fleprinted lrom BI0TECH]{0L0GY PR0GRESS, Seplember 1987

Extractive Fermentation of Acetone and

Butanol : Process Design and Economic
Evaluation
The econotnics of prod,ucing butanol bg extracthse
fermentation
u)ere eramined. Capital cost and energa requirements u)ere
significantlg reduced bA the use of extracthse
fermentation.
Steven Roffer, Harvey W. Blanch, and Charles R. Wilke,
Department of Chemical Engineering University of California, Berkeley
,
CA 94720
Introduction
Al though a wi de range of chemi cal s can be produced by
fermentati on, the accumul ati on of toxi c products i n the
fermentati on broth often i nhi bi ts further product forma-
tion. Reactor productivities are low and the products
are
obtai ned i n di l ute form. Fermentati on processes are thus
typically capital-intensive since large reactors and down-
stream processing equipment are required to handle the
large volumes of water introduced into the process. Large
amounts of energy must also be expended to recover the
dilute products from the broth.
The ef f ect s of end-product i nhi bi t i on can be reduced
by removi ng toxi c fermentati on products from the broth
i n si tu. Several methods of i n si tu product recovery have
been devel oped. Vol ati l e ferrnentati on products, such as
ethanol , can be removed from the broth by creati ng a vac-
uum i n t he f errnent or so t hat i nhi bi t ory product di st i l l
from the broth as they form
1,141.
Vol ati l e i nhi bi tory
product s have al so been removed i n si t u by st ri ppi ng
them from the broth into a gas stream. The gas strearn can
be passed di rectl y through the fermentor
[5,
6] or can be
conf i ned t o one si de of a semi perrneabl e membrane
[ 7, 8] .
A number of the methods have been devised to remove
nonvolatile inhibitory products from fermentation broth
in situ.Inhibitory products have been adsorbed onto ion
exchange resin
19-121,
activated carbon
U3-l6l
and poly-
meri c resi ns
117-201.
Li qui d-l i qui d extracti on has al so
been used for the i n si tu removal of i nhi bi tory products
from fermentation broth. Aqueous phases formed by the
addition of polymers to the broth
[21-27]
and organic sol-
vents
128-341have
both been used to extract i nhi bi tory
products as they form. Perstraction, in which the organic
solvent is separated from the fermentation broth by .
semi permeabl e membrane
[35,
36], has al so been
employed
The underlying purpose of all methods of in situ prod-
uct recovery i s to decrease the cost of produci ng chemi -
cals by fermentation. Maiorella, et al.
[37]
have evaluated
t he cost of produci ng et hanol i n f l ash f erment at i on and
Schout ens and Groot
[ 38]
have recent l y est i rnat ed t he
cost of produci ng i so-propanol /butanol /ethanol i n a novel
fbrmentati on process empl oyi ng pervaporati on to remove
the al coh al s i n si tu. Other than these studi es, however,
few economi c eval uati ons of i n si tu product recovery fer-
mentati ons have been made.
In thi s paper, the economi c feasi bi l i ty of produci ng ac-
et one and but anol by ext ract i ve f erment at i on i s exam-
i ned. Cl ost ri di um acet obut yl i cunr, whi ch can f . ennent
sugars or starch to a rni xture of acetone, butanol , trnd etha-
nol , i s t ot al l y i nhi bi t ed by but anol concent rat i ons of
10-15 gl L
[ 39, 40, 41] . Removal of bt rt anol duri ng f ermen-
tati on has been shown to reduce the effect of butanol i n-
hi bi ti on and i ncrease vol umetri c btrtanol prodtrcti vi ty i n
bat ch
[ 33]
and f ed-bat ch
[ 34] cul t ure. The f easi bi l i t y of
usi ng conti nuous processi ng steps i n extracti ve fermenta-
ti on has al so been demonstrated i n a bench scal e-process
i n whi ch f erment at i on brot h was cont i nuousl y "y"l "d t n
an ext ract i on col ul mn
[ 42] .
Resul t s of t hese st udi es are
used t o desi gn an ext ract i ve f ennent at i on pl ant wi t h an-
nual butanol producti on of 200 mi l l i on pounds. The cost
of produci ng but anol by ext ract i ve f erment at i on i s est i -
rnated and compared to the conventi onal batch fermenta-
t i on process.
The Conventi onal Butanol Fermentati on Process
Fermentati on prodtrcts are conventi onal l y produced i n
bat ch f erment at i on. A pl ant usi ng bat ch f er. ment at i on t o
produce butanol was desi gned to act as a benchmark for
compari son wi th the extracti ve fennentati on process. The
bat ch process desi gn rel i es heavi l y on descri pt i ons of
commerci al but anol f erment at i on f aci l i t i es
[ 43, 44), and
on a pri or economi c anal ysi s of the conventi onal butanol
fermentati on of mol asses
[45].
Fi gure I shows a schemat i c of t he bat ch f erment at i on
process. Mol asses, contai ni n g 55 wtVo fermentabl e sugars
and 30 wtVo nonfermentabl e sol i ds, i s di l uted to 60 g/L
sugar and mi xed wi t h nut ri ent s i n t he f eed mi x t ank.
