Liquid-liquid and Vapour-liquid Behaviour of Oleyl Alcohol

Applied to Extractive Fermentation Processing

JANUSZ J. MALlNO WSKl
Polish Academy of Sciences, Institute of Chemical Engineering, ul. Baltycka 5, 44-100 Gliwice, Poland

and
ANDREW J . DAUGULlS*
Queen ’s University, Department of Chemical Engineering, Kingston, Ontario, Canada K7L 3N6
Investigations into the product recovery step of the extractive ethanol fermentation through partition experiments
for ethanol-water-AdoP 85 NF ternary systems were undertaken. Experimental liquid-liquid equilibrium data for this
ternary system were compared with numerical predictions based on the UNIFAC method. The influence of salts on
distribution coefficients for ethanol extraction was also examined. An improvement in extraction characteristics was
observed for ternary systems with salts. Flash vaporisation was used to subsequently examine the effect of liquid-liquid
ternary compositions on vapour-liquid partitioning. The UNIFAC model was found to be very useful for semi-quantitative
analysis of such liquid extraction systems.

On a effectuC des recherches sur I’itape de rCcupCration des produits lors de la fermentation extractive d’kthanol
par des exgriences de separation pour des systtmes ternaires ethanol-eau-AdoP 85 NF. Les donnees d’kquilibreliquide-
liquide experimentales pour ce systtme ternaire ont CtC comparCes aux prCdictions numCriques basCes sur la mCthode
UNIFAC. On a Cgalement examine l’influence des sels sur les coefficients de distribution pour I’extraction de I’ithanol.
Une amklioration des caractCristiques d’extraction a CtC observCe pour les systbmes ternaires en presence de sels. Par
la suite, on a eu recours h la vaporisation Cclair pour examiner l’effet des compositions ternaires liqyide-liquide sur
la separation liquide-vapeur. Le modble UNIFAC s’est rCvClC trts utile pour I’analyse semi-quantitative de tels sys-
temes d’extraction liquide.
Keywords: extractive fermentation, liquid-liquid equilibria, UNIFAC, distribution coefficient, flash evaporation, ethanol-
water-oleyl alcohol.

T he growing prospects of using ethanol produced by

fermentation as an additive to conventional liquid fuels,
or a chemical feedstock have prompted considerable effort
in searching for energy-efficient separation methods for
recovering ethanol from fermentation broths. Conventional
distillation techniques applied to the recovery of ethanol from
dilute aqueous solutions require energy costs which are sub-
stantial fractions of the value of the ethanol product.
Several alternatives to distillation including adsorption
processes, membrane separation using materials that are
selectively permeable to either ethanol or water, and solvent
extraction using organic solvents or supercritical fluids such
as C 0 2 have been proposed.
Another constraint on ethanol fermentation processes is
the kinetic behaviour not frequently encountered in chem-
ical processing, namely a decrease in the product (ethanol)
formation rate because of the accumulation of end products.
Therefore, various methods have been proposed for the
integration of biological reactor systems with product
recovery with the aim of improving the productivity in the
bioreactor and reducing the downstream processing cost.
Reviews of different approaches to integrating reaction and
product recovery in biological systems have recently been
published (Daugulis, 1988, 1991). Among these alternatives,
the liquid-liquid extractive fermentation process has been
reported to be the cheapest (Maiorella et al., 1984). In this
process, a high boiling organic solvent is used for in situ
and continuous product removal from the fermentation broth.
Subsequently, the ethanol product can be thermally recovered
by flash vaporization, with concomitant regeneration of the
*To whom all correspondence should be addressed.
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 71, JUNE, 1993
solvent for recycle and reuse. Extractive ethanol fermenta-
tion has been the subject of considerable research during the
last ten years (Minier and Goma, 1981, 1982; Mattiasson
et al., 1981; Kollerup and Daugulis, 1986, 1987; Cho and
Shuler, 1986; Daugulis et al., 1987; Bruce et a]., 1991). The
choice of suitable extractants which must function optimally
for both the reaction and ethanol recovery steps is critical
to the development of an effective fermentation process.
Some important criteria for such solvents were given by Dau-
gulis (1988). Two desirable characteristics for a biocompat-
ible solvent are a high capacity for ethanol and a high
selectivity for ethanol over water. The capacity to extract
ethanol is described by the equilibrium distribution coeffi-
cient defined as a ratio of the weight fraction of ethanol in
the solvent phase to that in the aqueous phase, at equilibrium.
