Spotlight

New process for sustainable fuels

and chemicals from bio-based
alcohols and acetone
Klaas Breitkreuz, Andreas Menne and Axel Kraft, Fraunhofer UMSICHT, Oberhausen, Germany

Received November 20, 2013; revised February 20, 2014, and accepted February 27, 2014
View online April 23, 2014 at Wiley Online Library (wileyonlinelibrary.com);
DOI: 10.1002/bbb.1484; Biofuels, Bioprod. Bioref. 8:504–515 (2014)

Abstract: Synthesizing complex and large molecules out of small molecules derived by fermentation
processes is a key factor for future processes based on renewable resources. Promising steps are the
self-condensation of alcohols and the cross-condensation of alcohols with acetone. The presented
continuous heterogeneous-catalytic gas-phase process makes it possible to condense small alcohols
and ketones to larger hydrocarbon molecules containing only one atom of oxygen per molecule. After
an optional oxygen-removing step such as hydrotreatment, fuel-identical hydrocarbons including jet
fuel can be obtained. A tailor-made carbon chain distribution and additionally carbon-chain branching
can be achieved. The choice of raw materials, the process conditions and the recycling of intermediate
products are tuning factors. The crude or partially distilled product can be used neat as drop-in fuel
for diesel. The intermediates – longer ketones, primary and secondary alcohols – also serve as value-
added raw materials and intermediates for many chemical applications, i.e. plasticizers, surfactants,
alkenes, solvents, fatty alcohols, and lubricants. The presented process offers an attractive alternative
to other competing processes producing long-chain hydrocarbons, like Fischer-Tropsch or hydrotreat-
ment of fats and oils. Being based on inexpensive, long-term stable and commercially available cata-
lysts and designed for a wide range of possible raw materials optionally stemming from residues, the
suggested route is ready for scale-up. Future process development can be performed on data already
gathered on a bench-scale process allowing the production of 10 liters of purified product per week.
© 2014 Society of Chemical Industry and John Wiley & Sons, Ltd

Keywords: catalysis; ABE-fermentation; condensation; Ethanol; alcohols; chemicals; fuels; Jet fuel;
biorefinery

Introduction used. ABE-Fermentation provided a substantial contri-

bution as source for renewable raw materials for many
owadays the fermentation of ethanol is the most industrial processes. Low-molecular-mass compounds like

N important process for the production of bio-based

chemicals and fuels. Many decades ago also other
fermentation processes and in particular the acetone-buta-
nol-ethanol-fermentation (ABE-Fermentation) were widely
acetone, ethanol, or n-butanol can be produced carbon
efficiently at titers near the theoretical maxima via fermen-
tation processes. Nonetheless, the industrial significance of
ABE-fermentation-processes decreased with the improve-

Correspondence to: Axel Kraft, Fraunhofer UMSICHT, Osterfelderstr. 3, 46047 Oberhausen, Germany.
E-mail: axel.kraft@umsicht.fraunhofer.de

