase in system complexity. In
electrolyzer, Rankine power plant, and hydrogen production and these cycles, by increasing the steps, the maximum temperature could be
liquefaction cycles. The energy and exergy efficiencies of the system minimized about 1073 K to complete the water splitting process. Due to
were 65.1% and 62.3%, respectively. Yang et al. [35] developed an the high-temperature level of the required heat, the combined cycles
integrated hydrogen liquefaction plant system with a steam methane such as thermo-electrochemical are used to further reduce the maximum
reforming (SMR) process using liquefied natural gas (LNG). The system required temperature of the system. Thermo-electrochemical cycles are
was cooled by LNG and provided a part of the required cooling for the cycles in which electricity is used in at least one of the steps. In fact, in
hydrogen liquefaction process, and after regasification, entered the SMR these cycles, both heat and electricity are used for water splitting. Of
process with steam to produce pure hydrogen. Then hydrogen gas course, their power consumption is much less than the water electrolysis
entered the liquefaction section to obtain the final product of the system. process. With the increase of power consumption, these cycles tend to
Through performed integration, the specific energy consumption of the decrease to the maximum required temperature. By increasing the share
liquefaction cycle was reduced from 13.5 kWh/kg LH2 to 11.0 kWh/kg of the electrolysis process in thermo-electrochemical cycles, the
LH2. Results of the economic analysis showed that the current system maximum required temperature of the cycle decreases, and the elec­
was economically justifiable at the price of 2.5 $/kg liquid hydrogen. tricity consumption increases [36]. The main purpose of reducing the
Due to the high cost of hydrogen production units in one maximum required temperature is to use different low-temperature heat
geographical location, transferring hydrogen can be cost-effective. On sources such as excess heat of power generation cycles, nuclear and solar
the other hand, hydrogen gas storage requires a large volume and is energies.
difficult to transport, liquefaction can solve these problems. There are The developed integrated structure includes the sections of the Mg-Cl
numerous studies in the literature that suggest useful guidelines/tips on thermo-electrochemical water splitting process, hydrogen liquefaction
hydrogen liquefaction units using the mixed refrigerant cycles. The main cycle, and solar parabolic dish collector’s energy provider, which are
aim of the reported studies is to reduce the specific power consumption, described in detail below. Fig. 1 shows the block flow diagram (BFD) of
increase the performance coefficient and exergy efficiency and modify the novel integrated structure for the cogeneration of liquid hydrogen
the developed hydrogen liquefaction cycles. Also, in previous related and oxygen. According to this figure, the pure hydrogen produced by the
structures, extensive investigations have been conducted for the use of Mg-Cl thermo-electrochemical cycle enters the liquefaction cycle to
solar collectors to supply the heat thermochemical water splitting sys­ generate liquid hydrogen as a final product. The Mg-Cl cycle required
tems. Based on technical knowledge and previous related works, the heat is also provided by solar renewable energy.
supply of input hydrogen to the liquefaction structure using solar The assumptions for simulating the integrated structure are pre­
thermo-electrochemical water splitting systems and its thermal inte­ sented below:
gration by the pinch method has not been conducted yet. In this paper, 1. Pressure reduction in heat exchangers, reactors, and separation
an integrated system of hydrogen production and liquefaction based on units is ignored.
pinch analysis is presented. Pure hydrogen is produced through the 2. The minimum approach temperature of multi-stream heat ex­
magnesium-chlorine thermo-electrochemical water splitting cycle so changers is considered to be between 1 and 3 K.
that the required energy is supplied via solar renewable energy based on 3. Conductive heat transfer in collectors is ignored compared to heat
the climatic conditions of Isfahan city in Iran. Then the produced transfer due to convection and radiation.
hydrogen by the thermochemical hydrogen production plant enters the 4. Solar dish collectors follow the sun’s motion during the day, so the
liquefaction process to produce liquid hydrogen. incidence angle is considered zero.

4
A. Ebrahimi et al. Energy Conversion and Management 242 (2021) 114318

Fig. 2. Four-step the magnesium-chlorine thermo-electrochemical water splitting cycle reactions (modified from Ref. [37]).

Fig. 3. Process flow diagram of the present integrated system.

5
A. Ebrahimi et al. Energy Conversion and Management 242 (2021) 114318

5. The effect of wind on heat loss in solar collectors is considered to decomposition, and chlorination steps. The purpose of this type of
be negligible. reactor is to minimize the Gibbs free energy during the reaction. In this
way, the equilibrium constant of each reaction can be extracted and the
2.1. Mg-Cl thermo-electrochemical water splitting process amounts of products and reactants can be specified at the end of each
reaction. The Gibbs free energy equation is defined as follows: The dif­
The modern simulated Mg-Cl thermo-electrochemical cycle in the ference between the formation of products and reactants [39].
integrated structure has 4 steps which are hydrolysis, decomposition, ΔG0R = ΔG0F,proud − ΔG0F,Reac (5)
electrolysis, and chlorination. Fig. 2 indicates the schematic of the four-
step Mg-Cl thermo-electrochemical process. According to this figure, the where ΔG0R can be calculated through enthalpy and entropy of for­
only endothermic reaction of the cycle is related to the decomposition mation as follows [39]:
reaction, which occurs at a temperature of about 720 K. The three-step
Mg-Cl thermo-electrochemical process, which forms MgO instead of ΔG0f (T) = ΔH 0F (T) − TΔS0F (T) (6)
MgOHCl in the hydrolysis stage (an endothermic reaction), occurs at a
To obtain ΔH0F and ΔS0F , the functions H and S must be calculated in
higher temperature (about 820 K) and therefore requires a heat source
terms of temperature [39]:
with a higher temperature than the four-step Mg-Cl cycle. In the
developed four-step Mg-Cl cycle, hydrolysis and chlorination steps are ∫T
performed at a temperature of about 550 K and 770 K, respectively and 0
H(T) − H25C = Cp(T)dT (7)
both are exothermic. In the developed hybrid system, the Mg-Cl cycle 25

process is simulated by ASPEN PLUS software. According to the process ∫T

flow diagram (PFD) of the present integrated system shown in Fig. 3, Cp(T)
0
S(T) − S25C = dT (8)
water (stream 1) is mixed with process return water flow (stream 10) 25 T
and by increasing the temperature to 553.1 K along with MgCl2 output
In which Cp, heat capacity is considered as a function of temperature
from the chlorination step (stream 4) with a molar flow of 342757 kg/h,
and is estimated by the following equation. In equation (9), the co­
enters the hydrolysis reactor to produce MgOHCl and HCl(aq) through
efficients a and b are extracted experimentally [40].
the reaction between MgCl2 and steam (stream 5). Next, this stream,
which contains solid and gas, is introduced into the SEP1 separator to Cp(T) = a + bT (9)
separate MgOHCl particles from HCl. Then MgOHCl enters the decom­
By considering equation (9), relations (7) and (8) are calculated as
position stage after increasing the temperature by the HEX2 heat
follows [41]:
exchanger to decompose into MgO and dry HCl. The output stream from
the decomposition reactor is separated by passing through the SEP2 ∫T [ ]T
b
separator, anhydrous HCl, and MgO. Anhydrous HCl along with aqueous 0
H(T) − H25C = a + bT(T)dT = aT + T 2 (10)
2
HCl produced in the hydrolysis stage enters the electrolysis step to 25 25

