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The Techno-Economic Basis for Coproduct

Manufacturing To Enable Hydrocarbon Fuel
Production from Lignocellulosic Biomass

Article in ACS Sustainable Chemistry & Engineering April 2016

DOI: 10.1021/acssuschemeng.6b00243

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The Techno-Economic Basis for Coproduct Manufacturing To Enable

Hydrocarbon Fuel Production from Lignocellulosic Biomass
Mary J. Biddy,* Ryan Davis, David Humbird, Ling Tao, Nancy Dowe, Michael T. Guarnieri,
Jerey G. Linger, Eric M. Karp, Davinia Salvachua, Derek R. Vardon, and Gregg T. Beckham*
National Bioenergy Center, National Renewable Energy Laboratory, 15013 Denver West Parkway, Golden, Colorado 80401, United
States
*
S Supporting Information

ABSTRACT: Biorenery process development relies on techno-economic

analysis (TEA) to identify primary cost drivers, prioritize research directions,
and mitigate technical risk for scale-up through development of detailed
process designs. Here, we conduct TEA of a model 2000 dry metric ton-per-
day lignocellulosic biorenery that employs a two-step pretreatment and
enzymatic hydrolysis to produce biomass-derived sugars, followed by
biological lipid production, lipid recovery, and catalytic hydrotreating to
produce renewable diesel blendstock (RDB). On the basis of projected near-
term technical feasibility of these steps, we predict that RDB could be
produced at a minimum fuel selling price (MFSP) of USD $9.55/gasoline-
gallon-equivalent (GGE), predicated on the need for improvements in the
lipid productivity and yield beyond current benchmark performance. This cost
is signicant given the limitations in scale and high costs for aerobic
cultivation of oleaginous microbes and subsequent lipid extraction/recovery.
In light of this predicted cost, we developed an alternative pathway which demonstrates that RDB costs could be substantially
reduced in the near term if upgradeable fractions of biomass, in this case hemicellulose-derived sugars, are diverted to coproducts
of sucient value and market size; here, we use succinic acid as an example coproduct. The coproduction model predicts an
MFSP of USD $5.28/GGE when leaving conversion and yield parameters unchanged for the fuel production pathway, leading to
a change in biorenery RDB capacity from 24 to 15 MM GGE/year and 0.13 MM tons of succinic acid per year. Additional
analysis demonstrates that beyond the near-term projections assumed in the models here, further reductions in the MFSP toward
$23/GGE (which would be competitive with fossil-based hydrocarbon fuels) are possible with additional transformational
improvements in the fuel and coproduct trains, especially in terms of carbon eciency to both fuels and coproducts, recovery and
purication of fuels and coproducts, and coproduct selection and price. Overall, this analysis documents potential economics for
both a hydrocarbon fuel and bioproduct process pathway and highlights prioritized research directions beyond the current
benchmark to enable hydrocarbon fuel production via an oleaginous microbial platform with simultaneous coproduct
manufacturing from lignocellulosic biomass.
KEYWORDS: Biochemicals, Lignocellulose, Integration, Biorenery, Biofuels

INTRODUCTION
Lignocellulosic biomass oers signicant promise to oset a
large portion of mankinds fossil fuel usage as part of a balanced
renewable energy portfolio for transportation fuels, renewable
chemicals, and robust materials, and as a partial source of
sustainable power generation. Among all major renewable
energy technologies examined to date, biomass is the primary
source of renewable liquid fuels for vehicle, air, and maritime
transportation.1,2 As highlighted in a number of studies,
including the SCOPE Bioenergy and Sustainability study, well
over 50 countries have biofuels mandates or blending targets.3
These mandates are dominated by ethanol, with typically
smaller biodiesel mandates, in the range between 1% and 20%
of the transportation pool.3,4 The vast majority of ethanol
production today comes from starch- or sugar cane-based
industries, which exhibit a substantial scale limitation relative to
worldwide fuel demand and has caused signicant concerns
regarding osetting food production for fuels.5
As a means to ameliorate the concerns regarding the food
versus fuel debate and to further reduce greenhouse gas
emissions, support energy security, promote rural job develop-
ment, and achieve fuel-scale production beyond starch- and
sugar cane-based feedstocks, ethanol production from ligno-
cellulosic biomass is under intense development at the
industrial scale. The current predominant route for lignocellu-
losic ethanol production proceeds via biochemical conversion
processes that conventionally includes a mild thermochemical
pretreatment or fractionation step, enzymatic hydrolysis with
Received: February 2, 2016
Revised: April 27, 2016

