Biochemical Engineering Journal 49 (2010) 351–360

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Biochemical Engineering Journal

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Effect of surface contaminants on oxygen transfer in bubble column reactors

Maryam Asgharpour, Mohammad Reza Mehrnia ∗ , Navid Mostoufi
Biotechnology Group, School of Chemical Engineering, University College of Engineering, University of Tehran, PO Box 11155/4563, Tehran, Iran

a r t i c l e i n f o a b s t r a c t

Article history: Gas hold-up (εg ), sauter mean bubble diameter (d32 ) and oxygen transfer coefficient (kL a) were evaluated
Received 2 September 2009 at four different alkane concentrations (0.05, 0.1, 0.3 and 0.5 vol.%) in water over the range of superfi-
Received in revised form cial gas velocity (ug ) of (1.18–23.52) × 10−3 m/s at 25 ◦ C in a laboratory-scale bubble column bioreactor.
20 December 2009
Immiscible hydrocarbons (n-decane, n-tridecane and n-hexadecane) were utilized in the experiments
Accepted 27 January 2010
as impurity. A type of anionic surfactant was also employed in order to investigate the effect of addi-
tion of surfactant to organic-aqueous systems on sauter mean bubble diameter, gas hold-up and oxygen
transfer coefficient. Influence of addition of alkanes on oxygen transfer coefficient and gas hold-up, was
Keywords:
Bubble columns
shown to be dependent on the superficial gas velocity. At superficial gas velocity below 0.5 × 10−3 m/s,
Hydrodynamics addition of alkane in air–water medium has low influence on oxygen transfer coefficient and also gas
Mass transfer hold-up, whereas; at higher gas velocities slight addition of alkane increases oxygen transfer coefficient
Hydrocarbon contaminants and also gas hold-up. Increase in concentration of alkane resulted in increase in oxygen transfer coeffi-
Surface tension cient and gas hold-up and roughly decrease in sauter mean bubble diameter, which was attributed to
Surfactant an increase in the coalescence-inhibiting tendency in the presence of surface contaminant molecules.
Bubbles tend to become smaller with decreasing surface tension of hydrocarbon, thus, oxygen transfer
coefficient increases due to increasing of specific gas–liquid interfacial area (a). Empirical correlations
were proposed for evaluating gas hold-up as a function of sauter mean bubble diameter, superficial gas
velocity and interfacial surface tension as well as evaluating Sherwood number as a function of Schmidt,
Reynolds and Bond numbers.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction Effect of addition of an immiscible organic phase to a gas-

Bubble columns have found their wide application in biochem-
ical processing industries due to their simple construction, low
cost and ease of operation. These devices are intensively utilized
as multiphase contactors and reactors in chemical, petrochemi-
cal and biochemical industries as well as wastewater treatment
[1–3]. Gas–liquid–liquid systems are used in biological wastewater
treatment and aerobic bioprocesses. Effect of water-insoluble con-
taminants on oxygen mass transfer is important for evaluating their
impact on water quality and assessing water-based technologies
in biotreatment of crude, fuel oil contaminated waters and totally
in oxygen transfer from gas phase to microorganisms. Improving
oxygen supply in cell culture systems has always been a central
topic for many biochemical processes [4]. Therefore, presence of an
organic additives or contaminants to the aqueous phase improved
the efficiency of the bioprocess. A review of mass transfer enhance-
ment in gas–liquid–liquid systems has been reported by Dumont
and Delmas [5].
∗ Corresponding author. Tel.: +98 21 6696 7785; fax: +98 21 6695 7784.
E-mail address: mmehrnia@ut.ac.ir (M.R. Mehrnia).
aqueous system on hydrodynamic and mass transfer characteristics
has been less studied. Yoshida et al. [6] showed that addition
of kerosene and n-paraffin decreases the rates of oxygen diffu-
sion through oil droplets partially occupying the liquid film and
so reduces oxygen transfer. However, Linek and Benes [7] found
that reduction in the interfacial area caused the decrease in mass
transfer coefficient kL a. Hassan and Robinson [8] concluded that
kL a increases with increasing the oil fraction for n-hexadecane
and decreases for n-dodecane up to a certain level of oil addi-
tion. This change in the trend of kL a was attributed to opposing
changes in liquid-side oxygen transfer coefficient (kL ) and specific
gas–liquid interfacial area. It was found that addition of silicone
oils hinders oxygen mass transfer compared to air–water sys-
tem whereas addition of decane, hexadecane and perfluorocarbon
PFC40 has no significant influence on the mass transfer [9]. Kundu
et al. [10] showed that slight addition of n-decane, dodecane and
n-heptane in air–water system significantly enhances mass trans-
fer from the gas phase to the continuous aqueous phase whereas
toluene, anisole and 2-ethyl-1-hexanol retard mass transfer. Cents
et al. [11] also observed that addition of dodecane and heptane
caused decreasing of kL a.
Surfactants, both chemical and biological, are amphiphilic com-
pounds which can reduce surface and interfacial tensions by

