Paul G.

Blommel Production of  
and
Randy D. Cortright
Virent Energy Systems, Inc.
Conventional Liquid  
Madison, WI 53704, USA

August 25, 2008

Fuels from Sugars 
A white paper describing the conversion of biomass-derived sugars to conventional liquid fuels through a
multistep catalytic process.

Abstract
Virent Energy Systems, Inc. has discovered and is now developing innovative and novel catalytic
methods to convert plant sugars into high-energy hydrocarbons mixtures that can be used directly or
blended seamlessly to make conventional liquid fuels. The methods utilize Virent's patented Bio-
Forming® technology to produce renewable gasoline, diesel, and jet fuel from a wide range of bio-
mass feedstocks, including non-food varieties. The BioForming platform expands the utility of the
aqueous phase reforming (APR) process by combining APR with catalysts and reactor systems simi-
lar to those found in standard petroleum oil refineries to convert sugar-based compounds into non-
oxygenated hydrocarbons mixtures. The hydrocarbon mixtures have significantly higher volumetric
energy content than ethanol, do not require the energy intensive dewatering steps associated with
ethanol production, and can be brought to market using the current petroleum infrastructure and
pipelines, which are not available to the ethanol industry. Preliminary economic analysis suggests
that converting sugars to conventional liquid fuels using Virent’s BioForming process can economi-
cally compete with petroleum fuels at crude oil prices greater than $60/bbl.

BioForming Platform……….2 Background

Biomass Pretreatment………4 Conventional liquid fuels. Conventional liquid fu-
Hydrotreating………………5 transportation fuels, such as els are produced by first frac-
gasoline, jet fuel and diesel tionating crude oil into differ-
Aqueous Phase Reforming….5
fuel, are essential for modern ent boiling point fractions in-
Condensation Pathways to economies. Over the last 100 cluding light ends, straight run
Liquid Fuels………………...6 years, increasing demand for gasoline, naphtha, middle dis-
transportation fuels has re- tillates and resid. The fractions
Base Condensation…………8
sulted in significant advance- are then collected and/or up-
Dehydration/ ments in the development and graded by proven catalytic
Olgimerization…………….11 optimization of crude oil refin- processes such as hydrotreat-
ing technologies for the eco- ing, olefin formation, conden-
Summary…………………..11
nomic production of liquid sation (including alkylation) of
light hydrocarbons to form heavier hydrocar- ethanol.
bons, and reforming of low octane hydrocar-
Ethanol produced via fermentation of
bons to hydrogen, aromatics and branched hy-
carbohydrates is a well established renewable
drocarbons. The resulting product streams are
transportation fuel, although, ethanol has some
often blended to generate a mixture of hydrocar-
drawbacks. The fuel provides a low net energy
bons appropriate for gasoline, jet fuel or diesel
return on energy invested [1], has a lower volu-
fuel. Such fuels contain mixtures of compounds
metric energy content than hydrocarbon-based
made up of only carbon and hydrogen
gasoline, and cannot be readily integrated into
(hydrocarbons), thus providing the highest volu-
the existing fuel infrastructure. Other biofuel
metric energy density, high storage stability, and
alternatives are needed that can more effectively
vapor pressure and/or freezing point character-
capture the energy contained in biomass and
istics required for the particular fuel application.
that can use today’s infrastructure to deliver cost
Renewable replacements for gasoline, -effective, environmentally-friendly fuels to mar-
diesel and jet fuel are needed to maintain global ket.
economic activity while addressing environ-
Virent’s BioForming® Platform
mental and energy supply concerns. Plants ex-
ploit carbohydrates, i.e., sugars and starches, for Virent discovered in early 2006 that it is
either energy storage or as building blocks for possible to integrate aqueous phase reforming
structural materials, such as cellulose and hemi- (APR) with proven catalytic processing tech-
cellulose. As a consequence, carbohydrates are nologies to generate hydrocarbons for direct use
the most widely distributed, naturally occurring as a biofuel or as blending components for con-
organic compounds on Earth, and hold consid- ventional liquid fuels (gasoline, jet fuel, and die-
erable potential to serve as a primary energy sel) [2-5]. Virent has previously reported meth-
source. They are highly reactive and readily oxi- ods for the renewable production of alkanes and
dized by living organisms to generate energy, hydrogen from biomass derived carbohydrates
carbon dioxide and water. Commercial biofuel [6, 7], and recently reported methods for the
generation technologies attempt to utilize the renewable production of oxygenated compo-
naturally occurring biocatalytic capabilities of nents, such as alcohols, ketones, aldehydes, fu-
various living organisms, optimized through rans and other polyols [8].
natural selection and genetic engineering, to
Virent’s aqueous-phase reforming meth-
maximize the conversion of sugars into ethanol.
ods utilize heterogeneous catalysts at moderate
In these biocatalytic applications, the presence
temperatures (450 to 575 K) and pressures (10
of oxygen in the molecular structure of the car-
to 90 bar) in a number of series and parallel re-
bohydrate contributes to the reactivity of the
actions to reduce the oxygen content of the car-
sugar. Ethanol fermentation processes take ad-
bohydrate feedstock. The reactions include: (1)
vantage of this highly reactive nature to produce
reforming to generate hydrogen; (2) dehydroge-
ethanol. Through fermentation, the highly reac-
nation of alcohols/ hydrogenation of carbonyls;
tive sugars are essentially de-functionalized to
(3) deoxygenation reactions; (4) hydrogenolysis;
generate the partially oxidized hydrocarbon–
and (5) cyclization. A key feature of this

