Journal of CO₂ Utilization 27 (2018) 223–237

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Journal of CO2 Utilization

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

Promising catalytic synthesis pathways towards higher alcohols as suitable T

transport fuels based on H2 and CO2
⁎
Steffen Schemmea, , Janos Lucian Breuera, Remzi Can Samsuna, Ralf Petersa, Detlef Stoltena,b
a
Forschungszentrum Jülich GmbH, Electrochemical Process Engineering (IEK-3), 52425 Jülich, Germany
b
Chair for Fuel Cells, RWTH Aachen University, 52072 Aachen, Germany

A R T I C LE I N FO A B S T R A C T

Keywords: To address the pressing challenges of energy security and global warming, the coupling of the energy generation
Power-to-Fuel and transport sectors using Power-to-Fuel (PtF) technologies is an attractive strategy. PtF means the synthesis of
Electrofuels transport fuels based on CO2 from industrial exhaust gases and H2 produced from renewable electricity via
Synthetic fuels electrolysis.
Renewable energy storage
This paper provides a comprehensive overview of the synthesis possibilities and potentials of H2 and CO2-
CO2 utilization
based methanol and higher alcohols (C1–C8; from methanol up to octanol) as alternative transport fuels by
adapting established and novel alcohol synthesis pathways to the PtF concept and assessing their technical
maturity using the Technology Readiness Level (TRL) method. A literature review reveals that among the al-
cohols, methanol, ethanol, 1-/2-/iso-butanol and 1-octanol have the highest relevance for fuel blending. With
the aim to give a first impression, we roughly estimated and discussed the production costs depending on the H2
costs. We estimated the TRL of promising synthesis pathways towards alcohols at 8 for methanol and at 4 for
ethanol, 1-butanol and iso-octanol. For 1-octanol, no suitable synthetic pathway is currently known.

1. Introduction increasingly referred to as electrofuels [9–12] or e-fuels [7,9,13,14].

In the process of transitioning towards a sustainable energy system
(in German: the Energiewende), the replacement of conventional energy
sources with renewable ones, as well as the reduction of CO2 emissions
across all sectors, are fundamental objectives. Since renewable energy
sources are subject to natural fluctuations and thus may not always
match with demand, suitable energy storage technologies must be de-
veloped to ensure the security of supply. A promising storage option to
harness the energy that cannot be used directly in the system is the
production of H2 by means of electrolysis. The secondary energy carrier
H2 can then be used in the currently fossil fuel-based transport sector,
for instance in fuel cell vehicles. Aside from use in fuel cell cars, an
attractive strategy to surmount the challenges arising from the
Energiewende is coupling the energy generation, industrial and trans-
portation sectors using Power-to-Fuel (PtF) technologies: the synthesis
of transport fuels based on CO2 and H2 produced from renewable
electricity by electrolysis [1–8]. In the literature, these fuels are
In a sustainable system, CO2 can for instance be sequestrated from
biogas or industrial exhaust gases, e.g. from cement, steel and chemical
industry. Also CO2 sequestration from air can be considered. In cement
plants for instance, 70% of the emitted CO2 is chemical reaction [15]
related. According to Harp et al. [16], for an integrated steelwork, the
only economically feasible way to de-carbonize in the short term is to
use the CO2 emissions as a feedstock, e.g. for a Power-to-Methanol
process. In an integrated steelworks, the use of coke oven gas can also
be a source for the required H2 [16]. In Germany, around 19Mt CO2
were emitted by the cement industry in 2016 [15]. This amount of CO2
is more than 8 times higher than the CO2 demand which Power-to-Fuel
processes would have been required to cover Germany’s fuel ethanol
consumption in 2016 of 1485 million liters [17].
Beside the catalytic conversion based on H2 and CO2, the conver-
sions via biocatalytic systems [18,19], bioelectrocatalytic systems [20]
and electro-reduction [21] towards fuels and chemicals are emerging
fields.

Abbreviations: BuOH, butanol; CI, compression-ignition; EtOH, ethanol; EC, European Commission; DME, dimethyl ether; FT, Fischer-Tropsch; MAS, mixed-alcohol-
synthesis; MeOH, methanol; MON, motor octane number; MTD, methanol-to-DME; OME, polyoxymethylen dimethyl ether; PrOH, propanol; PtF, Power-to-Fuel; RFS,
renewable fuel standard; RON, researched octane number; rWGS, reverse water-gas shift; SI, spark-ignition; SoA, state-of-the-art, TRL > 9; STD, synthesis gas-to-
DME; TRL, technology readiness level
⁎
Corresponding author.
E-mail address: s.schemme@fz-juelich.de (S. Schemme).

