processes

Article
Process Design and Techno-ECONOMIC Evaluation of a
Decarbonized Cement Production Process Using Carbon
Capture and Utilization
Wei Wu 1, * , Zhong-Lin Jian 1 , Bang-Yan Chou 1 , Chun-Yang You 1 and Yu-Ning Kuo 2

1 Department of Chemical Engineering, National Cheng Kung University, Tainan 70101, Taiwan, China
2 New Energy Technology Division, Green Energy and Environment Research Lab,
Industrial Technology Research Institute, Tainan 711010, Taiwan, China
* Correspondence: [email protected]

Abstract: To address a decarbonized cement production process (DCPP), a calcium looping process is
connected to an industrial cement production process (CPP) for capturing CO2 by 93.5~96%. Since the
captured CO2 purity is up to 99.9 wt%, the carbon capture and utilization (CCU) process is connected
to generate the additional products of urea and methanol. An integration of DCPP and CCU, named
the DCPP-based polygeneration system, is being developed for three scenarios. To meet the power
demand for producing high-purity hydrogen and oxygen, Scenario 1 adopts water electrolysis and
the full green electricity grid; Scenario 2 adopts the Cu-Cl thermochemical cycle and the partial
green electricity grid; and Scenario 3 adopts water electrolysis and the heat recovery steam generator
(HRSG). Through the techno-economic analysis and comparisons, the CO2 avoided costs of three
scenarios are estimated between 16.53 and 21.42 USD/ton, which are lower than the conventional
DCPP of around 40 USD/ton. It is due to the fact that the polygeneration scheme could reduce the
LCOP (levelized cost of producing 1 ton of clinker) due to the production of valorized products. It is
noted that Scenario 2 is superior to other scenarios since the RenE2P cost in Scenario 2 is lower than
it is in Scenario 1 and the captured CO2 rate in Scenario 2 is lower than it is in Scenario 3.

Citation: Wu, W.; Jian, Z.-L.; Chou,

Keywords: calcium-looping; carbon capture and utilization; cement production process; economics
B.-Y.; You, C.-Y.; Kuo, Y.-N. Process
Design and Techno-ECONOMIC
Evaluation of a Decarbonized
Cement Production Process Using
Carbon Capture and Utilization. 1. Introduction
Processes 2023, 11, 2043. https:// The cement production process was energy- and carbon-intensive, accounting for
doi.org/10.3390/pr11072043 approximately 7% of global CO2 emissions. To meet the European regulations, such as
Academic Editors: Federica Raganati
a legal obligation to reduce EU emissions by at least 55% by 2030, the price of carbon
and Paola Ammendola contracts on the EU Emissions Trading Scheme (ETS) has hit $106.57 (€100) per tonne [1].
The recirculation of CO2 technology for capturing CO2 from the cement process could
Received: 6 June 2023 create a value chain where the cost of capturing pure carbon is quite high [2]. Several
Revised: 5 July 2023 different carbon-capture technologies have been used in the cement industry, where calcium
Accepted: 5 July 2023
looping (CaL) is a promising technology for capturing CO2 from the flue gas and achieving
Published: 7 July 2023
90% CO2 capture efficiency by recycling deactivated CaO sorbent reinserted into the
precalciner and mixing with the raw material of the kiln [3]. A study showed that the
CaL system has significant technical and economic advantages compared to the gas-liquid
Copyright: © 2023 by the authors.
absorption case using alkanolamine (MDEA) as a chemical solvent due to lower capital
Licensee MDPI, Basel, Switzerland.
and operational costs as well as lower CO2 avoidance costs [4]. A study showed that the
This article is an open access article CaL technology was superior to gas-liquid absorption using MDEA for post-combustion
distributed under the terms and capture configuration due to a lower carbon footprint and better economic indicators [5].
conditions of the Creative Commons Through the process design and integration of methanation of carbon dioxide and the CaL
Attribution (CC BY) license (https:// process, the simulation showed that this integrated process produces 1 ton of methane with
creativecommons.org/licenses/by/ a molar fraction of nearly 91% by consuming 344–370 GJ [6].
4.0/).

Processes 2023, 11, 2043. https://doi.org/10.3390/pr11072043 https://www.mdpi.com/journal/processes

Processes 2023, 11, 2043 2 of 16

The commercialization of CaL has not reached commercial-scale demonstration in the