2
 method is the use of in-situ generated hydrogen lytic hydrotreating and catalytic condensation
[6] for the de-functionalization of the highly re- processes, including ZSM-5 acid condensation,
active carbohydrate to a less reactive mono- base catalyzed condensation, acid catalyzed de-
oxygenated species. Virent has found that the hydration, and alkylation. Like a conventional
mono-oxygenated species (e.g., alcohols, ke- petroleum refinery, each of these process steps
tones, and aldehydes) can be converted to non- in the BioForming platform can be optimized
oxygenated hydrocarbons in a continuous proc- and modified to produce a particular slate of
ess using conventional catalytic condensation desired hydrocarbon products. For example, a
and hydrotreating techniques. Virent has now gasoline product can be produced using a zeolite
advanced the integration of APR with these (ZSM-5) based process, jet fuel and diesel can be
conventional catalytic processes to provide produced using a base catalyzed condensation
Virent’s BioForming® platform for converting route, and a high octane fuel can be produced
water soluble carbohydrates to renewable liquid using a dehydration/oligomerization route.
fuels having the same volumetric energy value as The key enabling step in the BioForm-
fossil fuel derived liquid fuels. Virent currently ing process is the APR step, which converts wa-
holds over 50 pending or issued patents in the ter soluble carbohydrates into hydrogen, lower
U.S. and abroad covering all aspects of this tech- alkanes, and high yields of condensable chemical
nology. intermediates. Once formed, the chemical inter-
The BioForming process, as depicted in mediates undergo further catalytic processing to
Figure 1, is based on the novel combination of generate the hydrocarbons for gasoline, jet fuel,
Virent’s core APR technology with conventional or diesel, or chemicals for use in other industrial
catalytic processing technologies such as cata- applications. The hydrogen is used in the pro-

Figure 1. Virent’s BioForming® process to produce conventional liquid transportation fuels from biomass
feedstocks. APR enables the process to partially defunctionalize carbohydrate feedstocks for
further catalytic upgrading.

