Journal of CO₂ Utilization 33 (2019) 461–472

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Journal of CO2 Utilization

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

Process development and techno-economic evaluation of methanol T

production by direct CO2 hydrogenation using solar-thermal energy
Thai Ngan Do, Jiyong Kim
⁎

Department of Energy and Chemical Engineering, Incheon National University, Incheon 22012, Republic of Korea

ARTICLE INFO ABSTRACT

Keywords: This study proposes and analyzes a novel methanol production process developed by integrating CO2 hydro-
CO2 genation and thermochemical splitting technologies. Using Sunshine-to-Petrol, which produces liquid hydro-
Methanol carbons using solar thermal energy, as the baseline framework, we developed a highly energy-efficient methanol
Process synthesis production process comprised of the solar field for CO2 and H2O splitting using concentrated solar thermal
Solar energy
energy, integrated with methanol production through the direct hydrogenation of CO2 and CO. The optimal
Techno-economic evaluation
process configuration and operating conditions for maximizing the amount of methanol were established using a
sequential quadratic programming. Consequently, the proposed process achieved a high energy efficiency of
15.5%, and the minimum selling price of methanol was established as 0.94 $/kg, accompanied by a 26% im-
provement over previous schemes and other CO2-to-methanol frameworks. Furthermore, we examined addi-
tional alternative scenarios to establish the optimistic conditions such that the minimum selling price of 0.53
$/kg is considered as a competitive price in the methanol market.

1. Introduction technologies, usually referred to as direct CO2 hydrogenation, has been

published, demonstrating the potential for solving economic and en-
The depletion of conventional energy sources and climate change vironmental issues [11]. Aresta et al. [12] presented a comprehensive
expressed clearly via the increase of greenhouse gas emissions are cri- view on the catalytic conversion of CO2 hydrogenation to many che-
tical issues [1]. The newly released Special Report on the impacts of micals by analyzing the opportunities and challenges associated with
Global warming of 1.5 °C in 2018 has demonstrated the potential im- the processes. Van-Dal et al. [13] developed the methanol production
pacts of limiting global warming below 1.5 °C, and it calls for the process utilizing captured CO2 from flue gases in which the optimiza-
concentration of global efforts towards reduce CO2 emission [2]. tion of an onsite energy recovery in a methanol unit, supplied to an
Therein, addressing such environmental and energy-related problems, energy intensive CO2 absorption unit, was achieved. Pérez-Fortes et al.
the framework of CO2 capture and utilization (CCU) is presented as [14] performed an environmental evaluation and techno-economic
both challenging and opportunistic [3–5]. The conversion of CO2 is one analysis for a captured CO2-based methanol production process via
of the best routes for producing alternative fuels and value-added direct hydrogenation. Similarly, Szima et al. [15] evaluated the me-
chemical products [6,7]. Jarvis et al. [8] investigated the mechanisms thanol process from captured CO2 and sustainable hydrogen feedstock
of CO2 to urea, methane, formic acid, and Fischer-Tropsch hydrocarbon on the technological, environmental, and economic metrics.
by utilizing low-carbon energy sources while comparing technical, en- In the previous studies [16–18], we developed new CO2 utilization
vironmental, and economic criteria. Among the fuels and chemicals frameworks, namely Sunshine to Petrol (S2P), that produced methanol
that can be obtained from CO2, methanol is the most important and has and liquid fuels from CO2, H2O, and solar energy. In the S2P process,
the most advanced production technologies compared to those of the the centralized solar energy converts the feedstock of CO2 and H2O into
others [3,9]. Balasubramanian et al. [10] examined rigorous models of synthesis gas in thermochemical engines, followed by several techno-
the CO2-based methanol production process that combined a number of logical separation and syngas processing, and fuel synthesis and pur-
optimal primary reforming reactors for the different ratios of syngas, ification. S2Ps exhibited outstanding improvement and potential to
and finally defined the best configuration for the highest CO2 conver- positively impact the environmental, exhibited high energy efficiency,
sion. Recently, a number of research on the current CO2 utilization and overcome economic issues [17,18]. Among the examined

⁎
Corresponding author.
E-mail address: jykim77@incheon.ac.kr (J. Kim).

https://doi.org/10.1016/j.jcou.2019.07.003
Received 31 May 2019; Received in revised form 3 July 2019; Accepted 3 July 2019
2212-9820/ © 2019 Elsevier Ltd. All rights reserved.
T.N. Do and J. Kim Journal of CO₂ Utilization 33 (2019) 461–472

