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Biochemical Engineering Journal 30 (2006) 245–252

Effect of organic solvents on oxygen mass transfer in multiphase systems:
Application to bioreactors in environmental protection
E. Dumont ∗ , Y. Andr`es, P. Le Cloirec
Ecole des Mines de Nantes, UMR CNRS 6144 GEPEA, 4 rue Alfred Kastler, BP 20722, 44307 Nantes Cedex 03, France
Received 23 March 2006; received in revised form 11 May 2006; accepted 11 May 2006

The absorption of oxygen in aqueous–organic solvent emulsions was studied in a laboratory-scale bubble reactor at a constant gas flow rate.
The organic and the gas phases were dispersed in the continuous aqueous phase. Volumetric mass transfer coefficients (kL a) of oxygen between
air and water were measured experimentally using a dynamic method. It was assumed that the gas phase contacts preferentially the water phase. It
was found that addition of silicone oils hinders oxygen mass transfer compared to air–water systems whereas the addition of decane, hexadecane
and perfluorocarbon PFC40 has no significant influence. By and large, the results show that, for experimental conditions (organic liquid hold-up
≤10% and solubility ratio ≤10), the kL a values of oxygen determined in binary air–water systems can be used for multiphase (gas–liquid–liquid)
reactor design with applications in environmental protection (water and air treatment processes).
© 2006 Elsevier B.V. All rights reserved.
Keywords: Absorption; Mass transfer; Multiphase reactors; Silicone oil; Oxygen; Bioprocesses

1. Introduction
Recent developments in bioreactor design have attempted to
address some of the limitations of existing bioreactors. However, further progress in innovative bioreactor design remains
a high priority, particularly for: (i) environmental bioreactors
and (ii) increases in oxygen transfer from the gas phase to the
microorganisms. In both cases, the addition of an organic solvent to the aqueous phase can be used to improve the efficiency
of the bioprocess [1,2].
The development of environmental bioreactors is important for waste gas purification and treatment because polluted
air has become of growing environmental and health concern.
Recent papers have demonstrated that biological techniques
often offer a cost-effective and environmentally friendly alternative to conventional air pollutant control technologies, such as
catalytic oxidation or incineration [3–6]. Studies carried out in
our laboratory have demonstrated the ability of bioscrubbing
to deodorize waste gases and remove volatile organic compounds (VOC) from an air stream [7]. However, conventional

Corresponding author. Tel.: +33 2 51 85 82 66; fax: +33 2 51 85 82 99.
E-mail addresses: (E. Dumont),
(Y. Andr`es), (P. Le Cloirec).
1369-703X/$ – see front matter © 2006 Elsevier B.V. All rights reserved.

bioscrubbers can only be used for compounds that are readily soluble in water. For waste gases containing hydrophobic
compounds having low solubility in water, the efficiency of
the biological treatment is limited by the poor mass transfer
of the pollutant from the gas phase to the aqueous phase. To
overcome this problem, a multiphase bioscrubber was developed using a mixture of a non-biodegradable organic solvent
and water to enable the absorption of the hydrophobic pollutant
in an absorber (gas–liquid–liquid contactor). The water–solvent
emulsion, with the absorbed pollutants mainly in the organic
phase, is then transported to a bioreactor in which microorganisms degrade the pollutant dissolved in the aqueous phase.
The lower pollutant concentration in the aqueous phase resulting from this process is the driving force for pollutant diffusion
from the organic to the aqueous phase (Fig. 1). Thus, complete
biological regeneration of the liquid is possible [8]. Numerous
applications for the biodegradation of toxic and poorly watersoluble compounds improved by organic liquids have been
described by D´eziel et al. [9]. In addition, it is assumed that
the organic solvent would enhance the oxygen mass transfer
from the gas phase to the microorganisms in order to improve
the degradation of the pollutant. Such a potential increase in
the oxygen mass transfer due to the presence of organic solvent is also taken into account for the development of oxygenlimited bioreactors, as in the case of the microbial fermentation