3
duction of the condensable chemical intermedi- 3.7 C5H10O5→ isoC12H26 + 10.5 CO2+ 5.5 H2O
ates, with any excess recycled for use in upgrad-
0.875 C12H22O11→ C8H10 + 2.5 CO2 + 4.6 H2O
ing aqueous solutions of complex sugars (C5 and
C6 sugar mixtures) or biomass hydrolysate prior Based on the above stoichiometry it can be seen
to processing in the APR reactor, or down- that it is theoretically possible for the resulting
stream in later process applications. The lighter hydrocarbons to capture 64% of the carbon
alkanes, such C1-C4 fuel gases, are useful for from the carbohydrates and over 94% of the
providing process heat so as to minimize the sugar lower heating value.
need for external fuel resources. Figure 1 illus-
Biomass Pretreatment
trates the BioForming platform, including the
integration of potential biomass pretreatment The BioForming process can convert a
technologies, catalytic hydrotreating, APR, and broad range of carbohydrates, including carbo-
various catalytic condensation processes. hydrates derived from non-food biomass, into
conventional liquid fuels. The feedstock is a
Unlike traditional biocatalytical proc- solution of water and water soluble oxygenated
esses, which are limited to working with only hydrocarbons (e.g., sugars, sugar alcohols, sac-
one specific sugar type, the BioForming process charides and other polyhydric alcohols). The
is able to convert a broad range of carbohy- oxygenated hydrocarbons can originate from a
drates into conventional liquid fuels. The Bio- variety of sources, such as sugar crops, grain
Forming process is not plant or carbohydrate crops, agricultural wastes (corn stalks, straw,
restrictive, but able to process any type of plant seed hulls, sugarcane leavings, bagasse, nutshells,
sugar once reduced to its water soluble form. and manure from cattle, poultry, and hogs),
Potential carbohydrates include sucrose (from wood materials (wood or bark, sawdust, timber
sugar cane or sugar beets), corn sugar (glucose slash, and mill scrap), municipal waste (waste
from conversion of corn starch), sugars derived paper and yard clippings), and energy crops,
from hydrolysis of hemicellulose and cellulose such as poplars, willows, alfalfa, switch grass,
(including polysaccharides, organic acids, and prairie bluestem, corn, soybean, and the like.
furfural byproducts), and water soluble oxygen-
ated compounds such as diols, glycerol and Prior to being fed into the BioForming
sugar alcohols. process the biomass is generally first processed
to extract the sugars or starches contained
The energy conversion benefits of the within the plant matter. For instance, lignocellu-
BioForming process can be understood by losic biomass will typically undergo fractionation
evaluating the stoichiometry of the overall proc- and pretreatment to separate the cellulose, hemi-
ess. For illustration purposes, the cellulose, and lignin. The fractionated cellulose
stoichiometries for two reactions (non-food xy- and hemicellulose is then further processed to
lose (C5H10O5) to a branched hydrocarbon with generate 5 and 6 carbon sugars using any one or
12 carbons (iso C12H26) for jet fuel blending and more of the various enzymatic or acid hydrolysis
sucrose (C12H22O11) to a high octane xylene techniques currently available. In most cases,
(C8H10) for gasoline blending): the lignin is combusted to provide energy for
the biorefinery or to produce electricity.

4
 Hydrotreating drogen, carbon dioxide, alcohols, ketones, alde-
hydes, and byproduct alkanes, organic acids, and
Depending on the particular application,
furans [8]. The aqueous-phase reforming proc-
the water soluble carbohydrates may undergo an
ess operates at moderate temperatures (450 to
initial hydrotreating step to convert the sugars
575 K) and pressures (10 to 90 bar), thereby
and organic acids into polyhydric alcohols. This
providing significant process efficiencies and
step consists of either hydrogenation [9, 10] to
beneficial operating conditions. At these condi-
form polyhydric alcohols or hydrogenolysis [11,
tions, a number of thermodynamically favorable
12] to form shorter-chain oxygenated com-
series and parallel reactions occur that reduce
pounds, such as glycerol, propylene glycol, ethyl-
the oxygen content of the oxygenated hydrocar-
ene glycol, etc. The hydrotreating step can use
bon to a more favorable intermediate product
hydrogen from an external source, hydrogen
for the downstream condensation reactions.
generated in situ using APR, or excess hydrogen
Without being held to a single theory, it is be-
recycled from the system.
lieved that the reactions include: (1) reforming
to generate hydrogen; (2) dehydrogenation of
Aqueous Phase Reforming alcohols/ hydrogenation of carbonyls; (3) de-
oxygenation reactions; (4) hydrogenolysis; and
Aqueous Phase Reforming (APR) is the
(5) cyclization. One key feature of this process
key step in the BioForming process. The aque-
is that the hydrogen is generated in-situ [6] and
ous product stream from the hydrotreating step
used to further de-functionalize the highly reac-
above is fed to the APR reactor where the oxy-
tive carbohydrate to the less reactive mono-
genated hydrocarbons react with water over a
oxygenated species–alcohol, ketones, and alde-
proprietary heterogeneous catalyst to form hy-

Figure 2. Carbon number and classification of intermediate products of sucrose conversion through hydro-
genation and APR.