processes, the most promise S2P-mixed pathway to methanol produc- alternatively through the different temperature zones, the material
tion is referred to in this work as a baseline process. works as a thermal cycle of redox reactions. In our studies, CR5 em-
In the present study, we examined the advanced solar-to-methanol ployed FeO/Fe3O4 as a converter material for splitting CO2 and H2O
(AS2M) processes that adopted the solar-thermal-energy-based splitters into CO and H2 [17,18]. A more detailed description of the dish and
of both CO2 and H2O into CO and H2 and the up-to-date direct CO2 CR5 can be found in References [16–18,25,26].
hydrogenation technology for methanol production. The direct hydro-
1/ MOx 1/ MOx + 1/2O2 (1)
genation technology is expected to offer advantages in energy saving,
economic, and environmental aspects. Basically, the AS2M processes 1/ MOx + CO2 1/ MOx + CO (2)
could significantly reduce the cost of methanol production compared to
CO2 CO + 1/2O2 (3)
the case in previous studies. In particular, the direct processing of the
mixture, CO2/CO/H2, from the CR5 solar engines facilitates the exclu- In the AS2M processes, the assumptions for solar field and captured
sion of very energy-intensive sub-processes in the base S2P framework, CO2 was obtained from the previous study for fair comparison [17,18]
such as CO/CO2 separation and syngas processing under extreme op- as follows:
erating conditions. Accordingly, this study aims to develop highly en-
ergy-efficient and economically viable methanol production processes
from CO2 by integrating the S2P framework, as a baseline, with the
• CO and H production are calculated using their higher heating
2
values (HHV)
direct CO2 hydrogenation technology. Using various process systems • Solar field includes 17,622 units of solar dish/CR5
engineering (PSE) centric methods such as simulation and optimization, • Daily collected solar energy: 445 MW
this study developed a rigorous process model for the proposed AS2M
frameworks, including an optimal production scheme, process config-
• Solar-to-chemical efficiency (energy transfer efficiency from solar to
chemical): 20%
uration, and operation conditions, to ensure high energy efficiency
[19]. In addition, the economics of the proposed AS2M processes were
• Overall reaction conversion (efficiency of CO to CO and H O to H
2 2 2
production): 25%
compared with those of the conventional S2P processes through a de-
tailed techno-economic study. Finally, this study carried out a sensi-
• The CO to CR5 is captured from flue gas of a coal fired power plant
2
with the composition of CO2 (20.7%), O2 (2.7%), N2 (66.1%) and
tivity analysis to identify major cost drivers of the proposed AS2M H2O (10.6%).
frameworks and analyzed the cost competitiveness against other con-
ventional options by examining various alternative scenarios for cost 2.2. Process configuration
reduction.
Fig. 2 (a) presents the baseline S2P process that converts captured
2. Technology overview and analysis methods CO2 to methanol (MeOH) using solar thermal energy. The CO2 captured
from a flue gas is re-energized into CO by solar-to-chemical splitter
2.1. Solar to petrol principle (similarly, H2O is converted into H2). The unconverted CO2 from solar-
chemical engine is removed by an amine-based absorption to ensure
Solar energy, which is an important renewable energy, can be uti- high-purity CO, while H2 is separated from H2O using a simple con-
lized using a variety of technologies such as photovoltaic [20,21], solar denser. The resulting streams (CO-rich and H2) are mixed and fed to the
heating [22], solar thermal energy [23], and artificial photosynthesis main MeOH synthesis process. Finally, raw MeOH is fed to the se-
[24]. The S2P frameworks adopt thermochemical technology that paration and purification process to ensure 99% purity. Note that in the
produces the intermediate fuel precursors (CO and H2) by splitting CO2 main facility, solar energy is used not only for the thermochemical
and H2O using a concentrated solar flux in the engines called Counter- splitting of CO2 and H2O but also for supplying the required utilities
Rotating-Ring Receive/Reactor/Recuperator (CR5) [17,18]. As shown (heat and electricity) for process operation. The direct utilization of
in Fig. 1(a), a parabolic dish collects solar thermal energy over its large CO2, as a feedstock, and on-site utility generation using solar energy
surface area and reflects the concentrated heat flux toward a single contributes to the mitigation of direct and indirect CO2 emission, which
focal point, which is an inlet point of CR5. This high-temperature implies that the S2P framework is an environment friendly process for
heating source is used to re-energize CO2 into CO (or H2O into H2) in value-added chemicals production. Nevertheless, the baseline S2P
two-step thermochemical process by a reactive metal oxide material process consumes a large amount of utilities, particularly heat load, in
that is mounted as outer fins of ring-shape CR5, as shown in Fig. 1(b). the amine-based separation process to supply the highly concentrated
The general conversion mechanism in CR5 begins with the reduction of CO from the mixture gas of CO and CO2 of the solar field. The adoption
reactants at a high temperature to release oxygen, as expressed in Eq. of the CO2 hydrogenation, which directly utilizes CO2 as a main carbon
(1). In the following step, the ring rotates into the relatively low tem- source for MeOH production, can be a very promising solution for
perature zone where the CO2/H2O oxidation reaction, expressed in Eq. overcoming the shortcomings of the baseline S2P process by elim-
(2), occurs and produces CO/H2 gas. As the ring continues to rotate inating the CO2/CO separation process results higher energy efficiency,

Fig. 1. (a) General schematic of parabolic dish and CR5 system, and (b) CO2/H2O splitting mechanism in CR5.

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T.N. Do and J. Kim Journal of CO₂ Utilization 33 (2019) 461–472

Fig. 2. Block-flow representation of the methanol production from CO2: (a) the baseline S2P process [17,18]; (b) AS2M #1: H2O pathway to methanol via CO2
hydrogenation; (c) AS2M #2: Mixed pathway to methanol via CO2 hydrogenation.