504 © 2014 Society of Chemical Industry and John Wiley & Sons, Ltd
Spotlight: Sustainable fuels and chemicals from bio-based alcohols and acetone
ment of crude oil refinery processes in the middle of the
twentieth century. A revival of fermentation technologies
has been observed over the past years caused by an increase
in global demand and a decrease in potential availabil-
ity of crude oil as well as an increase in productivity and
efficiency of the fermentation process triggered by better
downstream processing and metabolic engineering.1–4
As it is possible to use many kinds of organic wastes
or residues, non-food sugars, and even syngas from steel
mills to make acetone, ethanol or n-butanol, such fermen-
tation processes offer a big potential regarding raw materi-
als with no competition to food or feed.
Despite the great progress that has been made recently in
metabolic engineering, higher-molecular-mass products
like fatty alcohols are still not accessible at high space-
time-yields via fermentation processes. Another draw-
back is the limited use as such for typical oxygenated low
molecular-mass products with carbon chains typically
not exceeding 6 carbon atoms, since they can only be used
as gasoline blending components or solvents. As larger
molecules are essential for jet fuel and diesel, attempts
have already been made to realize the conversion of ABE-
fermentation products into fuel-range hydrocarbons via
C-C coupling reactions conducted in the liquid-phase.1
The chemical route proposed here opens up an oppor-
tunity for a process that includes a fast gas-phase conver-
sion of ABE-fermentation products yielding tailor-made
hydrocarbons with a specific carbon chain length distri-
bution. The reaction intermediates – secondary alcohols
and ketones – are added-value chemicals as such and can
directly be used for blending or substituting fuels like diesel
or gasoline. After an additional Hydrotreating step, the final
products – tailor-made linear and branched alkanes – could
be employed as diesel or jet fuel blending components.1 The
highest specifications are required by jet fuel in particular
with respect to chemical composition and physical param-
eters – boiling point distribution, freezing points, etc. – and
total absence of oxygen. Currently the worldwide accepted
norm for jet fuel is ASTM D7566-13.5 Since the future
demand for bio-based commodity chemicals and biofuels
like diesel and particularly jet fuel is expected to increase
strongly by about 4.5% globally, the focus of this paper will
be put on those topics.6
When discussing the future of biofuels one has to keep
in mind that no alternatives as for other fuels, for example
batteries for cars, exist for jet fuel. Biofuels for aviation are
in their infancy, but are state-of-the art for cars.
Besides ongoing activities in the USA and the European
Flight Path in Europe, Mexico,7 Australia,8 and Brazil9
also kicked-off strategic projects for bio-kerosene.
© 2014 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 8:504–515 (2014); DOI: 10.1002/bbb
K Breitkreuz, A Menne, A Kraft
State-of-the-art of non-fossil-fuels
The state-of-the-art technology for producing non-fossil-
oil-based alternative fuels is summarized in two recent
reports by the International Air Transport Association
(IATA).10 The development of all new technologies for jet
fuel and diesel are linked together for economic reasons
and can therefore not be considered independently.
First, there is the so-called Fischer-Tropsch (FT) process.
In particular CTL, GTL and BTL (coal-, gas-, and bio-
mass-to-liquid) products are addressed. Technology-wise,
it involves gasification of feedstock to syngas (CO, H2).
Syngas is converted further to a mixture of fuels contain-
ing naphtha, olefins, kerosene, diesel, and waxes, which
are treated in several steps by so-called hydro-processing
and isomerization to yield fuels including jet fuel. Since
those processing steps require very large units, typically
more than 50% of fuel costs are due to investment costs.
Secondly, there is so-called hydrogenated vegetable oil
(HVO) which always addresses diesel applications. The
corresponding jet fuel is called hydroprocessed renew-
able jet (HRJ). Because the character of the hydrocarbons
depends on the structure and chain length of the fatty
acids, no branched molecules or hydrocarbons with fewer
than 12 carbon atoms are produced by hydrogenation
only and costly additional processing steps are necessary.
Beside distillation, processing steps consist of hydrotreat-
ing, hydrocracking and isomerization.
New technologies based on alcohols
Besides the processes described above, there are several
new technologies not yet considered by ASTM but lining
up for testing.
Hydroprocessed ‘synthetic paraffi nic kerosene’ (SPK)
derived from fermented alcohols initially focused on
isobutanol. Other alcohols will be considered for future
projects, too.
Most technologies based on alcohols remove the oxygen
in a first processing step to form alkenes as intermedi-
ates. The alkenes are catalytically oligomerized, but such
processing leads to a broader carbon chain distribution.
This means that the process can not be tuned easily to
maximize yields of carbon chain distributions required for
gasoline, jet fuel, or diesel.
New selective technology
The method described in this paper is based on a continu-
ous, heterogeneous catalytic gas phase process. It offers a
new alternative way to produce long chain hydrocarbons for
chemicals and drop in fuels with narrow carbon chain distri-
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 K Breitkreuz, A Menne, A Kraft Spotlight: Sustainable fuels and chemicals from bio-based alcohols and acetone