5
hydes. results in a slightly lower estimate of hydrogen
produced to CO2 generated, 2/1.
The generation of hydrogen and con-
densable intermediates by APR is the critical Condensation Pathways to Liquid Fuels
step in the overall BioForming process. Figure
While oxygenates generated by APR are
2 shows the range of oxygenates generated from
generally limited to six or fewer carbon atoms,
a sucrose solution through consecutive deoxy-
their chemistries support the formation of car-
genation and APR processing. In this study, an
bon-carbon bonds and the production of hydro-
aqueous solution of sucrose was hydrogenated
carbons appropriate for liquid fuels. One bene-
over a Ru/C catalyst into a sorbitol/mannitol
fit of the BioForming process is that the system
mixture. The mixture was reacted across a zir-
and operating conditions can be readily modi-
conia supported Pt/Re catalyst. Approximately
fied to produce different intermediate com-
35% of the feed carbon was converted to CO2,
pounds appropriate for use in downstream con-
resulting in the production of the compounds
densation reactions structured to produce the
shown in Figure 2 and 0.76 moles of hydrogen
desired final liquid fuel product or chemical.
per mole of sugar monomer. The data shows
Depending upon the particular condensation
that besides the C1 through C6 alkanes, the APR
technologies employed, the BioForming process
catalyst system generated an oxygenated inter-
can generate hydrocarbons for gasoline, jet fuel,
mediate stream containing alcohols, ketones,
diesel fuel, or other industrial applications.
acids, and cyclized components suitable for con-
densation to longer-chain hydrocarbons. Acid Condensation (ZSM-5)

Hydrogen produced by APR may exit The BioForming process can convert
the system as molecular H2 or be consumed by alcohols, ketones, aldehydes, and organic acids
hydrogenation reactions. The total amount of to gasoline-range hydrocarbons, including aro-
reforming that has occurred within the reaction matics and isoalkanes, via direct catalytic con-
system (and thus the hydrogen generated in situ) densation over acid catalysts, such as solid acids
can be determined through overall reaction and zeolites [13-17]. In the case of a zeolite
stoichiometry. For sorbitol the stoichiometry is ZSM-5 catalyst, a series of reactions occurs, in-
as follows: cluding: (a) the dehydration of oxygenates to
alkenes; (b) oligomerization of the alkenes; (c)
C6H14O6 + 6 H2O -> 13 H2 + 6 CO2 cracking; (d) cyclization and dehydrogenation of
For each mole of CO2 generated, the overall larger alkenes to form aromatics; (e) alkane
stoichiometry of sorbitol reforming dictates that isomerization; and (f) hydrogen-transfer to form
13/6 mole of hydrogen was produced. Note alkanes [18, 17]. While most of the product hy-
that under these conditions, the water gas shift drocarbons have gasoline-range boiling points,
equilibrium heavily favors CO2 and H2. For this the heavier compounds can be separated by dis-
reason, carbon monoxide is only present at trace tillation and blended into jet fuel.
levels and may be excluded from the analysis. Virent has demonstrated the integration
Incomplete reforming, i.e. sorbitol to xylitol, of APR with a condensation step in a continu-
C6H14O6 + H2O -> CO2 + 2 H2 + C5H12O5 ous process for the conversion of sucrose and

6
xylose into gasoline-range hydrocarbons using a hydrogen stream was immediately passed over a
proprietary APR catalyst and ZSM-5. A reactor Pt/Re/Carbon APR catalyst at 523 K, where the
system containing four different catalyst beds sugar alcohols reacted with water to generate
operating at the same pressure and with no in- hydrogen, light alkanes, and condensable oxy-
termediate separations (Figure 3A) was used to genates. The resulting effluent was heated to
demonstrate the integrated process. 648 K and passed over two acid catalysts, tung-
stated zirconia and ZSM-5, where the oxygen-
Each catalyst bed operated at different ates were dehydrated and underwent a series of
temperatures and promoted different reactions. acid-catalyzed reactions to form the hydrocar-
External hydrogen was used to hydrogenate the bon products shown in Figure 3B. Importantly,
sucrose/xylose mixture to corresponding sugar 93% of the lower heating value of the sugar and
alcohols over a Ru/carbon hydrogenation cata- hydrogen feed was recovered in the products,
lyst. The combined water, sugar alcohol, and

Figure 3. Panel A illustrates the catalytic steps used to convert sucrose and xylose to gasoline-range
hydrocarbons. Panel B summarizes the molar carbon and heating value yields of the re-
sulting products.

