pubs.acs.

org/journal/ascecg Research Article

Prospects of Producing Higher Alcohols from Carbon Dioxide: A

Process System Engineering Perspective
Chi Hung Vo, Javier Pérez-Ramírez, Shamsuzzaman Farooq,* and Iftekhar A. Karimi*
Cite This: https://doi.org/10.1021/acssuschemeng.2c02810 Read Online

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ABSTRACT: Higher alcohols are promising products for large-scale

CO2 utilization due to their potential large volume use as chemical
energy carriers and fuel additives. Although the catalysts for these
transformations are still in early stages of development, it is
advantageous to examine their expected process level performance to
guide further scientific progress. Here, we performed prospective
techno-economic and environmental evaluations of 1-propanol, 1-
butanol, 1-pentanol, and 1-hexanol syntheses from captured CO2 and
green H2 via the syngas route (i.e., CO2 to syngas to higher alcohol) for
the best case (ideal) conversion and selectivity. While 1-pentanol and 1-
hexanol plants show economic viability, the costs of manufacturing the
other two alcohols exceed their respective revenues. In all the four
processes, the cost of raw materials, utilities, and wastewater treatment
accounts for about 83%, 12%, and 5% of the cost of manufacturing, respectively (neglecting CAPEX). Sensitivity analysis shows that
the cost of H2 has to drop to about 2100 and 1700 $ t−1 from the current level of ca. 2500 $ t−1 for 1-propanol and 1-butanol
processes to break even. In all four processes, the fraction of H2 feed lost to byproduct water ranges from 55 to 60%, which is an
inherent issue with thermocatalytic hydrogenation of CO2. Although a standalone green 1-propanol plant is not presently viable, a
hybrid process combining a recently studied synthesis route (using ethylene and CO2-derived syngas) and the novel route based
solely on CO2 can minimize the carbon footprint without sequestration and also be profitable at the prevailing hydrogen cost.
KEYWORDS: CO2 utilization, higher alcohol synthesis, hydrogen wastage, propanol, butanol, pentanol, hexanol

■ INTRODUCTION
Reducing anthropogenic carbon dioxide (CO2) emissions and
decarbonizing the economy require a multipronged approach
involving renewable energy generation, green hydrogen (H2)
production, carbon capture and utilization (CCU), and carbon
capture and sequestration (CCS). CCU refers to the process of
capturing CO2, either from the atmosphere or from a point
source, and using it for physical (enhanced oil recovery)1,2 or
chemical (mineralization, chemical/biochemical synthesis)3−5
utilization processes. A range of products from CO2 utilization
have been proposed and studied, including Fischer−Tropsch
fuels, aromatics, polymers, carbonates, carboxylic acids, ethers,
methanol, and higher alcohols (HAs).6−9 However, to
significantly impact global emissions, CO2 utilization should
focus on products produced in large quantities such as in
energy, construction, and polymer industries. In this context,
we examine the prospects of using CO2 to produce chemical
energy vectors in the form of HAs. Although alcohols have
relatively few applications as solvents, beverages, and
precursors to fine chemicals, they have a high potential as
chemical energy carriers. The combustion of petroleum-based
fuels is a major source of CO2 emissions,10 and alcohols
obtained from CO2 utilization can be used as a replacement or
fuel additives to reduce the consumption of the former. The
energy densities of methanol (C1OH), ethanol (C2OH), 1-
propanol (C3OH), 1-butanol (C4OH), 1-pentanol (C5OH),
and 1-hexanol (C6OH) are 22, 30, 33, 36, 38, and 39 MJ kg−1,
respectively, with the latter three approaching the lower ends
of natural gas, diesel, and gasoline (about 42 MJ kg−1).11 These
alcohols also have higher combustion efficiencies12 due to their
higher-octane numbers than gasoline. Blending of alcohols
with fuels has been shown to reduce the emissions of
greenhouse gases and particulate matter upon combustion,
while offering engine performance higher or comparable to
gasoline.13−17 In addition, the alcohols are liquid at ambient
temperature and pressure and can be stored in nonpressurized
tanks.
However, the production of alcohols from CO2 and H2 has
numerous economic and technological challenges. While the
Received: May 12, 2022
Revised: August 17, 2022
Accepted: August 18, 2022