Butanol i nhi bi ti on prevents the use of hi gher sugar con-
Sept ember, 1987 131 Biotechnology Progress (Vol. 3, No. 3)
FIGURE 1. Process flow diagram of a batch fermentation for production of butanol, ethanol, and acetone.
cw
ACETONE
STORAGE
THANOL
STORAGE
DECANTER
PRE.
FERMENTOR
STILLAGE EVAPORATORS
BUTANOL
STRIPPER
olm
ROTARY
DRYER
5Oosio
slebm-
50psi g
steom
E}
l5Oosio
slebm-
BUTANOL
STORAGE
DRIED-STILLAGE
STORAGE
centrati ons i n the fermentor. The di l uted feed i s conti nu-
ousl y st eri l i zed by di rect st eam i nj ect i on and charged
into batch fermentors. Fermentors are inoculated with ac-
ti vel y growi ng cel l s of a strai n of Cl ostri di unt
acet obugt l i cum produced i n smal l er seed f erment ors.
After 30 hours of fermentati on, the broth, contai ni ng (i n
SI L):
13. 7 but anol , 5. 4 acet one, 1. 5 et hanol , 0. 2 but yri c
aci d, 0. 3 acet i c aci d, and 3. 0 cel l s, i s di scharged t o t he
broth surge tank. The batch fermentors are operated on a
st aggered schedul e so t hat downst ream processi ng i s
conti nuous.
Butanol , acetone, and ethanbl are stri pped frorn the
broth wi th 50 psi g steam i n the beer stri pper after bei ng
heated to 100' C by heat exchange wi th the stri pper-
bottoms product. The stri pped broth, contai ni ng aceti c
and butyri c aci ds, cel l s, protei ns and nonfermentabl e mo-
l asses sol i ds, i s evaporat ed t o 5O wt % sol i ds i n t he
mul ti pl e-effect sti l l age evaporators and then dri ed to 85
wtTo solids in a rotary dryer to give a dried stillage prod-
uct that can be used as an ani mal feed suppl ement
[43].
The overhead vapor from the beer stri pper, contai ni ng
approxi matel y 7O wtVo water and 30 wt%o acetone, bu-
tanol , and ethanol , i s separated i n a seri es of four di sti l l a-
ti on col trmns. 99.5 wt%o acetone i s taken overhead from
t he f i rst col umn. Thi s col umn i s operat ed at 0. 7 at m so
that low pressure steam from the last effect of the stillage
evaporators can be used i n the reboi l er. The bottoms
product from the acetone column is fed to the ethanol col-
umn, whi ch operates at 0.3 atm pressure.
Vacuum operati on reduces the refl ux needed to pro-
duce the 95 wtTo ethanol overhead product and allows the
total reboi l er duty to be met by condensi ng the overhead
vapors from the beer stri pper i n the ethanol col umn
reboi l er. The bottoms product from the ethanol sti l l and
the overhead streams from the water and butanol stri p-
pers are fed to a decanter where an aqueous-rich phase is
allowed to separate from a butanol rich phase. The water-
ri ch phase, contai ni ng approxi matel y 9.5 wtVo butanol , i s
refluxed to the water stripper, which produces water con-
t ai ni ng l ess t han O. Ol wt %o but anol . The but anol -ri ch
phase, containing about 23 wt%o water, is refluxed to the
butanol stri pper, whi ch produces a 99.7 wtTo butanol
product. The operati ng pressures of the stri ppi ng col -
urnns are set such that about half of the heat duty in the
wat er st ri pper reboi l er i s met by condensi ng t he over-
head vapors from the butanol stripper.
Biotechnology Progress (Vol. 3, No. 3)
132 September,1987
Design of the Conventional Fermentation Process
A batch fermentati on process was desi gned to produce
200 mi l l i on pounds of butanol annual l y. The pl ant i s op-
erated 24 hours a day wi th a stream factor of 0.95. The
batch fermentors were assumed to operate at a butanol
producti vi ty of 0.58 g/L-hr, whi ch i s the producti vi ty of
Cl ostri di um acetobutyl i cum
(ATCC 824) grown i n batch
cul t ure on gl ucose
[ 33] ;
t hi s same st rai n of Cl ost ri di um
was used i n extracti ve fermentati on experi ments[34,42).
The yi el ds of products i n batch cul ture were the val ues
reported by Marl att and Datta
[46]
i n thei r economi c
evaluation of the fermentation of corn to butanol.
UNI FAC, a group-cont ri but i on met hod of est i mat i ng
acti vi ty coeffi ci ents i n noni deal l i qui d mi xtures
[47],
was
used t o model vapor-l i qui d equi l i bri um i n t he recovery
sect i on of t he process. Di st i l l at i on col umns were de-
si gned usi ng modi fted computer programs devel oped by
Fredensl und et aI .
[ aB] .
St ai nl ess st eel const ruct i on was speci f i ed f or equi p-
ment i n di rect contact wi th fermentati on broth because of
the presence of aceti c and butyri c aci ds. Carbon steel
constructi on was used for other equi pment.
Economic Evaluation of the
Conventional Fermentation Process
The costs of major equipment in the batch fermentation
process are l i sted i n Tabl e l . Costs were esti mated from
i nf ormat i on gi ven by Pet ers and Ti mmerhaus
[ 49] ,
Bar-
thol omew and Rei sman
[50],
Baasel
[5]l
and frorn vend-
or' s quotati ons
[52],
updated to a l ate f986 basi s (\{SI
:
800). The f erment at i on and st i l l age processi ng sect i ons
each account for about 4OVo of the total purchased equip-
ment cost of the conventi onal batch process. Di sti l l ati on
and product storage each account for onl y about LOVo of
equi pment cost.
