Reprinted from: Trends in new crops and new uses. 2002. J.

Janick
and A. Whipkey (eds.). ASS !ress" A#e$andria" %A.
Ethanol From Cellulose: A General Review
!.&. 'ad(er
INTRODUCTION
The use of ethano# as an a#ternati)e motor fue# has *een steadi#y increasin( around the wor#d for a num*er
of reasons. +omestic production and use of ethano# for fue# can decrease dependence on forei(n oi#" reduce
trade deficits" create ,o*s in rura# areas" reduce air po##ution" and reduce (#o*a# c#imate chan(e car*on dio$ide
*ui#dup. -thano#" un#ike (aso#ine" is an o$y(enated fue# that contains ./0 o$y(en" which reduces particu#ate
and 12$ emissions from com*ustion.
-thano# can *e made synthetica##y from petro#eum or *y micro*ia# con)ersion of *iomass materia#s throu(h
fermentation. 3n 455/" a*out 5.0 of the ethano# in the wor#d was produced *y the fermentation method and
a*out 60 *y the synthetic method. The fermentation method (enera##y uses three steps: (4) the formation of a
so#ution of fermenta*#e su(ars" (2) the fermentation of these su(ars to ethano#" and (.) the separation and
purification of the ethano#" usua##y *y disti##ation.
SUGAR FEEDSTOCKS
7ermentation in)o#)es microor(anisms that use the fermenta*#e su(ars for food and in the process
produces ethano# and other *yproducts. These microor(anisms can typica##y use the 89car*on su(ars" one of the
most common *ein( (#ucose. Therefore" *iomass materia#s containin( hi(h #e)e#s of (#ucose or precursors to
(#ucose are the easiest to con)ert to ethano#. owe)er" since su(ar materia#s are in the human food chain"
these materia#s are usua##y too e$pensi)e to use for ethano# production.
2ne e$amp#e of a su(ar feedstock is su(arcane. 'ra:i# de)e#oped a successfu# fue# ethano# pro(ram
from su(arcane for a num*er of reasons: (4) 'ra:i# traditiona##y re#ied hea)i#y on imported oi# for transportation
fue#s" which caused a se)ere economic drain on the country; (2) 'ra:i# can attain )ery hi(h yie#ds of
su(arcane; and (.) 'ra:i# has a#so e$perienced periods of poor su(ar markets. As a resu#t" the 'ra:i#ian
(o)ernment esta*#ished pro(rams supporti)e of the industry with the resu#t that 'ra:i# has *een a*#e to
successfu##y produce and use su(arcane for fue# ethano# production.
A#thou(h fun(i" *acteria" and yeast microor(anisms can *e used for fermentation" a specific yeast
(Saccharomces cerevisiae a#so known as 'akers< yeast" since it is common#y used in the *akin(
industry) is fre=uent#y used to ferment (#ucose to ethano#. Theoretica##y" 400 (rams of (#ucose wi## produce /4.>
( of ethano# and >?.? ( of car*on dio$ide. owe)er" in practice" the microor(anisms use some of the (#ucose for
(rowth and the actua# yie#d is #ess than 4000.
2ther *iomass feedstocks rich in su(ars (materia#s known as saccharides) inc#ude su(ar *eet" sweet
sor(hum" and )arious fruits. owe)er" these materia#s are a## in the human food chain and" e$cept for some
processin( residues are (enera##y too e$pensi)e to use for fue# ethano# production.
STARC!" FEEDSTOCKS
Another potentia# ethano# feedstock is starch. Starch mo#ecu#es are made up of #on( chains of (#ucose
mo#ecu#es. Thus" starchy materia#s can a#so *e fermented after *reakin( starch mo#ecu#es into simp#e (#ucose
mo#ecu#es. -$amp#es of starchy materia#s common#y used around the wor#d for ethano# production inc#ude
cerea# (rains" potato" sweet potato" and cassa)a. &erea# (rains common#y used in the @S for ethano# production
inc#ude mai:e and wheat.
Appro$imate#y >6/ mi##ion tonnes of mai:e were produced in the wor#d in 4550 with a*out 200 mi##ion t
produced in the @S. Appro$imate#y ? to 5 mi##ion t" or >0 of @S mai:e (rain went into ethano# in 4550. A
*ushe# of mai:e (rain (2/.. k( or /8 #*. at 4/0 moisture) can produce from 5.> to 40.5 A (2./ to 2.5 (a##ons) of
pure ethano#" dependin( on the techno#o(y used.