The measure of selectivity, i.e. the ability of the solvent to
remove ethanol preferentially over water, is the separation
factor, which is defined as a ratio of the distribution coeffi-
cient of ethanol to that of water.
The extraction of ethano1 from well defined aqueous solu-
tions has been investigated intensively (Roddy , I98 1;Wang
et al., 1981; Roddy and Coleman, 1983; Essien and Pyle,
1987; Egan et al., 1988; Arenson et al., 1990; Zhang and
Hill, 1991). Mixed solvent systems have also been consi-
dered for use as ethanol extractants (Munson and King, 1983;
Mitchell et al., 1987; Bruce and Daugulis, 1991).
A systematic and comprehensive search for ethanol extrac-
tion solvents has been provided by Kollerup and Daugulis
(1985, 1986). They have generated a computer program,
known as the Extractant Screening Program or ESP to predict
the behaviour of product molecules in solvent-aqueous
systems. They were able to rank a large number of potential
43 1
 TABLE1
Properties of AdoP 85 NF (Oleyl Alcohol)
(Manufacturer's Specifications)
____~
Structural Formula CH,(CHz),CH =CH(CH,),CHzOH
Mean Molecular Weight 267
Boiling Range, "C 282-349
Density, kgfm3 840
Composition (Alcohol), %wt
c
1 4 4 compositions. In distribution measurements with aqueous
c16 5 solutions containing strong electrolytes only aqueous phases
CI6-I 6 were analyzed for ethanol, with ethanol concentration in the
c18 3 Adol-phase being inferred from a mass balance.
C18-I 74
c18-2 7 The ethanol content in the aqueous phase was determined
czo Traces
Suggested Uses: Plasticizers for Hair Sprays, Lubricants for
Aerosols, Lotions, Creams, Bath Oils, etc.
solvents in terms of their predicted performance, after which
a smaller number of promising extractants was tested
experimentally. Their approach has made possible the selec-
tion of a solvent (comprised largely of oleyl alcohol) which
was experimentally verified as having favourable properties
(Kollerup and Daugulis, 1985, 1986, 1987; Bruce et al.,
1991).
The present investigation was undertaken to provide fun-
damental phase and distribution data basic to the thermal
product recovery step in an extractive ethanol fermentation
process (Kollerup and Daugulis, 1989). The process has
recently being scaled-up to 150 L bioreactor capacity. The
influence of some salts on water-ethanol-organic solvent ter-
naries behaviour was also examined.
Experimental
The biocompatible solvent used in this study was Adole
85 NF supplied by Sherex Chemical Co., Dublin, OH. Some
of its properties are shown in Table 1.
Ternary phase systems were prepared by mixing
appropriate volumes of solvent with distilled water-ethanol
solutions or with ethanol-aqueous solutions containing fer-
mentation medium salts, or strong electrolytes. The concen-
tration of the ethanol in the aqueous feed was 4 , 6 or 8 %wt.
These concentrations were selected to correspond to typical
conditions of a fermentation broth. However, a few experi-
ments with higher ethanol concentrationswere made to obtain
additional tie-lines in the two phase region of the ternary
phase diagram. In experiments with salts typically found in
fermentation medium, the following components per 1L of
distilled water were added: KH2P04; 5.1 g, (NH&SO,;
17.3 g, MgS04 7H20; 1.83 g. This salts concentration is
used in fermentation medium with glucose concentration of
500 g/L for extractive fermentation by Succhuromyces
cerevisiue (Kollerup and Daugulis, 1987). In separate experi-
ments with other salts, strong electrolytes such as KC1, NaC1,
CaC12, CH,COOK, CH3COONa were used with the
aqueous feed being prepared by addition of the salts to a
6 %wt ethanol solution.
Partition experiments were carried out using 100 mL of
ethanol-in-water solution and 500 mL of solvent, except in
the case of the experiments for the tie-line determinations,
when the volume ratio of solvent to aqueous feed was chosen
depending on the initial ternary mixture compositions. The
mixture was shaken vigorously in a glass separatory funnel
for 40 min. at room temperature ( = 25°C). These conditions
432 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 71, JUNE. 1993
were found to be necessary to ensure equilibrium. The con-
tents were allowed to settle under isothermal conditions until
the phases separated. The volume of Adolo- and aqueous-
phases were measured after phase separation. Equilibrium
compositions were determined by analysis of the alcohol in
both phases. Closure of the mass balance was always within
10%. Water concentrations in the organic phases were der-
ived from material balance based on starting quantities and
with a gas chromatograph (GOW-MAC 750P), using a flame
ionization detector and isopropanol employed as an internal
standard, as previously described (Kollerup and Daugulis,
1985).