https://doi.org/10.1016/j.jcou.2018.07.013
Received 6 February 2018; Received in revised form 9 July 2018; Accepted 24 July 2018
2212-9820/ © 2018 Elsevier Ltd. All rights reserved.
S. Schemme et al.
The use of non-food based feedstocks (lignocellulosic, algal biomass
and CO2, CO/H2 from industrial flue gases or from waste or biomass
gasification) is an emerging field [22]. Potential advantages of bioca-
talysis and bioelectrocatalysis are moderate temperatures and pres-
sures, toleration regarding trace amounts of contaminants in feed gas,
decreased sensitivity to syngas component ratio, higher conversion due
to irreversibility of biological reactions and high yield due to high en-
zymatic specificity [20,23]. Especially bioelectrocatalytic processes
show high economic potential [20]. Syngas fermentation is still a re-
latively immature technology but may play a role in future energy
systems [23,24]. Main challenges of biocatalytic processes are the up-
scale from laboratory-scale, the unclear sustainability and the many
examples of slow and resource intensive development [18].
According to Qiao et al. [21], beside low catalyst activity, low
product selectivity, insufficient fundamental understanding, and non-
optimized electrode/reactor and system design for practical applica-
tion, insufficient catalyst stability/durability is probably the biggest
challenge of electro-reduction processes. The CO2 reduction product
strongly depends on the electro catalyst material [25]. Mixtures of low
hydrocarbons and oxygenates can be produced with Cu catalyst. Using
Cu catalyst, direct electro-reduction of CO2 to ethene seems to be a
competent pathway [26].
The principles of sector coupling are described in detail by Robinius
et al. [27]. The roles of the transport sector and alternative fuels in the
context of the Energiewende for a carbon-neutral economy are also
outlined in detail in the literature [4,11,27,28]. Since electrofuels offer
a convenient storage option for renewables from all sources and can at
the same time be added to the existing infrastructure and used in
conventional vehicles, these fuels have great potential to harness re-
newable energy for the transport sector in the near future. Furthermore,
as outlined in the literature, especially for heavy duty vehicles, there is
a long-term need for liquid fuels [4]. The main conceivable electrofuels
can be subdivided into three groups [4]:
1. Hydrocarbons
2. Alcohols (methanol, ethanol, …)
3. Ethers (DME, OMEn)
In their recent review regarding the production costs of electrofuels,
Brynolf et al. [9] consider hydrocarbons, methanol and DME. This can
be accounted for by the gap in the literature concerning the production
of higher alcohols via the PtF concept. However, the suitability of al-
cohols as fuels is discussed in detail in the literature [29–34]. Apart
from methanol, synthesis processes for the selective production of
C1–C8 alcohols are biomass or petrochemistry-based. Based on the in-
terest in PtF on the one hand and alcohols as transport fuels on the
other, the aims of this contribution are to:
• Deliver a comprehensive overview regarding the suitability of me-
thanol and higher alcohols (C1–C8; up to octanol) as transport fuels
and corresponding possible synthesis pathways based on H2 and
CO2.
• Develop synthesis pathways by adapting known and novel processes
to the PtF concept.
• Estimate the technical maturities of the adapted processes.
• Make a first selection regarding the most promising synthesis
pathways.
• Identify further research gaps for further investigation.
It is worthwhile to note, that the discussed synthesis pathways also
offer promising syntheses for chemicals. This is especially the case for
methanol, since it is the one of the most important industrial bulk
chemicals. However, this paper is focusing on fuels since the transport
sector offers a big market volume.
According to Otto et al. [35], the potential of CO2 consumption for
fine chemicals in the EU corresponds to ∼0.029% of EU greenhouse gas
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Journal of CO₂ Utilization 27 (2018) 223–237
emissions. It thus can be concluded, that fine chemicals do not offer an
avoidance option for large amounts of CO2 [35]. Bulk chemicals other
than urea, which already uses CO2 as a feedstock, have a CO2 avoidance
potential of ∼20 million tons CO2, which corresponds to ∼0.43% of
the EU’s greenhouse gas emissions [35]. In contrast to that, the trans-
port sector accounts for ∼23% of the global anthropogenic CO2 emis-
sions [36].
In order to give a first impression, the production costs are roughly
estimated and compared with the current resale price of bioethanol,
methanol from natural gas and the refinery wholesale price of fossil
gasoline.
2. Methods
A future fuel produced with PtF technologies will need to fulfill two
key criteria: suitability as a fuel with easy integration into the existing
fuel systems and an economically-viable synthesis [3,4]. The focus of
this contribution is the development of synthesis pathways by adapting
known and novel processes to the PtF concept. At the same time, in this
step the technological maturities of the pathways are estimated to make
a closer selection in favor of the most promising synthesis pathways.
In this contribution, the technical maturity of the process steps and
synthesis pathways is evaluated via the technology readiness level
(TRL) method which ranks the maturity of a technology on a scale from
1 to 9. This method was developed by the United States Department of
Defense [37] and adopted by the European Commission in the Hor-
izon2020 program [38]. Since the adaption of the original TRL method
to other research fields lacks in clear definition, the European Com-
mission developed a guidance which is consistent among energy related
research fields [39]. This guidance does not replace existing definitions,
but rather clarifies the definitions to be consistent all energy related
research fields.
The adapted TRL steps from 1 to 9 referring to the guidance prin-
ciples for renewable energy technologies of the European Commission
[39] are listed in Table 1 Commercial industrial processes are defined
as state-of-the-art (SoA) in this work.
3. Suitability of alcohols as transport fuels
This section provides an overview of investigations regarding the
suitability of alcohols as blend partners for conventional gasoline and
diesel fuels. Due to their oxygen content, alcohols are in general not
suitable for usage as aviation fuels. One reason for this is the lower
calorific value compared to hydrocarbons [40]. This would reduce the
vehicle’s range and the fleet’s efficiency. According to the standard for
synthetic jet turbine fuels, ASTM D7566, oxygen-containing compo-
nents must be hydro-processed to remove essentially all of the oxygen
[41]. Besides the thermal stability, another reason for this is that oxy-
genated species can impact ground handling equipment by attacking
the materials [42].
Their physical properties limit or qualify alcohols as blending ad-
mixtures for conventional gasoline and diesel fuels. For European
countries, the requirements to be met by automotive diesel and gasoline
are described in the standards EN 590 [43] and EN 228 [44], respec-
tively. Leitner et al. [45] state that the impact of each property relates
to their various technical and environmental impacts, as well as to the
tendencies of the desired values of each property to enable a clean and
efficient combustion.
The basic physical properties of gasoline [46,47] and diesel
[4,47,48] fuels are extensively discussed in the literature. The funda-
mentals of compression-ignition (CI) and spark-ignition (SI) engines,
including their respective combustion processes, are for instance de-
