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t seemsthat everyoneis talkrng about advancedbiofuels,

p especiallyafter PresidentObama announcedlast year
--#"-thathis administrationwill take the necessarystepsto
foster biofuels researchand commercialization.In addition,
the U.S. Dept. of Energy(DOE) announcedthe releaseof
5786.5million in stimulusfundsunderthe AmericanRecovery and ReinvestmentAct of 2009 to accelerateadvanced
bioftiels research,development,and deployment.
The term advancedbiofuels refers tp fuels other than
com-basedethanolthat are derived from renewablebiomass
and whose greenhousegas (GHG) emissionsare no more
than half those of the fuei they replace.One of the most
common lypes of advancedbiofuels is celluiosic ethanol,
which is derived from the cellulose,hemicellulose,or lignin
that make up plant cell walls.
There are still many unknowns when it comesto cellulosic biofuels, but gne surething is that bioiogical engineers
are working togethertoward biofuei commercialization.
This months'SBE Supplementfocuseson variousaspectsof
producing lignocellulosic biofuels.
In the first feature article, Tim Eggeman and Can'ieAtiyeh provide an inhoduction to the U.S. biofuels industry and
the stridesit hasmadetoward displacingpetroleum-based
gasolinewith renewablealternatives.Ciirrently, the cellulosic
and advancedbiofuels industry is at a critical stageof development and deployment;the federalgovemmentwill play an
important role in facilitating their entry into the market.
In the secondarticle, Brad Cort, ThomasPschom,
and Bertil Shombergpoint out that even though uncertainties regardingprocesstechnology optimization exist,
commerciai-scaleequipmentalreadybeing used in the pulp
and paper industry can minimize scale-uprisks in biofuel
production from lignocellulosic feedstocks.
In the third article, Blake Simmons, SeemaSingh,
Bradley Holmes, and Harvey Blanch discussa new type
of pretreatmentfor breaking down cellulose.Pretreatment
is required to maximize ethanolyield, and most processes
employ acids,bases,steam,or heat.The new approach,
which uses'ionic liquids (saltscomposedof an anion and a
cation), reducesthe amount ofenzymes neededto achieve
high yields of glucosefrom lignocellulose.
The foulrthfeature.articlecomesfrom Michael Ladisch,
Nathan Mosier,Youngmi Kim, EduardoXimenes.and David
Hogsett.They describevarious biological, thermochemical,
and chemicaltechnologiesbeing developedto convertlignocelluiosic feedstockto liquid fuels and discusssomeof the

factors that must be consideredin developingeconomicprocesses,such as the feedstock,catalystrobustness,tradeoffs

betweenselectivify and conversionrate,and cost.
, AIChE's Institute for Sustainabilityhas beenexploring backgrounddata on establishingbiofuel metrics.The
RenewableEnergy Metrics Committee,under the leadership
of John Carberry,is working on metrics for the assessment
of biofliels developmentand use,with two primary goals:
to develop and adopt a cormon set of technically sor.tnd,
economically viable biofuels metrics that can be usedby the
federal interagencytask force workfng on energ,vmetrics;
and to identify enabling farming developmentsandrorprocessingtechnologiesthat would expandthe supply,improve
the economics,or improve the sustainabilityof biofuels. For
more information, visit www.aiche.com/ifs
SBE continuesits webinar seriesin 2010 with presentations from both academicand industry expertson a vanety
of exciting topics. Tune in to SangYup Lee's presentation
on systemsmetabologicengineeringonApr. 23 andChaitan
Khosla's discussionof modular biocatalysison June29.
For information aboutthe archived SBE webinars,visit
aspx.
www. aiche.org/SBElEducation/SBEwebinars.
Registernow for SBE's 2nd InternationalConference
on Stem Cell Engineering,May 2-5 in Boston,which
is co-chairedby PeterZands'tra(Univ. of Toronto) and
GeorgeDaley (Children's Hospitai Boston, HarvardMedical School).For more info, visit the conferencewebpageat
SBE is also co-sponsoringthe
www.aiche.orglstemcelleng.
5th InternationalConferenceon BioengineeringandNanotechnology in Biopolis, Singapore,Aug. l-4, chairedby ProfessorJackieYing (A*STAR lnstitute of Bioengineenngand
Nanotechnology).For details,visit www.icbn2010.com. Save
the datefor SBE's 3rd IntemationalConferenceon Biomolecular Engineering, which will take place at the Grand Hyatt
in San Franciscoon Jan. 16-19,2011. This conferenceis
co-chairedby Kurt Deshayes(Genentech)and JeffVamer
(Comell Univ.) We hope to seeyou at one of thesemeetingsl
SBE continuesto strive to becomea better societyfor
its members.If you have any ideasor commentq pleaseiet
me know at bio@aiche.org.We appreciateyour feedback
and value your involvement in making SBE a more dynamic
organization.If you aren't yet a member of SBE, simply go
to: http://bio.aiche.orgto check us out andjoin todayl
Miriam Codes-Caminero
Executive Director, SBE

th

GEP

March 2010 www.aiche.org/cep 35

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biofuelsindustryis at a
Theadvanced
anddeployment'
crlticalstaggof development

to
nergy drives every part of modem life' In addition
fuels
energy
potiAng factories,ofces,and homes,
'the
24-7 transportation and logistics infrastructure
be nearly 13 billion gallons(2)'
The RFS2 contmues to support the com ethanol industry'

meetthesetargets.

gasemissions
green*'l*use
Redrucing
In addition to establishing clear production targets'
resources- such as biofueis'
Renewabletransportationfuels, such as com-derived
are
ethanol,cellulosic ethanol,and other advancedbiofuels'

the original RFS.

