Bozell e Petersen (2010)

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Cutting-edge research for a greener sustainable future

www.rsc.org/greenchem Volume 12 | Number 4 | April 2010 | Pages 525–728
ISSN 1463-9262
Bozell and Petersen Dumesic et al.
Technology development to produce Catalytic upgrading of levulinic
biobased products acid
Song and Li et al. Ebitani et al.

Fe3O4 nanoparticle catalyst Glycerol carbonate synthesis
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CRITICAL REVIEW www.rsc.org/greenchem | Green Chemistry
Technology development for the production of biobased products from

biorefinery carbohydrates—the US Department of Energy’s “Top 10”
revisited
Joseph J. Bozell*a and Gene R. Petersenb
Received 23rd October 2009, Accepted 23rd December 2009
First published as an Advance Article on the web 5th March 2010
DOI: 10.1039/b922014c
A biorefinery that supplements its manufacture of low value biofuels with high value biobased
chemicals can enable efforts to reduce nonrenewable fuel consumption while simultaneously
providing the necessary financial incentive to stimulate expansion of the biorefining industry.
However, the choice of appropriate products for addition to the biorefinery’s portfolio is challenged
by a lack of broad-based conversion technology coupled with a plethora of potential targets. In
2004, the US Department of Energy (DOE) addressed these challenges by describing a selection
process for chemical products that combined identification of a small group of compounds derived
from biorefinery carbohydrates with the research and technology needs required for their
production. The intent of the report was to catalyze research efforts to synthesize multiple members
of this group, or, ideally, structures not yet on the list. In the six years since DOE’s original report,
considerable progress has been made in the use of carbohydrates as starting materials for chemical
production. This review presents an updated evaluation of potential target structures using similar
selection methodology, and an overview of the technology developments that led to the inclusion of
a given compound. The list provides a dynamic guide to technology development that could realize
commercial success through the proper integration of biofuels with biobased products.
Biobased products are the foundation of successful

biorefinery development
a
University of Tennessee, Forest Products Center, 2506 Jacob Drive, Biorefinery development has two strategic goals: the displace-
Knoxville, TN, USA 37996. E-mail: jbozell@utk.edu; Fax: +1 ment of imported petroleum in favor of renewable domestic
865-946-2085; Tel: +1 865-974-5991 raw materials (an energy goal) and the establishment of a
b
US Department of Energy, Golden Field Office, 1617 Cole Boulevard robust biobased industry (an economic goal). The energy goal
Golden, CO, USA 80401. E-mail: gene.petersen@go.doe.gov; Tel: +1
303-275-4937 is addressed by the current effort on ethanol, biodiesel and
advanced biofuel production (butanol, algal biodiesel, etc.)
to displace a portion of the huge amount of transportation
gasoline (~142 ¥ 109 gallons) and diesel (~60 ¥ 109 gallons)
Joseph J. Bozell joined the used annually in the US.1 But despite its high volume, fuel is
University of Tennessee Forest a low value product. As a result, the return on investment in
Products Center in 2006. biofuel-only operations presents a significant barrier to realizing
Prof. Bozell received his B.S. the biorefinery’s economic goal. For example, algal oil holds
in chemistry from South great promise as a source of biodiesel, but remains a long term
Dakota State University, and a opportunity as developers try to identify additional revenue
Ph.D. in organic synthesis and streams to cover the high cost of growing and processing algal
organometallic chemistry from biomass for oil recovery.2 Examination of the best means for
Colorado State University. leveraging existing and advanced fuel processes is needed to
Before joining UT, he did assure profitable biorefinery operation. Industrial adoption of
postdoctoral work at Princeton renewable carbon requires a financial incentive to justify the use
University, industrial research of unfamiliar building blocks, the development of processes to
at Monsanto, and government convert these building blocks to final products, and the capital
Joseph J. Bozell research as a principal scientist investment necessary to take the technology to commercial scale.
at DOE’s National Renewable Energy Laboratory. Prof. Bozell’s High value, lower volume biobased chemicals provide this
primary interests are in using the tools of organic synthesis for incentive. Even though chemical production accounts for only
converting renewable materials into chemical products. 7–8% of oil imports in the US,3–5 analyses reveal that a
This journal is © The Royal Society of Chemistry 2010 Green Chem., 2010, 12, 539–554 | 539
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biorefinery integrating biofuels and chemicals offers a much set of process costs, depending on the market and application. If
higher return on investment and meets its energy and economic a technology does not meet the price targets of one product,
goals simultaneously.6,7 Such projections have prompted efforts it need not be discarded, since it may be applicable to a
to add coproducts into existing biorefinery models, such as material with a different projected cost structure. For chemical
corn wet and dry mills or pulp and paper operations, as a production, focus on the choice of technology leads product
means to enhance revenue or repurpose existing underutilized identification.
infrastructure.8 However, incorporating chemical products into Nonetheless, target-based approaches using process analysis
the biorefinery’s portfolio faces two primary challenges: methodology employed for biofuels persist as a means to
(1) Biobased chemical production is challenged by a lack winnow a huge number of possible biobased chemical targets
of conversion technology. Conversion of renewable carbon to to a manageable size.11–13 Pre-identifying specific molecular
chemicals is the least developed and most complicated of all structures prior to research is perceived to have several ad-
biorefinery operations, especially when compared to conversion vantages, particularly in an industrial setting. It offers defined
processes available for nonrenewable hydrocarbons.9 Promising opportunities for decision makers when prioritizing limited
hypothetical scenarios integrating fuels and chemicals do not research funds. It can also reduce risk, as preliminary process
require that the necessary conversion technology exists. engineering estimates and life cycle analyses can address “what
(2) Biobased chemical production is challenged by an over- if” questions. The approach may also be more adaptable to a
abundance of targets. Integrated biorefinery development is still manufacturer’s existing infrastructure and equipment.
in its infancy, and as such has yet to identify a core group of However, the approach that is successful in existing single
primary chemicals and secondary intermediates analogous to product biofuel scenarios is poorly suited for multi-product
those used by the petrochemical industry. The range of poten- chemical scenarios, particularly when technology is in flux.