economics, and environmental benefits. Furthermore, the simple pro- improved energy efficiency and economics.
cess configuration of the CO2 hydrogenation allows us to cut down the
MeOH production costs by the reduction of the number and size of 2.3. Analysis method
costly equipment.
In this study, two advanced solar-to-methanol (AS2M) processes are The proposed processes are evaluated with technical (i.e., energy
proposed by applying the up-to-date direct CO2 hydrogenation tech- efficiency and carbon efficiency), environmental (i.e., global warming
nology, as shown in Fig. 2(b) and (c). In Fig. 2(b), the first alternative potential), and economic metrics (i.e., minimum selling price). Using
configuration (AS2M #1) employs all the solar dish/CR5 units to split the selected metrics, we analyzed the improvements of the proposed
H2O for H2 production. Note that while the key feature of the S2P AS2M processes in comparison with those of the baseline S2P process.
framework is CO2 splitting using the CR5, initial CR5 developments had The carbon efficiency (ηC) evaluates the amount of carbon in the sup-
focused on H2O splitting [15]. Herein, we re-considered H2O splitting plied CO2 converted to MeOH, which is expressed in Eq. (4).
to produce H2 for direct CO2 hydrogenation along with the transported
CMeOH
CO2 as the conceptual process scheme of AS2M #1 is as shown. The = [%]
C
Cfeed (4)
mixture stream of H2 and H2O from the solar field (i.e., solar dish/CR5
array) are supplied to the CO2 hydrogenation process after separating where ηC is the overall carbon efficiency, CMeOH, is the total carbon in
H2 from H2O using a simple flash tank. Subsequently, the resulting gas the produced MeOH stream [kmol/h]; and Cfeed, is the total carbon in
mixture is supplied to the MeOH synthesis process. The key design the feed stream (the used CO2) [kmol/h].
factor of AS2M #1 is the determination of the amount of transported For the second metric, two types of energy efficiencies are calcu-
CO2 directly supplied to the MeOH production process to adjust the lated. The process energy efficiency (ηpro) is a ratio of the chemical
ratio of CO2 and H2 for maximizing MeOH yield. energy of the produced MeOH to the total incorporated solar energy
Fig. 2(c) shows the second alternative (AS2M #2), which involves into chemicals (i.e., CO via CO2 splitting or H2 via H2O splitting), and
the concurrent splitting of H2O and CO2 into H2 and CO, respectively. In the consumed utilities (i.e., heat and electricity) [27], as shown in Eq.
this scheme, the streams of H2 after dewatering and the CO2/CO mix- (5).
ture are supplied into the MeOH synthesis process, where both CO2 and
Heat of reaction of MeOH
CO react with H2. Thus, the key design factor of AS2M #2 is the allo- pro = [%]
Incorporatedsolar energy + Consumed heat and electricity
cation of the solar dish/CR5 units for splitting H2O and CO2 to adjust
the optimal ratios of CO2, CO, and H2 for maximizing MeOH yield. (5)
Accordingly, an advantage of the proposed AS2M processes over the where the heat of reaction of MeOH denotes the higher heating value
baseline S2P process is the reduction in energy consumption, which is (HHV) of methanol. The quantities of heat and electricity used in the
primarily from the amine-based CO2 separation; this reduction leads to AS2M processes are calculated through process simulation.

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For a fair comparison with other alternative energy approaches Finally, the MSP was calculated by dividing the revenue by the
(e.g., artificial photosynthesis and electrochemical splitting using solar amount of MeOH producted, as in Eq. (14). In this study, we calculated
power), we analyzed the primary energy efficiency (ηpri), which is the minimum selling price (MSP) of methanol production in terms of
calculated as the ratio of the chemical energy of the product to the total USD per kilogram ($/kg).
energy entering the process, as shown in Eq. (6).
ROI + Expense + Tax
MSP = [$/kgMeOH]
Heat of reaction of MeOH TheamountofMeOH (14)
pri = [%]
Colledted solar energy + Primary energy for utilities (6)

Accordingly, to calculate the gross inlet energy in the solar field, we 3. Modeling and simulation
included the total collected solar energy through the dish/CR5 array
instead of the incorporated solar energy into CO and H2. Similarly, In this section, the unit process models of the involved sub-pro-
utilities (heat and electricity) are assumed to be supplied from an on- cesses, particularly of the CO2 hydrogenation reaction, in the AS2M
site utility facility. It is assumed that the utilities required in the CO2 processes are discussed. In addition, we introduce an optimization
capture process is supplied using conventional energy sources (grey box model for the allocation of the dish/CR5 unit for CO and H2 production,
in Fig. 2), whereas the main facility is operated with solar energy-based which is a critical factor for determining the amount of MeOH. Finally,
utilities (blue box in Fig. 2). For the environmental metric, the global owing to process simulation, details of mass and energy balances are
warming potential (GWP) is calculated as the ratio of the CO2 equiva- estimated to meet design specifications (e.g., the purity and flow of a
lent emission (kg CO2-eq.) per unit of MeOH production, as shown in Eq. product stream).
(7).
Direct CO2 eq.+Indirect CO2 eq. Used CO2 3.1. CO2 hydrogenation reactions modeling
GWP=
The total amount of MeOH (7)
Many recent published papers have reviewed, analyzed, and dis-
where direct CO2-eq. is the CO2 equivalent emission of considered GHGs
cussed the CO2 hydrogenation to methanol production technology such
[kg CO2-eq.] from the outlet streams of the process, apart from the
as catalysts innovation [30–32], reaction modeling and kinetics [33],
product stream during the production phase. The impact of all con-
and process designs [34,35]. In this study, we utilized the catalyst of
sidered greenhouse gases (GHGs) is converted and presented via the
fibrous Cu/Zn/Al/Zr in CO2 hydrogenation due to the high CO2 con-
term of CO2 equivalent emission (CO2-eq.). In this study, CO2 and CO,
version and high selectivity of MeOH at a relative low temperature
which are major GHGs, can be emitted from the processes. However,
(around 250°C) [36,37]. The CO2 hydrogenation involves three main
due to a relative small GWP of CO compared to that of CO2 [28], we
equilibrium reactions (R1, R2, and R3), which afford to MeOH and
only consider the effect of CO2 in the GWP evaluation of the examined
H2O:
processes. Indirect CO2-eq. accounts for GWP by utility consumption for
the facility operation. Reaction 1 (R1): CO + 2H2 ↔ CH2OH, H298K=−90.7 kJ/mol (15)
In the economic metric, this study used minimum selling price
Reaction 2 (R2): CO2 + H2 ↔ CO + H2O, H298K=+41.21 kJ/mol
(MSP) as a basic term for evaluating the economic competitiveness of
(16)
the AS2M processes. The MSP is the sale price of MeOH determined at
the break-even point, where the total income and outcome are equal. Reaction 3 (R3): CO2 + 3H2 ↔ CH3OH + H2O, H298K=−49.16 kJ/mol
The total income is the revenue generated from MeOH sales, whereas (17)
the outcome includes the return on investment (ROI), tax, and oper-
ating cost. The ROI, which depends on the total project investment cost The rigorous CO2 hydrogenation reaction was simulated based on
(TPI), the interest rate, and the economic project life, is obtained by kinetics, as shown in Table 1 [38]. The simulation of the direct CO2
applying Eq. (8). hydrogenation process was performed in Aspen Plus V10.0 [39]. The
simulation employed the RK-Soave property method due to the com-
i × (1+i )r ponents, CO2, CO, H2, H2O, and CH3OH, and the following operating
ROI = Annualized TPI = TPI ×
(1+i)r -1 (8) conditions: temperature of up to 250 °C and pressure of up to 50 bar
where i is the interest rate and r is the life time of the process. Based on [19,38]. The specific operating conditions for each equipment are de-
sizing and costing data obtained by a simulation model execution, the scribed in Table 2. By receiving the feedstocks of CO2 and H2O, the
TPI, which includes direct and indirect costs is calculated [29]. Simi- dish/CR5 system prepares the reactor feed of CO2/CO and H2, which is
larly, mass and energy stream information of the simulation models are mixed with the recycle stream before compression at 50 bar. As re-
utilized for the total expenses consisting of the fixed and variable op- cycling goes on, the MeOH synthesis feed stream contains CO2, CO, and
erating costs. The other terms were also calculated using Eq. (9) for H2 gas; the ratio of the three components is adjusted for the optimal
depreciation, and Eq. (10) for income tax. stoichiometric number of the supply stream.
The gas mixture is heated first by the high-temperature reactor
TPI outlet stream, which is due to the exothermic reactions in the reactor,
Depreciation =
Lifetime (9) after which it is introduced into the additional heater to ensure the
reactor inlet temperature is up to 250 °C. The reaction product stream is
Tax = (Profit Depreciation) × Tax rate (10)
cooled and further separated in liquid-vapor separator at 30 °C and 45
Profit = Revenue Expense (11) bar. The small off-gas is vented to release inert gases that brought to-
gether feed stream. The separated liquid stream containing almost
At the break-even point, the revenue is equal to the total of ROI, MeOH and H2O, is supplied to a partial condenser distillation column,
expense, and tax, as shown in Eq. (12). Subsequently, Eq. (13) calcu- while the unreacted gas is recycled. The MeOH product is purified to
lates the total revenue at the break-even point of cash flow. over 99%.
Revenue = ROI + Expense + Tax (12)
3.2. Optimal dish/CR5 allocation
(ROI-Depreciation × Tax rate) +Expense × (1-Tax rate)
Revenue =
1-Tax rate
Balancing the amount of CO2, CO, and H2 in the stream supplied to
(13) the CO2 hydrogenation reactor is one of the key factors determining the