generate pure H2 through electrochemical reaction using power. It ∫T

should be noted that the power consumption to electrolyze the aqueous a + bT(T)
0
S(T) − S25C = dT = [aln(T) + bT ]T25 (11)
HCl is higher than anhydrous HCl so that the required voltage in the first 25 T
reaction is 1.8 V and in the second one is 1.4 V. The required voltage for
By calculating ΔG0R using the above equations, the equilibrium con­
water electrolysis is 1.6 V. Therefore, to reduce power consumption,
stant of the reaction can be obtained as follows [39]:
aqueous HCl can be recovered to MgOHCl through the following re­
actions [37]. Meanwhile, when the produced hydrogen capacity is equal ΔG0R = RTln(Kp) (12)
in mol basis, system power consumption reduces, and instead the heat
demand increases [37]. The integrated structure has three reactors with thermochemical
reactions as hydrolysis, decomposition, and chlorination. The equilib­
MgO + 2HCl ↔ MgCl2 + H2 O (1) rium constant of these reactions in terms of relative fugacity is as
follows:
MgO + H2 O ↔ Mg(OH)2 (2) ⎡( ) ( ) ⎤
f f
MgO + HCl ↔ MgOHCl (3) ⎢ f0 MgOHCl f0 HCl ⎥
⎢
Kehyd =⎢ ( ) ( ) (aq) ⎥
⎥ (13)
In this paper, all the produced HCl in the hydrolysis and decompo­ ⎣ f f ⎦
f0 f0
sition stages enter the electrolysis step to produce hydrogen. The mini­ MgCl 2 H2 O

mum electrical energy required for this process can be calculated ⎡( ) ( ) ⎤

through the Nernst equation as follows [38]: f f
⎢ f0 f0 ⎥
⎢ ⎥
(4) ( MgO (14)
HCl
ΔG = − nFEo = − Wel Kedec = ⎢ ) ⎥
⎣ f ⎦
Where ΔG, F,Eo and n are Gibbs free energy, Faraday’s constant, f0
MgOHCl
standard cell potential, and the number of mole electrons involved in the ⎡( ) ( )1/2 ⎤
electrochemical reaction, respectively. The ΔG of the current electro­ f f
chemical reaction is 191.6 kJ/mol, so the theoretical standard potential ⎢ f0
⎢ f0 ⎥
O2 ⎥
(15)
MgCl
is calculated to be − 1.0 V. This value for water electrolysis reaction at Kechl =⎢
⎢ ( ) 2
( ) ⎥
⎥
⎣ f f ⎦
the temperature of 298 K and the pressure of 100 kPa is − 1.2 V. How­ f0 f0
ever, the required voltage for this process is extracted from practical
MgO Cl2

applications. The MgO produced from the decomposition step (stream MgO, MgCl2, and MgOHCl particles are solid, so their relative
24) and Cl2 produced from both electrolysis steps (streams 19 and 22) fugacity can be ignored. furthermore, the relative fugacity is approxi­
enter the chlorination step to form MgCl2 and pure O2. Then, by passing mately equal to partial pressure in gaseous compounds at pressures close
through the SEP6 separator, these are separated and MgCl2 enters the to ambient pressure. Therefore, equations (13) - (15) are simplified as
hydrolysis step after cooling by the HEX9 heat exchanger (stream 4). follows [39]:
The Gibbs reactor is used to simulate the reactions of the hydrolysis,

6
A. Ebrahimi et al. Energy Conversion and Management 242 (2021) 114318

Fig. 4. The direction of one atom spin in the para hydrogen vs. ortho hydrogen (modified from Ref. [51]).

⎡( ) ⎤ produce liquid hydrogen as the main product of the integrated system. A

p
⎢ p0 HCl ⎥ hydrogen liquefaction cycle consisting of a single mixed refrigerant
⎢ (aq) ⎥
Kehyd =⎢ ( ) ⎥ (16) cycle is used in the integrated structure. As shown in Fig. 3, streams 12
⎣ p ⎦
p0 and 21 are mixed and the pressure is increased to 2100 kPa by the C6
and C7 compressors. Then, by passing through the HX14, HX15, HX16,
H2 O

[( ) ]
p HX17, HX18, HX20, and HX19 heat exchangers and the temperature
Kedec = (17) decreases to 23.1 K (stream A12). Afterward, it enters the D5 separator
p0 HCl
by passing through the T9 expander, and liquid hydrogen is released
⎡( )1/2 ⎤ from the bottom (stream A15). The required cooling of the mentioned
⎢ p0
p
⎥ heat exchangers is supplied through mixed refrigerant, so that first the
⎢ O
Kechl = ⎢( ) 2
⎥
⎥ (18) stream B51 provides the required cooling of the HX14 multi-stream heat
⎣ p ⎦ exchanger, then passing through the C1, C2, C3, C4, and C5 compres­
p0
Cl2 sors, respectively (and subsequently passing through the HX12, HX13,
Partial pressure in the gaseous compounds can be obtained through HX21, HX10, and HX11 intercoolers) enters the HX14 heat exchangers
the following equation. by the temperature and pressure of 298.1 K and 2100 kPa respectively
(stream B1); its temperature drops to 233.1 K and subsequently enters
pY = XY pr (19) the D1 separator. A portion of gas-phase (stream B5) is mixed with
In which, pY , XY and pr are the partial pressure of component (Y ), separated liquid phase (stream B4) and after passing through the T1
expander is mixed with the reverse flow of stream B50 (stream B51) and
component (Y ) fraction, and operational pressure, respectively. By
as mentioned, the required cooling for the multi-stream the HX14 heat
considering equation (19), the equilibrium constants of the hydrolysis,
exchanger is provided. Then another portion of the gas phase detached
decomposition, and chlorination reactions are as follows [39]:
from the D1 separator (stream B8) enters the HX15 heat exchanger until
⎡ ( ) ⎤
pr its temperature reaches 165.1 K, afterward enters the D2 separator to
x
separate the liquid and gas phases. As mentioned about the output
HCl(aq) p0
⎢ ⎥
Kehyd = ⎢
⎣(( )⎥ (20)
pr
⎦ streams from the D1 separator, similarly a portion of the gas phase is
1 − xHCl ) p0
mixed with the liquid phase separated from the D2 separator, and after
[( )] passing through the T2 expander is combined with the reverse flow of
pr stream B48 and provides the required cooling of the HX15 multi-stream
Kedec = xHCI (21)
p0 heat exchanger. The required cooling of the HX16, HX17, HX18, HX20,
⎡ ( and HX19 heat exchanges is provided by the same procedure.
)1/2 ⎤
pr A hydrogen atom consists of a nucleus with a proton occupying most
xO2 p0
⎢
⎢
⎥ of its mass and an electron spinning around the nucleus. The nuclei of
Kechl = ⎢(( )⎥
⎥ (22)
⎣ pr ⎦ many atoms revolve around an axis called the spin. All diatomic mole­
1 − xO2 ) p0
cules with non-zero spin have nuclear isomers. The nucleus of a
hydrogen atom has a spin so that there are two different forms for
The fractions of HCl(aq) , HCl and O2 are calculated through the hydrogen molecule, ortho hydrogen, and para hydrogen. The direction
following relations [39]: of the nucleus spin determines whether the molecule is ortho or para. As
Ṅ HCl(aq) shown in Fig. 4, the direction of one atom spin in the para hydrogen
XHCl(aq) = (23) molecule rotates clockwise and the other counterclockwise, but in the
Ṅ HCl + Ṅ H2 O
ortho hydrogen molecule, the direction of the atoms spins is parallel,
meaning that both are clockwise [42]. The structure of ortho hydrogen is
Ṅ HCl
XHCl = (24) an excited state and has a higher energy level than para, but para
Ṅ HCl hydrogen has lower energy and is mostly formed at lower temperatures.
The states of molecular hydrogen are determined by the spin states of
Ṅ O2
X O2 = (25) the nucleus (2I + 1). Where I is the spin quantum number and is equal to
Ṅ O2 + Ṅ cl2 ½. According to the magnetic quantum number, α = + ½ and β = -½ ،, for
Information on the stream and equipment of the Mg-Cl thermo- ortho hydrogen I = (½ + ½) = 1, and therefore, this molecular shape has
electrochemical water splitting cycle is provided in the reference [6]. 3 states. In the para hydrogen I = (½-½) = 0 and as a result this type of
molecule has only one state. For this reason, at ambient temperature, the
ortho states are 3 times para. Therefore, this gas contains 75% ortho and
2.2. Hydrogen liquefaction cycle
25% para, which is called normal hydrogen [43]. The composition of
hydrogen is temperature-dependent in terms of ortho and para per­
Pure hydrogen produced by the MgCl thermo-electrochemical water
centage, and by decreasing temperature, the percentage of para
splitting cycle (streams 12 and 21) enters the liquefaction cycle to