Flash vaporisation was applied to remove ethanol from the
Adole-phase. This unit operation has been shown to be able
to successfully remove ethanol from the solvent phase in
actual extractive fermentation process operation (Daugulis
et al., 1987). Experiments were performed using a batch,
laboratory-scale, single stage vacuum flash evaporator
(Buchler Instruments, Fort Lee, NJ). Operation of this unit
is equivalent to differential distillation without reflux. The
samples of the Adolo-phase (before and after flash evapora-
tion) for ethanol analysis by gas chromatography were pre-
pared as follows: 5 mL of Adole rich-phase was equilibrated
with 5 mL of distilled water using a 10 mL MixxoP solvent
extraction glassware (Cole-Palmer). The liquids were mixed
by seven cycles of the piston and after centrifugation the
aqueous phase was analyzed for ethanol. The ethanol con-
centration was determined using external standards (ethanol
in Adolo) equilibrated with water as above described. The
vapour (condensate) collected during the flash evaporation
was also analyzed for ethanol by gas chromatography.
The amount of salt in the aqueous phase was determined
gravimetrically after drying a sample in the oven at 90°C.
All equilibrium distribution coefficients were calculated
as a ratio of the weight fraction ethanol in organic phase to
that in aqueous phase, unless otherwise noted.
Results and discussion
The Extractant Screening Program (ESP) (Bruce and Dau-
gulis, 1991) was applied to predict liquid-liquid equilibrium
(LLE) for the ethanol-water-AdoP 85 NF ternary phase
system. To the best of our knowledge, LLE data for that
system are not available in the literature. The program uti-
lizes the UNIFAC group contribution method to calculate
multicomponent LLE data (Fredenslund et al., 1977; Mag-
nussen et al., 1981). This work was undertaken in order to
provide a rough characteristic of the investigated ternary
phase systems. Whether coupled with fermentation or car-
ried out in a separate vessel, the equilibrium data are very
important for calculation of the liquid-liquid extraction
process. The phase diagram of the system under study
(weight fraction) generated by ESP is presented in Figure 1.
The tie-lines are not parallel and change their slope in one
direction with changing concentration of ethanol. Therefore,
the ethanol when added to a mixture of AdoP and water,
distributes itself unequally between the two phases, with a
greater Concentration in the aqueous phase. As more ethanol
is added to such a mixture the mutual solubility of Ado]@
and water increases. Accordingly, more water goes to the
 C TABLE3
Experimental(Exp.) and Calculated (ESP) LLE Data for Ethanol-
Water-Adol@ 85 NF Systems With Fermentation Salts
Feed Composition
Ethanol ( % wt) Water (%wt) Ado1 (%wt)
0.78 17.97 81.25
1.14 17.53 81.33
1.57 16.85 81.58
Top Phase Compositions (Adol-rich phase)
Exp. ESP Exp. ESP Exp. ESP
0.43 0.62 0.62 1.10 98.95 98.28
0.78 0.91 0.87 1.13 98.35 97.96
0.99 1.25 0.88 1.16 98.13 97.59
Bottom Phase Compositions (aqueous phase)
Exp. ESP Exp. ESP Exp. ESP
2.03 1.54 97.97 98.46 0 0
-Weight fraction of A - 2.99 2.27 97.01 97.73 0 0
Figure 1 - Ternary phase diagram for ethanol-water-Adol@ 85 3.77 3.15 96.85 96.23 0 0
NF system at 25°C (A - water, B - Adol@NF, C - ethanol); solid
lines - UNIFAC-LLE predictions, dashed lines - experimental).
by ESP, although the phase compositions are not predicted
TABLE2 so well. From Figure 1 it can be seen that the slope of
Experimental (Exp.) and Calculated (ESP) LLE Data for Ethanol- predicted tie-lines is not in agreement with the slope of
Water-Ado]@ 85 NF Systems (Without Salts)
experimental tie-lines. Therefore, relatively high errors in
Feed Composition distribution coefficient may be expected. This can be a con-
Ethanol (% wt) Water (% wt) Ado1 (%wt) sequence of the use of a phase composition objective func-
tion in the UNIFAC parameter estimation to represent
0.78 18.13 81.09 binodal curves (Magnussen et al., 1981). At the same time,
1.15 17.67 81.18
1.54 17.20 81.26
the UNIFAC predicted the two-phase region larger than it
18.13 50.63 30.95 was observed experimentally. This is in agreement with the
29.80 38.90 31.30 recent observation of Gupte and Danner (1987).