Under the RFS, the U.S' EnvironmentalProtection
Agency (EPA) is responsiblefor implementing regulathe
tions t ensurethat increasingvolumes of biofuels for

36

wwv.aicne.org/cep March2010 CEP

the

i ,-

' :SEerETY

,,

B,tL'EGTGAL
N E - I N E E R IN G
A n,-:'.l i;Tec hnol ogi c ai
C ommuni ty

Ec,:*rni* c:mslSerati*s's
Domesticeconomicdevelopmentis a significantadvan'
in rural areas.In'its
tageof the biofuels industr,v,especially
contributions of
the
economic
most recent amual updateof
firm
consulting
the ethanolindustryto the U.S. economy,
nearly
will
create
targets
LECG projectsthat the RFS2 ethanol
wili
and
jobs
the
economy
acrossall sectorsof
1.2 million
generatemore than $630 billion in expendituresto expandthe
industry (4). As advancedbiofuelstechnologiescapableof utilizing a diversevanefy ofnon-food feedstocksare deployed,
direct benefitsto local economieswill be realizeCin areasof
the country where biofuels are not currently produced
Cellulosic ethanoltechnologydefloyment is slowly
making progress rn the early years and is projected to rapidly
increaseover the next decade(following the proverbial
hockey-stickgrowth curve).The federal governmentis
committedto working with industry to meetthe MS2's
aggressive,yet achievable,goals.
The White House report "GrowingAmerica's Fuel,"
releasedin February2010, is a comprehensiveroadmapto
advancedbiofuels depioymentl5). This report definesthe
responsibilitiesofvarious federalagenciesfor eachsegment
of the industry,including feedstockdevelopment,research
and developmentof biofuels technology,piiot- and demonstration-scalebioreflnery projects,and commercial-scale
biorefineries.The plan is outcome-drivenand focusedon the
feasibility of the industry at eachcntlcal step,with consideration of technical,management,economic,market,financial,
and environmental issues.The report offers assuranceto the
advancedbiofuels industry and all of its partners,particulariy
in the finance sector,that biofuels are a national priority and a

viable industry.
Economic feasibility of the em.ergingadvancedbiofuels
industry is a critical factor in meeting the targets set forth
in the RFS2. Government has an important role to play in
facilitating the entry of advancedbiofuels into the market
and their ability to compete on an equal economic basis with
traditional fossil-fuel resources.
The finance sectorusesthe term "valley ofdeath" to
describethe period of project funding betweenproven earlystagedevelopment financed through venture capital and
commercial developmentusing traditional project financing.
The advancedbiofuels industry cunently sits in the valley of
death - milestones have been met in early development but
commercial production has ngt yet been realized. Tax credits,
grants, and other useful financial provisions will provide
nec-essarynear-trm ncentives to achieve long-term goals.
However, in orderfor any businessto be successful,it
cannot rely indefinitely cn govemment subsidiesnd incentives. Eventually, to be competitive and economically viable,

poplar
a 250,000-gal/yr
treeswillsupply
fromhybrid
A Figure
1. Biomass
Inc.
Zeachem
Source:
biorefinery.
demonstration-scale
the industry must be able to competewithout subsidiesagainst
the marginalproductioncost of crudeoil. At today's conditions, this is approximately$75ibb1.Govemmentsupportat
this stagewill help the industry meet this economic goal.

avaitabl{ity
fleedstoc!r.
Feedstockavailability is anothercntical issuefor the
advancedbioftiels industry,sinceroughiy 5O-15%of a biorefinery'soperatingcostsare tied to feedstock.The biofuels
industry is no different than the oil industry when it comesto
the importance of feedstock supply and cost: It is necessaryto
securereliable,low-cost,and long-term-viablesupplies.
In 2005,the U.S. Dept. of Energy(DOE) andU.S. Dept.
of Agriculture flJSDA) issueda report known asthe "Biliion
the ftasibility of displacrngoneTon Study," which assesses
petroleum
consumptionwith biomass
third of the nation's
that meetingsuch a goal
(6).Thereport
concludes
resources
annually- and that
of
biomass
tons
would require 1 billion
such supply is indeedfeasible.
The administration'srecentbiofuels report (5) also
addressesfeedstock feasibility. It points out that the lowestnsk and highest-potentialfeedstocksare dedicated(i'e.,
specifically grolvn) crops,such astrees,energygrasses,and
cane.Establishingcontractsbetweengrowersandbiofuels
producerswiil reducerisks asthe indus@ scalesup - by
ensuring that growers have a market for their product and that
biofuels producershave the feedstocknecessaryto meet their
production needs.In addition to dedicated crops, the report
that biorefieris seekto use local residuals
ie"o--ed.
(agricultural and forest), thereby making use of extra feedstocks in close proximity and providing additional income to
the local community. .
This feedstockmodel provides a useful context for the
articlesin this specialsupplementon cellulosicbiofuels.It is
the strategyused by companieslike ZeaCfiem Inc., a cellulosic biofuels and bio-based chemicalsproducer. ZeaChem

CEP

March2OlO wvwvaiche.org/cep37

Broru l-s
93E Spscrll 5uppLufl,rEflT:

has contractedwith GreenWoodResources,the nation's leading grower of hybrid poplar hees,to supply dedicatedwoody
biomass(Figure 1) for its 250,000gaVyrdemonshation-scale
biorefineryin Boardman,OR. Dedicatedpoplar tree feedstock
is also availablefor a commercialellulosic ethanolfacilrty.
Local agriculturaland forestresidualswill be usedto supplement the primary dedicatedpoplartree feedstocksupply.
Analysis has shown that the use of short-rotationhybrid
poplar treesfor feedstockinitially offers the lowest cost per
bone dry ton (BDT)/acrelyear.The feedstockinventory is
sroredon the stump until it is neededfor conversioninto
ethanolor a chemicalproduct, eliminating storageconcerns.
Short-rotationhybrid poplar treescan be harvestedas often as
every three years,and require replantingonly bnceevery five
harvests.Maintarningthis high-densityenergycrop approach
minimizes the transportationcostsassociatedwith delivery to
ihe piant and has a low carbonlifecycle.
It is also worth noting somegeneralbestpracticesin
fbedstockoperations.First, longterm supply agreements
with feedstocksupplierswill ensurethe availability of
sustainable,economical,and plentiful feedstock.Second,the
use of supplementallocal'residualswill provide additional
community investment,primarily in rural areaswhere such
operationswill be located.Finally, a "grow where you go"
approach,in which biorefinersco-locatecommercialfacilitres
in the marketsthey servewith dedicatedenergycrops,will
minimize transportationand logistics costs.
i-ooking alead
This SBE supplementexaminestechnicalbreakthroughs
in biofuels production and will assistthe advanced-biofuels
industry in realizing its long-termproduction goais.
The first article,by Cort e/ a/., discussesbiomasshandling
systems,pretreatmentreactors,and solid-liquid separations
equipment neededat the front end of a cellulosic biorefinery.
The authorspresenttheir views liom the perspectiveof a leading equipment supplier to the pulp and paper industry. Many
of the lessonsleamed in that mature industry are directly
applicableto the emergingcellulosicbiofuels industry.
The secondarticle,by Simmonset al., discussesa new
ionic liquid pretreatrnentprocessfor making lignocellulosic
biomassamenableto enzymatichydrolysis.This is an important issueas the industry searchesfor better,lower-costpretreatmentsystems.Ionic liquids have unique propertiesthat
make them promising altematives for biomass pretreatment.
The third article,by Ladisch et al., providesan overview
of biochemicaland thermochemicaltechnologiesfor converting lignocellulosic biomassint ethanol.The technical
'
hurdles for these two production pathways are explored as a
meansofnavigating the path forward.