scribed in detail by Bergthorson and Thomas [49]and Leitner et al.
[45].
Alcohols from methanol (C1) through to octanol (C8) are also ex-
tensively discussed. The most frequently discussed alcohols are
S. Schemme et al.
Table 1
Definition of the Technology Readiness Level (TRL) according to the EC Horizon2020 programm [38] and the EC TRL guidance [39].
TRL Definitions according to the EC Horizon2020 program [38]
1 Basic principles observed
2 Technology concept formulated
3 Experimental proof of concept
4 Technology validated in lab
5 Technology validated in relevant environment (an industrially-relevant environment in the case
of key enabling technologies)
6 Technology demonstrated in relevant environment (an industrially-relevant environment in the
case of key enabling technologies)
7 System prototype demonstration in operational environment
8 System complete and qualified
9 Actual system proven in operational environment (competitive manufacturing in the case of key
enabling technologies; or in space)
methanol, ethanol and butanol. A detailed discussion about the appli-
cation of methanol and ethanol as drop-ins or pure fuels can be found in
Menrad and König [29]. An overview of methanol as a drop-in or pure
fuel is also given by Zhen and Wang [50]. Yusri et al. [30] reviewed
engine performance and the exhaust emissions of the alcohols me-
thanol, ethanol, and butanol in CI and SI engines. A systematic review
of the use of methanol, ethanol and butanol in SI engines concerning
the effects of performance, emissions, combustion characteristics and
required car modifications was given recently by Awad et al. [51].
Reviews of the usage of butanol and pentanol are given in Vinod
Babu et al. [31], Trindade and Santos [32], as well as Rajesh Kumar and
Saravanan [33]. The review by Rajesh Kumar and Saravanan [33] also
includes hexanol, octanol, dodecanol (C12) and phytol (C20). Octanol is
identified as a promising alternative diesel fuel, for instance by Hoppe
et al. [52], Cai et al. [53], Kerschgens et al. [54] and Janssen et al. [55].
Analytical assessments for octanol as SI and CI engine fuels were carried
out by Wallner et al. [34] and Rajesh Kumar et al. [56,57], respectively.
Rajesh Kumar et al. [56] indicate 1-octanol to be an excellent next
generation diesel fuel. For comparison, the physical properties of the
primary C1-C8 alcohols can be found in Table A1 in the Appendix A.
Additionally, a brief evaluation of the influence of the molecular
structure on the physical properties is given in the Appendix A. The
differences in the energy content are negligible, while isomers have a
higher potential as drop-in for the Otto engine due to their higher oc-
tane number and the primary alcohols having a higher potential as
drop-in for the diesel engine with their higher cetane number.
Referring to their properties, which more closely resemble con-
ventional gasoline, Wallner et al. [34] note higher alcohols to be more
interesting than shorter alcohols like ethanol. Amongst others, Trindade
and Santos [32] confirm this statement by comparing ethanol with n-
butanol and pointing out its advantages and disadvantages.
According to many studies [32,33,52,53,57–62], alcohol-blended
fuels can improve the combustion process in engines and have the
potential to decrease pollutant emissions compared to pure fossil ga-
soline or diesel. In general, soot emissions are also significantly de-
creased. NOx, CO, and HC emissions depend on the test engine running
conditions, which are indicative of engine optimization potential. One
optimization, for instance, could be advanced injection timing [63]. To
summarize, the literature reveals that methanol, ethanol, 1-/2-/iso-
butanol and 1-octanol have the highest relevance with regard to the use
of alcohols as alternative fuels.
Methanol, ethanol and butanol are already commonly used as drop-
in fuels. Methanol is regulated as a fuel for the USA in the Energy Policy
Act of 1992, while ethanol and butanol are regulated and defined by the
Renewable Fuel Standard (RFS) [64,65]. In European gasoline, a 3%
blend is standard [44]. In Sweden and China, unblended methanol is
used in some instances. The RFS prescribes a legally-defined quantity of
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Journal of CO₂ Utilization 27 (2018) 223–237
Clarified definitions according to EC TRL guidance [39]
Identification of new concept, application and barriers
Definition of application, consideration of interfaces and commercial
offers
Proof of concept prototype ready: concept is laboratory tested
Integrated small-scale prototype with auxiliary system laboratory
validated
Large-scale prototype completed with auxiliaries, refined commercial
assessment
Technology pilot in relevant environment, manufacturing strategy
defined
Pilot demonstrated in operational environment, manufacturing
approach demonstrated
Technology in its final form, low-rate production
System fully operational and ready for commercialization
renewable fuels that must be used annually as a blending partner for
conventional fuel in the United States. This was created by the Energy
Policy Act of 2005 and was enhanced by the Energy Independence and
Security Act of 2007 [66,67].
4. Analysis of synthesis pathways and technical maturity
This section provides an overview of conventional and novel
synthesis pathways, which present conceivable pathways for the
synthesis of alcohols utilizing the PtF concept. Additionally, the tech-
nical maturity is estimated. Based on the technical maturity, as well as a
further estimation of the potential, the most promising synthesis
pathways are selected. The result of this selection is depicted in Fig. 3.
4.1. Conceivable reactions and processes
Conceivable processes for the synthesis of higher alcohols are the
modified methanol and Fischer-Tropsch (FT) syntheses, Ziegler alcohol
synthesis, aldol (aldehyde + alcohol) condensation and oxo synthesis.
Oxo synthesis is also known as hydroformulation and is today’s SoA
technology for selective alcohol synthesis.
An overview focusing on the catalysts of modified methanol and FT
syntheses for alcohol synthesis including conversion and selectivity is
given in Surisetty et al. [68]. Modified FT syntheses include, for in-
stance, the Synthol and Synol processes. A short critical review of re-
cent developments regarding alcohol synthesis on cobalt-copper cata-
lysts via the FT reaction is given by Xiang and Kruse [69]. The chain
growth reactions of both the modified methanol and Fischer-Tropsch
syntheses are dictated by the Schulz-Flory distribution [68,69] or
Gaussian distribution [70], depending on the catalyst and reaction
conditions. Based on the presence of pilot plants for the synthesis of
alcohols with modified methanol and Fischer-Tropsch catalysts [71],
the technical maturity of these processes is estimated with a TRL of at
least 8.
The Ziegler alcohol synthesis, like the Alfol process, is based on
oligomerization reactions of ethylene on aluminum catalyst with oxy-
genation of the resulting alkyl group [72]. The result is a broad range of
linear alcohols with a distribution corresponding to a Poisson curve
[73]. The product distributions of the modified methanol and FT
syntheses, as well as of the Ziegler alcohol processes, lead to insufficient
selectivity for a specific alcohol. Since the chain growth reaction is
completed when the product stream leaves the reactor, it is not rea-
sonable to recycle the unwanted products after separation. Therefore,
the modified Fischer-Tropsch and methanol syntheses are not con-
sidered in the following. In contrast, the aldol condensation and oxo
synthesis are explained. Fig. 1 shows the aldol condensation via the
example of the synthesis of butanol from ethanol.
S. Schemme et al. Journal of CO₂ Utilization 27 (2018) 223–237