cement sector yet. The main challenges included that the CaO-based adsorbent should
maintain its high sorbent activity during long-term cycling and that an air separation unit
(ASU) for the oxyfuel combustion in the calciner was necessary [7]. A pilot test of CaL
for a cement plant showed that the large limestone makeup flow was used in the calciner
to keep the Sorbent activity [8]. An experimental study showed that the carbonation
temperature, the CO2 concentration for CaO-based adsorbent, and the reactor type affected
the adsorption efficiency [9]. For high sorbent make-up flows in a 200 kW calcium looping
pilot plant, the CO2 capture efficiencies are up to 98% in the carbonator at a carbonation
temperature of around 600 ◦ C [10].
A carbon capture and utilization (CCU) technology using concrete wastes such as
alkali wastes could capture a portion of the CO2 emitted from the cement kiln flue gas to
produce recarbonate [11]. This study claimed that the cement plant usually emits much
more CO2 than can be utilized below 10% in a single CO2 utilization plant, such as in
the production of ethanol or food-grade CO2 [12]. A study showed that the CaL process
integrated with coal-based power plants or cement production processes could enhance
industrial symbiosis and reduce cost by adding the production of value-added products
such as methanol, polymers, and acetic acid [13]. Although the CaL process played an
important role in the decarbonization of cement plants, the promising chemical candidate
for mitigation of CO2 by chemical conversion dominated environmental impacts and
costs. A study showed that the high CO2 content (11–17 vol%) of flue gas from fluid
catalytic cracking has great economic potential for methanol production due to methane
and hydrogen as byproducts [14].
Regarding the economic comparisons of the decarbonization options for a cement
production process, it shows that the oxy-combustion CO2 capture is superior to the
chemical scrubbing system for post-combustion CO2 capture due to its higher carbon
capture rate and lower CO2 avoided cost [15]. A similar study showed that the cost of
oxy-combustion CO2 capture in the cement production process was effectively reduced
due to the generation of hydrogen products and byproduct oxygen via the electrolysis
of water [16]. For the economic evaluation of the polygenration system for olefins from
industrial off-gas such as coke oven gas or hydrogen, coke oven gas is more competitive
than hydrogen due to the feed price [17]. The CaL cluster treating the flue gas from
multiple industrial emitters could reduce the cost of capturing CO2 by connecting a cluster
of industrial sites with significant heat demands with a decarbonized cement production
process using the CaL system [18].
In this paper, the decarbonized cement production process (DCPP) using an integration
of a CPP and a CaL process is developed. The process design and simulation of the DCPP
in Aspen Plus® are shown in Section 2. The DCPP not only produces the clinker but also
releases high-purity and high-temperature CO2 . To drive a circular economy, DCPP-based
polygeneration systems using three types of carbon capture and utilization (CCU) are
proposed, which are described in Section 3. Regarding the market evaluations of potential
chemical products in Table 1, it shows that methanol as the fuel demand and urea as
the fertilizer demand are quite high in Taiwan, and the high-purity CO2 demand in the
world will be up to 230 million tons per year. Moreover, the economic evaluations of three
scenarios of DCPP-based polygeneration systems in terms of capital expenditure (CAPEX),
operating expense (OPEX), and CO2 avoided cost are described in Section 4.

Table 1. Comparisons of methanol, urea, and CO2 .

Methanol Urea CO2 (99.9 wt%)

Selling price (USD/ton) 310 303 11.3 [19]
Average demand 450.9 × 106 0.1 × 106 230 × 106
(ton/yr) in Taiwan [20] in Taiwan [21] in the world [22]
Urea; Food; Enhanced oil
Application Fuel Fertilizer
recovery (EOR)
 Methanol Urea CO2 (99.9 wt%)
Selling price
310 303 11.3 [19]
(USD/ton)
Average demand 𝟒𝟓𝟎. 𝟗 × 𝟏𝟎𝟔 in 𝟎. 𝟏 × 𝟏𝟎𝟔 in 𝟐𝟑𝟎 × 𝟏𝟎𝟔
(ton/yr) Taiwan [20] Taiwan [21] in the world [22]
Processes 2023, 11, 2043 3 of 16
Urea; Food; En-
Application Fuel Fertilizer hanced oil recovery
(EOR)
2. Decarbonized Cement Production Process
2.2.1. Cement Production
Decarbonized Cement Process
Production Process
This case
2.1. Cement study ofProcess
Production the cement production process (CPP) is based on the configuration
of the cement plant at Taiwan Cement Ltd., located in Hualien, Taiwan. Figure 1 describes
This case study of the cement production process (CPP) is based on the configuration
the CPP as consisting of three major processes. The first is two five-stage cyclone preheaters,
of the cement plant at Taiwan Cement Ltd., located in Hualien, Taiwan. Figure 1 describes
which are composed of ten cyclones (C1, C2, . . . , C10) in total. The cyclone preheater is the
the CPP as consisting
countercurrent of three major
heat exchanger processes.
that recovers theThe first
waste is two
heat five-stage
of flue gas fromcyclone preheat-
the pre-calciner
ers, which are composed of ten cyclones (C1, C2, …, C10) in total. The cyclone
and heats up two sets of raw materials as well. The second is the pre-calciner with the preheater
iscalcium
the countercurrent heat exchanger
carbonate decomposition that recovers the waste heat of flue gas from the pre-
reaction.
calciner and heats up two sets of raw materials as well. The second is the pre-calciner with
the calcium carbonate decomposition CaCO reaction.
3 → CaO + CO2 (1)

Flue gas

Mixer

Raw material Raw material

C1 C6

C2 C7
Cyclone
C3 C8
Preheater
C4 C9

C5 C10

Air Coal
Pre-calciner

Kiln gas Gas

Cyclone
Tertiary
gas Combustor Decomposer

Air Solid
Gas
Heat
Raw material Exchanger
Clinker
Coal Cyclone Kiln
Decomposer Combustor
Solid Air

Figure
Figure1.1.Cement
Cementproduction
productionprocess.
process.

It is part of the calcining work of a cement rotary kiln. The third is the cement rotary
3 → CaO + CO2
kiln to produce the clinker. Since theCaCO
operating (1)
temperatures of the pre-calciner and cement
◦ ◦
rotary kiln are around 900 C and 1250 C, respectively [23], two coal combustion units
are used to meet the heat demands of the pre-calciner and cement rotary kiln. Notably, the
outlet product of the kiln is reduced to 100 ◦ C by using an air cooler and the flue gas from
the top of the cyclone preheaters (C1 and C6), which are operated at 370 ◦ C.
Regarding the process simulation of the CPP in Aspen Plus® , first, the compositions
of coal and raw materials in Table 2 are slightly modified as compared to the coal and raw
materials for the cement plant in Taiwan Cement Ltd., where the amounts of CaO, Al2 O3 ,
SiO2 , and Fe2 O3 meet the specifications of hydraulic modulus, silica ratio, and alumina
ratio [23]. Second, the reactions in the Aspen Plus module of the kiln are shown in Table 3.
The simulation results, such as the outlet flowrates and their compositions of clinker and
flue gas, can be found in Table 2. Notably, the compositions of the flue gas are validated
Processes 2023, 11, 2043 4 of 16

according to the real data from Taiwan Cement Ltd., which are shown in Table S1 in the
Supplementary Materials.

