Journal of Cleaner Production 362 (2022) 132445

Contents lists available at ScienceDirect

Journal of Cleaner Production

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

A new scheme for ammonia and fertilizer generation by coal direct

chemical looping hydrogen process: Concept design, parameter
optimization, and performance analysis
Huairong Zhou a, c, Yingwen Ma a, c, Qingchun Yang b, Dongliang Wang a, c, **, Hongwei Li a, c,
Guixian Li a, c, Yong Yang a, c, Zongliang Fan a, c, Dong Ji a, c, Ning Li a, c, Dongqiang Zhang a, c, *
a
College of Petrochemical Technology, Lanzhou University of Technology, Lanzhou, 730050, PR China
b
School of Chemistry and Chemical Engineering, Hefei University of Technology, Hefei, 230009, PR China
c
Key Laboratory of Low Carbon Energy and Chemical Engineering of Gansu Province, Lanzhou, 730050, Gansu, China

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

Handling Editor: M.T. Moreira Ammonia is a very important chemical industry product. It has a wide range of applications in refrigeration,
energy, and fertilizers, and 80% of ammonia is used as a nitrogen fertilizer. China mainly produces ammonia and
Keywords: urea from coal gasification, which leads to difficult CO2 capture and high energy consumption. This study
Coal direct chemical looping proposed a new process for the production of ammonia and urea by coal direct chemical looping hydrogen
Concept design
production process (CDCLTU). The coal direct chemical looping hydrogen production replaces the air separation
Parameter optimization
unit and water gas conversion unit of the traditional coal-to-urea process (CTU), which effectively separates and
Techno-economic analysis
Environmental analysis captures CO2 and significantly reduces the energy consumption. A model of the CDCLTU was established using
Aspen Plus. Parameter optimization, technoeconomic, and environmental analysis were conducted through
simulations. The results showed that CDCLTU could completely replace the air separation system that the CTU
relies on. Compared with the traditional process, the utilization rate of C increased from 53.46% to 67.95% in the
new process. The energy consumption of CO2 separation and capture was reduced by 97.04%. The CDCLH had a
79.7% energy efficiency in the hydrogen production process and 99% capture rate of CO2. The total capital
investment was dropped by 41%, unit urea production cost dropped by 12.1%, and the payback period dropped
from 7.5 to 3.5 years. This paper provides a new direction for clean and efficient utilization of coal resources.

1. Introduction
Urea is a very important chemical product that plays a crucial role in
the food, medical, and industrial fields. In 2019, the global nitrogen
product totaled 183 Mt of ammonia. The top four producing countries
were China (29%), Russia (10%), the United States (9%), and India
(8%). About 80% of ammonia is used for synthetic urea (Chen et al.,
2020). The typical urea production process faces two significant short­
comings: high carbon dioxide emissions and high costs. As the largest
nitrogen fertilizer producer and an important urea exporter, China needs
to optimize the traditional urea production process to meet its new en­
ergy policy and carbon emissions requirements.
Industrially, ammonia is usually synthesized through the Haber­
–Bosch process, and more than 72% of ammonia is synthesized using
natural gas (Bicer et al., 2017). Owing to China’s unique energy struc­
ture, more than 97% of its ammonia is produced through coal gasifi­
cation (Xiang and Zhou, 2018). However, the air separation system,
which consumes a large amount of energy, provides pure oxygen and
needs to separate CO2 and H2. This results in a high energy consumption
in the gasification process. Researchers have found that a low concen­
tration of CO2 is the main reason for the high energy consumption of the
separation process (Yang and Jackson, 2012).
In response to the above problems, researchers have proposed
various solutions. Sircar et al. introduced pressure swing adsorption
technology to separate CO2 and H2, but this suffered from adsorbent
denaturation issues and complex procedures (Sircar and Golden, 2000).
Song et al. introduced a low-temperature CO2 capture process, which
could be highly efficient (>99%) and could easily transport CO2 for

* Corresponding author. College of Petrochemical Technology, Lanzhou University of Technology, Lanzhou, 730050, PR China.
** Corresponding author. College of Petrochemical Technology, Lanzhou University of Technology, Lanzhou, 730050, PR China.
E-mail addresses: wangdl@lut.edu.cn (D. Wang), zhangdq@lut.edu.cn (D. Zhang).