XXXX American Chemical Society A DOI: 10.1021/acssuschemeng.6b00243

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ACS Sustainable Chemistry & Engineering
cellulolytic enzymes, and fermentation by an ethanologen such
as Saccharomyces cerevisiae or Zymomonas mobiliz.6,7 Certainly
many variations exist on that theme including, for example,
many dierent types of pretreatment8,9 and process cong-
urations with separate or combined hydrolysis and fermenta-
tion.10,11 Multiple techno-economic analysis (TEA) and life-
cycle analysis (LCA) studies have been conducted for various
congurations of industrial cellulosic ethanol plants, all of
which point toward a path to produce ethanol that is at, or
close to, being competitive with petroleum-derived fuels with
the potential ability to oset substantial greenhouse gas (GHG)
emissions,1225 and indeed, several cellulosic ethanol plants are
currently being brought online worldwide. Going forward,
however, ethanol is a renewable additive primarily for gasoline-
range fuels, but it is not directly applicable to a broader pool of
transportation fuels including diesel, jet, and maritime fuels nor
does it typically suce as a complete substitute for gasoline in
most engines, a limit typically referred to as the blend wall.
Lastly, ethanol distribution does not follow the same channels
as petroleum-derived fuels. The issues of the limited fuel
market capacity, the need for another fuel distribution system,
and the ethanol blend wall have thus motivated research eorts
to move toward the production of drop-in infrastructure-
compatible hydrocarbon fuels.
Drop-in lignocellulosic biofuels beyond ethanol that are
derived from biological26 or catalytic routes2734 have been
examined primarily at the laboratory or pilot scale, with many
in the scientic literature rst focusing on the development of
processes starting from clean sugars. Many challenges remain
in both biological and catalytic routes to hydrocarbon fuels,
primarily related to realizing integrated processes that are able
to completely convert lignocellulosic biomass into a nished
fuel. For example, inorganic components found in biomass,
which are typically dicult to remove, oftentimes poison
chemical catalysts.3537 Biological production of hydrocarbons
from biomass-derived sugars typically suers from the
challenges of insucient titers, productivities, and yields
when a pathway is rst introduced as well as toxicity eects
stemming from inhibitors produced during biomass decon-
struction.3840 These challenges, among many others in process
integration and yield improvements, must be overcome to cost
eectively produce hydrocarbon biofuels from lignocellulosic
biomass.
To bring hydrocarbon fuel production to a level of
technological viability similar to that of ethanol production,
TEA and LCA studies will be key to consistently evaluate and
compare the myriad process options that exist and are being
constantly proposed and developed. To that end, Davis et al.
recently published a peer-reviewed publically available report
describing a projected TEA and LCA model that examines the
cost of producing hydrocarbon biofuels via a biological-
upgrading step from lignocellulosic sugars and sustainability
considerations within the bioenery conversion facility.41 The
primary purpose of this model was to identify research gaps and
cost drivers to achieve a near-term 2017 technical target to
produce hydrocarbon fuels at a cost of USD $5 per gasoline
gallon equivalent ($5/GGE). The modeled biochemical
conversion process described in that work employs a two-
step pretreatment process consisting of a deacetylation step
followed by dilute-acid pretreatment,42 enzymatic hydrolysis
with cellulase enzymes, and an aerobic cultivation step to
employ an oleaginous microbe to produce free fatty acids
(FFAs), which are secreted into the broth, recovered, and
B DOI: 10.1021/acssuschemeng.6b00243
Research Article
catalytically upgraded to a renewable diesel blendstock
(RDB).41 The predicted RDB cost from this process is
$5.10/GGE in 2011 USD (hereafter the basis for cost gures
unless otherwise noted). The main cost drivers, and thus
identied research needs, associated with realizing a process
based on this model include achieving FFA yield and
productivity of 0.28 g/g sugars and 1.3 g/L/hr, respectively,
coupled to the ability to (1) secrete FFAs and (2) convert a
mixed sugar stream to FFAs. The productivity target was
chosen at the time for consistency with what is achievable in
ethanol fermentation,22 and the yield is within reach from
literature values for FFA yields from glucose.41 However, we
note that both the previous productivity assumption and FFA
secretion have yet to be achieved to our knowledge in an
oleaginous microbe. FFA secretion has been achieved in several
nonoleaginous microbes, including the cyanobacteria Synecho-
cystis sp. PCC6803,43 Escherichia coli,44 and Saccharomyces
cerevisiae,4547 suggesting that fatty acid secretion is a distinct
possibility in oleaginous microbes. Moreover, the scale of
reactors considered previously did not account for the
substantial dierences in aerobic and anaerobic bioreactor
cultivation of microbes. As demonstrated here, these
assumptions have major eects on the estimated cost of an
oleaginous fuel platform.
The cost projection of $5/GGE would represent a milestone
toward the ultimate objective of producing hydrocarbon fuels at
prices concomitant with conventional petroleum fuels today
(e.g., $2$3/GGE).41 To achieve a lower price, signicant
process modications will likely need to be considered. One
option to signicantly lower the cost of fuel production from
biomass, as is practiced throughout the petroleum rening
industry, is to rely on the production of high-value coproducts
alongside fuels, as has been noted throughout the biomass
valorization literature.34,4859 Production of petrochemicals in
many cases employs oxidation of hydrocarbon platform
molecules, and relative to petroleum, biomass-derived platform
molecules from polysaccharides and lignin already exhibit
signicant oxygen content, making them, from a stoichiometric
perspective, more attractive building blocks for oxygen-
containing chemicals if appropriate molecular transformations
can be realized.53,59 The production of biobased chemicals,
however, also presents a substantial set of technical challenges.
For example, signicant emphasis has been placed in pioneering
reports on the production of single-platform molecules, often
from sugars for uses such as chemical and polymer
precursors.48,50,53 Especially for polymer and specialty chemical
applications, precursor purity is often of utmost importance,
which in an integrated process from lignocellulosic biomass will
require scalable cost-eective separations and cleanup strat-
egies. As a result, it has also been suggested that biobased
chemicals should rely on the intrinsic heterogeneity and
intrinsic polymeric structure already present in biomass to
make functional replacement materials rather than depolyme-
rization to monomers that can then go on to be converted to
building blocks.56 Regardless, whether biomass-derived sub-
strates are converted to new platform molecules or used
directly as polymers, process integration issues, including
separations, cleanup, and quality of the nal products, will be
of paramount importance to replace products used by
consumers currently derived from petroleum. Moreover, the
market size disparity between fuels and chemicals will be a key
driver in the attainable scale for a single process, further
warranting the need to develop modular processes that can be
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ACS Sustainable Chemistry & Engineering
Figure 1. Overview of design block ow diagrams from (A) baseline fuels only design and (B) coproduction of fuels and chemicals design.
adjusted to produce several dierent chemicals, either spread
across multiple bioreneries, or within the same biorenery,
depending on the economies of scale for a given process
conguration or coproduct. Overall, for the production of
hydrocarbon biofuels from lignocellulose, the basis for
manufacturing coproducts alongside fuels must be quantied
with TEA to ascertain the relative contributions that coproducts
can make to the overall economic viability.
To that end, here we present TEA models for several process
scenarios centering on the core concept of a biorenery
wherein hydrocarbon fuels and chemicals are produced in
parallel from lignocellulosic biomass similar to the simultaneous
production of fuels and chemicals practiced in petroleum
rening. The baseline process considers economics of fuel
production alone similar to that noted above as presented in
Davis et al. and is a two-step pretreatment approach of
enzymatic hydrolysis and biological production of lipids and a
catalytic step to produce RDB from both hemicellulose and
cellulose-derived sugars.41 However, for this case, a number of
updates are made to reect more realistic experimental
benchmarks (such as intracellular lipid productivity metrics
via oleaginous yeasts rather than more idealized high-
productivity FFA secretion) and to incorporate improved
design details (such as the use of revised design/cost estimates
for bubble column bioreactors). We then examine a coproduct
manufacturing scenario wherein succinic acid is produced
predominantly from hemicellulose-derived sugars fractionated
C DOI: 10.1021/acssuschemeng.6b00243
Research Article
after dilute-acid pretreatment, and the cellulose-derived sugars
are used to produce lipids for RDB. Succinic acid is chosen as a
representative molecule to demonstrate the potential for
coproduct pathways within this framework for an integrated
biorenery, with preliminary research demonstrating biological
production of succinic acid at encouraging performance levels.
When viewed as an intermediate molecule, there is a strong
potential for a greater demand of succinic acid given that there
are numerous known technologies for the production of a wide
slate of high-value large market commodity chemicals from
succinic acid.48,53,60
The model predicts that the production price of hydrocarbon
fuels can be signicantly improved by the simultaneous
production of chemicals from other biomass fractions. Key
ndings from this work regarding process selection are as
follows: (1) Maximizing carbon eciency, especially to higher
value coproducts, is paramount. (2) Recovery and purication
of both fuels and coproducts are major cost drivers that will
benet signicantly from research and development activities to
improve applicability at the biorenery scale. (3) Product
selection and price will greatly inuence the process exibility
and the ability to balance process severity. Overall, this study
quanties the economic baseline for the manufacturing of next-
generation hydrocarbon fuel bioreneries, demonstrates that
coproducts can enable the economics of hydrocarbon fuel
production, and provides a framework for further research and
ACS Sustainable Chem. Eng. XXXX, XXX, XXXXXX
ACS Sustainable Chemistry & Engineering
development in a next-generation integrated lignocellulosic
biorenery.
SUMMARY OF MODEL
As illustrated in Figure 1A, the base case design produces
hydrolysate via deacetylation and dilute-acid pretreatment of
biomass followed by enzymatic hydrolysis. Unconverted
biomass solids (mostly lignin) are removed from the hydro-
lysate through a occulant-aided solid/liquid separation, and
the remaining liquor fraction is concentrated prior to biological
upgrading. The hydrolysate, which is rich in both C5 and C6
sugars, is biologically converted in an aerobic process to lipids
that are stored intracellularly by an oleaginous microbe. The
lipid fraction is extracted from the cells in a wet extraction
process and subsequently upgraded in a hydrotreating unit to
produce RDB. Supporting processes, including wastewater
treatment, utilities (including cooling water, chilled water plant,
instrument air, and process water), and the combined heat and
power system (consisting combustor, boiler, and turbogener-
ator) are also incorporated in the design and economics.
A variation of the process design, as outlined in Figure 1B,
considers the conversion of a separate C5-rich hydrolysate
stream to a chemical coproduct. In this case, an additional
solid/liquid separation step is introduced after the pretreatment
process, and the C5-rich liquor is sent to a biological upgrading
process for continuous conversion to succinic acid, followed by
the required separation and purication steps. The solids (C6-
rich hydrolysate stream) continue to enzymatic hydrolysis and
follow the same process steps to RDB as outlined in the base
design.
Additional details of the design and the basis for both the
current experimental benchmark and an improved case are
summarized in the following subsections. The base case process
(whole hydrolysate to fuels alone) is discussed rst, followed by
the modications made for the alternative coproduction of
chemicals and fuels process (C6-to-fuels and C5-to-copro-
ducts).
Pretreatment. Milled biomass, with a composition
described in Table 1, enters the process facility and is assumed
to be throat-of-reactor ready, i.e., any preprocessing required
prior to the rst unit operation is included in the delivered
Table 1. Delivered Feedstock Composition Assumed in
Process Design
component composition (dry wt %)
glucan 35.05
xylan 19.53
lignin 15.76
ash 4.93
acetatea 1.81
protein 3.10
extractives 14.65
arabinan 2.38
galactan 1.43
mannan 0.60
sucrose 0.77
total structural carbohydrate 58.99
total structural carbohydrate + sucrose 59.76
moisture (bulk wt %) 20.0
a process heat and a portion of the power requirements for the
Represents acetate groups present in the hemicellulose polymer;
converted to acetic acid in pretreatment.
Research Article
feedstock cost. The biomass is conveyed to the pretreatment
area where it is rst processed in a deacetylation step that uses a
sodium hydroxide soaking process (loaded at 17 mg of NaOH/
g of dry biomass) at 80 C for 1 h in a set of parallel batch
reactors. This process step has been shown to remove various
components of the biomass that are either potentially toxic in
downstream biological upgrading or inert biomass components,
including acetate, lignin, extractives and ash, and improves
overall yields and reduces capital cost due to lower process
throughputs.41,42,61 The solubilized fraction of the biomass is
drained from the batch reactors and sent to wastewater
treatment. Overall, this liquor fraction consists of a range of
biomass components with solubilization and removal of 100 wt
% of the extractives, 75 wt % of the ash, 20 wt % of the lignin, 2
wt % of the xylan, 50 wt % of the sucrose, and 88 wt % of the
acetate. The conversion in the deacetylation step is consistent
for all of the cases studied.
The remaining solids are conveyed to the dilute-acid
pretreatment reactor at a total solids loading of 30 wt %,
where a large fraction of the hemicellulose carbohydrates are
converted to soluble sugars including xylose, arabinose,
galactose, mannose, and some glucose. The basis for the
design of the reactor system is described in a previous study.41
The biomass is treated with 9 mg of H2SO4/g dry biomass
(based on acid loading present in the pretreatment reactor),
with a total residence time in the reactor of 5 min at a
temperature of 165 C. The overall conversion reactions are
provided in Table 2 and summarize both the current
benchmark case as demonstrated in National Renewable
Energy Laboratory pilot plant runs and a projected improved
case.61 Following the acid pretreatment, the hydrolysate whole
slurry containing 30 wt % total solids and 16 wt % insoluble
solids is neutralized with ammonia in stoichiometric quantities
to raise the hydrolysate pH to 5, and the stream is diluted with
water to a total solids concentration of 20 wt % prior to
enzymatic hydrolysis.
Enzymatic Hydrolysis. In the base case, the whole slurry
hydrolysate stream is fed at a 20 wt % total solids to a high-
solids continuous reactor for enzymatic hydrolysis by a cellulase
enzyme prepared on-site. The partially hydrolyzed slurry is next
batched to one of several parallel bioreactors. Hydrolysis is
completed in the batch reactor with an overall hydrolysis time
of 3.5 days in the continuous and batch steps. This process
converts both glucan and residual xylan in the solids to
monomeric glucose and xylose, respectively. Table 2 summa-
rizes the key process conditions and yields for both the
benchmark and improved cases for the enzymatic hydrolysis
process.
Hydrolysate Conditioning: S/L Separations and
Concentration. The slurry is further conditioned for down-
stream biological upgrading by removal of insoluble solids
required for eective aerobic biological conversion and
subsequent product purication. A vacuum lter press is used
for this solid/liquid separation step. To facilitate and improve
ltration, polymer occulants at a loading of 10 g/kg insoluble
solids are added to reduce the overall required lter area. The
process conditions for both the benchmark and improved cases
are outlined in Table 2 for this step, with the benchmark values
based on data demonstrated from bench scale studies reviewed
in Sievers et al.62 The solids removed in the lter press are sent
to the combustor/steam turbogenerator, which provides all
integrated process design.
D DOI: 10.1021/acssuschemeng.6b00243
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ACS Sustainable Chemistry & Engineering Research Article

Table 2. Overall Yields for Benchmark and Improved Case (Biomass Deconstruction and Fuel Production Operations)
experimental benchmark case improved case
pretreatment
solids loading (%) 30% 30%
acid loading (mg H2SO4/g dry biomass present in reactor) 9 9
% Conversion: (Glucan)n + nH2O nGlucose 10% 10%
% Conversion: (Xylan)n + nH2O nXylose 76% 78%
% Conversion: (Galactan)n + nH2O nGalactose 90% 90%
% Conversion: (Arabinan)n + nH2O nArabinose 90% 90%
% Conversion: Acetate Acetic Acid 100% 100%
% Conversion: Lignin soluble lignin 5% 5%
S/L separation:soluble sugar loss to solids 4% 1%
enzymatic hydrolysis + hydrolysate conditioning
enzyme loading (mg/g cellulose) 12 10
enzymatic hydrolysis time (days) 5.0 3.5
% Conversion: (Glucan)n + nH2O nGlucose 86% 90%
% Conversion: (Xylan)n + nH2O nXylose 93% 93%
S/L separation: soluble sugar loss to solids 5% 5%
bioconversion (lipid production)
lipid productivity (g/L/hr) 0.34 0.4
lipid content (wt %) 60% 70%
% Conversion: Glucose Lipid [total glucose utilization]a 75% [100%] 82% [100%]
% Conversion: Xylose Lipid [total xylose utilization]a 44% [59%] 80% [98%]
bioconversion metabolic yield [process yield] (g/g)b 0.25 [0.24] 0.27 [0.27]
lipid recovery + upgrading
extraction pretreatment acid loading (wt % of feed liquor) 1% 1%
extraction solvent loading (g hexane/g cell mass) 5 5
extraction net lipid recovery 90% 90%
hydrotreating fuel yield (g RDB + naphtha/g lipid) 0.81 0.81
hydrotreating net H2 makeup demand (wt % lipid feed) 1.8% 1.8%
a
First number represents sugar conversion to desired product (lipids); values in brackets indicate total sugar utilization (including diversions to cell
mass). bMetabolic yield = g product per g sugars converted; process yield = g product per g total sugars available for bioconversion.