Table 2. Parameters of the cement production process.

Coal Compositions
Proximate analysis wt%
Moisture 4.0
Volatiles 6.5
Fixed carbon 74.85
Ash 16.85
Ultimate analysis wt%
C 74.85
H 3.25
N 0.98
S 0.38
O 1.82
16.85
Raw materials ton/day 13,440
CaO 9072.0
Al2 O3 672.0
SiO2 3306.2
Fe2 O3 389.8
Coal for pre-calciner ton/day 531.3
Coal for kiln ton/day 434.7
Air for pre-calciner ton/day 5769
Air for kiln ton/day 3462.1
Flue gas ton/day 16730.2
N2 wt% 55
CO2 wt% 26.1
H2 O wt% 12.1
O2 wt% 6.4%
Clinker ton/day 9578.8
C2 S wt% 25.5
C3 A wt% 7.9
C3 S wt% 48.4
C4 AF wt% 9.46

Table 3. Operating conditions and specifications of process units in the DCPP-based polygeneration
system.

Process unit: Aspen Plus module and specification

CPP [23]
Pre-calciner: RStoic module
Temperature = 900 ◦ C; Pressure = 1 bar
(1) CaCO3 → CaO + CO2 with 100% conversion
Kiln: RStoic module
Temperature = 1250 ◦ C; Pressure = 1 bar
(2) CaO + SiO2 → 2CaO·SiO2 (C2 S)with 27% conversion
(3) CaO + Al2 O3 → 3CaO·Al2 O3 (C3 A) with 8% conversion
(4) CaO + SiO2 → 3CaO·SiO2 (C3 S) with 58% conversion
(5) 4CaO + Al2 O3 + Fe2 O3 → 2CaO·Al2 O3 ·Fe2 O3 (C4 AF) with 4% conversion
CaL process [24]
Carbonator: RStoic module
Temperature = 650 ◦ C; Pressure = 1 bar
CO2 + CaO → CaCO3 with 90% conversion
Calciner: RStoic module
Temperature = 940 ◦ C; Pressure = 1 bar
CaCO3 → CO2 + CaO with 100% conversion
 Processes 2023, 11, 2043 5 of 16

Table 3. Cont.

Process unit: Aspen Plus module and specification

Ammonia synthesis reactor [25]: RPlug module
Temperature = 300 ◦ C; Pressure
 = 200 bar; H2 /N2 = 3
rNH3 = 1.8 × 106 exp −RT
20.5
P1.59 H2 P0.82 N2

Urea synthesis reactor [26]: RPlug module

Temperature = 200 ◦ C; Pressure = 100 bar; NH3 /CO2 = 4 
 
Rurea 8 − 94.5
= 2.5 × 10 exp RT × CT × XH2 NCOO− − KNH 1 XNH2CONH2 XH2O
K + 3 NH
4

Methanol synthesis reactor [27]: RPlug module

Temperature = 250 ◦ C; Pressure = 50 bar; H2 /CO2 = 3; Cu/ZnO/Al2 O3 catalyst;
Catalyst density = 1775 kg/m3 ; Fixed bed porosity = 0.5
−2
k1 PCO2 PH2 −k6 PH2 O PCH3 OH PH
rCH3 OH =  2
3
−1 0.5
1+k2 PH2 O PH +k3 PH2 +k4 PH2 O
2
−1
k5 PCO2 −k7 PH2 O PCO PH
rRWGS = −1
2
1+k2 PH2 O PH +k3 P0.5
H2 +k4 PH2 O
2

Three-step Cu-Cl cycle [28]: RStoic module

Temperature = 430 ◦ C; Pressure = 1 bar
Hydrolysis reaction: 2CuCl2(aq) + H2 O(g) → 2CuOCl2(s) + 2HCl(g) with 100% conversion
Oxygen reaction: CuOCl2(s) → 2CuCl(l) + 0.5O2(g) with 100% conversion
Electrochemical reaction: 2CuCl(l) + HCl(l) → 2CuCl2(aq) + H2(g) with 100% conversion

2.2. Calcium-Looping Process

Referring to the previous work for the simulation of the calcium-looping (CaL) pro-
cess [29], the CaL process is built by Aspen Plus® and shown in Figure 2. The CaL process
is composed of two individual reactors, a carbonator and a calciner, and two cyclones.
The flue gas (Fflue1 ) and active CaO are fed into the carbonator to carry out the following
PEER REVIEW 6 of 18
exothermic reaction at a temperature of around 650 ◦ C.
CaO + CO2 →CaCO3 (2)

CO2 lean air

Calciner Decomposer
Combustor
CaCO3
CaCO3
Cyclone 1 Coal
heating gas
(Fflue2)

O2
Solid Air
Flue gas CaO
Cyclone 2
(Fflue1)
O2 lean air
Carbonator CO2

Deactivated
CaO

Figure 2. Calcium-looping process.

Figure 2. Calcium-looping process.

In the carbonator, the solid product of CaCO3 is delivered to the calciner by conveyor,
and the CO2 -lean gasCaO(tail gas)
+ CO →CaCO
is 2emitted into3 the air after cyclone 1. In the calciner,
(2)
In the carbonator, the solid product of CaCO3 is delivered to the calciner by conveyor,
and the CO2-lean gas (tail gas) is emitted into the air after cyclone 1. In the calciner, the
calcium carbonate decomposition reaction described in Equation (1) is carried out at a
Processes 2023, 11, 2043 6 of 16

the calcium carbonate decomposition reaction described in Equation (1) is carried out
at a temperature of around 940 ◦ C; notably, the solid product of CaO flows back to the
carbonator by conveyor, and the high-purity CO2 gas is easily produced after cyclone 2.
The oxyfuel coal combustion is used to provide the heating source for the high-temperature
heating gas (Fflue2 ). The deactivated CaO is removed and the fresh CaCO3 is added to
maintain the stable operation of the calciner.