tial targets includes structures already made by the chemical The sheer number of new and existing structural possibilities
industry (and thus demonstrated as commercial products) as suggests that the chances of process analysis correctly identifying
well as new structures formed from biorefinery building blocks. a commercial winner are small. The analysis can be limited
Rational selection processes for sorting these opportunities and to structures currently manufactured by the petrochemical
portfolios would be a valuable tool. industry, but this approach can lead to uneconomical force fits
Addressing these challenges presents an interesting problem of highly oxidized renewables into processes designed for highly
for the integrated biorefinery. As the biorefining industry has reduced products.14–16 Finally, structural pre-identification ap-
expanded over the last ten years, its focus has been almost proaches have a short shelf life. Life cycle and process analyses
exclusively on single product operations making fermentation employed at the beginning of a search may become moot as new
ethanol or biodiesel. Since the molecular structure of the desired technology is developed, and approaches once thought to be too
output is known, engineering process analysis is ideally suited for expensive are rendered viable.
determining price targets and identifying technologies that offer Accordingly, a number of evaluations have appeared that
the best prospects for research investment.10 But when applied examine technology needs and opportunities.17–22 The primary
to multi-product chemical scenarios, these analysis techniques advantage of this approach is the tailoring of broad-based
are less useful because of fundamental differences between fuel processes to the building blocks available from biorefinery
and chemical research (Fig. 1). process streams. It identifies those structures most easily ob-
tained from a given conversion process, rather than trying to
force a conversion process to fit a pre-identified structure. A
technology-based approach also mirrors the experience of the
petrochemical industry whose success was the result of research
identifying technologies most applicable to the properties of
the raw material, and the structures most easily made from
these technologies. Distillation of crude oil provided kerosene.
Fig. 1 Research approaches for biobased fuels and chemicals. Kerosene production drove a study of thermal cracking, steam
cracking and catalytic cracking.23 Cracking technology led
Research in fuels tends to investigate a wide number of to olefins, gasoline and aromatics. In each case, the product
different technologies to produce a single or very small number slate from the processes changed and expanded. The primary
of pre-identified outputs, i.e., biofuels research is convergent. If a disadvantage of this approach is its high-risk nature and need
technology for a fuel process does not meet predetermined cost for longer-term programmatic commitment, making it harder
targets, it is discarded in favor of more economical processes. to justify in a commercial environment.
For biofuels, focus on product identification leads the choice of
technology.
If chemicals are included as part of the biorefinery’s portfolio, The DOE “Top 10” reports successfully marry
the number of possible outputs soars. The experience of the technology development needs with product
chemical industry shows that this complexity is best handled
identification
by using broad-based technologies (selective reductions and
oxidations, bond making/breaking processes, catalysis, etc.) to In light of these contrasting approaches to biorefinery develop-
produce multiple outputs, i.e., chemical production is divergent. ment, the challenge for integrating biobased chemicals is finding
Process analysis becomes complicated, as each target has its own the appropriate balance between the clear need for fundamental
540 | Green Chem., 2010, 12, 539–554 This journal is © The Royal Society of Chemistry 2010
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Table 1 The DOE top chemical opportunities from carbohydrates, Table 2 Criteria used in evaluating biobased product opportunities
2004 from carbohydrates
Succinic, fumaric and malic acids 1. The compound or technology has received significant attention in
2,5-Furan dicarboxylic acid the literature. A high level of reported research identifies both
3-Hydroxypropionic acid broad technology areas and structures of importance to the
Aspartic acid biorefinery.
Glucaric acid 2. The compound illustrates a broad technology applicable to
Glutamic acid multiple products. As in the petrochemical industry, the most
Itaconic acid valuable technologies are those that can be adapted to the
Levulinic acid production of several different structures.
3-Hydroxybutyrolactone 3. The technology provides direct substitutes for existing
Glycerol petrochemicals. Products recognized by the chemical industry
Sorbitol provide a valuable interface with existing infrastructure and
Xylitol/arabinitol utility.
4. The technology is applicable to high volume products. Conversion
processes leading to high volume functional equivalents or
technology while demonstrating that this technology will lead to utility within key industrial segments will have particular impact.
5. A compound exhibits strong potential as a platform. Compounds
identifiable marketplace products. In 2004, the US Department that serve as starting materials for the production of derivatives
of Energy (DOE) released the first of two reports outlining offer important flexibility and breadth to the biorefinery.
research needs for biobased products. This publication described 6. Scaleup of the product or a technology to pilot, demo, or full scale
a group of 15 (despite being colloquially known as the DOE is underway. The impact of a biobased product and the
technology for its production is greatly enhanced upon scaleup.
“Top 10” report) target structures that could be produced from 7. The biobased compound is an existing commercial product,
biorefinery carbohydrates.24,25 Its methodology was an effort to prepared at intermediate or commodity levels. Research leading to
provide a rational selection mechanism and a middle ground production improvements or new uses for existing biobased
chemicals improves their utility.
between a broad technology development approach and a target 8. The compound may serve as a primary building block of the
pre-identification approach. By developing a list of specific biorefinery. The petrochemical refinery is built on a small
structures, the report embraced product identification as a guide number of initial building blocks: olefins, BTX, methane, CO.
for research. The targets reflected a methodology that included Those compounds that are able to serve an analogous role in the
biorefinery will be of high importance.
factors such as known processes, economics, industrial viability, 9. Commercial production of the compound from renewable carbon is
size of markets, and the ability of a compound to serve as a well established. The potential utility of a given compound is
platform for the production of derivatives. The evaluation led to improved if its manufacturing process is already recognized
within the industry.
the identification of the products shown in Table 1.
Nonetheless, the report simultaneously embraced fundamen-
tal research needs as a guide for product identification. Table 1
not considered sufficient for inclusion on the list. Table 2 shows
was not a closed list. By using these initial structures as a
additional criteria used for prioritizing opportunities from the
backdrop, the report was able to identify broad technology
initial screen. The criteria are similar to those used in the 2004
needs for the biorefinery. The intent of the report and its
report, and listed roughly in the order of importance as used in
methodology was to catalyze identification and development
this evaluation, although the relative difference between adjacent
of the technologies necessary for synthesis of multiple members
criteria is small. Cost evaluations will ultimately be a crucial
of the list, or, ideally, structures not considered in the report.
issue in commercial utility, but in parallel with the original
DOE report, were not included in this evaluation. Since the
Evaluation of recent technology advances provides a technology base is still developing, cost structures will change
revised list of biobased product opportunities from as a result of ongoing research activity. Table 3 summarizes the
compounds discussed in this review and the criteria employed
carbohydrates—The “Top 10 + 4”
for their inclusion, plus the broad technology areas represented
In the six years since the original DOE report, considerable by each structure.