7
A. Ebrahimi et al. Energy Conversion and Management 242 (2021) 114318

Fig. 5. The validation of the Mg-Cl thermo-electrochemical cycle developed in this paper with reference [48].

hydrogen will increase, so that by cooling hydrogen to 21 K, approxi­ which 25% of the ortho is converted to para at each stage. The catalyst
mately 99.9% of hydrogen para will be obtained. Normally, ortho used by these converters is Fe2(OH)3. More theory and background in­
hydrogen tends to the para hydrogen slowly at low temperature over a formation on the hydrogen liquefaction cycle can be found in the source
long time, which evaporates stored liquid hydrogen and wastes it. Ortho [46].
hydrogen has a higher energy level than para hydrogen and some
amount of heat will be released when ortho is converted to para. The 2.3. Solar parabolic dish collector
heat generated by the spontaneous conversion of ortho to para is about
332.9 kcal/mol, but the latent heat of liquid hydrogen evaporation is The required heat of the MgCl2 thermochemical water splitting cycle
approximately 219.9 kcal/mol. As a result, some hydrogen is lost during is supplied through solar renewable energy. Solar parabolic dish col­
the storage of liquid hydrogen, which is called boiling off. The lost lector is used for this purpose. The solar parabolic dishes follow the sun
amount of the stored liquid hydrogen is initially about one percent of the in two axes. Also, to achieve the required temperature in the absorbent
stored amount in an hour, but eventually after a long time, 69.3% of the part, which is 1200 K, the structure of the materials must be carefully
liquid hydrogen will evaporate and about 30% of the primary liquid selected. For temperatures as high as 1473 K, resistant metals (niobium,
hydrogen mass will remain in the storage tank [44]. Therefore, ac­ molybdenum, and tantalum) or hard alloys should be used. The area of
cording to the mentioned point, the process of converting ortho each solar dish is 12.5 m2. The power product of each dish can be ob­
hydrogen to para is essential to store the liquid hydrogen for a long time tained from the following equation [47].
and minimize evaporation. Hence, most liquefaction processes are
designed in such a way that part of the process is dedicated to the Q s = I s Aa (26)
conversion of ortho hydrogen to para. The conversion of ortho hydrogen Aa is the solar dish area and Is refers to the solar direct radiation to
to para is normally very slow and takes a lot of time, but by applying each collector. In the steady-state, the energy used by the solar dish
certain conditions, the rate of conversion can be increased. These con­ represents Qu, which is obtained from the difference of the energy
ditions include the use of paramagnetic catalysts that can change the applied to the absorber (Qr) and the energy lost in the absorber (Ql) [11].
direction of the nuclei spin [45]. In this paper, ortho is converted to para
by simultaneously decreasing its temperature in four stages by Qu = Qr − Ql (27)
ortho–para hydrogen converters the R1, R2, R3, and R4 reactors, in η0 denotes the optical efficiency of the solar dish, which is obtained

8
A. Ebrahimi et al. Energy Conversion and Management 242 (2021) 114318

Table 1
Model Validation of the hydrogen liquefaction cycle.
Items Present Ref. Deviation
study [46] (%)

Hydrogen feed pressure (bar) 21 21 0

Hydrogen feed temperature (K) 298.1 298.1 0
Mixed refrigerant pressure (bar) 21 21 0
Liquid hydrogen temperature (K) 20.0 18.5 8.1
Liquid yield (%) 98.0 97.8 0.2
Specific power consumption (kWh/kg 7.6 7.6 0.2
LH2)

from the ratio of the energy removed from the reflector to the solar
energy received by the collector surface [11].
η0 = Qr /Qs (28)