1369-703X/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.bej.2010.01.010
352 M. Asgharpour et al. / Biochemical Engineering Journal 49 (2010) 351–360

accumulating at the interface of immiscible fluids and increase the

solubility, mobility, bioavailability and subsequent biodegradation
of hydrophobic or insoluble organic compounds [12]. These com-
pounds were commonly used or produced in biological processes
such as wastewater treatment, petroleum bioupgrading and bio-
surfactants production. Painmanakul et al. [13] studied the effect of
surfactants on a, kL and kL a values in aqueous solutions with anionic
(SDS) and cationic surfactants (Lauryl dimethyl benzyl ammonium
bromine) in a small scale bubble column with a single orifice as
gas sparger. They showed that the presence of surfactants affects
the bubble generation phenomenon and thus the interfacial area
and the different mass transfer parameters, such as the volumetric
mass transfer coefficient and the liquid-side mass transfer.
Previous investigations on kL a suggest that the fluid properties
(as determined by the type and concentration of the hydrocar-
bon) as well as the reactor geometry and operating parameters
strongly influence kL a behaviour in hydrocarbon-aqueous systems
[14]. Based on the above-mentioned survey, no general trend
can be derived from the reported results in the literature. The
purpose of the present study, therefore, was to evaluate kL a as
well as other hydrodynamic parameters in a bubble column using
emulsions of organic solvent in water at different superficial gas
velocities. A type of anionic surfactant was employed in order to
investigate the effect of addition of surfactant to organic-aqueous
Fig. 1. Schematic representation of the bubble column bioreactor.
systems on Sauter mean diameter of bubbles, gas hold-up and
volumetric oxygen transfer coefficient. The surfactant was chosen
based on their nature and application in wastewater treatment.
Effects of these surface contaminants on the interfacial area and on also added to distilled water and n-tridecane in water systems in
the liquid-side mass transfer coefficient were also analyzed sep- order to investigate the effect of addition of surfactants on hydro-
arately. The results are of importance in extending the influence dynamics properties as well as mass transfer rate in the system.
of surface contaminants on oxygen mass transfer characteristics in The physical properties of alkanes used in this work were listed
gas–liquid contactors. Especially, these results can be used in bio- in Table 1. Also, Table 2 shows the various concentrations of the
logical treatment of wastewaters of petroleum industries. In these oil–water with their properties and symbols used in this study.
wastewaters, hydrocarbons exist as contaminant where hydrocar- Surface tensions reported in this table were measured by the ring
bon content is about 1000 ppm (∼0.1%, v/v). method using a Ring Tensiometer KRUSS-Nr.2215.

2. Experiments and methods 2.3. Methods

2.1. Experimental setup
Measurements were carried out at 25 ◦ C in a cylindrical bubble
column. A schematic overview of the experimental set up is given
in Fig. 1. The column was made of Pyrex glass with a height of 1.1 m,
inner diameter of 95 mm and working volume of 6.3 × 10−3 m3 . The
sparger was located at 0.07 m above the base of the column. The gas
distributor was a 0.042 m diameter perforated plate with 26 orifices
of 0.3 mm diameter. Gas flow rate was measured using a calibrated
flow meter to give a nominal range of 0.5–15 L/min, equivalent to
superficial gas velocities of (1.18–23.5) × 10−3 m/s in the column.
2.2. Materials
Distilled water was utilized in the experiments, using immis-
cible hydrocarbons (n-decane, n-tridecane and n-hexadecane) as
impurity. The operation was batch with respect to the liquid. The
gas was air at room temperature and pressure. A type of anionic
surfactant namely SDS (sodium dodecyl sulfate from Merck) was
Volumetric oxygen transfer coefficient was measured using the
dynamic method [15,16]. Concentrations of oxygen dissolved in
the liquid were monitored continuously using a dissolved oxygen
meter (Mettler Toledo M300, Germany) with a rapid polarographic
dissolved oxygen probe (Mettler Toledo, Inpro 6800, Germany). The
probe was located 0.7 m from the sparger based on the recommen-
dation of Shioya and Dunn, with its tip pointing upward to minimize
bubble interference [17]. It was assumed that the signal from the
oxygen electrode was directly proportional to the oxygen concen-
tration in the liquid phase in the range of the measurements of
this work. First, the oxygen was stripped from liquid completely
by injection of pure nitrogen through the sparger into the liquid.
When all the oxygen was stripped out, air was sparged into the col-
umn and the oxygen uptake into the liquid phase was monitored
continuously by means of the oxygen sensor. The gas flow rate was
kept constant in order to maintain the hydrodynamic conditions of
the bubble column unchanged. The total time of measurement was
chosen large enough for oxygen to reach the saturation concentra-
tion.