The claried soluble sugar stream is split with roughly 15%
routed directly to bioconversion to initiate fed-batch
fermentation, and the majority (85%) concentrated from 20
to 50 wt % total sugars in a mechanical vapor recompression
(MVR) evaporation system. The concentrated sugar stream
exiting the evaporators is cooled and fed to the bioreactors.
Biological Conversion. The biological conversion step
consists of a seed train of increasingly larger stirred tank
reactors in series that are dedicated to biomass seed
propagation (grown with a 10% split of the starting available
hydrolysate sugars) and a system of aerobic bubble columns for
the production of lipids. Many experimental eorts in the
literature have focused on the development and evaluation of
intracellular lipid accumulation in model organisms such as
Saccharomyces cerevisiae63 or Escherichia coli6466 or oleaginous
microbes such as Yarrowia lipolytica,6769 Rhodosporidium
toruloides,7072 and Lipomyces starkeyi,7274 among many
others. The biomass composition in the current model is
based on L. starkeyi.74 The production bioreactors are modeled
as bubble columns each with 500 m3 (500,000 L) of total
internal volume operated in a fed-batch mode of operation,
with an initial 50% ll level up to a nal 80% ll level (400 m3
maximum ungassed working volume) over the course of the
fed-batch cycle. The reactors are cooled through an external
pump-around loop circulated through a chilled water heat
exchanger.
Key cost and design considerations for this system are
attributed to the aerobic nature of the bioconversion step, with
submerged aerobic production of the yeast cells dependent on
E DOI: 10.1021/acssuschemeng.6b00243
the target lipid productivity rate (g/L/hr) and the associated
oxygen uptake rate (OUR), which is set in the model to be
equal to the oxygen transfer rate (OTR). The required OTR is
achieved in the model by varying the aeration rate to the bubble
columns, given a xed vessel geometry and air compressor
pressure (liquid height plus hydraulic losses). Further details on
vessel design and operation, as well as underlying drivers
behind the OTR/OUR in the modeled system, are provided in
the Supporting Information. Table 2 provides a summary of key
conversion and yield parameters for the bioconversion step
attributed to the experimental benchmark and projected
improved cases.
Lipid Separations. The hydrocarbon intermediate product
is composed of intracellular lipids (primarily triglycerides). The
lipid fraction is extracted from the cells in a wet extraction
process. The extraction step follows a similar schematic as
published for extraction of lipids from algal biomass with
demonstrated yields up to 92.5%,75,76 consisting of a dilute-acid
treatment operation targeting 1% acid loading at 150 C,
followed by cooling, ashing, and neutralization (all steps being
similar to the initial biomass pretreatment step discussed
previously). The material is then routed to a countercurrent
extraction column with hexane solvent at a total 5:1 solvent
loading (solvent versus yeast dry cell weight). The extract
consisting of primarily solvent and lipids is sent to a stripping
column to recover the hexane, while the aqueous ranate
product is sent to wastewater treatment. The key process
conditions and yields for this step are summarized in Table 2.
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ACS Sustainable Chemistry & Engineering
Upgrading and Recovery. Finally, the recovered lipid
product exiting the extraction/separation step is upgraded via
hydroprocessing to a hydrocarbon product, primarily RDB with
a small naphtha coproduct. This operation is designed for
deoxygenation and saturation of the lipid material, yielding a
paranic end product suitable for blending. The process
conditions and yields for this step are summarized in Table 2
and are based on detailed experimental data documented in
Marker et al.77 for the upgrading of vegetable oils. The lipid
product is modeled as a representative triglyceride component
consisting of oleic (18:1), stearic (18:0), and palmitic (16:0)
acid chains, which constitute the majority of the fatty acid
prole characterized in many oleaginous yeast.74 On the basis
of this representative component, plus the targeted 81 wt % fuel
yield (79% RDB plus 2% naphtha versus lipid feed), the
modeled hydrogen consumption is roughly 1.8 wt % of the lipid
feed to the upgrading step. Final fuel blendstock yields
following the upgrading section are calculated based on the
total energy yield and are converted to a GGE basis according
to lower heating values (LHV), assuming standard published
LHV values for gasoline.78 O-gases from the upgrading section
are combined and routed to the boiler, while produced water is
sent to wastewater treatment.
Modications to the Base Design for Coproduction of
Fuels and Chemicals. While the base case design is focused
solely on the production of fuels in the biorenery, an
alternative scenario is investigated that considers the economic
impact of the coproduction of chemicals and fuels. For this new
basis with coproduction, the benchmark design is modied to
separate and upgrade the C5-rich hydrolysate stream to
chemicals via biological conversion, while the residual C6-rich
slurry is upgraded to fuels.
More specically, the hydrolysate slurry after dilute-acid
pretreatment is immediately processed in a vacuum lter to
separate solubilized hemicellulose sugars from cellulose and
residual unconverted solids. The current benchmark case for
this solid/liquid separation step is based on bench-scale
demonstrations on corn stover-derived pretreated hydrolysate.
It was demonstrated that recoveries of 96 wt % of the sugars
using a wash ratio of 12.4 L/kg (wash water versus liquor in the
lter cake) and a lter capacity of 15.8 kg insoluble solids (IS)/
m2 h could be achieved. The target case utilizes process
assumptions based on previously reported experimental results
outlined in Sievers et al.79 In that study, a hydrolysate produced
by dilute-acid pretreatment, but without deacetylation, was
separated with a sugar recovery eciency of 99 wt % utilizing a
wash ratio of 4.3 L/kg and lter capacity of 20 kg IS/m2 h.
The recovered solids that are rich in unconverted cellulose
are sent to the enzymatic hydrolysis step and further upgraded
to fuels, whereas the liquid, which will be referred to as the C5-
rich liquor, is sent to the C5 conversion train for the production
of chemicals. The solids fraction is routed to enzymatic
hydrolysis at a 17.5 wt % total solids loading, which diers from
the concentration commonly employed in whole slurry
processing and that was discussed earlier for the base case.
Since the coproduction of chemicals and fuels pathway employs
a washed solids hydrolysis whereby a large fraction of soluble
solids (namely, hemicellulose sugars) are removed, the overall
viscosity of this stream is increased due to the higher fraction of
insoluble solids relative to total solids. As the material
approaches 20% IS, it becomes considerably more dicult to
pump and agitate in the early stages of hydrolysis, often
resulting in reduced glucose yields. The total solids loading is
F DOI: 10.1021/acssuschemeng.6b00243
Research Article
therefore reduced to 17.5 wt % for this modied design.
However, the downstream yields and all process design
assumptions for the enzymatic hydrolysis and conversion/
upgrading steps are consistent with the fuel-only base case.
The C5-rich hydrolysate liquor continues to a parallel
biological upgrading train for chemical coproduction. For this
design, succinic acid has been identied as an example target
chemical product, utilizing a process modeled with Actino-
bacillus succinogenes as the production organism. This organism
can utilize pentose and hexose sugars, as well as hydrolysates,
with the production of succinic acid being greatly enhanced by
the presence of CO2.80,81 Succinic acid is meant to serve as a
representative molecule to demonstrate the potential enabled
by introducing coproduct pathways within this integrated
biorenery framework. This integrated biorenery concept
should thus be applicable to the coproduction of fuels and a
wide of array of other chemical intermediates.
In this design, the C5 liquor is initially split, with 10% of the
liquor being sent to the seed fermentor used to grow A.
succinogenes. The other 90% of the liquor is sent to the
continuous biological reactor system. CO2 is also fed to the
bioreactor at a rate of 0.1 VVM, which is adopted from
literature.82 Sodium hydroxide is added to the biological
conversion process to maintain the pH of the system near 7,
with stoichiometric amounts of NaOH added to the
fermentation broth. The near-term conversion for the
bioreactor for the improved case are set at 0.73 g succinic
acid/g pentose sugars (xylose and arabinose) and 0.73 g
succinic acid/g hexose sugars (glucose and galactose), with
pentose sugar utilization targeted to improve to similar levels as
those reported publicly for hexose sugars.83 Selectivity to acid
byproducts is assumed to be minimized to 0.078 g/g C5 sugars
and 0.081 g/g C6 sugars for acetic acid coproduction and 0.02
g/g C5 sugars and 0.03 g/g C6 sugars for formic acid
coproduction.83 The succinic acid productivity rate is targeted
to be 2.0 g/L/hr, which is realistic for the continuous
fermentation pursued for this design. Recent results have
demonstrated that succinic acid can be produced from corn
stover hydrolysates at productivities of 1.45 g/L/hr utilizing a
continuous fermentation process and overall metabolic yields at
0.78 g succinate/g of sugar consumed.84 These metrics are the
values incorporated for the experimental benchmark case.
Since A. succinogenes produces not only succinic acid but also
acetic and formic acids as byproducts, additional processing is
required to purify the succinic acid from the other organic
acids, as well as from salts and other contaminant components
present in the starting hydrolysate. The design basis for the
succinic acid purication operation is based on recent patents
by Myriant and Novasep for the recovery of succinic acid.85
The whole broth is rst ltered through an ultraltration step
to remove cells and large insoluble particles from the broth.
These recovered solids are sent to the boiler. The cleaned broth
is then introduced to a simulated moving bed unit (SMB-ICX),
which converts the sodium succinate to succinic acid via ion
exchange. The succinic acid-rich stream is then further puried
through nanoltration to help remove any residual solids and
impurities that might color the succinic acid crystals. The dilute
succinic acid stream is then further concentrated in an
evaporation process and then crystallized. The succinic acid
crystals are recovered via a centrifugation unit, dried via a belt
conveyor, and sent to storage. Approximately 90% of the
mother liquor from the crystallizer, which contains nearly all of
the unconverted sugar, is recycled back to the fermentation
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reactor for further conversion. The overall succinic acid improved cases was determined for both process pathways
recovery eciency is set to 82% with the bulk of the succinic and is summarized in Table 4. The overall MFSP for the fuel-
acid losses occurring in the crystallization process.
Economic Analysis Details. Utilizing the conceptual Table 4. Comparison of Economics for Two Scenarios
process design described above, Aspen Plus process models Considered (Improved Projection Cases)
were developed to estimate key material and energy ows in
the process. The overall variable and xed operating costs, as base case
model
coproduction of
fuels and
well as the capital costs, were then estimated for the integrated (fuels only) chemicals
design and the calculated ow rates. The capital costs, which MFSP ($/GGE) $9.55 $5.28
are outlined in Tables S3 and S4, are based on vendor designs annual fuel yield (MM GGE/yr) 24.1 15.0
and cost estimates for the major processing equipment. The chemical coproduct yield (MM tons/yr) 0 0.127
details of these equipment designs have been published in total capital investment (MM$) 921 1216
Humbird et al. and Davis et al. design reports.22,41 The cost total variable operating cost (MM$/yr) 89 135
associated with the recovery and purication stages in the coproduct credit (MM$/yr)a 6 247
design for chemicals production was taken from recent design total xed operating cost (MM$/yr) 21 27
estimates from external vendors. Raw material prices were a
The coproduct in the fuels-only model is electricity, while for the
drawn from a broad range of sources as reviewed in Table S5. fuels/chemicals case it is succinic acid.
A discounted cash ow analysis was used to determine the
overall minimum fuel selling price (MFSP) of the process
under a specic set of nancial assumptions. The nancial only base case is $9.55/GGE with a total capital investment of
assumptions used to calculate the MFSP are reviewed in Table $920 MM. The cost breakdown for the major process areas is
3 based on a mature nth plant and consistent with prior provided in Figure 2A. Roughly 39% of the capital cost is
attributed to the biological conversion section, which requires
Table 3. Financial Assumptions and Design Basis 97 bubble column reactors to process the full hydrolysate
plant life 30 years stream based on the projected lipid productivity of 0.4 g/L/hr.
plant throughput 2000 dry metric tons/day biomass This translates to intensive capital expenditures for this section
cost year dollar 2011 dollars of the process and leads to the greatest contribution to the fuel
capacity factor 90% price, accounting for 31% of the MFSP. The annual total
discount rate 10% variable cost of the process is $84 MM/year. Biomass feedstock
general plant depreciation 200% declining balance (DB) contributes the most to this value at $57.5 MM/year,
general plant recovery period 7 years accounting for roughly 25% of the MFSP. The second largest
steam plant depreciation 150% DB raw material cost occurs in the lipid extraction section, in which
steam plant recovery period 20 years the demand for sulfuric acid, hexane, and ammonia translates to
federal tax rate 35% an annual cost of $8.2 MM/year or 3.5% of the MFSP, while
nancing 40% equity the hydrogen required for fuel nishing accounts for 1% of the
loan terms 10 year loan at 8% APR MFSP. Enzymes represent a signicant driver accounting for
construction period 3 years 5% of the MFSP, even at the low loadings of 10 mg/g of
rst 12 months expenditures 8% cellulose projected in the improved design. The total variable
next 12 months expenditures 60% cost also includes a credit of $6 MM/yr associated with the sale
last 12 months expenditures 32% of excess electricity to the grid. The primary power consumer in
working capital 5% of xed capital investment the process is the bioconversion section, which requires 36% of
start-up time 6 months total biorenery electricity demand, attributed to aeration
revenues during start-up 50% requirements. Overall xed costs, which are partially a function
variable costs during start-up 75% of capital costs, are $21.2 MM/yr.
xed costs during start-up 100% Economics of Coproduction of Fuels and Chemicals.
When the base case is modied and the C5-rich stream is
separated from the unconverted biomass prior to enzymatic
published work.41,8688 All coproducts were treated using a hydrolysis and used to produce chemicals rather than fuel, the
market value allocation approach in a consistent manner with overall MFSP of the process is decreased by 45% to $5.28/
previously published studies, in which a credit is accounted for GGE in the projected improved case. Since this modied
in the operating costs and is allocated based on the coproduct design diverts some of the sugar stream originally available for
market value.41,8688 On a relative mass yield basis, a higher fuel production, the overall fuel production rates are reduced
yield of the chemical coproduct is observed relative to the fuel from 24 MM GGE/yr in the baseline case to 15 MM GGE/yr
yield for a number of the cases considered in this study. in the modied design. The addition of the C5 upgrading
Alternative strategies could be utilized to estimate the cost of strategy also results in an increase in the overall capital cost of
the chemical coproduct rather than the fuel if the fuel is the process, with the installed cost of this added process train
assigned a specic price. However, the primary focus of this being just below $225 MM or 32% of the overall capital cost of
study is to understand the cost of fuel production, and this the facility. There are two major areas that dominate this
evaluation is outside of the scope of this study.

additional capital cost. Recovery and purication of the succinic

acid product accounts for $134 MM, while the additional
RESULTS solidliquid separation processes add $45 MM and account for
Fuel-Only Base Case Economics. Utilizing the design and 21% of the capital costs of the C5 upgrading section. The
economic basis described above, an MFSP for the projected remaining 15% of the cost is the result of the continuous
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Figure 2. Cost breakout by process area for two scenarios considered (improved projection cases): (A) base case fuel-only design and (B)
coproduction of fuels and chemicals design.