was used to determine the volumetric mass transfer coefficients of oxygen during absorption. was continuously flowed via a circulating loop through the deoxygenated liquid system. [51] for PFC40. 2.e. In this method. air was supplied from a compressor and sparged through an elliptical distributor (75 mm × 150 mm) with 50 holes (1 mm diameter). Organic solvents would act as surface-active agents to lower the surface tension of water and increase the gaseous specific interfacial area. [52] for silicone oils. a known gas volume.33 m. The total volumes of gas and liquid were 2 and 10 L. The operation was batch wise with respect to the liquid system and the decrease in oxygen concentration in the gas phase was measured versus time. dodecane.5 L total volume (height 0. 1. Solubility ratios mR (i.246 E. the transfer mechanism of oxygen is not well understood and it is not possible to propose a unified theory to describe satisfactorily the effect of the presence of organic solvent on the enhancement of the mass transfer of oxygen [10]. and from Basheva et al. from MacMillan and Wang [48] for PFC40. perfluorocarbons and silicone oils. to date. Table 1 presents examples of organic solvents used in biological waste air treatment or to improve microbial production or fermentation. by a dynamic method. This multiphase system represents the most unfavourable one for oxygen mass transfer because it is assumed that there is no contact between the gas phase and the organic phase.1. The superficial velocity of gas (uG ) was 0. Dumont et al. However. Materials and methods 2. In the experiments.01 m s−1 (gas flow rate QG = 3. hexadecane.2. Spreading coefficients were obtained from Hassan and Robinson [47] for dodecane and hexadecane. . initially loaded with 20. solubility of oxygen in organic liquid divided by solubility of oxygen in water) were obtained from Vadekar [50] for dodecane and hexadecane.e. Schematic representation of possible mass transfers in a multiphase gas–aqueous–organic phase system. A dynamic method.9% oxygen. at a constant temperature of 20 ◦ C maintained by the jacket. and from Dumont et al. 2. dimethylpolysiloxane) were purchased from the Rhodia Company. As oxygen mass transfer has a strong influence on bioprocess efficiency. 2. the volumetric mass transfer coefficient (kL a) of oxygen in emulsions of water–organic solvent for the main organic liquids used in bioprocesses. extensively described in [53].21 m).3 × 10−4 m3 s−1 ). Chemicals Dodecane and hexadecane were obtained from the Sigma–Aldrich Company. we carried out experiments with a view to measuring. All experiments were carried out. The reactor used has an 11. Equipment Fig. Perfluorocarbon PFC40 Fluorinert (primarily compounds with 12 carbons) was purchased from the 3M Company and silicone oils (Rhodorsil® fluids 47V5 and 47V10. i. as presented in [53]. A schematic overview of the experimental set up is given in Fig. / Biochemical Engineering Journal 30 (2006) 245–252 Nomenclature a Cgas Corg Cwater ∗ Cwater D H kL kL a mR poxygen P QG R S T uG VG VL yoxygen interfacial area (m−1 ) oxygen concentration in air (mol m−3 ) oxygen concentration in organic solvent (mol m−3 ) oxygen concentration in water (mol m−3 ) equilibrium concentration of oxygen between water and gas phase (mol m−3 ) diffusion coefficient (m2 s−1 ) Henry constant (Pa m3 mol−1 ) mass transfer coefficient (m s−1 ) volumetric mass transfer coefficient (s−1 ) solubility ratio partial pressure of oxygen in the gas phase (Pa) total pressure of the gas phase (Pa) gas flow rate (m3 s−1 ) universal gas constant (J mol−1 K−1 ) spreading coefficient (N m−1 ) temperature (K) gas velocity (m s−1 ) volume of the gas phase (m3 ) volume of the liquid phase (m3 ) oxygen mole fraction Greek letters ε energy dissipation (W kg−1 ) µ dynamic viscosity (Pa s) ρ density (kg m−3 ) σ surface tension (N m−1 ) φ dispersed liquid phase hold-up of products of commercial interest. respectively. Experiments were carried out in a bubble column with the organic and gas phases dispersed in the continuous aqueous phase. [49] for silicone oil 47V5. diameter 0. The physical properties of these chemical products are summarized in Table 2. from van Sonsbeek et al.