https://doi.org/10.1016/j.jclepro.2022.132445
Received 6 January 2022; Received in revised form 30 March 2022; Accepted 26 May 2022
Available online 29 May 2022
0959-6526/© 2022 Elsevier Ltd. All rights reserved.
H. Zhou et al.
subsequent use or synthesis. However, low-temperature cold sources are
expensive, and the heater exchangers are prone to frost, which affects
the capture efficiency (Song et al., 2019). Tong et al. introduced mem­
brane separation technology to capture CO2. Membrane separation
technology has the advantages of a high energy efficiency, high selec­
tivity, low investment cost, and small footprint (Tong and Ho, 2017).
However, Xie et al. discovered it suffers from high maintenance costs,
reduced gas fluxes, and reduced selectivity (Xie et al., 2019). Al-Zareer
et al. proposed a coal gasification-based integrated system to produce
electrical power and hydrogen. The hydrogen produced is stored in a
chemical storage medium, ammonia. The system showed good perfor­
mance with 48.7% energy efficiency and 48.4% exergy efficiency
(Al-Zareer et al., 2017).
Coal direct chemical looping hydrogen (CDCLH) production is the
most attractive technology. It allows for high-efficiency hydrogen pro­
duction with low NOx emissions, and CO2 is generated separately. This
method is derived from coal chemical looping combustion (CLC). The
oxygen carrier (OC) oxidizes the fuel in the fuel reactor (FR) and then is
re-oxidized in the air reactor (AR). As shown in Fig. 1, a typical CDCLH
contains three reactors. In the FR reactor, the coal is completely
oxidized, and it is gasified into CO2. The CO2 concentration in the
reactor can reach 99%, which is very conducive to CO2 capture, and
metal oxides are simultaneously reduced. In the steam reactor (SR), the
reduced metal oxide reacts with water vapor to generate H2, and the
unreacted water vapor condenses to separate pure hydrogen. García-
Díez et al. discovered in the AR reactor, metal oxides are regenerated
and can be reused in the FR reactor, and pure N2 can be obtained by
controlling the air entering the AR (García-Díez et al., 2017).
In addition, some researchers have conducted considerable research
on the CDCLH production process. Zeng et al. used Aspen Plus to
establish a simulation of CDCLH production with electricity generation
and used conservative data to conclude that the CDCLH process may also
exhibit a thermal efficiency close to 78% (higher heating value, HHV)
when converts coal into hydrogen while capturing >90% of the CO2
produced (Zeng et al., 2012). Ohio State University (OSU) established a
three-reactor CDCLH pilot plant and obtained results for coal gasifica­
tion and conversion into CO2 using coal in a continuous reaction lasting
200 h. The high durability of the oxygen carrier was confirmed (Tong
et al., 2014). Aziz et al. proposed an integrated system for hydrogen and
electricity production based on coal drying, coal chemical looping,
combined cycle, and hydrogenation. The proposed system achieved high
values for hydrogen production and power generation efficiencies,
which are 71.4% and 19.9% (Aziz et al., 2017). Zhang et al. established a
250-kWh CDCLH plant pilot plant, and after 288 h of continuous use
with a coal conversion rate >96%, a CO2 purity of >97% was obtained,
indicating the huge energy and carbon capture advantages of CDCLH
technology in the power generation process (Zhang et al., 2021).
Fig. 1. Flowsheet of the CDCLH process.
2
Journal of Cleaner Production 362 (2022) 132445
Surywanshi et al. fully utilized the CO2 produced in the CDCLH process
through formic acid synthesis and improved the energy efficiency of
factory production (Surywanshi et al., 2019). Pan et al. established a
hydrogen and ammonia co-generation system based on double chemical
looping. It was found that the production of H2 and N2 using the double
chemical looping is higher than that of a single independent system (Pan
et al., 2021). Sun et al. proposed two methanol production routes from
biomass through direct chemical looping technology, and concluded
that the new process has a good techno-economic performance
compared with the traditional biomass-to-methanol (Sun and Aziz,
2021).
Moreover, the metal oxygen carrier in the CDCLH process has been
studied by various researchers. Adánez et al. prepared 240 potential
oxygen carriers based on four inorganic oxides and five inert materials,
and they investigated the properties of metal oxides with different
qualities (40%–80%) of the inert materials (Adánez et al., 2004). Leion
et al. studied the possibility of using ilmenite as an oxygen carrier and
confirmed its good prospects (Leion et al., 2008). In the past two de­
cades, nickel-based oxygen carriers have received widespread attention,
but they have been abandoned because of their high costs, susceptibility
to inactivation due to sulfur, and harmful characteristics to the human
body and the environment (Abad et al., 2006). Iron-based oxygen car­
riers are effective alternatives to nickel-based oxygen carriers. They are
not easily affected by sulfur and show high activity in the hydrolysis
reaction. This means that iron-based oxygen carriers produce synthesis
gas during chemical looping, chemical looping combustion, direct
chemical looping hydrogen production, and other processes, and thus,
they can be widely used. In addition, copper, manganese, and cobalt
have also been studied as potential oxygen carriers, but they have been
ignored due to their high prices (De Vos et al., 2020).
Based on the above investigation and analysis, the CDCLH process
can produce a large amount of high-concentration CO2, pure H2, and
pure N2 with low energy consumption. Available papers have generally
focused on the process of producing hydrogen and electricity from coal
by CDCLH technology, while there have been few studies on the sub­
sequent utilization of CO2, H2, and N2. Based on the characteristics of
CDCLH technology, we developed a CDCLH-based coal-to-urea process.
The CO2, H2, and N2 from CDCLH can be used as raw materials for
synthetic ammonia and urea, eliminating the air separation and the
traditional coal-to-gas conversion process with high energy consump­
tion. Aspen Plus was used to model and optimize the process in com­
bination with techno-economic and environmental analysis. Fe2O3 was
used as the metal oxygen carrier. Fe2O3 is a metal oxidizer with a low
price, excellent performance, and high stability (Adánez et al., 2004).
The purpose of this study was to optimize the process of the coal direct
chemical looping hydrogen production process (CDCLTU) system,
evaluate the economic investment extensively and environmental
H. Zhou et al. Journal of Cleaner Production 362 (2022) 132445

performance. Compared with the traditional coal-based urea process, the AR, and a large amount of heat is released to maintain the heat
this process has advantages in the energy efficiency, equipment costs, required by each reactor. The oxygen-deficient air is also discharged
urea production price, return on investment, and lower CO2 emissions, from the air reactor.
laying the foundation for its industrial application.
2.1. Coal gasification unit
2. Conceptual design and simulation model
As shown in Fig. 4, the lump coal is pulverized, ground, and mixed
Aspen Plus is process simulation software that can be used for
with a water-coal slurry at a water ratio of 60% (Qin et al., 2018). The
calculation tasks of different chemical processes and unit operations,
water-coal slurry and O2 from the air separation system are used to
including modeling, simulation, optimization, safety specifications, and
generate syngas in the gasifier, then the syngas and steam generates H2
process economic analysis, and it can accurately predict the results
and CO2 in the WGS reactor. The crude syngas is passed into the puri­
before plant construction (Kevat and Banerjee, 2018; Yan et al., 2015).
fication and separation unit. According to previous investigations, the
In this study, we adopt Aspen Plus V11 for modeling and simulation. The
low-temperature methanol scrubbing gas has the advantages of a high
key models and physical properties in Aspen Plus of the CDCLTU and
purification degree, high selectivity, and low solvent price. Therefore,
coal-to-urea process (CTU) are shown in Table 1.
low-temperature methanol scrubbing is selected to extract and separate
It is worth noting that coal cannot be defined as a conventional solid
the crude syngas (Li and Cheng, 2020). The crude syngas is removed in
in Aspen Plus and cannot be found from the Aspen Plus substance li­
the scrubber to remove soluble gases (e.g., H2S, COS, and CO2), and then
brary, so MIXCINC is used to define coal as an unconventional solid
H2 is separated. The CO2 and other soluble gases in the methanol solu­
(Huang et al., 2018). The approximate and elemental analysis results of
tion can be removed separately. Part of the separated CO2 is sent for
the coal are shown in Table 2.
ammonia synthesis, and the remaining CO2 could be stored.
Conventional coal-to-urea processes mainly include an air separation
unit (ASU), coal gasification unit (CGU), water-gas shift unit (WGSU),
acid gas removal unit (AGRU), ammonia production unit (APU), and 2.2. Coal direct chemical looping hydrogen unit
urea production unit (UPU). As shown in Fig. 2, the raw coal is crushed,
ground, dried, and underwent other pretreatment processes, after which As shown in Fig. 5, three reactors are unique to the specific CDCLH
it is mixed with water to form a coal-water slurry. The coal-water slurry system. The fuel reactor (FR) completely converts the carbon in the coal
and oxygen from the air separation unit react in the gasification reactor into high-concentration CO2. The fuel reactor is a moving bed model.
to form a crude syngas. The crude syngas is passed into the purification The coal is fed in the middle stage of the fuel reactor, and Fe2O3 is fed in
unit to remove acidic gases such as hydrogen sulfide, after which it is the top stage of the fuel reactor. The reactions that take place in the fuel
passed into the conversion unit. CO and water vapor reacted to generate reactor operating at 850–1050 ◦ C and 1–30 atm are as follows:
hydrogen and a large amount of CO2. By adjusting the production pro­
Coal → C + CH4 + H2 + O2 + N2 + S + H2O + Ash, (1)
cess, it is possible to generate a hydrogen ratio sufficient for the pro­
duction target and then pass the CO2-rich gas into low-temperature C + CO2 → 2 CO, (2)
methanol to extract pure CO2 for storage or use as a raw material for
the production of urea. The CO2-removed gas is purified by means of C + H2O → CO + H2, (3)
low-temperature liquid nitrogen scrubbing to extract pure hydrogen, CH4 + 4 Fe2O3 → CO2 + 2 H2O + 8 FeO, (4)
and the hydrogen and nitrogen from the air separation system are used
to synthesize ammonia. After the target ratio of CO2 and ammonia is 3 Fe2O3 + C → 2 Fe3O4 + CO, (5)
achieved, it is passed into the urea synthesis unit to begin synthesizing
2 Fe2O3 + C → 4 FeO + CO2, (6)
urea.
The CDCLTU process includes the CDCLH unit, AGRU, APU, and Fe3O4 + CO → 3 FeO + CO2, (7)
UPU. As shown in Fig. 3, compared with the conventional CTU, the coal
direct chemical looping hydrogen removes the high-cost air separation FeO + C → Fe + CO, (8)
unit and produces pure CO2, H2, and N2, eliminating the subsequent gas FeO + CO → Fe + CO2, (9
separation process. The Fe2O3 enters the fuel reactor (FR) and reacts
with coal. The coal is completely gasified into a large amount of carbon H2 + Fe2O3 → H2O + 2 FeO, (10)
dioxide. At the gas outlet of the combustion reactor, it is mainly a mixed
H2 + FeO → H2O + Fe. (11)
gas of CO2 and water vapor, and it can be separated by simple cooling
and separation. This results in a gas stream containing a large amount of Through the above reactions, Fe2O3 is completely reduced to Fe/FeO
carbon dioxide. Subsequently, the reduced oxygen carrier (Fe/FeO) is in the fuel reactor. In addition, a small amount of water vapor is passed
passed into the steam reactor (SR), where it reacts with water vapor to into the bottom of the reactor to strengthen the coal coking reaction. In
generate hydrogen, and the reduced oxygen carrier is oxidized to addition, a small amount of hydrogen in the coal is completely oxidized
magnetite (Fe3O4). Magnetite is further oxidized to iron oxide (Fe2O3) in to H2O. CO2 containing a small amount of steam and a very small
amount of acid gas is removed at the top of the reactor. The vapor can be
separated by a simple condensation operation. The simulation shows
Table 1
Selected models and property methods of each unit.
that the CO2 content in the gas is close to 99% at this time.
In the SR, water vapor and the reduced oxygen carrier react to
Unit Key equipment Model Property
generate H2. Fe/FeO is accessed at the top of the moving bed, and water
method
vapor is injected at the bottom of the moving bed. The Fe/FeO and water
Gasification unit Gasifier Ryield PR-BM
vapor are in countercurrent contact. The reactions in the steam reactor
FR, SR, SR reactor Rgibbs PR-BM
Gas purification Scrubber Flash PENG-ROB
at 600–900 ◦ C and 1–30 atm are as follows:
Ammonia synthesis Catalytic oxidation Rplug RK-ASPEN
unit reactor
Fe + H2O ↔ FeO + H2, (12)
Flash tank Flash PSRK
Urea synthesis unit Stripper RadFrac SR-POLAR
3 FeO + H2O ↔ Fe3O4+ H2. (13)
Synthesis reactor Rplug SR-POLAR
In the AR, Fe3O4 is completely oxidized to Fe2O3 and released a large

