DOI: 10.1002/cssc.201600936
Communications
Synthesis of Acetone-Derived C6, C9, and C12 Carbon
Scaffolds for Chemical and Fuel Applications
Cameron M. Moore,[a] Rhodri W. Jenkins,[a] Michael T. Janicke,[a] William L. Kubic, Jr.,[b]
A simple, inexpensive catalyst system (Amberlyst 15 and Ni/
SiO2–Al2O3) is described for the upgrading of acetone to
a range of chemicals and potential fuels. Stepwise hydrodeoxy-
genation of the produced ketones can yield branched alcohols,
alkenes, and alkanes. An analysis of these products is provided,
which demonstrates that this approach can provide a product
profile of valuable bioproducts and potential biofuels.
volume) is used for the production of gasoline, diesel, and jet
fuel, and this market is worth $935 billion annually. In contrast,
16% is used for production of chemicals in a market worth
$812 billion.[11] In a commercial biomass-upgrading process in
which volumetric output is limited, one strategy would be to
pursue small-volume, high-value chemical production in the
short term. If fuels could be produced using the same process,
this approach would allow the expansion to an almost limitless
market upon reaching the upper limit of the chemical market
as production volume increases.
Steady increases in global oil consumption aggravated by de-
clining fossil-fuel reserves necessitate the continued develop-
ment of technologies to manufacture chemicals and fuels from
non-petroleum sources of carbon. As the global population is
projected to continue to grow through the end of this centu-
ry,[1] consumption of alternative sources of energy must be
adopted to meet rising demand.[2–4] Non-food-based biomass
represents a vast source of renewable carbon for the synthesis
of chemicals and fuels.[3,5–8] The U.S. is projected to have the
ability to produce over a billion tons of biomass for the bioen-
ergy and bioproducts industry within the next six years
alone.[9] To effectively utilize this massive resource, however, ef-
ficient methodologies for transforming biomass-derived
carbon material into useful chemicals and fuels must be devel-
oped at a comparable rate. Moreover, one approach to enable
future biorefineries to produce fuels for the transportation
sector that are cost-competitive with traditional petroleum re-
fineries is to co-produce high-value chemicals from biomass to
offset the cost of producing inherently low-value fuels.[10] To il-
lustrate this point, in the U.S., 76% of a barrel of oil (by
Herein, we describe our preliminary efforts toward such an
approach for converting bio-derived isopropanol/acetone mix-
tures to known chemicals and molecules with promising fuel
properties for both gasoline and diesel applications. Specifical-
ly, we present an inexpensive dual catalyst system for the up-
grading of acetone through polyaldol condensations to pro-
vide C6, C9, and C12 aliphatic ketones, along with C9, C12, and
C15 aromatic compounds.[12,13] Additionally, we demonstrate
that the mild conditions for acetone upgrading can be modi-
fied to subsequently defunctionalize the aliphatic ketones and
readily produce branched alkanes. Along with being known
solvents and industrially used chemicals, predicted/measured
fuel properties of a selection of these molecules reveal that
certain compounds produced herein are candidates as drop-in
fuel replacements for spark- and compression-ignition engines.
Ketones are a versatile class of chemical building blocks that
can be renewably produced from biomass.[14–17] In particular,
methyl ketones have shown promise as bio-derived synthons
for the production of chemical/fuel precursors because their
carbon chain can be readily extended through aldol condensa-
tion.[17–19] Acetone, the simplest ketone building block, has
been industrially produced for nearly a century by the microbi-
al fermentation of biomass through the acetone–butanol–etha-
nol (ABE) fermentation process, with the products obtained in
roughly a 3:6:1 ratio, respectively. Recently, however, metabol-
ically engineered microorganisms were developed that can
produce mixtures of isopropanol and acetone in high titers
from carbohydrate inputs using strains that have the potential
to be scaled up industrially.[20] These isopropanol/acetone mix-
tures are much more attractive from a technoeconomic per-
spective because 1) the output stream from fermentation con-
tains a larger fraction of isopropanol/acetone, and 2) in situ de-
hydrogenation of the isopropanol fraction can be performed
to provide the system with bio-derived H2 sufficient for ace-
tone upgrading (Scheme 1). This is an advantage over other
processes that incorporate acetone from ABE fermentation,
such as furfural–acetone condensation[21,22] and acetone alkyla-
[a] Dr. C. M. Moore, Dr. R. W. Jenkins, Dr. M. T. Janicke, Dr. A. D. Sutton
Chemistry Division
Los Alamos National Laboratory
MS K558, Los Alamos, NM 87544 (USA)
[b] Dr. W. L. Kubic, Jr.
Applied Engineering and Technology Division
Los Alamos National Laboratory
MS E548, Los Alamos, NM 87544 (USA)
[c] Dr. E. Polikarpov
Applied Materials and Performance
Pacific Northwest National Laboratory
Richland, WA 99352 (USA)
[d] Dr. T. A. Semelsberger
Material Physics Applications Division
Los Alamos National Laboratory
MS K793, Los Alamos, NM 87544 (USA)
Supporting Information and the ORCID identification number(s) for the
ChemSusChem 2016, 9, 1 – 6
1
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