© XXXX American Chemical Society https://doi.org/10.1021/acssuschemeng.2c02810

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Table 1. Atom Economy and H2 Wastage of CO2-Based Reactions and Their Industrial Counterparts (Highlighted in Gray)a
a
Atom economy is the mass ratio of the desired product to the reactants. H2 wastage is the ratio of H2 used in water formation to the feed H2. N.A.:
not applicable.
hydrogenation of CO2 to C1OH using Cu-based catalysts has
demonstrated good conversion and selectivity9 with several
pilot plants under construction or in operation,8 the economic
viability remains a hurdle.6,18,19 On the contrary, higher alcohol
(HA) synthesis from CO2 has not yet achieved considerable
yield for industrial implementation.20 The electrocatalytic
route is challenging since a large number of both electrons
and protons need to be transferred to CO2.21 The Faradaic
efficiency is 2 to 5% for C3OH synthesis21 and 0.06% for
C4OH.22 Genetically engineered cyanobacteria have been used
to produce C4OH, but the yield is currently low (about 0.3
gC4OH L−1 day−1).23,24 For the remaining discussion, we will
only focus on the thermocatalytic hydrogenation of CO2. The
common thermocatalytic route of HA synthesis is to produce
synthesis gas (syngas) via reverse water−gas shift reaction,
followed by the conversion to alcohols.20 This latter reaction is
akin to the combination of Fischer−Tropsch synthesis and
methanol synthesis, and as a result, the product mixture
contains several compounds, including alcohols, alkanes,
alkenes, other oxygenates, and CO2.20 Liu et al.25 reported a
conversion of 76% using CuCo/LaFeO3 catalyst with a HA
selectivity of 29%. Using layered double hydroxides grown on
carbon nanotubes, Cao et al.26 achieved 45% conversion with
an increased selectivity (62%) for HAs. Luk et al.27 synthesized
K-promoted CuFe catalyst supported on carbon nanofibers
and attained 37% selectivity for HAs at 14% conversion, with a
state-of-the-art space-time-yield of 0.53 gHA gcatalyst−1 h−1. A
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comprehensive review of the status and prospects of HA
synthesis from syngas can be found in the literature.20 A direct
route for HA synthesis from CO2 has also been reported.28,29
While the current efforts are being directed toward catalyst
development, it is equally important to examine HA synthesis
from a process system engineering perspective. We focus on
HA synthesis from CO2 utilization via the syngas route.
Technological, economic, and environmental analyses of the
process can reveal its potential, underscore the gaps to
overcome, and set the direction for future research. Here, we
examine the prospects of HA synthesis from CO2 by designing
a process for each alcohol (C3OH to C6OH) and evaluate
their economic and environmental performances. We present
the maximum plant profitability by assuming an ideal catalyst
that gives full conversion and selectivity for HA synthesis. This
allows us to further highlight other challenges in the process
design of HA synthesis, which should be considered and
tackled simultaneously with catalytic development. Among the
four higher alcohols investigated in this study, only synthesis of
C3OH from syngas and ethylene was discussed in a recent
publication from this laboratory.6 This is the first compre-
hensive process evaluation study on the synthesis of the higher
alcohols only from syngas obtained by reacting captured and
concentrated CO2 with green H2. In the next section, we will
discuss the concept of hydrogen wastage (HW) and show that
HA synthesis from CO2 is advantageous due to its relatively
low HW in comparison to other products of the same carbon
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chain length. Following that, our evaluation method and results
will be presented.
■
METHODS
In any CO2 utilization process, the cost of H2 dominates the raw
material cost and therefore plays an important role in determining the
economic viability. We first present the concept of hydrogen wastage
(HW) and use it alongside with atom economy to evaluate CO2
utilization reactions. Thereafter, we study four ideal alcohol
manufacturing processes and perform simulations, which are then
used to assess economic and environmental impacts.
Atom Economy and Hydrogen Wastage of CO2 Utilization
Reactions. It is often advocated that product synthesis should
maximize atom economy.30 However, this concept has to be
downplayed in CO2 utilization. Since the carbon in CO2 is at its
highest oxidation state (+4), the catalytic conversion of CO2 to value-
added products requires a reducing agent. In several studies,31−33 H2,
preferably generated from a renewable source, has been used for this
purpose. The CO2 hydrogenation often entails the breakage of
carbon−oxygen bonds, and the oxygen moiety is scavenged by H2 to
form the byproduct water. This latter portion of H2 is “wasted” and
impacts the cost of raw materials for the process. We define HW as
the fraction of H2 feed used in byproduct water formation (eq 1).
H used in water formation
hydrogen wastage (HW) = 2
H 2 feed (1)
We computed and compared atom economy and HW for different
CO2 utilization processes and their respective conventional counter-