3
H. Zhou et al. Journal of Cleaner Production 362 (2022) 132445

Table 2
Approximate and elemental analysis results of coal.
Approximate analysis (wt.%, ad) Elemental analysis (wt.%, ad)

M FC V A C H O N S

Coal 6.1 50.01 24.71 19.18 66.31 4.43 8.5 0.76 0.82

Fig. 2. Simplified process flow diagram of the CTU process.

amount of heat. The temperature can reach 1050–1250 ◦ C, and the participating in the cycle contains a considerable amount of heat. Thus,
resulting Fe2O3 enters the fuel reactor at a high temperature. The high- the gas is divided into three parts, R1, R2, and R3, to exchange heat with
temperature oxygen-deficient air can be used for steam and electricity the feed N2 and the other feed stream.
generation. The reaction in the air reactor is as follows: This process involves the following reaction:

4 Fe3O4 + O2 → 6 Fe2O3. (14) N2 + 3H2 ↔ 2NH3. (15)

The corresponding rate equation is as follows (Morud and Skogestad,

1998):
( )
2.3. Ammonia production unit 2f PPN2 P1.5 PPNH3
(16)
PH2
rrNH3 = k1 − k− 1 1.5
ρcat PPNH3 PPH2
As shown in Fig. 6, the ammonia production unit performs a tradi­
tional ammonia synthesis process, which mainly includes a feed gas where P is the partial pressure (bar), ρcat is the bulk density of the
pretreatment part and a reaction part. Owing to the low conversion rate catalyst (kg/m3), f is the factor for correcting the catalyst activity (f =
of a single reaction, the recycling of raw materials is an important part of 4.75), the exponential factors for the forward and reverse reactions are
the process. After N2 is boosted by the compressor, a small amount of k1 = 1.79 × 104e− 10475/T, k-1 = 2.75 × 1016e− 23871/T, and T is the
oxygen contained in it is removed, and the ratio of H2 to N2 is H2/N2 = 3. temperature (K).
It then enters the dryer. After removing the small amount of H2O con­
tained in the gas, it enters the catalytic reactor after heat exchange and 2.4. Urea production unit
compression. After the reaction is complete, the product is condensed
through the heat exchanger to produce liquid ammonia. The remaining As shown in Fig. 7, the urea production unit uses the CO2 stripping
gas is continued to participate in the reaction through circulation, and a method. The CO2 stripping method mainly includes a CO2 stripping part,
small amount of gas is discharged as the purge gas. Since the ammonia a urea synthesis part, and a urea refinement part. In the CO2 stripping
production process involves an exothermic reaction, the gas part, a small amount of urea and a large amount of ammonium

4
H. Zhou et al. Journal of Cleaner Production 362 (2022) 132445

Fig. 3. Simplified process flow diagram of the CDCLTU process.

