Biochemical Engineering Journal 22 (2005) 105110

Gas hold-up and oxygen transfer in a draft-tube airlift bioreactor with petroleum-based liquids
Mohammad Reza Mehrniaa,b, , Jafar Towghib , Babak Bonakdarpourc , Mohammad Mehdi Akbarnejadd
b a Chemical Engineering Department, Tehran University, Tehran 11365-4563, Iran Biotechnology group, Chemical Engineering Department, Tarbiat Modarres University, Tehran, Iran c Chemical Engineering Department, Amir Kabir University of Technology, Tehran, Iran d Iranian Research Institute of Petroleum Industry, Tehran, Iran

Received 11 May 2004; received in revised form 25 August 2004; accepted 3 September 2004

Abstract Gas hold-up (g ) and volumetric gasliquid oxygen transfer coefcient (kL a) in a draft-tube airlift bioreactor (24 103 m3 in volume) were studied using pure kerosene and diesel and their water-in-oil microemulsions, as the model solutions for petroleum biodesulfurization. For comparison, experiments were also done with distilled water. The g and the kL a values for kerosene and diesel systems were in most cases signicantly higher than the water system. Increase in water-to-oil phase volume ratio () of the microemulsion systems resulted in decrease in the values of g , which was attributed to a decrease in the coalescence-inhibiting tendency of the petroleum liquids. Increase in the viscosity (v) of the microemulsion systems to around 32 106 m2 /s resulted in the occurrence of the churn turbulent regime with an associated decrease in the value of g , which could not be solely accounted for by the increase in . Furthermore, the kL a values decreased with increase in the viscosity of the petroleum-based liquids. However, when churn turbulent conditions prevailed, increase in viscosity alone could not account for the decrease observed in the kL a values. Empirical correlations were developed that related g and kL a to and , respectively, under the bubbly ow regime inside the bioreactor. 2004 Elsevier B.V. All rights reserved.
Keywords: Airlift bioreactors; Gas hold-up; Oxygen transfer; Petroleum; Microemulsions; Viscosity

1. Introduction Airlift bioreactors are being considered for use in a variety of biotechnological processes, such as biocatalytic desulfurization (BDS) of petroleum, in which a slurry of bacterial cells or aqueous biocatalytic agent (as the dispersed phase) is mixed with high-sulfur distillate to produce a homogenous emulsion, preferably a microemulsion [15]. The majority of hydrodynamics and oxygen transfer data for airlift bioreactors have been obtained with air/water-based systems, with properties different from the real conditions of the BDS processes, in which petroleum-based media are em

Corresponding author. Tel.: +98-21-6498982; fax: +98-21-6461024. E-mail address: jtd mrm@yahoo.com (M.R. Mehrnia).

ployed that have much lower surface tensions, higher viscosities and bubble coalescence inhibiting rather than promoting properties. It is known that both liquid viscosity and surface tension affect gas hold-up (g ) [68] and volumetric oxygen transfer coefcient (kL a) [912] in airlift bioreactors containing water-based media. The small bubbles formed in liquids with reduced surface tension may enhance both g and kL a [9,10]. An increase in liquid viscosity results in the formation of larger bubbles that reduce g , while at the same time the viscose drag increases which can lead to a decrease in bubble rise velocity and hence increase in g [12,13]. Some researchers have, therefore, reported a decrease in the value of g with increasing liquid viscosity [1215] whereas others have found that there is no signicant effect of viscosity on g [9,10,16].

1369-703X/$ see front matter 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.bej.2004.09.007

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Nomenclature a AN D ESF H kL kL a TS ugr v W/D W/K W/O specic gasliquid interfacial area (m2 /m3 ) two-pair non-ionic surfactants (Arkopal N100 and N40) column diameter (m) two-pair non-ionic surfactants (Ethoxylated soya fatty acid 2 and 10 M) draft-tube height (m) liquid-side oxygen transfer coefcient (m/s) volumetric oxygen transfer coefcient (1/s) two-pair non-ionic surfactants (Tween 80 and Span 80) riser supercial gas velocity (m/s) kinematic viscosity (m2 /s) water-in-diesel microemulsion water-in-kerosene microemulsion water-in-oil microemulsion

the effect of the type of surfactant used in the preparation of the microemulsion system was also investigated. Additionally, correlations describing the effect of the physicochemical characteristics of petroleum liquids and W/O microemulsions on the gas hold-up and the volumetric oxygen transfer coefcient in the DTAB have been obtained.