3. DCPP-Based Polygeneration System

3.1. Carbon Capture and Utilization
The decarbonized cement production process (DCPP) is an integration of the CPP and
CaL processes. Based on the prescribed operating conditions and inlet flowrates of the
DCPP in Tables 2 and 3, the emitted gases from the DCPP include the tail gas at 940 ◦ C
from the carbonator, the high-purity CO2 at 650 ◦ C from the calciner, and the pure N2 gas
from the air separation unit (ASU). To address carbon capture and utilization (CCU), these
gases are converted to chemicals through the following processes:
1. Ammonia synthesis reactor (ASR): N2 and H2 are synthesized to produce NH3 in the
Haber process. Based on the operating conditions and kinetics of the ASR in Table 3,
Figure 3a shows that the ASR model by using the RPlug reactor module in Aspen
Plus® is validated due to the acceptable curve fitting of experimental data as shown
in Table S1 in the Supplementary Materials [30].
2. Urea synthesis reactor (USR): Urea is produced through the following reactions:
2NH3 + CO2 → NH2 OCONH4
(3)
NH2 OCONH4 → NH2 CONH2 + H2 O
where CO2 and NH3 are supplied from the calciner in the CaL process and the ASR,
respectively. Based on the operating conditions and kinetics of the USR in Table 3, Figure 3b
shows that the USR model by using the RPlug reactor module in Aspen Plus® is validated
due to the acceptable curve fitting of experimental data as shown in Table S1 in the
Supplementary Materials [26].
3. Methanol synthesis reactor (MSR): Methanol production from CO2 is achieved through
a catalytic process in the gas phase assuming that the following CO2 hydrogenation is
the only desired reaction [27].

CO2 + 3H2 → CH3 OH + H2 O (4)

The reactants CO2 and H2 are supplied from the calciner in the CaL process and the
hydrogen production process, respectively. Based on the operating conditions, specifica-
tions for catalyst, and kinetics of the MSR in Table 3, Figure 3c shows that the MSR model
by using the RPlug reactor module in Aspen Plus® is validated due to the acceptable curve
fitting of experimental data as shown in Table S1 in the Supplementary Materials.
According to the above reactions for producing ammonia, urea, and methanol, a
large amount of hydrogen is required. To address the more efficient and clean hydrogen
production process, the polymer electrolysis membrane (PEM), water electrolysis, and the
Cu-Cl thermochemical cycle are illustrated. PEM electrolysis usually has a higher energy
efficiency (80–90%) as well as a larger hydrogen production rate than alkaline electroly-
sis [31]. Referring to the modeling of a PEM electrolyzer [32], the mathematical models of
the PEM water electrolysis in Table S2 and the corresponding Simulink block diagram in
Figure S1 can be found in the Supplementary Materials. The Cu-Cl thermochemical cycle is
another option for hydrogen production by using the thermochemical method for water
splitting. It is validated that the three-step Cu-Cl thermochemical cycle with prescribed
reactions in Table 3 could reduce the electricity demand by using an electrochemical reactor
in place of the PEM water electrolysis [33]. Based on the previous work [28], the simulation
of a three-step Cu-Cl thermochemical cycle could be achieved in Aspen Plus® .
Processes 2023, 11, x FOR PEER REVIEW 7 of 18

Processes 2023, 11, 2043 7 of 16

CO2 + 3H2 → CH3OH + H2O (4)

(a)

(b)

(c)
Figure
Figure3. Model validation:
3. Model reactions
validation: of (a) ammonia
reactions synthesis,
of (a) ammonia (b) urea synthesis,
synthesis, and (c) methanol
(b) urea synthesis, and
synthesis.
(c) methanol synthesis.
Processes 2023, 11, 2043 8 of 16

3.2. Process Integration

Regarding the integration of the DCPP and CCU, three types of DCPP-based polygen-
eration systems are proposed, which are shown in Figures 4–6, respectively. Integration of a
renewable energy source to the power grid named RenE2P is treated as “the green electric-
Processes 2023, 11, x FOR PEER REVIEW 9 of 18
ity grid” which is the uninterruptible power supply for the cold/heat utilities, compressors,
ASU, and water electrolysis.

Processes 2023, 11, x FOR PEER REVIEW 10 of 18

Figure 4. Scenario 1: DCPP-based polygeneration system using PEM water electrolysis.

Figure 4. Scenario 1: DCPP-based polygeneration system using PEM water electrolysis.

Scenario 2: A DCPP-based polygeneration system for producing clinker, urea, and

methanol simultaneously, shown in Figure 5, is named Scenario 2. As compared to Sce-
nario 1, the Cu-Cl thermochemical cycle replaces the PEM water electrolysis in Scenario
1. In the Cu-Cl thermochemical cycle, the waste heat from a part of the tail gas from the
CaL process is recovered through heat exchanger 3. Similarly, the CO2 gas with a concen-
tration of 99.96% from the calciner in the CaL process is split into three streams: 100% of
H2 is consumed, 94% of N2 is not consumed, and 100% of CO2-lean gas (tail gas) from the
carbonator is emitted into the air.

Figure 5. Scenario 2: DCPP-based polygeneration system using the Cu-Cl thermochemical cycle.
Figure 5. Scenario 2: DCPP-based polygeneration system using the Cu-Cl thermochemical cycle.

