R ES E A RC H

SUSTAINABLE CHEMISTRY to these latter reactions together as nitrilation

(Fig. 1B, reactions 2 and 3). Little work has been
published on nitrilation overall, especially in sys-
Renewable acrylonitrile production tems where ester and ammonia vapors are passed
over heterogeneous catalysts to form nitriles
(16–18).
Eric M. Karp,1* Todd R. Eaton,1* Violeta Sànchez i Nogué,1* Vassili Vorotnikov,1* Given sparse mechanistic information for this
Mary J. Biddy,1 Eric C. D. Tan,1 David G. Brandner,1 Robin M. Cywar,1 Rongming Liu,2 chemistry, we performed periodic density func-
Lorenz P. Manker,1 William E. Michener,1 Michelle Gilhespy,3 Zinovia Skoufa,3 tional theory (DFT) calculations to probe the
Michael J. Watson,3 O. Stanley Fruchey,4 Derek R. Vardon,1 Ryan T. Gill,2 catalytic mechanism over a TiO2(101) surface.
Adam D. Bratis,2 Gregg T. Beckham1† Alcohol dehydration was predicted to proceed
via an E2 mechanism (fig. S2), similar to well-
Acrylonitrile (ACN) is a petroleum-derived compound used in resins, polymers, acrylics, known dehydration reactions (19). For the ami-
and carbon fiber. We present a process for renewable ACN production using nolysis of ethyl acrylate, DFT results suggested
3-hydroxypropionic acid (3-HP), which can be produced microbially from sugars. The a stepwise mechanism catalyzed by partial dis-
process achieves ACN molar yields exceeding 90% from ethyl 3-hydroxypropanoate sociation of NH3 on TiO2. H-NH2 bond scission
(ethyl 3-HP) via dehydration and nitrilation with ammonia over an inexpensive titanium exhibits the highest barrier, +111 kJ/mol, in this
dioxide solid acid catalyst. We further describe an integrated process modeled at scale mechanism (Fig. 1C). DFT results for the final
that is based on this chemistry and achieves near-quantitative ACN yields (98 ± 2%) from reaction suggest that acrylamide undergoes de-
ethyl acrylate. This endothermic approach eliminates runaway reaction hazards and hydration to form ACN via surface-mediated
achieves higher yields than the standard propylene ammoxidation process. Avoidance of tautomerization to its enol form followed by

Downloaded from http://science.sciencemag.org/ on December 13, 2020

hydrogen cyanide as a by-product also improves process safety and mitigates product dehydroxylation (Fig. 1D). The highest-barrier
handling requirements. step in the nitrilation reaction was predicted