parts (Table 1). The atom economy in the CO2 utilization routes is
about 28%, dwarfed by 100% in the industrial routes (except for
alkane produced from the Fischer−Tropsch synthesis). The prospect
of CO2 as a platform chemical is impeded by its oxygen moiety, which
is often not incorporated fully in the desired product and has to be
removed at the expense of consuming additional H2. This H2 wastage
increases with the carbon chain length in the desired product. The
issue is absent in the industrial synthesis routes, where alkenes are
commonly used to lengthen the carbon chain.
Given the costly production of H2, HW should be factored in
reaction design. As the number of carbon atoms in the product
increases, the HW quickly approaches 66.67%, regardless of its
chemical composition (Figure 1). This is expected since each carbon
atom in a long carbon chain is bonded to approximately two hydrogen
atoms, while the two oxygen atoms from CO2 require four hydrogen
atoms. Therefore, the ratio of “useful” hydrogen to “wasted” hydrogen
is 2:4, yielding a HW of 66.67%. In general, the HW observes the
Figure 1. Hydrogen wastage of different products derived via
hydrogenation of CO2.
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following trend: alkene > aldehyde/ketone > alkane > carboxylic acid
> alcohol/ether, justifying our choice of alcohols as the product of
CO2 utilization. Formic acid has zero HW, but this compound has a
low market value (about 80 $ t−1), and the cost of H2 needs to be
almost zero for this process to be economically viable. In addition,
formic acid is unsuitable for use as a fuel due to its low heat of
combustion (seven times lower than that of gasoline).
Having established the advantages of HAs over other products of
CO2 utilization through the concept of HW, we will now present the
method and results of our study.
Process Description. In this study, the HA synthesis process
consists of three steps: syngas generation, HA formation, and
purification. In the first step (Figure 2a), CO2 and H2 are preheated
before entering the gas-phase reactor. There, the reaction is catalyzed
by Ni/Al2O3 catalyst at 1173 K and 2.3 bar.34 The ratio of H2 to CO2
in the feed is adjusted to achieve syngas with H2/CO ≈ 2. Thereafter,
the syngas undergoes a series of compressions with intercooling (at
313.15 K) and water removal, followed by preheating. The reactor
conditions for HA synthesis were selected to be 50.0 bar and 543 K,
based on the work of Luk et al.,27 which reports the state-of-the-art
space-time-yield. In each case, the catalyst was assumed to be ideal
(100% conversion and 100% selectivity), yielding the respective
alcohol as the sole carbon product (eqs 3−6).
CO2 + H 2 F CO + H 2O ΔH° = + 41.1 kJ mol−1 (2)
3CO + 6H 2 → CH3CH 2CH 2OH + 2H 2O
ΔH° = − 407 kJ mol−1 (3)
4CO + 8H 2 → CH3(CH 2)2 CH 2OH + 3H 2O
ΔH° = − 558 kJ mol−1 (4)
5CO + 10H 2 → CH3(CH 2)3 CH 2OH + 4H 2O
ΔH° = − 710 kJ mol−1 (5)
6CO + 12H 2 → CH3(CH 2)4 CH 2OH + 5H 2O
ΔH° = − 862 kJ mol−1 (6)
The product mixture undergoes a separation process for water
removal, which varies for each alcohol. Due to the formation of a
homogeneous azeotrope, the separation of C3OH from water requires
extractive distillation with an entrainer such as ethylene glycol35
(Figure 2b). This process was studied and rigorously modeled by Pla-
Franco et al.,35 and a brief description is given here after. The
entrainer and C3OH−water mixture enter an extractive column
operating at atmospheric pressure. C3OH is removed as the overhead
product at 369.05 K. The bottom stream is sent to a second
atmospheric column for entrainer recovery.
Unlike C3OH, C4OH forms a heterogeneous azeotrope with
water. Therefore, entrainer is not needed and the purification process
is implemented using a phase-separation decanter and two
atmospheric reboiled absorbers36 (Figure 2c). The C4OH−water
mixture is cooled to 313.15 K before entering a decanter where phase
separation occurs. The light and heavy phases are sent to C4OH-
concentrating and water-concentrating columns, respectively. C4OH
(390.85 K) and water (373.15 K) are withdrawn as the bottom
products from the respective reboiled absorbers at high purities, while
the overhead streams of both columns are recycled to the decanter.
Finally, C5OH and C6OH, each can be separated from water using a
phase-separation decanter and a single reboiled absorber (Figure 2d).
The alcohol−water mixture is allowed to separate in a decanter at
313.15 K. The light phase, consisting of about 90 wt % of the alcohol,
is sent to an atmospheric reboiled absorber for further purification.
Additional information about the energy requirements for the four
processes can be found in the Supporting Information. All heating
requirements (e.g., steam generation and fired furnaces) in the four
processes are provided by natural gas. Energy integration was
achieved using pinch analysis.37
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Figure 2. Process flow diagrams of HA synthesis plants: (a) syngas generation and alcohol production, (b) separation process for C3OH−water
mixture, (c) separation process for C4OH-water mixture, and (d) separation process for C5OH−water and C6OH−water mixtures. aq, aqueous
dilute mixture; l, concentrated liquid; WW, wastewater.