39.73 27.55 32.72 Experimental and predicted LLE data for the investigated
systems are given in Tables 2 and 3. Examination of both
Top Phase Compositions (Adol-rich phase) Tables shows some lack of accuracy of the numerical predic-
Exp . ESP Exp. ESP Exp . ESP tions of phase compositions. The UNIFAC-LLE model does
0.42 0.62 0.66 1.10 98.92 98.28 not represent low concentrations very well (Magnussen et
0.65 0.92 0.76 1.13 98.59 97.95 al., 1981), hence higher errors appear for small concentra-
0.89 1.23 0.87 1.16 98.24 97.61 tions of components present in the system. Another reason
9.67 7.56 0.77 1.85 89.56 90.59 for discrepancies between experimental and calculated LLE
17.88 11.02 3.77 2.25 78.35 86.73 is that UNIFAC calculations could be performed only for
29.34 15.16 5.74 2.71 64.92 82.13 pure oleyl alcohol, which is not identical to AdoF 85 NF,
Bottom Phase Compositions (aqueous phase) which was used in experiments. In the case of ternary systems
with salts, it is known that the UNIFAC model does not
Exp. ESP Exp. ESP Exp. ESP handle electrolyte solutions very well, although recent
2.18 1.53 97.82 98.47 0 0 attempts to construct a UNIFAC-based model applicable to
3.27 2.28 96.73 97.72 0 0 VLE and LLE calculation of mixtures with strong electro-
4.30 3.09 95.70 96.91 0 0 lytes are very encouraging (Dahl and Macedo, 1992). The
23.05 24.02 76.92 75.98 0.03 0 concentration of salts used in our experiments was very low,
38.85 40.33 61.12 59.62 0.03 0.05
49.59 55.67 49.99 43.79 0.42 0.54
so the quality of predictions (Table 3) was the same as for
ternary systems without salts. One may conclude that ESP
utilizing the UNIFAC-LLE model is useful for semi-
quantitative analysis of ternary phase systems behaviour and
solvent phase. The resulting binodal (two phase) curve selection of promising solvents for liquid extraction for
resembles an unsymmetrical parabola. However, the solu- different applications. In this way a considerable amount of
bility of A d o P in water is very low, even at high ethanol experimental work can be avoided.
concentration in the aqueous feed. It does not exceed The solvent-to-aqueous feed ratio is one of the important
0.5 %wt at ethanol concentration in the feed of 60 %wt. In operational parameters in liquid-liquid extraction, where an
the region of interest for the extractive fermentation process increase in driving force for mass transfer means selecting
this organic solvent is practically insoluble in water. a solvent with higher distribution coefficient or increasing
Comparison of some experimental tie-lines with predic- the solvent-to-feed ratio. The last, in turn,leads to an increase
tions based on the UNIFAC method reveals that experimental in solvent recovery requirement due to the larger equipment
points are situated very close to the binodal curve calculated needed to be used, and more energy consumed for solvent
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 71, JUNE, 1993 433
 -
f 55, TABLE4
Experimental and ESP Data for Distribution Coefficients and
Separation Factors for Ethanol-Water-Adol@ 85 NF Ternary
Systems
Ethanol in Water-Ethanol D S
solution (%wt) Exp. ESP Exp. ESP
Systems without salts
4.12 0.19 0.40 28.41 36.25
6.12 0.20 0.40 25.13 34.80
8.24 0.21 0.40 22.68 33.20
5 6 7 8 9 10 11 12 13 14 15
26.70 0.42 0.31 42.00 12.93
V l f v2 (4 43.40 0.46 0.27 7.46 7.23
59.00 0.59 0.27 5.15 4.39
Figure 2 - Predictions of ethanol concentration in the condensate
for different aqueous feed vs. volume ratio of AdoP (V,)to Systems with salts added
ethanol-water mixture (V&, obtained using UNIFAC-VLE model.
4.18 0.21 0.40 33.56 36.25
56 6.12 0.26 0.40 28.72 34.80
-
c
8.50 0.26 0.40 28.98 32.24

-
$
3
volume ratio was later chosen for experiments. In the extrac-
w 50 tive fermentation process the flow ratio of solvent to aqueous
5
2
W
feed expressed as a ratio of the appropriate dilution rates is
usually set at 5 to 10 (Bruce et al., 1991) for satisfactory
0 operation.