Figure 3. Sensitivity analysis results for the coproduction of fuels and chemicals process design (improved case, $5.28/GGE MFSP basis).

biological reactor design and the auxiliary equipment required
for succinic acid fermentation. These additional costs of the C5
upgrading section are partially oset by reduced overall
throughput in the C6 fuel train, which decreases the number
of bubble column reactors to 60 and reduces the installed
capital cost of the biological upgrading section by $30 MM. In
H DOI: 10.1021/acssuschemeng.6b00243
total, however, there remains a 30% increase in the total facility
capital investment to $1,216 MM for this process scenario.
The addition of the C5 upgrading train also increases the
variable operating cost of the process by 50% when excluding
any coproduct credits. The process requires $42 MM/yr for
raw materials required for product separations and purication
with nearly 90% of this total cost being attributed to
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regeneration of the resin (sulfuric acid and caustic) utilized in
the recovery design and the caustic required in biological
conversion. Beyond this, the process now requires an electricity
import of 11 MW at a cost of $6.1 MM/yr due to the
introduction of a recovery and purication process that is
power intensive demanding 990 kWh/ton of succinic acid
produced. This import is on the same order of magnitude as the
export estimated in the baseline design. Due to the higher
capital cost and increased complexity of the modied design,
the overall xed operating cost of this scenario was $27 MM/yr.
Sensitivity Analysis for Coproduction of Fuels and
Chemicals. A number of the underlying process design
parameters projected in the improved case have a signicant
impact on the economics of the overall integrated design. As
highlighted in the single-point sensitivity analyses summarized
in Figure 3 for the coproduction of fuels and chemicals, cost
drivers exist throughout the process design. Therefore, it is
critical to understand the impact that each of these drivers has
on improving the MFSP and to prioritize further research. In
particular, sugar production and conversion are major drivers
throughout the process. In the biomass pretreatment section, if
xylose yields could be increased from the target value of
78.5%80%, the MFSP would be reduced by $0.15/GGE due
to the higher amount of xylose available for the production of
succinic acid. Since the succinic acid biological conversion can
utilize minor sugars, an increase in arabinose production by 5%
would further decrease the MFSP by $0.06. In the enzymatic
hydrolysis step, conversion to glucose also has a major impact;
an increase in glucose yield from 90% to 95% reduces the
MFSP by $0.23/GGE, while a decrease in glucose yield to 86%
results in an increase in the MFSP by $0.11/GGE.
When considering conversion eciency of the sugars to the
desired product, glucose conversion is a major driver in the
lipid production train as lowering the yield by 20% would
increase the MFSP by $0.49/GGE. In comparison, a similar
reduction in xylose conversion in the lipid train only increases
the MFSP by $0.05/GGE due to signicantly lower levels of
xylose available for conversion in this train. In the succinic acid
train, decreasing the conversion of xylose by 20% would
increase the MFSP by $0.75/GGE. This change is much higher
than the impact from glucose on lipid production since succinic
acid is substantially more valuable than the fuel on a mass basis.
Glucose conversion in the succinic acid train also impacts the
MFSP, despite the lower level of glucose in this train, with a
20% reduction increasing the MFSP by $0.23/GGE. Although
the minor sugar concentration is low, a reduction in conversion
still has a signicant economic impact. For example, a reduction
in arabinose conversion by 20% increases the MFSP by $0.11/
GGE.
Ecient recovery of the nal products, as well as the sugar
intermediates, at the lowest cost possible is also a key driver in
the overall cost of the process. For the case of lipid recovery,
the cost of extraction and recovery accounts for roughly 20% of
the overall MFSP. If the lipids could hypothetically be
recovered from cells triggered to autolyse, the extraction and
recovery process could be eliminated, and assuming consistent
recovery eciency with the standard extraction basis, the MFSP
would be lowered signicantly by $1.10/GGE. Alternatively,
making use of the extraction operation for lipid recovery, even
small deviations from the target lipid extraction eciency
translate to signicant MFSP impacts, e.g., $0.43/GGE
attributed to a 7% deviation from the targeted 90% recovery;
this is due to the signicant capital and operating expenditures
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that have been invested throughout the process up to this nal
step, where it is critical to recover as much product as possible.
In the case of recovery and purication of the chemical
coproduct, the cost of the recovery section accounts for over
65% of the capital cost of the chemical production train and has
a signicant impact on the overall MFSP of the process. Indeed,
when the capital cost of the coproduct recovery and purication
section is modied by 25%, the MFSP changes by $0.68/GGE.
These results highlight that both fuel and chemical coproduct
recovery processes are paramount to controlling costs for this
biorenery scenario.
For recovery of sugar intermediates, the solidliquid
separation following pretreatment is also a key cost driver as
it impacts succinic acid yields, while separations after enzymatic
hydrolysis is a driver for fuels production. For the separation
performed after pretreatment, reducing the eciency from the
improved target value of 99% to the experimental baseline of
96% increases the MFSP by $0.36/GGE, whereas 100%
separation eciency reduces the MFSP by $0.11/GGE. As
noted previously, this solid/liquid separation step represents
21% of the C5 upgrading capital cost, and if the cost for this
operation increased or decreased by 50% (also a measure of
ltration capacity), then the MFSP would change by $0.45/
GGE. The biggest driver in this section is the wash ratio
utilized. If the wash ratio were increased by 50%, then the
MFSP would be increased by $0.52/GGE due to the higher
throughput of water sent to the C5 train and the additional
capital required to process and purify the diluted stream.
Similar to the solidliquid separation immediately following
pretreatment, for the solidliquid separation process after
enzymatic hydrolysis, the lter costs, wash ratio, and recovery
eciencies are major drivers; however, their impact on costs is
varied. The lter cost has the largest impact, as modifying this
parameter by 50% will result in a $0.19/GGE impact on the
MFSP. The impact on the MFSP is diminished in this section
relative to this parameter for the unit following pretreatment, as
the absolute lter capital costs are roughly 60% lower due to
the reduced throughput in this portion of the process.
Variations in the wash ratio also have less of an impact on
costs (variations of 50% result in $0.16/GGE change to the
MFSP), owing to the use of a concentration unit immediately
downstream of this lter step, thus a more dilute hydrolysate
stream in this case merely impacts the cost of concentration
rather than the entire processing train. Yield impacts are also
smaller, such that a 5% reduction in sugar yield increases the
MFSP by $0.08/GGE. Finally, varying the occulant loading
requirements by 50% aects the MFSP by $0.09/GGE.
Raw material prices are also key drivers throughout the
process. Changes of 50% in the amount of acid required in
pretreatment impacts the MFSP by $0.08/GGE due to both the
change in acid required as well as the change in ammonia
required for neutralization. In the enzymatic hydrolysis section,
enzyme loading is a more important driver. Increasing the
required enzyme loading from 10 mg/g of cellulose to the
current benchmark value of 12 or even higher to 20 mg/g
loading increases the MFSP by $0.12/GGE and $0.78/GGE,
respectively.
The primary biological metrics dictating economics in the C6
fuel train are achievable lipid productivity and lipid content of
the cell. As shown in the tornado plot in Figure 3, productivity
has one of the biggest impacts on the MFSP of the entire
process, particularly at lower values. Given the large capital
costs of the aerobic bioreactors in the C6 train, increasing the
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ACS Sustainable Chemistry & Engineering
productivity from 0.4 to 0.6 g/L/hr would decrease the MFSP
by $0.53/GGE, while decreasing the productivity to 0.2 g/L/hr
would increase the MFSP dramatically by $1.54/GGE. In light
of this strong nonlinear sensitivity, the impact of productivity is
explored further in Figure 4A, which expands to consider a
Figure 4. Impact of (A) productivity and (B) lipid content on the
MFSP for a range of chemical coproduct prices.
broader productivity curve. The analysis highlights the
asymptotic cost responses, where productivity dramatically
inuences the MFSP below a value of roughly 0.5 g/L/hr and
then begins to approach a limit beyond which costs do not
signicantly improve (roughly 1 g/L/hr, which represents the
point at which bioconversion costs no longer dominate the
overall system economics). If lipid productivity could be
improved to a hypothetical 2 g/L/hr, which is more
commensurate with the chemicals production step, the MFSP
would decrease to $4.07/GGE.
In the case of lipid content, if the lipid content in the cells
could theoretically be improved from 70 to 95 wt % (although
such a high value is unlikely practical), the MFSP would
decrease by 10%. This suggests that for such large improve-
ments in the process, the productivity reduces the MFSP by a
greater amount than the lipid content. However, if the focus
were on incremental improvements for near-term success, then
a 25% improvement in lipid content would achieve a larger
reduction in the MFSP than a 25% improvement in
productivity. Specically, a 25% enhancement in the lipid
content would reduce the MFSP by $0.38/GGE, while the
same improvement in productivity would reduce the MFSP by
$0.30/GGE.
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Research Article
It is also important to highlight that the assumed price of the
coproduct carries a dramatic eect on the overall MFSP of the
process. If the coproduct value were decreased from $0.97/lb to
$0.75/lb, then the 0.4 g/L/hr productivity basis would increase
the MFSP by more than 70% to $9.04/GGE. In contrast, if the
coproduct was valued at a higher price of $1.20/lb, then the
MFSP for the 0.4 g/L/hr basis would decrease to $1.42/GGE.
Similar trends are seen in the lipid content curve as well (Figure
4B), highlighting the dramatic eect of coproduct price on the
MFSP.
One additional scenario was considered for the coproduction
process. Since both the C5 and C6 trains can convert C5 and
C6 sugars to the desired products, the design was modied to
consider splitting the sugar stream after enzymatic hydrolysis.
This approach not only allows for the expensive solidliquid
separation process after pretreatment to be eliminated but also
allows for exibility in the amount of sugar that is converted to
fuels versus chemicals, as might be dictated by the relative value
of each fuel or product or other dynamic constraints imposed
on the biorenery. Further, we estimate that the removal of the
solidliquid separations process reduces the cost of the
concentrated sugar intermediate price from $0.20/lb of sugar
for the split case to $0.18/lb of sugar.
The impact of this design modication on the process
economics is illustrated in Figure 5. It is observed that increased
Figure 5. Impact of the split fraction of whole hydrolysate for chemical
coproduction on the minimum fuel selling price for a range of
chemical coproduct prices.
production of the chemical coproduct relative to the fuel