Fig. 4. Simulation flowsheet of the coal gasification unit.

carbamate from the urea synthesis reactor enter the CO2 stripping tower.
Ammonium methylate is decomposed into CO2 and NH3 and is recycled
into the urea synthesis part. The high content of urea at the bottom of the
CO2 stripper is sent to the urea refining part.
In the urea synthesis part, the high-pressure NH3 and the mixed gas
from the CO2 stripping part enter the high-pressure condensation reactor
R2 together. In this reactor, CO2 and NH3 generate ammonium carba­
mate, and the product is sent to the plug flow reactor to synthesize urea.
After the reactor product is flashed, the gaseous substance is passed into
the scrubber from the top of the flash tank, and the ammonium carba­
mate from the urea refining part is passed into the scrubber to absorb
unreacted CO2 and NH3, discharging O2, N2, and other gases at the same
time.
In the urea refining part, the urea from the CO2 stripper enters the
reactor R2. In the reactor R2, the unreacted ammonium carbamate is
decomposed into CO2 and NH3. Then, the liquid-phase urea is extracted
as the final product, and the gas-phase CO2 and NH3 are regenerated into
ammonium carbamate, which then enter the scrubber to absorb CO2 and
NH3.
The main reaction equation for the synthesis of urea is as follows:
2 NH3 + CO2 → NH₂COONH₄, (17)
NH₂COONH₄ → Urea + H2O. (18)
3. Parameter optimization and simulation
3.1. Parameter optimization
The proposed CDCLTU adopts the state-of-the-art CDCLH technology
replaces the air separation and water gas conversion of the traditional
CTU. Thus, in this paper, three key parameters must be optimized for the
FR, SR, and AR of the CDCLH technology, respectively. The first
parameter is to optimize the consume of Fe2O3 in the FR. In the litera­
ture, the O/C ratio has often been investigated to optimize the reaction
parameters, but in actual production, it is more practical to use the mass
ratio of Fe2O3 to coal. The O/C ratio only includes the carbon in coal.
Coal is consisted of C, H, O, N, and S, other than C in coal, the H, N, and S

5
H. Zhou et al. Journal of Cleaner Production 362 (2022) 132445

Fig. 5. Simulation flowsheet of the CDCLH unit.

Fig. 6. Simulation flowsheet of ammonia production unit.

Fig. 7. Simulation flowsheet of the urea production unit.

6
H. Zhou et al. Journal of Cleaner Production 362 (2022) 132445

in coal also consume oxygen in Fe2O3 to be converted to stable com­

pounds. Therefore, the mass ratio of Fe2O3 to coal can better reflect the
actual consumption of Fe2O3.
Fig. 8 shows the carbon products of the FR under different mass ra­
tios of Fe2O3 to coal. As the Fe2O3/coal mass ratio changes from 0.1 to
3.8, the CO content gradually increases, while that of the CO2 increases
slowly. This mainly means that the O carried by the Fe2O3 is insufficient,
which leads to insufficient combustion. As the Fe2O3/coal mass ratio
gradually increases to about 7.3, the CO content gradually decreases and
CO is converted to CO2. Since the coal is gasified earlier, the main re­
action of CO combustion into CO2 is occurred. Thus, in the FR, the rate of
CO2 generation gradually increases. In addition, in the FR, only a small
amount of CH4 is produced, and the combustion is completed as the O
content gradually increases. Therefore, in this simulation, the optimal
Fe2O3/coal mass ratio is determined to be 7.3.
The second optimized parameter is the mass ratio of seam to Fe in the
SR; and the corresponding effect on the material flow at the outlet of the
SR is shown in Fig. 9. It is found that as the steam/Fe mass ratio in­
creases, more steam promotes reactions (12) and (13), resulting in
improved H2 quality, better Fe/FeO conversion to Fe3O4. When the
steam/Fe mass ratio reaches 0.47, the Fe/FeO is completely converted
into Fe3O4, the flow rate of H2 reaches the maximum and then no longer Fig. 9. Influence of steam/Fe on the material flow rate at the reactor outlet.
increase. Therefore, in this study, the steam/Fe mass ratio is determined
to be 0.47 to achieve complete conversion of Fe/FeO and maximum H2
production.
The third optimized parameter is mass flow rate of air in the AR.
Fig. 10 shows the influence of the air flow rate on the iron oxide flow
rate and the outlet gas compositions. At the beginning, air enters the AR,
and Fe3O4 is oxidized by O2 to Fe2O3. Since O2 is consumed, the outlet
gas is basically only N2. The purity of N2 is very high, and it can
participate in the subsequent ammonia synthesis process. As the Fe3O4 is
converted, the N2 content of the outlet gas began to decrease. To ensure
the complete conversion of the Fe3O4 and higher concentration of N2
added in the ammonia synthesis process, the air inlet flow rate is finally
determined to be 21,000 kg/h.

3.2. Verification and simulation

The CDCLH simulation results are shown in Table 3 and are similar to
reference data. However, there is still some inconsistencies in the FR of
the CDCLH. The H2O purity in this study is 9.2 percentage points lower
than the reference, while CO2 purity is 9.2 percentage points higher,
Fig. 10. Influence of the air mass flow on the material flow and gas ratio at the
reactor outlet.

because the coal fuel in this study is different from the natural gas used
in the reference. Based on the simulation of the CDCLH, the whole
CDCLTU is simulated. Detailed simulation results are shown in Tabel A2
in the Appendix. Tabel A1 in the Appendix is the simulation results for
the CTU.

4. Technical analysis

In this section, C utilization, CO2 emissions, process energy con­

sumption of the CDCLTU, and public works consumption are selected for
evaluation, and the CDCLTU and CTU are compared.

4.1. Hydrocarbon element flow

Fig. 11 compares the flow of C and H in raw coal under different

Fig. 8. Influence of Fe2O3/coal on carbon fraction and hydrogen fraction at the
reactor outlet.
process flows. In the CTU, the C and H in the coal are gasified at the same
stage, and the C is gasified into CO2 and CO. The H is vaporized into H2
and water vapor. The CO with steam generates CO2 and H2 in the WGS
unit, and then H2 and CO2 are separated into the APU and UPU units,
respectively. In the CDCLTU, all the C in the coal is oxidized to CO2, and