A
crylonitrile (ACN) is one of the most widely
used monomers in the chemical industry,
with more than 14 billion pounds produced
annually for use in plastics, rubbers, resins,
acrylic fibers, and polyacrylonitrile (PAN)–
based carbon fibers (1, 2). The market outlook
for PAN-derived carbon fibers in particular is
projected to grow by 11 to 18% annually, driven
by interest in reducing the weight of vehicles and
aircraft (2). Today, industrial ACN production is
conducted via the Sohio process, which converts
propylene to ACN via ammoxidation over a bis-
muth molybdate–based catalyst. First-generation
catalysts for the process were developed in the
1950s, achieving ~55% molar ACN yields from
propylene (3). This discovery spurred decades of
research to improve ACN yields (4), resulting in
state-of-the-art materials capable of producing
ACN at molar yields of 83% from propylene (5).
However, fluctuations in the price of the propyl-
ene feedstock translate directly to ACN price vol-
atility. The carbon fiber industry is especially
sensitive to these ACN price fluctuations, because
roughly 2 lbs of ACN are required to generate 1 lb
of fiber (6). Thus, concerns about propylene price
volatility have motivated the search for alterna-
tive approaches to propylene ammoxidation to
produce ACN. Substantial efforts have focused
on the ammoxidation of propane, which is a
cheaper substrate than propylene and has a low-
er carbon footprint, but propane is still derived
from fossil-based sources (7). Environmentally
sustainable routes to ACN have been described
from renewable feedstocks such as glycerol (8–10)
1
National Bioenergy Center, National Renewable Energy
Laboratory, Golden, CO 80401, USA. 2Department of
Chemical and Biological Engineering, University of Colorado,
Boulder, CO 80309, USA. 3Johnson Matthey Technology
Centre, Billingham, Cleveland TS23 1LB, UK. 4MATRIC, South
Charleston, WV 25303, USA.
*These authors contributed equally to this work.
†Corresponding author. Email: gregg.beckham@nrel.gov
and glutamic acid (11); these efforts are summa-
rized in (2). The most promising method to date
is glycerol dehydration to acrolein followed by
ammoxidation to ACN, achieving yields of ~60%
(8). Accordingly, there is a clear need to develop
sustainable, cost-effective bio-based ACN manu-
facturing routes.
To that end, we present a route from ethyl 3-
hydroxypropanoate (ethyl 3-HP, derived from
microbially produced 3-hydroxypropionic acid,
3-HP) to ACN at molar yields of ≥90%. This
approach originates from reports of carboxylic
acids being converted to nitriles when passed
over solid acids with ammonia (12). However,
this reaction is made difficult by the relatively
low volatility of carboxylic acids and the cor-
rosiveness of their vapors on equipment. Esters
are less corrosive, more volatile, and in general
more stable than their acid counterparts; using
esters as substrates with this chemistry could
enable a more viable route to renewable ACN.
To test the viability of converting ethyl 3-HP to
ACN, we first conducted a steady-state temper-
ature scan by passing ethyl 3-HP over TiO2 with
an 8:1 molar excess of ammonia (Fig. 1A and fig.
S1). Ethyl 3-HP was consumed in conjunction
with the appearance of ethyl acrylate as the tem-
perature was increased from 150°C to 230°C. In-
creasing the temperature further, from 230°C to
320°C, produced ACN at the expense of ethyl ac-
rylate. From this result, we posit that three se-
quential reactions occur (Fig. 1B) to form ACN.
First, the primary alcohol undergoes dehydration
to form ethyl acrylate and water, then ethyl ac-
rylate undergoes aminolysis (Fig. 1B, reaction 2)
to form acrylamide and ethanol, and finally acry-
lamide is dehydrated to produce ACN and water
(Fig. 1B, reaction 3).
The primary alcohol of 3-HP (or ethyl 3-HP) is
known to readily dehydrate to an acrylate (13).
Ester aminolysis to an amide has been reported
using wet chemistry techniques (14), and amide
dehydration to nitriles is also known (15). We refer
to be the deprotonation of the N-H group, with
a barrier of +101 kJ/mol. See figs. S3 to S17 and
tables S1 to S5 for details and energetics of
these pathways.
Kinetic measurements performed at low con-
versions (figs. S18 and S19) revealed apparent
activation energies consistent with the energe-
tics of the rate-limiting steps from DFT. For the
ester dehydration, an apparent activation energy
of +100 ± 4 kJ/mol was determined from low-
conversion experiments of ethyl 3-HP over TiO2
(fig. S18). The measured activation energy com-
pares favorably to the +112 kJ/mol calculated for
dehydration (figs. S2 and S7). The apparent acti-
vation energy of nitrilation was measured by
performing low-conversion experiments with ethyl
acrylate and ammonia over TiO2 (fig. S19). Here,
an apparent activation energy of +103 ± 12 kJ/
mol also compares favorably to the +111 kJ/mol
barrier for the H-NH2 bond scission from DFT
(figs. S11 and S12), which is the highest predicted
nitrilation barrier.
Results of total-conversion experiments per-
formed in a tandem bed reactor are shown in
Fig. 2 and fig. S20. In the first reactor, ethyl 3-
HP was dehydrated over TiO2 to form ethyl ac-
rylate and water in quantitative yield at 260°C.
A molar excess of 2:1 ethanol to ethyl 3-HP was
used as the feed to the first reactor to suppress
acrylic acid formation (figs. S20 and S21). The
product vapors from the first reactor were then
mixed with ammonia and passed over a second
bed of TiO2 at 315°C to form ACN, ethanol, and
water. This operation achieved ACN yields of 90
to 92% for ~12 hours on stream with minimal
deactivation. The overall heat of reaction is
calculated to be endothermic by +203 kJ/mol
(fig. S22).
At the 12-hour time point for each run, the
reaction was stopped and the catalyst removed
and regenerated in air at 550°C. Images of fresh,
spent, and regenerated catalyst, as well as data
from pyridine diffuse reflectance infrared Fourier
transform spectroscopy, Brunauer-Emmett-Teller