progress in biobased product development has been made. This Omission of a specific compound does not mean a target
review revisits that report and presents an updated group of or process is without merit. Rather, the compounds that are
candidate structures based on advances since 2004. Some of included represent those with the best balance between criteria
the compounds described in this review are members of DOE’s given the current state of technology. The reader must note
original list, and loosely represent advances made as a result of that categorizations such as those in Table 2, as well as other
successful product pre-identification. Several new compounds evaluations of biorefinery technology and opportunities,26–42
also appear, and represent advances in technology development. include some subjectivity because the biorefining industry is
The need for improved conversion technology remains a in a state of rapid change and expansion. Three examples
challenge for the biorefinery. Thus, the amount of research provide some illustration how the criteria of Table 2 were
activity reported in the literature was used as an initial screen to employed. Furandicarboxylic acid (FDCA) retains its place
identify high interest compounds or processes. Correspondingly, in the revised list. Neither FDCA nor any of its derivatives
limited research activity suggested that a given compound from the 2004 report were, or have yet become, commercial
should receive lower priority. Several organic acids (fumaric, products. Nonetheless, improvements in the production of
malic, aspartic, glucaric, glutamic and itaconic) from the 2004 FDCA and its derivatives offer the potential of providing
list were in this category. However, research activity alone was biobased replacements for polymers—the largest segment of
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Table 3 New top chemical opportunities from biorefinery carbohydrates, criteria for their inclusion and resulting technology needs
Compound Criteria for inclusion Illustrative general biorefinery technology needs

Ethanol 1, 2, 3, 4, 5, 6, 7, 8, 9 Selective alcohol dehydrations; improved biochemical production of alcohols from

biomass (rate, yield, titer, product, pH, inhibitor tolerance); engineering of optimal
fermentation organisms
Furans Furfural: 1, 2, 7, 8, 9 Selective dehydrations of carbohydrates; new catalysts and reaction media for
dehydration; reactive separations; selective oxidations of alcohols; improved oxidation
and dehydration catalysts; catalytic systems for reactions in aqueous solution
HMF: 1, 2, 5, 8
FDCA: 1, 4, 5
Glycerol and derivatives 1, 2, 3, 4, 5, 6, 7, 8, 9 Reactions in aqueous solution; selective reductions and oxidations of polyols;
improved biological conversions of polyols
Biohydrocarbons Isoprene: 1, 2, 3, 4, 6, 7 Improved biohydrocarbon production; engineering of organisms to convert sugars to
hydrocarbons; optimizing rate, yield, titer, product tolerance
Biohydrocarbons: 1, 2, 6
Lactic acid 1, 2, 4, 7 Optimization of bioconversion of carbohydrates; bioprocesses with high rate, yield,
titer, product, pH and inhibitor tolerance; engineering of organisms to produce single
materials
Succinic acid 1, 2, 5, 6 Bioconversion of carbohydrates; optimization of yield, rate, titer, separation;
engineering of organisms for optimal production of target
Hydroxypropionic acid/aldehyde 1, 3, 4, 5 Optimization of bioconversion of carbohydrates; bioprocesses with high rate, yield,
titer, product and inhibitor tolerance; engineering of organisms to produce single
materials; selective dehydrations of alcohols; selective reductions of carbonyl groups,
new selective hydrogenation catalysts; chemical processes in aqueous solution
Levulinic acid 1, 2, 3, 5, 6, 8 Selective dehydrations of carbohydrates; improved separations of products; utility of
co-product schemes by biorefinery; improved catalysts for selective carbohydrate
conversion processes
Sorbitol 1, 2, 3, 4, 5, 6, 7, 8, 9 Selective hydrogenolysis of polyols; new catalysts for reduction of carbohydrate
derivatives; selective dehydrations of polyols; comparative assessment of chemical and
biochemical conversion technology; selective bond breaking/bond making
technology for polyols
Xylitol 1, 2, 5, 8, 9 Selective hydrogenolysis of polyols; new catalysts for reduction of carbohydrate
derivatives; selective dehydrations of polyols; comparative assessment of chemical and
biochemical conversion technology; selective bond breaking/bond making
technology for polyols
the chemical industry. A combination of this potential with the Overview of the revised top chemical opportunities
development of more efficient HMF production and one pot from biorefinery carbohydrates
dehydration/oxidation of sugars to FDCA led to its retention.
Conversely, glutamic acid was included in 2004 because its status The following sections provide a more detailed overview of the
as an existing commercial product suggested high potential as recent technology advances that contributed to identification of
a source of new, albeit speculative, derivatives. Since glutamic the compounds in Table 3 and the ability of these compounds
acid has remained a terminal product of the chemical industry to address the criteria of Table 2.