3A

The biofuels industry in the U.S. has made great strides

to date in displacingpetroieum-basedgasolinewith renewable alternatives.Now, the cellulosic and advancedbiofuels
industry is at a critical stageof developmentand deployment. With the RFS2 rn place and a clear roadmapguiding
the federal governmeirtand the bioftiels industry 36 billion
gallonsof bioftrelcan be achieved in2022.
ffire

Lrtsntrun Clro
U.S, Dept. ofEnergy, "Annual Energy Review 2008,"
wwweia,doe. gov/aeripdflaer.pdf, DOE, Energy lnformatiorr
Administration, Washington, DC (June 2009).
R.enewableFuels Association, '12009Ethanol lndustry Outloolg"
www. ethanolfa. orglobjectsipdfloutlook/RFA_Outlook_2009 pdf,
RFA, Washington,DC (2009),

t.
T
B

U.S. Environmental Protection Agenc "EPA Finalizes New

Regulations for the National Renewable Fuel Standard Program
for 2010 and Beyond," www.epa.gov/OMS/renewablefuelsi
420fl0007.htrn, EPA, Washington,DC (Feb. 2010).
Urbanchuk, J. M., "Contribution of the Ethanol Industry to the
Economy of the United States," www.etlanolrfa.org/objects/
documents/2I 8712008 ethanol-economic_contribution.pdf,
prepared by LECG LLC for the Renewable Fuels Association,
Washington, DC (Feb. 2009).
5.

"Growing America's Fuel: An Innovation Approach to Achieving the President's Biofuels Target," www-whitehouse.gov/
sites/defaulVfiles/rss viewer/growin g_americas_fuels.PDF
(Feb.20l 0).

6. U.S. Dept of Energy and U.S. Dept. of Agriculture, "Biomass as Feedstock for a Bioenergy and Bioproducts Industry:
The Technical Feasiblity ofa Billion-Ton Aual Supply,"
http ://feedStoclaeview.oml.gov/pdf/bi11ion_ton_vision.pdf,
DOE and IJSDA (Apr: 2005).

]
L

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ll

TIM EGGEMAN,
P.E.,is chieftechnotogy
officerofZeaChem
Inc.(1655. LJnion
Btvd.,Suite38o,Lakewood,
CO8ozz8-2257;
Phone:Go3) 279-7045;
Fax:Go3)279-9537i
E-mail:
of
time@zeachem.com)
anda co-inventor
process.
theZeaChem
Priorto foundingZeaChem,
hewasan independentconsultant
servngclientsin the biofuels,
syngasandFischerTropschareas.Previously,
manager
at
hewasthe process
development
Chronopol,
wherehe supervised
a groupthatdevetoped
manufacturng
ptasticsbasedon po{ytactic
technology
to producebiodegradable
acid,
anda process
designengineer
with ihe C.W.Nofsinger
Co.,wherehe
workedon proiectsin the pharmaceutical,
cornwet
speciatty
chemical,
anddry mtting,
andpetroteum
industries.
Heis an expertnchemical
processmodeting
patents.Hehotdsa PhDandMS
andhasnumerous
fromthe Unv.of Kansas
anda BSfromthe UniV.
of lllinois,all in chemi'
calengineering,
andis a licensedprofessionat
engineer.
CABRIE
ATIYEH
is directorof pubticaffairsat Zeachem
Inc.(Phone:$o3)
248-7778i
E-mail:catiyeh@zeachem.com).
Shehasa decadeof experiencedeveloping
energyandenvironmental
initiatives
for [ocatand
federalgovernments,
nongovernmentat
organizations,
andpublcand
privatecorporatons.
Priorto ioiningZeaChem
in 2oo8,shewasGreenhouseGasProgram
Administrator
for the cityandcountyof Denver,
wheresheplanned,managed,
andevaluated
coJporate
andresidential
programs
gasemissions.
to reducegreenhouse
Shehasalsoworkedat
Evergreen
Energy,Environmentat
Defense,the FederalTiadeCommission,andthe DutkoGroup.Shegraduated
with honorsfromHobartand
WitliamSmithCotleges
with a bachetor's
degreein political'science.

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Bi*chemicatandthernrochernica{pr0ce55
to convert
belngdeveloped
technoiogies
feedstocks
woodanCothertignocellulosic
to {iquiclfueisrilldrivethe transitiott
biofuels'
to advanced
ethanoL
frcmcorn-based

Drvlo Hocssrr
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MRscoun
"America's
he recentNational Academiesreport
liquid
alternative
that
Bt.tgy ettute" concluded
on
dependence
"tr-uu. the potential to reduce

andn"t",
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energy
imported
r'rvur Leuoi
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well as nonrenewable
-^felvqhle
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il:;;":;t"*"iot

consumPtionlevels (1)'
Biochemicalandthermochemicalprocessesthatffans-

rate- selectivity
The radeoff is selectivityvs' conversion
whereasconthermal'
for
is high for bioprocessesand low
for thermal.
high
and
u"rri"onratesare low for bioprocesses
factors that
key
are
costs
and
Feedstock,cataiystrobustness,
mustbeaddressedtoachieveeconomicalplocessesforboth
biochemicaland thermochemicaltechnolcgies'
celiulosehave a
Bioprocessesfor making ethanolfrom
from celethanol
produce
iong history Q)-Thepotentiai to
prior to
demonstrated
was
lulo"seusin! min"ral acid catalysts
obtainfor
routes
acid
Wbrld War iI' Thermochemicaland
technologiesmore than
ing fermentablesugarswere mature
that perform
Tdyears ago,whereasen4'rne biocatalysts
(?' 3/ These
recently
similar functronswere identifled more
the genes
and
enzylneshave beenpunfied and characterized'
producCurrent
thaiencode them have been sequenced'
fungal and bacteriai
tion methodsuse geneticaltymlaifiea
enzymesthat are
microorganismsto producecellulolytic
industries' as well
used in the food and consumerproducts
as in the emergingbiofuels industry'

a'ai[abillL"v
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Pretreatment

HydrolYsis

Fermentation

Product
Separation

Fermentation
tJrotn

Ethanol
Coproducts

Enzymes

,It"i:}"

Residue
(ProcessFuel)

and
fefmenttion
hydrolysis'
pretieatment'
involves
to ethanol
ofligocellulose
1. Bioprocessing
Figure
( / //'
Source:
seoaraton.