ηr = Qu /Qr (29)
ηr refers to the absorber efficiency which is obtained from the ratio of Fig. 6. The change of convection heat transfer versus the tilt angle of the cavity
the useful energy of the solar dish to the energy applying to the absorber for solar dish collectors in this paper with reference [49].
[11].
The thermal efficiency of the solar dish can be obtained from the The results of variation in the output stream combinations of the
following equation [11]: chlorination and hydrolysis reactors used in the thermo-electrochemical
water splitting cycle compared to the temperature change with refer­
ηc = Qu /Qs (30)
ence [48] are presented in Fig. 5. According to the figure, appropriate
The optical efficiency can also be calculated from the following compatibility is revealed. Table 1 shows the model validation of the
equation [11]: hydrogen liquefaction cycle simulated in this study with reference [46].
As a result, proper agreements are achieved. The main parameters of the
η0 = λρταγcos(θ) (31)
hydrogen liquefaction cycle including the liquid hydrogen temperature,
where θ is the angle of incidence, and since solar collectors follow the liquid yield, and specific power consumption were examined in relation
motion of the sun during the day, the value of this angle is zero. to the reference cycle. Fig. 6 illustrates the variations of the convective
heat transfer (at temperature 923 K) in solar parabolic dish collector
η0 = λρταγ (32)
compared to the tilt angle of the cavity with reference [49]. The results
The total energy loss from the absorber dish can be obtained by the illustrate that by decreasing the tilt angle of the cavity, the convective
equation (33). heat transfer rate increase.
Ql = Qlk + Qlc + Qlr (33)
4. Results and discussion
where Qlk is the heat loss of conduction in the absorber; Qk refers to
the heat loss of convection at the absorber opening and Qlr represents the In the integrated structure, 7116 kg/h of liquid hydrogen is pro­
heat loss of the radiant heat at the absorber opening [11]. duced, so that initially in the magnesium-chlorine thermo-electro­
The wind effect is not noticeable and it’s not considered. Transparent chemical water splitting cycle, 7258 kg/h of pure hydrogen is produced
glass is installed on the absorber opening to prevent dust from entering. and then enters the hydrogen liquefaction cycle for liquefaction. ASPEN
To calculate the useful energy obtained from the solar dish, the PLUS software is used to simulate the thermo-electrochemical water
following equations are used [47]. splitting cycle and ASPEN HYSYS software is applied to simulate the
hydrogen liquefaction cycle. To simulate radiation and solar collectors,
(34)
1/3
Nul = 0.106Grl (Tw /Ta )0.18 (4.256Ac /Aw )s h(φ1 ) TRNSYS software and MATLAB programming are used, respectively.
The thermal integration of the heat exchangers and the connection of the
Grl = gβ(Tw /Ta )L3 /v2 (35) three software are examined by MATLAB programming. In the
comprehensive design method of hydrogen liquefaction systems by
h(φ1 ) = 1.1677 − 1.0762sin(φ0.8324
1 ) (36) thermo-electrochemical water splitting cycle, the designer simulates the
The heat transfer coefficient is obtained from equation (37) [47]. core of the process structure, i.e. the reactors of the integrated config­
uration. Based on the strategy presented in the onion diagram for
hc = Nul K/L (37) simulating the integrated structure, in the second step, the multi-stream
The convective heat loss through the receiver aperture can be exchangers are simulated. The minimum temperature difference be­
calculated from equation (38). tween hot and cold composite curves in heat exchangers is assumed as
an output parameter. Thermal integration between converters is done
Qlc = hc Aw (Tw − Ta ) (38) using pinch analysis. Then, according to the required cooling rate, a
cryogenic plant appropriate to the core of the process is selected from
3. Validation of the proposed integrated system valid references in industry and articles as the initial guess. Solar col­
lectors are used to supplying high-temperature heat to reactors. Fig. 7
To validate the developed hybrid configuration, the subsystem units illustrates the proposed design method to give the optimal arrangement
are compared with similar systems in the industry or the resources in of novel integrated configuration. The integration of the refrigeration
which the process data is reported. The present integrated system con­ unit with the process core is provided in the form of hot and cold
sisting of thermo-electrochemical water splitting magnesium-chlorine composite curves in the multi-stream heat exchangers.
cycle and hydrogen liquefaction cycle are validated in the section that The liquid yield of the present liquefaction cycle is obtained from the
follows. following equation.

9
A. Ebrahimi et al. Energy Conversion and Management 242 (2021) 114318

Fig. 7. Proposed design method to give the optimal arrangement of novel integrated configuration.

Molar flow of the produced liquid hydrogen

Liquid Yield(%) = × 100 Total power consumption of the liquifaction cycle
Molar flow of the inlet hydrogen SEC = (40)
Liquid hydrogen mass flow rate
(39)
Based on this equation, the specific power consumption of the
According to this relation, the liquid yield is calculated to be 98.0%.
liquefaction cycle is 7.6 kWh/kg LH2, which is competitive with similar
Net power consumption of the hydrogen liquefaction cycle is calculated
cycles. The required power of the electrolysis step of the hydrogen
at 61775 kW. The specific power consumption (SEC) of this cycle is
production cycle, which produces H2 through HCl electrolysis, is
obtained from the following equation.
308750 kW. In the four-step thermo-electrochemical process, the only

10
A. Ebrahimi et al. Energy Conversion and Management 242 (2021) 114318

Table 2 Due to the geographical conditions of Isfahan and the presence of desert
The main parameters of solar dish collector [11,50]. lands, the design of the desired solar system is possible. Molten lithium is
Parameter Symbol Value used as a working fluid at the desired temperature conditions to transfer
heat between solar collectors and the hydrogen production system.
Solar dish area Aa 12.5m2
The changes in the specifications of simulated collectors to supply
Non-shadow coefficient λ 0.9
heat to the integrated structure during the day are illustrated in Fig. 8.
Dish surface reflection ρ 0.9
Fig. 8 (a) shows the parameters of solar direct normal irradiance and
The produced transfer absorption coefficient τα 0.9
ambient temperature from 8 to 18 h (July 5, 2020). According to this
Absorbent penetration coefficient 0.9
figure, most of these values occur at noon when solar direct normal
γ
Absorber length L 0.2 m
Geometric density ratio C 3000
irradiance and ambient temperature reach 907.3 W/m2 and 309.1 K,
Thermal conductivity of surroundings air K 0.02 W/m K respectively.
The internal area of the absorber cavity Aw 0.06m2 The inlet heat to the developed integrated structure during the day is
The slope angle of the cavity φ1 π/2 a constant value, part of which is supplied by the solar dish collectors
The cavity surface diffusion intensity εc 0.9 and the rest by the auxiliary boiler with natural gas fuel. Useful energy
absorbed by the collectors and auxiliary energy are shown in Fig. 8(b) in
terms of different hours, which in total should supply 748357 MJ/h of
endothermic step is related to the decomposition reaction, which occurs heat required by the system per hour. According to this figure, it is clear
at a temperature of 720 K. The amount of 207877 kW of required heat is that the most solar useful energy occurs at noon when all the required
supplied through solar renewable energy. For this purpose, solar dish heat is provided by the solar system, and in the remaining hours, the
collectors with the specifications presented in Table 2 are used. The farther it goes from noon, the share of solar useful energy decreases and
number of collectors used to supply the hydrogen production cycle and the share of auxiliary energy increases.
the required area are 22,000 and 276320 m2, respectively. In this re­ In the hybrid system, the whole system power consumption is 72362
gard, the city of Isfahan in Iran is selected with latitude (51◦ 40′ ), kW, part of which is produced by expanders in the amount of 7209 kW.
longitude (32◦ 39′ ), altitude (1590 m). It should be noted that solar The total thermal efficiency of the whole integrated system is obtained
information in the mentioned area has been obtained since July 5, 2020. according to the following equation.

Fig. 8. Changes in the specifications of simulated collectors to supply heat to the integrated structure during the day.