Scenario 3: A DCPP-based polygeneration system for producing clinker, urea, and

methanol simultaneously, shown in Figure 6, is named Scenario 3. As compared to Sce-
narios 1 and 2, the heat recovery steam generators (HRSG) in Scenario 3 provide continu-
ous power supply by recovering the waste heat of tail gas from the CaL process. The HRSG
Processes 2023,
Processes 11,11,
2023, 2043
x FOR PEER REVIEW 11 of9 of
18 16

Figure 6. Scenario 3: DCPP-based polygeneration system using HRSG.

Figure 6. Scenario 3: DCPP-based polygeneration system using HRSG.

The CaL 1:
Scenario process plays an important
A DCPP-based role in producing
polygeneration system forhigh-purity
producingCO 2 for the CCU,
clinker, urea, and
so the corresponding CO 2 capture efficiency is expressed by
methanol simultaneously, shown in Figure 4, is named Scenario 1. Notably, the hydrogen
production unit is the PEM water electrolysis, heat 𝐹𝐶𝑂2 × 𝑤𝐶𝑂2 1 and 2 are added to recover
exchangers
CO ⁡capture⁡efficiency = × 100%⁡ (5) is
the waste heat2of the outlet gas streams 𝐹𝑓𝑢𝑒𝑙1from the CaL+process,
× 𝑤𝑓𝑢𝑒𝑙1,𝐶𝑂2 𝐹𝑓𝑢𝑒𝑙2 × 𝑤 and the deactivated CaO
𝑓𝑢𝑒𝑙2,𝐶𝑂2
added to the pre-calciner. The CO2 gas with a concentration of 99.96% from the calciner
𝐹𝐶𝑂2 is the outlet tail gas flowrate from the calciner, 𝐹𝑓𝑢𝑒𝑙1 is the inlet flue gas
iswhere
split into three streams. The first stream is the CO2 product due to its concentration of
over 99.9%; the
flowrate of the carbonator,
second stream and is𝐹𝑓𝑢𝑒𝑙2 is the
fed into theinlet
ureaheating
synthesisgas process
flow of thefor calciner.
producing 𝑤𝐶𝑂2 ,
urea;
𝑤𝑓𝑢𝑒𝑙1,𝐶𝑂2
and , and,
the third 𝑤𝑓𝑢𝑒𝑙2,𝐶𝑂2
stream is fedrepresent
into thethe CO2 concentrations
methanol of the for
synthesis process inlet/outlet
producing flows of tail
methanol.
gas, flue gas, and heating gas, respectively. Table 4 shows the
Hydrogen from the PEM water electrolysis is split for the processes of ammonia synthesiscomparisons of three sce-
narios in terms of captured CO 2 rate and CO2 capture efficiency. The captured CO2 rate,
and methanol synthesis; oxygen from the ASU and the PEM water electrolysis is fed into
i.e.,combustor;
the CO2 gas from andthenitrogen
calciner from
(ton/day),
the ASUin Scenario 3 is higher
is fed into than in other
the ammonia scenarios
synthesis due It
process.
to the coal and air flowrates in the CaL in Scenario 3 being higher
is noted that the flue gas from the CPP is fully captured by the CaL process; 100% of H2 than in other scenarios,
issoconsumed,
it implies that 94%theof CO
N22 iscapture efficiency and
not consumed, in Scenario
100% of 3 isCOlower than in other scenarios.
2 -lean gas (tail gas) from the
The Cu-Cl thermochemical
carbonator is emitted into the air. cycle added in Scenario 2 increases the heat demand by recov-
eringScenario
the waste heat of tail gas from the CaL process, so that
2: A DCPP-based polygeneration system for producing clinker, the consumption of coal
urea,and
and
CaCO3 for the CaL process increases. The HRSG added in Scenario 3 meets the power
methanol simultaneously, shown in Figure 5, is named Scenario 2. As compared to Scenario
demand of the PEM water electrolysis, so it indirectly increases the consumption of coal
1, the Cu-Cl thermochemical cycle replaces the PEM water electrolysis in Scenario 1. In
and CaCO3 for the CaL process. Regarding total CO2 emissions evaluations, Figures 4–6
the Cu-Cl thermochemical cycle, the waste heat from a part of the tail gas from the CaL
show that the CO2 emissions of Scenarios 1–3 are 179.83 tons/day, 217.71 tons/day, and
process is recovered through heat exchanger 3. Similarly, the CO2 gas with a concentration
280.04 tons/day, respectively, according to the flowrates of tail gas with prescribed CO2
of 99.96% from the calciner in the CaL process is split into three streams: 100% of H2
concentrations. As compared to the CO2 emissions of the CPP of 4366.9 tons/day according
is consumed, 94% of N2 is not consumed, and 100% of CO2 -lean gas (tail gas) from the
to the flue gas (Fflue1) with 26.1% CO2, it is validated that the CaL process could capture
carbonator is emitted into the air.
CO2 of Fflue1 by 93.5~96%.
Scenario 3: A DCPP-based polygeneration system for producing clinker, urea, and
methanol simultaneously, shown in Figure 6, is named Scenario 3. As compared to
Scenarios 1 and 2, the heat recovery steam generators (HRSG) in Scenario 3 provide con-
tinuous power supply by recovering the waste heat of tail gas from the CaL process. The
HRSG is designed to cover the demand of the PEM water electrolysis such that the duty
of the RenE2P is effectively reduced. After the HRSG, the CO2 gas with a concentration
of 99.96% from the calciner in the CaL process is split into three streams: 100% of H2
Processes 2023, 11, 2043 10 of 16

is consumed, 94% of N2 is not consumed, and 100% of CO2 -lean gas (tail gas) from the
carbonator is emitted into the air.
The CaL process plays an important role in producing high-purity CO2 for the CCU,
so the corresponding CO2 capture efficiency is expressed by
FCO2 × wCO2
CO2 capture efficiency = × 100% (5)
Ff uel1 × w f uel1,CO2 + Ff uel2 × w f uel2,CO2