[17] Naphthalene. Rhodococcus sp.28] Cesario et al. [24] Budwill and Coleman [37] Cesario et al.3 +4. [41] Hekmat and Vortmeyer [42] Acetobacter suboxydans Penicillium chrysogenum A.7 −9.4 5. Pseudomonas sp. [15] Jianlong [16] Lai et al. kL a calculation Table 2 Physical properties of the organic phase used (T = 25 ◦ C) Dodecane Hexadecane Perfluorocarbon PFC40 Silicone oil 47V5 Silicone oil 47V10 Viscosity (mPa s) Density (kg m−3 ) Spreading coefficient (mN m−1 ) Solubility ratio mR 1. ethylmethylketone. the ideal gas law is applicable to calculate the number of moles of oxygen absorbed by the liquid.6 – 6 5 12 7 7 . [25. Pseudomonas stutzeri. phenanthrene Polyaromatic hydrocarbons B12 vitamin production Polycyclic aromatic hydrocarbons Yeast fermentation Citric acid production Lovastatin production Sphingomonas aromaticivorans B0695 Two species of Sphingomonas Propionibacterium shermanii S. The 3. [13] Janikowski et al.. [46] Polycyclic aromatic hydrocarbons Pseudomonas putida GJ40 Streptomyces coelicolor Claviceps purpurea Pseudomonas aeruginosa Mixed culture Mixed culture Mixed culture P.21] Giridhar and Srivastava [22] Ho et al. P. [29] Elibol and Mavituna [30] Menge et al. Microbial consortium Organic solvent: hexadecane Brink and Tramper [18] Daugulis and Boudreau [19] Davidson and Daugulis [20.1.E. butylacetate Styrene Hexane (80%) + hydrocarbons Xylene. [44] Osswald et al. [33] Ascon-Cabrera and Lebeault [34] Bouchez et al. butyl acetate Methyl ethyl benzene Diethyl benzene Toluene Styrene Styrene Vannek et al.0 740 773 1850 910 930 −2. [45] Hexane 2-Butanol. [27. aeruginosa. [35] Bouchez et al. Assumptions analysis technique. putida Consortium of slightly-halophile marine bacteria 3. propene Toluene (a) Toluene. [36] Isopropyl-benzene Ethyl butyrate Phenanthrene Polycyclic aromatic hydrocarbons Rhodococcus erythropolis T902 Candida sp. [23] Yeom et al. xylosoxidans Y234 Organic solvent: perfluorocarbon PFC40 Cesario et al. which has been proved a relevant measurement method [54–56]. [38] El Aalam et al. hexane. benzene (b) Benzene l-Sorbose fermentation Penicillin fermentations Benzene Mycobacterium E3 Alcaligenes xylosoxidans Y234 A.0 +6. toluene. / Biochemical Engineering Journal 30 (2006) 245–252 247 Table 1 Examples of organic solvents used to improve bioprocess efficiency (waste air treatment and fermentation) Authors Pollutant or fermentation Microorganisms Organic solvent: dodecane Daugulis and Janikowski [11] Daugulis and McCracken [12] Galaction et al. CF3 Pseudomonas sp. xylosoxidans Y234 Lebeault [43] Lebeault et al.0 3.3 3. aromaticivorans Saccharomyces cerevisiae AY-12 Aspergillus niger Aspergillus terreus Oxygen. kL a measurement is supported by some assumptions: The dynamic method for kL a measurement in air–water–oil systems is based on the gas phase mass balance and on the off-gas 1. Dumont et al. [14] Jia et al.0 10. [32] Ethane Toluene Toluene Antibiotic production Alkaloid production Fermentation of insect cells (Spodoptera frugiperda) Mycobacterium parafortuitum Organic solvent: silicone oil Aldric et al. [31] Takeshi et al. [39] Fazaelipoor and Shojaosadati [40] Gardin et al.26] Cesario et al. In the reactor.