11
A. Ebrahimi et al. Energy Conversion and Management 242 (2021) 114318

Table 3
Operating conditions of the system streams.
Stream Temperature (K) Pressure (kPa) Molar Flow (kmol/h) Stream Temperature (K) Pressure (kPa) Molar Flow (kmol/h)

1 298.2 100.0 64855.0 A9 41.0 2100.0 7257.6

2 339.2 100.0 713405.1 A10 31.6 2100.0 7257.6
3 553.2 100.0 713405.1 A11 33.1 2100.0 7257.6
4 553.2 100.0 342757.4 A12 23.2 2100.0 7257.6
6 553.2 100.0 779808.4 A14 20.1 130.0 141.4
7 343.2 100.0 779808.4 A15 20.1 130.0 7116.2
8 343.2 100.0 779808.4 A16 298.2 100.0 7257.6
10 343.2 100.0 648550.1 A18 298.2 458.0 7257.6
11 343.2 100.0 3628.6 A19 482.3 2100.0 7257.6
13 553.2 100.0 276354.1 B2 233.2 2100.0 413811.0
14 723.2 100.0 276354.1 B3 233.2 2100.0 309563.8
15 723.2 100.0 276354.1 B4 233.2 2100.0 104247.2
17 343.2 100.0 131258.3 B6 233.2 2100.0 119717.4
18 343.2 100.0 131258.3 B7 198.7 300.0 119717.4
19 343.2 100.0 127629.7 B8 233.2 2100.0 294093.6
21 298.2 100.0 3628.6 B10 165.2 2100.0 182696.5
22 343.2 100.0 127629.7 B11 165.2 2100.0 111397.1
23 343.2 100.0 255259.4 B12 165.2 2100.0 6287.6
25 773.2 100.0 255259.4 B14 152.1 300.0 188984.2
26 773.2 100.0 400355.3 B15 165.2 2100.0 105109.4
28 773.2 100.0 57597.8 B17 123.2 2100.0 26539.8
29 298.2 100.0 57597.8 B18 123.2 2100.0 78569.6
A1 298.2 2100.0 7257.6 B19 123.2 2100.0 8238.7
A2 233.1 2100.0 7257.6 B20 123.2 2100.0 34778.5
A3 165.1 2100.0 7257.6 B21 88.4 300.0 34778.5
A4 122.8 2100.0 7257.6 B22 123.2 2100.0 70330.9
A5 123.3 2100.0 7257.6 B23 73.2 2100.0 70330.9
A6 73.4 2100.0 7257.6 B24 73.2 2100.0 1029.0
A8 41.4 2100.0 7257.6 B26 73.2 2100.0 20302.5
B27 73.2 2100.0 21331.5 S1 297.2 600.0 12401.9
B28 40.8 300.0 21331.5 S2 713.2 600.0 12401.9
B29 73.2 2100.0 48999.5 S3 297.2 400.0 597903.0
B30 41.2 2100.0 48999.5 S4 548.2 400.0 597903.0
B33 41.2 2100.0 26603.9 S7 297.2 400.0 35436.7
B34 28.4 700.0 26603.9 S1 297.2 600.0 12401.9
B35 41.2 2100.0 483.7 S8 763.2 400.0 35436.7
B36 29.7 2100.0 483.7 S9 416.9 400.0 35436.7
B38 21.5 300.0 483.7 S10 379.8 400.0 661527.0
B39 18.6 300.0 26603.9 S11 547.4 400.0 661527.0
B40 27.7 300.0 26603.9 S12 783.2 400.0 661527.0
B41 27.3 300.0 27087.6 S13 743.3 400.0 661527.0
B42 35.2 300.0 27087.6 S14 297.2 400.0 348006.9
B43 29.0 300.0 48999.5 S15 328.2 400.0 348006.9
B44 71.9 300.0 48999.5 S16 297.2 400.0 363453.2
B45 62.7 300.0 70330.9 S17 328.2 400.0 363453.2
B46 121.7 300.0 70330.9 S18 297.2 400.0 365633.1
B47 115.4 300.0 105109.4 S19 328.2 400.0 365633.1
B48 163.6 300.0 105109.4 S20 297.2 400.0 367379.6
B49 149.3 300.0 294093.6 S21 328.2 400.0 367379.6
B50 231.8 300.0 294093.6 S22 297.2 400.0 349775.2
B51 214.5 300.0 413811.0 S23 323.2 400.0 349775.2
B52 296.9 300.0 413811.0 S24 344.8 400.0 2496442.5
B53 330.7 450.0 413811.0 S25 297.2 400.0 6854.4
B54 298.2 450.0 413811.0 S26 297.2 400.0 13475.7
B55 332.1 675.0 413811.0 S27 338.2 400.0 13475.7
B59 332.2 1519.0 413811.0 S31 297.2 400.0 6861.7
B60 298.2 1519.0 413811.0 S32 473.2 400.0 6861.7
B61 325.2 2100.0 413811.0 S33 298.2 400.0 2496442.5

ṁLH 2 × LHV LH2 structure, there are seven multi-stream heat exchangers which are
Total thermal efficiency(%) = + Ẇ liquifactioncycle × 100
Q̇solar + Ẇ electrolyser designed based on the pinch method. The following describes how to
(41) design a heat exchanger network of the HX14 to HX20 multi-stream
exchanger in detail. Based on the method, the thermodynamic infor­
Based on this relationship, total thermal efficiency is 71.4%. Table 3 mation of each stream of these multi-stream exchangers is first extracted
shows the operating conditions of the system streams. The results of the and is shown in Table S1 in Supplementary Materials. It is necessary to
pinch analysis and parametric study are described below. Table 4 pre­ mention that to perform pinch analysis, ΔTmin, which depicts the min­
sents the specifications of the equipment used in the developed inte­ imum driving force for heat transfer, must be specified first. In the
grated configuration. developed structure, due to the very low-temperature range (cryogenic
temperature), the external utility was not used in the design to save the
4.1. Pinch analysis results operating costs of the system. Therefore, this constraint is used to
determine ΔTmin. According to the provided description, the ΔTmin of
In the hydrogen liquefaction cycle simulated in the developed multi-stream heat exchangers HX14 to HX20 are 1.2, 1.3, 1.6, 1.4, 1.2,