and research activity in either glutamic acid production or its
use as a platform was minimal, other products received higher
Ethanol
priority. Similarly, glucaric acid, a renewable building block
used in new polyamides,43,44 was omitted because it failed to Biochemical transformation of biomass into fuel is represented
pass the first screen. Little new information appeared since almost entirely by fermentation ethanol. Many excellent reviews
the original DOE report, yet its production is currently being are available describing processing technology, cost structure,
investigated at the pilot scale by Rivertop Renewables. The energy balance and research needs.46–55 Ethanol was specifically
proprietary carbohydrate oxidation technology is reported to omitted from DOE’s original list because its expected high
be cost effective, environmentally benign and free of the waste production volume categorized it as a so-called supercommod-
products associated with conventional HNO3 oxidation.45 A ity. Recent technology developments and strategic commercial
commercial success would return glucaric acid to the list. partnerships have positioned ethanol as a feedstock for chemical
The criteria used in this evaluation may be insufficient production, improving its platform potential. Ethanol and
for others developing their own list. A commercial chemical related alcohols (propanol, butanol) are of interest as precursors
producer assessing issues such as unique market position, to the corresponding olefins via dehydration, providing a direct
proprietary access to a specialized feedstock, experience in the interface between the biorefinery and the conversion infrastruc-
field, specific IP, or existing infrastructure would probably end ture of the petrochemical industry.56
up with a much different group of opportunities. However, we Ethanol dehydration was the source of most ethylene in the
believe that the criteria of Table 2 offer a reasonable starting early part of the 20th century, and can be carried out at extremely
point for identifying promising technologies and products for high conversion and selectivity in fluidized bed reactors over
the biorefinery. A summary of the performance of the final group activated alumina. Vapor phase dehydration of ethanol at 400 ◦ C
of compounds against these criteria is provided in Table 4. affords a 99.9% selectivity to ethylene at 99.5% conversion.57
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Table 4 Ranking of compounds against criteria in Table 2a
1. Extensive 2. Multiple 4. High 7. Existing 8. Primary

recent product ap- 3. Direct volume 5. Platform 6. Industrial commercial building 9. Commercial
Compound literature plicability substitute product potential scaleup product block biobased product
Ethanol +++ +++ +++ +++ +++ +++ +++ +++ +++
Furfural +++ ++ + ++ + + +++ ++ +++
HMF +++ ++ + + ++ + + ++ +
FDCA +++ + + +++ ++ + + + +
Glycerol/derivatives +++ +++ +++ +++ +++ +++ +++ +++ +++
Isoprene +++ ++ +++ +++ + +++ +++ + +
Biohydrocarbons +++ ++ +++ + + + + ++ +
Lactic acid +++ +++ + +++ ++ + ++ + +
Succinic acid +++ +++ + + +++ +++ + + +
HPA +++ + +++ +++ ++ + + + +
Levulinic acid +++ ++ +++ ++ +++ +++ + +++ +
Sorbitol +++ +++ +++ +++ +++ +++ +++ +++ +++
Xylitol +++ +++ + + +++ + ++ +++ ++
a
+++ = Good performance against criterion; ++ = emerging performance against criterion; + = lower performance against criterion.
However, with the advent of the petrochemical industry and In each case, the selectivity of the dehydration was moderate,
the concomitant availability of cheap oil, production of ethylene consistent with the low yield/selectivity normally observed for
from ethanol was discarded in favor of steam cracking processes. the conversion of xylose to furfural. However, dehydration using
More recently, the low cost of sugar cane in Brazil coupled a micro-mesoporous silica functionalized with sulfonic acid
with increasing crude oil prices has spurred renewed interest in groups gave an 82% selectivity to furfural at 91% conversion.69
ethanol dehydration. Dow,58 Braskem (Brazil’s largest plastics
producer)59 and Solvay60 have announced separate projects to Hydroxymethylfurfural. C6 sugars are converted to HMF
build ethanol-to-ethylene plants based on sugarcane. Dow and upon dehydration. HMF is reactive, and can undergo conversion
Braskem will ultimately manufacture “green” polyethylene while to levulinic and formic acids subsequent to its formation, leading
Solvay will use ethylene to supply its polyvinylchloride capacity. to product mixtures and modest yields. Much higher yields
The Braskem (180 000 tonnes per year) and Solvay (55 000 of HMF are realized in ionic liquid media. Dehydration of
tonnes per year) projects are currently underway, while Dow fructose in methyl imadizolium chloride gives a 92% yield of
(estimated polyethylene capacity of 320 000 tonnes per year) HMF.70 A recent report describes the conversion of glucose
recently announced a delay in their construction plans. to HMF in 70% yield using a CrCl2 catalyst in 1-ethyl-3-
Ethanol can also be oxidized to commodity chemicals using methylimadazolium chloride. The CrCl2 is thought to promote
nanoscale gold catalysts. Ethanol oxidation over Au/TiO2 or isomerization of glucose to the furanoid form of fructose,
Au/MgAl2 O4 gives nearly 95% selectivity to acetic acid at leading to an intermediate more susceptible to dehydration.71
>90% conversion.61 Kinetic isotope experiments and Hammett Separation of the HMF from the ionic liquid is difficult, and
correlations suggest that the oxidation proceeds by generation in one case, required a continuous extraction of the reaction
of a cationic site at the alcohol, stabilized by the gold.62 Further, medium for several hours.70 An alternative dehydration used
ethanol can be oxidized in high yield over gold nanocatalysts choline chloride/citric acid as the ionic liquid medium to give
or Mo–V–Nb mixed oxides63 to give acetic acid and ethyl HMF yields of 90% at 80 ◦ C. The process could be carried out in
acetate.61,64 a biphasic ionic liquid/EtOAc system to achieve 70% extraction
of HMF in 20 min.72
Furans Fructose is commonly employed as a starting material for
The dehydration of 5- and 6-carbon sugars to give furans is HMF production. In acetone–water or methanol–water, fruc-
a well-known transformation for the preparation of furfural tose is converted to HMF at 77 and 78% selectivity and 98
and hydroxymethylfurfural (HMF). These compounds were and 99% conversion, respectively. DMSO offers advantages for
omitted from the original DOE list because of a static market dehydration of fructose as it eliminates HMF decomposition
for furfural, and the lack of high yield, selective conversion to levulinic and formic acids. In DMSO solution and in the
processes for HMF. Technology development has improved the presence of lanthanide ions, fructose is catalytically dehydrated
dehydration of sugars to furans, improving their potential as to HMF in >90% yield. As observed for ionic liquids, the use
platform chemicals in the biorefinery (Fig. 2). of DMSO presents difficulty in separating the HMF for further
use.73 To minimize the use of DMSO, fructose was dehydrated
Furfural. Xylose is the conventional starting material for in a 70/30 mixture of acetone–DMSO with a strongly acidic ion
furfural production. Treatment of xylose in a toluene–water exchange resin to give nearly 90% yield of HMF after 20 min.74
mixture at 160◦ using modified acidic zirconia catalysts gave Furanix, a division of the Dutch company Avantium, has
a 45% selectivity to furfural at 95% conversion.65 Titanate and developed technology to minimize levulinic and formic acid
niobate catalysts,66 silica-supported heteropolyacid catalysts67 formation by isolating HMF as the corresponding ether or ester.
and niobium silicate catalysts have also been investigated.68 Dehydration of fructose with ethanol in the presence of a variety
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Fig. 2 Synthesis and transformation of furans.