Table 1
Physical properties of the hydrocarbons used at 25 ◦ C.

Hydrocarbon MW   (kg/m3 ) DO2 −org  (mN/m) Solubility  ow  go  gw mR

(kg/kmol) (mPa s) (×10−9 m2 /s) (mN/m) (mN/m) (mN/m)
◦ ◦
Mass% at 0 C g/L at 0 C

n-Decane 142.28 0.838 726.6 4.4742 23.37 1.5 × 10−6 1.5 × 10−5 52.0 23.8 72.7 8.8
n-Tridecane 184.3 1.724 756.4 2.4752 25.55 3.3 × 10−8 0.3 × 10−6 52.6 25.95 72.2 –
n-Hexadecane 226.44 3.032 770.1 2.5155 27.05 0.6 × 10−6 0.6 × 10−5 53.3 27.2 71.8 7.53
 M. Asgharpour et al. / Biochemical Engineering Journal 49 (2010) 351–360 353

Table 2
Properties of liquids at 25 ◦ C.

Liquid Oil-in-water volume m (kg/m3 )  m (mN/m) Symbol

ratio (ϕdisp )

Distilled water 0% 997.1 74 W

Distilled water-SDS 0% – 35 W/SDS

Water–n-decane 0.05% 999.9 65 D/W 0.05

0.1% 999.7 63 D/W 0.1
0.3% 999.2 61 D/W 0.3
0.5% 998.6 60 D/W 0.5

Water–n-tridecane 0.1% 999.8 61 TD/W 0.1

Water–n-tridecane-SDS 0.1% – 33 TD/W 0.1/SDS

Water–n-hexadecane 0.05% 999.9 67 HD/W 0.05

0.1% 999.8 64 HD/W 0.1
0.3% 999.3 62 HD/W 0.1
0.5% 998.9 60 HD/W 0.5

The overall gas hold-up (εg ) was determined by visual mea-
surements using the volume expansion method [15]. This was
determined by measuring the difference between the ungassed and
gassed liquid volume. The gas hold-up was calculated from:
H − H0
εg =
H
The gas flow rate was measured by a rotameter. Sufficient time
was given for steady state to be reached in the column after which
the increase in dispersion height was recorded.
Bubble average diameter (d32 ) was measured by photographic
method. Bubble images were obtained with a Canon Power Shot
S5IS digital camera at middle section of the column (0.70 m from the
sparger). Fig. 2a–c illustrates examples of photographs of bubbles
for water, n-decane in water (0.05%, v/v) and SDS/water systems
at ug = 0.353 cm/s obtained by this measurement technique. Shape
of bubbles was assumed to be ellipsoidal. Major and minor axes
of the projected ellipsoid were measured and the diameter of the
volume-equivalent sphere was taken as the representative bubble
dimension:

3 as compared to hydrocarbons. Therefore, it can be observed that
d= E2 e
The mean bubble size (Sauter mean diameter) was then evalu-
ated by [18,19]:
 3
ni di
d32 = i 2
nd
i i i
3. Results and discussion
3.1. Gas hold-up
Fig. 3 shows the overall gas hold-up in the air-water system as
well as in 0.1% (v/v) hydrocarbons as a function of superficial gas
velocity. The Error bars shown on this figure represent the standard
deviations of the measured value. The error bars are presented only
for water system to indicate the sample error. The errors for other
mixtures were in the same range and are not shown to avoid making
the figure difficult to understand. As expected, the values of εg for
all the fluids increases by increasing the power input per unit vol-
ume by increasing the aeration rate (ug ). Increasing the gas velocity
increases the dispersion of small bubbles with slower bubble rise
velocities within the system, thus increasing the gas hold-up of the
system. The longer residence time of smaller bubbles allow more
time for the oxygen to transfer to the liquid phase [14]. On the other
hand, a larger ug increases the bubble collision frequency leading
to a higher coalescence [20] with correspondingly larger bubbles.
The preferential release of larger bubbles may result in greater pro-
portion of smaller bubbles in the fluid and consequently, a larger
gas hold-up [14].
Table 1 provides that the surface tension of water saturated
with hydrocarbon ( ow ) is lower than the surface tension of dis-
tilled water. According to Girifalco and Good [21], when two liquids
(1) become in contact with each other, the liquid with lower surface
tension places on the surface of liquid with higher surface tension
and both become mutually saturated, thus, the surface tension of
both liquids will change.
According to the experimental values of surface tension in
Table 2, adding hydrocarbons to water decreases the surface ten-
sion. The change in surface tension, though insignificant, is believed
to affect hydrodynamics and mass transfer. Gas hold-up increases
with decreasing of surface tension since smaller bubbles are pro-
duced when surface tension is lower. Smaller bubbles have lower
rise velocity, resulting in higher gas hold-up.
As shown in Fig. 3, when surfactant (SDS) was added to n-
tridecane in water system (0.1%, v/v), gas hold-up increases. As it
can be observed at Table 2, surfactants decrease the surface tension
more than hydrocarbons because of their high solubility in water
(2)
presence of surfactants causes the bubble size to decrease and εg
increases.
Fig. 3 also demonstrates that at low superficial gas velocities
(ug ≤ 0.5 cm/s), addition of organic phase to water has low influence
on the gas hold-up of the mixture. At low gas flow rates the surface
(3)
tension has little effect on gas hold-up since the largest bubbles in
the column are still smaller than the maximum bubble size dictated
by the surface tension. Therefore, the gas hold-up at this region is
not affected by the surface tension of the liquid.
Fig. 4 illustrates the influence of hexadecane concentration on
gas hold-up at various superficial gas velocities. According to Fig. 4,
the gas hold-up increases moderately with increasing of the hydro-
carbon concentration, especially at higher concentrations. The rise
velocity of bubbles decreases by increasing the hydrocarbon con-
centration. This decrease can be attributed mainly to a proportional
rise in the concentration of surface contaminant molecules in the
liquid and on the bubble surface and decreasing of surface tension
(Table 2) with increasing hydrocarbon concentration [22]. Also,
increasing the hydrocarbon concentration produce smaller bubbles
which in turn increases the gas hold-up.
3.2. Bubble size
Fig. 5 shows Sauter mean bubble diameter in the bubble col-
umn for various hydrocarbons at 0.1% (v/v) and surfactant in water
systems as a function of superficial gas velocity. The values of d32
obtained in this work are in the range of 4–7 mm which is in agree-
354 M. Asgharpour et al. / Biochemical Engineering Journal 49 (2010) 351–360

Fig. 3. Gas hold-up for hydrocarbon in water systems (0.1%, v/v) with and without
surfactant as a function of superficial gas velocity. W: water; D/W: n-decane in
water; TD/W: n-tridecane in water; HD/W: n-hexadecane in water; SDS: sodium
dodecyl sulfate (error bars are standard deviations).

Fig. 4. Gas hold-up for n-hexadecane in water system at various superficial gas
velocities as a function of concentration (error bars are standard deviations).

Fig. 2. Examples of photographs of bubbles at ug = 0.353 cm/s for (a) water system;
(b) n-decane in water 0.05% (v/v); (c) SDS/water.