2. Experimental system The DTAB was made of Pyrex glass with 0.14 m inside diameter. The height of draft-tubes was 1.48 m. The inside diameter of draft-tubes was 0.095 m with a wall thickness of 0.0025 m, yielding an Ad /Ar ratio of 0.707. There was a 0.024 m annular gap beneath the bottom edge of the draft-tube for uid circulation. Air was introduced into the draft-tube through a set of perforated pipes (ladder-like shape sparger) with 30 equally spaced 0.001 m holes. The sparger was located 0.06 m above the lower end of the draft-tube. The distance between the static liquid surface and the upper edge of the draft-tube was 0.1 m. The liquids employed in the present work were distilled water, kerosene, diesel and different W/O microemulsion systems employing different hydrocarbon base and ratios in the range 1030%. Table 1 lists the properties of those liquids at the experimental temperature, i.e., 25 C. Three different non-ionic pair of surfactants namely Arkopal N100 and N40 (Ethoxylated nonylphenol 10 and 4 M) (AN) [Clariant, Germany], Ethoxylated soya fatty acid 10 and 2 M (ESF) [Hooman shimi Co., Iran], Tween 80 and Span 80 (TS) [Aldrich Co. Ltd.] were used in the preparation of the microemulsion systems. These systems were prepared as described previously [19,20]. Surfactant pair AN was also added to kerosene in one of the experimental runs inside the DTAB in order to investigate the inuence of the addition of surfactants to petroleum liquids on gas hold-up and kL a. The bed expansion method was used to evaluate the overall gas hold-up in the airlift reactor [12,27]. This was determined by measuring the difference between the ungassed and gassed liquid volume. The volumetric oxygen transfer coefcient was determined by the dynamic physical method [12,20,27]. Dissolved oxygen concentrations were monitored continuously using a dissolved oxygen meter (Mettler Toledo 4220X, Germany) with a rapid polarographic dissolved oxygen probe (Mettler Toledo, Inpro 6100/120/T/P, Germany).

Greek letters g gas hold-up density (kg/m3 ) surface tension (N/m) water-to-oil phase volume ratio

Furthermore, increase in liquid viscosity results in decrease in the value of kL due to decrease in internal recirculation of bubbles [11,12]. Therefore, an increase in liquid viscosity generally leads to a decrease in kL a [1015,17]. On the other hand, increase in the bubble coalescence inhibiting tendencies of the liquid phase has been reported to affect the relationship between g and gas velocity [18,19]. Mehrnia et al. [20,21] used a water-in-kerosene (W/K) microemulsion with a water-to-oil phase volume ratio () of 20%, as a cold model of the BDS inside a draft-tube airlift bioreactor (DTAB) with different geometries and found somewhat different hydrodynamic and oxygen transfer characteristics of the bioreactor compared to the results reported for water-based media. In BDS processes, various hydrocarbon fractions are used as substrate and also the ratio is an important operational variable [14,2224]. The latter, together with the type of hydrocarbon fractions used in making the microemulsion, determines the viscosity of these systems [25,26]. The purpose of the present work, therefore, has been to obtain gas hold-up and the kL a values inside a DTAB employing different petroleum liquids and water-in-oil (W/O) microemulsion systems with the in the range 1030%. Higher ratios was not considered since, in BDS processes, the use of microemulsions with low water-to-oil ratios is recommended to reduce vessel size, lower the cost of downstream processing operations and minimize biocatalyst and water utilization with respect to the amount of oil [25,2224]. Furthermore,

3. Results and discussion 3.1. Gas hold-up In Fig. 1, the gas hold-up data obtained inside the DTAB with kerosene, diesel, and their various W/O microemulsions as a function of riser supercial gas velocity (ugr ) is presented and compared with the data for distilled water. As

M.R. Mehrnia et al. / Biochemical Engineering Journal 22 (2005) 105110 Table 1 Properties of liquids at 25 C Liquid Water/oil ratio () 0 0 10 20 20 20 30 0 20 Surfactants Petroleum soluble AN4 AN4 Span 80 AN4 ESF4 AN4 AN4 Water soluble AN10 Tween 80 AN10 ESF10 AN10 AN10 Density (kg/m3 ) 801.8 815.5 839.9 862.6 869.5 873.3 883.8 826.3 892.2 997 Kinematic viscosity (106 m2 /s) 1.74 1.92 3.7 4.87 6.52 9.34 31.15 8.07 32.3 0.897 Surface tension (mN/m) 29.5 29 29 29.5 29.5 30 30 32 33 72

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Symbol in the gures Kerosene W/K 0, AN W/K 10, AN W/K 20, TS W/K 20, AN W/K 20, ESF W/K 30, AN Diesel W/D 20, AN Water