of solid acid catalysts at 175–225 ◦ C gave ethoxymethylfurfural attempt to carry out the reaction in water gave only minimal
in 38% selectivity at 98% conversion.75 Similar reaction with conversion to FDCA.81 Alternatively, Co(acac)3 in a silica sol–
acetic acid gave acetoxymethylfurfural in 20% selectivity at 98% gel system gave 99% selectivity to FDCA from fructose at 72%
conversion.76 Execution of the same reaction in ionic liquids conversion.82 Very recently, formation of the dibutyl ester of
resulted in a marked improvement. Dehydration of fructose FDCA in yields of 50–60% by the reaction of galataric acid and
in a mixture of 1-ethyl-3-methylimadazolium chloride and 3- butanol in the presence of sulfuric acid has been reported.83
methylimadazolium bis(trifluoromethanesulfonyl) imide gave
75% yield of acetoxymethylfurfural and a 20% yield of HMF.77 Glycerol and derivatives
Furan-2,5-dicarboxylic acid and diformylfuran. Furan-2,5- Glycerol is not a carbohydrate, but structurally it can be consid-
dicarboxylic acid (FDCA) has been suggested as an important ered as a “mini-sugar”, in that transformations appropriate to
renewable building block because it can substitute for tereph- glycerol may be applied to carbohydrates. Moreover, glycerol is a
thalic acid in the production of polyesters.78 Several routes particularly important material because of its ready availability
to FDCA have been reported, but all proceed via oxidation and strong potential to become a primary building block for
of HMF with air over different catalysts. Thus, improvements the biorefinery. Technology for its manufacture is established,
in HMF synthesis benefit production of FDCA. Oxidation of and processes for its conversion into higher value materials
HMF under strongly alkaline conditions over a Pt/Pb catalyst has received significant recent research attention. An expanding
gives quantitative formation of FDCA with 99% selectivity in biodiesel market and the demand for green biofuels suggests
two hours.79 HMF oxidation was also studied with a series of that large amounts of inexpensive glycerol will be available.
conventional metal bromide catalysts (Co, Mn, Zr) used for Indeed, higher value products from glycerol could provide an
the oxidation of para-xylene to terephthalic acid.80 Depending important revenue stream and reduction of dependence on
on the oxidation conditions, either 2,5-diformylfuran or FDCA subsidies for an industry that faces overcapacity issues on the
was isolated in 57% and 60% yield respectively. fuel side.84 Biodiesel-derived glycerol could be burned for process
One pot dehydration and oxidation of fructose to FDCA via fuel value if the market becomes saturated, but higher value
intermediate HMF has been investigated. Vanadyl phosphate uses allow expanded production of biobased chemicals from an
catalysts in DMSO converted fructose to FDCA in 97% inexpensive feedstock. Some projections indicate costs as low as
selectivity at 84% conversion. When the solvent was changed $0.11 per kg for crude glycerine solutions. Several technologies
to DMF, 93% selectivity at 56% conversion was observed. An have emerged as candidates for conversion of glycerol into
Fig. 3 Glycerol as a primary biorefinery building block.
chemicals (Fig. 3) particularly in glycerol reduction, dehydration via catalytic hydrogenolysis. Additional industrial projects have
and fermentation.85–87 been announced by Cargill, Virent and Dow.90
Alternative reductions of glycerol give different product
profiles. Treatment of glycerol with hydrogen in the presence
Glycerol reduction processes. Catalytic hydrogenolysis con- of Ru/C or Pt/C leads to mixtures of ethylene and propylene
verts glycerol into a family of derivatives, including ethylene glycol. Carrying out the reduction in the presence of hydroxide
glycol, propylene glycol, acetol and lactic acid. Suppes has bases induces formation of lactic acid as the major product.91 In
reported a selective hydrogenolysis of glycerol to propylene contrast, propylene glycol is formed in greater than 80% selectiv-
glycol, a commercial material with an annual production of ity at 80% conversion using Ru/TiO2 and Li2 CO3 as the base.92
over 450 million kg.88 Reduction of glycerol at 200 psi H2 and A number of papers describe related catalytic hydrogenolysis
200 ◦ C over a copper chromite catalyst gives propylene glycol of glycerol to propylene glycol, including processes using Ru/C
selectivities of nearly 90% at 65% conversion. The mechanism of and an Amberlyst resin,93–95 and Cu/ZnO catalysts.96 Treatment
the reaction is suggested to be an initial dehydration of glycerol ◦
of neat glycerol with hydrogen and RANEY R Ni at 190 yields
to acetol, followed by selective reduction of the carbonyl group. propylene glycol in 71% selectivity at 97% conversion. 97
Suppes’ route also offers product control. By altering the process

conditions, acetol can be made as the primary product in greater Glycerol dehydration processes. Catalytic and thermal de-
than 90% selectivity by eliminating the hydrogen and using hydration of glycerol provides several derivatives. Depending
reactive distillation to convert glycerol to acetol.89 Industrial on the conditions employed, dehydration occurs via loss of a
interest in biobased propylene glycol has been significant. Sen- primary hydroxyl group, leading to hydroxypropionaldehyde
ergy has licensed Suppes’ technology and is reportedly piloting and acrolein, or at the secondary hydroxyl group, leading to
the process. Archer Daniels Midland (ADM) announced that a hydroxyacetone. Acrolein has received recent attention as a
new propylene glycol plant will be starting in 2010. The plant precursor to acrylic acid, a high volume chemical with an
will have a capacity of 100 000 tonnes per year and is closely annual production of 1.2 ¥ 109 kg. Acrolein is produced
linked to ADM’s existing biodiesel production. Glycerol from in 86% selectivity at 70% conversion by treating glycerol in
biodiesel will be purified and converted to propylene glycol hot compressed water for 8 s under supercritical conditions
View Article Online
in the presence of H2 SO4 or Zn(SO4 )2 promoters.98 Glycerol production of glycerol carbonate from glycerol and carbon
dehydration has also been carried out in the gas phase over dioxide under supercritical conditions or in the presence of tin or
supported acid catalysts. Acrolein was formed in 65% selectivity cerium catalysts has also been reported.116,117 Recently, glycerol
at 100% conversion over 15 wt% WO3 /ZrO2 .99 A related catalyst, carbonate has been synthesized biochemically in high yield by
mesoporous silicotungstic acid, gave 85% selectivity to acrolein the reaction of glycerol and dimethyl carbonate in the presence
at nearly 100% conversion at 275 ◦ C.100 of an immobilized lipase from Candida antarctica.118
Glycerol as a biochemical feedstock. Glycerol is a feedstock Epichlorohydrin. Recent work has examined the use of glyc-
in biochemical transformations, with the majority of current erol as a starting material for the production of epichlorohydrin.