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T.N. Do and J. Kim Journal of CO₂ Utilization 33 (2019) 461–472

Table 1
Kinetic expressions for fibrous Cu/Zn/Al/Zr catalyst: CO2 hydrogenation [38].
Reaction Kinetic expressions

R1 1.5 KCO f
K CO fCO f H f 0.5
2 KA CH3 OH H2
r 1 = k1 K K K
0.5 +
fH
H 2 O
f 0.5 +
+ KCO fCO f H
CO H 2 O
fCO fH2 O + KCO 2 fCO2 f H 0.5 + KCO 2 K H2 O f
2 0.5 H2 O 2 0.5 2 0.5 CO 2 fH2 O
KH KH KH
R2 K CO2
KCO 2 fCO 2 fH2 f f
KB H2 O CO
r2 = k2 K H2 O KCO K H2 O
0.5
fH + f 0.5
+ KCO fCO f H + 0.5 + KCO 2 K H2 O f
fCO f H2 O + KCO 2 fCO 2 f H
2 0.5 H2 O 2 0.5 2 0.5 CO2 f H2 O
KH KH KH
R3 1.5 K CO2
KCO2 fCO f H f f f 1.5
2 2 K C H2 O CH3 OH H2
r3 = k3 K H2 O KCO K H2 O
0.5
fH + f 0.5
+ KCO fCO f H + 0.5 + KCO 2 K H2 O f
fCO f H2 O + KCO 2 fCO 2 f H
2 0.5 H2 O 2 0.5 2 0.5 CO2 f H2 O
KH KH KH
Kinetic factors, constants 11,695 112,860 226,010
k1 = 4.0638 × 10 6 × e RT [kmol/kgcat sPa], k2 = 9.0421 × 10 8 × e RT [kmol/ kgcat sPa0.5], k3 = 1.5188 × 10 33 ×e RT [kmol / kgcat sPa],
and Ki factors
98,438 43,939 54,499 118,270
KA = 2.3714 × 10 23 × e RT [Pa 2], KB = 281.1780 × e RT , K C = 6.6687 × 10 21 × e RT [Pa 2], K CO = 8.3965 × 10 11 ×e RT [Pa 1],
81,287 K H2 O 956,775
K CO2 = 1.7214 × 10 10 × e RT [Pa 1], 0.5 = 4.3676 × 10 12 × e RT
KH