Fixed capital and total capital investments for the batch
fermentati on pl ant are shown i n Tabl e 2. The batch pro-
cess i s capi t al i nt ensi ve, requi ri ng a t ot al i nvest ment of
$154
mi l l i on. Tabl e 3 shows t he n-ranuf act uri ng cost s f or
the batch fermentati on process. The costs of the co-
products, acetone and ethanol , were taken from the
Chemi cal Market i ng Report er
[ 53] .
The val ue of dri ed
sti l l age i s updated from Mai orel l a et al .I54l . A conserva-
ti ve credi t of
$0.
f0nb hydrogen i s used because gas sepa-
rati on equi pment i s not i ncl uded i n thi s esti mate. In addi -
t i on, a credi t of $0. 85/ 1000 l bs l ow pressure st eam
generated i n the l ast effect of the sti l l age evaporators i s
taken
[55].
No credi t i s taken for carbon di oxi de.
The rati onal pri ce of butanol for an 18% di scounted
cash f l ow rat e of ret urn on i nvest ment i s 61. 7 cent s/ l b.
The purchase of mol asses accounts for 67Vo of the fi nal
cost of butanol . Sti l l age processi ng al so represents a ma-
j or
component of the cost of produci ng butanol by batch
fermentation. The large amounts of steam required in the
stillage evaporators could be reduced by pre-concentrat-
ing the stillage by precipitation or filtration. Soluble nu-
trients, however, are lost in these operations. In addition,
large volumes of spent broth would have to be treated to
reduce i ts hi gh BOD l evel before di scharge. Mol asses
sti l l age has a BOD of 15 to 55 Kg O2l m3
[54,56).
At a BOD
of 25 Kg Orlm3, the fermentation process requires the re-
moval of L.7 x 108 kg O2l yr. At a treatment cost of
$98.4/1000 lb BOD
[46],
waste treatment would add over
18 cents/l b to the cost of butanol . Thus, al though the cost
of evaporati ng the di l ute sti l l age i s hi gh, pre-concentra-
tion of molasses stillage does not appear attractive.
The est i mat ed cost of produci ng but anol by bat ch f er-
mentati on i n thi s study i s about twi ce the cost esti mated
by Marlatt and Datta
146l
for the {'ermentation of butanol
from corn. The di fference i n butanol cost i s due to di ffer-
ent assumpt i ons used i n t he eval uat i ons. Fi rst , Marl at t
and Dat t a assumed a vol umet ri c but anol product i vi t y
about t hree t i mes hi gher t han t he product i vi t y used i n
t hi s st udy, t hus f ewer f erment ors were requi red i n t hei r
desi gn. Second, Marl at t and Dat t a assumed st eam was
produced by coal combusti on, wi th a credi t for cogenera-
ti on and a credi t for the heati ng val ue of fermentor off-
gases. Thi s resul t ed i n a net st eam cost of
$0. 49/ f
000 l b
150 psi g steam. The 150 psi g steam was charged at
$4. 00/ 1000
l b i n t hi s st udy. Fi nal l y, a credi t of 25. 2
cents/l b of butanol for corn based co-products was taken
for a net raw materi al cost of 13.9 cents/l b butanol . In thi s
study, a co-product credi t of 9.5 cents/l b butanol i s taken,
gi vi ng a net raw materi al cost of 32.7
l /l b
butanol . Ifi the
butanol producti vi ty, steam cost, and net raw matei i al s
cost used by Marl att and Datta are used i n thi s study, the
rati onal cost of butanol i s 28
@/l b,
wi thi n \Vo of the
butanol cost esti mated by them.
The butanol producti vi ty, steam cost, and net raw mate-
ri al cost used i n here are bel i eved t o be appropri at e f or\
the batch fermentati on of butanol from mol asses. Produc-
t i vi t i es rangi ng f rom 0. 16 t o 0. 51 g/ L hr have been re-
ported for Cl ostri di um acetobutql i cum growi ng i n batch
cul t ure on gl ucose or whey
[ 25, 31, 4] ,
57f . The but anol
producti vi ty used i n thi s study,0.58 g/L hr, i s the produc-
ti vi ty of the strai n of Cl ostri di um acetobutgl i cum (ATCC
824) used i n ext ract i ve f erment at i on st udi es
[ 34,
42]
when grown i n bat ch cul t ure
[ 33] .
The 150 psi g st eam
was charged at
$4. 00/ f 000
l b because t he f easi bi l i t y of
provi di ng steam at $0.49/1000
l b by burni ng the fermen-
tor off-gas, whi ch contai ns l arge amounts of carbon di ox-
i de, has not been demonstrated.