Karp et al., Science 358, 1307–1310 (2017) 8 December 2017 1 of 4

R ES E A RC H | R E PO R T

isotherms, x-ray diffraction, and acid site density
measurements (figs. S23 to S26 and table S6),
indicate that the regeneration cycle restores
the measured characteristics to those of the
fresh sample. The regenerated catalyst showed
identical performance to the fresh sample (Fig. 2).
Thermogravimetric analysis with Fourier trans-
form infrared spectroscopy (TGA-FTIR) mea-
surements of the gas released during catalyst
regeneration showed that NOx was not produced
(fig. S27), thereby abating the need for exhaust
cleanup during regeneration.
To ascertain whether this chemistry exhibits
different behavior on a biologically derived sub-
strate, we produced 3-HP via glucose cultivation
using an engineered Escherichia coli strain (20)
(fig. S28). The cultivation used fed-batch dissolve
oxygen–based control to feed glucose to the bio-
reactor, and resulted in a titer of 25.8 g/liter (sup-
plementary text and figs. S29 and S30). After
glucose cultivation, ethyl 3-HP was separated
and recovered from the broth (figs. S31 and
S32), yielding 97% purity. The ethyl 3-HP was
catalytically processed (Fig. 2) and achieved
performance identical to that of synthetic ethyl
3-HP.
The high yields of the nitrilation chemistry
to produce ACN from microbially derived ethyl
3-HP (Fig. 2) allow us to propose a potential
industrial-scale process for the hybrid biological
and catalytic transformation of lignocellulosic
sugars to ACN. This process (Fig. 3) exhibits
several notable modifications from the process
demonstrated at bench scale. First, 3-HP pro-
duction ideally would be conducted at low pH
[below the pKa of 3-HP (21)]. The advantage

Fig. 1. Catalytic scheme for ethyl 3-HP

dehydration and nitrilation to produce ACN.
(A) Steady-state yields of relevant reaction
products produced when passing ethyl 3-HP over
TiO2 as a function of reactor bed temperature.
Complete reaction conditions and data set

Downloaded from http://science.sciencemag.org/ on December 13, 2020

are provided in fig. S1. (B) The three reactions
that are proposed to yield the results in (A).
(C) Proposed mechanism from DFT calculations
for the aminolysis of ethyl acrylate to form
acrylamide and gaseous ethanol [reaction 2
in (B)]. (D) Proposed mechanism from DFT
calculations for dehydration of adsorbed
acrylamide to release gaseous acrylonitrile
and water [reaction 3 in (B)].

Fig. 2. Catalytic conversion of synthetic and biologically derived ethyl 3-HP to ACN. Total-conversion reactions
of ethyl 3-HP in tandem catalytic beds demonstrate 90 to 92% yields of ACN. The percent yield of ACN is shown
with the carbon balance for the reaction. See fig. S20 for the complete data set for all observed reaction products
and the reaction conditions used. Approximately every 12 hours, the reaction was stopped and the catalyst
regenerated. The rightmost graph represents data collected using ethyl 3-HP separated from a 3-HP cultivation on
glucose using an engineered E. coli strain, showing performance identical to that of the synthetic ethyl 3-HP
substrate. As illustrated in the reactor schematic, glass beads were packed in the headspace of the reactors to
achieve uniform gas mixing over the catalyst.

Karp et al., Science 358, 1307–1310 (2017) 8 December 2017 2 of 4

R ES E A RC H | R E PO R T

gained from low-pH cultivation is that the
acidification step is no longer required during
separations, and neutralization is not required
during cultivation, thus avoiding generation of
waste salt. This would improve the process
economics and sustainability (22). Low-pH
strains to produce 3-HP at industrially relevant
titers, rates, and yields are under development
(21, 23). The second difference is that dew-
atering would occur at scale using a simulated
moving bed (SMB) where 3-HP is adsorbed to
a resin and eluted off with ethanol. Results in
fig. S33 indicate that polybenzimidazole (PBI)
works well for this, allowing 3-HP to be com-
pletely recovered (24). Third, ethyl acrylate,
instead of ethyl 3-HP, would be separated via
reactive distillation. Reactive distillation com-
bines esterification, alcohol dehydration (Fig.
1B, reaction 1), and product separation into a
single unit operation. This is accomplished
using the same industrial process previously
developed for the production of acrylate esters
from b-propiolactone (BPL) (25). In that pro-
cess, BPL is added to an ethanol solution aci-
dified with sulfuric acid in a continuous stirred
tank reactor, where ring opening occurs to form
3-HP and then esterifies and dehydrates to form
the acrylate ester (25). The solution is then fed
to a distillation column where the acrylate
ester is recovered and purified in the column
overhead (25, 26); see figs. S34 and S35 for
details. The process could be stopped here and
ethyl acrylate sold as the product at a predicted
selling price of $0.48/lb, which may be at-
tractive given that the current market price
of ethyl acrylate is $0.79/lb. However, the
market for ACN is approximately 10 times as
large, and the potential for lowering carbon
fiber prices has much greater societal impact
to lower the greenhouse gas footprint of auto-
mobile transportation by reducing vehicle weight
(27, 28).
Recognizing that ethyl acrylate (rather than
ethyl 3-HP) would be fed to the nitrilation
unit in the conceptual process shown in Fig. 3,
we performed total-conversion experiments
with ethyl acrylate and ammonia over TiO2
in a single catalytic bed (Fig. 4 and fig. S36).
These runs resulted in a 98 ± 2% maximum
yield of ACN with ethyl acrylate as a sub-
strate. The ACN yield from ethyl acrylate is
higher than that from ethyl 3-HP because of
decreased carbon deposition on the catalyst,
which is likely attributable to the reduced
presence of water when using ethyl acrylate
as the substrate. The carbon balance shown
in Fig. 4 is slightly above 100% because of
slightly decreased ethyl acrylate conversion
after 12 hours on stream, leading to a slight
buildup of ethyl acrylate (fig. S36). A small