4.2. Reverse water-gas shift reaction

In the PtF concept, synthesis pathways start from H2/CO2. However,

Fig. 1. Aldol condensation of ethanol to n-butanol.
as stated above and also as the following shows, some processes require
a process step wherein the reverse water-gas shift (rWGS) reaction
appears upstream to convert CO2 and H2 into CO and H2O to provide
synthesis gas (H2/CO). Thermodynamically reasonable temperatures
are above 900 °C [86,87]. These temperatures are technically realistic
[88]. Unde [89] proved a commercial Ni/Al23O16-catalyst to be stable
under these conditions. Schmidt et al. [90] estimate a TRL of 6 for the
rWGS technology.

During conventional aldol condensation, an unsaturated Cn+1 al-

4.3. Methanol synthesis
dehyde is formed from two Cn aldehydes with the elimination of water.
The Cn aldehydes are formed by the dehydrogenation of Cn alcohols
The synthesis of methanol is conceivable via two different path-
(compare Fig. 1: ethanal). To transform unsaturated Cn+1 aldehydes
ways: synthesis from H2/CO2 [91–95] and synthesis from H2/CO
(see Fig. 1: crotonaldehyde) into Cn+1 alcohols (see Fig. 1: butanol),
[96–98]. The SoA is the synthesis from H2/CO via the “low-pressure
either a Cannizzaro reaction or hydrogenation with H2 is carried out. In
methanol process” [99]. According to Ott et al. [99], the production
the Cannizzaro reaction, the aldehyde reacts in a strongly basic medium
volume of methanol was 47 Mt in 2011, of which the largest part was
to alcohol and the salt of a carboxylic acid [74], whereas in the hy-
synthesized with H2/CO. The estimated TRL of methanol synthesis from
drogenation only alcohol is produced. The Cannizzaro reaction is used
H2/CO2 differs in the literature. Referring to Schmidt et al. [90] and
in the Guerbet process [75–77], while hydrogenation is used in the
Buddenberg et al. [100], the TRL of the methanol synthesis from H2/
Alfol process [72].
CO2 is 9 and 8, respectively. Perez-Fortes et al. [101] estimate a TRL of
Fig. 1 shows the pathway via hydrogenation with the product n-
6–7. The TRL estimation can be justified with the presence of two pilot
butanol. The aldol condensation is carried out with two identical al-
plants: one operated by the company CRI in Iceland opened in 2012
cohol molecules, as mentioned before, or with two alcohol molecules of
with 1300 t/yr capacity and expanded in 2014 to 4000 tMeOH/yr, which
different chain lengths. In the literature, the availability of data for the
is today’s worldwide largest plant [102], and the other operated by
condensation of alcohols with different chain lengths is worse, which is
Mitsui Chemicals Incs. in Osaka since 2008 producing 100 tMeOH/yr
caused by low selectivities and yields. An example of the comparatively
[103]. Table 1, Since the existing synthesis process is stable enough for
poor selectivities and yields for alcohols of different chain length is the
a low-rate production and the company CRI sells the H2/CO2 based
aldol condensation of propanol from ethanol and methanol, which is
methanol to customers, we estimate the TRL at 8, referring to the de-
described by Ueda et al. [78].
finitions given by the European Commission (see Table 1).
The dehydrogenation of ethanol to ethanal is a SoA process carried
According to the company’s website of CRI [104], commercial scale
out over Cu-catalysts with 90% yield. An alternative is the oxidation of
plants with 50 MtMeOH/yr are actively planned in projects (FreSMe
ethanol [79]. Although process like the Veba-Chemie process show
project and MefCO2 project). The projects aim to demonstrate the
yields of 97–99%, the loss H2 due to water formation would sig-
technology’s readiness for commercialization, which would lead to a
nificantly decreases the process efficiency in the Power-to-Fuel concept.
TRL of 9.
Oxo synthesis, also known as hydroformylation, is the second way
The commercially used catalyst for methanol synthesis based on H2/
to expand the carbon chain in alcohols [80–82]. It was developed in
CO/CO2 is the CuO/ZnO/Al2O3 system [105]. However, these catalysts
1938 by Otto Roelen [83] and is the SoA for the production of alcohols,
suffer from low selectivity and insufficient stability when using H2/CO2
whereby over 50% of worldwide production is the result of the synth-
[106]. Moreover, the presence of water resulting from the CO2 hydro-
esis of butyraldehyde from propanol [80,83,84]. According to Todic
genation leads to catalyst deactivation [105]. Rodriguez et al. [107]
et al. [85], who discuss the development of hydroformylation in
provide an overview for the CO2 hydrogenation on Cu and Au centers
1980–1995, hydroformylation is most often used in industrial pro-
and state that metal-oxide and metal-carbide interfaces are promising
cesses, such as the UCC or BASF processes. Industrial processes can be
to increase the synthesis efficiency.
subdivided in such, which use rhodium based catalysts and such, which
Reviews regarding the experimental or theoretical CO2 conversion
use cobalt based catalysts. A more detailed discussion of the different
and selectivity of various Cu-, Ag-, Au-, Pd- and LaCr0.5Cu0.5O3 and
industrial processes, including process selectivities and catalyst systems
regarding Cu-based, Pd-based and other catalysts including CO2 con-
is given by Bahrmann et al. [80].
version and selectivity and technological advances are published by
Fig. 2 shows the oxo synthesis of propene to butanol. During hy-
Saeidi et al. [108] and Jadhav et al. [105], respectively.
droformylation, a Cn olefin (Fig. 2: propene) reacts with H2/CO
Martin et al. [106] unveiled that In2O3 supported ZrO3 could be a
(synthesis gas) and an unsaturated Cn+1 aldehyde (Fig. 2: butanal),
promising alternative. We estimate the TRL at 3 since Martin et al.
which is then converted into a Cn+1 alcohol (Fig. 2: butanol) via hy-
[106] did successful catalyst screening in a micro reactor. Although the
drogenation. The required olefins are currently obtained exclusively
TRL is relatively low, Martin et al. [106] state that In2O3/ZrO2 catalysts
through petrochemical processes [83].
show a high efficiency, remarkable stability, 100% selectivity and
outstanding activity under industrially relevant conditions and thus
could pave the way for new technologies for methanol synthesis via
CO2 hydrogenation.