Process Modeling. To standardize our comparison, a processing production cost of green H2 were varied to reflect the impact of
capacity of 0.704 MtCO2 a−1 (2000 kmol h−1) was assumed for all four source-dependent variation and different methods of production. The
alcohols. The feed gases, CO2 and H2, were assumed to be at 298 K market values of C5OH and C6OH were based on import data from
and 17.0 bar. The processes were modeled using Aspen HYSYS V10. India,40,41 and those of other chemicals were from China domestic
A nonrandom two-liquid (NRTL) model was used in the C3OH prices.42 Other costs were adopted from Turton.37
plant since it well describes the azeotrope.35 The other three plants The plants were assumed to have annual operations of 8000 h. The
were modeled by UNIQUAC. Specific to C3OH plant, the utilities cost of manufacturing (COM, $ a−1), was estimated based on eq 7,37
required for separation was adopted from Pla-Franco et al.35 The where the capital cost contribution of the process equipment and the
kinetics of syngas generation from CO2 and H2 were adopted from cost of catalyst are neglected.
the literature.34
Economic Evaluation. The parameters used in the economic COM = 2.73COL + 1.23(CUT + CRM + C WT) (7)
evaluation are presented in Table 2. The capture cost of CO2 used in
the study is a representative average of the values reported in the
In eq 7, COL, CUT, CRM, and CWT are labor, utilities, raw materials,
literature for carbon capture and concentration from dilute gas
streams (90 $ t−1).38 Green H2 was assumed to be obtained from and waste treatment costs, respectively. Since the capital cost is
water electrolysis using renewable energy at a cost of 2500 $ t−1.39 In annualized over the plant life of 25 years, its contribution to the COM
the subsequent sensitivity analysis, the capture cost of CO2 and is usually a minor component. In addition, due to the assumption of
ideal catalysts, the lack of kinetic parameters for HA synthesis renders
Table 2. Parameters Used in the Economic Evaluation of size and cost estimation for the reactor impractical. Neglecting of
the C3OH to C6OH Synthesis Plants capital cost contribution results in an underestimate of the COM, but
it is unlikely to affect our conclusions.
Environmental Evaluation. To evaluate CO2 emissions, the
material cost ($ t−1) utilities and others
boundary was set to encompass all the processes within the plants,
captured CO2 90 electricity ($ kWh−1) 0.130
including the emissions associated with the raw materials. The raw
green H2 2500 cooling water ($ m−3) 0.0317
material CO2 was assumed to be captured using an amine-based
ethylene glycol 900 low pressure steam ($ t−1) 9.45
absorption process, which generates about 0.220 tCO2 tcaptured CO2−1.43
selling price (profit) ($ medium pressure steam ($ 9.54
t−1) t−1) Green H2 was assumed to be produced with negligible emission. An
C3OH 1340 natural gas ($ 10−6 Btu−1) 4.50 emission factor of 3.2 tCO2 tethylene glycol−1 was used for the entrainer.44
C4OH 1260 labor ($ labor−1 a−1) 60000 Other sources of CO2 emissions include exiting waste streams, flare
C5OH 2730 waste treatment ($ t−1) 36.0 gases from the combustion of natural gas, and indirect emissions
C6OH 2900 associated with electricity generation.

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Table 3. Key Simulation Results for C3OH to C6OH Synthesis Processesa

C3OH C4OH C5OH C6OH
material stream (Mt a−1)
CO2 0.704 0.704 0.704 0.704
H2 0.089 0.094 0.093 0.094
product 0.282 0.284 0.248 0.254
wastewater 0.490 (0.440) 0.495 (0.490) 0.524 (0.497) 0.520 (0.507)
utilities (TJ a−1)
electricity 691 796 (40) 748 744
heating 1991 (1388) 2545 (1904) 794 (154) 789 (155)
cooling 4364 (1008) 5735 (2176) 4362 (694) 4379 (713)
a
For wastewater, the numbers in the parentheses indicate the quantity of water alone (i.e., after subtracting other chemicals). For utilities, the
numbers in parentheses indicate the values associated with alcohol−water separations.