Downloaded from http://science.sciencemag.org/ on December 13, 2020

Fig. 3. Conceptual process diagram for renewable ACN production from biomass sugars. Process depiction of the unit operations proposed to
produce ACN from lignocellulosic sugars via a hybrid biological-catalytic upgrading approach.

Fig. 4. Catalytic conversion of ethyl acrylate to ACN. Total-conversion reactions of ethyl acrylate in a single catalytic bed, demonstrating
maximum ACN yields of 98 ± 2%. The percent yield of ACN is shown with the carbon balance for the reaction. See fig. S36 for the complete
data set for all observed reaction products and the reaction conditions used. Approximately every 12 hours, the syringe was refilled (as shown) and
every 18 hours the reaction was stopped and the catalyst removed and regenerated.

Karp et al., Science 358, 1307–1310 (2017) 8 December 2017 3 of 4

R ES E A RC H | R E PO R T
amount of ethyl acrylate present in the re-
actor outlet leads to measurement uncertainty
because of a low signal-to-noise ratio. The
overall heat of ethyl acrylate nitrilation is
calculated to be endothermic by +81 kJ/mol
(fig. S37).
In a scaled process (Fig. 3), it would be eco-
nomically beneficial to operate the nitrilation
reactor in a pure ammonia atmosphere with-
out the use of N2 as a diluent. Our online an-
alytical system precludes measurements in a
pure ammonia atmosphere (see supplementary
text), but catalyst deactivation studies (figs. S38
to S40) performed using ethyl acrylate as a
substrate allowed calculation of a regenera-
tion cycle time needed under more concen-
trated conditions (fig. S41 and supplementary
text). These calculations estimate that under
full-scale conditions (310°C, 0.89 atm NH3,
0.11 atm ethyl acrylate), the entire catalytic
bed must be regenerated every 30 s to main-
tain ACN yields above 98%. Thus, the fourth
modification in the full-scale process model
is that the recovered ethyl acrylate is fed to a
riser reactor with continuous catalyst regen-
eration (Fig. 3 and fig. S42). This continuously
regenerates the catalyst with a cycle time of
30 s. The liberated alcohol is recovered down-
stream and recycled (figs. S43 and S44). A
simplified schematic of the modeled process is
shown in Fig. 3; see figs. S34, S35, and S42 to
S44 for details of the unit operations.
On the basis of this proposed process, we per-
formed a techno-economic analysis predicting
the selling price of ACN at $0.89/lb from ligno-
cellulosic sugars and $0.76/lb from sucrose. These
target prices are in the range of fossil fuel–derived
ACN prices between $0.40 and $1.00/lb over the
past decade (29). Additionally, the greenhouse
gas emissions from this process were estimated
to achieve a 14.1% improvement relative to
propylene-derived ACN. In addition to the sugar
platform, other low-value feedstocks including
glycerol (30, 31) and waste gases are being pur-
sued for the production of 3-HP. If realized, these
platforms could further lower the ACN selling
price when coupled to nitrilation. See tables S7
to 15 and figs. S34, S35, and S42 to S46 for de-
tails of these analyses, a discussion of the pa-
rameters used, and model sensitivity to these
parameters.
Beyond ACN, nitrilation may have broader
applications by providing a facile link from
carboxylic acid or ester production to nitriles.
Several biologically derived carboxylates are
now being operated at industrial scale (e.g.,
succinic, lactic, itaconic, and fumaric acid)
(32, 33) and the nitrile derivatives of these
acids could likely be readily obtained via ni-
trilation. An economic advantage also may
exist in coupling nitrilation to bioprocesses,
because separation of the ester can often be
more economical than separating the free
acid (34, 35).
For ACN production, nitrilation provides a
number of green chemistry benefits over pro-
pylene ammoxidation: (i) Near-quantitative
Karp et al., Science 358, 1307–1310 (2017) 8 December 2017
yields of ACN can be obtained from this re-
action, whereas state-of-the-art ammoxida-
tion catalysts achieve ~80 to 83% ACN yield
(5). (ii) The reaction is endothermic (figs. S22