ment with the experimental values reported by others [23,24]. As

it can be observed in Fig. 5, the mean bubble size increases with
increasing superficial gas velocity up to ug = 0.5 cm/s while slightly
decreases at higher velocities. Initial increase in bubble diameter
can be explained by increase in dispersion of small bubbles within Fig. 5. Sauter mean bubble diameter for hydrocarbon in water systems (0.1%, v/v)
the system with increasing aeration rate and increasing the bub- and aqueous solution of surfactants as a function of superficial gas velocity. W:
ble collision frequency that leads to higher coalescence rate and an water; D/W: n-decane in water; TD/W: n-tridecane in water; HD/W: n-hexadecane
increase in stable bubble diameter [20]. Decrease in bubble size at in water; SDS: sodium dodecyl sulfate (error bars are standard deviations).
velocities higher than 0.5 cm/s can be attributed to increasing the
 M. Asgharpour et al. / Biochemical Engineering Journal 49 (2010) 351–360
Fig. 6. Sauter mean bubble diameter as a function of superficial gas velocity for
(a) n-hexadecane in water (b) n-decane in water system at various concentrations.
W: water; D/W: n-decane in water; HD/W: n-hexadecane in water (error bars are
standard deviations).
proportion of small bubbles due to bubble breakage. It was shown
that an increase in ug leads to higher liquid velocity, which can
be responsible for enhancement of turbulent intensity [25–27]. In
other words, higher gas velocity results in greater turbulent inten-
sity, which in turn causes more bubble breakage and leads to a
decrease in average bubble size, as illustrated in Fig. 5.
Fig. 5 also illustrates that adding hydrocarbon to water reduces
the bubble size. This decrease can be attributed to decrease of sur-
face tension of the liquid when hydrocarbon is added to water.
Moreover, presence of hydrocarbon molecules on the surface of
bubbles may reduce the tendency to coalescence of bubbles which
results in presence of smaller bubbles in the system. In either
case, smaller bubbles result in higher gas hold-up. The phenomena
observed in the presence of surface contaminants can be related
to the surface tension gradient around the bubble that limits the
interface mobility and as a consequence, its velocity [28]. Accord-
ing to Fig. 5, bubble size decreases with adding of surfactant more
than hydrocarbons. Surfactants decrease bubble size due to higher
reduction in surface tension of solution than hydrocarbons.
Values of d32 as a function of volumetric ratio for n-hexadecane
and n-decane in water systems at various superficial gas velocities
are shown in Fig. 6. As can be seen in this figure, increasing the
hydrocarbon concentration decreases d32 at constant gas velocity
through greater decreasing of surface tension (Table 2). As men-
tioned above, this decrease can be attributed to greater coalescence
hindrance effects of contaminant molecules on the bubbles surface.
355
Fig. 7. Oxygen transfer coefficient for hydrocarbon in water systems (0.1%, v/v) as
a function of superficial gas velocity. W: water; D/W: n-decane in water; TD/W:
n-tridecane in water; HD/W: n-hexadecane in water (error bars are standard devi-
ations).
3.3. Volumetric oxygen transfer coefficient
In the application of the dynamic method for measuring of kL a,
the following assumptions were made: both gas and liquid phase
are perfectly mixed, oxygen concentration in bubbles remains con-
stant while passing through the column, the main resistance of
oxygen transfer into the emulsion exists in the liquid film around
the gas bubbles and the oxygen transfer from the oil-to-water is
much faster than from air to oil. The liquid phase was de-aerated
by purging with nitrogen until only minimum levels of dissolved
oxygen remain. Then, air was sparged into the bioreactor until satu-
ration and dissolved-oxygen concentration was monitored through
operation time [13,29,30].
As the oxygen concentration increases, the mass transfer rate is
given by the following equation:
dC
= kL a(C ∗ − C) (4)
dt
or, in its integral form by
 C −C 
0
Ln = −kL at (5)
C ∗ − C0
This equation is valid for probes with very short response time.
In the case when the oxygen probe has a large response time it is
necessary to calculate kL a by following formula [31]:
C ∗ − CL kp e(−kL at) − kL ae(−kp t)
∗
= (6)
C − C0 kp − kL a
The response time of the probe ( p = 1/kp ) is defined as the time
necessary to reach 63% of the final value measured when exposed to
a step change in concentration. This constant can be determined by
transferring the oxygen probe from a solution with sodium sulfite
(in which oxygen concentration is zero) to another solution satu-
rated with air [31]. The response time of the oxygen probe used in
this study was measured to be 25 s at 25 ◦ C. Therefore, Eq. (6) was
used to evaluate the volumetric mass transfer coefficient kL a.
Fig. 7 presents the volumetric oxygen transfer coefficient in the
bubble column for various hydrocarbons 0.1% (v/v) in water sys-
tems as a function of superficial gas velocity. As it can be observed
in this figure, the values of kL a for all of liquids are increased with
increasing gas velocity. The exception in this trend, for which kL a
decreases with increasing gas velocity, is from 0.353 to 0.470 cm/s.
The first part of the curve (gas velocity less than 0.353 cm/s) cor-
responds to the homogeneous regime, where kL a increases with
356 M. Asgharpour et al. / Biochemical Engineering Journal 49 (2010) 351–360