where FCO2 is the outlet tail gas flowrate from the calciner, Ff uel1 is the inlet flue gas flowrate
of the carbonator, and Ff uel2 is the inlet heating gas flow of the calciner. wCO2 , w f uel1,CO2 ,
and, w f uel2,CO2 represent the CO2 concentrations of the inlet/outlet flows of tail gas, flue
gas, and heating gas, respectively. Table 4 shows the comparisons of three scenarios in
terms of captured CO2 rate and CO2 capture efficiency. The captured CO2 rate, i.e., CO2
gas from the calciner (ton/day), in Scenario 3 is higher than in other scenarios due to the
coal and air flowrates in the CaL in Scenario 3 being higher than in other scenarios, so it
implies that the CO2 capture efficiency in Scenario 3 is lower than in other scenarios. The
Cu-Cl thermochemical cycle added in Scenario 2 increases the heat demand by recovering
the waste heat of tail gas from the CaL process, so that the consumption of coal and CaCO3
for the CaL process increases. The HRSG added in Scenario 3 meets the power demand of
the PEM water electrolysis, so it indirectly increases the consumption of coal and CaCO3
for the CaL process. Regarding total CO2 emissions evaluations, Figures 4–6 show that the
CO2 emissions of Scenarios 1–3 are 179.83 tons/day, 217.71 tons/day, and 280.04 tons/day,
respectively, according to the flowrates of tail gas with prescribed CO2 concentrations. As
compared to the CO2 emissions of the CPP of 4366.9 tons/day according to the flue gas
(Fflue1 ) with 26.1% CO2 , it is validated that the CaL process could capture CO2 of Fflue1 by
93.5~96%.

Table 4. Main parameters of Scenarios 1–3 in terms of the calcium looping process.

Scenario 1 Scenario 2 Scenario 3

Coal ton/day 231.7 247.4 283.1
Air ton/day 840 870 1026
CaCO3 ton/day 204.0 218 250
CO2 gas from calciner ton/day 4417.62 4484.71 4652.02
CO2 wt% 99.96 99.96 99.96
N2 -rich gas from carbonator ton/day 12798.1 12794.3 12822.2
N2 wt% 71.9 71.8 71.8
H2 O wt% 16.1 16.0 16.2
O2 wt% 6.3 6.2 6.4
CO2 wt% 2.4 2.5 3.0
CO2 capture efficiency % 91.7 92.1 90.8

4. Economics
4.1. Cost Estimation
The economic evaluation of DCPP-based polygeneration systems such as Scenario 1,
Scenario 2, and Scenario 3 in terms of capital expenditure (CAPEX) and operating expendi-
ture (OPEX) is addressed as follows:
i. CAPEX: The equipment cost of the DCPP-based polygeneration systems is based on
the prescribed cost functions in Table 5, which provide the cost information for the
scale-up. Notably, the input parameters of cost functions, including the heat transfer
areas for the heat exchanger (AHX ), the different flowrates for the compressor (Finlet ),
the load duty of the pump (Wpump ), chemical reactors, kilns, cyclones, ASU, Cu-Cl
thermochemical cycles, and PEM water electrolysis, can be found by Aspen Plus
simulation. Moreover, the total equipment costs of Scenarios 1–3 named CS1 , CS2 , CS3
as the summation of the cost functions of process units and the corresponding total
Processes 2023, 11, 2043 11 of 16

investment costs of Scenarios 1–3 named TICS1 , TICS2 , and TICS3 as 105% of total
equipment costs are shown in Table 5.
ii. OPEX: The annual costs for labor, maintenance, insurance, raw materials of the CCP
and CaL, fuel (coal), and chemicals (H2 O, CuCl2 ) are shown in Table 6, in which
these values and the evaluations are related to the illustrated literature. Notably, the
purchasing/selling prices of materials/products and the carbon tax are quoted on the
internet. The calculation of the number of laborers for the CCP and CCU is based on a
specific correlation formula.

Table 5. CAPEX estimations of DCPP-based polygeneration system.

Equipment Unit
0.67 0.67
h i
VCalc VCarb
Pre- or calciner (including Coal combustion unit) Ccalciner = 4.6 × 107 0.15( 1150.5 m 3 ) + ( 1150.5 m 3 )
i !0.64
Cement rotary kiln (including Coal combustion Fclinker
h
ton
day
unit) [34] Ccement = 9.5 × 107 4000

 0.66
Cyclone Fgas
Ccyclone = 17, 640 × 4.7m3
s
 0.5
Air Separation unit (ASU) FO2 ,Cal
C ASU = 58, 252, 320 ×
3900.1 kmol
hr

0.9 0.67 0.67

h i
QCalc VCalc VCarb
Calcium looping CCaL = 4.6 × 107 [0.85( 534 MW )] + 0.15 ( 1150.5 m 3 ) + ( 1150.5 m 3 )
 0.78
Heat exchanger A HX
CHEX = 130 × 0.093 m2
 0.75
Cu-Cl thermochemical cycle FH2
Ccu−cl = 1.64 × 108 × 100 ton/day
 0.65
PEM water electrolysis FH2
CPEM = 9.3 × 107 × 100 ton/day
.
Steam turbine CST = 6000 × W ST 0.7
71.7× Finlet

Ccomp = 0.92 −ηcomp × πcomp × ln πcomp
Compressor Finlet : mass flow rate (kg/s)
πcomp : pressure ratio
ηcomp : compressor isentropic efficiency (0.85)
.
Pump C pump = 1120 × W pump 0.78
 0.6
Ccond = 8000 × A100
cond
Condenser
Acond : heat transfer area (m2 )
 0.58
Ammonia synthesis reactor CNH3 = 108 × 1000 Fton/day
NH3