research focused on its conversion to 1,3-propanediol (1,3- Traditional routes to epichlorohydrin hydroxychlorinate propy-
PDO). 1,3-PDO is one of the components of DuPont’s Sorona lene, and proceed through 1,3-dichloro-2-propanol as an inter-
(1,3-PDO and terephthalic acid), a polymer used in textiles mediate, which is treated with base to form epichlorohydrin.9
and carpeting. Glucose is the current feedstock for 1,3-PDO This process also forms the 1,2-dichloro isomer, which is much
using a transgenic Escherichia coli developed by Genencor and less reactive. In contrast, glycerol forms the 1,3-isomer with high
DuPont.101 This organism is the basis of a recently opened selectivity, making it a viable starting material for epichloro-
commercial production facility in Loudon, TN. hydrin. The kinetics and mechanism of this reaction have
Glycerol can also be biochemically converted to 1,3-PDO.102 been examined.119 A new Dow process exploits this selectivity,
Inexpensive glycerol offers an alternative to glucose fermen- providing an interface between biobased building blocks and
tation, and the advantage of a higher yield of 1,3-PDO. high volume industrial products (Fig. 4).120
Glucose-based processes give high 1,3-PDO concentrations
(>125 g L-1 ), but their yield (g 1,3-PDO per g glucose) is
only 30–40%. In contrast, the theoretical yield from glycerol
is 67%. Fermentation of glycerol approaches the theoretical
limit with genetically modified Clostridium acetobutylicum,103
achieving concentrations of over 84 g L-1 in fed-batch cultures
at a rate of 1.7 g L-1 h-1 . A drawback to production of 1,3-PDO Fig. 4 Conversion of glycerol to epichlorohydrin.
from glycerol has been a need to use purified glycerol sources
for most organisms. Various research groups are addressing this Reaction of glycerol with 2 equivalents of HCl in the presence
limitation with new fermentative organisms.104,105 Fermentation of a carboxylic acid catalyst (generally HOAc) forms 1,3-
of unpurified glycerine with engineered C. acetobutylicum gave dichloro-2-propanol and very small amounts of the 1,2-isomer.
no loss in productivity.106 1,3-PDO is also formed at a concentra- Further treatment with base induces ring closure and elimina-
tion of 53 g L-1 and a productivity of 1.7 g L-1 h-1 by treatment of tion of a single equivalent of NaCl. The reaction sequence offers
crude or purified glycerol with Klebsiella pneumoniae in fed batch several advantages over the commercially practiced route via
processes,107 and from crude glycerol by Clostridium butyricum propylene hydrochlorination, including improved regioselectiv-
transgenics. The latter fermentation has been projected as an ity of the chlorination step, reduction of byproduct formation,
economical source of 1,3-PDO if the glycerol cost is $0.31 and a decrease in chlorinated waste from 2 equivalents to
per kg.108 one. Under optimum conditions, glycerol is chlorinated to the
Cameron and coworkers have reported that minimizing the 1,3-isomer in 93% yield. A similar process with a proprietary
amount of methyl glyoxal and glycerol-3-phosphate produced catalyst has been patented by Solvay and is under commercial
during fermentation using engineered E. coli improves the development. By using glycerol as the starting material, the
conversion of glycerol to PDO by removing these two enzyme Solvay process reduces chlorinated residues eightfold and water
inhibitors.109 Cameron et al. have also described engineering use by 90% over conventional epichlorhydrin processes. The
E. coli for a biochemical production of 1,2-propanediol.110 company is planning to build a 100 000 tonne per year facility
This process proceeds through dihydroxyacetone as a metabolic in Thailand to be operational by the end of 2009.121
intermediate, implying that proper choice of organism could lead
to either 1,2- or 1,3-PDO from glycerol, since one of the first in- Biohydrocarbons
termediates in 1,3-PDO production is also dihydroxyacetone.102
Considerable work has appeared describing new processes for
Glycerol carbonate. Glycerol carbonate offers interesting the biochemical production of hydrocarbons from biorefinery
opportunities to the chemical industry, as it can be prepared sugars. Such processes will be important for expansion of the
directly and in high yield from glycerol. Glycerol carbonate has biorefinery, as they provide a direct drop-in interface between
been investigated as a component in gas separation membranes, the biorefining industry and the existing petrochemical industry.
polyurethane foams111 and surfactants,112 as a nonvolatile reac-
tive solvent, as a component in coatings, and as a source of Isoprene. Isoprene is a high value hydrocarbon with a world
new hyperbranched polymers.113 At low glycerol costs, glycerol market of $1–2 billion. The immediate precursor to isoprene and
carbonate could replace dimethyl carbonate in the production naturally occurring polyisoprenoids is isopentenyl diphosphate
of green polycarbonates and polyurethanes. Glycerol carbonate (IPP). Two biosynthetic routes to IPP have been described.122,123
is prepared by the reaction of glycerol with urea at 120◦ In eukaryotes and archaea, IPP is formed by via mevalonate.
in diethylene glycol for 24 h (58% yield)114 or the treatment In certain bacteria, an alternate path is followed that proceeds
of glycerol with ethylene or propylene carbonate.115 Direct through methylerythritol phosphate.
View Article Online
In late 2008, Genencor and Goodyear announced a joint Arthrobacter species were reported to synthesize long chain C29
program to commercialize the manufacture of isoprene from alkenes.133
bacterial sources by 2012 as a domestic approach to rubber
production. Although Genencor has not revealed the exact pro- Organic acids
cess under development, they have licensed patented technology
Organic acids constitute a significant fraction of those com-
from the University of Colorado.124 This patent describes the use
pounds available in a minimum number of steps from biorefinery
of several Bacillus species (B. subtilis and B. amyloliquefaciens)
carbohydrate streams, and as such have received much attention
as high yield producers of isoprene.125 In March 2009, Genencor
as platform chemicals.134 The following section presents addi-
announced delivery of the first shipments of bioisoprene to
tional details on recent advances in the utility of selected organic
Goodyear.126
acids.