signicantly reduces the cost of the process. When 10%20%
of the hydrolysate stream is upgraded to chemicals, the
coproduct price has a minor impact on the MFSP (e.g., the
dierence is $0.55/GGE for the lowest and highest value
coproduct when 10% of the hydrolysate is split to chemicals
production). As the fraction of the hydrolysate upgraded to
chemicals increases beyond 30%, then the relative production
split and the price of the coproduct have a greater impact on
the MFSP of the process.
DISCUSSION
As demonstrated here, the inclusion of coproduct opportunities
into an integrated process design shows great potential to lower
the MFSP of hydrocarbon biofuels produced from lignocellu-
losic biomass. The target case that includes production of a
chemical coproduct enables the potential to achieve an MFSP
more than $4/GGE (45%) lower than the equivalent design
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ACS Sustainable Chemistry & Engineering
that solely produces fuel when maintaining the same perform-
ance and yield targets for fuel production. Given this key point,
and in light of signicant cost sensitivities around the projected
improved case performance parameters presented above, it is
important to understand current experimental performance and
to prioritize research and development directions. When
considering the current benchmark case for production of
fuels and chemicals, the MFSP is higher than either the targeted
fuel-only design or the fuels/chemicals design. Namely, the
estimated benchmark MFSP is $11.37/GGE for the fuel/
chemicals coproduction pathway, more than twice the
projected cost for the fuels/chemicals coproduction improved
case and 20% higher than the fuel-only improved case. Figure
6 illustrates the variation of the cost breakout by process
Figure 6. Cost breakout comparison of benchmark and improved
cases for coproduction of fuels/chemicals scenario and improved case
for fuel-only scenario. The gray bar and reported total value
correspond to the MFSP for each case.
section for all three cases. Comparing the two improved
cases, the overall cost breakouts are similar for all sections on a
$/GGE basis (in fact somewhat higher for the fuel/chemical
pathway given a lower fuel yield which increases $/GGE cost
contributions). It is clear that the reduction in the overall
MFSP cost is due to the chemical coproduct, which provides
for substantial coproduct revenue. When comparing the
benchmark and improved cases for the coproduction of fuels
and chemicals pathway, given the higher cost of the benchmark
case, a number of process improvements are needed moving
forward to reduce the overall cost of the design to the projected
values. It is promising, however, that there are a number of
additional opportunities to further reduce costs.
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Research Article
Consistent with established approaches for process design
and engineering, the overall economics of a process can be
enhanced by understanding the extent of process integration
and identifying key approaches for intensication. For the
biological conversion to fuels and chemicals considered here,
there are a myriad potential improvements. One of the primary
conclusions of our analysis is that for near-term incremental
improvements the lipid content is a bigger cost driver than
productivity for the process as long as productivity can remain
over at least 0.3 g/L/hr. This may help guide R&D priorities, as
it is well established that productivity and lipid content are
inversely related, i.e., operational strategies may be employed to
target increased organism lipid content but typically at the
expense of slower production rates.
Another demonstrated advantage in the proposed design is
that the organisms being pursued are capable of producing
value-added products from a wide range of sugars and can
tolerate impurities common in hydrolysates. To date, promising
results have been reported in the literature for several
oleaginous yeast species on biomass-derived hydrolysates,
although substrate toxicity is still a major issue that limits
lipid content and productivity.70,89100 There are a similar
number of opportunities on the C6 train that involve
enhancing organism performance; for example, Blazeck et al.
describe an engineered Y. lipolytica strain that has been
observed to produce up to 71% lipids at a reasonable
productivity rate of 0.2 g/L/hr in small-scale batch culture
conditions.69 Higher lipid levels approaching 90% have also
been observed with variants of Y. lipolytica. 31 Quite
interestingly, Qiao et al. recently reported another engineered
variant of Y. lipolytica that is able to achieve 84.7% of theoretical
lipid yield at 55 g/L titers and a productivity of 0.71 g/L/hr.101
However, the bulk of these studies has been focused on small
scale cultivations with glucose, and such results will likely not to
directly translate to hydrolysates. Thus, while 90% lipids may be
too optimistic today for a realistic commercial-scale system
utilizing biomass hydrolysate, even incremental changes to both
the lipid content and the productivities would improve the
overall economics.
Beyond near-term organism targets based on intracellular
lipid pathways, there are other promising options with the
potential to signicantly improve process economics. For
example, published literature describes an autolysing yeast
strain currently utilized in the wine industry for its resulting
avor prole, whereby the cell is triggered to lyse and release its
intracellular contents without the need for a dedicated
extraction step.102,103 If such an organism could be utilized
and/or engineered in this context for lipid accumulation and
self-induced release, the resulting cost would drop substantially
to $4.18/GGE as shown previously in Figure 3. Furthermore,
other organisms capable of product secretion (whether bacterial
or otherwise) possess the potential to reduce costs even further.
Cost savings brought about by removal of extraction capital and
operating costs, combined with improved carbon eciencies to
fuel, suggest signicant room for improved economics moving
forward. Additionally, we stress that lipid production in
oleaginous microbes are merely one of many variations of
biological fuel precursor production, and indeed, many
strategies are being pursued that target other intermediates.
As demonstrated here, detailed TEA in each case will be of
signicant importance to understand the technology drivers for
attaining cost-eective production of any given fuel precursor.
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For the production of chemicals, A. succinogenes is able to
tolerate impurities common in hydrolysates, including furfural
and HMF at concentrations relevant to biomass hydrolysate
without substantial decreases in yield.84,104 It readily converts
mixed sugar streams of both C6 and C5 sugars common in
hydrolysates. The capability of the organism to utilize minor
sugars, including arabinose and galactose, as well as to enhance
the yield for production when CO2 is included in the
conversion, may lead to improved carbon eciency in the
overall process and allow for an additional low cost feed stream
and carbon source to further improve the economics of the
process. If the productivity of this organism could reach the 4
g/L/hr values reported for engineered E. coli105 on clean
commodity C6 sugars, the MFSP would decrease by $0.10/
GGE. It is important to further note that the overall succinic
acid yields from these E. coli strains are lower than those
demonstrated by A. succinogenes.
A major driver in the economics of the C5 chemicals
production train is the cost of separating succinic acid from the
fermentation broth. The bulk of this cost is not in purication
or polishing of the nal product but rather the requirement for
handling the succinate salt produced in the biological
conversion step. The need to maintain the pH of the
fermentation near neutral conditions dramatically increases
the complexity and operations for this separation. If the cost
associated with only the caustic added to the biological
conversion could be completely removed, the MFSP would
decrease by over $1/GGE. In part, this could be accomplished
by developing separation strategies in which the salt is
recovered and recycled.106,107 Another more promising
approach would be to perform the biological upgrading at
low pH such that the addition of salt was not required, and the
separation strategy could be simplied to completely eliminate
the need for the SMB unit. Approaches such as this are under
development in acid-tolerant yeast such as Issatchenkia
orientalis.108 If this design strategy is possible and the yield of
the succinic acid remained constant, the overall MFSP would
be substantially reduced to $2.32/GGE. If a low pH
fermentation would not exhibit as high of a yield as that
being projected in this design, however, we estimate that the
succinic acid yield could decrease by about 18% and still
achieve cost parity with the improved coproduction of fuels
and chemicals case. Due to this clear potential cost advantage as
well as the potential for a more simplied recovery scheme, a
number of commercial companies producing organic acids have
highlighted ongoing R&D to develop low pH fermentation
routes. Lastly, we also note that the details of the fermentation
and separations technology modeled here are specic to
succinic acid production; however, many other products can be
produced biologically or catalytically from C5-enriched hydro-
lysate.
It is also important to consider the rationale for coproduct
selection and the implications of scale-up in terms of the
market and commercial biorenery economics (here specically
considering succinic acid). In 2009, worldwide consumption of
succinic acid was 30,000 tons per year with a projected growth
of 5% per year.109 The current design would almost quadruple
the 2009 production level with an estimated production rate of
127,000 tons of succinic acid per year from a single biorenery
if succinic acid were intended to be the nal and only product.
However, we stress that the intent for this design strategy is to
utilize succinic acid as a representative molecule to demonstrate the
potential for coproduct pathways within the f ramework of an
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Research Article
integrated bioref inery, specically using our research data that
demonstrates biological production of succinic acid at
encouraging performance levels. Moreover, when viewed as
an intermediate, there is a strong potential for a greater demand
of succinic acid given that there are numerous known
technologies for the production of a wide slate of high-value
large market commodity chemicals from succinic acid as
illustrated in Figure 7. On the basis of these potential routes to
chemicals alone, the market size for succinic acid has the
potential to be well over 2,000,000 tons/year.60,110
Figure 7. Known succinic acid derivatives.41,48,53,114,115
The concept of improving the overall economics of a
biorenery through the production of high-value chemical
coproducts from a fraction of lignocellulosic hydrolysate can be
applied to a wide array of other intermediates.48,53,109,111113
This modular approach will allow for exibility when
developing bioreneries to avoid overwhelming a single
individual commodity chemical market, while supporting the
nancial feasibility using realistic process and market scenarios
for modeling coproduct pathways. As outlined previously, the
underlying price of the coproduct can have a large impact on
the MFSP as some products will not garner a high enough value
to overcome the additional cost in both capital and operating
expenses attributed to additional processing steps.
Beyond the projections and additional improvements specic
to fuels and chemicals production discussed here, additional
opportunities exist regarding overall process integration to
maximize yields to the desired products. The fuels and chemical