 0.78
Methanol synthesis reactor Fmethanol
C MeOH = 7 × 109 × 54,794.5 ton/day
 0.64
Urea synthesis reactor Furea
Curea = 7.5 × 106 × 200 ton/day

CPP CCPP = Ccemnet + Ccalciner + 10 Ccyclone

CaL process CCaL = 2 × Ccyclone + Ccarbonator + Ccalciner
HRSG CHRSG = 8 × CHEX + 3 × CST + C pump
Ammonia synthesis process (ASP) C ASP = CNH3 + 2 × Ccomp
Urea synthesis process (USP) CUSP = Curea + 2 × Ccomp
Methanol synthesis process (MSP) C MSP = C MeOH + 2 × Ccomp
CCU of Scenario 1 CCCU,S1 = CPEM + C ASP + CUSP + C MSP
CCU of Scenario 2 CCCU,S2 = Ccu−cl + C ASP + CUSP + C MSP
Processes 2023, 11, 2043 12 of 16

Table 5. Cont.

Equipment Unit
CCU of Scenario 3 CCCU,S3 = CHRSG + C ASP + CUSP + C MSP
Total equipment cost of Scenario 1 CS1 = CCPP + CCaL + C ASU + CCCU,S1
Total equipment cost of Scenario 2 CS2 = CCPP + CCaL + C ASU + CCCU,S2
Total equipment cost of Scenario 3 CS3 = CCPP + CCaL + C ASU + CCCU,S3
Fees (land, auxiliary devices, and site preparation, etc.) 5% × CS1 , 5% × CS2 , 5% × CS3
Total investment costs (TIC) of Scenarios 1–3 TICS1 = 105% × CS2 , TICS2 = 105% × CS2 , TICS3 = 105% × CS3

Table 6. Economic conditions and assumptions.

Coal (Ccoal ) USD/ton 77.12

Raw materials of CPP (C f eed,CCP ) USD/ton 5.92
CaCO3 (CCaCO3 ) USD/ton 10
H2 O (CH2O ) USD/m3 0.74
CuCl2 (CCuCl2 ) USD/ton 25,000
RenE2P (Celec ) USD/kWh 0.17
CO2 (99.9wt%) selling price (SCO2 ) USD/ton 11.3
Methanol selling price (SMeOH ) USD/ton 310
Urea selling price (Surea ) USD/ton 303
Cement selling price (Scement ) USD/ton 80
Carbon tax (CCO2 ) USD/ton 55
Annual payment per labor USD/yr 20,000
Annual maintenance and insurance
USD/yr 5.25% × CCPP
costs of the CPP
Annual maintenance, labor, and
USD/yr 12% × CCaL
insurance costs of the CaL
5.25% × CCCU,S1 ,
Annual maintenance and insurance
USD/yr 5.25% × CCCU,S2 ,
costs of the CCU
5.25% × CCCU,S3
Discount rate % 6
Annual working day hr 300
Construction time yr 3
Total plant life yr 17

 0.5
2
NO = 6.29 + 31.7Nsolid + 0.23N f luid (6)

where NO is the number of operators per shift, Nsolid is the number of processing steps
involving the handling of particulate solids, and N f luid is the number of non-particulate
processing steps regarding compression, heating, cooling, mixing, and reaction. The
operating shifts are 900 shifts per year by 300 days/year × 3 shifts/day, and the operating
shifts are 215 shifts by 43 weeks/year × 5 shifts/week. The number of shifts needed in the
plant NS was calculated by
365 days 3 shi f t
year × day
NS = 5 shi f t
(7)
43 weeks
year × week

and the total number of laborers Ntot for the CPP and CCU is shown by

Ntot = NO × NS (8)

The OPEX estimations of Scenarios 1–3 are shown as follows.

Scenario 1 : OPEXS1 = (Ccoal × Fcoal + C f eed,CPP × Ff eed,CPP + CCaCO3 × FCaCO3

+CH2O × FH2O + Celect × Pelec ) × 300 + Ntot × 20, 000 (9)
+5.25% × CCPP + 12% × CCaL + 5.25% × CCCU,S1
Processes 2023, 11, 2043 13 of 16

Scenario 2 : OPEXS2 = (Ccoal × Fcoal + C f eed,CPP × Ff eed,CPP + CCaCO3 × FCaCO3

+CCuCl2 × FCuCl2 + CH2O × FH2O + Celect × Pelec ) × 300 + Ntot × 20, 000+ (10)
5.25% × CCPP + 12% × CCaL + 5.25% × CCCU,S2

Scenario 3 : OPEXS3 = (Ccoal × Fcoal + C f eed,CPP × Ff eed,CPP + CCaCO3 × FCaCO3 +

CH2O × FH2O + Celect × Pelec ) × 300 + Ntot × 20, 000+ (11)
5.25% × CCPP + 12% × CCaL + 5.25% × CCCU,S3

where the flowrates of the raw materials of CPP, CaCO3 , H2 O, and ChCl2 are Ff eed,CCP , FCaCO3 ,
FH2O , and FCuCl2 , respectively, and the purchased prices of the raw materials and fuel (coal)
of CCP, CaCO3 , H2 O, and ChCl2 are C f eed,CCP , Ccoal FCaCO3 , FH2O , and FCuCl2 , respectively.

4.2. Economic Evaluation

The economic models of Scenarios 1–3 named S1, S2, and S3 are described by the
following cash flow,


CF |i,t+3 = S MeOH × FMeOH + Surea × Furea + SCO2 × FCO2,p + Scement × Fclinker × 300 t+3
(12)
− (OPEXi + CCO2 × ( FCO2 × wCO2 ) × 300)|t+3 − TICi,t , I = {S1, S2, S3}, t = 1, 2, . . . , 14

For three-year construction, it is assumed that TICi,1 = 0.4 × TICi , TICi,2 = 0.3 × TICi ,
and TICi,3 = 0.3 × TICi . Moreover, the internal rate of return (IRR) is obtained by solving
the following equation:

17 CF |i,t
∑ t =1 (1 + r ) t = 0, i = {S1, S2, S3} (13)

where r is the discount rate.