Other hydrocarbons. Production of long chain hydrocar- Lactic acid. Lactic acid is a well-recognized biobased chem-
bons from Botryococcus braunii, a green microalga, has been ical, commercially produced by glucose fermentation using
suggested as a biological source of hydrocarbons and ether organisms such as Lactobacillus delbrueckii,135 as well as other
lipids. Depending on the race of B. braunii, hydrocarbons, ether organisms and biomass sources.136 Current commercial fer-
lipids, epoxides, triacylglcerols or sterols have been identified. mentation gives about a 90% yield of calcium lactate based
The biosynthesis of botryococcene hydrocarbons has been on glucose fed, which is neutralized to give pure lactic acid.
examined, and is suggested to proceed through a nonmevalonate The neutralization produces approximately 1 ton of CaSO4 for
formation of isoprenoid building blocks.127 Currently, large- every ton of lactic acid, presenting a waste disposal problem in
scale cultivation of these species has not proven economically commercial operation. Alternative separation and purification
viable, but advances in genetic engineering of these materials as technologies based on desalting and water splitting electrodial-
a potential solution to the limiting factors has been reviewed.128 ysis have been examined to eliminate the neutralization step.135
Bioproduction of long chain hydrocarbons was reported More recently, engineered yeast species, such as Pichia stipitis
using a bacterium isolated from sewage disposal sludge and have been reported to ferment xylose to lactate.137 The process
identified as Vibrio furnissii. Using short chain fatty acids offers the possibility of converting all lignocellulosic sugars to a
as the feedstock, extracellular production of hydrocarbons high value chemical, and performing the fermentation at lower
ranging from C15 to C24 in yields as high as 120% of cell pH, perhaps eliminating the need for subsequent neutralization.
dry weight was observed.129 Further examination showed that The primary use for lactic acid is the production of polylactic
V. furnissii M1 could produce a variety of hydrocarbons using acid (PLA, Fig. 5). Although lactic acid can undergo direct
either volatile organic acids or sugars commonly found in polymerization, the process is more effective if lactic acid is
organic waste sources.130 The mechanism of formation was first converted to a low molecular weight pre-polymer (MW ~
suggested to be a stepwise reduction of the starting organic 5000) and then depolymerized to the lactide. A wide range of
acid group to the aldehyde, alcohol, and finally, alkane.131 catalysts is known to promote the lactide polymerization.138,139
More recently, attempts to reproduce this work have failed to The resulting polymer exhibits performance properties similar to
produce alkanes using V. furnissii.132 Further work is necessary to or exceeding polystyrene, a storage resistance to fatty foods and
confirm whether the original observations are accurate. Several dairy products equivalent to polyethylenterephthalate, excellent
Fig. 5 Overview of lactic acid conversions.
Fig. 6 Succinic acid as a platform chemical.
barrier properties for flavors and aromas, and good heat various pyrrolidinone derivatives. As with lactic acid, succinic
sealability.140 Cargill-Dow has published an extensive life cycle acid is isolated initially as a salt. Electrodialysis has been
analysis of the polymer.141 examined as a means to convert the salt to the corresponding
Lactic acid has been suggested as a platform chemical for acid while minimizing waste. Direct hydrogenation of the
the production of several downstream chemicals. Lactic acid aqueous fermentation broth has also been studied.153 Succinic
undergoes ready esterification to give lactate esters, of interest acid is a component of biobased polymers, such as nylons or
as new “green” solvents.142 Catalytic reduction of lactic acid polyesters.154,155 A recent publication describes the conversion of
leads to propylene glycol, which can be further dehydrated to succinic acid into a new polyester for coating applications upon
give propylene oxide. Alternatively, lactic acid can be dehydrated polymerization with isosorbide, a renewable building block also
to give acrylic acid and esters, but in practice this conversion available in high yield from glucose.156 The market potential for
proceeds in low yield.143 Lactic acid can be spun using wet, dry, succinic acid and its immediate derivatives has been projected
and electrospinning techniques to give biodegradable fibers for to be as much as 245 ¥ 103 tonnes per year, with an estimated
apparel, furniture, and biomedical materials, such as dissolving market size for succinic acid-derived polymers being as high as
sutures.144 New nanostructural materials prepared from lactic 25 ¥ 106 tonnes per year. The use of succinic acid as a platform
acid using electrospinning have found use in neural tissue chemical is summarized in Fig. 6.
engineering.145
3-Hydroxypropanoic acid and 3-hydroxypropionaldehyde.
Succinic acid. Succinic acid is a widely investigated chemical Glycerol is converted to 3-hydroxypropionaldehyde (3-HPA)
building block available from biochemical transformation of via fermentation.157 Although research on 3-HPA is still ex-
biorefinery sugars.146 Using Anaerobiospirillum succinicipro- ploratory, it is of interest as the central component in a network
ducens as the fermentative organism and a three stage con- of several high volume biorefinery products. Bioproduction of
tinuous cell recycle bioreactor, optimized processes produc- HPA suffers from product inhibition because of its toxicity.158
ing 10.4 g L-1 h-1 and a final concentration of 83 g L-1 , New processes mediate its toxic effects, including product
equivalent to 1.35 mol succinic acid per mol sugar have been removal during fermentation,159 conversion of 3-HPA into
reported.147 Recent investigations using engineered Mannheimia its semicarbazide derivative in situ after fermentation with
succiniciproducens have commercial potential, as high yields of Klebsellia pneumonia,160 or fermentation using Lactobacillus
succinic acid are observed with little or no formation of acetic, reuteri. In aqueous solution, L. reuteri exhibits significantly
formic or lactic acid byproducts.148 Recombinant E. coli also higher tolerance toward 3-HPA than other organisms and
gives effective production of succinate from glucose (1.3 moles converts glycerol to reuterin, a natural antimicrobial that is an
succinate per mol glucose).149 The process has been licensed equilibrium mixture of 3-HPA, 3-HPA hydrate, and the 3-HPA
by Roquette, and is part of a Roquette/DSM joint venture to dimer. The antimicrobial properties of reuterin have been used
commercialize succinic acid by the end of 2009.150 An alternative in the food industry to inhibit growth of Listeria or E. coli in
E. coli strain originally developed by the US Department meat and dairy products.
of Energy151 has been licensed by Bioamber, which recently Fig. 7 summarizes several possible derivatives of 3-HPA.
commissioned a 2000 tonne per year production facility.152 Large scale use of 3-HPA would result from combining the high
Succinic acid offers strong potential as a platform chemical. yield of 3-HPA from L. reuteri or other processes with con-
Succinate esters are precursors for known petrochemical prod- ventional catalytic hydrogenation to give 1,3-propanediol.161–163
ucts such as 1,4-butanediol, tetrahydrofuran, g-butyrolactone or A one-pot approach is possible, as 3-HPA hydrogenations in
Fig. 7 Production of 3-HPA and related derivatives.