Starchy materia#s re=uire a reaction of starch with water (hydro#ysis) to *reak down the starch into fer9
menta*#e su(ars (saccharification). Typica##y" hydro#ysis is performed *y mi$in( the starch with water to
46
Trends in 1ew &rops and 1ew @ses
form a s#urry which is then stirred and heated to rupture the ce## wa##s. Specific en:ymes that wi## *reak the
chemica# *onds are added at )arious times durin( the heatin( cyc#e.
CE##U#OSIC FEEDSTOCKS
Aike su(ar materia#s" starchy materia#s are a#so in the human food chain and are thus e$pensi)e.
7ortunate#y" a third a#ternati)e e$istsBce##u#osic materia#s. -$amp#es of ce##u#osic materia#s are paper"
card*oard" wood" and other fi*rous p#ant materia#.
&e##u#osic resources are in (enera# )ery widespread and a*undant. 7or e$amp#e" forests comprise a*out
?00 of the wor#d<s *iomass. 'ein( a*undant and outside the human food chain makes ce##u#osic materia#s
re#ati)e#y ine$pensi)e feedstocks for ethano# production.
&e##u#osic materia#s are comprised of #i(nin" hemice##u#ose" and ce##u#ose and are thus sometimes ca##ed
#i(noce##u#osic materia#s. 2ne of the primary functions of #i(nin is to pro)ide structura# support for the p#ant.
Thus" in (enera#" trees ha)e hi(her #i(nin contents then (rasses. @nfortunate#y" #i(nin which contains no su(ars"
enc#oses the ce##u#ose and hemice##u#ose mo#ecu#es" makin( them difficu#t to reach.
&e##u#ose mo#ecu#es consist of #on( chains of (#ucose mo#ecu#es as do starch mo#ecu#es" *ut ha)e a
different structura# confi(uration. These structura# characteristics p#us the encapsu#ation *y #i(nin makes
ce##u#osic materia#s more difficu#t to hydro#y:e than starchy materia#s.
emice##u#ose is a#so comprised of #on( chains of su(ar mo#ecu#es; *ut contains" in addition to (#ucose (a
89car*on or he$ose su(ar)" contains pentoses (/9car*on su(ars). To comp#icate matters" the e$act su(ar
composition of hemice##u#ose can )ary dependin( on the type of p#ant.
Since /9car*on su(ars comprise a hi(h percenta(e of the a)ai#a*#e su(ars" the a*i#ity to reco)er and
ferment them into ethano# is important for the efficiency and economics of the process. Recent#y" specia#
microor(anisms ha)e *een (enetica##y en(ineered which can ferment /9car*on su(ars into ethano# with
re#ati)e#y hi(h efficiency.
2ne e$amp#e is a (enetica##y en(ineered microor(anism de)e#oped *y the @ni)ersity of 7#orida that has the
a*i#ity to ferment *oth /9 and 89car*on su(ars. This microor(anism was issued @S patent /"000"000. 2ther
researchers ha)e de)e#oped microor(anisms with the a*i#ity to efficient#y ferment at #east part of the su(ars
present.
'acteria ha)e drawn specia# attention from researchers *ecause of their speed of fermentation. 3n (enera#"
*acteria can ferment in minutes as compared to hours for yeast.
ET!ANO#$FRO%$CE##U#OSE
3n times of fue# shorta(es" fermentation ethano# has *een commercia##y manufactured in the @S from
ce##u#osic *iomass feedstocks usin( acid hydro#ysis techni=ues. &urrent#y" some countries in #ocations with
hi(her ethano# and fue# prices" are producin( ethano# from ce##u#osic feedstocks. owe)er" it is on#y recent#y that
cost9effecti)e techno#o(ies for producin( ethano#9from9ce##u#ose (-7&) in the @S ha)e started to emer(e.
There are three *asic types of -7& processesBacid hydro#ysis" en:ymatic hydro#ysis" and thermochemica#B
with )ariations for each. The most common is acid hydro#ysis. %irtua##y any acid can *e used; howe)er" su#furic
acid is most common#y used since it is usua##y the #east e$pensi)e.
ACID !"DRO#"SIS
There are two *asic types of acid processes: di#ute acid and concentrated acid" each with )ariations.
+i#ute acid processes are conducted under hi(h temperature and pressure" and ha)e reaction times in the ran(e of
seconds or minutes" which faci#itates continuous processin(.
