Table Of Contentg Renewable and Sustainable
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In Renewable and Sustainable Polymers; Payne, G., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2011.
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In Renewable and Sustainable Polymers; Payne, G., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2011.
1063
ACS SYMPOSIUM SERIES
Renewable and Sustainable
Polymers
Gregory F. Payne, Editor
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DistributedinprintbyOxfordUniversityPress,Inc.
In Renewable and Sustainable Polymers; Payne, G., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2011.
LibraryofCongressCataloging-in-PublicationData
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cs.01 Renewableandsustainablepolymers/GregoryF.Payne,editor;PatrickB.Smith,editor.
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1 | 20 1. Polymers--Congresses. I.Payne,G.(GregoryF.)II.Smith,PatrickB.,Dr.III.American
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PRINTEDINTHEUNITEDSTATESOFAMERICA
In Renewable and Sustainable Polymers; Payne, G., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2011.
Foreword
The ACS Symposium Series was first published in 1974 to provide a
mechanism for publishing symposia quickly in book form. The purpose of
the series is to publish timely, comprehensive books developed from the ACS
g sponsoredsymposiabasedoncurrentscientificresearch. Occasionally,booksare
or developed from symposia sponsored by other organizations when the topic is of
cs.01
a0 keeninteresttothechemistryaudience.
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1 | 20 papersmaybeexcludedtobetterfocusthebook;othersmaybeaddedtoprovide
5, 20121/bk- comprehensiveness. When appropriate, overview or introductory chapters are
20 added. Draftsofchaptersarepeer-reviewedpriortofinalacceptanceorrejection,
ptember doi: 10.1 andmanuscriptsarepreparedincamera-readyformat.
on Se011 | incluAdesdainrutlhee, voonlluymoersi.giVnaelrbraetsimearrcehprpoadpuecrtsionansdofoprirgeivniaolusrepvuiebwlishpeadpepraspaerres
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In Renewable and Sustainable Polymers; Payne, G., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2011.
Chapter 1
The Emergence of Renewable and Sustainable
Polymers
org PatrickB.Smith*,1andGregoryF.Payne2
cs.01
a0
ubs.3.ch 1Michigan Molecular Institute, 1910 West St. Andrews Road,
http://p11-106 2Center for BiosystemMsiRdelasnoudr,cMesIa4n8d64F0ischell Department of
25, 2011 | 021/bk-20 Bioengineering,5115PClaonltl*eSsgmceiiePtnhac@reksm,BMmuiiD.lodr2ing0g7,4U2niversityofMaryland,
ptember doi: 10.1
n Se11 |
o0 Theseareexcitingtimesforbiofuelsandrenewablechemicals!
AN 1, 2 A sense of urgency is driving a frenzy of activity on both
HIGpril 2 research and commercialization fronts. Presciently, the ACS
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In this introductory chapter we provide a broad perspective
on the motivation for these activities and an overview of the
likely paths forward. We especially focus on reviewing the
explosion of commercialization activities in the hope that this
staticsnapshotcanprovideaglimpseofanincrediblydynamic
situation.
Introduction
Throughout history, humans have enlisted biological polymers – especially
proteins and polysaccharides - to meet their needs for food, fuel, clothing
and shelter. This situation changed dramatically during the last century.
©2011AmericanChemicalSociety
In Renewable and Sustainable Polymers; Payne, G., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2011.
Stunning technical advances enabled petroleum to be recovered and processed
inexpensively providing cheap fuels that powered the economic growth for
much of the world. Further advances in industrial organic chemistry allowed
the petroleum feedstock to be processed into a handful of building blocks
(e.g., ethylene, propylene, benzene, toluene and xylene) for the synthesis of
petroleum-derived chemicals for applications ranging from consumer goods to
agriculturalchemicals. Manyofthesebuildingblocksalsobecamethemonomers
forthegenerationofsyntheticpolymers. Insomecases,thesesyntheticpolymers
offered inexpensive alternatives to biological polymers and in other cases,
these synthetics enabled entirely new capabilities (e.g., engineering plastics and
non-stickcoatingsforfryingpans). Fromtheperspectiveoftheearly21stcentury,
it is easy to overlook the impact that advances in petroleum processing had on
g
or ourwayoflife.
cs.01
a0
pubs.63.ch The Push Away from Fossil Resources
5, 2011 | http://21/bk-2011-10 roefliraenAacsseownosen.ppFreotirrjeostcl,etutihmneto(foothrsesoitlfhureteursrofeou,srtschielesrreethsaoerumerscgeerlsov)weisisnagnroectofisnuncsietteran.insaRtbhelaectefanotrsieagsntviimafircaieatetnyst
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ptember doi: 10.1 ippnrrdiocidecuacitnetieotlnha”asttiicsoiitnlyo.ptreoWqduhuiecvntaiolsenunptwptilolyl“pcraeenasokunbrocyelotdhneegpenlreetbxioetnda”edcijtuadsdteoeed(s1t)ionadmnicdeaetwtehianilcperoe“ianpsteinaogkf
n Se11 | demand,economicspredictsthatpriceswillbepronetosubstantialincreasesand
o0
AN 1, 2 fluctuationsinresponsetothemarket.