Fig. 9. Oxygen transfer coefficient as a function of superficial gas velocity for n-

tridecane in water system (0.1%, v/v) with and without surfactant. W: water; TD/W:
n-tridecane in water; SDS: sodium dodecyl sulfate (error bars are standard devia-
tions).

transfer coefficient increases by increasing the concentration of

hydrocarbon especially at higher gas velocities. This is consistent
with the fact that with increasing the concentration of hydrocarbon,
the presence of oil droplets in the liquid film around gas bubbles
increases and causes reduction of the tendency to coalescence of
bubbles. As a result, as shown previously in Fig. 6, with increasing
hydrocarbon concentration, the bubble size decreases and hence
specific gas–liquid interfacial area and kL a increase. However at
lower gas velocity, the mentioned effect of bubble size decreasing
is not significant to affect kL a.
Fig. 8. Oxygen transfer coefficient as a function of concentration for (a) n-
hexadecane in water and (b) n-decane in water at various superficial gas velocities Fig. 9 demonstrates the effect of surfactant (SDS) on kL a in dis-
(error bars are standard deviations). tilled water system and 0.1% tridecane–water system as a function
of gas velocity. As shown in this figure, by addition of surfac-
the gas velocity. Size and number of bubbles increase with increas- tant to hydrocarbon in water system, the mass transfer coefficient
ing the superficial gas velocity in this regime which leads to higher decreases. The presence of surfactants over a gas–liquid interface
specific gas–liquid interfacial area and higher mass transfer coeffi- increases the interfacial area at constant gas hold-up (by reducing
cient. Visual observation of the bubble column also indicated that the average bubble diameter), but decreases the mass transfer coef-
at ug = 0.353 cm/s, bubbles started to coalesce and large bubbles ficient kL by increasing the liquid phase mass transfer resistance.
were created. As a result, specific gas–liquid interfacial area at gas Further insight is obtained when the variation of the volumet-
velocities higher than 0.353 cm/s increases with a lower rate. At ric mass transfer coefficient per unit volume of bubbles (kL a/εg ) is
superficial gas velocity higher than 0.470 cm/s, kL a continues to plotted against gas velocity. Such a graph can be seen in Fig. 10
increase due to more turbulence which leads to enhanced bubble for the experimental data of this work. At low superficial gas
break-up and creating more small bubbles, thus, increasing inter- velocity (ug < 0.5 cm/s) the values of kL a/εg decrease sharply with
facial area and kL a. increasing gas velocity. However, at higher superficial gas veloci-
Fig. 7 indicates that the values of kL a for the hydrocarbon in ties (ug > 1.3 cm/s) the value of kL a/εg is practically independent of
water systems are significantly higher than the corresponding val-
ues for the distilled water system. This increase can be attributed to
the lower bubble size for hydrocarbon in water systems as shown
in Fig. 5 through decreased surface tension. Compared to surfac-
tants, hydrocarbons have much less solubility in water, thereby,
reduce the surface tension of water to a lower extent. Typically,
oxygen solubility in aqueous solutions is less than 10 mg/L [32].
However, the oxygen solubility in alkanes is more than 20 times of
that in water (solubility ratio mR > 1) [14]. Under these conditions,
the increased oxygen transfer rate is likely to compensate for the
greater requirement for oxygen transfer. Therefore, the presence of
dispersed liquid droplets can significantly enhance the transfer rate
of gas phase into the continuous liquid phase. According to results,
at low superficial velocities, the surface tension has little effect on
kL a, although the lower surface tension liquids give slightly higher
kL a values.
The values of the volumetric mass transfer coefficient for the
various concentrations of n-hexadecane and n-decane in water Fig. 10. Influence of superficial gas velocity on kL a/εg for hydrocarbon in water
are shown in Fig. 8. It is evident from this figure that the mass systems.
 M. Asgharpour et al. / Biochemical Engineering Journal 49 (2010) 351–360 357