As an e$amp#e" usin( a di#ute acid process with 40 su#furic acid in a continuous f#ow reactor at a
residence time of 0.22 minutes and a temperature of 2.6C& (>/?C7) with pure ce##u#ose pro)ided a yie#d o)er /00
su(ars. 3n this case" 0.5 t (4 ton) of dry wood wou#d yie#d a*out 4?5 A (/0 (a##ons) of pure ethano#. The
com*ination of acid and hi(h temperature and pressure dictate specia# reactor materia#s" which can make the
reactor e$pensi)e.
Dost di#ute acid processes are #imited to a su(ar reco)ery efficiency of around /00. The reason for this is
that at #east two reactions are part of this process. The first reaction con)erts the ce##u#osic materia#s to
4?
1ew &rops and 'io9'ased !roducts
su(ar and the second reaction con)erts the su(ars to other chemica#s. @nfortunate#y" the conditions that cause the
first reaction to occur a#so are the ri(ht conditions for the second to occur. Thus" once the ce##u#osic
mo#ecu#es are *roken apart" the reaction proceeds rapid#y to *reak down the su(ars into other productsBmost
nota*#y furfura#" a chemica# used in the p#astics industry. 1ot on#y does su(ar de(radation reduce su(ar yie#d"
*ut the furfura# and other de(radation products can *e poisonous to the fermentation microor(anisms.
The *i((est ad)anta(e of di#ute acid processes is their fast rate of reaction" which faci#itates continuous
processin(. Their *i((est disad)anta(e is their #ow su(ar yie#d. 7or rapid continuous processes" in order to
a##ow ade=uate acid penetration" feedstocks must a#so *e reduced in si:e so that the ma$imum partic#e dimension
is in the ran(e of a few mi##imeters.
Since /9car*on su(ars de(rade more rapid#y than 89car*on su(ars" one way to decrease su(ar de(radation
is to ha)e a two9sta(e process. The first sta(e is conducted under mi#d process conditions to reco)er the /9
car*on su(ars whi#e the second sta(e is conducted under harsher conditions to reco)er the 89car*on su(ars.
@nfortunate#y" su(ar de(radation is sti## a pro*#em and yie#ds are #imited to around 262 AEt (?0 (a##ons of
ethano#Eton) of dry wood.
The concentrated acid process uses re#ati)e#y mi#d temperatures and the on#y pressures in)o#)ed are usua##y
on#y those created *y pumpin( materia#s from )esse# to )esse#. 2ne concentrated acid process was first
de)e#oped *y @S+A and further refined *y !urdue @ni)ersity and the Tennessee %a##ey Authority.
3n the T%A concentrated acid process" corn sto)er is mi$ed with di#ute (400) su#furic acid" and heated to
400F& for 2 to 8 hours in the first (or hemice##u#ose) hydro#ysis reactor. The #ow temperatures and pressures
minimi:e the de(radation of su(ars. To reco)er the su(ars" the hydro#y:ed materia# in the first reactor is
soaked in water and drained se)era# times.
The so#id residue from the first sta(e is then dewatered and soaked in a .00 to >00 concentration of
su#furic acid for 4 to > hr as a pre9ce##u#ose hydro#ysis step. This materia# is then dewatered and dried with the
effect that the acid concentration in the materia# is increased to a*out 600. After reactin( in another )esse#
for 4 to > hr at 400F&" the reactor contents are fi#tered to remo)e so#ids and reco)er the su(ar and acid. The
su(arEacid so#ution from the second sta(e is recyc#ed to the first sta(e to pro)ide the acid for the first sta(e
hydro#ysis. The su(ars from the second sta(e hydro#ysis are thus reco)ered in the #i=uid from the first sta(e
hydro#ysis.
The primary ad)anta(e of the concentrated process is the hi(h su(ar reco)ery efficiency" which can *e on
the order of o)er 500 of *oth hemice##u#ose and ce##u#ose su(ars. The #ow temperatures and pressures
emp#oyed a#so a##ow the use of re#ati)e#y #ow cost materia#s such as fi*er(#ass tanks and pipin(. @nfortu9
nate#y" it is a re#ati)e#y s#ow process and cost effecti)e acid reco)ery systems ha)e *een difficu#t to de)e#op.
Without acid reco)ery" #ar(e =uantities of #ime must *e used to neutra#i:e the acid in the su(ar so#ution. This
neutra#i:ation forms #ar(e =uantities of ca#cium su#fate" which re=uires disposa# and creates additiona# e$pense.