z The results of experiments undertaken to verify numer-
8 46
ical predictions of VLE for ternary systems with and without
z salts added, performed on the flash evaporation unit are
presented in Figure 3. From this figure, it can be seen that
J
0 a condensate with ethanol concentration above 40 %wt. (the
f rest being water) may be obtained, with higher concentra-
a
I
40
I-
tions of ethanol in the condensate resulting from higher liquid
W phase ethanol concentrations. Higher concentrations of
ethanol in the condensate were measured when the aqueous
feed contained salts. This can be a result of the alteration
36 of extraction equilibria by unextractable salt present in the
4 6 8 system. At the same time, the liquid phase separation for
ternary systems in which salts were present proved to be more
Ethanol in feed (%wt)
difficult compared to the ternary systems without salts. Based
Figure 3 - Comparison of experimental data for ethanol-water- on the data from Figure 3, it may be inferred that UNIFAC-
AdoI@85 NF ternaries from flash evaporation unit with predictions VLE predictions are very close to the experimental results.
based on UNIFAC-VLE method. Data with salts correspond to fer- In Table 4,experimental and calculated distribution coeffi-
mentation salts described in Experimental. cients for ethanol together with selectivities (separation
factors) are presented. Comparison with results obtained for
regeneration. In our study, it was interesting to evaluate the ternary systems with salts added shows that improvement
performance of the flash vaporisation unit, which is used in the capacity of Adol@for ethanol can be achieved. This
simultaneously to recover ethanol and to regenerate solvent, trend was observed by Kollerup and Daugulis (1986) for a
especially from the point of view of composition of the con- variety of investigated solvents when distribution coefficients
densate. Computer simulations of flash evaporation to exa- were also measured in fermentation broths. Fermentation
mine the effect of liquid-liquid ternary composition on broths typically contain salts, cells etc., which can influence
vapour-liquid partitioning, were performed using UNIFAC the extraction process. The selectivity for ethanol was better
to predict vapour-liquid equilibrium. Calculations were made for ternary systems with fermentation salts, and this is
for several compositions of the solvent-rich phase predicted encouraging for the application of Ado!@for ethanol recovery
by ESP at different volume ratio V , lV2 of AdoP ( V , ) to from fermentation broths. Experimental distribution coeffi-
water-ethanol solution ( V2). The chosen range of volume cients increase with an increase in ethanol concentration in
ratios is typical for practical application in the extractive fer- the aqueous feed. Close examination of the ternary phase
mentation process. The results from the predictions were diagram (Figure 1) and data in Table 4 reveals that the trend
plotted in Figure 2. It can be seen that a higher ethanol con- of changes of distribution coefficient with changing ethanol
centration in the condensate may be expected at lower volume concentration in the aqueous feed predicted by ESP was
ratios. Taking into account that a product of the volume ratio different from that observed experimentally. Such behaviour
and distribution coefficient must be greater than one for good was also found for a similar (water-ethanol- 1-heptadecanol)
recovery in a counter-current extractor, the ratio 5 cor- system when UNIQUAC (common parameters) was applied
responds to a minimum required to remove ethanol from to calculate liquid-liquid equilibria (Smensen and Arlt,
dilute aqueous solution using Adol@as an extractant. This 1980). As can be seen from Table 4, lower selectivities were
434 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 71, JUNE, 1993
 TABLE5 Acknowledgement
The Effect of Strong Electrolytes on Performances of Adol@85 NF
as Extractant for Ethanol (Ethanol Concentration in the Aqueous One of us (J. J. M.) thanks the Natural Sciences and Engineering
Feed - 6 % wt) and Subsequent Ethanol Recovery by Vaporization; Research Council (NSERC) of Canada for granting a postdoctoral
Distribution Coefficients Based on Concentrations fellowship making it possible to conduct research at Queen’s
~ ~ ~~~ ~ ~

University.
Ethanol in
Salt added DIDo %E condensate, %wt Nomenclature
no salts 1 53 46 D = distribution coefficient
KCI 17.0 %wt 1.82 68 43 Do = distribution coefficient for system without salt
CH3COOK 22.6 %wt 2.18 73 32 ESP = Extractant Screening Program
CH,COONa 33.1 %wt 2.86 71 72 %E = percentage of extraction efficiency, %
CH,COOK 36.9 %wt 3.22 76 72 LLE = liquid-liquid equilibrium
CaClz 33.7 %wt 3.68 81 71 s = selectivity
NaCl 25.8 %wt 4.18 81 67 v, = volume of extractant. m’
vz = volume of water-ethanol solution, m’
VLE = vapour-liquid equilibrium
obtained for the systems with higher ethanol concentrations
in the feed. The higher distribution coefficient for water, and References
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Manuscript received November 9, 1992; revised manuscript
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