production strategies outlined can convert both C5 and C6
sugars with a high tolerance to impurities in hydrolysates.
Customizing the biomass deconstruction strategies to maximize
the desirable sugar intermediates through improvements to
pretreatment9,116 and cellulase eciency117 may further
improve economics, while ensuring high eciencies of the
solidliquid separation strategies. Additionally, lignin, acetate,
and other components in biomass represent an opportunity for
additional coproducts.118122
CONCLUSION
The detailed analysis of an integrated biorenery performed
here presents (a) an economic potential for a whole
hydrolysate to hydrocarbon fuels process based on plausible
near-term improvements to key conversion parameters and (b)
a similar potential for introducing a chemical coproduction
pathway into the biorenery schematic. We show that the
inclusion of coproducts can dramatically improve the overall
economic viability of an integrated process for fuel production,
ACS Sustainable Chem. Eng. XXXX, XXX, XXXXXX
ACS Sustainable Chemistry & Engineering
similar to the approach commonly employed in petroleum
rening. However, there are underlying challenges as the
additional processing steps increase the complexity of the
process and result in higher overall capital and operating costs
for this integrated design. The overall coproduct value also can
play a major role in the economics of the process. Key drivers
in the integrated design are tied to achievable yields within the
individual biological conversion strategies and product
separations and also to improving the eciency in the
production and retention of sugars.
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acssusche-
meng.6b00243.
Model overview, reaction stoichiometries, lipid recovery
yields, and capital cost breakdown. (PDF)
AUTHOR INFORMATION
Corresponding Authors
*E-mail: Mary.Biddy@nrel.gov (M.J.B.).
*E-mail: Gregg.Beckham@nrel.gov (G.T.B.).
Notes
The authors declare no competing nancial interest.
ACKNOWLEDGMENTS
We thank the U.S. Department of Energy BioEnergy
Technologies Oce for funding this work through Contract
No. DE-AC36-08GO28308 at the National Renewable Energy
Laboratory. We thank Rick Elander for a critical reading of the
manuscript and Michael Bradeld, Adam Bratis, Rick Elander,
Jacob Kruger, Jim McMillan, and Willie Nicol for helpful
discussions. 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.
REFERENCES
(1) Pacala, S.; Socolow, R. Stabilization Wedges: Solving the Climate
Problem for the Next 50 Years with Current Technologies. Science
2004, 305 (5686), 968972.
(2) Ragauskas, A.; Williams, C.; Davison, B.; Britovsek, G.; Cairney,
J.; Eckert, C.; Frederick, W.; Hallett, J.; Leak, D.; Liotta, C.; Mielenz,
J.; Murphy, R.; Templer, R.; Tschaplinski, T. The Path Forward for
Biofuels and Biomaterials. Science 2006, 311, 484489.
(3) Souza, G. M.; Victoria, R. L.; Joly, C. A.; Verdade, L. M. Bioenergy
& Sustainability: Bridging the Gaps; Scientic Committee on Problems
of the Environment (SCOPE), 2015.
(4) Lane, J. Biofuels Mandates around the World; Biofuels Digest,
December 31, 2014.
(5) Tilman, D.; Socolow, R.; Foley, J. A.; Hill, J.; Larson, E.; Lynd, L.;
Pacala, S.; Reilly, J.; Searchinger, T.; Somerville, C.; Williams, R.
Beneficial Biofuelsthe Food, Energy, and Environment Trilemma.
Science 2009, 325 (5938), 270.
(6) Himmel, M. E.; Ding, S.-Y.; Johnson, D. K.; Adney, W. S.;
Nimlos, M. R.; Brady, J. W.; Foust, T. D. Biomass Recalcitrance:
Engineering Plants and Enzymes for Biofuels Production. Science 2007,
315 (5813), 804807.
(7) Chundawat, S. P. S.; Beckham, G. T.; Himmel, M. E.; Dale, B. E.
Deconstruction of Lignocellulosic Biomass to Fuels and Chemicals.
Annu. Rev. Chem. Biomol. Eng. 2011, 2, 121145.
M DOI: 10.1021/acssuschemeng.6b00243
Research Article
(8) Wyman, C. E.; Dale, B. E.; Elander, R. T.; Holtzapple, M.;
Ladisch, M. R.; Lee, Y. Coordinated Development of Leading Biomass
Pretreatment Technologies. Bioresour. Technol. 2005, 96 (18), 1959
1966.
(9) Mosier, N.; Wyman, C.; Dale, B.; Elander, R.; Lee, Y.;
Holtzapple, M.; Ladisch, M. Features of Promising Technologies for
Pretreatment of Lignocellulosic Biomass. Bioresour. Technol. 2005, 96
(6), 673686.
(10) Lynd, L. R.; Van Zyl, W. H.; McBride, J. E.; Laser, M.
Consolidated Bioprocessing of Cellulosic Biomass: An Update. Curr.
Opin. Biotechnol. 2005, 16 (5), 577583.
(11) O hgren, K.; Bura, R.; Lesnicki, G.; Saddler, J.; Zacchi, G. A
Comparison between Simultaneous Saccharification and Fermentation
and Separate Hydrolysis and Fermentation Using Steam-Pretreated
Corn Stover. Process Biochem. 2007, 42 (5), 834839.
(12) Sheehan, J.; Aden, A.; Paustian, K.; Killian, K.; Brenner, J.;
Walsh, M.; Nelson, R. Energy and Environmental Aspects of Using
Corn Stover for Fuel Ethanol. J. Ind. Ecol. 2003, 7 (34), 117146.
(13) Aden, A.; Foust, T. Technoeconomic Analysis of the Dilute
Sulfuric Acid and Enzymatic Hydrolysis Process for the Conversion of
Corn Stover to Ethanol. Cellulose 2009, 16 (4), 535545.
(14) Kazi, F. K.; Fortman, J. A.; Anex, R. P.; Hsu, D. D.; Aden, A.;
Dutta, A.; Kothandaraman, G. Techno-Economic Comparison of
Process Technologies for Biochemical Ethanol Production from Corn
Stover. Fuel 2010, 89, S20S28.
(15) Williams, P. R.; Inman, D.; Aden, A.; Heath, G. A.
Environmental and Sustainability Factors Associated with Next-
Generation Biofuels in the Us: What Do We Really Know? Environ.
Sci. Technol. 2009, 43 (13), 47634775.
(16) Wooley, R.; Ruth, M.; Sheehan, J.; Ibsen, K.; Majdeski, H.;
Galvez, A. Lignocellulosic Biomass to Ethanol Process Design and
Economics Utilizing Co-Current Dilute Acid Prehydrolysis and Enzymatic
Hydrolysis Current and Futuristic Scenarios; NREL/TP-580-26157;
National Renewable Energy Laboratory: Golden, CO, 1999.
(17) Aden, A.; Ruth, M.; Ibsen, K.; Jechura, J.; Neeves, K.; Sheehan,
J.; Wallace, B.; Montague, L.; Slayton, A.; Lukas, J. Lignocellulosic
Biomass to Ethanol Process Design and Economics Utilizing Co-Current
Dilute Acid Prehydrolysis and Enzymatic Hydrolysis for Corn Stover;
NREL/TP -510-32438; National Renewable Energy Laboratory:
Golden, CO, 2002.
(18) Hamelinck, C. N.; Hooijdonk, G. v.; Faaij, A. P. Ethanol from
Lignocellulosic Biomass: Techno-Economic Performance in Short-,
Middle-and Long-Term. Biomass Bioenergy 2005, 28 (4), 384410.
(19) Klein-Marcuschamer, D.; Simmons, B. A.; Blanch, H. W.
Techno-Economic Analysis of a Lignocellulosic Ethanol Biorefinery
with Ionic Liquid Pre-Treatment. Biofuels, Bioprod. Biorefin. 2011, 5
(5), 562569.
(20) Wright, M. M.; Brown, R. C. Comparative Economics of
Biorefineries Based on the Biochemical and Thermochemical
Platforms. Biofuels, Bioprod. Biorefin. 2007, 1 (1), 4956.
(21) Sassner, P.; Galbe, M.; Zacchi, G. Techno-Economic Evaluation
of Bioethanol Production from Three Different Lignocellulosic
Materials. Biomass Bioenergy 2008, 32 (5), 422430.
(22) Humbird, D.; Davis, R.; Tao, L.; Kinchin, C.; Hsu, D.; Aden, A.;
Schoen, P.; Lukas, J.; Olthof, B.; Worley, M. Process Design and
Economics for Biochemical Conversion of Lignocellulosic Biomass to
Ethanol; NREL/TP-5100-47764; National Renewable Energy Labo-
ratory: Golden, CO, 2011.
(23) Jacobson, J. J.; Searcy, E.; Caerty, K.; Dunn, J. B.; Johnson, M.;
Wang, Z.; Wang, M.; Biddy, M.; Dutta, A.; Inman, D. Supply Chain
Sustainability Analysis of Three Biofuel Pathways; ANL/ESD-14/5;
Argonne National Laboratory (ANL): Argonne, IL, 2013.
(24) Canter, C. E.; Dunn, J. B.; Han, J.; Wang, Z.; Wang, M. Policy
Implications of Allocation Methods in the Life Cycle Analysis of
Integrated Corn and Corn Stover Ethanol Production. BioEnergy Res.
2016, 9 (1), 7787.
(25) Murphy, C. W.; Kendall, A. Life Cycle Analysis of Biochemical
Cellulosic Ethanol under Multiple Scenarios. GCB Bioenergy 2015, 7
(5), 10191033.
ACS Sustainable Chem. Eng. XXXX, XXX, XXXXXX
ACS Sustainable Chemistry & Engineering
(26) Peralta-Yahya, P. P.; Zhang, F.; del Cardayre, S. B.; Keasling, J.
D. Microbial Engineering for the Production of Advanced Biofuels.
Nature 2012, 488 (7411), 320328.
(27) Serrano-Ruiz, J. C.; Dumesic, J. A. Catalytic Routes for the
Conversion of Biomass into Liquid Hydrocarbon Transportation
Fuels. Energy Environ. Sci. 2011, 4 (1), 8399.
(28) Narula, C. K.; Li, Z.; Casbeer, E. M.; Geiger, R. A.; Moses-
Debusk, M.; Keller, M.; Buchanan, M. V.; Davison, B. H.,
Heterobimetallic Zeolite, Inv-Zsm-5, Enables Ecient Conversion of
Biomass Derived Ethanol to Renewable Hydrocarbons. Sci. Rep. 2015,
5.1603910.1038/srep16039
(29) Mettler, M. S.; Vlachos, D. G.; Dauenhauer, P. J. Top Ten
Fundamental Challenges of Biomass Pyrolysis for Biofuels. Energy
Environ. Sci. 2012, 5 (7), 77977809.
(30) Luque, R.; de la Osa, A. R.; Campelo, J. M.; Romero, A. A.;
Valverde, J. L.; Sanchez, P. Design and Development of Catalysts for
Biomass-to-Liquid-FischerTropsch (Btl-Ft) Processes for Biofuels
Production. Energy Environ. Sci. 2012, 5 (1), 51865202.
(31) Van de Vyver, S.; Geboers, J.; Jacobs, P. A.; Sels, B. F. Recent
Advances in the Catalytic Conversion of Cellulose. ChemCatChem
2011, 3 (1), 8294.
(32) de Beeck, B. O.; Dusselier, M.; Geboers, J.; Holsbeek, J.; Morre,
E.; Oswald, S.; Giebeler, L.; Sels, B. F. Direct Catalytic Conversion of
Cellulose to Liquid Straight-Chain Alkanes. Energy Environ. Sci. 2015,
8, 230.
(33) Prasomsri, T.; Nimmanwudipong, T.; Roman-Leshkov, Y.
Effective Hydrodeoxygenation of Biomass-Derived Oxygenates into
Unsaturated Hydrocarbons by Moo 3 Using Low H 2 Pressures.
Energy Environ. Sci. 2013, 6 (6), 17321738.
(34) Rinaldi, R.; Schuth, F. Design of Solid Catalysts for the
Conversion of Biomass. Energy Environ. Sci. 2009, 2 (6), 610626.
(35) Besson, M.; Gallezot, P.; Pinel, C. Conversion of Biomass into
Chemicals over Metal Catalysts. Chem. Rev. 2014, 114 (3), 1827
1870.
(36) Serrano-Ruiz, J. C.; Luque, R.; Sepulveda-Escribano, A.
Transformations of Biomass-Derived Platform Molecules: From
High Added-Value Chemicals to Fuelsvia Aqueous-Phase Processing.
Chem. Soc. Rev. 2011, 40 (11), 52665281.
(37) Lange, J.-P. Renewable Feedstocks: The Problem of Catalyst
Deactivation and Its Mitigation. Angew. Chem., Int. Ed. 2015, 54 (45),
1318613197.
(38) Lee, S. K.; Chou, H.; Ham, T. S.; Lee, T. S.; Keasling, J. D.
Metabolic Engineering of Microorganisms for Biofuels Production:
From Bugs to Synthetic Biology to Fuels. Curr. Opin. Biotechnol. 2008,
19 (6), 556563.
(39) Klinke, H. B.; Thomsen, A.; Ahring, B. K. Inhibition of Ethanol-
Producing Yeast and Bacteria by Degradation Products Produced
During Pre-Treatment of Biomass. Appl. Microbiol. Biotechnol. 2004,
66 (1), 1026.
(40) Pienkos, P. T.; Zhang, M. Role of Pretreatment and
Conditioning Processes on Toxicity of Lignocellulosic Biomass
Hydrolysates. Cellulose 2009, 16 (4), 743762.
(41) Davis, R.; Tao, L.; Tan, E.; Biddy, M. J.; Beckham, G. T.;
Scarlata, C.; Jacobson, J.; Caerty, K.; Ross, J.; Lukas, J.; Knorr, D.;
Schoen, P. Process Design and Economics for the Conversion of
Lignocellulosic Biomass to Hydrocarbons: Dilute-Acid Prehydrolysis and
Enzymatic Hydrolysis Deconstruction of Biomass to Sugars and Biological
Conversion of Sugars to Hydrocarbons; NREL/TP-5100-60223; Na-
tional Renewable Energy Laboratory: Golden, CO, 2013.
(42) Chen, X.; Shekiro, J.; Franden, M. A.; Wang, W.; Zhang, M.;
Kuhn, E.; Johnson, D. K.; Tucker, M. P. The Impacts of Deacetylation
Prior to Dilute Acid Pretreatment on the Bioethanol Process.
Biotechnol. Biofuels 2012, 5, 8.
(43) Liu, H.; Yu, C.; Feng, D.; Cheng, T.; Meng, X.; Liu, W.; Zou,
H.; Xian, M. Production of Extracellular Fatty Acid Using Engineered
Escherichia Coli. Microb. Cell Fact. 2012, 11 (1), 4154.
(44) Meng, X.; Shang, H.; Zheng, Y.; Zhang, Z. Free Fatty Acid
Secretion by an Engineered Strain of Escherichia Coli. Biotechnol. Lett.
2013, 35 (12), 20992103.
N DOI: 10.1021/acssuschemeng.6b00243
Research Article
(45) Michinaka, Y.; Shimauchi, T.; Aki, T.; Nakajima, T.; Kawamoto,
S.; Shigeta, S.; Suzuki, O.; Ono, K. Extracellular Secretion of Free Fatty
Acids by Disruption of a Fatty Acyl-Coa Synthetase Gene in