and S37) and does not require O2, enabling
facile process control. By comparison, ammox-
idation is highly exothermic, requiring spec-
ialized reactors to avoid runaway reactions (36).
(iii) Unlike ammoxidation, nitrilation does not
produce hydrogen cyanide, mitigating toxicity
and handling requirements. (iv) The cost of
TiO2 is approximately 30% that of ammox-
idation catalysts (4, 37). (v) The process provides
a cost-comparable, sustainable route to ACN
with potential greenhouse gas emission offsets
from a renewable feedstock.
Because the Sohio process depends on pro-
pylene, ACN prices have historically been tied
to petroleum prices and therefore volatile. In-
dustrial deployment of an ACN production pro-
cess using an alternative feedstock, such as
described in this work, could stabilize the ACN
price by unhinging it from sole dependence on
fossil resources. Combined with further process
development, the use of nitrilation could lead
to a sustainable process for bio-based ACN, and
ultimately to products such as renewable car-
bon fiber.
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AC KNOWLED GME NTS
Supported by U.S. Department of Energy (DOE) Bioenergy
Technologies Office grant DE-FOA-0000996. Computer
time was provided by Extreme Science and Engineering
Discovery Environment (XSEDE) allocation MCB-090159
at the Texas Advanced Computing Center and by the
National Renewable Energy Laboratory Computational
Sciences Center, supported by the DOE Office of Energy
Efficiency and Renewable Energy under contract DE-AC36-
08GO28308. We thank L. Berstis, S. Kim, and P. Kostestkyy
for helpful discussions regarding the catalytic mechanism;
D. Salvachúa and X. Wang regarding bioreactor cultivation;
B. Black, K. Ramirez, and M. Reed for analytical assistance;
and members of the Renewable Carbon Fiber Consortium
for helpful discussions. E.M.K., T.R.E., D.R.V., and
G.T.B. are inventors on patent application WO 2017/
143124 A1, US 2017/018272 submitted by the Alliance
for Sustainable Energy that covers nitrile production
from bio-based feedstocks. R.T.G. is a co-inventor on
intellectual property related to biological 3-HPA production,
which is now owned by Cargill. All data generated in
this study are in the supplementary materials. The U.S.
Government retains and the publisher, by accepting
the article for publication, acknowledges that the U.S.
Government retains a nonexclusive, paid up, irrevocable,
worldwide license to publish or reproduce the published
form of this work, or allow others to do so, for U.S.
Government purposes.
SUPPLEMENTARY MATERIALS
www.sciencemag.org/content/358/6368/1307/suppl/DC1
Materials and Methods
Supplementary Text
Figs. S1 to S48
Tables S1 to S15
References (38–100)
5 March 2017; accepted 2 November 2017
10.1126/science.aan1059
4 of 4
Renewable acrylonitrile production
Eric M. Karp, Todd R. Eaton, Violeta Sànchez i Nogué, Vassili Vorotnikov, Mary J. Biddy, Eric C. D. Tan, David G. Brandner,
Robin M. Cywar, Rongming Liu, Lorenz P. Manker, William E. Michener, Michelle Gilhespy, Zinovia Skoufa, Michael J.
Watson, O. Stanley Fruchey, Derek R. Vardon, Ryan T. Gill, Adam D. Bratis and Gregg T. Beckham

Science 358 (6368), 1307-1310.

DOI: 10.1126/science.aan1059

A sweet source to make acrylonitrile

Much of the attention directed toward displacing petroleum feedstocks with biomass has focused on fuels.

Downloaded from http://science.sciencemag.org/ on December 13, 2020

However, there are also numerous opportunities in commodity chemical production. One such candidate is acrylonitrile, a
precursor to a wide variety of plastics and fibers that is currently derived from propylene. Karp et al. efficiently
manufactured this compound from an ester (ethyl 3-hydroxypropanoate) that can be sourced renewably from sugars. The
process relies on inexpensive titania as a catalyst and avoids the side production of cyanide that accompanies propylene
oxidation.
Science, this issue p. 1307

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SUPPLEMENTARY http://science.sciencemag.org/content/suppl/2017/12/06/358.6368.1307.DC1
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