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The suPPlYoffeedstock for use

in biorefi.neriesis a key parameter
in achievingsignif cant economical'
oroduction of alternativeliquid biofuels. Becauseof the low densttY
of biomass,transPorlationcosts
arehigh, suchthat 40-50 miles ts
the mximum distanceconsidered
economically feasible for biomass
transport.Figure 3 plots the number

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Biomass

of sitesin the U.S. that could supply

varions amountsof biomasswithin a
Bosyngas,
40-mi radius of potential biorefinery
Organics,
proTar,
can
i7
sites
exampie,
For
locations.
Dryer
Syngas
Inorganrcs,
Because
ton/d.
dry
7,500
than
more
vide
Particles
(co, H?,co,)
of the wide variationin potentialsupply,
the size of biorefineriesis likely to vary
Oxygen
P adi cl es,
or Ar,
considerably(1).
l norgani cs
Steam
pt'intarconsists
biolnass
Cellulosic
ily of celluloseand hemicellulose,which
upon pretreatmentand hydrolysis are
Comoressor FT Reactor
princiconvertedto monosaccharides,
Product HYdrocracker
(a hexose)and xylose(a
Separaton
pally glLrcose
I HelormerI
pentose).Basedon the compositionsof
Y
the various sourcesof biomass(Table
Syngas
the potential (co,
1), it is possibleto caicr-riate
H,,cor)
quantify of sugarsthat would be obtained
lron-Based I Used
l'romcompletehydrolysis.and from Lhis.
Catalyst(Co) i Catalyst
the maximum yield of ethanolcan be
Water
EnergY
EnergY
estimated.Although actualyields will
are
t0syngas
be lower, since some of the sugars
gasification
ofbiomass
involves
route
to biofuel
thermochemical
2.Atypical
Figure
(7/).
(FT)
Source:
t0 biodiesel
conversion
Fischer-Tropsch
directed to cell biornassand energy for
bycatalytic
followed
carrying out various metabolic functions
of the microorganisms,the data in Table
162
estimatesof achievableconverston'As
1 provide reasonable
@ 160
a rule of thumb, maximurrrethanolyieids are on the order of
.9
129
?po
100 galiton for both thermalandbiochemicalprocessing'
o
Pretreatmentis requiredto maximize ethanoiyield' and
380
E
various pretreatments(e.g, acids,bases,water, steam,
z40
and/or heat in sotne combination)have similar effects(4' 5)'
17
celfrom
Without pretreanent,yields of fermentablesugars
0
>7,000
lulosic biomassby enzymatchydrolysis are3-20oAof theo800-2,200 2,20A-4,OOO 4,000-7'000
90%o
retical. After appropnatepretreatment,yields exceeding
Biomass Availabilitywithin 40 miles, dry ton/d
of theoreticalcan be achieved.The remaining organic solid
within
availability
vs.biomass
ofsiiesin theU.S.
3.Number
,* Figure
material is lignin, which has a cmbustionvalue sufficient to
morefian
0fthesite.NotethatlT sitescanprovide
radius
a 40-mile
to morethan
supply the energyfor the rest of the plant when bumed in a
perday,whichisequivalent
7,000drytonsofbiomass
toniyr.
Source:
2.5million
lil.
cogenerationfaciiity.

---r--

fi i*qh'*rnieai p-roces*mg
The processingof cellulosicbiomassrequiresfive steps,

sufficient through the combustion'orgasificationof residual

the remaining
lignocellulose.If only corn grain is processed,
solids that are high in protein arerecoveredas coprodttcts
and sold as animal feed, which has a higher value than boiler
fuel. Carbon dioxide is recycled into plant matterthrough
crop-productionagriculture.
Efcient conversionof celluloseto biofuels requires
that the cellulosic feedstock,whetherwood, corn stalks,
sugarcanebagasse;grasses,or other non-food crops,first
be pretreated.Pretreatmentsinclude processesthat cook the
material in liquid hot water, or use steam,acid or base,to
open-theplant cell wall structurein a way that exposesthe

CEP

March2O1O www,aiche.org/cep57

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Xylan
Arabinan,Mannan,
Galactan
Acetyl
Extractives
Protein
Lgnin
Ash
Total
Estimated Maximum Ethanol
Yield-,gauoryrot
. TheoreticalmaximumYield(ler

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43.8o/o

41 .Oo/o

34.60/o

332%

14.9%

15.Oo/o

18.3o/o

21.o%

5.6%

0.0%

2.5%

3.2%

3,6%

Not
Available

2.5o/o

^'70/^

3.o/o

3.0%

10.8%

10.2%

Not
Available

Not
Available

Not
Available

5.7o/o

29. 1%

29.1%

17.70/o

17.9%

1.0o/o

10.2%

3.70/o

1 .1 o /o

101.7%
' 111

93'8o/o

94.1o/o

97.4o/o

95

99

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v v'r - - anrt 1 007o fermentation
I w /u
short ton), assul I rrrrv ^^o/- ' ''