bution. Small alcohols and aldehydes are combined to form

larger alcohols and are subsequently condensed with acetone
to form long-chain hydrocarbons containing only one oxy-
gen atom per molecule. This selective and controlled con-
densation reaction leads to well defined product mixtures.
During the chain elongation process most of the oxygen is
removed via elimination of water (Fig. 3 and Fig. 9). Long-
term tests showed neither a shift of selectivity for weeks nor
disadvantages due to high water content, a very positive
aspect in matters of the use of fermentation products that
often cause catalyst deactivation or at least inhibition. This
infers that, regarding the acetone-coupling step in particular,
even the direct use of ABE fermentation product mixtures
coming from the fermentation of residues and lignocellulosic
material is possible. Hence, the often discussed issue of com-
petition with food-production is avoided.
The new and innovative carbon-based basic catalyst
delivers excellent yields, up to 90% based on acetone, at
process conditions ranging from 280 °C to 380 °C and
pressures up to 80 bars. High temperatures are needed
to avoid condensation of high boiling products at suited
pressures. Typical acetone-to-alcohol molar ratios are 1:2.
Alcohol conversion rates are in the range of 40% to 60%, Figure 1. Schematic flowsheet of the process.
with recycling not taken into account.
area is achieved (Table 1). For more information regarding
Methods catalyst see PCT/EP2012/005152 and PCT/EP2011/002233
/ US20130211146 A1.
Experimental set-up The minerals found in the ash of the activated carbon,
All experiments were carried out in a single flow tube predominantly alkali metals, are shown in Table 2.
reactor. A schematic flowsheet is shown in Fig. 1. Both the detected species and the types of reactions
The reactants (1) are pumped (2) into an evaporator (3) observed indicate the basic character of the catalyst. An
where they vaporize at elevated temperatures and at reac- irreversible increase in mass during the beginning of an
tion pressure. Via a preheater, (4) the gas enters a single experiment may indicate changes on the surface caused by
tube reactor (5) with a catalyst volume of 120 mL. In the an activation process.
following water-cooled condenser (6) the reaction mix- Further analysis and experiments regarding catalyst
ture is cooled down to room temperature. In an automatic properties are currently in progress and will be published
valve (7), which controls the system’s pressure, the product elsewhere.
mixture is expanded to ambient pressure. Finally the liq-
uid product is collected at the end (8). Table 1. Physical properties of the used
Product samples were analyzed by gas chromatography- catalyst.
mass spectrometry (GC-MS): Agilent 6890N with MS Ash content BET Bulk density
5975B and Agilent FFAP 30 m×0,25 mm×0,25 μm column [weight-%] [m2/g] [g/l]
and identified by a NIST library of spectra. 18,1 1300 454

Catalyst
Table 2. Ash composition of the used catalyst.
The used catalyst is based on activated carbon. During
the production process additives like K 2CO3 or CaCO3 Na K Mg P Ca Total
[mg/g] [mg/g] [mg/g] [mg/g] [mg/g] [mg/g]
are added resulting in a high ash content of the final acti-
10,7 360 13,9 36,5 110 531,1
vated carbon. At the same time a high specific surface