Kerosene Surfactant-added kerosene Water/kerosene microemulsion Water/kerosene microemulsion Water/kerosene microemulsion Water/kerosene microemulsion Water/kerosene microemulsion Diesel Water/diesel microemulsion Water

expected, the value of g for all of the uids generally increases with increasing gas velocity. The results also show that most of the values of g for the petroleum liquids and the W/O microemulsion systems are signicantly higher than the water system except for the g values obtained for 30% W/K and the 20% water-in-diesel (W/D) microemulsions at ugr 0.06 m/s. This difference can generally be attributed to the much lower surface tension and perhaps the higher coalescence hindering characteristics of the petroleum liquids and the microemulsions compared to water, which results in the generation of smaller sized bubbles in the bioreactor lled with these systems. Observation of the two-phase ow in the DTAB with petroleum-based systems and distilled water conrmed the presence of smaller sized bubbles in the former systems. Similar g values are obtained for diesel and kerosene although the former has a viscosity that is more than four times higher than the latter (see Table 1). Similarly, results presented in Fig. 1 also show that there is no signicant

Fig. 1. Gas hold-up for kerosene, diesel and their various water-in-oil microemulsions, and distilled water as a function of supercial gas velocity.

change in the value of g when the viscosity is increased by a change in the type of surfactant used in making the 20% W/K microemulsion systems. However, the addition of water-todiesel and -kerosene, with an associated increase in viscosity, has resulted in a signicant reduction in the value of g . These results seem to suggest that for all the petroleum-based systems, except 30% W/K and the 20% W/D microemulsions, and with the bioreactor conguration employed in the present study, the enhancing effect of viscosity on g due to smaller bubble rise velocities (which results in higher residence time of bubbles in the draft-tube and a higher rate of recirculation of bubbles into the downcomer) balances the negative effect of viscosity on g as a result of the generation of larger bubble sizes. Different results might be obtained in DTABs that have a larger gas disengagement section, such as those employed by Mehrnia et al. [20]. The smaller g values obtained with microemulsion systems as compared to the pure petroleum liquids, with an indirect relationship being found between g and , can perhaps be attributed to a decrease in the coalescence inhibiting tendency of these liquids through the addition of the highly coalescence promoting distilled water. For all the petroleum-based liquids employed, except the 30% W/K and the 20% W/D microemulsions, bubbly ow was observed over the whole range of ugr employed in the present study, and as the results in Fig. 1 show there is no signicant decrease in the rate of rise of g with ugr over this range. On the other hand, the results for the 30% W/K and the 20% W/D microemulsions, as well as distilled water, show a signicant lowering of the rate of rise of g with ugr . Visual observations also indicated the occurrence of the churn turbulent at ugr around 0.020.04 m/s for distilled water and around 0.040.06 m/s for the other two microemulsion systems. Observation of Fig. 1 also shows a signicant drop in the slope of the curve for distilled water at ugr around 0.04 m/s and the two microemulsion systems at around 0.06 m/s.

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Fig. 2. Correspondence between predicted and experimental values of gas hold-up.

In terms of the above discussion, for conditions employed in the present study which lead to bubbly ow, the gas holdup was affected by the ugr and the water-to-oil phase volume ratio. An exponential multiple regression used on the data from the gas hold-up experiments in the DTAB containing different petroleum-based uids for bubbly ow regime gave the following correlation: g = 1.320[ugr ]0.927 [1 + ]0.673 (1)

A comparison between experimental data and calculated values of gas hold-up for petroleum-based media is shown in Fig. 2. It can be seen that Eq. (1) predicts about 83% of the experimental data with 15% error. The data obtained under conditions in which the churn-turbulent regime prevailed in the DTAB could not be satisfactorily correlated with the above equation. However, due to the smaller number of data points available, a suitable correlation for this regime cannot be presented here. It should also be noted that change in the geometry of the gas disengagement section could also have a bearing on the relationship between g and ugr in DTABs employing petroleum-based media. 3.2. Volumetric oxygen transfer coefcient Fig. 3 shows the measured kL a as a function of ugr for the same liquids employed for gas hold-up measurement presented in Fig. 1. Again, the value of kL a for all of the uids increases with increasing gas velocity, the only exception being the kL a data for the 30% W/K and the 20% W/D microemulsions in which kL a drops when ugr is increased from 0.04 to 0.06 m/s but further increase in ugr up to 0.08 m/s again had lead to an increase in kL a. The kL a data for distilled water also shows a signicant decline in the slope of the plot for ugr > 0.02 m/s. Visual observations of the ow regime in the DTAB indicated the occurrence of the churn turbulent regime somewhere between 0.02 and 0.04 m/s for distilled water and somewhere between 0.04 and 0.06 m/s for the 30% W/K and the 20% W/D microemulsions. Therefore, the above-mentioned trends could be attributed to a change in

