Bioresource Technology 66 (1998) 75-78
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ELSEVIER PI 1:S0960-8524(98)
Short Communication
Selection of Adsorbents to be used in
an Ethanol Fermentation Process.
Adsorption Isotherms and Kinetics
Abstract
Adsorption equilibrium assays were carried out in
order to find adsorbents selective for ethanol to use in
a fermentation process. Three hydrophobic adsorbents
- - silicalite, ZSM-5 and CMS-5A - - were tested.
Results of adsorption equilibrium at 298 K of ethanol,
glucose, fructose and glycerol from aqueous solutions
of each single solute are given. Ethanol adsorption
isotherms were described by Langmuir-type equations.
Some kinetic assays of ethanol adsorption are also
presented. The results obtained appear to be useful for
practicioners on the fermentation-processes field.
© 1998 Elsevier Science Ltd. All rights reserved
Key words: ethanol adsorption, CMS-5A, silicalite,
ZSM-5.
INTRODUCTION
In ethanol fermentation relatively high concentra-
tions of ethanol increase the product inhibition
effect (Maiorella et al., 1984; Letourneau & Villa,
1987). This limits the amount of ethanol which can
be produced per unit of time and volume of
fermentor. Several methods to improve the alcohol
productivity by reducing the ethanol concentration
in the broth have been suggested; such as reduction
of the pressure in the reactor (Cysewski & Wilke,
1977; Finn & Ramalingam, 1977), on-line solvent
extraction (Miner & Goma, 1982) or selective
ethanol adsorption (Milestone & Bibby, 1983; Lee &
Wang, 1982; Pitt et al., 1983; Lencki et al., 1983).
Continuing our research on ethanolic fermenta-
tion (Bravo & Gonzfilez, 1991), we are developing a
device for a fermentation process in a fluidized bed
bioreactor with immobilized cells of Saccharomyces
cerevisiae in calcium-aiginate, together with simulta-
neous extraction of the product ethanol by adsorp-
tion on to an adsorbent. An initial phase of this
study consists of screening possible sorbents. The
aim of the present work was to provide results for
75
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ethanol adsorption on three different adsorbents as
an aid towards the assessment of the potential of
that process.
We have focused on the hydrophobic adsorbents
silicalite, ZSM-5 and CMS-5A because it could be
expected that they would show higher selectivity for
ethanol than for water and the other components of
the fermentation broth. Nevertheless, we have also
tested the adsorption characteristics of sugars and
glycerol on to the solids in concentration ranges
usually found for those components in ethanolic
fermentation processes.
METHODS
Materials
Adsorbents
Two synthetic silica molecular sieves, silicalite
(UOP), ZSM-5 (Mobil Chemical International) and
an activated carbon molecular sieve, CMS-5A
(Takeda Chemical Industries), were tested as adsor-
bents. The size of the pelletized cylindrical solids
was: 3 × 1 mm for pellets of ZSM-5, 5 × 1 mm for
silicalite and 8 ×4 mm for CMS-5A. Before each
run, ZSM-5 and silicalite were regenerated by
washing repeatedly with ultrapure boiling water and
drying at 200-220°C. CMS-5A was directly used,
after washing, as a wet solid, because preliminary
tests showed that its adsorption capacity when wet
was slightly higher than when dried.
Adsorbates
Ethanol, glucose, fructose and glycerol were used in
concentration ranges large enough to cover all levels
which typically appear in fermentation broths.
Synthetic solutions in the ranges 0-50% (w/w) for
ethanol-water mixtures, 0-2-15% (w/w) for glucose-
water solutions, 0-2-8% (w/w) for fructose-water
and 0.2-0.7% (w/w) for glycerol-water were
prepared.
Kinetic and equilibrium experiments
The equilibrium adsorption measurements at
25_0"1°C and pH 4.0+0.1 were conducted by
immersing in stoppered flasks known masses of
adsorbent and solution of initial solute concentra-
76 Short communication