4.4. Ethanol synthesis

Ethanol is industrially produced via fermentation of sugar (from

grain starches, sugar beets or sugar crops) using microorganisms
[68,109]. Another bio-based pathway is the fermentation of non-sugar
lignocellulose. The development of this process is on the demonstration
Fig. 2. Oxo synthesis of propene and synthesis gas to 1-butanol. level and has a TRL of 7 [109]. An overview of production pathways

226
S. Schemme et al.
Fig. 3. Overview of synthesis pathways developed.
towards ethanol from sugar, lignocellulosic and algal biomass including
advances and future direction in syngas fermentation is provided by
Devarapalli and Atiyeh [22]. Synthetic ethanol is industrially produced
by means of the hydration of ethylene from the petrochemical industry
[110,111]. These pathways however do not match with the PtF con-
cept.
Direct ethanol synthesis via CO2 hydrogenation is complex and
suffers from a low selectivity and conversion rate [71,112]. A com-
prehensive review regarding thermodynamics, catalyst and reactor
development, as well as the status of the technology underlying various
catalytic pathways from H2/CO to ethanol, is given by Subramani and
Gangwal [71]. According to their analysis, the commercial success of
the direct synthesis from H2/CO is thermodynamically- and kinetically-
limited by low yields and selectivity. In 2011, the TRL of the direct
synthesis of ethanol from H2/CO was at a maximum of 4, since there
were no prototype plants at that time [113], but the reaction has al-
ready been successfully carried out in a laboratory setting [114,115].
Other possible synthesis pathways are direct syntheses (Mixed-
Alcohol-Synthesis (MAS) or Fischer-Tropsch synthesis) from H2/CO
[71,110,113–126], or synthesis from DME and H2/CO [118,127–130].
In the latter case, DME and CO are converted to methyl acetate which is
then hydrogenated to ethanol and methanol [130]. As stated in Section
4.1, direct syntheses have insufficient selectivity. The intermediate
product DME can be synthesized directly by means of a bifunctional
catalyst from H2/CO (Synthesis gas-to-DME; STD) [131,132] or H2/CO2
[93,133–141] or indirectly via the intermediate product methanol
(Methanol-to-DME; MTD [98,142–148]) [149].
The non-biomass-based SoA processes for DME comprise the in-
direct synthesis via methanol and direct synthesis via H2/CO, where the
indirect route is used more frequently [150]. An example for MTD is the
Lurgi MegaDME process using standard γ-Al2O3 with typical per pass
methanol conversion of 70–85 % [148]. The synthesis gas (H2/CO) used
in conventional plants mostly comes from the petrochemical industry.
The TRL of direct synthesis of DME from CO2 and H2 is estimated to be
4, since suitable catalysts already exist and tests have been carried out
at the laboratory scale [133]. A current challenge is to increase the
selectivity and durability of the catalysts [133].
The TRL of the synthesis of ethanol from DME and H2/CO is
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Journal of CO₂ Utilization 27 (2018) 223–237
estimated to be 4, since tests have already been carried out at the la-
boratory scale [127]. The synthesis gas, which is required for direct and
indirect synthesis, can be produced via the reverse water-gas shift re-
action from CO2 and H2.
Since ethanol cannot be synthesized via oxo synthesis from methane
and synthesis gas, in 1951 Wender et al. [151] presented a special case
of the ethanol synthesis pathway via the homologation of methanol
with synthesis gas. Due to the poor data availability and low selectivity
for ethanol, this pathway is not considered in the following. However,
referring to Subramani and Gangwal [71], this approach might be
promising in terms of yield and selectivity.
4.5. Propanol synthesis
The SoA process for the industrial production of propanol is the oxo
synthesis using H2/CO and petrochemical ethene [152]. As explained in
4.1 before for the oxo synthesis in general, industrially used catalyst for
the oxo synthesis of ethane to propanol are mainly rhodium- or cobalt
based [152]. A global player in this synthesis is, for instance, OXEA
[153]. A novel approach is direct synthesis from ethene, CO2 and H2
[154–156]. Since there are already suitable catalysts and tests have
been carried out in the laboratory, the TRL is estimated to be 4.
Besides production via oxo synthesis, the hydrogenation of propanal
is the most important pathway in the industry [152], whereby the
propanal is supplied by the petrochemistry. The hydrogenation of
propanal corresponds to the hydrogenation of the aldehyde in the scope
of oxo synthesis (see Fig. 2). Both process pathways are SoA.
An uninvestigated alternative pathway is the aldol condensation
from ethanol and methanol [78,152]. The TRL of this pathway is esti-
mated at 2, since no catalyst has been investigated thus far.
The ethene needed for the oxo synthesis can be produced by cata-
lytic dehydration from ethanol [157–161]. This process is particularly
relevant for the production of ethylene from bioethanol, for which
several plants already exist [161]. According to Mohsenzadah et al.
[161], the used catalyst can be subdivided in the four main categories
phosphoric acid-, oxide-, molecular sieve- and hereropoly acid catalyst.
In their work, Mohsenzadah et al. [161] give a detailed overview of
already existing industrial plants and catalyst systems. On the basis of
S. Schemme et al.
the already existing plants, the TRL of the ethene synthesis from ethanol
is estimated at 9. Industrial ethene is produced from naphtha derived
from the petrochemical industry [162].
4.6. Butanol synthesis
Until mid-1950, 1-butanol was industrially produced by the croto-
naldehyde hydrogenation of acetaldehyde. The crotonaldehyde hydro-
genation is subdivided in the aldolization of acetaldehyde to acetaldol
over alkaline catalysts, the acidification of acetaldol to crotonaldehyde
and the hydrogenation of crotonaldehyde to Butanol over copper cat-
alysts [163]. According to Eckert et al. [79] the appropriation of
acetaldehyde strongly depends on prices and availability of raw mate-
rials. At that time, acetaldehyde was mainly produced from acetylene or
petrochemically produced ethanol [79]. The crotonaldehyde hydro-
genation was replaced in the mid-1950s by the hydroformylation (oxo
synthesis) of propene, which was invented through Otto Roelen in 1938
[164] and gained industrial attention in the mid-1950s. Until 1970 the
oxo synthesis was done over cobalt-based catalysts at high pressures
[80,163]. From mid-1970s to today, the oxo synthesis is done as low-
pressure oxo (LPO) process over rhodium catalysts, which was jointly
developed by Union Carbide, Davy McKee, and Johnson Matthey [80].
A detailed overview of the industrially used catalysts of the oxo
synthesis, including working conditions and process developers, can be
found in Tuta and Bozga [165]. Today, the low-pressure oxo process
from H2/CO and propene is the SoA process for 1-butanol production
[166–170], whereby the propene is supplied by petrochemistry [171]
or as a by-product from ethene production [171]. However, this creates
a direct correlation of the butanol price with the oil price [159]. Widely
uninvestigated alternative propene syntheses are the dehydration of
2propanol [172–174] and 1-propanol [171]. Since no suitable catalysts
with sufficient selectivity and yield have been identified thus far, the
TRL of the propanol dehydration is estimated to be 2. The products of
the oxo synthesis are 1-butanal and iso-butanal, which must subse-
quently be hydrogenated to butanol (see Fig. 2). Besides the propene
hydroformylation (oxo synthesis) and crotonaldehyde hydrogenation
(aldol condensation), the Reppe process developed in 1942 has
achieved industrial importance for 1-butanol production [163]. In the
Reppe process (also called carbonylation) olefins, carbon monoxide and
water react under pressure to butanol [175]. However, the process
technology is more expensive, and as a result the oxo synthesis with Co
catalyst has been more successful [163]. A novel direct synthesis en-
ables both hydroformylation and hydrogenation, in parallel, in one
reactor over Shvo catalyst [176]. Catalysts and kinetics have already
been researched [176], and so the TRL of this synthesis is estimated to
be 4.
Caused by improved bioethanol production and the already men-
tioned strong dependence of the butanol price from the oil price, there
is an increased research activity [177–184] in using the aldol con-
densation to produce butanol from ethanol in one reactor. According to
Dowson et al. [178] and Pang et al. [180], the aldol condensation is a
perfect possibility to upgrade from biomass produced ethanol to bu-
tanol for utilization as drop-in for gasoline. Beside the use as drop-in for
gasoline, Iso-butanol can be used to produce renewable jet fuels
[185,186]. This is beside Fischer-Tropsch one of the few possibilities to
produce jet fuels based on renewable electricity.
A current challenge is the achievement of a higher selectivity
[178–180]. Since most researchers are working on laboratory scale with
micro-reactors [177,179,180], the TRL of the aldol condensation of 1-
butanol from ethanol is estimated to be 3–4.
Other research activities to produce butanol are the synthesis of iso-
butanol directly from synthesis gas, which is limited due to low se-
lectivity [187] and the aldol condensation of ethanol and methanol to
iso-butanol, for which suitable catalysts have not been found yet [188].
For that reason, the TRL of the aldol condensation of ethanol and me-
thanol is assumed to be 2. Another possibility, which has to be
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Journal of CO₂ Utilization 27 (2018) 223–237
mentioned at this point, is the production of butanol with the so-called
ABE (acetone, butanol, ethanol) fermentation [163]. However, this
fermentation cannot be used in the defined methodology of the PtF
concept.
2-butanol, favored as a drop-in for gasoline, can be hydrated from
butene [83,163]. This petrochemistry-dependent process is SoA
[163,189]. Aside from the petrochemistry, butene can be synthesized
via the dehydration of 1-Butanol [189–192]. This dehydration is esti-
mated with a TRL of 3–4, since on the one hand catalysts are being
researched [191] and on the other, laboratory tests have already been
carried out to determine suitable synthesis conditions [190,192]. Re-
ferring to the investigation of Geilen et al. [189] regarding the in-
dustrial synthesis of butene, the dehydration of butanol has shown no
industrial significance up until now.
4.7. Pentanol synthesis
Pentanol is produced industrially by oxo synthesis from butene and
synthesis gas [193]. An alternative is aldol condensation from ethanol
and propanol [194]. The technical maturity of this synthesis pathway is