■ RESULTS
Technical Evaluation. The key simulation results are
study, but the C4OH mixture before purification (5 wt %) is
more dilute than that in our work (42 wt %). This may explain
the higher heating duty in their work.
reported in Table 3. The detailed design specifications are
Economic Evaluation. The COM values of the C3OH to
compiled in Tables S1−S4 (Supporting Information). In this
C6OH synthesis plants are 1486, 1590, 1765, and 1721 $
scenario of ideal catalysts, each tonne of CO2 is transformed
tproduct−1, respectively (Figure 3). While these costs are of the
into 0.401, 0.403, 0.352, and 0.361 tonne of C3OH to C6OH,
respectively. The difference in product quantities is mainly due
to a varying amount of unreacted CO2 leaving the plants in the
wastewater. Common to the four plants, there are five
wastewater streams, four of which are in the compression
train. The fifth wastewater streams in C3OH and C4OH
processes exit from a distillation column with little dissolved
CO2, while those in C5OH and C6OH processes exit from a
phase-separation decanter with more dissolved CO2. The
higher losses of CO2 in the latter cases result in lower product
quantities.
The amount of byproduct water in the HA synthesis follows
the trend: C3OH (0.440 Mt a−1) < C4OH (0.490 Mt a−1) <
C5OH (0.497 Mt a−1) < C6OH (0.507 Mt a−1) (Table 3).
This is equivalent to wasting about 55−60% of the H2 feed.
Due to the differences in separation processes and solubilities
of the alcohols in water, there is a varying degree of leakage
into the wastewater streams. For instance, the C3OH synthesis
process produces the least amount of water, but a large amount Figure 3. Economic analysis of the C3−6OH synthesis plants.
of C3OH is lost to the wastewater due to the difficult C3OH−
water separation. Consequently, the wastewater discharged in
the C3OH synthesis plant (0.490 Mt a−1) is almost the same as same order, the market values of the alcohols result in different
that in the C4OH synthesis plant (0.495 Mt a−1) (Table 3). economic prospects. Despite assuming ideal catalysts and only
Overall, the four alcohol synthesis plants discharge 0.490− considering COM, C3OH and C4OH manufacturing will incur
0.524 Mt a−1 of wastewater. losses (146 and 330 $ t−1, respectively) at the assumed costs of
At reactor outlets, the concentrations of C3OH to C6OH CO2 (90 $ t−1) and H2 (2500 $ t−1). On the contrary, the
are 45.6, 41.9, 38.9, and 37.7 wt %, respectively. After revenues from the sale of C5OH and C6OH at the prevailing
purification, the alcohols are obtained at high purities (99.9 wt market rate exceed their respective COM. While this does not
%), with the exception of a slightly lower purity (99.4 wt %) confirm profitability since we have ignored capital cost in our
for C3OH. Compared to the other two alcohols, C3OH and cost calculations, the wide margins (965 and 1179 $ t−1,
C4OH synthesis processes require significantly higher heating respectively) suggest that these two alcohols are more
utilities due to the complexity in the azeotropic separation promising targets for manufacturing from CO2. Catalyst
units. In the C4OH case, the overhead streams of both development, therefore, should strive for higher fractions of
columns are recycled to the decanter, where the liquid is C5OH and C6OH in the products instead of the other two
cooled to induce phase separation. Therefore, the cooling duty alcohols.
is the highest in the C4OH synthesis process. The heating duty In all four plants, the utilities account for about 12% of the
required for C4OH−water separation in our study is about 6.7 COM. The separation cost for C3OH to C6OH and their
GJ t−1 of C4OH, which is of the same order of magnitude as water mixtures are 33.8, 57.4, 8.9, and 8.9 $ tproduct−1,
the values reported by Matsumura et al.45 (about 3 GJ t−1) and respectively, which are less than 5% of their corresponding
Vane et al.46 (10 GJ t−1). Matsumura et al.45’s result was revenues. However, these relatively low costs of separation are
obtained from a simplified analytical energy balance and, due to high concentrations of alcohols at the reactor outlet
therefore, may differ from our rigorous simulation. Vane et under ideal assumptions. A dilute product stream will increase
al.46 used the same reboiled absorber−decanter system as our the cost of separation. For instance, Luyben36 showed that the
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heating duty required for C4OH−water separation increases
by more than 6-fold if the feed C4OH concentration drops
from 40 to 3 wt %. There is a 25-fold increase in the required
heating duty, if the feed C4OH concentration drops to 0.5 wt
% instead.45