12
A. Ebrahimi et al. Energy Conversion and Management 242 (2021) 114318

Table 4 1.7, and 2.3 K, respectively. Also, their logarithmic mean temperature
The specifications of the equipment used in the developed integrated difference (LMTD) are 6.3, 11.8, 6.9, 4.6, 4.3, 3.3, and 4.8 K, respec­
configuration. tively. It should be noted that by increasing the minimum approach, of
Compressor course, heat exchangers can be designed more relaxed, but the complete
Parameter Adiabatic Power ΔP P Operating mode overlap between cold and hot composite curves does not occur. In this
efficiency ratio case, the external utility must be used. After ΔTmin extraction, the hot
Unit % kW kPa – – and cold composite curves of each of the multi-stream exchangers are
C1 90.0 12870.0 150.0 1.5 Centrifugal plotted and shown in Figure S1 in Supplementary Materials. To deter­
C2 90.0 12920.0 225.0 1.5 Centrifugal
mine the exact location of the pinch, hot streams should be reduced by
C3 90.0 12920.0 338.0 1.5 Centrifugal
C4 90.0 12880.0 506.0 1.4 Centrifugal ΔTmin /2 and added to the cold streams accordingly, and after per­
C5 90.0 10180.0 581.0 1.3 Centrifugal forming the energy cascade, the exact location of the pinch point in each
C6 90.0 5280.0 358.0 4.5 Centrifugal of the multi-stream exchangers is determined. The pinch point in the
C7 90.0 5307.0 1642.0 4.5 Centrifugal HX14 to HX20 occurs at 297.5, 232.5, 164.4, 122.4, 72.5, 19.4, and
Turbine
28.4 K. After the pinch point is determined, the heat exchanger network
Parameter Isentropic Power ΔP P Polytrophic
efficiency ratio efficiency is drawn based on the pinch method procedure shown in Fig. 9. The
Unit % kW kPa – % obtained heat exchanger network using the pinch design method is a
T1 90.0 1781.0 1800.0 0.1 89.2 network in which no heat is transferred from hot streams whose tem­
T2 95.0 1317.0 1800.0 0.1 94.7
perature is higher than the pinch point to a cold stream whose tem­
T3 95.0 1273.0 1800.0 0.1 94.0
T4 95.0 1559.0 1800.0 0.1 93.2 perature is lower than the pinch point. Table S2 in Supplementary
T5 90.0 662.0 1800.0 0.1 88.4 Materials presents the thermodynamic characteristics of the extracted
T6 95.0 532.1 1400.0 0.3 94.0 heat exchangers.
T7 90.0 4.9 1800.0 0.1 88.9
T8 90.0 36.5 400.0 0.4 89.7
T9 95.0 44.2 1970.0 0.06 92.9
4.2. Parametric analysis results
Heat Exchanger
Parameter LMTD Heat duty UA Parametric study is a very widely used tool to study the performance
Unit ◦
C kW kJ/h.◦ C of a system in different operating conditions and also to find the opti­
HX1 96.9 546765.0 20305040.3
mum conditions of the system. Since in this paper, an integrated system
HX3 18.5 484832.8 94317088.5
HX4 23.5 11214.9 1710794.7 of liquid hydrogen production by using the magnesium-chlorine thermo-
HX5 2.4 640.7 927681.2 electrochemical water splitting cycle, hydrogen liquefaction cycle, and
HX6 2.4 640.7 927681.2 solar dish collectors as renewable energy is proposed, so by changing the
HX7 83.1 15613.1 526002.0 important parameters of each section of the integrated system, its impact
HX8 3.9 14748.6 13558283.8
HX9 76.3 33109.6 1560783.4
is reported.
HX10 2.1 13204.0 21938460.4
HX11 1.4 10542.7 25720840.9 4.2.1. The effect of temperature and steam/Mg ratio on the performance of
HX12 1.6 12507.8 27182560.6 hydrolysis and decomposition reactions
HX13 2.1 13062.9 22045952.8
The effect of temperature and steam/Mg ratio on the performance of
HX14 6.3 37506.2 21149480.7
HX15 11.8 45588.2 13825147.8 the hydrolysis reaction and subsequently on the performance of the
HX16 6.9 13934.3 7195362.0 decomposition reaction is shown in Figs. 10-12. According to Figs. 10
HX17 4.6 10892.9 8454161.8 and 11, by increasing temperature and also the steam/Mg ratio, the MgO
HX18 4.3 5632.7 4614990.7 production increases. According to Le Chatelier’s principle for endo­
HX19 3.3 2347.6 2527022.2
HX20 4.8 593.4 443480.1
thermic reactions, as the temperature increases, the reaction tends to
HX21 2.1 13141.3 21851593.9 lower yields, and vice versa. Also, for exothermic reactions, with
HX22 24.4 89820.0 13222968.0 increasing temperature, the reaction tends to higher yields and vice
HX24 3.6 5274.4 5177558.7 versa. Therefore, MgO increases with increasing temperature, and in
HX25 3.6 5280.0 5174601.4
contrast, MgOHCl will decrease. Figs. 10 and 11 show the molar flow
Heater
Parameter Delta T Heat duty Outlet Mass Enthalpy and molar fraction of MgO and MgOHCl for steam/Mg: R = 1–4,
Unit K kW kJ/kg respectively. Fig. 12 illustrates the effect of temperature on the molar
HX2 346.3 7778 − 13296.6 flow of HCl and steam in the reactions. According to this figure, with
Cooler increasing temperature, more HCl is produced and more steam is
Parameter Delta T Heat duty Outlet Mass Enthalpy
Unit K kW kJ/kg
consumed. The trend of changes examined corresponds with the results
HX23 240.9 118057.0 − 1322.3 of sensitivity analysis in reference [48].
HX26 46.7 134969.9 − 15865.8
Reactor 4.2.2. The effect of temperature and pressure on chlorination reaction
Parameter Type Pressure Temperature
Fig. 13 depicts the effect of temperature on the chlorination reaction.
Unit – kPa K
R1 Conversion 2100.0 123.2 According to this figure, with increasing temperature, the amount of
R2 Conversion 2100.0 73.3 products decreases, and the reactant increases (due to the exothermic
R3 Conversion 2100.0 40.9 nature of the reaction), so that at 673.1 K, the highest yield is obtained.
R4 Conversion 2100.0 33.1 In this case, the mole fraction of MgCl2 reaches more than 0.4. Fig. 14
R5 Gibbs 100.0 553.1
R6 Gibbs 100.0 280.1
illustrates the effect of pressure on this reaction. As the pressure in­
R7 Gibbs 100.0 280.1 creases, the reaction leads to a higher yield, so that at a pressure of 100
R8 Gibbs 100.0 773.1 kPa, the mole fraction of MgCl2 is 0.226, and at a pressure of 400 kPa,
R9 Gibbs 100.0 723.1 this parameter increases to 0.3905. In contrast, the amount of MgO will
decrease with increasing pressure. The simultaneous effect of tempera­
ture and pressure changes on the chlorination reaction is shown in
Fig. 15. In this figure, by examining the temperature from 673 to 973 K
and in three pressure levels of 100, 200, and 300 kPa, the values of

13
A. Ebrahimi et al. Energy Conversion and Management 242 (2021) 114318

Fig. 9. Heat exchanger networks of the multi-stream heat exchangers.

Fig. 10. The molar flow of MgO and MgOHCl for steam/Mg: R = 1–4.

14
A. Ebrahimi et al. Energy Conversion and Management 242 (2021) 114318

Fig. 11. The mole fractions of MgO and MgOHCl for steam/Mg: R = 1–4.

Fig. 12. The molar flow of HCl and steam for steam/Mg: R = 1–4.

Fig. 13. The effect of temperature on the chlorination reaction.

15
A. Ebrahimi et al. Energy Conversion and Management 242 (2021) 114318

Fig. 14. The effect of pressure on the chlorination reaction.

Fig. 15. The simultaneous effect of temperature and pressure changes on the chlorination reaction.

Fig. 16. The effect of simultaneous change of solar direct normal irradiance and geometric concentration ratio on solar collector thermal efficiency.