aqueous solution have been reported.164 Alternatively, 3-HPA a proprietary two reactor system to minimize conditions suitable
is a precursor to acrolein and acrylic acid. Heating of aqueous for side product formation.174 Reactive extraction of levulinic
3-HPA solutions gives acrolein, the current industrial precursor acid from aqueous media with a family of different solvents
to acrylic acid. However, no commercial process based on this containing Amberlite LA-2 has been investigated as a means
technology has been developed.165 to improve isolation and purification.175 Recently, production
3-HPA is also a precursor to 3-hydroxypropanoic acid, which of levulinic acid from lignocellulosic feedstocks such as wheat
has been observed in low concentrations from a number of straw and water hyacinth has been reported.176,177 The latter work
biosynthetic conversions of glycerol.166 Catalytic dehydration of showed good agreement between experimentally observed rates
3-hydroxypropionic acid forms acrylic acid and acrylate esters.167 and the kinetic models established in earlier studies, to give a
A recent study has described potential routes and an economic 53% molar yield of levulinic acid.
evaluation for the direct biochemical production of acrylate The use of levulinic acid as a platform chemical continues to
based on the observation of the acrylate coenzyme A ester be studied.178 Manzer has reported elegant, high yield catalytic
as a common intermediate in several metabolic pathways.168 transformations of levulinic acid into substituted pyrrolidones,
Research has been carried out to engineer appropriate metabolic lactones and levulinate esters.179 Supported heteropoly acids
pathways to favor acrylate production, but yields remain (HPAs) have been investigated as catalysts for the conversion of
low.169,170 levulinic acid into diphenolic acid, a potential green replacement
for bisphenol A in the production of polycarbonates.180 With
Levulinic acid. Levulinic acid is of interest as a primary
Cs substituted HPAs, diphenolic acid selectivities of greater
biorefinery building block and platform chemical because of its
than 80% for the para, para isomer at 30–40% conversion have
simple and relatively high yield production from acid treatment
been reported.181 Ketals of levulinic acid are being investigated
of C6 sugars. However, its isolation and purification can be
commercially by Segetis as a source of new biobased monomers
complicated by the presence of intractable materials. Accord-
and polymers for applications as solvents, polyurethanes and
ingly, the complex mechanism behind its formation continues
thermoplastics.182 Acid-catalyzed reaction of levulinic acid with
to be investigated (Fig. 8). Heeres and coworkers have reported
glycerol affords good yields of a polymeric material that is
a series of kinetic investigations on the formation of levulinic
cleaved by subsequent treatment with NaOMe in MeOH.183
acid and its intermediates from both monomeric sugars and
cellulose. Formation of levulinic acid proceeds by initial loss of
Sugar alcohols
water to form HMF as an intermediate. Readdition of water
to HMF induces ring cleavage to form levulinic acid and an Xylitol. Xylitol is prepared commercially by catalytic hydro-
equivalent of formic acid. Kinetically accessible reactions also genation of xylose but several biochemical reductions have also
drive formation of intractable humins from the starting sugar been investigated. Although biochemical reduction cannot yet
or intermediate HMF.171–173 The results of the mechanistic study compete with chemical reduction economically,184 an important
suggest that ideal conditions for levulinic acid formation from advantage would be the ability to use crude biomass hemicel-
glucose may be obtained with dilute sugar solutions and high lulose hydrolysate (the primary source of xylose) as a starting
acid concentrations. material, rather than isolated and purified xylose. Engineered
High yield industrial production of levulinic acid from C6 Saccaromyces cerevisiae and various Candida yeasts have been
polysaccharides has been achieved by Biofine Renewables using examined, with Candida having the advantage of being natural
Fig. 8 Formation and transformations of levulinic acid.
xylose consumers, and being better able to maintain the redox of sorbitol to light alkanes via aqueous phase reforming.191
balance necessary for high yield xylitol production.185,186 Xylose Pt/Al2 O3 is the preferred catalyst for the transformation, and
concentrations of up to 38 g L-1 were observed in batch systems promotes conversion of sorbitol into hexane at 50% selectivity.
using engineered E. coli expressing xylose reductase from The remainder of the sugar is converted to lighter materials
C. boidinii.187 An issue in biochemical and chemical production (Fig. 9). The bifunctional catalyst induces several reactions.
of xylitol is the parallel reduction of arabinose frequently Sorbitol is dehydrated on the catalyst’s acidic sites, and the
present in hemicellulose solutions used as starting material. The resulting intermediates are hydrogenated on the metal sites.
formation of arabinitol as a side product complicates product Through several dehydration and reduction cycles, sorbitol is
isolation. Using directed evolution of fungal sources of xylose converted to hexane. Reforming of the sorbitol on metal sites
reductase, a mutant was identified that exhibited a 16.5-fold leads to the formation of CO2 and H2 , which is converted to
preference for xylose over arabinose. When expressed in E. coli, methane. Light hydrocarbons result from hydrogenolysis of the
highly selective production of xylitol from a mixed solution of sorbitol.
xylose and arabinose was observed.188
Sorbitol. Biochemical production of sorbitol has also been

investigated, although chemical reduction of glucose is well
established and produces over 500 000 tons of sorbitol per year.
A number of high yielding biochemical routes to sorbitol have
been reported, focusing primarily on Zymomonas mobilis as
the fermenting organism. Starting from sucrose or mixtures of
fructose and glucose, production of sorbitol and gluconic acid
as co-products in nearly quantitative yield has been observed.189
More recently, efficient conversion of glucose to sorbitol in
97% of the theoretical yield using resting cells of an engineered
Lactobacillus plantarum has been reported.190
Sugar alcohols are promising intermediates for the production
of hydrocarbons as drop-in products for the petrochemical refin- Fig. 9 Proposed intermediates in the aqueous phase reforming of
ery. Huber and Dumesic have reported the chemical conversion carbohydrates to light alkanes.
View Article Online
Concluding comments prospect for a similar outcome within a mature biorefining

industry.
Integrating biobased products into the biorefinery faces a
tension between “what structures result easily from a given tech-

nology?” (i.e., a lack of conversion processes) and “what product
Notes and references
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