506 © 2014 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 8:504–515 (2014); DOI: 10.1002/bbb
Spotlight: Sustainable fuels and chemicals from bio-based alcohols and acetone
Results
The exemplification of the results is divided into alcohol
condensation experiments and alcohol with acetone con-
densation experiments. It needs to be underlined that it is
possible to do the condensation reactions subsequently or
simultaneously. The ethanol peak is blanked out for tech-
nical reasons in all chromatograms shown here.
Alcohol condensations
The first step is the gas-phase conversion of biomass-based
alcohols to linear and branched alcohols. The basic reaction,
proposed by Yang et al. who employed zeolites as catalysts, that
takes place on an activated α-carbon atom is shown in Fig. 2.11
Subsequent works used different basic catalysts like
hydroxyapatites12 or magnesium oxides13 and impregnated
activated carbon or aluminum oxides.14–16
Beside the condensation reaction hydrogenation and
dehydrogenation with subsequent aldol condensation as
main reactions are possible.
Figure 2. Dimerization of ethanol.
Figure 3. Schematic reaction mechanism for the condensa-
tion of alcohols.
Figure 4. Condensation of ethanol to n-butanol and n-hexanol.
© 2014 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 8:504–515 (2014); DOI: 10.1002/bbb
K Breitkreuz, A Menne, A Kraft
In contrast to the cited works, the catalyst used for the
presented experiments is a carbon-based basic catalyst with
high ash content. It is long-term stable insensitive against
water and active at temperatures even below 350 °C. High
conversion rates and excellent selectivity for target mole-
cules and only small amounts of side products are observed.
The products are explainable by the reaction mecha-
nism shown in Fig. 2 but are not limited to the con-
densation of ethanol. The received products are similar
to a liquid-phase aldol condensation of corresponding
aldehydes but without any unsaturated product. Figure 3
shows a schematic reaction mechanism for the observed
condensation of ethanol or higher alcohols to linear and
branched alcohols and the simultaneous elimination of
water.
Figure 4 depicts a typical chromatogram of a product
mixture where only ethanol is condensed.
The main peaks visible in Fig. 4 are n-butanol and its
corresponding aldehyde butanal, ethanal corresponding
to ethanol. The condensation product 2-ethylbutan-1-ol
results from the condensation of n-butanol and ethanol
and the product n-octanol represents the product of the
condensation of n-hexanol and ethanol.
Figure 5 displays the basic reaction sequence of con-
secutive reactions of ethanol derived from experimental
findings.
As stated in the reaction mechanism, there are always
linear and branched alcohols and the corresponding
aldehydes in the product mixture. Additionally a variable
mixture of alkanes, alkenes, and alkylated benzenes can
be detected in the liquid phase, in particular at the higher
end of the investigated temperature range.
The non-condensable off-gas consists to about 80
mole-% of hydrogen next to CO2 , alkanes and alkenes.
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 K Breitkreuz, A Menne, A Kraft Spotlight: Sustainable fuels and chemicals from bio-based alcohols and acetone

as shown in Fig. 6. Long-chain alcohols with a high

Figure 5. Proposed consecutive reactions of ethanol.
The observed gas yield depends somewhat on the carbon
chain length of the reactants and is between 4 and 10
wt.-%. The degree of branching and consecutive reactions
can be influenced by pressure, temperature and resi-
dence time or of course by recycling part of the product
mixture.
The aforementioned consecutive reactions can be used to
extend the carbon-chain of alcohols made out of ethanol
amount of branched alcohols and a low level of aldehydes
are obtained.
In contrast to Fig. 4 there are more side products in
Fig. 6 as there is a higher degree of consecutive reactions
needed to form higher alcohols out of ethanol and hence
more possible side reactions are occurring.
Figure 7 shows the product distribution of an experi-
ment where ethanol and n-butanol are condensed in a
molar ratio of 1:1.
In Fig. 7 there are less side products than in Fig. 6 as
there are fewer consecutive reactions needed (Fig. 5) for
a similar amount of higher alcohols when n-butanol is
already present.
If alcohols with more than two carbon atoms are used
as raw materials, the products are so-called Guerbet-
alcohols.17 The prototype for the guerbet-reaction that
leads to β-branched alcohols has been the dimerization of
n-butanol to 2-ethyl-1-hexanol.17

Figure 6. Production of higher alcohols out of ethanol.

Figure 7. Condensation of ethanol and n-butanol (molar 1:1).