Extractive Fermentation of Butanol
I n ext ract i ve f erment at i on, end-product i nhi bi t i on i s
reduced by extracti ng toxi c fermentati on products out of
the broth i nto an organi c sol vent. The sel ecti on of the or-
gani c sol vent to be used i n extracti ve fermentati on i s an
i mportant process deci si on. The most severe constrai nt i n
the sel ecti on of a sol vent i s that i t must be bi ocompatabl e
wi th the fermenti ng rni croorgani sms. Moreover, traces of
sol vent remai ni ng i n the broth shoul d not affect the val ue
of sti l l age byproducts. The extracti on sol vent shoul d have
a high capacity for the fermentation products in order to
mi ni mi ze sol vent i nventory and product recovery costs. If
t he ext ract ed product s are recovered by di st i l l at i on, t he
sol vent shoul d be l ess vol at i l e t han t he product s so t hat
l arge amounts of sol vent wi l l not have to be vapori zed i n
t he di st i l l at i on col umn. The ext ract i on sol vent shoul d
not, however, be so nonvol ati l e that expensi ve hi gh pres-
sure st eam i s requi red i n t he reboi l er of t he sol vent re-
generat i on col umn. Fi nal l y, t he sol vent shoul d be onl y
spari ngl y sol ubl e i n wat er i n order t o mi ni mi ze sol vent
l osses.
Ol eyl al cohol , di l uted to 50 wtVo i n decane, was chosen
as the extracti on sol vent i n the extracti ve fermentati on
Sept ember, 1987 133 Biotechnology Progress
{Vol.
3, No. 3)
TABLE l. Puncmsno EgunMENT Cosrs ron B.lrcn FBrursNTATroN oF BurANoL.
Item
Si ze Units
Cost
(rtrVo)
STORAGE (2 weeks)
Molasses
Butanol
Acetone
Ethanol
Dried stillage
FERMENTATION
Fermentor
Prefermentor
Sterilizer
Sterilizer heat recovery
exchanger
Feed mix tank
Feed mix tank agitator
Broth surge tank
PRODUCT RECOVERY
Steam stripper
Stripper preheater
Intercolumn heat exchanger
Acetone column feed cooler
Acetone column
Acetone column condenser
Acetone column reboiler
Ethanol column
Ethanol column condenser
Water stripper
Water stripper condenser
Water stripper intercolumn
reboiler
Water stripper reboiler
Butanol stripper
Butanol stripper reboiler
STILLAGE HANDLING
Stillage evaportor
Rotary dryer
Heat recovery exchanger
3.3 x 106 gal (c.s.)
1.3 x 106 gal (c.s.)
5.4 x 105 gal (c.s.)
1.5 x 105 gal (c.s.)
1.0 x 105 gal (c.s.)
1.3 x 105 gal (s.s.)
1.1 x l Oa gal (s.s.)
insulated tubing (c.s.)
7000 ft2 (c.s.)
2.6 x l Oa gal (s.s.)
130 HP (s.s.)
1.32 x 105 gal (s.s.)
8.25 ft dia,25 plates (s.s.)
7000 ff (s.s.)
1430 ft2
(c.s.)
3290 ft2 (c.s.)
8.8 ft dia, 50 trays (c.s.)
2190 ft2 (c.s.)
1870 ft2
(c.s.)
8.5 ft dia, 58 trays (c.s.)
5500 ft' (c.s.)
7.5 ft dia, 20 plates (c.s.)
l2B0 ft2 (c.s.)
1500 ft2 (c.s.)
1330 ft2 (c.s.)
7.9 ft dia, 20 plates (c.s.)
24OO ft2 (c.s.)
16,000 ft2 per effect, 5 effects
7740 ft2, 29.4 HP
50 ft2 (s.s.)
2
I
I
I
30
62
3l
8
32
8
8
4
I
I
I
I
4
D
D
860
zto
r07
40
l , gl I
3,028
lo,7go
1,390
r38
l,[x0
?2A
165
759
4
I
I
I
t
I
I
2
I
2
I
15,386
1,364
872
?5
40
a$
37
29
uo
53
r93
%l
u
?4.
r05
u
3,6l ?
L2,3il
2,UO
55
15,%g
$37,280
Total Purchased Equipment Costs:
process. Oleyl alcohol, a commercially available mixture
of C-16 to C-18 unsaturated pri mary al cohol s, wi th C-18
predominating, is a liquid at room temperature with a
density of 0.84 g/cm3. Oleyl alcohol has a high capacity for
butanol with a distribution eoefficient (g/L butanol in
solvenVg/L butanol in broth) of 4.3
[34].
Bench-scale ex-
tractive fermentations using oleyl alcohol as the extrac-
ti on sol vent have been demonstrated i n batch
[3I,33],
fed-batch
[34], and continuous extracti on
[42]
systems.
Volumetric butanol productivity was increased from 0.58
g/L hr in batch culture to 1.5 glLhr in fed-batch extractive
fermentation using oleyl alcohol
[J4]. Glucose solutions
up to 500 g/L could be ferrnented and ftnal waste water
volume was decreased about fourfold. In a bench-scale
extractive fermentation system in which butanol was con-
tinuously extracted from fed-batch culture, rapid fermen-
tation was maintained for 55 hours at an overall butanol
productivity about twice that obtainable in regular batch
or fed-batch culture
[42].