The wastewater treatment costs, although only 5% of the
COM, are comparable with the utilities costs. Once again, this
highlights the fact that a significant amount of aqueous waste is
generated in HA synthesis from CO2.
Common to all four alcohols, the raw material costs
constitute about 83% of the COM, emphasizing the need of
cheaper green H2. In fact, a sensitivity analysis (Figure 4)
Figure 4. Sensitivity analysis for the cost of manufacturing of the
C3OH to C6OH synthesis. The manufacturing costs ($ tproduct−1) are
represented by the colors. The market values of C3OH to C6OH
used in this study are 1340, 1260, 2730, and 2900 $ t−1, respectively
(indicated by black lines for C3OH and C4OH). The upper region of
the black line represents the combinations of raw material costs at
which the cost of manufacturing is lower than the market price of the
product and vice versa for the lower region. For C5OH and C6OH,
the cost of manufacturing is lower than the market price of the
product at all examined combinations of the raw material costs.
shows that the COM values of C3OH and C4OH synthesis
plants match their respective revenues when the cost of H2
drops from 2500 to about 2100 and 1700 $ t−1, respectively,
assuming that the cost of CO2 is maintained at 90 $ t−1. These
scenarios are not achievable at the moment, given that the
current cost of green H2 ranges from 2500 to 8000 $ t−1.47
THe availability of low-cost renewable energy for green H2
production will be the key factor in determining the viability of
these two processes. Furthermore, appreciation in market
values of C3OH and C4OH can also alter the prospects of
these processes. Based on historical trends, the market values
of the two alcohols at some points48,49 had exceeded 1700 $
t−1, which is more than their COM.
Environmental evaluation. The CO2 emissions in the
C3OH to C6OH plants are 0.452, 0.444, 0.386, and 0.347
MtCO2 a−1, respectively (Figure 5). With a capacity of 0.704
MtCO2 a−1, the net CO2 utilizations normalized by product
quantities are 0.894, 0.915, 1.28, and 1.41 tCO2 tproduct −1,
respectively. The emissions associated with raw materials are
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Figure 5. Breakdown of CO2 emissions in the C3−6OH synthesis
plants; each has a capacity of 0.704 MtCO2 a−1.
sizable, contributing 0.155 MtCO2 a−1 in the C4OH to C6OH
manufacturing. The value is higher in C3OH manufacturing
(0.160 MtCO2 a−1) due to the emissions associated with the
entrainer ethylene glycol. The more energy intensive
separation processes in C3OH and C4OH plants translate to
higher emissions in flare gases (0.130 and 0.164 MtCO2 a−1,
respectively).
■ DISCUSSION
Challenges and Options in the Design of Higher
Alcohol Synthesis Processes. Despite the assumption of
ideal catalysts, it is evident that HA synthesized from CO2 has
other challenges. The high cost of raw materials and high HW
have been examined in the foregoing discussion. In addition,
the current global capacity of green H2 production is
insufficient to support the CO2 utilization endeavor.6 These
challenges have to be addressed to make HA synthesis from
CO2 feasible. Furthermore, this CO2-based alcohol synthesis
necessitates alcohol−water separation. The industrial produc-
tion of HAs first produces aldehyde from syngas and alkene,
which is followed by hydrogenation.50 Water is not generated
in these processes, eliminating the need for difficult water−
alcohol mixture separation. As shown earlier, C3OH−water
and C4OH−water separations are energy intensive and
contribute sizable amounts of CO2 emissions (Table 3 and
Figure 3). The synthesis of these two alcohols will benefit from
innovative reactor design such as membrane reactors, which
simultaneously allow for partial water removal and enhance
reaction conversion. Membrane reactors for CO2 trans-
formation to useful products have been studied in the
literature.51,52 In addition, considering the large volume of
wastewater in HA synthesis, an on-site wastewater treatment
system will be beneficial in high-capacity plants.
Evidently, the following trade-offs are inherent in
thermocatalytic transformation of CO2. One, products with
longer carbon chain length generally have higher market values
but also a higher HW. Two, a higher degree of saturation
(fewer double and triple bonds) and oxygenation in the
products reduces HW but leads to a lower heat of combustion.
Finally, as elaborated in a later section, a hybrid strategy of
using both CO2 and alkenes in product synthesis has a positive
impact on the economic performance. However, instead of
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Table 4. Comparison of gC3OH6 and mC3OH Routes