508 © 2014 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 8:504–515 (2014); DOI: 10.1002/bbb
Spotlight: Sustainable fuels and chemicals from bio-based alcohols and acetone
Figure 8. Condensation of n-butanol to 2-ethylhexan-1-ol.
Figure 8 shows the chromatogram of a product of a reaction
mixture where only n-butanol has been used as raw material.
It can be seen that the main product is 2-ethyl-1-hexanol,
a guerbet-alcohol. If a mixture of alcohols is used as raw
materials, crossed guerbet-alcohols can also be detected in
the product mixture. Alcohols that are already branched in
β-position like 2-methyl-1-propanol (isobutyl alcohol), do not
undergo any further branching reactions on that position.
The main reaction products are similar to the prod-
ucts of an aldol condensation. However, the main side
products alkanes, alkenes, and CO2 can be explained by
a so-called Tishchenko or Cannizzaro reaction18 where
esters are formed by the disproportionation of aldehydes.
Since esters are not stable under reaction conditions they
decompose and eliminate CO2 resulting in alkanes and
alkenes, and are only detectable as traces. Other side prod-
ucts are xylene and ethyl-dimethyl-benzene. Both aromat-
ics are probably formed by the reaction of aldehydes as
experimental results showed an increase of these products
when ethanal or butanal are added to the feed. If ethanal
is added, a significant increase of xylene in the product
can be observed. A significant increase of ethyl-dimethyl-
benzene can be observed if butanal is added. Furthermore
also an increase of alkanes, alkenes and CO2 is observed
by decomposition of intermediately formed esters from the
disproportionation of aldehydes.
Alcohol to acetone coupling
The obtained mixture of alcohols can be blended with
acetone and be converted in a similar, selective gas-phase
© 2014 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 8:504–515 (2014); DOI: 10.1002/bbb
K Breitkreuz, A Menne, A Kraft
reaction but via a different pathway. The resulting mixture
consists of a multitude of branched and linear secondary
alcohols and ketones. Figure 9 shows the condensation of
alcohols with acetone and subsequent conversion to alkanes.
Liquid-phase aldol condensation of acetone is well
known, for example the aldol cross-condensation with
furfural.19 In contrast to that, the presented technology is
carried out in the gas-phase and couples alcohols, ketones
as well as aldehydes.
Some side products are well-known condensation
products of acetone - mesityl oxide, isophorone and
3,3,6,8-tetramethyl-1-tetralone.20
The acetone alcohol condensation is more selective com-
pared to alcohol coupling and leads to longer hydrocar-
bons. The required alcohols can either be generated in-situ
or prior to this step by the alcohol condensation described
Figure 9. Proposed condensation of alcohols with acetone
and subsequent conversion to alkanes.
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 K Breitkreuz, A Menne, A Kraft Spotlight: Sustainable fuels and chemicals from bio-based alcohols and acetone

Figure 10. Condensation of 2-ethyl-1-hexanol with acetone (molar 2:1).

above. Alternatively alcohols and ketones can be obtained
via fermentation processes, either pure or as a mixture.
Figure 10 shows the condensation of 2-ethylhexan-1-ol
to acetone in a molar ratio of 2:1. There are only two main
product peaks in the chromatogram. As stated above,
there are alkanes in the product mixture (unlabeled
peaks). Besides these unlabelled peaks two additional
peaks at retention times of approximately 5 and 12 min,
which belong to the reactant 2-ethylhexan-1-ol and its
corresponding aldehyde, show up. Th is outlines the high
selectivity towards the condensation products of acetone
and alcohol.
The peak at approximately 12.7 min belongs to the
mono-condensation-product of one mole of acetone with
one mole of alcohol. The peak at approximately 24 min
corresponds to the condensation product of acetone with
two moles of alcohol. Once a double condensation product
is formed, no further reactions on the α-carbon atoms can
be observed no matter if the added alcohol is branched
or linear. Additionally the condensation of acetone with
branched alcohols is more selective compared to linear
ones, since no self-condensation occurs.
As the experiment in Fig. 10 was carried out with a ratio
of two moles of alcohol to one mole of acetone, the peak
of 5,11-diethylpentadecane-8-one (double-condensation-
product) is much higher than the peak of 5-ethylno-
nan-2-one (mono-condensation-product).
Figure 11 shows the corresponding reaction sequence of
acetone with 2-ethylhexan-1-ol derived from the experi-
mental finding in Fig. 10.

Figure 11. Consecutive condensation of 2-ethyl-1-hexanol with acetone.