the ow regime from bubbly to churn-turbulent. It should be noted that this trend was also observed to some extend with the g data for these liquids (Fig. 1). Similar observations have been previously reported in internal loop airlift reactors employing aqueous sucrose solutions [18] and sea water [19]. Similar to the gas hold-up data, in nearly all cases the kL a values for all the petroleum-based liquids is higher than distilled water. However, kL a data for diesel is signicantly lower than those for kerosene at all ugr employed although similar g values were obtained for these liquids inside the DTAB. Higher viscosities of solutions generally result in lower diffusivities of solutes [28], which in turn results in a lowering of kL [17,29]. This can, at least partly, explain the difference between the kL a and g results for these two liquids. The W/K microemulsions in nearly all cases shows higher kL a values. Increase in the value of viscosity, as a result of increase in (from 10 to 30%), type of surfactant (in the order TS, AN and ESF) or type of petroleum base (from kerosene to diesel), has resulted in decrease in the values of kL a at constant ugr inside the DTAB. The only exception is the kL a values at ugr = 0.08 m/s where kL a values for 10% and 20% W/K microemulsion (prepared with AN surfactant) are similar or higher than those for kerosene even though these microemulsions have higher viscosities than pure kerosene. A closer examination of Fig. 3 shows that for kerosene a drop in the rate of rise of kL a with ugr is observed at ugr 0.02 m/s whereas for all W/K microemulsions with 20% there is no signicant drop in this rate for ugr up to 0.08 m/s. When kerosene was employed inside the DTAB, stable foam was observed at ugr 0.02 m/s, with the rate of foaming significantly increasing with increasing ugr . However, this phenomenon was not observed inside the DTAB when the other petroleum-based liquids were employed. With kerosene, the milky appearance of the uid inside the DTAB at all air rates was also more prominent compared to the other petroleum liquids. Foaming, together with the milky appearance, is indicative of the presence of very small bubbles, and visual observations seem to suggest that their population increases with increasing ugr . This can result in a decrease in the values

Fig. 3. kL a for kerosene, diesel and their various water-in-oil microemulsions, and distilled water as a function of supercial gas velocity.

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the bubbly ow regime prevailed. However, an increase in viscosity to around 32 106 m2 /s either through change in the petroleum base or the of the microemulsion resulted in the onset of churn turbulent regime over most of the air rates employed in present study. Appropriate correlations relating g to and also kL a to viscosity were developed for bubbly ow regime, which were found to be less able to accurately predict the experimental data in the churn turbulent regime. The correlations obtained in this work can be further developed for churn turbulent regime and by taking design parameters effects into consideration.

Acknowledgement
Fig. 4. Correspondence between predicted and experimental values of kL a.

of kL [1113,17,29], which might explain the drop in the rate of rise of kL a with ugr at ugr 0.02 m/s. The kL a values for 20% W/D is higher than 30% W/K microemulsion especially at ugr 0.06 m/s although these two microemulsions have similar viscosities. This seems to indicate an additional inuence of water content on kL a, independent of its effect on viscosity, which probably results in a decrease in the bubble coalescence-inhibiting tendency of the microemulsion system. The results show that this phenomenon has a more pronounced effect on kL a in the churn turbulent regime where due to the high concentration of bubbles, bubble coalescence is expected to be more prominent. A multiple-regression analysis, conducted on the data from the volumetric oxygen transfer coefcient experiments for the different petroleum-based uids in the DTAB, under conditions in which bubbly ow regime prevailed, gave the following correlation: kL a = 0.235[ugr ]0.757 [v]0.11 (2)

The nancial support of Iranian Research Institute of Petroleum Industry is gratefully acknowledged.

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Fig. 4 compares the predicted values and experimental data for kL a in the bioreactor containing petroleum-based medium. The correlation predicts about 85% of the experimental data with an error of 20% or less. More work is required to develop a suitable correlation for conditions in the DTAB in which the churn-turbulent regime prevails.

4. Conclusions Petroleum fractions (i.e., kerosene and diesel) and their water-in-oil microemulsions with different water-to-oil volume ratio and surfactant types were used to study the gas hold-up (g ) and volumetric oxygen transfer coefcient (kL a) in a draft-tube airlift bioreactor for application in BDS processes. The addition of water as the coalescence promoting liquid to the petroleum-based systems, with an associated increase in and viscosity, resulted in a decrease in g and kL a, respectively. Moreover, for all petroleum-based liquids with viscosities up to about 8 106 m2 /s, as reported previously for 20% water-in-kerosene microemulsion [20,21],

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