tion Co. T h e stirred solutions were allowed to reach
equilibrium and, after filtration, clear samples were
taken and analysed in o r d e r to d e t e r m i n e the
concentration of solute in solution at equilibrium,
Ce.
A similar p r o c e d u r e was followed in some experi-
ments with e t h a n o l - w a t e r solutions. In this case,
samples of solution were intermittently taken by
means of a h y p o d e r m i c syringe through a r u b b e r
septum on the top of the closed flask. T h e evolution
of ethanol concentration with time was d e t e r m i n e d
by analysing each sample.
Analytical m e t h o d s and mass balances
Concentrations of ethanol, carbohydrates and
glycerol were m e a s u r e d by H P L C using an A m i n e x
Ion Exclusion H P X - 8 7 H Bio Rad column and
0"01 N H 2 5 0 4 solution at 60°C as mobile phase and
a flow rate of 0.7 cm 3 m i n - l . E l u t e d materials were
detected using a Waters differential r e f r a c t o m e t e r
d e t e c t o r 410 (Waters C h r o m a t o g r a p h y Division/
Millipore Corporation, 34 Maple Street/Milford,
M A 01757).
T h e adsorption uptake Cs, g adsorbed solute/g
solid adsorbent, was found by a mass balance on the
adsorbed species, assuming water was not signifi-
cantly adsorbed.
W h e n using dry adsorbents, the mass balance
yielded to the equation:
M ( C o - - C,,)
Cs -
S(1 O0 - - Ce)
M and S being the mass (g) of initial solution and
dry adsorbent, respectively.
W h e n using wet adsorbent, the following equation
was used:
M C o - - (M+Sw -- S ) C e
Cs = (2)
S ( I O 0 - Ce)
Sw being the mass (g) of wet adsorbent.
RESULTS AND DISCUSSION
Kinetics
Kinetic experiments on silicalite and CMS-5A were
conducted at two initial ethanol concentrations:
Co = 10"15% and 5.09% (w/w).
For both adsorbents, the decrease of ethanol
composition in solution was slightly higher when the
initial solution was m o r e concentrated. In general,
an initial fast adsorption of ethanol followed by a
second slow stage was observed. A similar perform-
ance was found when checking the adsorption on
ZSM-5. As suggested from the kinetic profiles, the
kinetic results were assayed to fit a first-order kinetic
model:
C t = Coe-k' (3)
Ct (% w/w) and k (min 1) being the ethanol
concentration in solution at time t (min) and the
kinetic rate constant, respectively.
By linearization of eqn (3), an acceptable fit was
achieved for the two successive first-order steps.
(1) Table 1 shows the linear fitted parameters, together
with experimental results. F o r ethanol adsorption on
silicalite at Co = 10-15%, a low k-value resulted for
the second step, this fact showing that the overall
adsorption occurs in the first stage.

Table 1. Kinetics of ethanol adsorption onto silicalite and CMS-5A: experimental results and linear parameters fitted to
a two-stage first order model

Silicalite Silicalite CMS-5A CMS-5A

Ct t Ct t Ct t Ct t

10.15 0 5"09 0 10-15 0 5"09 0

9.92 5 4.92 8 10.05 5 4"85 5
9.75 15 4.81 23 9.93 10 4.71 20
9.73 35 4.78 39 9.63 50 4.63 35
9.75 70 4.75 57 9.51 65 4.53 52
9.79 80 4.74 72 9.50 85 4.49 83
9"78 110 4.73 90 9.46 105 4.48 107
9"76 125 4.71 500 9"40 144 4.42 137
9"73 500 9.36 500 4-32 500

Constants of eqn (3) Constants of eqn (3) Constants of eqn (3) Constants of eqn (3)
Step 1 Step 1 Step 1 Step 1
10.15 > C t > 9"75 5"09 > C t > 4"78 10.15 > C t > 9"70 5.09 > Ct > 4.71
k = 2-55 x 1 0 - 3 k = 2"37 x 1 0 - 3 k = 2"02 x 10 3 k = 5.74 x 10 3

Step 2 Step 2 Step 2 Step 2

Ct < 9-75 Ct _<4-78 Ct < 9-70 Ct < 4.71
k = 1.26 x 10 .5 k = 1.33 x 1 0 -4 k = 2.70 x 10 4 k = 4.80 x 10 - 4
 Short communication 77

Table 2. Adsorption isotherms of ethanol onto silicalite, CMS-5A and ZSM-5 at 298 K: experimental results and
Langmuir-type adsorption parameters

Silicalite CMS-5A ZSM-5

C~ C~ C~ C¢ Cs C~
1.274 0-016 0.322 0.032 0"365 0.023
2-753 0.025 0.753 0.039 0.739 0"036
4-700 0.034 2.144 0"055 1'641 0"045
7"778 0"051 4.222 0.074 0.614 0.052
11.548 0.056 6.164 0.089 5"539 0'056
14.609 0.064 9.705 0.107 7"576 0"057
22-109 0.065 13.685 0"116 13"692 0.058
29-704 0.066 26.502 0.115 25"418 0.064
40-484 0.072 30.323 0"116 28.921 0"068
49-656 0.075 33"078 0.117 39.309 0-071

Langmuir parameters Langmuir parameters Langmuir parameters

a = 0.015 a = 0"058 a = 0-095
b = 0"179 b = 0"464 b = 1'437
Norm = 0"008 Norm = 0-023 Norm = 0-009
Langmuir equation C~ = a'Ce/(1 +b'Ce).