510 © 2014 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 8:504–515 (2014); DOI: 10.1002/bbb
Spotlight: Sustainable fuels and chemicals from bio-based alcohols and acetone
Figure 12. Hydrogen-transfer-reaction and reaction prod-
ucts of the condensaton of butanal and 1-propanol (alde-
hydes of products not shown).
Another fact that can be observed in every experiment is
the existence of secondary alcohols that are formally derived
from the hydrogenation of ketones, just like there are always
aldehydes corresponding to every alcohol. It is assumed that
hydrogen-transfer-reactions at the catalyst surface must
occur. This has been confirmed by an experiment with
1-propanol and butanal as raw materials and both propanal
and 1-butanol have been detected in high amounts as well as
the condensation products of the alcohols (Fig. 12).
The hydrogen-transfer-effect can also be observed
for branched alcohols. This observation is confirmed
also by hydrogen-transfer-effect between second-
ary alcohols and ketones. To illustrate this effect an
experiment where 2-methylbutan-1-ol was converted
with acetone in a molar ratio of 2:1 is shown in Fig. 13.
2-Methylbutan-1-ol can be obtained by the presented
method via condensation of n-butanol with methanol in
a molar ratio of 1:1.
Figure 13. Condensation of 2-methyl-1-butanol with acetone (molar 2:1).
© 2014 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 8:504–515 (2014); DOI: 10.1002/bbb
K Breitkreuz, A Menne, A Kraft
An important commodity alcohol that can be obtained
from fermentation of bio-based sugars is 2-methylpropan-
1-ol (isobutyl alcohol).21 As shown in Fig. 14 the conver-
sion of 2-methylpropan-1-ol with acetone in a molar
ratio of 2:1 is also viable. The expected branched double-
condensation-product is 2,8-dimethylnonan-5-one.
The first two peaks at approximately 2 and 3 min
belong to the reactant – 2-methyl-1-propanol – and its
corresponding aldehyde – 2-methylpropanal. As shown
in Fig. 14 and Fig. 15, the two peaks at approximately
4 and 10 mins belong to the mono-condensation-product
(5-methylhexan-2-one) and the double-condensation-
product (2,8-dimethylnonan-5-one).
Regarding the availability of a broad raw-material basis
an all-in-one conversion of an ABE fermentation broth
(acetone, n-butanol, ethanol) is a very interesting option.
A synthetic mixture consisting of acetone, n-butanol and
ethanol in the typical molar ratio of 3:6:122 has been tested
as well. As the fermentation process is done in an aque-
ous phase, 10 weight-% of water has been added. Figure 16
shows the corresponding chromatogram.
The assumed condensation reactions leading to the major
identified molecules in Fig. 16 are depicted in Fig. 17.
As the intermediate 1:1-condensation products
heptan-2-one and heptan-2-ol can be converted to the
1:2 condensation products by recycling, the use of an
ABE fermentation immediately leads to linear and
branched molecules in the range of 9 to 15 carbon atoms.
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 K Breitkreuz, A Menne, A Kraft Spotlight: Sustainable fuels and chemicals from bio-based alcohols and acetone

Figure 14. Condensation of 2-methyl-1-propanol with acetone (molar 2:1).

Figure 15. Consecutive reaction of 2-methyl-1-propanol with acetone.

The remaining oxygen can be removed completely in an
extra hydrotreatment step23 or subsequently via hydro-
genation to alcohols, dehydration to alkenes and further
hydrogenation to alkanes. These steps are state of the art.
Acetone can be replaced by isopropanol and reacts in
very similar fashion as shown in Fig. 17. In this case the
product mixture contains more secondary alcohols and less
ketones. Interestingly also cyclohexanol and cyclohexanone
can be employed instead of acetone, leading to mono- and
di-alkyl branched cyclohexanols and cyclohexanones.
Process development
considerations
Based on the experimental results, an overall process has
been developed to use the described pathway for the tar-
geted production of high added-value compounds.
Common fermentation products like acetone, n- and
iso-butanol as well as ethanol or any other alcohol can
be used as feedstock, pure or mixed in arbitrary combi-
nations. Care must to be taken to operate at a pressure,
at which the expected product mixture remains still in
the gas-phase. This was the case for all presented results.
The manufactured product mixture mainly consists of
branched and linear higher alcohols and ketones.
A possible process scheme leading to chemicals and fuels
is depicted in Fig. 18. The raw-material mixture is evapo-
rated and fed through a catalytic fi xed bed reactor.
Afterwards the product is separated by flash-distillation
into a colorless distillate, consisting mainly of uncon-
verted reactants, low-boiling intermediates, water and a
non-viscous bottom product, which sometimes displays a
slight yellowish color and contains very little water. Both
phases contain as main side-products the aldehydes of the
corresponding alcohols. In case an increased carbon-chain
branching or a maximum yield of longer carbon-chains
is desired, low-boiling intermediates including ketones
with a keto-functionality at the 2-position can be recycled.
Subsequent to the flash-distillation water has to be
removed from the recycle stream, since at higher concen-
trations it will lower the space-time-yield and increase the
energy required when recycling is conducted. Separation

512 © 2014 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 8:504–515 (2014); DOI: 10.1002/bbb
Spotlight: Sustainable fuels and chemicals from bio-based alcohols and acetone K Breitkreuz, A Menne, A Kraft

Figure 16. All-in-one conversion of acetone, n-butanol and ethanol (molar 3:6:1) and 10
weight-% of water.