7
with 59% of this heating value contained in hy- hydroxyaldehyde; (2) β-hydroxyketone or β-
drocarbons having greater than 5 carbons. hydroxyaldehyde dehydration to form a conju-
gated enone; (3) hydrogenation of the conju-
Figure 4 shows the breakdown by car-
gated enone to form a ketone or aldehyde,
bon number of hydrocarbon species generated,
which may be further condensed or hydrogen-
with the majority being alkanes or aromatics. In
ated to an alcohol; and (4) the removal of hy-
addition, low levels of alkenes, oxygenates and
droxyls by dehydration/hydrogenation or hydro-
cyclic alkanes were observed in the product
genolysis to form alkanes. This multi-functional
stream. Although hydrogen was fed into the
process enables the generation of longer
system prior to hydrogenation, 60% of the hy-
branched-chain hydrocarbons from shorter-
drogen required for deoxygenation was pro-
chain oxygenated compounds[20-23]. The re-
duced in situ by APR.
sulting hydrocarbon mixture is primarily in the
Base Condensation jet fuel-range, but the product can be distilled to
provide gasoline and diesel fuel fractions as well.
The BioForming process is also able to
convert alcohols, ketones, and aldehydes into jet Carbon-carbon bonds are formed in
fuel range hydrocarbons via direct catalytic con- base condensation reactions by the catalytic
densation over a base catalyst. In this applica- processing of oxygen-containing precursors
tion, oxygenates are passed over multifunctional through aldol and decarboxylative condensation.
solid-base catalysts to promote condensation Many oxygenates generated by APR, including
reactions to occur, including: (1) aldol condensa- alcohols, carbonyls, and acids, can be condensed
tion to form a β-hydroxyketone or β- through these reactions [23-25]. In general,

Figure 4. Carbon number distribution and classification of products from sucrose and xylose conver-
sion to hydrocarbons using a four step, continuous catalytic process.

8
aldol condensation is equilibrium limited and ates generated by APR. The overall alkane
more favorable at lower temperatures. How- forming reaction starting from 2-pentanone
ever, by coupling the condensation with hydro- would be: 2C5H10O + 3 H2 Î C10H22 + 2
genation of the resulting condensed product, H2O. This reaction is very favorable at moder-
high yields of hydrocarbons appropriate for ate temperatures, with free energy changes rang-
gasoline and jet fuel can be obtained at higher ing from -146 KJ/mole at 300K to -45 KJ/mole
temperatures. Figure 5 shows equilibrium con- at 700K. Two zinc aluminate catalysts were de-
versions for aldol condensation and coupled veloped to complete this process, operated at
aldol condensation and hydrodeoxygenation. 573K to 648K and at 42 bar pressure. The first
The aldol condensation of acetone becomes less catalyst possessed basic and metal functions to
favorable as temperatures are increased (solid accomplish condensation, dehydration, and
line). When coupled with dehydration and hy- enone hydrogenation. A second catalyst, placed
drodeoxygenation, the overall reaction is more downstream from the first and possessing basic,
favorable as shown by the dash-dot series for acidic, and metal functions, hydrogenated the
acetone and the dotted line series for 2- condensed ketones from the first step to al-
pentanone. kanes. Mixed acid-base functionality was
achieved by lowering the ratio of zinc oxide to
The potential of base catalyzed conden- alumina. Deoxygenation reactions were also
sation coupled with hydrogenation to produce promoted through substitution of palladium
longer-chain alkanes was demonstrated using with platinum. The multiple functionalities de-
model feeds containing 3 and 5 carbon oxygen- signed into the second catalyst worked together

Figure 5. Equilibrium conversions for aldol condensation, coupled aldol condensation, and hydrode-
oxygenation.

9
as follows: the basic sites supported further con- Hydrogen was combined with the feed
densation and reacted carbonyls with hydrogen at a ratio of 2 moles of hydrogen per mole of
to form alcohols; and the acidic sites promoted feed. With 100% 2-propanol feed delivered at
the dehydration of alcohols formed on basic and WHSV=1, the reaction system yielded 78% con-
metal sites to form alkenes; the metal sites satu- densation products (those containing 4 or more
rated alkenes to alkanes and may have partici- carbon atoms) on a molar carbon basis, with
pated in the hydrogenation of carbonyls to alco- 90% of the conversion products being al-
hols, both reactions requiring hydrogen. kanes. Likewise, a pure 2-pentanone feed re-

Table 1. Results from characterization of coupled condensation/hydrodeoxygenation product produced

from 3-, and 5- carbon oxygenates.