Univ'
ResourcesEngineering'Purdue
Data from Laboratory of Renewable

Coproducts

enzymes.Other than feedstock'

cost
enzymesaccountfor the major
to
rr'ateriais
cellulosic
of converting
pretreatof
combination
ethanol.The
that
ment with CBP producesa lignin
and
fuel
boiler
a
as
use
is suitaUtefor
the
contins enough energy to run
conversionProcess'
The selectionofProcessand
the
processconditions dePendson
wood
examPle'
For
fre of feedstock'
to
themselves
lend
ot .o* stalksmay
fermentaby
pretreatmentfollowed
iion,leaving a solid lignin coproduct that can be used as a chemical
feedstockor boiler fuel' Gasification
may
followed by catalyic reforming
municiPal
for
be more aPProPnate
mxflffe
solid wastes'which maYbe a
types
other
and
of plastic, cellulose
not
are
that
ofrganic components
ano
enzymes
bY
readiiy broken down
microbial fermentatron'
*licroa:rgan!5fiI5 f*r
et&ianot ferrnerta*uiosl

hydrolysis' Yeastis mostcommonlyusedin

pfeprJigl:lf119^ltjlent'
inabiorefinefy
unitopefatons
the
4.Thebasic
making
to
a Figure
combusted'
or
-afe-feedstock
u"-*ptoouttno'gasifieo
industrialethanolfermentations
ril isiecovereo
anddistiilarcn.
fermeniation,
22'
Ref'
beverages'
from
produceboth fuelsand
;ilffi;r'sr;rit;-iutririrnt. dource:Adapted

oiit, ab'ity to produceethanol

cellulosetoenzymesthathydrolyzethesemacromolecules.T:.::thedifferenttypesofyeasls,Saccharomycesce
b";r.
six-carbon
and
bothfive-carbon
reliablyin commerproduces
"r*ro"'l*'il"f"r.d
(5, 6). Hydrorysis
at high .ol".nt utionsandto perform
metabolizes'
facilities's' cerevisiae
sugarsin a ratio of about5:3.
modiflcation "iat star"',-to-ethanol
emproysgenetic
(7)
conditionsthroughthe
Modembiotechnorogy
glucoseinto ethanolunderanaerobic
nr*or",
to
them
con asa byproduct'
of.yeastandbacteriato enable
1"r*:1g.;*
*u"n-tvr"yerhofpathway,making
Ji"
substrates
of celluiosic
derivedfro ceilulosic
ro' ttreconversion
andpentoses
"rrr*"r
Th;;;i*it'o'g*itm
il;Figure
of
in
4
i;;;
(Step
tolerant
.
ethanolshouldbe
or orherbiotuelmolecules
?
bi"-;';;;oiy'ut"'loto

*r**t'tt"p'
(CBP)
substrates
of
bioprocessine
fast, consolidated
andpioducts'consuma wide range
*d ,";i;;;"production
lfrfilors
high productivcellulase
integrating
by
4
and
h"*or" andpentosesugars),andhave
lborh
n;"fii,
carrying
mostof these
tation i onemicroorganismd
""d
"",
ity to resultin hig-hyield.s. cerevisiaemeeti rangeof
5).
(Figure
a wide
in a singrevesser
fermentation
ttt"uUilityto consume
of yeast
engineering
"iit"",;"'iifuJt'
CBp is madepossibieby the genetic
58

CEP
wwwaiche org/cep March 2010

f
I
i

$lo"r ' EtY

B' ,or - ' ber tr AL

E * t l" r y E E -l fN G*
An

' -Tec hnol ogi c al

C ommuni ty

substrates- it is unable to processfive-carbon (pentose)sugars.

The rnajor focus for the past
years
f5
has been on introducing
genesthat allow microorganisms,
suclr as S. cerevisiae.Zvmomonas ntobilis, Pichia stipitis and
Escherichia coli. to ferment
xylose to ethanol.Metabolicengineering has createda variety of
Henricelii,riose
microbial strains,both prokarylnteoration,
otic bacteria and eukaryotic yeast,
Sierililv
r"
that are able to ferment five- and
six-carbon sugarsfrom cellulosic
biomass.
Both metaboiic engineering and traditionalselective

culturing approacheshave been

Lab
0.002 K
applied to various microorganisms to enhancebiofuel produc.2008
2009
tion performance.This requires
vessel
usinga
finding new micioorganismsor
combines
hydrolysis
ina single
bioprocessing
andfermentation
A Figure
5. Consolidated
genetically
specifically
engineered
forthesedualpurposes.
microorganism
improving the e.xistingindustrial
microoreanismsto increasethe
rangeof sugarsthat can be metabolized,to improve
NAD(P)H
B".t"*il
E
{ toleranceto ethanol or other fuel molecules,and to
' \* NAD(P)I
*
rrng"lI
|
improve toleranceto other inhibitors presentin celiulosic materiai processingstreams(e.g., acetic acid
and sugar-degradationproducts such as furfural and
f trar"bi** |
5-hydroxymethylturfural).
Metabolic engineeringof S. cerevisiaeto enable
it to fement pentosesugarscommonly found in celf ;bu"*-l
lulosic biomass.such as D-xylose and L-arabinose,
has been a areaof active developmentfor more than
a decade(8). Figure 6 illustratesthe rnetabolicpathD-xylulose-5L-ribulose-5ways for D-xylose and L-arabinoseto enter central
Central Metabolism
phosphate
phosphate
metabolism.Pathwaysfound in bacteria(blue) do not
involve the production ofsugar alcohols orreliance on A Figure
viabacterial
metabolism
6. D-xylose
andL-arabinose
canentercentral
(green)
pathways.
(blue)
metabolic
orfungal
NAD(P)H and NAD(P)+. which is typical of tungal
pathways (green).
enzymaticcofactorsN'AD(P)+ and NAD(P)H. The bacterial
Becausexylan is the largestpentoseconstituentof
pathway for L-arabinoseutilization has a similar advantage.
cellulosic biomassand D-xylose metabolism is conceptually
In addition to introducing genesfor pentosemetabolism,
simpler than that of L-arabinose,engineeringof D-iylose
improvementsin utilization of pentosehave beenrealized
utilization has been the focus of significant effort. Two main
by introducing additional modifications relatedto pathway
approacheshave been pursued,relying on either fungal
. regulation, cofactor utilization, and sugartransport.
or bacterial genesto convertD-xyloseto D-xyhilse-5Organismsfor CBP need to producehydrolytic enzymes
phosphate,which can subsequentlybe convertedto ethanol
(e.g., cellulasesand hemicellulases)that will depolpenze
by genesnative to S. cerevisiae.Ofthe two approaches.the
and debranchthe polysaccharidesin pretreatedbiomassto
use of bacterial geneshas shown somewhatgreaterpromise,
form sugars that it can feiment. The number of hydrolytic
sincethe bacterial pathway doesnot require balancingthe