gC3OH mC4OH
raw materials CO2 and H2 CO2, H2, and ethylene
(1) (1)
reactions
CO2 + H 2 F CO + H 2O CO2 + H 2 F CO + H 2O
(2) (2)
3CO + 6H 2 → CH3CH 2CH 2OH + 2H 2O CH 2CH 2 + CO + H 2 → CH3CH 2CHO
(3)
CH3CH 2CHO + H 2 → CH3CH 2CH 2OH
economic performance unviable viable
CO2 emissions net negative net positive
references this study 6

Figure 6. Process strategies for CO2 emissions reduction in C3OH synthesis with and without sequestration: (a) CO2 emissions from the mC3OH
process are captured, concentrated, and stored, and (b) CO2 emissions from the mC3OH process are captured, concentrated, and used in a parallel
gC3OH synthesis process. The representative values shown are for 1 tonne of C3OH produced in both strategies. The numbers in black below the
chemical compounds indicate their quantities (in tonne). The numbers in red (in $) are the profit (with + sign) or loss (with − sign). Carbon
capture and concentration is assumed to have an efficiency of 90%, and the remaining 10% is released to the atmosphere. In addition, the carbon
emissions associated with carbon capture and concentration is 0.22 tCO2 tcaptured CO2−1. A tax of 90 $ t−1 is imposed on the CO2 emissions to the
atmosphere. 100 $ t−1 is assumed as the cost of sequestration.