10
sulted in 58% yield of condensed products solid phosphoric acid or zeolite catalysts [26].
(those containing 6 or more carbons), with In this case, the oxygenates derived from the
>95% of these being alkanes. Mixed feeds con- APR process are converted into paraffins and
taining 2-propanol, acetone, and 2-pentanone olefins through dehydration reactions and/or
showed similar results. In all cases, a second successive hydrogenation-dehydration reactions.
pass through the system of the first pass product In dehydration cases, alcohols are further de-
resulted in essentially complete deoxygenation to functionalized to olefins by the removal of the –
yield >99.5% hydrocarbons. OH group through the interaction between the
hydroxyl group and acid sites on the dehydra-
The products from these experiments
tion catalyst. If ketones, acids and aldehydes are
were combined and fractionated in a batch labo-
present, they too can be defunctionalized by first
ratory still, reserving the material with boiling
reducing the carbonyl compound in the ketone,
points between 423K and 523 K. The material
acid or aldehyde to a primary or secondary alco-
was submitted for ASTM D1655 aviation tur-
hol by a hydrogenation reaction involving the
bine fuel analysis. Detailed results of that analy-
introduction of H2 over a hydrogenation cata-
sis are shown in Table 1. All specifications were
lyst, followed by a subsequent dehydration reac-
met except for the flash point, due to inadequate
tion as described above to provide olefins and,
removal of light components in the laboratory
in some instances, paraffins.
still and the density, due to low aromatic con-
tent. Note that the fuel’s freeze point was <-70° Summary
C, the testing method’s limit. Some unconven-
tionally produced jet fuels (primarily those pro- In summary, APR integrated with con-
duced by Fischer-Tropsch chemistry) have diffi- ventional catalytic processing can convert bio-
culty meeting this important characteristic due mass-derived sugars to hydrocarbons for use as
to high normal alkane content. The majority of conventional gasoline, jet fuel, and diesel fuel.
alkanes produced through aldol condensation With crude oil prices currently over $100/bbl,
contain a single branch, significantly reducing these integrated processes provide a cost-
their freeze points. The C9+ aromatics from the effective method for generating conventional
ZSM-5 condensation process and the moder- liquid fuels from non-food biomass, resulting in
ately branched alkanes from the base condensa- increased energy efficiencies and lower CO2
tion route can be combined to produce a com- footprints. By altering conditions and catalysts,
plete biomass-derived aviation turbine fuel that the BioForming® process can be easily tailored
meets current fuel specifications. to produce the specific desired liquid fuel. The
BioForming process uses a wide variety of food
Dehydration/Olgimerization and non-food sugars, broadening the range of
cost-effective feedstocks available for conver-
Dehydration of alcohols produced by
sion to fuels. Unlike ethanol, the process uses
APR can also generate alkenes as feedstocks for
minimal energy to generate fuels compatible at
alkylation or condensation. Alkenes may also be
high blends with today’s engines, fuel pumps,
dimerized to produce gasoline-range product or
and pipelines. The biofuel product separates
oligomerized for kerosene or diesel fuel using
naturally from water, thereby eliminating the

11
energy-intensive distillation step required in
ethanol processes and providing more net en-
ergy, and match petroleum fuels in composition,
functionality, and performance. These advan-
tages position the BioForming process to pro-
vide a cost effective renewable fuel with minimal
impact on global food and water resources.