@sin( some assumed ce##u#ose con)ersion and fermentation efficiencies" ethano# yie#ds from (#ucose
can *e ca#cu#ated for corn sto)er (the a*o)e9(round part of the corn p#ant #ess the ears) as shown in Ta*#e 4
showin( ethano# yie#d from (#ucose. Simi#ar#y" ethano# yie#ds from the $y#ose can *e ca#cu#ated as shown in
Ta*#e 2.
Thus" in this e$amp#e" the tota# yie#dEt of dry sto)er is a*out 226 A (80 (a##ons) of ethano#. These num9
*ers a#so show how critica# su(ar con)ersion and reco)ery efficiencies and fermentation efficiencies are. 3f
one cou#d attain 5/0 for *oth efficiencies" then the yie#d wou#d *e appro$imate#y ./0 AEt (40. (a##ons of
ethano#Eton).
Ta&le '( -thano# yie#d from (#ucose.
+ry sto)er 4 tonne (4000 k()
&e##u#ose content G 0.>/
&e##u#ose con)ersion and reco)ery efficiency G 0.68
-thano# stoichiometric yie#d G 0./4
H#ucose fermentation efficiency G 0.6/
Iie#d from (#ucose 4.4 k( ethano# J 4/4 A (>0 (a##ons)
45
Trends in 1ew &rops and 1ew @ses
Ta&le )( -thano# yie#d from $y#ose.
+ry sto)er 4 tonne (4000 k()
emice##u#ose content G 0.25
emice##u#ose con)ersion and reco)ery efficiency G 0.50
-thano# stoichiometric yie#d G 0./4
Ky#ose fermentation efficiency G 0./0
Iie#d from $y#ose 88 k( ethano# J 68 A (20 (a##ons)
EN*"%ATIC !"DRO#"SIS
Another *asic method of hydro#ysis is en:ymatic hydro#ysis. -n:ymes are natura##y occurrin( p#ant proteins
that cause certain chemica# reactions to occur. owe)er" for en:ymes to work" they must o*tain access to the
mo#ecu#es to *e hydro#y:ed. 7or en:ymatic processes to *e effecti)e" some kind of pretreatment process is thus
needed to *reak the crysta##ine structure of the #i(noce##u#ose and remo)e the #i(nin to e$pose the ce##u#ose and
hemice##u#ose mo#ecu#es. +ependin( on the *iomass materia#" either physica# or chemica# pretreatment methods
may *e used.
!hysica# methods may use hi(h temperature and pressure" mi##in(" radiation" or free:in(Ba## of which
re=uire hi(h9ener(y consumption. The chemica# method uses a so#)ent to *reak apart and disso#)e the crysta##ine
structure.
An e$amp#e of an en:ymatic hydro#ysis9*ased process is under de)e#opment *y the 1ationa# Renewa*#e
-ner(y Aa*oratory (1R-A). After a di#ute acid pretreatment" the s#urry is deto$ified to remo)e materia#s that
wou#d *e poisonous to the microor(anisms used in the process. A sma## part of this s#urry is sent to a separate
)esse# that is used to (row microor(anisms that produce the ce##u#ase en:yme for the process. Another part of
the s#urry is sent to another )esse# to maintain and (row a yeast cu#ture for fermentation. 3n the 1R-A pro9
cess" *oth en:ymes and the fermentation microor(anisms are added at the same time to the s#urry" and su(ar
con)ersion and fermentation occur simu#taneous#y in a process ca##ed simu#taneous saccharification and co9
fermentation (SS&7).
+ue to the tou(h crysta##ine structure" the en:ymes current#y a)ai#a*#e re=uire se)era# days to achie)e
(ood resu#ts. Since #on( process times tie up reactor )esse#s for #on( periods" these )esse#s ha)e to either *e
=uite #ar(e or many of them must *e used. -ither option is e$pensi)e. &urrent#y the cost of en:ymes is a#so
too hi(h and research is continuin( to *rin( down the cost of en:ymes.
owe)er" if #ess e$pensi)e en:ymes can *e de)e#oped en:ymatic processes ho#d se)era# ad)anta(es: (4)
their efficiency is =uite hi(h and their *yproduct production can *e contro##ed; (2) their mi#d process condi9
tions do not re=uire e$pensi)e materia#s of construction; and (.) their process ener(y re=uirements are re#a9
ti)e#y #ow.