technical and economic performance of the S2P processes [40]. In Maximize{Methanol production / fed CO2 }
x,y
general, the carbon (i.e., CO2 and CO) and H2 balance is defined as R =
Subject to:
(H2 − CO2)/(CO + CO2), and the most favorable R value for max-
imizing the MeOH amount in the CO2 hydrogenation reaction is 2.0 − Limits of total solar-to-chemical energy
2.1 [41,42]. Accordingly, the design and operation of the solar field Limits of process capacity(m)
(e.g., allocation of the dish/CR5 array for CO2 and H2O splitting) to Limits of operating conditions(T , P )
h (x , y ) = 0
deliver a large-quantity and favorable-R feed is a critical strategy. Mass&energy balance
g (x , y ) 0
For AS2M #1, which employs all the solar dish/CR5 units for H2O The optimal stoichiometric number(R)
splitting, the amount and R value of the inlet stream of the CO2 hy- Split fraction for purge
drogenation process is determined by the flow rate of raw CO2 stream, Non-negative constraints
since the H2 amount is constant regardless of the amount of the raw CO2
x Rn, y Rn
stream. Conversely, AS2M #2 is more complex than AS2M #1 due to a
trade-off between the amounts of H2 and carbon (CO2 and CO). Since
The objective function is to maximize the amount of raw MeOH per
this study assumed 17,622 units of the dish/CR5 array in the solar field,
supplied CO2, which is subjected to the set of equality (h (x , y ) = 0 ) and
the available solar-to-chemical energy (445 MW) should be shared be-
inequality ( g (x , y ) 0 ) constraints. The operation variables ( x , y Rn )
tween splitting CO2 and H2O. For instance, the more CR5 units are used
that indicate stream information, e.g., flow rate and composition, are
for CO2 splitting into CO, the lesser the amount of H2 produced from
determined to obtain the best value of the objective function within the
H2O splitting. To achieve the most favorable R value of the inlet stream
upper and lower boundary of the operating conditions and the max-
of the CO2 hydrogenation process, the optimal numbers of the dish/CR5
imum capacity of the involved equipment. In particular, a crucial
for splitting CO2 and H2O are determined using a optimization algo-
condition for obtaining the most favorable R value of the inlet stream of
rithm in Aspen Plus [39]. Sequential Quadratic Programming (SQP)
the CO2 hydrogenation process is as follows: R should be greater than 2
was selected, which is very efficient to find out the optimal operating
and less than 2.1. Due to the optimization, all the design and opera-
conditions by allowing infeasible path of equality or inequality con-
tional variables, e.g., CR5 allocation, temperature and pressure of the
straints and/or tear streams converged simultaneously [19,43]. While
involved sub-processes, and the recycle stream, were determined using
detailed SQP model applied to each AS2M process, as well as the pro-
the maximum value of the objective function (i.e., the maximum
cedure SQP model, is provided in the Supplementary Information, the
amount of MeOH per supplied CO2).
model structure implemented in this study is as follows:
Fig. 3 shows the change in the produced amount of MeOH according
to the allocation strategy of the dish/CR5 for CO2 and H2O splitting,

Table 2
Major equipment and operation conditions of CO2 hydrogenation and distillation.
Process Equipment Block type Parameter description

Temperature (ºC) Pressure (bar)

CO2 hydrogenation Reactor Rplug 250−350 35−55

Heat exchanger HeatX 30−270 25−55
Feed preheater Heater 200−350 25−55
Water cooler Cooler 30−60 25−55
Separator Flash 30−95 25−55
MeOH separation Column RadFrac Top: 35−65 Top: 1−1.1
Bottom: 105 Bottom: 1−1.3

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Fig. 3. Changes of the produced amount of methanol according to different design strategies: (a) the supplied amount of CO2 in AS2M #1 and; (b) the allocation of
dish/CR5 in AS2M #2.

i.e., the amount of MeOH produced by changing the amount of CO2 and 1114 kmol/h, respectively, which ensure the most favorable R value of
H2 supplied to the CO2 hydrogenation reactor. Overall, it is obvious that the inlet stream of the reactor along with the recycle stream (stream #7
the produced amount of raw MeOH varies according to the amount of in Fig. 4). After the reaction, the flash tank separates the unreacted gas
CO2 and the H2 supplied to the hydrogenation reactor. For AS2M #1, from the liquid components (MeOH and H2O) to be recycled. The raw
since all the units of the dish/CR5 are used for splitting H2O, MeOH in the liquid stream is further purified to over 99% in the dis-
1114 kmol/h of H2 (1.52 kmol/day of H2 from each CR5) are produced tillation column. Overall, the AS2M #1 process can produce MeOH of
from the solar field. With this constant flow of H2, 381 kmol/h of CO2 is 367 kmol/h using CO2 of 381 kmol/h.
required to produce the maximum amount MeOH per supplied CO2 by The major stream information of the AS2M #2 process that includes
satisfying the optimal R value (H2:CO2:CO ratio of 0.74:0.23:0.02). both H2O and CO2 splitting using the dish/CR5 array are shown in
Conversely, the SQP optimization is executed to determine the optimal Fig. 5. Since the dish/CR5 array in this process is occupied for splitting
numbers of CR5 for CO2 and H2O splitting for AS2M #2. Consequently, both CO2 and H2O, the SQP optimization finds out the optimal ratio
8.41% of the solar-to-chemical energy (i.e., 1482 out of the 17,622 between the number of the dish/CR5 for CO2 and H2O. This means that
units of the dish/CR5) are used for re-energizing CO2 into CO, which the SQP optimization identified the flow rates of CO2, CO, and H2 of the
leads to the best objective function (i.e., 0.969 kmol MeOH production reactor inlet stream (stream #9 in Fig. 5) for ensuring the most favor-
using 1 kmol CO2). able R value, thereby leading to the maximum amount of MeOH from
the direct CO2 hydrogenation reaction. Consequently, CO2 of 382 kmol/
3.3. Simulation results h (i.e., stream #1) and H2O of 1024 kmol/h (i.e., total amount from
stream #2 and #15) were supplied into the solar field to produce the
Fig. 4 presents the major stream information of the AS2M #1 pro- mixture of CO2 and CO of 287 and 95 kmol/h, respectively, and H2 of
cess that produces MeOH through the direct CO2 hydrogenation reac- 1014 kmol/h. The further downstream process is similar to the AS2M
tion using raw CO2 transported from a remote site and H2 generated in #1 process, followed by flash separation and distillation to achieve the
the solar field. The supplied amounts of CO2 and H2 to the direct CO2 MeOH product of over 99% purity. Overall, the AS2M #2 process
hydrogenation process (streams #5 and #6 in Fig. 4) are 381 and produces MeOH of 365 kmol/h using CO2 of 382 kmol/h.

Fig. 4. Simple process flow diagram and major stream information of the AS2M #1 process.

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Fig. 5. Simple process flow diagram and major stream information of the AS2M #2 process.