7
H. Zhou et al. Journal of Cleaner Production 362 (2022) 132445

Table 3
Coutput Curea
Verification of the CDCLH. δ1 = × 100% = × 100% (19)
Cinput Ccoal
Ref. result Sim. Unit Ref.
result ( )
Cinput − Coutput Curea
FR parameters Khan and Shamim δ2 = × 100% = 1 − × 100% (20)
Cinput Ccoal
Heat duty 0.0 0.0 MW (2016)
CO purity ~0.0 ~0.0 mol.
%
where Cinput represents the carbon input of the system, Coutput represents
CO2 purity 33.0 42.2 mol. the carbon output of the system, Curea represents the amount of C in
% urea, and Ccoal represents the amount of C in the feed coal.
H2O purity 67.0 57.8 mol. Fig. 12 compares the urea production and C utilization rates under
%
the two processes. The CTU and CDCLTU use the same coal fed at 200 t/
Fe2O3 conversion 100 100 %
Fe2O3/Coal – 7.3 kg/kg hr and carbon input is 11751.8 kmol/hr. The urea production of the CTU
SR parameters Edrisi et al. (2014a) is 6982.69 kmol/hr and that of the CDCLTU is 8861.17 kmol/hr. By
Operating 700–750 700 ◦
C integrating the CDCLH process into the traditional coal gasification urea
temperature production process, the C utilization rate increases from 59.42% to
Heat duty 0.0 0.0 MW
Steam conversion 97 98 %
75.40%. This is mainly because the CDCLH process H2 comes from
Steam/Fe – 0.47 kg/kg reduced oxygen carriers and water vapor in the reaction. The H2 pro­
AR parameters Edrisi et al. (2014b) duction depends on the content of reduced oxygen carriers, and the
Operating 1200 1200 ◦
C content of reduced oxygen carriers depend on the contents of C and H in
temperature
the coal. In the CTU, H2 comes from H in the coal and CO conversion.
Fe3O4 conversion 100 100 %
N2 purity 99.8 99.7 mol. This source is usually unstable. The excessive gasification of C in coal
% leads to an increase in the CO2 content and a decrease in the CO content.
Operating pressure 1.0 1.0 MPa The H in coal is also oxidized to form H2O, resulting in slightly less H2 in
the CTU than in the CDCLTU. Low H2 production leads to low produc­
tion of synthetic ammonia and urea, so CDCLTU has a higher CO2 uti­
H is completely oxidized to H2O in the fuel reactor. Subsequently, the
lization rate than CTU, and CO2 emissions are lower than CTU.
oxidized oxygen carrier reacts with water vapor to generate H2 in the
Although the H2 production is higher than that in the CTU, it still
steam reactor, and CO2 and H2 are produced at different stages. In the
causes high CO2 emissions. The novel coal-to-urea process adopts
CTU, the source of H2 is the H in the coal itself and the conversion of CO
advanced coal chemical looping hydrogen production technology,
with water vapor in the conversion unit. In the CDCLTU, all the H2
which makes it has higher energy efficiency, lower CO2 capture energy
comes from the hydrolysis reaction between the reduced oxygen carrier
consumption, and higher hydrogen production comparing to that of the
and water.
conventional CTU process. However, for the novel or conventional CTU
process, the CO2 and H2 in urea synthesis reaction are both converted
4.2. Carbon utilization
from coal. The new and the conventional process have the same coal
processing capacity. The elements of C and H in coal are finally con­
The C utilization rate and C emissions rate are necessary indices for
verted into CO2, H2, and H2O. The new process has higher hydrogen
investigating the CDCLTU and CTU. The C element utilization rate and
production than that of the conventional process as higher efficiency,
the C emissions rate are defined respectively as follows:
which will consume more CO2 to urea. However, there is a limit to this
transformation. This is determined by the nature of coal (rich in carbon

Fig. 11. C and H flow diagrams for the (a) CTU and (b) CDCLTU.

8
H. Zhou et al. Journal of Cleaner Production 362 (2022) 132445

Fig. 12. Differences in the urea production and carbon utilization rates under
the two processes.
Fig. 13. Energy consumption of carbon dioxide capture in CTU and CDCLTU.

and poor in hydrogen). Therefore, the novel CDCLTU process also has
high CO2 emissions. In order to further reduce CO2 emissions, there is 4.4. Energy efficiency of hydrogen production
need to introduce other sources of hydrogen for realizing complemen­
tary of carbon and hydrogen, such as coke oven gas hydrogen produc­ According to the first law of thermodynamics, the energy efficiency
tion and electrolysis hydrogen production. In our next work, we have is defined as the ratio of the total output energy to total input energy:
conducted to adopt coke oven gas for hydrogen supplement by chemical Eout
looping hydrogen technology or reforming technology. η= (22)
Ein

4.3. Energy consumption of CO2 capture
Since the CDCLTU produces almost pure CO2 gas, it is expected to
have a huge advantage in the energy consumption of CO2 capture. The
excess CO2 remaining after CO2 participated in the synthesis of urea is
captured. The traditional process undergoes CO2 separation and capture
after the WGSR. Since CO2 needs to be separated from the hydrogen in
the syngas, it is expected to consume a considerable amount of energy.
CO2 capture mainly considers the energy consumption of gas sepa­
ration, which is calculated as follows:
xCO2 ln xCO2 + (1 − xCO2 )⋅ln(1 − xCO2 )
Wsep = − RT0 Fsep
xCO2 ηsep
where Eout represents the total energy output during the process,
including H2 and electricity, and Ein represents the total energy input in
the process (including utilities, water vapor, electricity, and raw mate­
rials) (Zhang et al., 2011).
Fig. 14 shows that the CDCLH had a 79.7% energy efficiency in the
hydrogen production process and had a CO2 capture rate of 99%. The
traditional coal hydrogen production process has only a 58% energy
efficiency at a CO2 capture rate of 90%. In the hydrogen production
process stage, the new process shows a high energy efficiency and CO2
capture rate. Owing to the combined production of hydrogen and elec­
tricity, about 12.5 MW of net electricity can be generated during the
(21) process of synthesizing 10 t of hydrogen. Because CO2 is used in the
subsequent urea synthesis process, a higher CO2 capture rate would be

where R is the molar gas constant of 8.314 J/(mol⋅K), T0 is 298.15 K,

xCO2 is the concentration of mixed gas carbon dioxide, Fsep is the molar
flow rate of the separated gas (kmol/s), and ηsep is the separation effi­
ciency. It should be noted that the application of this formula is based on
the assumption that the gas composition is a binary system of CO2 and
other inert gases.
Fig. 13 shows the energy consumption of CO2 capture in the CTU and
CDCLTU. To better illustrate the difference between the two, it is
assumed that the separation efficiencies of both are 1. Typically, with a
high concentration, the separation efficiency of CO2 is higher than that
with a low concentration. The traditional CTU has a CO2 capture energy
consumption of 26850.64 kW, while the CDCLTU using the chemical
looping hydrogen process has a CO2 capture energy consumption of
796.018 kW, which is a 97.04% reduction in the energy consumption.
This is mainly because the chemical looping hydrogen process allows
CO2 and H2 to be produced at different times, resulting in high con­
centrations of CO2. The CO2 concentration is close to 99%. Moreover,
because CO2 is produced alone, the total flow rate is also reduced by
0.57 kmol/s. CO2 is the mainly responsible for the significant reduction
in energy consumption for capture.

Fig. 14. Energy efficiency of hydrogen production process.

9
H. Zhou et al. Journal of Cleaner Production 362 (2022) 132445

beneficial for urea synthesis. Compared to the traditional coal-to- Table 5

hydrogen CO2 capture of up to 90%, the CO2 produced by the new Ratio factors for capital investment.
process is more conducive to urea synthesis and reduction of the energy Component Range (%) Assumed value (%)
consumption.
(1) Direct investment
(1.1) Equipment 16–40 30
5. Economic analysis (1.2) Equipment installation 7–14 8
(1.3) Piping 3–9 5
5.1. Evaluation method (1.4) Electrical systems 2–10 6
(1.5) Buildings (including services) 5–16 12
(1.6) Instruments and controls 2–7 5
The economics of the CDCLTU are evaluated by the total capital (1.7) Land 1–2 1
investment (TCI), total production cost (TPC), and payback period (2) Indirect investment
(PBP). As shown in Table 4, these assumptions are used to estimate the (2.1) Engineering and supervision 4–19 11
(2.2) Construction expenses 4–18 10
economic performances of the CDCLTU and the traditional CTU.
(2.3) Contractor’s fee 2–7 5
(2.4) Contingency 5–17 7
5.1.1. Total capital investment (3) Fixed capital investment (1) + (2) 100
The TCI consists of the fixed capital investment (FCI) and the (4) Working capital 10–20 15
working capital (WC) (Orhan et al., 2008). The fixed capital investment (5) Total capital investment (3) + (4) 115