Fig. 12. Liquid-side mass transfer coefficient for hydrocarbon in water systems
Fig. 11. Interfacial area of gas for hexadecane in water at various concentrations
(0.1%, v/v) and aqueous solutions of surfactants as a function of superficial gas
in comparison with n-decane and n-tridecane in water (0.1%, v/v) as a function of
velocity. W: water; D/W: n-decane in water; TD/W: n-tridecane in water; HD/W:
superficial gas velocity. W: water; D/W: n-decane in water; TD/W: n-tridecane in
n-hexadecane in water; SDS: sodium dodecyl sulfate (error bars are standard devi-
water; HD/W: n-hexadecane in water.
ations).

gas velocity. This is consistent with the findings of Vandu et al. [33] sion has been related to the interfacial area through its effect on
that showed, εg and kL a/εg are virtually scale independent for the bubble size [20,14].
churn-turbulent regime of operation. The results presented in the Fig. 12 shows the variation of kL as a function of superficial gas
present study, therefore, are usable for scale up purposes. velocity for 0.1% concentration of different hydrocarbons in water
and the SDS-water system. According to Fig. 12, kL decreases with
3.4. Liquid-side oxygen transfer coefficient and gas–liquid increasing the gas velocity for some liquids. The presence of surface
interfacial area contaminants decreases kL due to lower degree of turbulence in
the liquid film around bubbles and a reduction of liquid renewal at
The volumetric mass transfer coefficient (kL a) is composed two interface, thus, increasing the liquid phase mass transfer resistance.
parameters, i.e., liquid-side mass transfer coefficient (kL ) and spe- These results demonstrate that the lowest kL is directly linked to
cific interfacial area (a). Liquid-side mass transfer coefficient was the presence of surfactants at the gas–liquid interface which makes
reported to be a function of turbulence, liquid properties and bub- the diffusion coefficients of oxygen be reduced [35]. As pointed out
ble size. It depends also on the diffusion coefficient and on the by Painmanakul et al. [13], the presence of surfactants at the bubble
flow pattern around the bubbles [34]. The liquid-side mass transfer interface affect the mass transfer by modifying the composition or
coefficient can be simply determined by the thickness of liquid film around the air bubbles.
kL a Fig. 13 shows the values of kL /kL(water) for n-decane and n-
kL = (7) hexadecane in water systems as a function of oil-to-water phase
a
volume ratio at different superficial gas velocities. According to this
The local interfacial area can be obtained from the mean diam- figure, for systems with n-alkanes as dispersed phase, the kL value
eter of bubbles and the gas hold-up: initially decreases and remains almost constant afterwards. There-
6εg fore, it can be concluded that the increase in kL a is solely due to an
a= (8) increase in gas–liquid interfacial area values, whereas kL decreases
d32 (1 − εg )
and in some cases remains practically constant.
Eq. (8) relates interfacial area per unit volume to the volume-
surface mean diameter, or Sauter mean diameter d32 , through the
fractional gas hold up εg . Variation of the experimental gas–liquid
interfacial area with gas superficial velocity is illustrated in Fig. 11
for different concentrations of n-hexadecane in water in compari-
son with n-decane and n-tridecane in water (0.1%, v/v). As can be
observed in this figure, the interfacial area increases with increasing
ug . However, the rate of this increase at ug < 0.5 is lower than that
at ug > 0.5. As mentioned earlier, the interfacial area increases with
increasing ug due to increase in gas hold-up. On the other hand,
further increase in superficial gas velocity increases the number of
larger bubbles. This increase in the bubble size has a negative effect
on the gas–liquid interfacial area and reduces the positive effect
caused by the gas hold-up. This is the reason for slower increase of
interfacial area at ug < 0.5 cm/s.
Fig. 11 also reveals that the interfacial area of the aqueous solu-
tions contaminated with hydrocarbon is larger than that of distilled
water. Increasing the hydrocarbon concentration reduces the bub-
ble size through due to decrease in surface tension. Therefore, the Fig. 13. The values of kL /kL(water) as function of ϕdip in different superficial gas veloc-
interfacial area increases according to Eq. (8). Thus, the surface ten- ity. D/W: n-decane in water; HD/W: n-hexadecane in water.
358 M. Asgharpour et al. / Biochemical Engineering Journal 49 (2010) 351–360
Fig. 14. Predicted versus experimental overall gas hold-up. W: water; D/W: n-
decane in water; TD/W: n-tridecane in water; HD/W: n-hexadecane in water.
3.5. Empirical correlations