-T-

T-

bEP

Harch2O1O wrwaiche,org/cep 59

*"-q,

Blorust-s
5BESpeclnlSUppLEMENT:

enzymesrequiredis substantial most organismsthat are

naturally capableof breaking down plant biomassexpress
m'orethan 50 such enzymes.
Significantprogrcsshasbeen made in engineeringstrains
of S. cerevisiaethat are capableofbreaking down both
xylan and cellulose (9). Expressionofas few as two to five
enzymesappearsto be sufficient to achievesome degreeof
sugarreleasefrom xylan and cellulose' However' there is
substantialroom for improvement in both extent and rate of
conversionof cellulosic biomassto ethanol.
As additional and improved hydrolytic enzymesare successfully expressedin S. cerevisiae,eSpeciallywhen coupled
with improvementsin pentosesugarutilization and tolerance
to inhibitors, the cost for CBP will fall.

irhl
bitors
Ferrnertation
The major inhibitors presentin biomasshydrolysates
- weak acids,furan derivatives,and phenolics- exert
inhibitory effects by different mechanisms. Furan derivatives
(i. e., furfural and'5-hydroxymethylfurfiral) resuit from the
degradationof the sugarsfound in the hemicelluloseand
cellulosefractions during processing.Phenolic compounds
are formed by the degradationof the lignin fraction. Portions
ofhemiceliulose are acetylated,and acetylatedgroupsare
releasedas acetic acid during the pretreatmentprocess.
Theseinhibitors negatively affect product yield, volumetric productivity (grams of product per liter per hour),
and microorganism growth rate. For exampie,furfural
and 5-hydroxymethyl furfural strongly inhibit cell growth
through direct inhibition of key dehydrogenaseenzymes
in the metabolism of sugars.-Fuelmoleculesproducedby
fermentation(i. e., ethanol,butanol, isobutanol)become
toxic to the microorganism as their concentrationsincrease
during the courseof the fermentation (7' l0' 11)'From a
processeconomicsstandpoint,concentrationsof biofuel
product in excessof 5% (w/v) alcohol in aqueousfermentation medium is desired.Higher concentrationsreduce
productrecoverycosts.
Direct geneticmanipulation of eukaryotic organismsto
improve toleranceto inhibitors is difficult becausecellular
responseto stressinvolves multiple genes,cell signaling,
and various transcription ftors. Selective cultunn'g of
metabolically engineeredmicroorganismsralreadyableto
ferment the sugarsfrom cellulosic biomassis the method
that has generallybeenmore successfulfor imprving
tolerance.
Selectiveculturing involves.applyingDarwinian seiec. tive pressuresto favor microorganisms with improved
fermentation performance in the presenceof inhibitors.
Through spontaneousor induced mutations,a population .

6Gl'

www.aiche.org/cep March 2010 CEP

of microorganismsis grown through multiple generations

in media containingth inhibitors toward which improved
resistanceis desired.More-tolerant organismsgrow more
quickly and eventually dominatethe population.Two-, five-,
and even ten-fold improvernentsin volumetric productivity
are not uncommon after 100-200 generations.

inh:bitors
Hn:yn':e
Enzymesconstitutea major cost in the bioconversion
of celluloseto ethanol (12). Factotsthat reduce enrpe
activity inciude: nonproductiveadsorptionof enzymeonto
lignocellulosic substratesprior to reaction; intermediateand
end-productinhibition; mass-transferlimitations affecting
the transportof e enzyineto and from insolublesubstrates;
the distribution of lignin in the ceUwall; the presenceof
hemicellulose,phenolic compounds,proteins and fats;
lignocelluloseparticle size; and crystallinity and degreeof
polymerization of the cellulose substrate.
Enzyme hydrolysis of pretreatedcellulosic materials
slows as the concentation of solid biomassincreases,even
if the ratio of enzymeto celluloseis kept constant(l 3, 14)'
This form of inhibition is distinct from substrateand product
inhibition, and has been observedin lignocellulosic materials such as wood, com stover,switchgrass,and com wet
cake at solids concentrationsabove 10 g/L.
Identifying enzyme inhibitors and moderating thetr
effects is very important. Achieving favorable ethanolproduction economics requires at least 200 glL of cellulosic
substratesto produce monosaccharideconcentrationsof
100 gA and, in turn, ethanoltiters (concentrations)of50 g/L'
Most inhibitors that reduce hydrolysis activity of cellulase
enzymesare releasedas the cellulosicbiomassis broken
down in the pretreatment and hydrolysis steps.These compoundsinclude vanillin, syringaldehyde,ffans-cinnamicacid,
hydroxybenzoicacid, solublexylans (xylo-oligosaccharides)
and xylose, and the productsofcellulase action (i'e., cellobiose and glucose)(14). Allsignificantly inhibit hydrolysis of
cellulose and must be removed to maiimize enzyme activity,
either by hydrolysis or other means.

n
icaleonversio
Yherrnochern
Unlike bioconversionprocesses,thermal processing
requires high temperatures and a source of heat to initiate
and propagate reactions that convert the chemical backbone
of plant matter (r.e.,cellulose,hemicellulose,lignin and
organic extractives)to CO, H' and water.In biochemical processes,the pretreatmentstepthat precedesceilulose
hydrolysis may constitute a significant expense,whereas
in thermal processingroutes,gasificationand gasclean-up
are significant expenses.In pretreatment,plant biomassis