refers to the facility costs and construction costs required for factory
construction, and it consists of direct and indirect investments. Working
capital investment is used to maintain operation. It is composed of in­ Table 6
ventor of raw materials, finished products, semi-finished products, and Total production cost (TPC) for the CDCLTU.
taxes, etc.(Liu et al., 2017). The calculation of the TCI is based on the (A) Raw material Coal 457.63 CNY/t (Zhang et al., 2020)
calculation of the ratio factor of the FCI and the component capital in­ Oxygen carrier 1909.29 CNY/t (Li et al., 2020)
vestment, expressed as follows (Man et al., 2016): (B) Utilities Electricity 0.65 CNY/kWh; Water 3 CNY/t
(C) Maintenance and operating
( )
∑ (i) Clerical labor and
TCI = FCI⋅ 1 + RFi (23) direct supervisory 20% of (iii)
i (ii) Repairs and maintenance 2% of FCI
(iii) Operating labor 30 laborers (60,000 CNY/laborer/year)
RFi represents the ratio factor of the component capital investment, (iv) Operating supplies 0.7% of FCI
and the ratio factors are shown in Table 5 (Li et al., 2020). (v) Laboratory charge 15% of (iii)
(D) Depreciation Lifetime 25 years; salvage value 4%
(E) Administrative cost 2% of (H)
5.1.2. Total production cost
(F) Administrative cost 2% of (H) D
TPC includes the raw material costs, utility consumption, labor costs, (G) Plant overhead cost 60% of (i) + (ii) + (iii)
factory depreciation and residual value, administrative investment, and (H) Total production cost (A) + (B) + (C) + (D) + (E) + (F) + (G)
maintenance and operating costs. Table 6 shows the main assumptions
*Urea production cost = TPC/urea yield.
when calculating the TPC. It should be noted that Okoli et al. developed
a straight-line method to estimate the depreciation based on a 4%
for 77% of the total FCI). This is because the lower investment in CDCLH
salvage value and a 25-year lifetime. TPC is calculated for the CDCLTU,
of the CDCLTU process replaces air separation and water gas conversion
as shown in Table 6 (Okoli and Adams, 2014).
of the traditional CTU. Thus, the FCIs of the CDCLTU and CTU are 95.4
× 108 CNY and 313.1 × 108 CNY. The FCI of the CDCLTU is 69.53%
5.1.3. Investment payback period
smaller than that of the CTU.
The investment payback period (PBP) is calculated as follows:
The higher FCI of the CTU leads to a higher TCI, which means that
FCI the CDCLTU requires less investment in the initial stage of production.
PBP = (24)
PAT + D The TCIs of the CDCLTU and CTU are 368.35 × 108 CNY and 112.24 ×
108 CNY, respectively. The TCI of the CDCLTU is reduced by 69.53%
where PAT is the profit after tax, and D is the depreciation (Cho et al., compared to that of the CTU, which represents huge investment
2013). potential.
Fig. 16 shows the TPCs and payback period of the two processes. A
5.2. Investment and cost analysis Lower TPC at close urea production results in lower unit urea cost,
which is expected to bring more profits. The unit urea cost of the
Fig. 15 shows the FCIs of the CDCLTU and CTU processes. The FCIs of CDCLTU is 590.0 CNY/t-urea, which is 12.10% lower than that of the
the ammonia synthesis unit and urea synthesis unit are almost the same, conventional CTU (671.18 CNY/t-urea). Detailed compositions of the
but the largest difference is in the hydrogen production process. The FCI production cost are shown in Fig. 16. It is concluded that the cost
of the hydrogen production of the CDCLTU is 30.53 × 108 CNY (ac­ effectiveness of the CDCLTU benefits from the lower depreciation cost
counts for 32% of the total FCI), as shown in Fig. 15, which is 87.34% brought by a lower FCI and increased urea production. The cost of raw
lower than that of the conventional CTU at 241.09 × 108 CNY (accounts materials accounted for 62.18% and 86.74% of the TPC respectively for
the CTU and CDCLTU processes, showing the importance of coal prices
Table 4 for the production cost. In addition, the economic performance is also
Assumptions for economic analysis. reflected in the payback period. Compared with the payback period of
Value 7.5 years for the CTU, the CDCLTU only needed 3.5 years to recover the
initial investment. This is mainly due to less post-maintenance, labor,
Benchmark year 2020
Operating hour, h per year 7200 and utility consumption caused by a lower FCI. The huge advantages of
Plant lifetime, years 25 the total capital investment and the investment payback period
Tax rate 25% demonstrated the broad prospects of the CDCLTU to replace the CTU.
Discount rate 10%
Urea price, CNY/t 1845.3

10
H. Zhou et al. Journal of Cleaner Production 362 (2022) 132445

Fig. 15. Fixed capital investment (FCIs) of CTU and CDCLTU.

Fig. 16. Total production costs (TPCs) and payback period of CTU and CDCLTU.

5.3. Sensitivity analysis drops to 487.65 CNY/t and rises to 692.42 CNY/t, respectively. The
factory life and labor prices have little impact on the urea prices. The
Economic sensitivity analysis investigates the factors that have the factory life increases by 5 years, and the urea price drops by about 11
greatest impact on urea product terminal prices. Coal prices, plant CNY. If it increases for 5 years, it will increase by about 16 CNY. The
lifetime, and labor prices are used as parameters to analyze the factors impact of labor prices on the urea prices is around 2 CNY.
affecting the urea product prices, assuming that each parameter deviates
from the benchmark condition by 20%. Fig. 17 shows the relevant re­ 6. Environmental analysis
sults. In the case of coal prices falling and rising by 20%, the price of urea
The CO2 emission includes direct emission and indirect emission, as
shown in Eq (22).
d ind d
∑
ECO + ECO ECO + ECj × pj,CO2
ECO2 = 2 2
= 2
(25)
mpro mmeth

In Eq. (25), EdCO2 and Eind

CO2 present the direct emission and indirect
emission of the urea production process; ECj is the utilities consumption
(steam and electricity) of the urea production process and pj,CO2 is the
CO2 emission factor from process utilities consumption. Fig. 18 shows
the CO2 emissions of the CTU and CDCLTU processes. In Fig. 18, the CO2
emission consists of direct emission and indirect emission of the process
energy consumption of coal, steam, and electricity. The CO2 emission of
the CTU process is 3.08 t⋅CO2/t-urea and that of the CDCLTU process is
1.39 t⋅CO2/t-urea. The CO2 emission of the CDCLTU process is 65.93%
lower than that of the CTU process. The CDCLTU process has higher urea
Fig. 17. Sensitivity study of the effects of variables on the urea production cost.