CHIGApril 2 AsthTehpursi,cteheofsepceotrnodlecuomncienrcnrefoasretshethuens-esuarsctahinfoabrialilttyeronfatpivetersolweuilmlbiesceocmoenommoirce.
F MIeb): urgent–atboththeindividualandthenationallevels. Importantly,thepetroleum
OW reservesarenotdistributedequally,astheOPEC-producingnationscontrolnearly
NIV ate ( 80% of the world’s oil reserves (1). Nations that rely on substantial oil imports
y Un D tomaintaintheireconomieswillfaceparticularlydifficultpolicydecisionswhen
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Do Thethirdconcernfortheun-sustainabilityoffossilresourcesisthecost/risk
tosafety,healthandtheenvironment. Muchofthediscussionhasfocusedonlinks
amongfossilfuelconsumption,greenhousegasemissionandglobalwarming,and
what actions could/should be taken. Yet the recovery and processing of fossil
resources presents additional costs/risks. Sadly, 2010 has also been marked by
numerousdeathsincoalminingaccidentsandbytheworstoilspillinUShistory.
The Likely Path Forward
Itseemslikelythatthe20thcentury-trendtoanincreasingrelianceonfossil
resourcesforfuels,chemicalsandmaterialswillnotcontinueintothe21stcentury.
Thischangeinparadigm,however,doesnotmarkademisebutratheratransition.
This transition cannot reasonably be expected to be rapid as it is difficult (or
2
In Renewable and Sustainable Polymers; Payne, G., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2011.
impossible) to imagine completely replacing US consumption of fossil fuels in
thenearterm. EveniftheUSmeetstheambitioustargetforproducing35billion
gallonsofethanolby2017(2),thiswouldonlyrepresentabout12%oftheannual
USpetroleumconsumption.
We anticipate three features of the transition from fossil to renewable
resources for chemicals and materials. The first expectation is that many
of the renewable chemicals and polymers will be driven by successes in
biofuels production. Historically, the success of petroleum-based fuels relied
on inexpensive large-scale processing. Once the refining capabilities were in
place,thentheyprovidedaninexpensivesupplyofbuildingblockchemicalsthat
could drive developments in the petrochemical industry. By analogy, advances
in the processing of renewable feedstocks (e.g., cellulosics) for biofuels should
g
or enable the generation of inexpensive building blocks for value-added chemical
cs.01 and polymeric products. While this “biorefinery” concept is not new it has
a0
ubs.3.ch considerableappealfor“extracting”valuefromtherawmaterial. Infact,eachof
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ptember doi: 10.1 CinliLnotound,oInA,,TaNnd. Tate&LylewithitsBio-PDO™1,3-propandiolproductionfacility
n Se11 | The second expectation is that the development of renewable chemicals
o0 and polymers will significantly benefit from the previous advances in industrial
AN 1, 2 chemistry. In some cases, the transition to renewable polymers may simply
HIGpril 2 mean a switch in raw materials. Examples include the dehydration of
F MICeb): A afenrdmeanctraytiloicn-daecridiv,edreesptheacntiovlelayn.d 3O-hnycderoxthyepsreopiinotneircmeadciidatetso ayrieeldgeentehryalteende,
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the practice of medicine in part by providing capabilities for the biosynthesis of
protein-basedtherapeutics(e.g.,insulin)andthesecapabilitiesarebeingenlisted
for lower-value applications. Already, protein engineering is yielding improved
enzymes(e.g.,cellulases)forfeedstockprocessingwhilemetabolicengineeringis
providing intermediates that cannot be readily obtained through chemical routes
(e.g.,1,3-propandiolforpolyesterproduction). Potentially,syntheticbiologywill
provideevenmorecapabilitiestoaccesscomplexfeedstocksandgeneratelow-cost
intermediatesandproductswithsuperiorfunctionality.
3
In Renewable and Sustainable Polymers; Payne, G., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2011.
Potential Chemical Building Blocks Derived from Biofuels
The development of technology for the biofuels market will likely, as
stated earlier, provide feedstocks for the chemical industry. If the processes
and target molecules currently under development are any indication, trends in
this field might provide direction for the nascent renewable chemicals industry.