The response time for the paramagnetic oxygen analyser is less than 5 s. The presence of an organic solvent in the emulsion does not change the Henry constant for oxygen in water. which is nearly always permitted [57]. 3. since temperature and pressure are low. 4. Oxygen dissolves much better in organic solvents than in water (Table 2). (4): dCgas P dyoxygen = (5) dt RT dt Combining Eqs. There is no contact between the gas and the organic liquid phase. Cwater and Corg are the concentrations of oxygen in water and organic phases. the mass transfer rate in the gas liquid system is given by: −VG P dyoxygen ∗ = kL aVL (Cwater − Cwater ) RT dt (7) kL a is based on the total volume of the liquid (aqueous and organic phases) instead of the aqueous volume to avoid an appar- . Derivation of kL a In the system including three phases. Dumont et al. Eq. This may be assumed considering the convective recirculation and turbulence caused by the rising gas bubbles leading to a much shorter mixing time than the characteristic mass transfer time. After differentiating with respect to time t. the overall mass transfer coefficient is considered as the liquid phase mass transfer coefficient kL a. 7. after integrating between t = 0 (Cwater = 0 and yoxygen = yoxygen (t=0) ) and t: Cwater = − 1 VG P (yoxygen(t) − yoxygen(t=0) ) VL 1 + φ(mR − 1) RT (6) According to assumptions 3 (liquid phase perfectly mixed) and 6 (no contact between the gas and the organic phase).248 E. As the water phase and the organic phase are assumed to be in equilibrium at any time (assumption 7): Corg = mR Cwater (2) mR is the solubility ratio defined as the ratio of the solubility of oxygen in the organic phase to that in water. 5. 2. (5) is obtained from Eq. the total change in concentration of oxygen in air Cgas is due to the amount of oxygen absorbed in the water phase (continuous liquid phase) and to the amount of oxygen absorbed in the organic phase (dispersed liquid phase): −VG dCgas dCorg dCwater = VL (1 − φ) + VL φ dt dt dt (1) VL is the total volume of the liquid phase and VG is the total volume of the gas phase. Thus. φ is the dispersed liquid phase hold-up (volume of organic liquid phase as a fraction of total liquid phase volume). 2. Eqs. 8. The liquid phase can be reasonably estimated as perfectly mixed. As liquid–liquid mass transfer is very fast compared to gas–liquid mass transfer. (5) and (3) gives. 1/kL a. / Biochemical Engineering Journal 30 (2006) 245–252 Fig. a liquid–liquid equilibrium in terms of oxygen concentration can be assumed during oxygen absorption. respectively. The resistance of oxygen transfer in the gas phase is neglected. Schematic overview of the experimental set up used to determine kL a (TIC: temperature indicator control). 6. (1) and (2) lead to: − dCgas VL dCwater = (1 + φ(mR − 1)) dt VG dt (3) The oxygen concentration in the constant volume of gas is obtained from mass balance: P (4) yoxygen Cgas = RT where yoxygen is the mole fraction of oxygen in the gas phase and P is the total pressure in the gas phase considered constant during the experiment.2. 3. The gas phase is considered as plug flow in the closed flowing circuit as in the oxygen analyser circuit. operating conditions justify such an assumption. which is less than the mass transfer response time of the system: 1/kL a.