E IE LE GItrA L
FerN
E E R rN E i
b
A n !,,.i :;aTec hnol oqi c al
C ommun-i ty

processedin a soiid or aqueousform before it is incubated

with enzymesto achievefurther hydrolysis. In thermal
processing,the solid feedstockis converteddirectly to a
synthesisgasby thermal or auto-catalyticgastfication(i.e.,
partial combustion)of the organicmaterial in the presenceof
conholled amountsof oxygen. The costsof enz)rmes,in the
caseofbioconversion, or inorganic catalysts,in the caseof
thermal processing,add significant additional expense,and
hence,motivate researchin biocatalysis/catalysisresearch
aimed at reducing thesecosts.Overall, thermochemical
processesare more complex than cellulosebioconversion
processes(compareFigures 1 and2), but the technologies
Iremore mature.
Cellulosemay be broken down throughthermal processing that gasifieslignocellulosicmaterials,including the lignin
fraction, to a mixture of CO, tlr, *d CO, athigh temperatures.When th gasesare cleanedup and then passedover
solid catalysts,alcoholshigher than ethanolor other fuel
moleculesare formed. Sincethe reactionsare carried out by
the Fischer-Tropschprocess,the resultingfuels are sometimes termed FT tiquids.An alternativeprocessin which the
gasesare fermentedby bacteriathat are capableofconverting
CO and H, to ethanolhas alsobeenproposed(23).
The processesthat occtu in a gasifier are drying, pyrolysis,
combustion,and gasification (I 5, I 6). Wood and biomass
form tars, particularly in updraft gasifiers;consequently,
downdraft configurations(in which the cellulosicbiomass
flows through the gasifier in a downward direction) are more
common. Air is injected near the bottom of the gasifier, where
combustionoccursat an oxidationtemperatureabove 1,000'C
(the theoreticalmaximum is 1,450'C).Heat releasedduring
combustion dries and pyrolyzes the biomass above it. Organic
acids are releasedfrom the biomass during the drying process,

necessitatinga corrosion-resistant
construclion(15).
The combustionreactionsare:

c+ oz*cq
zHz+ 02---2HzO
C+CO2
-2CO
c+H2O*CO+H2
CO+Hr
-COz+Hz
2Hz; CH+
COr+F1"-CO+HzO

(+ 393MJlkg-mole) (1)
(+ 393MJ/kg-mole) (2)
(-64.9MJ,&g-mole) (3)
(- 122.6MJ/kg-mole)(4)
(+ 42 MJ/kg-mole) (5)
(+ 75 MJ/kg-mole) (6)
(- 42.3MJ/kg-mole) (7)

Endothermic reduction (Reactions3,4 andT) reduces

the temperatureof the reaction mixture to the range of

800-1,000.c.

Pyrolysis products (i.e., tars) are also formed during

combustion.In theory thesepyrolysis products should be
crackedinto smaller moleculesas they passthrough the bed
of hot charcoalcreatedbythe partial combustionof the biomassat the bottom of the gasifier.In practice,however,the
cracking of pyrolysis products in a gasifier is lessthan 1.00%
efficient, so filtration of the hot gasesor other separation
methods are neededto remove the tars before the synthesis
gas is passedover the catalyst.
The gasmust be cleanedup to reducecatalystfouling
and achievethe catalystlife required for economic operation. When the reactionis carried out in the absenceof
oxygen and the miterialis heatedto about 800'C, an oily
material forms. This oil may be processedfurther (through
cracking) into diesel-likemolecules,sometimesreferredto
as green diesel.The viscosity ofthe oil and its tendencyto
form a tar-like material are issuesthat need to be addressed
by researchifrobust scale-upis to be achieved(17).
An alternative approachto chemical catalysisfor
conveding CO and H2 to fuels is a biocatalytic process.A group ofbacteria known
collectively as acetogenscan convert these
gasesinto a mixture of ethanol,butanol,
acetic acid, butyric acid, and methane.
Low ethanol yields, relatively low productivities, and the challengesinherent in
gas/liquid masskansfer must be solved to
make this a commercially viable approach.
The recovery oflow concentrationsofthe
final products requires separationsthat add
to the cost. Hence, the cost of pretreatment
and enzyme hydrolysis is replacedby a
different set of coststhat include catalyst
Neutr"alizing
separationand recovery.
.
The.benefit of simplified front-endproduced
A Figure7. Bodiesel
canbe
fromvegetable
oilsandanmal
fatsviachemical
processing.
(17).
Source'.
processingin a thermochemicalprocessis

. eEPl

Mrch 2O1O www.aiche.org/cep Ci.l,

5BESeresnrSqjppt-EME
tsr;Blorue-s

Sugar/Starch Ethanol
CelluloseEthanol
P-Series
Biodieseland HDRDSynthetic Bio. FT Diesel
Methanol
DmerhytEther (DME)
Biomethane
BiosyntheticNatural Gas
Green PyrolysisDiesel
' HDRD = nyur
Hydrogenation-Derived
uger raron_uenveo Henewable
FlenewableDesel
(/.e., NEXBTL)
Diesel (r'.e..

a Figure
L Biomass-to-biofuel
conversion
technologies
areinvarious
stages
ofdevelopment.
(17.
Source:
ofFsetby the increasedcomplexity of post-gasificationprocessingand the loss of the sugars'functionality.pretreatment
is preferredwhen the goal is to obtain sugarsfor biochemi_
cal and biological fermentationroutes.
Ch*rnicat {$nverson
Through a seriesofcatalytic reactions,lignocellulosic
biomasscan be convertedinto levulinic acid, which can then

octanenumber as regular gasoline(87), tow Reio vapor

pressure(5.7 psi), and a lower heatingvalue (32 MJ/kg) that
is slightly higher than that of ethanol(26.7 MJkg). This set
of propertiesallows it to be mixed with ethanoland natural
gas iiquids to createa transportationfuel.
A mixture of ethanol,MTHF, butane,pentanes,and

|ElEl

www.aiche.orglcep
March20.10 cEp

higher alkanesis known as a p-seriesfuel

(19, 20). Dependingon the composition,
P-seriesfuels can be derived from nonpetroleum sources,such as waste paper,
agricultural residues,and urbadindustrial
waste.The Biofine processdevelopeCat
Pacific Northwest National Laboratory
producesMTHF from lelulinic acid in a
single stepwith high yielde.
The developmentof industrially
robust catalysts,optimization of reactions to'achievehigh yields,and securing
cost-effectivesourcesof relatively pure
sugarsare challengesthat must stili be
addressed
(17, 19,20).

eornparing
hieefNernieaI
andtherrllocl'e-r
ica{ paff?ways
Starch- and sugar-basedethanolprocessesare mature
commercialtechnologies,with com the dominantfeedstock
in the U.S. and sugarcanein Brazil. Corn (including the
corn stalks) has the potential to provide up to 22 billion
gallons ofethanol per year ifboth celluloie and starch are
convefted to ethanol(21).

wastesgeneratebiomethane.
Biodiesel has beenproducedboth for use as a chemical
and as a biofuel in the U.S. Vegetableoils are the pnncipal
feedstockfor a process(Figure 7) that reactsmethanol with
liquid vegetableoil using an acid catalystto form methyl