11
H. Zhou et al.
Fig. 18. CO2 emission of the CTU and CDCLTU processes.
production than that of the CTU process. Therefore, the unit urea
emission of the CDCLTU process created by coal consumption is lower
than the CTU process based on the same coal processing capacity. The
conventional CTU consumes more steam for coal gasification and water-
gas shift, and much more electricity for process consumption, which
leads to higher CO2 emission. For the CDCLTU process, electricity
cogeneration in the CDCLH unit will compensate for most of the
consumed electricity, bringing lower CO2 emission. These conclusions
can be justified by the above thermodynamic analysis.
7. Conclusion
This study proposes a new process that integrates a chemical looping
process into the traditional coal-to-urea process. The coal chemical
looping hydrogen process replaces the coal gasification and shift puri­
fication process in the traditional coal-to-urea process, reducing the
process flow of coal synthesis of ammonia and urea, which reduces the
energy consumption of CO2 capture and yields pure H2 and greatly
improves the economic benefits. Through modeling and techno-
economic and environmental analysis of the CTU and CDCLTU, the
conclusions are as follows.
1. When the Fe2O3/coal (kg/kg) ratio is 7.3, the CDCLTU can convert
all the C in coal into CO2 and produce 99% CO2 in the fuel reactor,
which is 97.04% lower than the CTU CO2 capture energy consump­
tion. This eliminates the high energy consumption of CO2 capture in
the traditional coal-to-urea process.
2. In the steam reactor, pure H2 can be produced. Compared with the
CTU, the energy required by the conversion unit to separate H2 is
Appendix
Flow diagram and main simulation data of CTU and CDCLTU processes are as follows:
12
Journal of Cleaner Production 362 (2022) 132445
removed, with a higher CO2 capture rate. A higher hydrogen pro­
duction energy efficiency is achieved, which increases to 79.7%
compared to the 58% energy efficiency of the CTU.
3. The carbon utilization rate of CDCLTU is 14.49% higher than that of
CTU, and the energy consumption of CO2 capture is reduced by
97.04%. The CDCLH has a 79.7% energy efficiency in the hydrogen
production process and 99% of CO2 capture rate. The traditional coal
gasification for hydrogen production process has only a 58% energy
efficiency at a CO2 capture rate of 90%.
4. The fixed capital investment of the CDCLTU is 69.53% lower than
that of the CTU. The unit urea (t) production cost is reduced by
12.10% and the investment payback period is reduced from 7.5 to
3.5 years. A good return on capital could greatly increase the interest
of investors, and it also means that the coal direct chemical looping
hydrogen process has broad development and application prospects.
In conclusion, coal direct chemical looping for ammonia and fertil­
izer production has higher energy efficiency and better economic per­
formance. However, the ammonia and fertilizer generation by coal
direct chemical looping hydrogen process does not significantly reduce
CO2 emissions. We hope that the chemical looping technology can break
through some of its own limitations and be successfully used in com­
mercial applications. If a clean source of hydrogen can be obtained, the
CO2 emissions can be greatly reduced by the complementary of carbon
and hydrogen. In the next work, we adopt coke oven gas as a hydrogen
source assisted coal to produce ammonia and urea to reduce the CO2
emissions.
CRediT authorship contribution statement
Huairong Zhou: Conceptualization, Methodology, Software. Ying­
wen Ma: Data curation, Writing – original draft. Qingchun Yang:
Validation. Dongliang Wang: Visualization, Investigation. Hongwei
Li: Supervision. Guixian Li: Supervision, Project administration. Yong
Yang: Writing – review & editing. Zongliang Fan: Project administra­
tion, Supervision. Dong Ji: Formal analysis. Ning Li: Validation.
Dongqiang Zhang: Funding acquisition.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
We thank LetPub (www.letpub.com) for its linguistic assistance
during the preparation of this manuscript.
Financial supports from the Foundation of Gansu Province Education
Department (No. 2021QB-041) are gratefully acknowledged.
H. Zhou et al. Journal of Cleaner Production 362 (2022) 132445

Fig. A1. Simplified block diagram of CTU process

Table. A1
Simulation data of CTU process

Stream No. 1 2 3 4 5 6 7

Molar fraction (%)

CO – 43.79 1.02 – – – –
CO2 – 8.12 40.21 – – 32.45 –
H2 – 30.39 58.11 76.16 0.82 – –
H2O – 17.15 0.26 – – – 0.98
N2 – 0.27 0.22 23.84 0.18 – –
H2S+SOx – 0.28 0.18 – – – –
NH3 – – – – 99 67.55 –
Urea – – – – – – 99.02
Molar flow (kmol/h) – 19591.76 24571.38 19366.1 9231.04 13904.15 3766.42
Coal (tonne/h) 200 – – – – –
Temperature (◦ C) 40 1350 40 38 200 100 72
Pressure (MPa) 0.1 6.5 0.1 1.2 6.5 14 14

Fig. A2. Simplified block diagram of CDCLTU process

Table. A2
simulation data of CDCLTU process

Stream No. 1 2 3 4 5 6 7

Molar fraction (%)

CO2 – 64.00 – – 100 32.45 –
H2 – – 96.00 – – – –
H2O – 34.40 4.00 – – – 0.98
N2 – – – 100 – – –
H2S+SOx – 1.60 – – – – –
NH3 – – – – – 67.55 –
Urea – – – – – – 99.02
Molar flow (kmol/h) – 18361.225 10449.462 19366.1 2352.395 9801.3 3360.01
Coal (tonne/h) 200 – – – – –
Temperature (◦ C) 40 1350 1350 1000 40 100 72
Pressure (MPa) 0.1 3 3 1.2 0.1 14 14