Oleyl alcohol may be diluted with decane to improve
Biotechnology Progress (Vol. 3; No. 3)
134 September,l 987
TABLE 2. C.lptrl.r INvnsrNrENT FoR Barcn
FnnurNrarroN oF BuuNor-.
fermentor to the extraction colurnn where inhibitory f'er-
mentati on products are extracted i nto the ol eyl al cohol /
decane sol vent. Extracted broth i s recycl ed to the
fermentor whi l e l oaded sol vent, contai ni ng an average of
2L gl L butanol , 3.5 g/L acetone, and 0.4 g/L ethanol , i s
sent t o t he sol vent -regenerat i on col umn where but anol ,
acetone, and ethanol are di sti l l ed from the sol vent. The
sol vent -regenerat i on col umn operat es under vacuum so
that the bottoms temperature i s l ow enough to use 150
psi g st eam i n t he reboi l er. But anol i s mai nt ai ned bel ow
severel y i nhi bi tory l evel s i n the fermentor and the fed-
batch fermentation is carried out for 75 hours. The flow of
sugar to the fermentor is stopped near the end of the fer-
ment at i on i n order t o al l ow resi dual sugar t o be con-
sumed.
At the end of fermentati on, products remai ni ng i n the
broth are recovered in the same way as in the batch fer-
ment at i on process. Resi dual but anol , acet one, and et ha-
nol are stri pped from the broth i n the beer stri pper and
separated i n a seri es of four di sti l l ati on col umns. Sti l l age
i s dri ed to 85 wtTo sol i ds and stored for sal e. Products re-
covered from the extraction solvent are purified in a sepa-
rate seri es of col umns. The overhead vapor from the
sol vent -regenerat i on col umn i s f i rst condensed i n t he
sol vent-si de ethanol col umn reboi l er to provi de the heat
duty for that col umn and then fed to the sol vent-si de
butanol col umn. Because l i ttl e water i s extracted i nto the
decane/ol eyl al cohol sol vent, butanol can be recovered
di rectl y as the bottoms product of the fi rst di sti l l ati on col -
umn. The overhead product i s sent t o t he sol vent -si de
ethanol col umn where 95 wt%o ethanol i s recovered as the
bottoms product. The remaining water and acetone in the
overhead product is sent to the broth side acetone column
for further rectification.
Design of the Extractive Fermentation Process
The ti me-dependent concentrati ons of products i n the
fermentor and extraction solvent during fed-batch extrac-
ti ve fermentati on were esti mated by numeri cal si mul a-
ti on of the fermentati on process. The vol umetri c produc-
ti on rates of butanol , acetone, ethanol , aceti c and butyri c
aci ds, cel l s, hydrogen, and carbon di oxi de over the course
of extractive fermentation were estimated from a model of
the acetone-butanol fermentation developed by Votruba,
Vol esky and Yerushal mi
[58],
modi fi ed to fi t data of fed-
batch extracti ve fermentati on. The ti me-dependent con-
cent rat i ons of product s i n t he brot h and sol vent phases
exi t i ng t he ext ract i on col umn were al so est i mat ed. The
desi gn assume that a Karr reci procati ng-pl ate extracti on
col umn i s used to contact broth and extracti on sol vent. A
Karr col umn was used i n the desi gn because i t has been
successful l y used to remove butanol i n-si ,tu from a bench-
scal e fed-batch fermentati on[42]. Operati on of the Karr
col umn i s descri bed el sewhere
[59,
60]. The phase hol d-
ups and mass-transfer coeffi ci ents i n the col umn were es-
ti mated from a model devel oped bv Hafez, Bai rd, and
Ni rdosh
161, 621.
The esti mati on of the product concentrati ons i n the ex-
tractor outl et streams, however, was compl i cated by the
presence of backmi xi ng i n the col umn and by the conti n-
ued formati on of products by vi abl e cel l s i nsi de the
extracti on col umn duri ng extracti ve fermentati on. Equa-
ti ons were thus deri ved to predi ct the outl et concentra-
ti ons from a di fferenti al contactor when product forma-
$MM
l . Di rect Cost s
purchased equi pment
equ i pment i nstal l ati on
i nstmmentati on and control s
pi pi ng
el ectri cal
bui l di ngs
yard i mpr<l vements
servi ce faci l i ti es
l and
Total Di rect Costs
Indi rect Costs
engi neeri ng and contractor' s f' ee
constructi on expenses
Worki ng Capi tal
feedstocks
fi ni shed products
accounts recei vabl e
cash
spare parts
2.
37.28
14. 91
5.59
r6. 78
3. 73
5.97
2.98
22.37
2.24
l l t 35
17. 89
I I . 93
3.
29.82
r. 70
1. 79
6.80
0.58
t . 52
Total Capi tal Investrnent:
I2.39
154.06
the physi cal properti es of the extracti on sol vent. Because
ol eyl al cohol i s vi scou' s, mass t ransf er and phase separa-
ti on are sl ow when undi l uted ol eyl al cohol i s used as the
extracti on sol vent. At 37"C, ol eyl al cohol has a vi scosi ty of
L7 cp, while a 50/50 wt%o mixture of oleyl alcohol and dec-
ane has a vi scosi ty of onl y 3.1 cp. In addi ti on, ol eyl al co-
hol is nonvolatile with a boiling range of 282-349oC; ex-
pensi ve hi gh-pressure st eam i s requi red t o regenerat e
undi l ut ed ol eyl al cohol . Di l ut i on of ol eyl al cohol wi t h
decane l owers the boi l i ng poi nt of the sol vent mi xture so
t hat cheaper, I ow-pressure st eam can be used i n t he
reboi l er. It has been assumed that ol eyl al cohol di sti l l ed
wi thout denaturati on; l i mi ted experi mental studi es sup-
port thi s assurnpti on
I
2l .