To address the economics of the CCP with/without the use of CaL and CCU, the CO2
avoided cost is described as
LCOPCaL+CCU,i − LCOPre f
 
$
CO2 avoided cost|i = , i = {S1, S2, S3} (14)
CO2tot, re f − CO2tot,CaL+CCU,i ton

where LCOPCaL+CCU and LCOPre f represent the levelized cost of producing 1 ton of
clinker from the CCP with/without the use of CaL and CCU, respectively. Similarly,
CO2tot, CaL+CCU and CO2tot, re f represent the CO2 emission intensity of producing 1 ton of
clinker from the CCP with/without the use of CaL and CCU, respectively.

17 CF |i,t 17 Pclinker |t
LCOPCaL+CCU,i = ∑ (1 + r ) t / ∑ (1 + r ) t
, i = {S1, S2, S3} (15)
t =1 t =4

where Pclinker (ton/yr) = Fclinker ×300.

According to the above economic evaluations of Scenarios 1–3, the corresponding
economic comparisons in terms of CO2 avoided cost and economic indicators (IRR and
payback period) are shown in Table 7. Referring to some literature for the cost analysis of the
CPP with the use of the CaL process, the CO2 avoided cost was around 40 USD/ton [35,36].
It is noted that the CO2 avoided costs of three scenarios of DCPP-based polygeneration
systems are between 16.53 and 21.42 USD/ton. It is validated that the CCU method could
effectively reduce the LCOP due to producing multiple products. Scenario 1 has a lower
CO2 avoided cost due to a lower captured CO2 rate from the calciner, but it consumes
more green energy (RenE2P) to do the CCU, such that its IRR is lower than other scenarios,
and Scenario 3 has a higher CO2 avoided cost due to a higher captured CO2 rate from the
calciner, but its IRR is higher than Scenario 1 due to HRSG in place of RenE2P. The IRR and
the payback period of Scenario 2 are superior to other scenarios since the RenE2P cost in
Processes 2023, 11, 2043 14 of 16

Scenario 2 is lower than it is in Scenario 1 and the captured CO2 rate in Scenario 2 is lower
than it is in Scenario 3. Notably, the IRR of the DCCP is lower than the IRR of the CPP by
5.7%, at least since the CAPEX and OPEX of the CaL process increase the total cost of the
DCCP. Finally,

Table 7. Economic evaluations of Scenarios 1–3.

CPP Scenario 1 Scenario 2 Scenario 3

CO2 avoided cost
-- 16.53 18.92 21.42
($/ton)
IRR (%) 23.87% 20.49% 22.51% 22.21%
Payback period
6.05 6.60 6.26 6.30
(year)

5. Conclusions
Three types of the DCPP-based polygeneration system have the same products (clinker,
methanol, and urea), but the power sources and hydrogen production processes are dif-
ferent. In Scenario 1, the PEM water electrolysis requires an expensive green electricity
grid. In Scenario 2, the Cu-Cl thermochemical cycle in place of the PEM water electroly-
sis can effectively decrease the green electricity grid supply, although the CAPEX of the
Cu-Cl thermochemical cycle is higher than the PEM water electrolysis. In Scenario 3, the
HRSG system fully replaces the electricity grid but indirectly increases the OPEX of the
CaL process, such that its CO2 avoided cost is higher than in other scenarios. From the
cement market viewpoint, the CPP is superior to the DCPP if the carbon tax is below
55 USD/ton. From a circular economy perspective, the DCPP-based polygeneration system
is superior to DCPP due to its ability to produce valorized products. For the future study,
the more valorized chemical products would be addressed to enhance the economics of the
DCPP-based polygeneration system.

Supplementary Materials: The following supporting information can be downloaded at: https://
www.mdpi.com/article/10.3390/pr11072043/s1. Figure S1: Flowchart of PEM water electrolysis
with Simulink; Table S1: Experimental data in the processes of kiln, NH3 , urea, MeOH; Table S2:
Mathematical models of PEM water electrolysis
Author Contributions: Conceptualization, W.W. and Y.-N.K.; Formal analysis, Z.-L.J., B.-Y.C. and
C.-Y.Y.; Investigation, W.W. and Z.-L.J.; Writing—Original draft, W.W.; Funding acquisition, W.W. All
authors have read and agreed to the published version of the manuscript.
Funding: This work was financially supported by the Ministry of Science and Technology of R.O.C.
(Taiwan) under grant 11126228006029 and the Industrial Technology Research Institute under grant
3000621068.
Data Availability Statement: Not applicable.
Conflicts of Interest: The authors declare no conflict of interest.

Nomenclature
ASR Ammonia synthesis reactor
ASU Air separation unit
CAPEX Capital expenditure
CCU Carbon capture and utilization
CaL Calcium looping
CPP Cement production process
DCPP Decarbonized cement production process
HRSG Heat recovery steam generator
IRR Internal rate of return
LCOP Levelised cost of producing 1 ton clinker
MSR Methanol synthesis reactor
Processes 2023, 11, 2043 15 of 16

OPEX Operating expense

PEM Polymer electrolysis membrane
USR Urea synthesis reactor
WGS Water gas shift
PSA Pressure swing adsorption
RenE2P Renewable energy source for power grid
TIC Total investment cost
CS1 , CS2 , CS3 The summation of the cost functions of process units in Scenarios 1–3
Ntot The total number of labors
NS The number of shifts needed in the plant
NO The number of operators per shift

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