13
H. Zhou et al. Journal of Cleaner Production 362 (2022) 132445

References Man, Y., Yang, S., Qian, Y., 2016. Integrated process for synthetic natural gas production
from coal and coke-oven gas with high energy efficiency and low emission. Energy
Convers. Manag. 117, 162–170.
Abad, A., Mattisson, T., Lyngfelt, A., Rydèn, M., 2006. Chemical-looping combustion in a
Morud, J.C., Skogestad, S., 1998. Analysis of instability in an industrial ammonia reactor.
300 W continuously operating reactor system using a manganese-based oxygen
AIChE J. 44 (4), 888–895.
carrier. Fuel 85 (9), 1174–1185.
Okoli, C., Adams, T.A., 2014. Design and economic analysis of a thermochemical
Adánez, J., de Diego, L.F., García-Labiano, F., Gayán, P., Abad, A., Palacios, J., 2004.
lignocellulosic biomass-to-butanol process. Ind. Eng. Chem. Res. 53 (28),
Selection of oxygen carriers for chemical-looping combustion. Energy Fuel. 18 (2),
11427–11441.
371–377.
Orhan, M., Dincer, I., Naterer, G., 2008. Cost analysis of a thermochemical Cu-Cl pilot
Al-Zareer, M., Dincer, I., Rosen, M.A., 2017. Development of an integrated system for
plant for nuclear-based hydrogen production. Int. J. Hydrogen Energy 33 (21),
electricity and hydrogen production from coal and water utilizing a novel chemical
6006–6020.
hydrogen storage technology. Fuel Process. Technol. 167, 608–621.
Pan, X., Ma, J., Hu, X., Guo, Q., 2021. Energy and economic analysis of a hydrogen and
Aziz, M., Zaini, I.N., Oda, T., Morihara, A., Kashiwagi, T., 2017. Energy conservative
ammonia co-generation system based on double chemical looping. Chin. J. Chem.
brown coal conversion to hydrogen and power based on enhanced process
Eng. 36, 190–198.
integration: integrated drying, coal direct chemical looping, combined cycle and
Qin, S., Chang, S., Yao, Q., 2018. Modeling, thermodynamic and techno-economic
hydrogenation. Int. J. Hydrogen Energy 42 (5), 2904–2913.
analysis of coal-to-liquids process with different entrained flow coal gasifiers. Appl.
Bicer, Y., Dincer, I., Vezina, G., Raso, F., 2017. Impact assessment and environmental
Energy 229, 413–432.
evaluation of various ammonia production processes. Environ. Manag. 59 (5),
Sircar, S., Golden, T., 2000. Purification of hydrogen by pressure swing adsorption.
842–855.
Separ. Sci. Technol. 35 (5), 667–687.
Chen, C., Zhu, X., Wen, X., Zhou, Y., Zhou, L., Li, H., et al., 2020. Coupling N2 and CO2 in
Song, C., Liu, Q., Deng, S., Li, H., Kitamura, Y., 2019. Cryogenic-based CO2 capture
H2O to synthesize urea under ambient conditions. Nat. Chem. 12 (8), 717–724.
technologies: state-of-the-art developments and current challenges. Renew. Sustain.
Cho, H.J., Kim, J.K., Cho, H.J., Yeo, Y.K., 2013. Techno-economic study of a biodiesel
Energy Rev. 101, 265–278.
production from palm fatty acid distillate. Ind. Eng. Chem. Res. 52 (1), 462–468.
Sun, Z., Aziz, M., 2021. Comparative thermodynamic and techno-economic assessment of
De Vos, Y., Jacobs, M., Van Der Voort, P., Van Driessche, I., Snijkers, F.,
green methanol production from biomass through direct chemical looping processes.
Verberckmoes, A., 2020. Development of stable oxygen carrier materials for
J. Clean. Prod. 321, 129023.
chemical looping processes - a review. Catalysts 10 (8), 926.
Surywanshi, G.D., Pillai, B.B.K., Patnaikuni, V.S., Vooradi, R., Anne, S.B., 2019. Formic
Edrisi, A., Mansoori, Z., Dabir, B., 2014a. Using three chemical looping reactors in
acid synthesis - a case study of CO2 utilization from coal direct chemical looping
ammonia production process - a novel plant configuration for a green production.
combustion power plant. Energy Sources, Part A Recovery, Util. Environ. Eff. (1),
Int. J. Hydrogen Energy 39 (16), 8271–8282.
1–16.
Edrisi, A., Mansoori, Z., Dabir, B., Shahnazari, A., 2014b. Hydrogen, nitrogen and carbon
Tong, A., Bayham, S., Kathe, M.V., Zeng, L., Luo, S., Fan, L.S., 2014. Iron-based syngas
dioxide production through chemical looping using iron-based oxygen carrier - a
chemical looping process and coal-direct chemical looping process development at
Green plant for H2 and N2 production. Int. J. Hydrogen Energy 39 (20),
Ohio State University. Appl. Energy 113, 1836–1845.
10380–10391.
Tong, Z., Ho, W.W., 2017. Facilitated transport membranes for CO2 separation and
García-Díez, E., García-Labiano, F., de Diego, L., Abad, A., Gayán, P., Adánez, J., et al.,
capture. Separ. Sci. Technol. 52 (2), 156–167.
2017. Steam, dry, and steam-dry chemical looping reforming of diesel fuel in a 1
Xiang, D., Zhou, Y., 2018. Concept design and techno-economic performance of
kWth unit. Chem. Eng. J. 325, 369–377.
hydrogen and ammonia co-generation by coke-oven gas-pressure swing adsorption
Huang, H., Yang, S., Cui, P., 2018. Design concept for coal-based polygeneration
integrated with chemical looping hydrogen process. Appl. Energy 229, 1024–1034.
processes of chemicals and power with the lowest energy consumption for CO2
Xie, K., Fu, Q., Qiao, G.G., Webley, P.A., 2019. Recent progress on fabrication methods of
capture. Energy Convers. Manag. 157, 186–194.
polymeric thin film gas separation membranes for CO2 capture. J. Membr. Sci. 572,
Kevat, M.D., Banerjee, T., 2018. Process simulation and energy analysis of chemical
38–60.
looping combustion and chemical looping with oxygen uncoupling for sawdust
Yan, L., Yue, G., He, B., 2015. Exergy analysis of a coal/biomass co-hydrogasification
biomass. Energy Technol. 6 (7), 1237–1247.
based chemical looping power generation system. Energy 93, 1778–1787.
Khan, M.N., Shamim, T., 2016. Investigation of hydrogen generation in a three reactor
Yang, C.J., Jackson, R.B., 2012. China’s growing methanol economy and its implications
chemical looping reforming process. Appl. Energy 162, 1186–1194.
for energy and the environment. Energy Pol. 41, 878–884.
Leion, H., Lyngfelt, A., Johansson, M., Jerndal, E., Mattisson, T., 2008. The use of
Zeng, L., He, F., Li, F., Fan, L.S., 2012. Coal-direct chemical looping gasification for
ilmenite as an oxygen carrier in chemical-looping combustion. Chem. Eng. Res. Des.
hydrogen production: reactor modeling and process simulation. Energy Fuel. 26 (6),
86 (9), 1017–1026.
3680–3690.
Li, G., Chang, Y., Liu, T., Yu, Z., Liu, Z., Liu, F., et al., 2020. Hydrogen element flow and
Zhang, D., Duan, R., Li, H., Yang, Q., Zhou, H., 2020. Optimal design, thermodynamic,
economic analyses of a coal direct chemical looping hydrogen generation process.
cost and CO2 emission analyses of coal-to-methanol process integrated with chemical
Energy 206, 118243.
looping air separation and hydrogen technology. Energy 203, 117876.
Li, J., Cheng, W., 2020. Comparative life cycle energy consumption, carbon emissions
Zhang, M., Li, G., Mu, H., Ning, Y., 2011. Energy and exergy efficiencies in the Chinese
and economic costs of hydrogen production from coke oven gas and coal
transportation sector, 1980–2009. Energy 36 (2), 770–776.
gasification. Int. J. Hydrogen Energy 45 (51), 27979–27993.
Zhang, Y., Wang, D., Pottimurthy, Y., Kong, F., Hsieh, T.L., Sakadjian, B., et al., 2021.
Liu, Y., Qian, Y., Zhou, H., Xiao, H., Yang, S., 2017. Conceptual design of the coal to
Coal direct chemical looping process: 250 kW pilot-scale testing for power
synthetic natural gas (SNG) process based on BGL gasifier: modeling and techno-
generation and carbon capture. Appl. Energy 282, 116065.
economic analysis. Energy Fuel. 31 (1), 1023–1034.

14