Figure 2 shows the flow sheet for an extractive ferrnen-
tati on process usi ng a 50 wtVo mi xture of ol eyl al cohol i n
decane as the sol vent. Fed-batch operati on of the fer-
ment ors i s used t o prevent subst rat e i nhi bi t i on of t he
cel l s by hi gh concentrati ons of sugar i n the fermentor.
The fermentors are charged with molasses diluted to 100
g/L sugar, i nocul ated wi th cel l s grown i n the seed fer-
mentor, and operated as batch fermentors until the sugar
concentrati on decreases to about 15 gl L, at whi ch ti me
fed-batch operati on i s i ni ti ated. Mol asses, at an equi va-
lent of 50A glL sugar, is fed to the fermentors as needed to
mai ntai n the resi dual sugar l evel at 12-15 gl L. A concen-
trated feed is used to minimize the amount of water intro-
duced i nto the process. Whol e broth i s ci rcul ated from the
September,l 987 Biotechnology Progress (Vol. 3, No. 3) 135
TABLE 3. MeNurAcruRrNG Cosrs ron BmcH FsnMnNTATroN on Bur,llrlor,.
Item Basi s
otlb
butanol
Raw Materials
nutrients
water
mol asses
Uti l i ti es
power
cool i ng water
atm steam
50 psig steam
150 psi g steam
Co-products
acetone
ethanol
hydrogen
dri ed sti l l age
atm steam
Total Variable Cost
operating labor
.
supervi si on
maintenance
operati ng suppl i es
laboratory charges
taxes & insurance
pl ant overhead
@/lb BuOH
$1.10/1000 eal
$100/ton, 55Vo sugar
$0.08/kwh
$0.2511000
gal
$0.85/rooo
Ib
$.50/1000 lb
$4.00/1000 lb
.
$0.27nb
$0.26llb
$0.l0nb
$60/ton,857o
solid
$0.85/1000 lb
$I2lman
hr, 42 operators
LSVo operating labor
4Vo frxed capital'cost
LSTo maintenance
LSVo operating labor
L.1Vo fixed capital cost
22 people,
$80,00o/year
Total fixed cost
1. 0
0. 8
4L. 2
0.6
o.4
0.2
11. 0
0.8
(10.6)
(2.8)
(0.7)
(e.5)
(1. 3)
31. 1
2. L
0.3
2. 8
0.4
0. 3
1. 0
0.9
Capital charges (30Vo of total capital cost)
Rational Price (variable * fixed cost * capital charges)
7. 8
22.8
61. 7
ti on occurs i n one of the phases and there i s some degree
of backmi xi ng i n both phases
[63].
Product forrnati on rates i nsi de the extractor were as-
sumed to be the same as those inside the fermentor at any
gi ven ti me. The degree of backmi xi ng i n the extracti on
col umn was esti mated usi ng effecti ve axi al di spersi on
coefficients measured in a 7.6 cm dia column
164) and 5
cm di a col umn
[65].
The effect of col umn di ameter on the
degree of backmi xi ng was esti mated from equati ons
gi ven by Karr for col umn scal e-up
[66].
A si mul ati on of
the fed-batch extractive fermentation process operating at
the condi ti ons l i sted i n Tabl e 4 gave an overal l butanol
producti vi ty of 0.89 g/L hr. Thi s i s a conservati ve esti -
mate, since productivities as high as 1.5 glL hr have been
measured in laboratory scale fed-batch extractive fermen-
tati ons
[34].
Di sti l l ati on col umns were desi gned as previ -
ousl y descri bed.
Economic Evaluation of the Extractive
Fermentation Process
Equipment costs for a plant using extractive fermenta-
ti on to produce 200 x 106Ib butanol annual l y are l i sted i n
Tabl e 5. The total purchased equi pment cost for the ex-
tracti ve fermentati on process i s
$29.7
mi l l i on, ZOVo l ess
than the equi pment cost of the conventi onal batch fer-
mentation process. The lower cost reflects the higher pro-
ducti vi ty and reduced vol ume of broth that must be
treated in extractive fermentation; fewer fermentors and
sti l l age evaporators are requi red i n the extracti on pro-
cess. The extractive fermentation process requires a total
capi tal i nvestment of
$f25
mi l l i on.
Table 6 shows a breakdown of the manufacturing costs
associated with extractive fermentation. Byproduct cred-
its and raw materials costs were the same as those used in
the batch fermentati on process eval uati on. In addi ti on,
the cost of oleyl alcohol was taken to be $1.35/lb [67]
and
the cost of decane was esti mated to be
$0.75l gal [53].
Manufacturi ng costs are decreased frorh 38.9 cents/l b
butanol i n batch fermentati on to 30.4 cents/l b i n extrac-
ti ve fermentati on, pri mari l y because l ess steam i s re-
qui red to produce a dri ed sti l l age product. The rati onal
pri ce of butanol produced by extracti ve fermentati on i s
48. 9 cent sl l b, ZOVo l ower t han t he 61. 7 cent s/ l b cost of
butanol produced by the batch fermentation of molasses.