5o

= I'ETY

E3' * - EGr tr AL
FrsTN E E R i N G
l-

esters(1.e.,biodiesel).In this case,the preflx blo- refersto

the sourceof the feedstock- a biologically derived vegetableoil (ratherthan the type ofprocess, such as fermentation or digestion).
Biomethaneis a common product of someiandf'lls'
as well as digestionprocessesthat handle animal wastes

material. Methane is less likely to be usqdas a transportatlon

fuel becauseof its low physical and energy density anclthe
limited infrastn-rcturefor its distriblltion (17)'
Figure 8 compalesvarious chemical,therrnochemical
and biogical tehologies for kansforming lignocelluiosic
feedstocksto ethanoland their stagesof development'

An :

Technol ogi c al
C o mmuni tY

i:3 1"1-f,.t
{ Ii}s,i:1.:i 1.'::
Ethanol is produced in iarge quantities, and an estimafed12 biliion gal will be derivedfrom corn in 2010'
Sincethe celluiosicportion ofthe corn kernel is a potential
sourceof an advancedbiofliel as well, cellulosicethanolis
likely to be the first such fuel on the market' The technologiesio processwood and other lignocellulosicfeedstocks
urrentlyunder developmentwiil enablethe rapid expansion of cellulosicethanoiproductionfrom non-food feedstocks and lead the way for other advancedbiofliels oYg,*.=
l'"'i{:i
the next ten years.

AcxowlroGMENTs
Corpfor ther
of luascoma
TheauthorsthankJmFtattandToddPolanowicz
Thematerialin thisworkwas
reviewofthis articteandhe{pfutsuggestions'
L0rp'
andMascoma
supportedby DOEcontractDE-FC-3'o8Gor8ro3

Lrrsutunr rso
1

",
Biotechnol Bioeng, 16, pp. 1411-149i (1974)'
NIandels, M.o et al.,"lvleasurementof Saccharifting Cellulase""
Biotechnol. Bioeng. Symp ' 6, pp- 21--23(1916)'
LignoSierra. R., e/ a/., "Producing Fuels and Chemicals from
cellulosic Biomass," SBE Special Section, Chem' Eng' Progress'
1 0 4 ( 8 ) ,p p S 1 0 - S1 8( Au g .2 0 0 8 ) .
Wyman, C.8., et al., "Coordinated Deveiopment of Leading
Biomass PretreatmentTechnologies,"BoresourceTbch'' 96'
pp. t9s9-1966 (2005).
for
Mosier, N. S', e! trL, "Featuresof Promising Technologies
Tech 96'
Prereent of Lignocellulosic Biomass," Bioresource
'
1

pp. 673-686 (2005)'

Mosier, N., and M. Ladisch, "Modem Biotechnology: ConnectEngineering
ing Innvaiions in Microbiology and Biochemistry to
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Pentose
Hahn-Hgerdal ,8., et aL, "Metabolic Engineering for
Eng'
Utilrzation in Sccharomycescerevisiae,"Adv' B iochem
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g. Van Zyl, W. fi'., et aL, "Consolidated Bioprocessingfor Bioethanol
Eng'
Production usrng Saccharomycescerevisiae,"Adv' Biochem'
!
Biotechnol.,108,pp.205-235 (2001)'
for
Scenaris
and
10, Ladisch, M. R' "Fermentation-DerivedButanol
73'
Technol
Miuob'
Enz'
'
its Uses in Energy-RelatedApplications,"
p p . 2 8 0 - 2 8 3( 1 9 9 1 ) .
of
11. Shota, A'' ef /., 'Non-Fermentative Pathl/aysfo;: Synthesis
451 (3)'
Brnched-Chain Higher Alcohols as tsiofueq" Iy'ature'
pp. 86-89 (2008).
to
12. Ifoughton, J' C., et al., "Breaking the Biologicai Barriers
No'
Cellulose Ethanol' A Joint ResearchAgenda," Publication
(2006)'
DOE/SC-0095, U.S. Dept' of Energy, Washington'DC

Kumar, R., and C. E. Wyman, "Effect of Supplementationat

Release
Moderate CellulaseLoadings on Initial Glucose and Xylose
from Com Stover Solids Pretreatedby Leading Technologies"'
Biotechnol Bioeng., 102 (2), pp- 4547 Q009)'
Enz
14. Ximenes, 8., et al,, "Inhibition oICellulases by Phenols"'
Microb. Technol.,46 (34), pp. 170-176 (2009)'
in
15. Rajvanshi, A. IC, "Biomass Gasification," Chapter 4 "AlternaCRC
ed''
Y',
D
Goswami,
II,
Vol.
tive Energy inAgriculture,"
Press,Boca Raton,FL, pp. 83-102 (1986)'
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ifiers for Inciustrial Heating Appl ications"' Biomass and Bioenergy'
i3 (3), pp. 141-146 (199'7)Gaps in
17. Schwietzke,5., et aL, "Analysis and Identificatin of
TransporResearchfor the Production ofsecond GenerationLiquid
tation Fuels," www.ieabioenergycom, T41 (2) (2008)'
of Biomass
18. Pacific Northwest National Laboratoryo "Conversion
gov'/biobased/
Wastesto Levulinic Acid and Derivatives"' www pnl
completed.stm(1999)"
and
19. U.S. Dept. of Energy, "P-Series," DOE Energy Efficiency
Data
Renewalld Energy,lternative Fuels andAdvanced Vehicles
grseries'html
e1s/emergiir
gov/afdc/fu
c.energy'
afcl
www.
Center,

(19ee).
ftom
ofTransportationFuels
al-,"Synthesis
20. Iluber,G.'W.,.et

Biomass: Chemistry, Catalysts, and Engineering," Chemical

Reviews,106 (9), pp. 40444098 (2006)'
tn
21. Schwietzke,S., et al',."Erhaol Production ftom Maize"'
Kris'
Improvement"'
toMaize
Approaches
"Molecular Genetirc
63' pp'
A. L., and B. A. Larkins, eds., Springer Verlag, Berlin'
347-364 (2009).
Ecoomic Analysis
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96 (lE)'
Technolog'
resource
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of-iretreatment Technologies''l

(200s).
pp.2019-202s
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(2004)'
Gas to Ethanol,' Biotechnol- Bioeng ,86 (5),pp' 587-594

GEP

March 2010 www arcneorg/cep Gi3