12
1. Hammerschlag, R., Ethanol’s Energy Return on Investment: A Survey of the Literature 1990-Present,
Environmental Science & Technology, 2006. 40(6): p. 1744-1750.
2. Cortright, R.D., Blommel, P.G., Synthesis of Liquid Fuels and Chemicals from Oxygenated Hydrocarbons,
(Publication No. US 2008/0216391, Published September 11, 2008).
3. Cortright, R.D., Blommel, P.G., Synthesis of Liquid Fuels and Chemicals from Oxygenated Hydrocarbons
(Publication No. WO 2008/109877, Published September 12, 2008).
4. Cortright, R.D., Blommel, P.G., Synthesis of Liquid Fuels and Chemicals from Oxygenated Hydrocarbons
(U.S. Application No. 12/044,908, Anticipated Publication Date of December 4, 2008).
5. Cortright, R.D., Blommel, P.G., Synthesis of Liquid Fuels and Chemicals from Oxygenated Hydrocarbons
(U.S. Application No. 12/044,876, Anticipated Publication Date of December 4, 2008).
6. Cortright, R.D., R.R. Davda, and J.A. Dumesic, Hydrogen from catalytic reforming of biomass-derived
hydrocarbons in liquid water, Nature, 2002. 418: p. 964-967.
7. Cortright, R.D., Vollendorf, N.W., Hornemann, C.C., McMahon, S.P., Catalysts and Methods for
Reforming Oxygenated Compounds, (Publication No. WO 2007/075476, Published July 5, 2007)
8. Cortright, R.D., Blommel, P.G., Methods and Systems for Generating Polyols, (Publication No. US
2008/0025903, Published January 31, 2008, and Publication No. WO 2008/069830, Published
June 12, 2008)
9. Gallexot, P., et al., Glucose Hydrogenation on Ruthenium Catalysts in a Trickle-Bed Reactor. J. Catal.,
1998. 180: p. 51-55.
10. Kluson, P. and L. Cerveny, Selective hydrogenation over ruthenium catalysts. Applied Catalysis A:
General, 1995. 128: p. 13-31.
11. Abreu, C.A.M., N.M. Lima, and A. Zoulalian, Catalytic Hydrogenolysis of Starch: Kinetic and Evaluation
of Selectivity in Polyol and Monoalcohol Formation. Biomass and Bioenergy, 1995. 9(6): p. 487-492.
12. Ling, G.V., C. Ruijterman, and J.C. Vlugter, Catalytic Hydrogenolysis of Saccharides. Carbohyd. Res.,
1967. 4: p. 380-386.
13. Chang, C.D., Mechanism of Hydrocarbon Formation from Methanol. Studies in Surface Science and
Catalysis, 1988. 36: p. 127-143.
14. Chang, C.D., Methanol to gasoline and olefins. Chemical Industries, 1994, 57: p. 133-173.
15. Chang, C.D., W.H. Lang, and A.J. Silvestri, Conversion of carbonyl compounds to aromatics. 1975, U.S.
patent 3,907,915.
16. Chang, C.D. and A.J. Silvestri, MTG. Origin, evolution, operation. CHEMTECH, 1987. 17(10): p.
624-631
17. De Klerk, A., R.J.J. Nel, and R. Schwarzer, Oxygenate conversion over solid phosphoric acid. Ind. Eng.

13
 Chem. Res., 46(8): p. 2377-2382.
18. Goguen, P.W., et al., Pulse-Quench Catalytic Reactor Studies Reveal a Carbon-Pool Mechanism in Methanol
-to-Gasoline Chemistry on Zeolite HZSM-5. J. Am. Chem. Soc., 1998. 120(11): p. 2650-2651.
19. Song, W., et al., An Oft-Studied Reaction That May Never Have Been: Direct Catalytic Conversion of
Methanol or Dimethyl Ether to Hydrocarbons on the Solid Acids HZSM-5 or HSAPO-34. J. Am. Chem.
Soc., 2002. 124(15): p. 3844-3845.
20. Chheda, J.N., G.W. Huber, and J.A. Dumesic, Liquid-phase catalytic processing of biomass-derived oxy-
genated hydrocarbons to fuels and chemicals. Angewandte Chemie - International Edition, 2007. 46(38):
p. 7164-7183.
21. Holmgren, J.S. and B.J. Arena, Solid Bases as Catalysts in Aldol Condensations. 1993: U.S. Patent
5,254,743.
22. King, F., G.J. Kelly, and E.H. Stitt, Improved base catalysts for industrial condensation reactions. Studies
in Surface Science and Catalysis, 2003. 145: p. 443 - 446.
23. Dooley, K.M., A.K. Bhat, C.P. Plaisance, and A.D. Roy, Ketones from acid condensation using supported
CeO2 catalysts: Effect of additives. Applied Catalysis A: General, 2007. 320: p. 122 - 133.
24. Chheda, J.N. and J.A. Dumesic, An overview of dehydration, aldol-condensation and hydrogenation processes
for production of liquid alkanes from biomass-derived carbohydrates. Catalysis Today, 2007. 123(1-4): p. 59-
70.
25. Huber, G.W., J.N. Chheda, C.J. Barrett, and J.A. Dumesic, Chemistry: Production of liquid alkanes by
aqueous-phase processing of biomass-derived carbohydrates. Science, 2005. 308(5727): p. 1446 - 1450.
26. Ipatieff, V.N., B.B. Corson, and G. Egloff, Polymerization, a New Source of Gasoline. Ind. & Eng.
Chem., 1935. 27(9): p. 1077 - 1081.

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