estimated with a TRL of 3 due to a current challenge in the development
of suitable catalysts [194].
4.8. Hexanol synthesis
Cyclohexanol can be produced via the intermediate products of
cyclohexene or phenol [195], both of which are SoA. Iso-hexanol can be
produced via aldol condensation from propanol [196]. Since tests have
already been carried out in a laboratory setting [196], the TRL of this
process is estimated to be 4. Industrially, 1-hexanol is produced via the
Ziegler process from ethene or from coconut or palm oils [73]. A the-
oretical possibility more selective processwould be the synthesis of 1-
hexanol via hydroformylation based on pentene and synthesis gas,
whereby the TRL of this synthesis path is conservatively estimated to be
1 due to lack of evidence in the literature.
4.9. Heptanol synthesis
Pure 1-heptanol has very little commercial importance and can be
produced by oxo synthesis from petrochemical 1-hexene [73]. In pre-
sence of Rh-catalyst, the intermediate heptanal is produced highly se-
lective. The oxo synthesis towards 1-heptanol is a SoA process
[153,197]. Greish et al. [197] discovered promising Ni-Cr-Pt-catalysts
for selective hydrogenation of heptanal into 1-heptanol.
4.10. Octanol synthesis
1-Octanol does not belong to the industrially-important alcohols
and is currently mainly used in the perfume industry [73]. Today, 1-
octanol is predominantly produced from petrochemical ethylene via
Ziegler alcohol synthesis and petrochemical n-heptene via oxo synthesis
[56]. Both processes yield mixtures of alcohols. Examples for industrial
1-octanol produced by means of Ziegler alcohol synthesis are Alfol 8 by
Condea and Lorol C 8 by Henkel [73]. As a biomass-based pathway, 1-
octanol can be synthesized from biomass-produced furfural [45,198]. In
the literature, there is no process for the synthesis of 1-octanol either on
a laboratory, prototype or industrial scale to be used in the PtF concept.
Iso-octanol (2-ethyl-hexanol) can be synthesized via oxo synthesis
[199] or via aldol condensation [167,200–202] from n-butanol.
According to Sasol North America Inc. [202], there has been an
industrial plant for octanol production via aldol condensation in the
USA since 1962 and other plants in Germany (1964), Russia (1981) and
China (1998). With regard to the molecular structure of the octanol
produced, no statement is made in the reference. However, based on the
general data, it is assumed that iso-octanol is produced in these plants.
The required butanol for the aldol condensation is produced from
S. Schemme et al.
ethanol, whereby this process ends at butanal, since it is the required
educt for the aldol condensation (see Fig. 1). The hydrogenation of
butanal to butanol is therefore omitted in the scope of this process.
As is shown in Fig. 1, in the conventional process the aldol con-
densation and subsequent hydrogenation are carried out stepwise in
separate reactors. Industrially used catalysts are e.g. sodium hydroxide
for the aldol condensation of n-butanol and Cu- or Ni-catalyst for the
hydrogenation to iso-octanol [196].
A novel process investigated by Patankar and Yadav [196] and
Liang et al. [203] is the direct synthesis of iso-octanol from n-butanol
via aldol condensation. In this synthesis approach, both reactions take
place in parallel in one reactor over bi/tri-functional catalysts (e.g. Co/
Al2O3, Ru/Al2O3, Cu/Al2O3 [203]). Direct synthesis would simplify the
process design.
The technical maturity of the direct synthesis in one reactor to iso-
octanol is evaluated with a TRL of 4, since catalysts have already been
successfully tested with conversions of 100% [203] and one pot
synthesis on a laboratory scale with selectivities of 90% [196].
4.11. Alkenes
The alkenes needed for the oxo syntheses presented are synthesized
by the dehydration of the next lower alcohols (see Fig. 2). Alternative
alkene syntheses include the Methanol-to-Olefins process [204], pro-
duction via the Fischer-Tropsch process [205,206] or the DME-to-Ole-
fins process [207]. In these processes there is always a product dis-
tribution and selectivity regarding a particular alkene cannot be
guaranteed, so these processes are not considered in the subsequent
analysis.
5. Results and discussion
The assessment of the technical maturity and analysis of possible
synthesis pathways in the context of the Power-to-Fuel concept result in
the developed pathways shown in Fig. 3.
The dotted lines mark the synthesis pathways, which are neglected
from further consideration due to inadequate product selectivity or
technological maturity. The alcohols pentanol, hexanol and heptanol
are also not considered further in the following, since according to
Section 3, the alcohols methanol, ethanol, butanol and octanol have the
highest fuel drop-in potential and should therefore be further in-
vestigated. Additionally, synthesis is barely possible via oxo synthesis
with many intermediate products for the excluded fuels. Furthermore,
the technological maturity of the hexanol synthesis and heptanol
synthesis is very low. Branched and unbranched alcohols are sum-
marized in Fig. 3 with the name of the respective primary alcohol. To
provide a complete overview, the technical maturity, process descrip-
tion, educts and references of the developed synthesis pathways to-
wards the intermediate products and alcohols are listed in Tables 2 and
3, respectively.
In a direct comparison, the oxo synthesis generally offers a higher
selectivity than the aldol condensation. However, a recent publication
showed increased selectivity of the aldol condensation [196], wherein
the carbon chain length is doubled in one process step, unlike in the oxo
synthesis, in which the carbon chain grows only by one carbon atom per
two process steps. Therefore, for the examples described in Figs. 1 and
2, the synthesis of 1-butanol from ethanol via oxo synthesis requires
four process steps, while the synthesis via aldol condensation requires
only one. It can be concluded that for the oxo synthesis, many more
process steps are needed, thus increasing the energy input, for example
by separating columns and recycling loops.
According to Atsonios et al. [118], the ethanol synthesis via the
intermediate DME offers a higher selectivity, is more effective and less
cost-intensive compared to the ethanol synthesis from synthesis gas
produced using the rWGS reaction. The latter is therefore not con-
sidered in the following. Simplifying Fig. 3 with the non-promising
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Journal of CO₂ Utilization 27 (2018) 223–237
pathways results in the synthesis pathways shown in Fig. 4. Ad-
ditionally, our estimated technical maturity (TRL, SoA) is also pre-
sented.
Fig. 5 illustrates the technical maturity of a complete route shown in
Fig. 4 limited by the lowest TRL occurring along the route.
The presented synthesis pathways to produce higher alcohols based
on H2 and CO2 provide a basis for further investigations regarding
process evaluation and goal-oriented catalyst research. As highlighted
by Saeidi et al. [108], not only the catalyst, but also the reactor con-
figuration has significant influence on the synthesis performance. Thus,
innovative reactor designs are also necessary.
Compared with Power-to-Fuel synthesis pathways relating to hy-
drocarbons (Fischer-Tropsch) and ethers (DME, OME3-5), the synthesis
pathways of higher alcohols generally show lower degrees of technical
maturity. Fischer-Tropsch is already a globally-established technology
and can be adapted to the synthesis from H2 and CO2 with the rWGS
technology. OME3-5, meanwhile, is industrially-produced in China from
coal, with the intermediate product of methanol. A comparative as-
sessment regarding various aspects such as, for example, techno-eco-
nomic analyses, process efficiencies, further potential and in-vehicle
fuel suitability, as well as integration in a holistic assessment of the
transport sector, would reveal the potential of a future fuel system.
6. Economical aspects
With the aim to give a first impression, the production costs de-
pending on the H2 costs [$/kgH2] are roughly estimated and compared
with the current resale prices of bioethanol, methanol from natural gas
and the refinery wholesale price of fossil gasoline.
Since the different substances vary in their lower heating value (see
Tables A1 and A2 in the Appendix A), the term liter gasoline equivalent
(lGE) was used. 1 lGE represents the amount of alternative fuel it takes to
equal the energy content of 1 liter gasoline (32.2 MJ/l [217]).
To determine the required H2 demand, we used the net reaction
equation and assumed a product selectivity of 100%, which means that
the only byproduct is water. The availability of data for methanol en-
ables us to make a more detailed cost analysis. A detailed description of
the evaluation of production costs of methanol based on H2 and CO2
can be found in the Appendix A.
Fig. 6 shows the productions costs [$/lGE] dependent on the raw
material costs for H2 [$/kgH2]. In the case of methanol, also CAPEX and
other OPEX are considered to deliver a more realistic value. Detz et al.
[218] calculated the costs for a Power-to-Fuel pathway towards me-
thanol. In their case, an intermediate H2 cost of 7.1 $/kg leads to me-
thanol production costs of 1.5 $/kg. For comparison, this value was
added to the diagram. It can be seen, that the costs for CAPEX and other
OPEX have marginal impact on the production costs. The production
costs are mainly dominated by the costs for H2. A comprehensive
comparison of cost ranges of biofuels is given by Brynolf et al. [9]. In
comparison, the production costs of electrofuels are in the upper range,
or more expensive than most biofuels.
For ethanol, butanol and octanol, the plant investment costs are
expected to be notably higher. However, it can be expected that costs
for H2 still dominate. Using base cost assumptions from literature,
Brynolf et al. [9] calculated electrofuel production costs of 2.17–3.04
$/lGE for 2015 and 1.73–2.23 $/lGE for 2030. According to the calcu-
lations of Detz et al. [218], in 2050, beside electricity costs also costs for
CO2 become crucial for the electrofuel production, representing
32–48% of the total production costs.
Comparing electrofuel price in dependency of the H2 costs with the
market prices excluding taxes of gasoline from crude oil [219], me-
thanol from natural gas [220] and bioethanol [221], represented as
horizontal lines in Fig. 6, it can be concluded, that electrofuels can
become competitive with cheap conventional fuels, if the costs for H2 is
around 2 $/kg. The price of iso-butanol produced from corn was as-
sumed to be 1.21 $/lGE [222]. This value can be met with a H2 price
S. Schemme et al. Journal of CO₂ Utilization 27 (2018) 223–237