Equilibrium was made. No measurable adsorption of glucose,

Adsorption of ethanol
Ethanol adsorption equilibrium results on to silica-
lite, ZSM-5 and CMS-5A from ethanol-water
mixtures are given in Table 2. The shape of the
isotherms displays the adsorption type favourable in
all cases. Therefore, a Langmuir-type equation was
used to represent equilibrium adsorption. Values of
model parameters, a and b, were determined by
fitting the experimental data to the proposed
equation, using the program SigmaPlot Scientific
Graphing System. The magnitude of the norm is
also shown in Table 2.
The asymptotic uptakes at ethanol adsorption
equilibrium, a/b, increase in the order: 0-068
(ZSM-5)<0.084 (silicalite)<0.126 (CMS-5A). The
calculated saturation capacities of silicalite and
ZSM-5 are smaller than those given by Farhadpour
(Farhadpour & Bono, 1988) and Milestone
(Milestone & Bibby, 1983), respectively, for the
same systems at similar temperatures: 0-131g
ethanol/g microcrystalline silicalite and 0-12 g
ethanol/g microcrystalline ZMS-5. The discrepancy
might be due to the use of pelletized adsorbents,
which diminishes the hydrophobicity by the presence
of the agglomerant. The content of A1203 in the
adsorbent ZSM-5, even while low, could justify the
observed capacity difference between ZSM-5 and
silicalite.
Concerning the CMS-5A equilibrium adsorption
data, we have not found any references in the litera-
ture. For the purpose of comparison, Lee and Wang
(1982) found an adsorption capacity value of 0.13 g
ethanol/g adsorbent for the adsorption of ethanol on
to a conventional activated carbon.
Adsorption of glucose, fructose and glycerol
An experimental adsorption study of the systems
glucose-water, fructose-water and glycerol-water
fructose and glycerol on silicalite and ZSM-5 was
found. However, a maximal adsorption of glucose
(0"011g glucose/g adsorbent), fructose (0.010g
fructose/g adsorbent) and glycerol (0-014 g glycerol/g
adsorbent) on CMS-5A was found.
The non-adsorption of substrate, together with a
good selectivity for ethanol, make the use of silica-
lite or ZMS-5 as sorbents in removing ethanol from
fermentation broths attractive. The CMS-5A sieve
shows minimal adsorption of substrate. We also
checked the multicomponent adsorption of ethanol,
glucose and fructose on to this adsorbent. The
results (not shown) indicated that the adsorption of
ethanol did not decrease significantly from the
binary to the multicomponent, while the adsorption
of the substrates glucose and fructose in the multi-
component system was even lower than in their
respective binary systems. In conclusion, the adsor-
bents screened in this work seem to be promising to
use in ethanol fementation processes. Nevertheless,
we should stress that the results of this preliminary
study correspond to batch processes and these do
not mimic the conditions which would be found in a
real fermentation. Further work would be needed to
examine aspects of mass transfer.
REFERENCES
Bravo, P. & Gonz~ilez, G. (1991). Continuous ethanol
fermentation by immobilized yeast cells in a fluidized-
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Cysewski, G. R. & Wilke, C. R. (1977). Rapid ethanol
fermentations using vacuum and cell recycle. Biotechnol.
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Farhadpour, F. A. & Bono, A. (1988). Adsorption from
solution of nonelectrolytes by microporous crystalline
solids: ethanol-water/silicalite system. Journal of Colloid
and Interface Science, 124, 209-227.
78 Short communication
Finn, R. K. & Ramalingam, A. (1977). The vacuferm
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A. Cart6n, G. Gonz~ilez Benito*,
J. A. Rey & M. de la Fuente
Department of Chemical Engineering,
Faculty of Sciences, University of Valladolid,
47011 Valladolid, Spain
(Received 14 July 1997; revised version received
6 February 1998; accepted 12 February 1998)
*Author to whom correspondence should be addressed.