4. Technical performance analysis Table 3

Global warming potential of the AS2M processes compared to the baseline S2P
Based on the mass and energy information identified using rigorous and conventional natural gas-based process.
process models, the technical capabilities including carbon efficiency, kg CO2-eq./kg MeOH Classical-NG Baseline S2P AS2M#1 AS2M#2
energy efficiencies and net CO2 reduction of the proposed processes are [17]
comparatively analyzed. Fig. 6 compares the overall carbon balance
Feedstock inventory
and efficiency of two examined processes. Both advanced processes
Natural gas 0.133 – – –
exhibited relatively high carbon efficiencies compared to that of the CO2 – −1.521 −1.427 −1.439
baseline process (90.4%). Note that due to the large number of sub- Indirect emission
processes in the baseline S2P process (i.e., CO2 and CO separation, Heat consumption 0.067 0.000 0.000 0.000
water gas shift reaction for syngas processing, MeOH synthesis, and Electricity consumption 0.068 0.000 0.000 0.000
Direct emission 0.380 0.146 0.031 0.038
separation), the baseline S2P process involves four different recycle Total 0.647 −1.375 −1.397 −1.401
loops, which result in the corresponding number of vent-gas streams Relative emission (%) 100 −212.4 −215.7 −216.4
that includes a variety of carbon atoms (e.g., CO2, CO, CH4, and MeOH)
[18]. Conversely, the configurations of AS2M processes are simple
compared to that of the baseline process: a recycle loop in the reaction

Fig. 6. Carbon flows and efficiency of (a) AS2M #1 and (b) AS2M #2 processes.

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Table 4
Energy efficiency of the examined S2P processes.
Energy consumption (kW) Base S2P AS2M#1 AS2M#2

Solar energy collected (Qsolar) 439,584 439,584 439,585

(a) Chemical energya (from solar_20% Qsolar) 87,917 87,917 87,917
Solar-to-H2 (QH2) 56,728 87,917 80,385
Solar-to-CO (QCO) 31,189 − 7,532
(a) Process utility 65,613 12,665 14,799
Process electricity 16,309 3,945 6,446
Process heat 49,304 8,720 8,353
(a) Heat of reaction of the methanol flux (QMeOH) 72,374 74,012 73,608
(a) Process Energy efficiency [=c/(a + b)] (ηpro - %) 47.1 73.6 71.7
Primary energy efficiency – conventional utilities
(a) Solar energy 439,584 439,584 439,584
(a) Conventional generation for process energy 101,409 20,803 27,134
Electricityb 44,078 10,663 17,422
Heatc 57,330 10,140 9,713
(a) Primary energy efficiency [=c/(e + f)] (ηpri - %) 13.4 16.1 15.8
Primary energy efficiency - solar-based utilities
(a) Solar for process energy 180,153 37,167 48,936
Electricity from solar thermald 81,545 19,727 32,230
Heat using solar thermale 98,608 17,440 16,706
(i) Primary solar-based energy efficiency [=c/(e + h)] (ηpri - %) 11.7 15.5 15.1

a
Solar-to-chemical efficiency is assumed to be 20% [17].
b
Efficiency of conventional electricity ranges 32–38% depending on energy mix; 37% is used [44].
c
Efficiency of conventional heat ranges 85–90% according to feedstock and capacity; 86% is assumed [44].
d
Solar-to-electricity efficiency is assumed at 20% [45].
e
Solar-to-heat efficiency of 50% is assumed [46,47].

and a residue gas in distillation. This simplicity in the process config- considerable amount of heat utility in the desorption column for amine
uration of the AS2M processes leads to improved carbon efficiency regeneration [18]. Based on analysis, the syngas process in the baseline
compared to that of the baseline S2P process. process consumes 16 MW and 49 MW in electricity and heat, respec-
The S2P framework offers environmental advantages with negative tively, which accounts for 60−83% of the total energy consumption in
impact of global warming potential (GWP) since it not only uses CO2 as the main facility.
a feedstock but also incorporates solar energy as a process utility Furthermore, Table 4 shows two different primary energy effi-
[16–18]. While environmental impacts of the advanced processes are ciencies (ηpri) from conventional and solar-energy utilities. For the
expected to be similar to those of the baseline, this study in detail conventional utilities, electricity and heat are assumed to be supplied
analyzes the GWP score, as shown in Table 3. All the S2P processes from an energy mix at 37% efficiency and natural gas at 86% efficiency
display negative GWP scores compared to a conventional natural gas- [18,44]. For the solar-based utility supply, the efficiencies of the pro-
based route [17,18] due to direct use of CO2 as a raw material. Two cess electricity and heat are assumed to be 20% and 50%, respectively
AS2M processes show a little improved values compared to the con- [18,45–47]. Compared to that of the baseline process, both advanced
ventional route. The major reason behind the improved GWP score is processes exhibit improved primary energy efficiencies. Specifically,
that the direct emission, contributed by vent-gas and off-gas, of two the primary energy efficiency of the AS2M #1 process is 16.1% (+2.7%
AS2M processes is much lesser than the baseline S2P process. This over that of the baseline) with conventional utilities and 15.5% (+3.8%
means that most carbon species in the fed CO2 in the AS2M processes over that of the baseline) with solar-based utilities. The primary energy
are converted to methanol. efficiency compares the feasibility of the examined S2P processes from
Another reason is that the S2P and AS2M processes utilize solar- the viewpoint of the energy efficiency. For instance, the baseline S2P
based utility for the operation of the frameworks, thereby resulting in process consumes more primary energy (101,409 kW; (f) in Table 4) as
indirect emissions. Note that while the GWP score of the solar-based a utility than the energy contained in the produced MeOH (i.e.,
utility is not essentially zero due to the contributions during the con- 72,374 kW; (c) in Table 4), which means that this process is inefficient
struction and disassemble phases, this study considers only the manu- from the energy perspective. Conversely, the AS2M processes produce
facturing (plant operation) phases for simple comparison [16,17]. This more energy flux than consumed energy (comparing values of (c) and
assumption of solar-based utility seems to be unfair to the conventional (f) in Table 4). The solar-based primary energy efficiency more clearly
natural gas-based production that uses conventional utilities (e.g., heat shows the excellence of the AS2M processes over the baseline process.
from natural gas and electricity from an energy mix). However, the use Therefore, it is revealed that the relative low energy efficiency of the
of solar-based utility always leads to lower energy efficiency and higher baseline S2P process can be dramatically improved by adopting the
operating cost compared to conventional utilities. Thus, the offsets of
the solar-based utility from the energy efficiency and economics per-
Table 5
spectives will be discussed in the following sections. Major assumptions and parameters for economic evaluation [17,18].
Table 4 shows the energy efficiency of the examined AS2M pro-
cesses and baseline. The AS2M #1 and #2 processes exhibit dramati- Parameters and assumptions Value