Table 2
Overview of alcohol synthesis, including estimated technological maturity.
Alcohol TRL Synthesis Educts Reference

Methanol 9 Direct synthesis CO2, H2 [91–94]

SoA Direct synthesis CO, H2 [96–98]
Ethanol 4 – DME + CO, H2 [118,127–129]
5–9 Direct synthesis, CO, H2 [71,110,113–125]
Fischer-Tropsch,
Mixed-Alcohol-Synthesis
Propanol SoA Oxo synthesis Ethene, CO, H2 [152]
4 Direct synthesis Ethene, CO2, H2 [154–156]
SoA – Propanal [152]
2 Aldol condensation Ethanol, methanol [78,152]
Butanol SoA Oxo synthesis, Reppe process Propene, CO, H2 [85,163,166–170,208]
4 Oxo direct synthesis Propene, CO, H2 [176]
3–4 Aldol condensation Ethanol [177–184,209]
Iso-butanol 2 Aldol condensation Ethanol, methanol [188]
3 Direkt synthesis CO, H2 [187]
2-butanol SoA Hydration Butene, H2O [83,163]
Pentanol SoA Oxo synthesis Butene, CO, H2 [193]
2-pentanol 3 Aldol condensation Ethanol, iso-propanol [194]
Cyclohexanol SoA – Cyclohexene [195]
Phenol
Iso-hexanol 4 Aldol condensation Propanol [196]
(2-methyl-pentanol)
Hexanol 1 Oxo synthesis Pentene, CO, H2 –
Heptanol SoA Oxo synthesis Hexene, CO, H2 [153]
Octanol 1 – – –
Iso-octanol (2-Ethyl-Hexanol) SoA Oxo synthesis Heptene, CO, H2 [199,210]
SoA Aldol condensation Butanal [167,200–202]
4 Aldol condensation Butanal [196,203]
(direct synthesis)

Table 3 7. Conclusion
Synthesis pathways of intermediate products.
Product TRL Comments Educt Reference
The syntheses of methanol and higher alcohols via Power-to-Fuel
technologies offer an alternative that is petrochemically-independent
CO, H2 8–9 ATR Hydrocarbons [211] and does not compete with food production or land use. Alcohols can be
CO, H2 6 rWGS reaction CO2, H2 [90] used as transport fuel blend partners with the potential to increase
DME SoA MTD Methanol [98,142–147]
4 – CO2, H2 [93,133–141]
engine efficiency and decrease emissions.
SoA STD CO, H2 [131,132] As is indicated in Section 3, the most preferred alcohols for use as
Ethene 9 Dehydration Ethanol [157–161] blend partners in transport fuels are methanol, ethanol, 1-butanol, 2-
Propene 2–3 Dehydration Propanol [171,212] butanol and 1-octanol. Methanol and ethanol are already used con-
2-3 Dehydration 2-propanol [172–174]
ventionally as fuel blend partners. Within the framework of the Power-
Butene 3–4 Dehydration 1-butanol [189–192]
Butanal 4 Dehydrogenation 1-butanol [213] to-Fuel (PtF) concept, the syntheses of these alcohols based on H2 and
Penten 3–4 Dehydration 3-pentanol [214] CO2 vary in their preferable pathways and technical maturity.
Hexene 3 Dehydration Hexanol [215] The direct synthesis of methanol from H2 and CO2 has already
Heptene 3 Dehydration Heptanol [216] achieved a high level of technical maturity (TRL 8). The high technical
Alkenes SoA Methanol-to-Olefins Methanol, H2, CO [204]
(mixture) SoA Fischer-Tropsch H2, CO [205,206]
maturity and probably high efficiency of this synthesis allows for a
Olefins simple adaption to commercial-scale plants.
SoA DME-to-Olefins DME [207] Starting at H2 and CO2, the most promising synthesis pathway to-
wards ethanol is via the intermediates DME and synthesis gas. We es-
timate a TRL of 4 for this synthesis pathway.
around 4 $/kg. Octanol was neglected in the market price comparison Conceivable synthesis pathways for butanol in the context of the PtF
since it is a fine chemical nowadays. concept are via aldol condensation and oxo synthesis. Since the re-
It is worthwhile to note, that the cost comparison with conventional quired propane for oxo synthesis is currently a petrochemical product,
fuels does not consider the benefits of electrofuels (CO2 reuse, use of the aldol condensation has a higher potential with respect to the PtF
surplus electricity, fossil independency, de-fossilization, CO2 mitiga- concept. For both pathways, process engineering analyses can provide
tion, carbon footprint etc.). The answer regarding the difference be- conclusions about techno-economic potential. We estimate a TRL of 4
tween a single process efficiency and impact on the effectivity of a for the aldol condensation of ethanol to 1-butanol.
whole energy system requires further investigations, e.g. greenhouse According to the investigations described in Section 4.10 (see
gas analyses, life cycle analyses, energy system analyses. Table 2), no suitable synthetic pathway is currently known for the
The main objective of Power-to-Fuel technologies is not to be fully synthesis of 1-octanol. That is why we estimate a TRL of 1 here. The
competitive on the market, but more to help to effectively counteract stepwise oxo synthesis is discouraged at this point due to the dis-
climate change. Beside Bio-to-Fuel technologies which might suffer proportionate number of necessary process steps. A possible synthesis
from land usage and food production competition, Power-to-Fuel pathway could be the aldol condensation of 1-butanol. This is the
technologies are the only technologies that can lead to de-fossilization current state of the art (SoA) process for iso-octanol. At this point,
of liquid fueled transport modes. targeted catalyst tests can provide information about potentials for the
synthesis of 1-octanol by means of aldol condensation. As a first

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Fig. 4. Most promising pathways towards higher alcohols based on H2 and CO2 and their technical maturity.

for H2 is around 2 $/kgH2. However, the aim of electrofuel production is

Fig. 5. Technical maturity of complete synthesis routes towards higher alcohols
based on H2 and CO2.
not to be cost competitive with conventional fuels. Benefits such as CO2
reuse and mitigation, use of surplus electricity, fossil independency, de-
fossilization as well as impact on the effectivity of a whole energy
system need additionally be considered.
To summarize, although alcohol synthesis via aldol condensation
was replaced by oxo synthesis in the 1950s, which is the current SoA
process, we conclude from our investigations that the aldol condensa-
tion pathway is preferable within the PtF concept due to its having
fewer necessary process steps. However, catalysts still show insufficient
selectivity. There is therefore a need for research, especially in catalyst
and reactor development, to increase the selectivity, on the one hand,
and process design and techno-economic assessment of the novel syn-
thetic pathways, on the other.

Acknowledgements

The authors would like to thank Joachim Pasel, Maximilian Decker,

Fig. 6. Production costs of alcohols as electrofuels depending on H2 costs.
impression, methanol and ethanol based on H2 and CO2 can compete in
terms of production cost with cheap conventional fuels when the price
Stefan Weiske – all Forschungszentrum Jülich GmbH, Institute of
Energy and Climate Research, IEK-3 – Electrochemical Process
Engineering – for valuable input. Further thanks are addressed to the
members of the JARA Energy seed fund, “Power to Fuel,” and its suc-
cessor - The Competence Center Power to Fuel. JARA (Jülich-Aachen
Research Alliance) is an initiative of RWTH Aachen University and the
Forschungszentrum Jülich. Additionally, this work was performed
partly in the frame of the project house TESYS (Technology based en-
ergy systems analysis) of RWTH Aachen University financed by the
Excellence Initiative of the German federal and state governments to
promote science and research at German universities.