The savings obtained by using extractive fermentation
to produce butanol may be even greater i n actual prac-
ti ce. A conservati ve val ue of butanol producti vi ty was
Biotechnology Progress (Vol. 3, No. 3) Sept ember, 1987
FIGURE 2. Process flow diagram of a fed-batch fermentation employing Oleyl alcohol-decane as extractant.
Molosses
PRE-
FERMENTC}R
STERILIZER
c02
H2
EEDBATCII
DffRACNON
@Lt
,lN
STILLAGE EVAPORATORS
DECANTER
BROTH
9JRGE
TANK
BEER
1.5 otm
WATER
STRIPPER
STORAGE
TABLE 4. OprruruNc CoNDITToNs Usnn IN FED-
B.n tcn Exrru.crrvs FnRMnNTATToN Srlrur.ltrorus.
Parameter Val ue
used i n the exracti ve fermentati on desi gn. Hi gher
producti vi ti es, si mi l ar to those measured i n l aboratory ex-
peri ments, woul d reduce the number of fermentors re-
qui red i n the pl ant. More i mportantl y, the yi el d of
butanol was assumed to be the same i n batch fermenta-
tion and fed-batch extractive fermentation. Butanol yield,
however, i s i ncreased by the use of extracti ve fermenta-
ti on
[34],
probabl y due to greater conversi on of co-
product aci ds to butanol . Si nce butanol cost i s roughl y
i nversel y proport i onal t o but anol yi el d, t he savi ngs ob-
tained frorn the use of extractive fermentation should be
greater than indicated. Also, any increase in the length of
fermentation time would result in a higher concentration
of sol i ds and cel l s at the end of fermentati on; sti l l age pro-
cessi ng costs woul d be further reduced. Fi nal l y, the prod-
uct recovery process coul d be si mpl i fted i f a strai n of
Cl ostri di um acetobutgl i cum was used that di d not pro-
duce ethanol . By extracti ng al l the butanol i nto the or-
ganic solvent, acetone and butanol can be readily recov-
ered. Thi s recovery process el i mi nat es f our di st i l l at i on
columns from the extractive fermentation design.
Broth flowrate to extractor
Solvent flowrate to extractor
Extractor height
Height of an ideal (plug-flow)
butanol transfer unit
Butanol distribution coefffcient
Acetone distribution coeffi cient
Ethanol distribution coefficient
Water solubility in extractive
solvent
Solvent solubility in broth 100 ppm
Sugar concentration in feed 500 g/L
Length of fermentation cycle 75
hours
50,(D0 L/hr
28,800 L./hr
50f t
2.4 ft
2.6
0.3
0. 1
50 ppm
100 ppm
500
e/L
75 hours
Biotechnology Progress (Vol. 3, No. 3) September,1987 137
TABLB 5. PuncnasED EeUIrMENT Cosrs FoR Fno-B.lrcH Exrnacuvn FnnuENTATroN or Butlxor,.
Item Si ze Units
Cost
(1tr$)
Storage (2 weeks)
Mol asses
Butanol
Acetone
Ethanol
Dried stillage
Solvent
Fermentation
Fermentor
Prefermentor
Karr, extraction column
Broth circulation pump
Sterilizer
Sterilizer heat recovery exchanger
Feed mix tank
Feed mix tank agitator
Broth surge tank
Solvent inventorv
Product Recovery
Steam stripper
Stripper preheater
Intercolumn heat exchanger
Acetone column feed cooler
Acetone column
Acetone column condenser
Acetone column reboiler
Ethanol column
Ethanol column condenser
Water stripper
Water stripper condenser
Water stripper reboiler
Butanol stripper
Butanol stripper reboiler
Butanol stripper condenser
Solvent heat recovery exchanger
Extract surge tank
Regenerated solvent surge tank
Solvent regeneration column
Solvent regeneration reboiler
Intercolumn reboiler
Solvent regeneration condenser
Butanol column
Butanol column reboiler
Butanol column condenser
Ethanol column
Ethanol column condenser
Stillage Treatment
Stillage evaporator
Rotary dryer
Heat recovery exchanger
3.3 x 106 gal (c.s.)
1.3 x 106 gal (c.s.)
5.4 x 105 gal (c.s.)
1.5 x 105 gal (c.s.)
1.0 x 105 gal (c.s.)
2.O x 105 gal (c.s.)
L.2 x 105 gal (s.s.)
5300 gal (s.s.)
4.5 ft dia, 50 ft (s.s.)
6600 gallhr (s.s.)
insulated tubing (c.s.)
7000 ft' (c.s.)
2500 gal (s.s.)
12. 5 HP ( s. s. )
1.32 x 105 gal (s.s.)
2 x 106 lb
5.5 ft dia, 25 plates (s.s.)
6L25 ft' (s.s.)
650 ff (c.s.)
775 ftz (c.s.)
8 ft dia, 50 plates (c.s.)
2950 ft2 (c.s.)
1050 ft2 (c.s.)
6.75 ft dia, 57 plates (c.s.)
650 ft2 (c.s.)
4.8 ft dia, 20 plates (".r.)
550 ft' (c.s.)
f45 ft' (c.s.)
3.5 ft dia, 20 plates, (c.s.)
495 ft' (c.s.)
325 ft2 (c.s.)
7000 ftz (c.s.)
1.32 x 105 gal (c.s.)
1.32 x 105 gal (c.s.)