Saccharomyces Cerevisiae. J. Biosci. Bioeng. 2003, 95 (5), 435440.
(46) Leber, C.; Polson, B.; Fernandez-Moya, R.; Da Silva, N. A.
Overproduction and Secretion of Free Fatty Acids through Disrupted
Neutral Lipid Recycle in Saccharomyces Cerevisiae. Metab. Eng. 2015,
28, 5462.
(47) Scharnewski, M.; Pongdontri, P.; Mora, G.; Hoppert, M.; Fulda,
M. Mutants of Saccharomyces cerevisiae Deficient in Acyl-Coa
Synthetases Secrete Fatty Acids Due to Interrupted Fatty Acid
Recycling. FEBS J. 2008, 275 (11), 27652778.
(48) Werpy, T.; Petersen, G.; Aden, A.; Bozell, J.; Holladay, J.; White,
J.; Manheim, A.; Eliot, D.; Lasure, L.; Jones, S. Top Value Added
Chemicals from Biomass. Volume 1Results of Screening for Potential
Candidates from Sugars and Synthesis Gas; Pacic Northwest National
Laboratory and National Renewable Energy Laboratory, 2004.
(49) Corma, A.; Iborra, S.; Velty, A. Chemical Routes for the
Transformation of Biomass into Chemicals. Chem. Rev. 2007, 107 (6),
24112502.
(50) Bozell, J. J.; Holladay, J. E.; White, J. F.; Johnson, D. K. Top
Value-Added Chemicals from Biomass. Volume IIResults of Screening for
Potential Candidates from Biorenery Lignin; Pacic Northwest National
Laboratory, National Renewable Energy Laboratory, and University of
Tennessee, 2007
(51) Amidon, T. E.; Wood, C. D.; Shupe, A. M.; Wang, Y.; Graves,
M.; Liu, S. Biorefinery: Conversion of Woody Biomass to Chemicals,
Energy and Materials. J. Biobased Mater. Bioenergy 2008, 2 (2), 100
120.
(52) Bozell, J. J. Feedstocks for the FutureBiorefinery Production of
Chemicals from Renewable Carbon. Clean: Soil, Air, Water 2008, 36
(8), 641647.
(53) Bozell, J. J.; Petersen, G. R. Technology Development for the
Production of Biobased Products from Biorefinery Carbohydrates-the
Us Department of Energys Top 10 Revisited. Green Chem. 2010, 12
(4), 539554.
(54) Vennestrm, P.; Osmundsen, C. M.; Christensen, C.; Taarning,
E. Beyond Petrochemicals: The Renewable Chemicals Industry.
Angew. Chem., Int. Ed. 2011, 50 (45), 1050210509.
(55) Wettstein, S. G.; Alonso, D. M.; Gurbuz, E. I.; Dumesic, J. A. A
Roadmap for Conversion of Lignocellulosic Biomass to Chemicals and
Fuels. Curr. Opin. Chem. Eng. 2012, 1 (3), 218224.
(56) Gallezot, P. Conversion of Biomass to Selected Chemical
Products. Chem. Soc. Rev. 2012, 41 (4), 15381558.
(57) Tuck, C. O.; Perez, E.; Horvath, I. T.; Sheldon, R. A.; Poliakoff,
M. Valorization of Biomass: Deriving More Value from Waste. Science
2012, 337 (6095), 695699.
(58) Koutinas, A. A.; Vlysidis, A.; Pleissner, D.; Kopsahelis, N.; Lopez
Garcia, I.; Kookos, I. K.; Papanikolaou, S.; Kwan, T. H.; Lin, C. S. K.
Valorization of Industrial Waste and by-Product Streams Via
Fermentation for the Production of Chemicals and Biopolymers.
Chem. Soc. Rev. 2014, 43 (8), 25872627.
(59) Dusselier, M.; Mascal, M.; Sels, B. Top Chemical Opportunities
from Carbohydrate Biomass: A Chemists View of the Biorenery. In
Selective Catalysis for Renewable Feedstocks and Chemicals; Nicholas, K.
M., Ed.; Springer International Publishing: 2014; Vol. 353, pp 140.
(60) Cheng, K.-K.; Zhao, X.-B.; Zeng, J.; Zhang, J.-A. Biotechno-
logical Production of Succinic Acid: Current State and Perspectives.
Biofuels, Bioprod. Biorefin. 2012, 6 (3), 302318.
(61) Tao, L.; Schell, D.; Davis, R.; Tan, E.; Elander, R. T.; Bratis, A.
NREL 2012 Achievement of Ethanol Cost Targets: Biochemical Ethanol
Fermentation via Dilute-Acid Pretreatment and Enzymatic Hydrolysis of
Corn Stover; NREL/TP-5100-61563; National Renewable Energy
Laboratory: Golden, CO, 2014.
(62) Sievers, D. A.; Tao, L.; Schell, D. J. Performance and Techno-
Economic Assessment of Several SolidLiquid Separation Technol-
ogies for Processing Dilute-Acid Pretreated Corn Stover. Bioresour.
Technol. 2014, 167, 291296.
ACS Sustainable Chem. Eng. XXXX, XXX, XXXXXX
ACS Sustainable Chemistry & Engineering
(63) Runguphan, W.; Keasling, J. D. Metabolic Engineering of
Saccharomyces Cerevisiae for Production of Fatty Acid-Derived
Biofuels and Chemicals. Metab. Eng. 2014, 21, 103113.
(64) Davis, M. S.; Solbiati, J.; Cronan, J. E. Overproduction of Acetyl-
Coa Carboxylase Activity Increases the Rate of Fatty Acid Biosynthesis
in Escherichia Coli. J. Biol. Chem. 2000, 275 (37), 2859328598.
(65) Lu, X.; Vora, H.; Khosla, C. Overproduction of Free Fatty Acids
in E. Coli: Implications for Biodiesel Production. Metab. Eng. 2008, 10
(6), 333339.
(66) Clomburg, J. M.; Gonzalez, R. Biofuel Production in Escherichia
Coli: The Role of Metabolic Engineering and Synthetic Biology. Appl.
Microbiol. Biotechnol. 2010, 86 (2), 419434.
(67) Beopoulos, A.; Cescut, J.; Haddouche, R.; Uribelarrea, J.-L.;
Molina-Jouve, C.; Nicaud, J.-M. Yarrowia Lipolytica as a Model for
Bio-Oil Production. Prog. Lipid Res. 2009, 48 (6), 375387.
(68) Tai, M.; Stephanopoulos, G. Engineering the Push and Pull of
Lipid Biosynthesis in Oleaginous Yeast Yarrowia Lipolytica for Biofuel
Production. Metab. Eng. 2013, 15, 19.
(69) Blazeck, J.; Hill, A.; Liu, L.; Knight, R.; Miller, J.; Pan, A.;
Otoupal, P.; Alper, H. S. Harnessing Yarrowia Lipolytica Lipogenesis
to Create a Platform for Lipid and Biofuel Production. Nat. Commun.
2014, DOI: 10.1038/ncomms4131.
(70) Li, Y.; Zhao, Z. K.; Bai, F. High-Density Cultivation of
Oleaginous Yeast Rhodosporidium Toruloides Y4 in Fed-Batch
Culture. Enzyme Microb. Technol. 2007, 41 (3), 312317.
(71) Zhu, Z.; Zhang, S.; Liu, H.; Shen, H.; Lin, X.; Yang, F.; Zhou, Y.
J.; Jin, G.; Ye, M.; Zou, H.; Zhao, Z. K. A Multi-Omic Map of the
Lipid-Producing Yeast Rhodosporidium Toruloides. Nat. Commun.
2012, 3, 1112.
(72) Zhao, X.; Kong, X.; Hua, Y.; Feng, B.; Zhao, Z. K. Medium
Optimization for Lipid Production through Co-Fermentation of
Glucose and Xylose by the Oleaginous Yeast Lipomyces Starkeyi.
Eur. J. Lipid Sci. Technol. 2008, 110 (5), 405412.
(73) Gong, Z.; Wang, Q.; Shen, H.; Hu, C.; Jin, G.; Zhao, Z. K. Co-
Fermentation of Cellobiose and Xylose by Lipomyces Starkeyi for
Lipid Production. Bioresour. Technol. 2012, 117, 2024.
(74) Huang, C.; Chen, X.-F.; Yang, X.-Y.; Xiong, L.; Lin, X.-Q.; Yang,
J.; Wang, B.; Chen, X.-D. Bioconversion of Corncob Acid Hydrolysate
into Microbial Oil by the Oleaginous Yeast Lipomyces Starkeyi. Appl.
Biochem. Biotechnol. 2014, 172 (4), 21972204.
(75) Laurens, L. M. L.; Nagle, N.; Davis, R.; Sweeney, N.; Van
Wychen, S.; Lowell, A.; Pienkos, P. T. Acid-Catalyzed Algal Biomass
Pretreatment for Integrated Lipid and Carbohydrate-Based Biofuels
Production. Green Chem. 2015, 17 (2), 11451158.
(76) Dong, T.; Knoshaug, E.; Davis, R.; Laurens, L.; Wychen, S. V.;
Pienkos, P. T.; Nagle, N. Combined Algal Processing: A Novel
Integrated Biorefinery Process to Produce Algal Biofuels and
Bioproducts. Algal Res. 2016, DOI: 10.1016/j.algal.2015.12.021.
(77) Marker, T. L.; Petri, J.; Kalnes, T.; McCall, M.; Mackowiak, D.;
Jerosky, B.; Reagan, B.; Nemeth, L.; Krawyczyk, M.; Czernik, S.;
Elliott, D.; Shonnard, D. Opportunities for Biorenewables in Oil
Reneries; Final Report; UOP: Des Plaines, IL, 2005.
(78) Dillich, S.; Ramsden, T.; Melina, M. U.S. Department of Energy
Hydrogen and Fuel Cells Program, Program Records; U.S. Department of
Energy: 2012.
(79) Sievers, D. A.; Lischeske, J. J.; Biddy, M. J.; Stickel, J. J. A Low-
Cost SolidLiquid Separation Process for Enzymatically Hydrolyzed
Corn Stover Slurries. Bioresour. Technol. 2015, 187, 3742.
(80) Guettler, M. V.; Rumler, D.; Jain, M. K. Actinobacillus
Succinogenes Sp. Nov., a Novel Succinic-Acid-Producing Strain from
the Bovine Rumen. Int. J. Syst. Bacteriol. 1999, 49 (1), 207216.
(81) Van der Werf, M. J.; Guettler, M. V.; Jain, M. K.; Zeikus, J. G.
Environmental and Physiological Factors Affecting the Succinate
Product Ratio During Carbohydrate Fermentation by Actinobacillus
Sp. 130z. Arch. Microbiol. 1997, 167 (6), 332342.
(82) Yu, J.; Li, Z.; Ye, Q.; Yang, Y.; Chen, S. Development of Succinic
Acid Production from Corncob Hydrolysate by Actinobacillus
Succinogenes. J. Ind. Microbiol. Biotechnol. 2010, 37 (10), 10331040.
O DOI: 10.1021/acssuschemeng.6b00243
Research Article
(83) Liu, Y.-P.; Zheng, P.; Sun, Z.-H.; Ni, Y.; Dong, J.-J.; Zhu, L.-L.
Economical Succinic Acid Production from Cane Molasses by
Actinobacillus Succinogenes. Bioresour. Technol. 2008, 99 (6), 1736
1742.
(84) Bradfield, M. F.; Mohagheghi, A.; Salvachua, D.; Smith, H.;
Black, B. A.; Dowe, N.; Beckham, G. T.; Nicol, W. Continuous
Succinic Acid Production by Actinobacillus Succinogenes on Xylose-
Enriched Hydrolysate. Biotechnol. Biofuels 2015, 8 (1), 1.
(85) Gerberding, S. J.; Singh, R., Purication of Succinic Acid from
the Fermentation Broth Containing Ammonium Succinate. EP Patent
EP2519491 A2, 2010.
(86) Davis, R.; Tao, L.; Scarlata, C.; Tan, E. C. D.; Ross, J.; Lukas, J.;
Sexton, D. Process Design and Economics for the Conversion of
Lignocellulosic Biomass to Hydrocarbons: Dilute-Acid and Enzymatic
Deconstruction of Biomass to Sugars and Catalytic Conversion of Sugars to
Hydrocarbons; NREL/TP-5100-62498; National Renewable Energy
Laboratory: Golden, CO, 2015.
(87) Tan, E. C. D.; Talmadge, M.; Dutta, A.; Hensley, J.; Schaidle, J.;
Biddy, M.; Humbird, D.; Snowden-Swan, L. J.; Ross, J.; Sexton, D.;
Yap, R.; Lukas, J. Process Design and Economics for the Conversion of
Lignocellulosic Biomass to Hydrocarbons via Indirect Liquefaction:
Thermochemical Research Pathway to High-Octane Gasoline Blendstock
through Methanol/Dimethyl Ether Intermediates; NREL/TP-5100-
62402; National Renewable Energy Laboratory: Golden, CO, 2015.
(88) Jones, S. B.; Meyer, P. A.; Snowden-Swan, L. J.; Padmaperuma,
A. B.; Tan, E. C. D.; Dutta, A.; Jacobson, J.; Caerty, K. Process Design
and Economics for the Conversion of Lignocellulosic Biomass to
Hydrocarbon Fuels: Fast Pyrolysis and Hydrotreating Bio-Oil Pathway;
NREL/TP-5100-61178; Pacic Northwest National Laboratory,
National Renewable Energy Laboratory, and Idaho National
Laboratory: 2013.
(89) Galafassi, S.; Cucchetti, D.; Pizza, F.; Franzosi, G.; Bianchi, D.;
Compagno, C. Lipid Production for Second Generation Biodiesel by
the Oleaginous Yeast Rhodotorula Graminis. Bioresour. Technol. 2012,
111, 398403.
(90) Huang, C.; Chen, X.-f.; Xiong, L.; Yang, X.-y.; Chen, X.-d.; Ma,
L.-l.; Chen, Y. Microbial Oil Production from Corncob Acid
Hydrolysate by Oleaginous Yeast Trichosporon Coremiiforme.
Biomass Bioenergy 2013, 49, 273278.
(91) Huang, C.; Wu, H.; Li, R.-f.; Zong, M.-h. Improving Lipid
Production from Bagasse Hydrolysate with Trichosporon Fermentans
by Response Surface Methodology. New Biotechnol. 2012, 29 (3),
372378.
(92) Chang, Y.-H.; Chang, K.-S.; Hsu, C.-L.; Chuang, L.-T.; Chen,
C.-Y.; Huang, F.-Y.; Jang, H.-D. A Comparative Study on Batch and
Fed-Batch Cultures of Oleaginous Yeast Cryptococcus Sp. In Glucose-
Based Media and Corncob Hydrolysate for Microbial Oil Production.
Fuel 2013, 105, 711717.
(93) Huang, C.; Chen, X.-f.; Xiong, L.; Chen, X.-d.; Ma, L.-l. Oil
Production by the Yeast Trichosporon Dermatis Cultured in
Enzymatic Hydrolysates of Corncobs. Bioresour. Technol. 2012, 110,
711714.
(94) Tsigie, Y. A.; Wang, C.-Y.; Truong, C.-T.; Ju, Y.-H. Lipid
Production from Yarrowia Lipolytica Po1g Grown in Sugarcane
Bagasse Hydrolysate. Bioresour. Technol. 2011, 102 (19), 92169222.
(95) Yu, X.; Zeng, J.; Zheng, Y.; Chen, S. Effect of Lignocellulose
Degradation Products on Microbial Biomass and Lipid Production by
the Oleaginous Yeast Cryptococcus Curvatus. Process Biochem. 2014,
49 (3), 457465.
(96) Yu, X.; Zheng, Y.; Dorgan, K. M.; Chen, S. Oil Production by
Oleaginous Yeasts Using the Hydrolysate from Pretreatment of Wheat
Straw with Dilute Sulfuric Acid. Bioresour. Technol. 2011, 102 (10),
61346140.
(97) Zeng, J.; Zheng, Y.; Yu, X.; Yu, L.; Gao, D.; Chen, S.
Lignocellulosic Biomass as a Carbohydrate Source for Lipid
Production by Mortierella Isabellina. Bioresour. Technol. 2013, 128,
385391.
(98) Yousuf, A. Biodiesel from Lignocellulosic Biomass Prospects
and Challenges. Waste Manage. 2012, 32 (11), 20612067.
ACS Sustainable Chem. Eng. XXXX, XXX, XXXXXX
ACS Sustainable Chemistry & Engineering Research Article