16
A. Ebrahimi et al. Energy Conversion and Management 242 (2021) 114318

reactant and products are reported. According to this figure, by energy.

increasing the pressure to 300 kPa and also reducing the temperature to
673 K, the maximum amount of MgCl2 can be achieved, which is 2890 CRediT authorship contribution statement
kmol/h, and in contrast, by reducing the pressure to 100 kPa and
increasing the temperature to 973 K, the lowest amount of MgCl2 is Armin Ebrahimi: Investigation, Software, Writing - original draft,
obtained, which is 380.2 kmol/h. The trend of changes examined cor­ Validation. Mohammad Hossein Monajati Saharkhiz: Investigation,
responds with the results of sensitivity analysis in reference [48]. Software, Writing - original draft, Validation. Bahram Ghorbani:
Investigation, Software, Writing - original draft, Validation, Conceptu­
4.2.3. The impact of changes in solar parameters alization, Methodology.
The effect of simultaneous change of solar direct normal irradiance
and geometric concentration ratio on solar collector thermal efficiency
is shown in Fig. 16. According to this figure, by increasing the geometric Declaration of Competing Interest
concentration ratio to 4000 and also increasing the solar radiation in­
tensity to more than 1000 W/m2, the solar collector thermal efficiency The authors declare that they have no known competing financial
can be increased to more than 80%. As direct normal irradiance in­ interests or personal relationships that could have appeared to influence
creases, the ratio of heat losses from the receiver to the surroundings to the work reported in this paper.
the solar energy incident on the dish concentrator aperture decreases.
Since the solar collector thermal efficiency is obtained from the differ­ Appendix A. Supplementary data
ence of optical efficiency from Ql /Qs , so with increasing solar direct
normal irradiance, the solar thermal efficiency increases. Also, as the Supplementary data to this article can be found online at https://doi.
geometric concentration ratio increases, the entrance aperture area of org/10.1016/j.enconman.2021.114318.
the receiver decreases. By increasing the value of the entrance aperture
area of the receiver, the Nusselt number and the heat losses from the References
receiver to the surroundings decrease, respectively. By decreasing the
Ql /Qs , the solar collector thermal efficiency increases, so with increasing [1] Ebrahimi A, Ziabasharhagh M. Energy and exergy analyses of a novel integrated
process configuration for tri-generation heat, power and liquefied natural gas based
geometric concentration ratio, the solar thermal efficiency increases.
on biomass gasification. Energy Convers Manage 2020/04/01/ 2020.;209:112624.
[2] Ozcan H, Dincer I. Energy and exergy analyses of a solar driven Mg–Cl hybrid
5. Conclusion thermochemical cycle for co-production of power and hydrogen. Int J Hydrogen
Energy 2014;39(28):15330–41.
[3] Veneri O. “Hydrogen as future energy carrier,” in Hydrogen fuel cells for road
In this paper, an integrated liquid hydrogen production system vehicles. Springer 2011:33–70.
consisting of the magnesium-chlorine thermo-electrochemical water [4] Yukesh Kannah R, et al. Techno-economic assessment of various hydrogen
splitting cycle and hydrogen liquefaction cycle has been developed using production methods – A review. Bioresour Technol 2021/01/01/ 2021.;319:
124175.
solar dish collectors as a renewable energy resource. As water is split [5] Ozcan H, Dincer I. “Exergoeconomic optimization of a new four-step
into hydrogen and oxygen by the thermo-electrochemical cycle, the heat magnesium–chlorine cycle,” international journal of hydrogen energy 2017;42(4):
required for this cycle is provided by solar dish collectors. Pure 2435–45.
[6] H. Ozcan and I. Dincer, “Comparative performance assessment of three
hydrogen is produced, and then enters the liquefaction cycle, and finally configurations of magnesium–chlorine cycle,” international journal of hydrogen
liquid hydrogen is released as the final product. The following points can energy, vol. 41, no. 2, pp. 845-856, 2016.
be considered as the most important points extracted from the devel­ [7] Holladay JD, Hu J, King DL, Wang Y. An overview of hydrogen production
technologies. Catal Today 2009;139(4):244–60.
opment integrated structure. [8] Mehrpooya M, Habibi R. A review on hydrogen production thermochemical water-
splitting cycles. J Cleaner Prod 2020/12/01/ 2020.;275:123836.
1. This integrated structure, by absorbing 207.9 MW of heat from solar [9] Mao Y, et al. Hydrogen production via a two-step water splitting thermochemical
cycle based on metal oxide – A review. Appl Energy 2020/06/01/ 2020.;267:
energy and 373.9 MW of power, produces 7116 kg/h liquid 114860.
hydrogen and also 57597 kg/h pure oxygen. [10] Cui B, Zhang J, Liu S, Liu X, Zhang Z, Sun J. A low-temperature electro-
2. The specific power consumption of the hydrogen liquefaction cycle is thermochemical water-splitting cycle for hydrogen production based on LiFeO2/Fe
redox pair. Int J Hydrogen Energy 2020/08/21/ 2020.;45(41):20800–7.
7.6 kWh/kg LH2. The total thermal efficiency of the entire integrated
[11] Ahangar N, Mehrpooya M. Thermaly integrated five-step ZnSI thermochemical
system is 71.4%. cycle hydrogen production process using solar energy. Energy Convers Manage
3. Sensitivity analysis is investigated and identified the important and 2020;222:113243.
influential parameters on the developed integrated structure. The [12] Myagmarjav O, Tanaka N, Nomura M, Kubo S. Module design of silica membrane
reactor for hydrogen production via thermochemical IS process. Int J Hydrogen
sensitivity analysis illustrates that the mole fraction of MgCl2 and O2 Energy 2019/04/23/ 2019.;44(21):10207–17.
increase up to 19.73 mol% and 20.17 mol%, respectively when the [13] Noguchi H, et al. R&D status in thermochemical water-splitting hydrogen
chlorination reaction temperature decreases from 1073.1 K to 6.73.1 production iodine-sulfur process at JAEA. Energy Procedia 2017;131:113–8.
[14] Xu L, Wang L, Zhang P, Hu S, Li D, Chen S. INET’s catalysts study for HI
K. Also, by increasing the chlorination reaction pressure in the decomposition in the thermochemical water-splitting iodine–sulfur process for
hybrid system from 100 kPa to 400 kPa, the mole fraction of MgCl2 hydrogen production. Int J Hydrogen Energy 2017/02/09/ 2017.;42(6):3593–7.
and O2 have a rising trend and increases by 39.05 mol% and 19.5 mol [15] Safari F, Dincer I. A study on the Fe–Cl thermochemical water splitting cycle for
hydrogen production. Int J Hydrogen Energy 2020/07/31/ 2020.;45(38):
%, respectively. The molar fraction of MgO for R = 2 increases up to 18867–75.
25 mol% with the increase of hydrolysis reaction temperature from [16] Orfila M, Linares M, Molina R, Marugán J, Botas JÁ, Sanz R. Hydrogen production
703.1 K to 853.1 K. by water splitting with Mn3-xCoxO4 mixed oxides thermochemical cycles: A
thermodynamic analysis. Energy Convers Manage 2020/07/15/ 2020.;216:
4. By applying the pinch method on the multi-stream heat exchangers, 112945.
the heat exchanger networks related to each are extracted. The re­ [17] Villafán-Vidales HI, Arancibia-Bulnes CA, Riveros-Rosas D, Romero-Paredes H,
sults show that ΔTmin of these multi-stream exchangers are 6.3, 11.8, Estrada CA. An overview of the solar thermochemical processes for hydrogen and
syngas production: Reactors, and facilities. Renew Sustain Energy Rev 2017;75:
6.9, 4.6, 4.3, 3.3, and 4.8 K, respectively, and include 2, 2, 2, 2, 3, 3,
894–908.
and 2 simple heat exchangers, respectively. [18] Chuayboon S, Abanades S. An overview of solar decarbonization processes,
reacting oxide materials, and thermochemical reactors for hydrogen and syngas
To future researches on the developed integrated structure, the production. Int J Hydrogen Energy 2020/09/30/ 2020.;45(48):25783–810.
[19] Sayyaadi H, Saeedi Boroujeni M. Conceptual design, process integration, and
exergoeconomic and environmental assessment can be done. Other en­ optimization of a solar CuCl thermochemical hydrogen production plant. Int J
ergy sources such as nuclear energy can also be used to replace solar Hydrogen Energy 2017/02/02/ 2017.;42(5):2771–89.