Using the data obtained in this work, the following correlation
can be proposed for the hold-up:
0.101 0.925 −0.54
εg = 0.55d32 ug  (9)
Correlation coefficient of this equation was evaluated to be 0.96.
A comparison between measured and calculated values of hold-up
can be observed in Fig. 14. It can be seen in this figure that Eq. (9)
predicts about 95% of the experimental data within 14% relative
error.
The rate of mass transfer has been correlated to the interfacial
motion, which in turn is attributed to hydrodynamic and molecular
effects. These effects can be described in terms of forces acting on
the bubbles (i.e., inertial, viscous, surface tension and body force
or gravitational). Therefore, dimensionless numbers affecting the
mass transfer coefficient are Re (inertia force/viscous force) and Bo
(body force/surface tension) [4]. Another effective dimensionless
number is Schmidt which is the ratio of momentum diffusivity (vis-
cosity) and mass diffusivity, and is used to characterize fluid flows
in which there are simultaneous momentum and mass transfer pro-
cesses. Consequently, liquid-side mass transfer coefficient can be
correlated with Sherwood number, using the experimental data of
this work, as:
Sh = 0.15 Re2/3 Sc 1/2 Bo2/3
Correlation coefficient of this equation was evaluated to be
0.904. Comparison between experimental and calculated Sher-
wood numbers is given in the parity plot as shown in Fig. 15.
Comparison between experimental Sherwood numbers and those
calculated based on the other available correlations in the litera-
ture (Table 3) is also provided in Fig. 15. This figure demonstrates
that the correlation developed in this work is considerably better
than previous correlations reported in literature for prediction of
experiments in rang studied. It is worth noting that he correlation
developed in this work is superior to that of Bird et al. [36] and
Table 3
Sherwood number correlations for liquid-side mass transfer coefficient in a bubble
column as a function of Reynolds number, Schmidt number, and Bond number.
Correlations Remark Ref.
2/3
Sh = 0.15 Re Sc Bo 1/2 2/3
0.118 < ug < 2.35 cm/s This study
Sh = (4/)1/2 Re1/2 Sc1/2 Higbie’s model Bird et al. [36]
Sh = 0.53 Re2/3 Sc1/2 db > 2.5 mm Calderbank and
Moo-Young [37]
Sh = 0.6 Re1/2 Sc1/2 Bo3/8 Homogeneous flow Akita and Yoshida [38]
Fig. 15. Sherwood number calculated from literature correlations; correlation pro-
posed in this study versus experimental Sherwood number.
Calderbank and Moo-Young [37] since it contains Bond no. which
takes the interfacial tension into account. Moreover, the proposed
correlation suggests that the effect of Bond no. (or interfacial ten-
sion) on mass transfer coefficient is greater than that presented by
Akita and Yoshida [38].
4. Conclusion
The hydrodynamics and mass transfer characteristics of bubble
column bioreactors were investigated. Volumetric mass trans-
fer coefficients of oxygen between air and water for various
gas–aqueous–organic systems were measured using a dynamic
method. Experiments were carried out in the most unfavorable
multiphase system for oxygen mass transfer (i.e., organic phase
dispersed in the aqueous phase). It was shown that the presence
of surface contaminant molecules, including hydrocarbon com-
pounds, affect the bubble generation process, hence the interfacial
area and the different mass transfer parameters such as kL a and kL
by decreasing of surface tension. The following major conclusions
can be drawn from this work.
(10)
• The volumetric mass transfer coefficient and the overall gas hold-
up increases with increasing superficial gas.
• At superficial gas velocity below 0.5 × 10−3 m/s, addition of
alkane to air–water system has low influence on kL a and εg while
at higher superficial gas velocity addition of alkane increases kL a
and εg .
• The value of kL a increases by adding hydrocarbons to water since
the surface tension decreases at such a condition and through
increasing of solubility of oxygen in hydrocarbons. Bubbles tend
to become smaller with decreasing surface tension.
• Increase in concentration of alkane results in increasing kL a and
εg and decreasing d32 , which can be attributed to increasing the
coalescence-inhibiting tendency in the presence of surface con-
taminant molecules and decreasing of surface tension, including
hydrocarbon compounds and surfactants.
• The interfacial area increases with increasing of gas velocity and
with adding of contaminants.
• Surface contaminants decrease the mass transfer coefficient kL
for some liquids by increasing the liquid phase mass transfer
resistance. The kL values remain roughly constant at higher con-
centrations.
 M. Asgharpour et al. / Biochemical Engineering Journal 49 (2010) 351–360 359

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