The biomass conversion technologies being commercially developed today are
basedonthreemaintypesofprocesses; fermentation, thermochemicalandalgal
processes, but there are many variants within them. Table 1 lists many of the
companiesactiveinbiofuelstechnology,categorizingthemwithintheconversion
technologyframework. Mostoftheinformationincludedinthistablecamefrom
companywebpages. Thistableisnotmeanttoincludeallthecompaniesinthis
g
or areabecausethelistwouldchangealmostweekly, butrather, itismeanttohelp
cs.01 define trends. Some of the companies listed are also active in more than one
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ptember doi: 10.1 hcoymdrmocearrcbiaolnizsin(4g).aSciamrbiloahrlyyd,rbatieofufeerlms efrnotmatioanlgatol cpornovdeurcseionpotleycfhanrnoelosgeniees-boafsteend
n Se11 | targetethanolandoilsforbiodieselandgreendieselproduction. Thermochemical
o0 biomass conversion technologies most often produce syngas or bio-oil which
AN 1, 2 canbeupgradedtofuelsusingconventionalcrudeoilrefiningprocessessuchas
HIGpril 2 hydroforming/hydrotreating, catalytic upgrading and Fisher Tropsch processes.
F MICeb): A ASosmreenteewchabnloelobgiioefsueplrsobdeuccoemseynlegsassewxpheicnhsivisetahnednmfeorrmeeanvtaeidlatboleetthheaynowli(l5l,al6s)o.
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Ethanolproduction,primarilyfromcornintheUS,appearstobeviablebecause
reformulated transportation fuels require an oxygenate and ethanol is the
oxygenateofchoice. However,theUSethanolbusiness,evenwiththefederaltax
credits, wasonlymarginallyprofitablewhenthepriceofoildroppedbelow$70
perbarrel. Withoilpriceswellabovethatleveltodayandtrendingupward, this
businessisexpectedtocontinuetogrow. Biodiesel, ontheotherhand, hasseen
considerablecapacityreductionin2009and2010intheUSasaresultoftheloss
offederaltaxcredits.
Ethanol from sugar cane or corn starch and biodiesel from seed oils are the
lowcostrenewablefuelsinproductiontoday,butmuchresearchisdevotedtothe
commercialization of the so-called second (cellulosic feedstocks), third (algal)
and fourth (thermochemical) generation biofuels. There are many hurdles to
thecommercializationofthesenextgenerationprocesses, theirbusinesssuccess
4
In Renewable and Sustainable Polymers; Payne, G., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2011.
depending on breakthrough technologies which will significantly reduce their
costs. The future cost of oil is another unknown but fossil fuels are a limited
resource. In our opinion, the transition from this limited resource to renewable
fuels is inevitable. The only question is with regard to the timing. And as the
biofuels industry grows, we believe there will be a synergistic growth in the
commercializationofchemicalsandmaterialsfromrenewableresources.
Renewable Chemicals and Polymers
There is also increasing interest in obtaining chemicals from renewable
resources and this has spurred a myriad of commercial activities. Table 2 lists
g
or many of the commercial organizations active in this area and the renewable
cs.01 chemicals they are targeting. (Table 2 has the same disclaimers associated with
a0
ubs.3.ch Table 1.) As indicated, much of the interest in renewable chemicals is targeted
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n Se11 | the market with excellent projected growth rates of nearly 13% over the period
o0 between 2009 and 2014 (8). Obviously, the growth potential of renewable
AN 1, 2 polymersismotivatingthecommercialactivityoutlinedinTable2.
HIGpril 2 The primary feedstocks for the renewable chemical industry today are
CA
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natural sources and these pre-formed polymers could be subsequently modified
to adjust properties. Pre-formed renewable polymers include carbohydrates
(e.g., starch, cellulose and chitin), proteins (e.g. gelatin), natural rubber and
lignin. More recently, chemical-synthesis methods were developed to generate
polymers from renewable monomers. Examples include poly(lactic acid), PLA,
andpoly(butylenesuccinate),PBS.Also,fermentation-derived1,3-propanediol
isbeingconvertedtopoly(propyleneterephthalate),PPT,andthedehydrationof
ethanolprovidesthemonomerforrenewablepolyethylene,PE.Athirdcategory
ofrenewablepolymersarethosethataregeneratedfromrenewablesubstratesvia
fermentationprocesses. Theclassicexampleofafermentation-derivedrenewable
polymerisxanthangumwhiletheemergingexampleispoly(hydroxyalkanoate),
PHA,thatisproducedbyengineeredbacteriatomakecopolymerswhichdonot
existinnature.
5
In Renewable and Sustainable Polymers; Payne, G., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 2011.