17
A. Ebrahimi et al. Energy Conversion and Management 242 (2021) 114318

[20] Sadeghi S, Ghandehariun S, Naterer GF. Exergoeconomic and multi-objective [35] Yang J-H, Yoon Y, Ryu M, An S-K, Shin J, Lee C-J. Integrated hydrogen liquefaction
optimization of a solar thermochemical hydrogen production plant with heat process with steam methane reforming by using liquefied natural gas cooling
recovery. Energy Convers Manage 2020/12/01/ 2020.;225:113441. system. Appl Energy 2019/12/01/ 2019.;255:113840.
[21] Roeb M, et al. Operational strategy of a two-step thermochemical process for solar [36] Yan XL, Hino R. Nuclear hydrogen production handbook. CRC Press; 2016.
hydrogen production. Int J Hydrogen Energy 2009;34(10):4537–45. [37] H. Ozcan and I. Dincer, “Modeling of a new four-step magnesium–chlorine cycle
[22] Galvez M, Frei A, Albisetti G, Lunardi G, Steinfeld A. Solar hydrogen production via with dry HCl capture for more efficient hydrogen production,” international
a two-step thermochemical process based on MgO/Mg redox journal of hydrogen energy, vol. 41, no. 19, pp. 7792-7801, 2016.
reactions—thermodynamic and kinetic analyses. Int J Hydrogen Energy 2008;33 [38] Dincer I, Rosen MA. Exergy: energy, environment and sustainable development.
(12):2880–90. Newnes; 2012.
[23] Cumpston J, Herding R, Lechtenberg F, Offermanns C, Thebelt A, Roh K. Design of [39] Ozcan H, Dincer I. Performance investigation of magnesium–chloride hybrid
24/7 continuous hydrogen production system employing the solar-powered thermochemical cycle for hydrogen production. Int J Hydrogen Energy 2014;39
thermochemical S-I cycle. Int J Hydrogen Energy 2020/09/21/ 2020.;45(46): (1):76–85.
24383–96. [40] Pope K, Wang ZL, Naterer GF, Secnik E. Interfacial thermodynamics and X-ray
[24] Brendelberger S, Rosenstiel A, Lopez-Roman A, Prieto C, Sattler C. Performance diffraction of hydrolysis products in multiphase reacting flow of the Cu–Cl cycle.
analysis of operational strategies for monolithic receiver-reactor arrays in solar Int J Hydrogen Energy 2012/10/01/ 2012.;37(20):15011–9.
thermochemical hydrogen production plants. Int J Hydrogen Energy 2020/10/02/ [41] Green DW, Southard MZ. Perry’s chemical engineers’ handbook. McGraw-Hill
2020.;45(49):26104–16. Education; 2019.
[25] Corgnale C, Ma Z, Shimpalee S. Modeling of a direct solar receiver reactor for [42] Kutz M. Mechanical Engineers’ Handbook, Volume 4: Energy and Power. John
decomposition of sulfuric acid in thermochemical hydrogen production cycles. Int Wiley & Sons 2015.
J Hydrogen Energy 2019/10/18/ 2019.;44(50):27237–47. [43] Timmerhaus KD, Flynn TM. Cryogenic process engineering. Springer Science &
[26] Fu M, Xu H, Ma H, Li X. “Theoretical assessment of hydrogen production and Business Media; 2013.
multicycle energy conversion via solar thermochemical cycle based on nonvolatile [44] Baker C. Economics of Hydrogen Production and Liquefaction updated to 1980.
SnO2,” Journal of Energy. Chemistry 2019;38:177–84. Langley Research Center 1979.
[27] Hoskins AL, Millican SL, Czernik CE, Alshankiti I, Netter JC, Wendelin TJ, et al. [45] Fradkov AB, Troitskii VF. Liquefier with two-stage conversion to obtain 98 per cent
Continuous on-sun solar thermochemical hydrogen production via an isothermal parahydrogen. Cryogenics 1965;5(3):136–7.
redox cycle. Appl Energy 2019;249:368–76. [46] Sadaghiani MS, Mehrpooya M, Ansarinasab H. Process development and exergy
[28] Bhosale RR. Solar hydrogen production via thermochemical magnesium oxide – cost sensitivity analysis of a novel hydrogen liquefaction process. Int J Hydrogen
Magnesium sulfate water splitting cycle. Fuel 2020/09/01/ 2020.;275:117892. Energy 2017;42(50):29797–819.
[29] Krasae-in S, Stang JH, Neksa P. Development of large-scale hydrogen liquefaction [47] Ebrahimi A, Ghorbani B, Lohrasbi H, Ziabasharhagh M. Novel integrated structure
processes from 1898 to 2009. Int J Hydrogen Energy 2010;35(10):4524–33. using solar parabolic dish collectors for liquid nitrogen production on offshore gas
[30] Aasadnia M, Mehrpooya M. Large-scale liquid hydrogen production methods and platforms (exergy and economic analysis). Sustainable Energy Technol Assess
approaches: A review. Appl Energy 2018;212:57–83. 2020/02/01/ 2020.;37:100606.
[31] Chang H-M, Kim BH, Choi B. Hydrogen liquefaction process with Brayton [48] H. Ozcan, “Experimental and theoretical investigations of magnesium-chlorine
refrigeration cycle to utilize the cold energy of LNG. Cryogenics 2020/06/01/ cycle and its integrated systems,” 2015.
2020.;108:103093. [49] Mohammadi A, Mehrpooya M. Exergy analysis and optimization of an integrated
[32] Yilmaz C, Kaska O. Performance analysis and optimization of a hydrogen micro gas turbine, compressed air energy storage and solar dish collector process.
liquefaction system assisted by geothermal absorption precooling refrigeration J Cleaner Prod 2016;139:372–83.
cycle. Int J Hydrogen Energy 2018/11/01/ 2018.;43(44):20203–13. [50] Moradi M, Mehrpooya M. Optimal design and economic analysis of a hybrid solid
[33] Ansarinasab H, Mehrpooya M, Sadeghzadeh M. An exergy-based investigation on oxide fuel cell and parabolic solar dish collector, combined cooling, heating and
hydrogen liquefaction plant-exergy, exergoeconomic, and exergoenvironmental power (CCHP) system used for a large commercial tower. Energy 2017;130:
analyses. J Cleaner Prod 2019;210:530–41. 530–43.
[34] Yuksel YE, Ozturk M, Dincer I. Energetic and exergetic assessments of a novel solar [51] A. Hammad, “ANALYSIS AND ASSESSMENT OF ADVANCED HYDROGEN
power tower based multigeneration system with hydrogen production and LIQUEFACTION SYSTEMS,” Doctor of Philosophy Degree in Mechanical
liquefaction. Int J Hydrogen Energy 2019/05/21/ 2019.;44(26):13071–84. Engineering, University of Ontario Institute of Technology Oshawa, Ontario,
Canada, 2019.

18