Appendix A

Influence of the molecular structure on the physical properties

To evaluate the influence of the molecular structure of alcohols on physical properties and fuel suitability, the physical properties of 1-butanol, 2-
butanol, iso-butanol, tertiary butanol, 1-octanol and iso-octanol are compared in Table A2. The differences in the lower heating value are negligible,
while the isomers have a higher potential as drop-in for the Otto engine due to their higher octane number and the primary alcohols having a higher
potential as drop-in for the diesel engine with their higher cetane number. Amongst the butanol isomers, tertiary butanol is least suitable for fuel

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Table A1
Physical properties of the primary C1-C8 alcohols.
Fuel Property n-methanol n-ethanol n-propanol n-butanol n-pentanol n-hexanol n-heptanol n-octanol
Formula CH3OH C2H5OH C3H7OH C4H9OH C5H11OH C6H13OH C7H15OH C8H17OH

Lower heating value [MJ/kg] 19.92 26.81 30.68 33.11 34.76 35.97 36.88 37.59
[223] [223] [223] [223] [223] [223] [223] [223]
Boiling point 64.7 78.3 97.1 117.5 137.9 157 175 195
[°C] [224] [224] [224] [224] [224] [225] [225] [225]
Flash point 11 13 22 35 49 59 71 81
[°C] [50] [226] [227] [30] [228] [225] [225] [225]
Self-ignition temperature [°C] 465 423 371 343 300 304 275 253
[50] [226] [225] [225] [225] [225] [225] [225]
Research Octane Number (RON) 108.7 108.6 [229]; 102.6 96 78 – – –
[50,229] 111.2 [230] [230] [230]
[230]
Motor Octane 88.6 89.7 [229] – – – – – –
Number (MON) [50,229]
Cetane Number 3 8 12 17 20 23.3 29.5 39.1
[50] [231] [232] [232] [232] [233] [233] [233]
Vapor pressure 168 79 28 9 3 1 < 10−3 < 10−3
[kPa] [223] [223] [223] [223] [223] [223] [223] [223]
at 25 °C
Heat of evaporation [kJ/kg] 1169 924 798 722 648 625 599 555
[223]; [223]; [223]; [223]; [223]; [223]; [223]; [223];
1109 918 728 585 509 605 575 545
[50] [30] [30] [30] [225] [225] [225] [225]
Viscosity 0.07 0.14 0.24 0.32 0.42 0.55 0.71 0.89
[mm/s²] [223] [223] [223] [223] [223] [223] [223] [223]
at 25 °C, 1 bar
Density 790 786 800 804 812 816 821 826
[kg/m³] [223] [223] [223] [223] [223] [223] [223] [223]
at 25 °C, 1 bar
Solubility in water 1000 1000 1000 68 22 5.9 1.67 0.54
[g/L] [225] [225] [225] [225] [225] [225] [225] [225]
25 °C

Table A2
Physical properties of primary butanol and octanol, as well as their isomers.
Fuel Property 1-butanol iso-butanol 2-butanol tert-butanol 1-octanol iso-octanol
Formula C4H9OH C4H9OH C4H9OH C4H9OH C8H17OH C8H17OH

Lower heating value 33.11 33.04 33.00 32.70 37.59 37.57

[MJ/kg] [223] [223] [223] [223] [223] [223]
Boiling point 117.5 107.9 [234] 99.6 82.4 195 183
[°C] [224] [234] [234] [225] [225]
Flash point 35 [30]; 28 24 11 81 81
[°C] 29 [235] [235] [235] [235] [225] [225]
Self-ignition temperature 343 415 405 478 253 270
[°C] [225] [235] [235] [235] [225] [225]
Research Octane Number (RON) 96 105 105 105 – –
[230] [46,236] [46] [237]; 103 [236]
Motor Octane Number (MON) 85 90 93 89 – –
[46] [46] [46] [237]
Cetane number 17 – – – 39.1 34
[232] [233] [238]
Vapor pressure 9 1.4 2.3 5.6 < 10−3 < 10−3
[kPa] [223] [223] [223] [223] [223] [223]
at 25 °C
Heat of vaporization 722 702 680 629 555 559
[kJ/kg] [223]; [223] [223] [223] [223]; [223]
585 545
[30] [225]
Viscosity 0.32 0.42 0.38 0.58 0.89 0.91
[mm/s²] [223] [223] [223] [223] [223] [223]
at 25 °C, 1 bar
Density 804 798 802 783 826 830
[kg/m³] [223] [223] [223] [223] [223] [223]
at 25 °c, 1 bar
Solubility in water 68 66,5–90.9 181 1000 0.54 0.88
[g/L] [225] [225] [225] [225] [225] [225]
at 25 °C

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S. Schemme et al. Journal of CO₂ Utilization 27 (2018) 223–237

blending due to the high solubility of 1000 g/L in water.

Details of economic assessment of methanol production based on H2

In general, production costs [€/lGE] depend on capital expenditures (CAPEX) and operational expenditures (OPEX). Since the plant investment
costs depend on the plant size, a plant size needs to be determined for the comparison. Referring to the values given by the IPCC [239], the
worldwide average cement plant emits 0.79 Mt CO2/a. The assumptions that 80% of the emitted CO2 is used as a feedstock for fuel production with
100% conversion and a plant operating time of 8000 h/a leads to a plant size of around 300 MWFuel output. 300 MWFuel output is a realistic value since it
is in the upper range of FAME and expected Biomass-to-Liquid plants [109]. Based on this rough calculation the plant size for the case study in this
S d
contribution is determined to be 300 MWFuel output. Plant investment costs can be calculated with the equation FCI = FCI0 ∙ ( ) , where FCI = fixed
S0
capital cost, CO = reference fixed capital cost, S = capacity, S0 = reference capacity and d = degression coefficient [240]. The described calculation
approach leads to an AACE class 5 estimation [241]. For the reference fixed capital cost of a 200 MW methanol plant, we chose 300€2015/kWFuel [9].
This leads to plant investment costs of 76.5 M€ for a 300 MW methanol plant. Using the annuity method, the annual capital costs (ACC) can be
qn ⋅ (q − 1)
calculated with ACC = FCI ⋅ qn − 1 , with q being the interest factor. With the approach from Turton et al. [242], which is similar to that presented
by Peters et al. [243] and Ulrich [244], the direct and indirect operational expenditures (OPEX) can be calculated with Eq. (1).
(CRM + CUT ) + 2.265∙COL + 0.307∙FCI
OPEX =
0.99 (1)
Here, costs for operating labor COL and utility costs CUT are not considered. Eq. [1] includes the following direct and indirect operational ex-
penditures according to Turton et al. [242]:

• Maintenance and repairs: 0.1 * FCI

• Operating supplies: 0.1 * FCI
• Patents and royalties: 0.01 * OPEX (for OPEX, see Eq. [1])
• Insurance: 0.032 * FCI
• Plant overhead costs: 0.6 (C + C + C )
RM UO OL

• Administrative costs: 0.15 (C + C + C )

RM UO OL

With OPEX and ACC, production costs are calculated with.

€ OPEX + ACC
Production costs ⎡ ⎤ =
⎢ kg
⎣ ⎦ ⎥ m˙ Produkt (2)

Assumptions

Value / Note Reference

Plant operating life time 20 years –

Interest rate 8% –
Plant operating time 8000 h/a –
Calculated depreciation annuity –
Exchange rate 1.21 US$/€ [245]
Costs for CO2 50 $/tCO2 [218]

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