T!ER%OC!E%ICA# +ROCESSES
There are two ethano# production processes that current#y emp#oy thermochemica# reactions in their
processes. The first system is actua##y a hy*rid thermochemica# and *io#o(ica# system. An e$amp#e is a process
under de)e#opment *y 'ioen(ineerin( Resources in 7ayette)i##e" Arkansas. 'iomass materia#s are first
thermochemica##y (asified and the synthesis (as (a mi$ture of hydro(en and car*on o$ides) *u**#ed throu(h
specia##y desi(ned fermenters. A microor(anism that is capa*#e of con)ertin( the synthesis (as is introduced
into the fermenters under specific process conditions to cause fermentation to ethano#.
The second thermochemica# ethano# production process does not use any microor(anisms. 3n this
process" *iomass materia#s are first thermochemica##y (asified and the synthesis (as passed throu(h a reactor
containin( cata#ysts" which cause the (as to *e con)erted into ethano#. An intensi)e effort was made *y
Hermany in Wor#d War 33 to de)e#op these processes for fue#. 1umerous efforts ha)e *een made since then to
de)e#op commercia##y )ia*#e thermochemica#9to9ethano# processes.
-thano# yie#ds up to /00 ha)e *een o*tained usin( synthesis (as9to9ethano# processes. Some processes
that first produce methano# and then use cata#ytic shifts to produce ethano# ha)e o*tained ethano# yie#ds in the
20
1ew &rops and 'io9'ased !roducts
Ta&le ,( A partia# #istin( of companies de)e#opin( ethano#9from9ce##u#ose techno#o(ies.
&ompany L !rimary
head=uarters #ocation Techno#o(y feedstock -thano# capacity &omments
'&3" +edham" DA +i#ute acid 'a(asse 6/80 mi##ion AEyr !#ant to *reak
(20 mi##ion (py
:
) (round in 2002
'ioen(ineerin( Resources" Thermochemica# !i#ot p#ant
7ayette)i##e" AR (asification operatin(
with fermentation
-th$$ 3nternationa#" Thermochemica# Wood !i#ot p#ant
Aurora" 21 (asification with operatin(
cata#ytic con)ersion
7ue# &e## -ner(y" Thermochemica# Wood !i#ot p#ant
Aakewood" &2 (asification with operatin(
cata#ytic con)ersion
3o(en" 2ttawa" 21 -n:ymatic 2at hu##s" .6? mi##ion AEyr -$perimenta#
switch(rass" (4 mi##ion (py) p#ant
wheat straw" operatin(
and corn sto)er
Dasada" 'irmin(ham" AA &oncentrated acid DSW .6?0 mi##ion AEyr !#ant to *reak
(40 mi##ion (py) (round
ear#y 2002
!as:ner Techno#o(ies" 3nc" Acidified a=ueous Wood &ommercia#
Surrey" '& acetone process p#ants under
construction
!ure%ision Techno#o(y" -n:ymatic Wood &onstructin(
7t. Aupton" &2 pi#ot p#ant
:
(pyJ(a##ons per year
ran(e of ?00. @nfortunate#y" #ike the other processes" findin( a cost9effecti)e a##9thermochemica# process has
*een difficu#t.
CO%%ERCIA#I*ATION EFFORTS
Se)era# -7& p#ants were *ui#t and operated in )arious countries in Wor#d War 33" when wartime conditions
chan(ed economic conditions and priorities. These countries inc#uded Hermany" Russia" &hina" Morea"
Swit:er#and" the @nited States" and other countries. Today" due to competition from synthetica##y produced
ethano#" on#y a few of these p#ants are sti## operatin( with )irtua##y a## of them in Russia.
A paper manufacturin( p#ant in Temi9schammai(" Nue*ec" operates off of *yproduct su(ars contained in
Osu#fite #i=uor"P which contains a*out 20 fermenta*#e su(ars. This is the on#y faci#ity of its kind in 1orth
America. This faci#ity is operated *y Tem*ec" 3nc." and produces > mi##ion (a##ons per year of industria# (rade
ethano#.
Se)era# efforts are underway in 1orth America to commercia##y produce ethano# from wood and other
ce##u#osic materia#s as a primary product. Ta*#e . partia##y summari:es these companies and their acti)ities"
which are in )arious states of pro(ress.
SU%%AR"
-thano#9from9ce##u#ose (-7&) ho#ds (reat potentia# due to the widespread a)ai#a*i#ity" a*undance" and
re#ati)e#y #ow cost of ce##u#osic materia#s. owe)er" a#thou(h se)era# -7& processes are technica##y feasi*#e"
cost9effecti)e processes ha)e *een difficu#t to achie)e. 2n#y recent#y ha)e cost9effecti)e -7& techno#o(ies
*e(un to emer(e.
24