Figure 17. Condensation reactions of a synthetic ABE fermentation broth.

of water can be achieved by distillation or pervaporation.

The latter is preferred; it is more selective and requires less
energy.
Future process development can be performed on data
already gathered on a separate bench-scale set-up includ-
ing downstream processing and allowing the production
of 10 liters of purified product per week, which is not
described in detail here.

Figure 18. Overall process scheme to chemicals and fuels.
Applications of products
and intermediates
As depicted in Fig. 19, the primary products, comprising
ketones and alcohols, provides a basis for a wide range of
chemicals that can be used in a variety of applications.

© 2014 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 8:504–515 (2014); DOI: 10.1002/bbb 513
 K Breitkreuz, A Menne, A Kraft
Figure 19. Raw materials, intermediates and product applications. Also n- and iso-butanol,
as well as cyclo-hexanol and cyclo-hexanone are possible, already tested reactants.
It is known, that ketones can be hydrogenated to second-
ary alcohols.1 This way a pure alcohol fraction can be gen-
erated. Secondary alcohols can be transformed to alkenes,
ethoxylates, or amines by known process steps. Esterification
or etherification of primary alcohols are further possible
process steps to produce value added chemicals.
Alcohols and ketones are currently used as surfactants,
flavors, fragrances, plasticizers, and lubricants. Beside
the use as a basis for specialty chemicals, the mixture of
ketones and alcohols can be blended without any prior
hydrotreatment with diesel. Detailed investigations are
ongoing at Fraunhofer.
Removing the oxygen completely leads to linear and
branched alkanes. By choosing branched alcohols with a
suitable chain length an alkane mixture - boiling mainly
in the kerosene range - with tunable freezing and flash-
point is yielded.
Conclusions and outlook
A technology for the production of mono oxygenated
long-chain hydrocarbons, based on short-chain alcohols
and acetone has been presented. The presented catalytic
conversion and downstream-processing steps can handle
a broad range of water containing raw materials typically
coming from fermentations of edible and non-edible sug-
ars. Demonstration of the overall process including down-
stream processing steps on a larger scale is still required.
The catalytic part is already fully tested and ready for
scale up by multiplication of the existing single tube
514 © 2014 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 8:504–515 (2014); DOI: 10.1002/bbb
Spotlight: Sustainable fuels and chemicals from bio-based alcohols and acetone
reactor to a multi-tube reactor suitable for a demonstra-
tion scale plant.
The selectivity of the catalytic reactions can be influ-
enced to a large extent via alternating process conditions
and by selecting the right ratio and nature of alcohols and
ketones. Besides acetone and iso-butanol, cyclohexanone
and cyclohexanol can also be employed as commodity
feedstock. The product distribution and the degree of
branching, which is a key enabler for the flexible produc-
tion of value-added fuels with more desirable features than
current complex fossil fuel mixtures, can be tuned in a
wide range. Examples for the targeted production of linear
and branched molecules in the range of 9 to 19 carbon
atoms have been presented. After a subsequent oxygen
removal, for example, by hydrotreating, these molecules
could be used for direct blending into fossil jet fuel.
The reaction intermediates – secondary alcohols and
ketones – provide a broad platform of applications in the
commodity and specialty chemicals sector alike. This will
render possible a simultaneous production of green chemi-
cals and fuels, making it more profitable and less risky to
start-up a new technology.
The bio-based content of any product mixture will go
up to 100% in future when a higher amount of bio-based
acetone will be commercially available, for example via
carbon monoxide fermentation.24
Acknowledgements
The authors gratefully acknowledge the Federal Ministry
of Food, Agriculture and Consumer Protection (BMELV)
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© 2014 Society of Chemical Industry and John Wiley & Sons, Ltd | Biofuels, Bioprod. Bioref. 8:504–515 (2014); DOI: 10.1002/bbb 515