cally improved process energy efficiencies (ηpro) compared to that of the Project’s economic life [year] 30
baseline S2P process (increase by 26.5% and 24.6%, respectively). The Working capital [% of capital expense] 5%
main reason for this high efficiency over the baseline process is the Operating charges [% of operating labor cost] 15%
direct use of CO2 in MeOH production without syngas processing (see Plant overhead [% of labor and maintenance costs] 25%
Desired rate of return [% per year] 8%
Fig. 2(a)). In the baseline process, CO2/CO separation is required to
Tax rate [% per year] 35%
ensure the most favorable R value for the MeOH synthesis is obtained, Depreciation method Straight line
which is an energy-intensive MEA-based separation process, e.g., a

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Table 6
Capital and operating costs of the examined processes.
Baseline [18] (%) AS2M#1 (%) AS2M#2 (%)

Total capital investment ($) 618,946,622 100 616,909,103 100 624,252,271 100
(a) Direct capital cost
Solar field 532,326,686 86.0 525,039,686 85.1 532,326,686 85.3
CO/CO2 separation 5,964,836 1.0 – –
MeOH synthesis 4,324,100 0.7 – –
CO2 hydrogenation – 7,639,296 1.2 7,669,939 1.2
MeOH distillation – 1,196,698 0.2 1,206,912 0.2
(a) Indirect capital cost 76,330,000 12.3 83,033,423 13.5 83,048,734 13.3
Total operating cost ($/yr) 70,607,510 100 16,204,627 100 21,139,365 100
(a) Variable cost 67,758,761 14,726,727 17,918,940
Electricity 25,894,998 36.7 5,184,203 32.0 8,470,044 40.1
Heat 29,054,732 41.1 3,811,038 23.5 3,658,614 17.3
Cooling water 1,766,797 2.5 872,233 5.4 934,780 4.4
CO2 feedstock 11,042,235 15.6 4,859,253 30.0 4,855,503 23.0
(a) Fixed cost 2,848,749 1,477,900 3,220,425
Operate labor & charge 998,900 1.4 874,000 5.4 1,058,000 5.0
Maintenance cost 578,200 0.8 203,000 1.3 486,000 2.3
Plant overhead 563,800 0.8 240,500 1.5 703,000 3.3
G&A cost 739,949 1.0 160,400 1.0 973,425 4.6

direct CO2 hydrogenation instead of a two-stage MeOH production the industrial prices; for instance, the price of conventional elec-
route (i.e., CO2 to syngas and syngas to MeOH). tricity and heat is 0.06 and 0.02 $/kWh, respectively [17,18].

5. Economic evaluation
5.1. Minimum selling price (MSP)
In this section, the economic feasibility of the proposed AS2M
processes is analyzed. Major cost components (e.g., capital and oper- Table 6 summarizes the capital and operating costs. The TPI of
ating costs) are estimated using Aspen Process Economic Analyzer [39]. AS2M processes range between $616 and $624 million, which is rela-
The capital cost consists of direct (e.g., purchased equipment) and in- tively similar to the TPI of the baseline process ($617 million) [18].
direct (e.g., engineering and contingency) costs, while the operating This is because the cost of the dish/CR5 array at which the same unit of
cost includes variable operating (CO2 purchase, and costs for H2O, 17,622 is assumed, accounts for approximately 85−86% of TPI. Con-
steam, and electricity) and fixed operating (labor, plant overhead, op- versely, the operating cost of the AS2M processes is dramatically re-
erating charge, maintenance, and general and administration) costs duced compared to that of the baseline S2P process. By eliminating
[18]. The major assumptions and parameters applied to the economic energy-intensive sub-processes (e.g., CO2/CO separation and water gas
evaluation are summarized in Table 5 [17,18]. The energy and material shift reaction for syngas processing), the AS2M processes consume
costs assumed in this study are as follows: smaller utilities compared to that of the baseline process, thereby
leading to less operating costs.
• CO 2 price: Using amine-based CO2 absorption technology, the
Fig. 7 presents the MSP and the breakdown cost of its components:
ROI, income tax, and purchasing cost for CO2, as a feedstock and utility.
supply cost of CO2 based on a capture unit in a power station is
assumed to be 0.035 $/kg [48]. Note that the annual production rates of MeOH by the AS2M #1 and #2
• H2O price: De-ionized water is uses as cooling water with a price of processes are 94,932 and 94,489 ton/year, respectively, determined by
assuming the operability of 8000 h operation per year. The MSP of
0.03 $/m³ [17,18].
• Solar-based utility: Electricity and process heat is assumed to be MeOH produced by the AS2M processes are lower than that of MeOH
produced by the baseline S2P process (1.265 $/kg) (approximately
generated by a parabolic dish/stirling engine and a parabolic
trough, respectively. Accordingly, the price of electricity and heat reduced by 20−25%) [18]. While the ROI, which is a dominant cost-
generated from solar thermal energy is 0.15 and 0.05 $/kWh, re- driver, is almost constant across three processes. The considerable re-
spectively. Notably, the prices considered here are much higher than duction of utilities and CO2 supply costs in two advanced processes
leads to the decrease in the MSP of MeOH. The AS2M #1 process shows

Fig. 7. Breakdown of MSP and major components of the baseline and AS2M frameworks.