7.25 ft dia, 30 plates (c.s.)
2890 ft' (c.s.)
730 ft' (c.s.)
615 f t ' ( c. s. )
3 ft dia, 35 plates (c.s.)
180 ff
(c.s.)
225 fP (c.s.)
4.8 ft dia, 38 plates (c.s.)
f255 ft' (c.s.)
11,000 ft2 per effect, 5 effects
7740 ft2,29.4 HP
50 f t ' ( s. s. )
Total Purchased Equipment
2
I
I
I
30
t
860
zto
r07
40
1, 81I
50
3,078
5,990
7 i 1
DltD
5,7L6
1, 138
199
2,L82
349
316
759
L,470
lB,6g
220
r80
16
18
215
38
2L
r97
t 6
53
15
n
t
37
T4
l l
788
r00
r00
373
37
r8
16
53
B
I
90
24
2,483
2,UO
F F
DD
5,378
$29,784
I
2
I
I
I
I
I
36
18
18
72
l 8
36
l 8
r8
4
t
t
I
1
I
13
2
2
3
I
I
I
I
t
I
I
I
I
D
D
Biotechnology Progress (Vol. 3, No. 3)
September,1987
TABLE 6. M.c,NurAcruRrNG Cosrs ron Fnn-BATcH Exrnlcrrvs FrnMnNTATroN oF BurANoL.
Item Basi s
c/lb
butanol
Raw Materials
nutrients
water
molasses
Utilities
power
coolirrg water
atm steam
5O psig steam
150 psig steam
Co-products
acetone
ethanol
hydrogen
dried stillage
atrn steam
Total Variable Cost
operating labor
supervision
maintenance
operating supplies
laboratory charges
solvent make-up
insurance and taxes
plant overhead
Total
Capital charges (SOVo of total
Rational Price of Butanol
I cenUlb Butanol
$t.t0/1000
gal
$100/ton,
55Vo sugar
$0.08/kwH
$0.2511000 eal
$0.85/1000
gal
$3.50/1000
lb
$4.00/1000 lb
$o.27
tlb
$0.26nb
$0.1Onb
$60/ton,857o
solid
$0.85/1000
lb
$I2lman
hr,44
operators
LSVo operating labor
4Vo ftxed capital cost
ISVo maintenance
lSVo operating labor
l57o solvent inventory
l.1Vo fixed ctrpital
22 people,
$80,000/year
Fixed Cost
capital cost)
1. 0
0. 1
4r . 2
0.9
0.3
0. 1
1. 6
I . 9
(10.6)
(2.8)
(0.7)
(e.5)
(0.2)
23.3
2.2
0.3
2.2
0.3
0.3
0. 1
0. 8
0.9
n
r8.5
48.9
Other {' ermentati ons may al so benefi t from the use of
extractive fermentation. The productivity of iso-propanol
and butanol fermentati on usi ng Cl ostri di um beyeri ncki i
has been shown to be increased by the in situ removal of
these al cohol s duri ng fermentati on
17,8].
Extracti ve fer-
mentation of iso-propanol and butanol uslng oleyl alcohol
as the extraction solvent may also increase fermentor pro-
ducti vi ty and al l ow concentrated substrates to be fer-
mented. Product separation may also be simplified in an
extracti ve fermentati on process. Iso-propanol , l i ke etha-
nol , forms an azeotrope wi th water; pure i so-propanol
cannot be obt ai ned by di st i l l i ng a di l ut e sol ut i on of i so-
propanol i n water. In extracti ve fermentati on, however,
little water is extracted into the alkane/oleyl alcohol sol-
vent and pure i so-propanol can be produced di rectl y.
Some of the advantages of extractive fermentation will
be lost if a dilute substrate is used. The capability of fed-
batch extracti ve fermentati on to uti l i ze concentrated
feed-stocks i s a maj or advantage over conventi onal fei -
mentati on. If di l ute feed-stocks are used, however, the
need to preconcentrate the feed reduces the savi ngs
achi eved i n the sti l l age handl i ng secti on of the pl ant.
Conclusions
Butanol can be produced from molasses for abolt 20Vo
less by extractive fermentation than by conventional
batch fermentation. Product inhibition is reduced during
extractive fermentation by the in situ removal of butanol.
Butanol productivity is increased and fewer fermentors
are required in the extractive fermentation process. Con-
centrated feed-stocks can be fermented and stillage treat-
ment costs are significantly reduced. Capital costs for a
fed-batch extractive fermentation plant producing 200 x
106 lb of butanol annually are estimated to be about 207o
lower than the capital costs of a conventional batch-
fermentation plant. Energy requirements of the extrac-
tion process are also reduced.
Extractive fermentation can most benefit fermentations
that are strongly inhibited by the accumulation of toxic
products in the broth, which require the treatment of
large volumes of stillage, and that can use the stlgars
Pfes-
ent in concentrated feedstocks. However, potential loss
of solvent in the broth and carry over of solvent in stillage
are problems to be addressed in any actual process. The
Biotechnology Progress (Vol.'3, No. 3) September,1987
139
9.
10.
l I .
12.
13.
t4.
t 5.
effect of carry over of trace amounts of the solvent em-
ployed in the present analysis on the saleability of the
stillage for animal feed is beyond the scope of the present
analysis, but would be common to all extractive fermenta-
tions.
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