(99) Xue, Y.-P.; Jin, M.; Orjuela, A.; Slininger, P. J.; Dien, B. S.; Dale, M.; Langan, P.; Naskar, A. K.; Saddler, J. N.; Tschaplinski, T. J.;
B. E.; Balan, V. Microbial Lipid Production from Afex[Trade Mark Tuskan, G. A.; Wyman, C. E. Lignin Valorization: Improving Lignin
Sign] Pretreated Corn Stover. RSC Adv. 2015, 5 (36), 2872528734. Processing in the Biorefinery. Science 2014, 344 (6185), 1246843.
(100) Jin, M.; Slininger, P. J.; Dien, B. S.; Waghmode, S.; Moser, B. (119) Linger, J. G.; Vardon, D. R.; Guarnieri, M. T.; Karp, E. M.;
R.; Orjuela, A.; Sousa, L. d. C.; Balan, V. Microbial Lipid-Based Hunsinger, G. B.; Franden, M. A.; Johnson, C. W.; Chupka, G.;
Lignocellulosic Biorefinery: Feasibility and Challenges. Trends Strathmann, T. J.; Pienkos, P. T.; Beckham, G. T. Lignin Valorization
Biotechnol. 2015, 33 (1), 4354. through Integrated Biological Funneling and Chemical Catalysis. Proc.
(101) Qiao, K.; Imam Abidi, S. H.; Liu, H.; Zhang, H.; Chakraborty, Natl. Acad. Sci. U. S. A. 2014, 111 (33), 1201312018.
S.; Watson, N.; Kumaran Ajikumar, P.; Stephanopoulos, G. Engineer- (120) Vardon, D. R.; Franden, M. A.; Johnson, C. W.; Karp, E. M.;
ing Lipid Overproduction in the Oleaginous Yeast Yarrowia Lipolytica. Guarnieri, M. T.; Linger, J. G.; Salm, M. J.; Strathmann, T. J.;
Metab. Eng. 2015, 29, 5665. Beckham, G. T. Adipic Acid Production from Lignin. Energy Environ.
(102) Tabera, L.; Munoz, R.; Gonzalez, R. Deletion of Bcy1 from the Sci. 2015, 8 (2), 617.
Saccharomyces Cerevisiae Genome Is Semidominant and Induces (121) Zakzeski, J.; Bruijnincx, P. C. A.; Jongerius, A. L.; Weckhuysen,
Autolytic Phenotypes Suitable for Improvement of Sparkling Wines. B. M. The Catalytic Valorization of Lignin for the Production of
Appl. Environ. Microbiol. 2006, 72 (4), 23512358. Renewable Chemicals. Chem. Rev. 2010, 110 (6), 35523599.
(103) Cebollero, E.; Martinez-Rodriguez, A.; Carrascosa, A. V.; (122) Salvachua, D.; Karp, E. M.; Nimlos, C. T.; Vardon, D. R.;
Gonzalez, R. Overexpression of Csc11. A Plausible Strategy to Beckham, G. T. Towards Lignin Consolidated Bioprocessing:
Obtain Wine Yeast Strains Undergoing Accelerated Autolysis. FEMS Simultaneous Lignin Depolymerization and Product Generation by
Microbiol. Lett. 2005, 246 (1), 19. Bacteria. Green Chem. 2015, 17 (11), 49514967.
(104) Salvachua, D.; Mohagheghi, A.; Smith, H.; Bradfield, M. F. A.;
Nicol, W.; Black, B. A.; Biddy, M. J.; Dowe, N.; Beckham, G. T.
Succinic Acid Production on Xylose-Enriched Biorefinery Streams by
Actinobacillus Succinogenes in Batch Fermentation. Biotechnol. Biofuels
2016, DOI: 10.1186/s13068-016-0425-1.
(105) Jantama, K.; Haupt, M. J.; Zhang, X.; Moore, J. C.;
Shanmugam, K. T.; Ingram, L. O. N. Materials and Methods for
Ecient Succinate and Malate Production. World Patent
WO2008115958A3, 2014.
(106) Urbanus, J.; Roelands, C. P. M.; Verdoes, D.; ter Horst, J. H.
Intensified Crystallization in Complex Media: Heuristics for
Crystallization of Platform Chemicals. Chem. Eng. Sci. 2012, 77, 18
25.
(107) Datta, R.; Glassner, D. A.; Jain, M. K.; Roy, J. R. V.
Fermentation and Purication Process for Succinic Acid. U.S. Patent
5168055, 1992.
(108) Xiao, H.; Shao, Z.; Jiang, Y.; Dole, S.; Zhao, H. Exploiting
Issatchenkia Orientalis Sd108 for Succinic Acid Production. Microb.
Cell Fact. 2014, DOI: 10.1186/s12934-014-0121-4.
(109) de Jong, E.; Higson, A.; Walsh, P.; Wellisch, M. Product
Developments in the Bio-Based Chemicals Arena. Biofuels, Bioprod.
Biorefin. 2012, 6 (6), 606624.
(110) Guzman, D. D. Bio-Succinic Acid Market Ready to Roar. ICIS
Chemical Business 2012, 281 (5), 28.
(111) Sheldon, R. A. Green and Sustainable Manufacture of
Chemicals from Biomass: State of the Art. Green Chem. 2014, 16
(3), 950963.
(112) Yim, H.; Haselbeck, R.; Niu, W.; Pujol-Baxley, C.; Burgard, A.;
Boldt, J.; Khandurina, J.; Trawick, J. D.; Osterhout, R. E.; Stephen, R.;
et al. Metabolic Engineering of Escherichia Coli for Direct Production
of 1,4-Butanediol. Nat. Chem. Biol. 2011, 7 (7), 445452.
(113) Dusselier, M.; Van Wouwe, P.; Dewaele, A.; Makshina, E.; Sels,
B. F. Lactic Acid as a Platform Chemical in the Biobased Economy:
The Role of Chemocatalysis. Energy Environ. Sci. 2013, 6 (5), 1415
1442.
(114) Dietrich, J. US Maleic Anhydride Contracts Flat. ICIS Chemical
Business 2014, 285 (25), 2121.
(115) Ebert, J. The Quest to Commercialize Biobased Succinic Acid.
Biomass Magazine, 2007
(116) Chen, X.; Wang, W.; Ciesielski, P. N.; Trass, O.; Park, S.; Tao,
L.; Tucker, M. Improving Sugar Yields and Reducing Enzyme
Loadings in the Deacetylation and Mechanical Refining (DMR)
Process through Multi-Stage Disk and Szego Refining and
Corresponding Techno Economic Analysis. ACS Sustainable Chem.
Eng. 2016, 4, 324.
(117) Payne, C. M.; Knott, B. C.; Mayes, H. B.; Hansson, H.;
Himmel, M. E.; Sandgren, M.; Stahlberg, J.; Beckham, G. T. Fungal
Cellulases. Chem. Rev. 2015, 115 (3), 13081448.
(118) Ragauskas, A. J.; Beckham, G. T.; Biddy, M. J.; Chandra, R.;
Chen, F.; Davis, M. F.; Davison, B. H.; Dixon, R. A.; Gilna, P.; Keller,

P DOI: 10.1021/acssuschemeng.6b00243
ACS Sustainable Chem. Eng. XXXX, XXX, XXXXXX