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Table 7
Comparison of different solar-to-methanol processes.
This study Baseline S2P [17,18] Alsayegh et al. [49]

Principles
H2 supply Thermochemical H2O splitting Thermochemical H2O splitting Photoelectrochemical H2O splitting
MeOH synthesis Direct CO2 hydrogenation Thermochemical CO2 splitting/ Syngas to MeOH Direct CO2 hydrogenation
Assumption and parameters
Solar-to-chemical efficiency [%] 20 20 10
Plant life [years] 30 30 30
Interest rate [%] 8 8 8
CO2 price [$/kg] 0.035 0.035 0.02
Electricity price [$/kWh] 0.15 0.15 0.06
Results
MeOH yield [kgMeOH/kgCO2] 0.70 0.66 0.67
Primary energy efficiency [%] 15.1a 11.7 6.25
MeOH MSP [$/kgMeOH] 0.941 1.265b 1.106c

a
The original efficiency (15.5%) is adjusted to include energy consumption for CO2 supply: 0.3 kW h/kgCO2 [49].
b
The original price (6.37 $/GGE of MeOH) of baseline S2P is converted to express in $/kgMeOH [18].
c
The original price (0.96$/kgCO2) is adjusted to include tax using 35% tax rate assumed in this study [49].

better economics, as well as better carbon and energy efficiencies than the flexible market or new improvement in technology. Thus, this study
the AS2M #2 process. On the other hand, the AS2M #2 process was analyzes the effects of changes of major parameters, particularly the
identified as an environmental friendly option for MeOH production lowering of utility prices, in the following section.
over the AS2M #2 process by achieving lower GWP score.
As discussed in Sections 1 and 2, the production of MeOH using 5.2. Sensitive analysis
solar energy is one of very interesting R&D topics from new material
development to practical process demonstration. Interestingly, Al- To analyze the effects of major processes and economic parameters
sayegh et al. [49] developed a new CO2 hydrogenation process for on MSP, an economic sensitivity analysis was performed for the AS2M
MeOH production using a photo-electrochemical route (i.e., photo- #1 process (referred to as base case), which showed the most favorable
catalytically produced H2 for CO2 hydrogenation), which is comparable MSP as well as carbon and energy efficiencies. The results of the eco-
to the proposed AS2M processes. Table 7 briefly summarizes the main nomic sensitivity analysis are presented in Fig. 8. For all the selected
principles, assumptions, and performance of different solar-to-methanol parameters, ± 20% change is considered based on the primary values
processes. The direct CO2 hydrogenation clearly exhibits improved used in this study. Initially, it is observed that the MSP is very sensitive
technical and economic performance over a conventional two-stage to the TPI, particularly the dish/CR5 unit price, which is the dominant
route (syngas from CO2 and H2, and MeOH from syngas). While the cost contributor of the TPI. The interest rate among the economic
MSPs of MeOH produced from the two CO2 direct hydrogenation parameters affecting the calculation of ROI is also a critical factor that
pathways (this study and Alsayegh et al.) are similar, they are ap- contributes to lowering the MSP, followed by tax rate. Another factor is
proximately 13−26% lower, than the MSP of the conventional two- the solar to chemical efficiency (currently at 20%). The over 21% im-
stage route. In addition, in the direct hydrogenation processes, the provement of the MSP can be possible by increasing the solar-to-che-
primary energy efficiency of the thermochemical route is 2.4 times mical efficiency by 4% (i.e., from 20% to 24%). Overall, it is obvious
higher than that of the photochemical route due to its high solar-to- that any improvements in the dish/CR5 array, such as cost reduction by
chemical conversion efficiency. Finally, it should be noted that while mass production and high efficiency using new materials, is a curial for
this study and Alsayegh et al. show very similar economics, this study enhancing the competitiveness of the proposed processes. Furthermore,
assumed very high prices of CO2 and utilities that are almost 75% and if active governmental policies, such as tax reduction and concessional
150% more expensive, respectively, than those in the work of Alsayegh investment are implemented along with the dish/CR5 improvements,
et al. [17,47]. This pessimistic current cost of solar utilities along with the AS2M processes can compete in a real methanol market.
other economic parameters can be, or has been, lowered according to The sensitive analysis in Fig. 8 provides good insights for further

Fig. 8. Sensitive analysis ( ± 20%) of major parameters on the MSP of the AS2M #1 process.

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Fig. 9. MSP and cost contribution of promising scenarios for AS2M #1.

examination to find out the optimistic scenario (Sc), which has the Declaration of Competing Interest
lowest MSP by combining the different positive changes of major
parameters. Fig. 9 presents the MSP and its breakdown costs in pro- The authors declare that they have no known competing financial
mising scenarios. The first scenario (Sc1) shows the change in the MSP interests or personal relationships that could have appeared to influ-
by assuming −20% CR5 price, which is reasonable with mass pro- ence the work reported in this paper.
duction and deployment lowering the price on a learning curve. In the
second scenario (Sc2), 20% improvement of the solar-to-chemical ef- Acknowledgments
ficiency, along with cost reduction of the dish/CR5 leads to a huge
reduction in the MeOH MSP from 0.94 to 0.7 $/kg. Sc3, based on the This work was supported by “Next Generation Carbon Upcycling
possibility of policy incentives or infrastructure, banks reducing tax or Project” (Project No. 2017M1A2A2043137) through the National
interest rates, exhibits a MeOH MSP of 0.75 $/kg, which decreases the Research Foundation (NRF) funded by the Ministry of Science and ICT,
base case MSP by 21%. A little decrease of MSP in Sc4 is due to the Republic of Korea.
minor effect of utility and CO2 price, as shown in sensitivity analysis.
Finally, the most optimistic scenario (Sc7) that includes all promising Appendix A. Supplementary data
changes presents the lowest MSP at 0.53 $/kg of MeOH that is de-
creased by 43.6% compared to that of the base case. This implies that if Supplementary material related to this article can be found, in the
successfully demonstrated, the AS2M process could commercially online version, at doi:https://doi.org/10.1016/j.jcou.2019.07.003.
compete in the current methanol market, where the price was 0.51 $/kg
in November 2018 (www.methanex.com). References

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