removing CO2, this hybrid strategy is at best carbon neutral.
These trade-offs are applicable to not only valorization of CO2
to HA synthesis but also any catalytic process using CO2 and
H2.
Hybrid Synthesis Route to Minimize CO2 Emissions
without Sequestration. Although HA synthesis using CO2
as the sole carbon feed is a desirable outcome, a hybrid
synthesis route involved both CO2 and fossil fuel-based alkenes
as reactants can be beneficial. C3OH synthesis will be used to
illustrate this point. For clarity, we call the product produced
from captured CO2 and green H2 (assuming an ideal catalyst),
i.e., the synthesis route explored in this study, gC3OH (green
C3OH). Recently, another process route (mixed-feed C3OH
or mC3OH) using syngas (produced from CO2 and green H2)
and fossil fuel-based ethylene has been studied.6 This mC3OH
route is similar to the industrial oxo process,50 where syngas is
used to form propionaldehyde, followed by hydrogenation to
C3OH. However, instead of using steam methane reforming,
the mC3OH route uses reverse water−gas shift to form syngas
from CO2 and H2. A detail description of this mC3OH route
can be found in the literature.6 A comparison of gC3OH and
mC3OH is presented in Table 4.
At a market value of 1340 $ t−1, the mC3OH route is
economically viable. This route uses ethylene (106 $ t−1), a
G https://doi.org/10.1021/acssuschemeng.2c02810
cheaper source of carbon and hydrogen atoms. In fact, one
tonne of ethylene provides 0.857 tonne of carbon and 0.143
tonne of hydrogen, which will cost 462 $ if separately supplied
by CO2 and H2. In addition, C3OH−water separation is
avoided since water is not formed in the hydrogenation step.
The mC3OH route presents an interesting option: it has a
better economic performance than the gC3OH route and
significantly reduces CO2 emission compared to the industrial
process. The CO2 emissions in mC3OH route require capture,
concentration, and sequestration (CCS). As further detailed
next, by appropriately adjusting gC3OH and mC3OH in a
hybrid route, it is possible to attain the same minimum level of
CO2 emissions achievable in the mC3OH process with CCS.
The additional cost of CCS to minimize CO2 emissions
from the mC3OH route will reduce its profit margin from 463
to 239 $ tC3OH−1 (Figure 6a). However, sequestration option is
not readily available in every country or plant location.
Therefore, an alternative to sequestration with comparable
CO2 emissions reduction is beneficial. This is achievable by
appropriately balancing the two synthesis pathways (mC3OH
and gC3OH) comprising the hybrid route such that CO2
captured and concentrated from the mC3OH pathway is
completely used in the gC3OH pathway (Figure 6b). The
hybrid strategy has a comparable profit (239 $ tC3OH−1 versus
ACS Sustainable Chem. Eng. XXXX, XXX, XXX−XXX
ACS Sustainable Chemistry & Engineering
207 $ tC3OH−1) and CO2 emissions (0.337 tCO2 tC3OH−1 versus
0.310 tCO2 tC3OH−1) compared to CCS. In essence, this
synergistic integration allows a win−win exchange of economic
and environmental benefits.
■
CONCLUSION
The urgency of emissions mitigation demands a system level
approach to evaluate the CO2 utilization products currently
investigated to identify the catalyst attributes necessary for
their translational success. In this study, we have performed a
techno-economical and environmental assessment of four HA
synthesis processes with a capacity of 0.704 tCO2 a−1,
individually producing C3OH, C4OH, C5OH, and C6OH.
Since no HA synthesis catalyst looks promising yet for
industrial deployment, we assumed ideal conversion and
selectivity in order to evaluate the best-case performances.
While all four processes have net positive CO2 consumption,
only C5OH and C6OH demonstrate economic viability
presently. The COM of C3OH and C4OH synthesis processes
exceeds their revenues due to their relatively lower market
values and more energy intensive separations. Different
emerging separation strategies, such as membrane reactors,
may be advantageous for these two alcohols. The cost of raw
materials accounts for about 83% of the COM in the four
plants, highlighting the need of more economical green H2
production and CO2 capture processes. Under the ideal
conversion and selectivity assumptions, alcohol concentration
is modest. Therefore, the cost of separation is relatively low,
but it will increase considerably for a mixed product and/or
incomplete conversion. The large amount of water byproduct
consumes 5% of the COM for wastewater treatment, and on-
site treatment system is recommended for large-scale
production of HA synthesis. These results highlight the
technological and economic hurdles beyond their catalyst
development.
As a bigger picture, we have demonstrated the concept of
HW and showed that any product of thermocatalytic CO2
utilization has an unavoidable high HW, approaching 66.67%
as the carbon chain length increases. Given the current high
cost of green H2 production, this inherent inefficiency should
be considered while choosing the products to be manufactured
from CO2 utilization. In this regard, HAs are preferred over
other options for CO2 utilization.
It has been shown that a hybrid route using a combination of
gC3OH and mC3OH has comparable profit (239 versus 207 $
tC3OH−1) and CO2 emissions (0.337 versus 0.310 tCO2 tC3OH−1)
compared to the mC3OH process with CCS. This synergistic
integration can be an alternative solution to avoid sequestra-
tion.
While our study centers on the four HAs, the results discern
generic issues in HA synthesis and CO2 utilization, entailing
raw materials cost, HW, difficulties in separation, and
wastewater treatment, and emphasizing the need of a holistic
approach in tackling the CO2 emission conundrum.
■
ASSOCIATED CONTENT
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acssuschemeng.2c02810.
Tables of design specifications for C3OH to C6OH
processes (PDF)
H https://doi.org/10.1021/acssuschemeng.2c02810
■
pubs.acs.org/journal/ascecg Research Article
AUTHOR INFORMATION
Corresponding Authors
Shamsuzzaman Farooq − Department of Chemical and
Biomolecular Engineering, National University of Singapore,
117585, Singapore; orcid.org/0000-0002-6501-5540;
Email: chesf@nus.edu.sg
Iftekhar A. Karimi − Department of Chemical and
Biomolecular Engineering, National University of Singapore,
117585, Singapore; orcid.org/0000-0001-7122-0578;
Email: cheiak@nus.edu.sg
Authors
Chi Hung Vo − Department of Chemical and Biomolecular
Engineering, National University of Singapore, 117585,
Singapore; orcid.org/0000-0002-8242-8494
Javier Pérez-Ramírez − Institute for Chemical and
Bioengineering, Department of Chemistry and Applied
Biosciences, ETH Zürich, 8093 Zürich, Switzerland
Complete contact information is available at:
https://pubs.acs.org/10.1021/acssuschemeng.2c02810
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This study was supported by the National University of
Singapore under its Flagship Green Energy Programme (R-
279-000-553-646, and R-279-000-553-731). Process flow
diagrams and molecules were drawn using Visual Paradigm
Online (https://online.visual-paradigm.com/) and MolView
(https://molview.org/), respectively, under their noncommer-
cial free use.
■
ABBREVIATIONS USED
$, U.S. dollar; a−1, per annum; C1OH, methanol; C2OH,
ethanol; C3OH, 1-propanol; C4OH, 1-butanol; C5OH, 1-
pentanol; C6OH, 1-hexanol; CCS, carbon capture and
sequestration; CCU, carbon capture and utilization; COM,
cost of manufacturing; HA, higher alcohol; HAs, higher
alcohols; HW, hydrogen wastage; Mt, megaton; t, tonne; TJ,
terajoule
■
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