(11). In the latter case.0132 to 0. (8). Addition of silicone oils hinders the volumetric mass transfer coefficient of oxygen compared to air–water systems. For each experiment. noted. For our apparatus and the hydrodynamic conditions (uG = 0.53]. 3). where poxygen is the partial pressure of oxygen in the gas phase and H is the Henry constant for oxygen in water: poxygen ∗ Cwater = (8) H Dividing by the total pressure P. hexadecane and perfluorocarbon PFC40.0178 s−1 (mean value kL aref : 0. grey zone in Fig. The effects are greater for the most viscous silicone oil (47V10). we obtained a straight line whose slope gives the volumetric mass transfer coefficient kL a for the aqueous phase in the presence of organic phase. the decrease in the mole fraction of oxygen (yoxygen ) in the gas phase versus time was recorded. dodecane and hexadecane. (11) allows the determination of kL a in a binary air–water system. Introducing φ = 0 in Eq. Conversely. (8) becomes: ∗ Cwater = P poxygen P = yoxygen H P H (9) ∗ Introducing the expression of Cwater and Cwater in Eq. (7) gives: − VG P dyoxygen VL RT dt  1 P VG = kL a yoxygen + H VL 1 + φ(mR − 1)  P × (yoxygen(t) − yoxygen(t=0) ) RT whose integration between t = 0 and t gives:   1 α + (1/(1 + φ(mR − 1)) ⎧ ⎪ ⎪ ⎪ ⎨ αyoxygen(t=0)  × ln  ⎪ α + (1/(1+ φ(mR −1))) yoxygen(t) ⎪ ⎪ ⎩ − yoxygen(t=0) /1 + φ(mR −1) (10) ⎫ ⎪ ⎪ ⎪ ⎬ ⎪ ⎪ ⎪ ⎭ = kL at (11) with α = VL RT/VG H. standard deviation 15%. 4. Experimental kL a values for oxygen absorption in emulsions of aqueous–organic phase as a function of the organic phase volume fraction (uG = 0. 3. Fig. 3 shows that organic phase addition has no significant influence on kL a results in the cases of dodecane. Decreases in kL a of up to 25% are Fig. Fig. By plotting the left-hand side of Eq.01 m s−1 ). Dumont et al. Cwater is the equilibrium concentration between water ∗ and the absorbed gas phase. kL a values ranged from 0. Cwater is defined according to Eq. Typical representations of kL a determinations have previously been published [52.E.0156 s−1 . varying from 0 to 4% for PFC40 and from 0 to 10% for silicone oils. taking into account the accuracy of measurement. / Biochemical Engineering Journal 30 (2006) 245–252 249 ent increase in value solely due to a decrease in the aqueous phase ∗ volume. 3 presents the kL a results for all organic solvents (maximum deviation: ±15%) compared with those obtained for an air–water system without an organic phase in the same hydrodynamic conditions.01 m s−1 ). Air–water–organic phase: experiments were carried out in triplicate using several emulsion compositions. Experimental results and discussion Binary air–water system: 39 measurements were carried out. Eq. the high density (1850 kg m−3 ) of the organic phase leads to a specific behaviour . The determination of kL a from experimental data was then obtained by using Eq. (11) versus time.

the interface between the organic phase and water is continuously moved by the recirculating flow of water in the reactor. for the same experimental conditions. Dumont and Delmas [10] reported that the kL a value can decrease. these authors were not able to explain these opposing results. To date. Unfortunately. the perfluorocarbon remains under the gas distributor and it is not possible to disturb it sufficiently to disperse droplets in the bulk of the water. Hassan and Robinson [47] found. MacMillan and Wang [48]. [1] for PFC loading up to 60% (v/v). Considering the influence of organic phase addition on kL a only. that hexadecane addition increases kL a whereas dodecane addition decreases kL a. a recent model has been proposed [58]. For instance. Dumont et al. Similar trend was reported by Yamamoto et al. a satisfactory assessment of the influence of the addition of small amounts of organic phase on the mass transfer of oxygen remains difficult. showed that the interfacial area in PFC40 dispersions was independent of PFC loading from 0 to 15% (v/v). In this case. This model takes both shuttle effects and hydrodynamic effects into account to calculate the enhancement factor due to the presence of the organic liquid droplets. PFC40 settles at the bottom of the reactor for all the amounts added. Due to the absence of droplets and the non-miscibility of PFC40 in water. Nonetheless. / Biochemical Engineering Journal 30 (2006) 245–252 of the liquid phase. The general expression of this model is: (kL a)φ = (kL a)φ=0 . In a review devoted to gas absorption in oil-in-water systems. contrasting results have been reported in the literature. remain unaffected or increase upon addition of the organic phase. which is consistent with the experimental kL a measurements. Whereas bubbling leads to oil droplet formation in the continuous water phase for organic phases lighter than water. However.250 E. it could be assumed that the organic phase does not influence the hydrodynamic conditions and the interfacial area. measuring the air bubble size distribution by a photographic method.

Dφ Dφ=0 1/2 .

According to [60]. particularly by the spreading coefficient defined as: S = σAW − σOW − σOA (13) where σ are interfacial tensions and the subscripts AW. respectively. [60] and Kawase and Moo-Young [61] suggested that these opposing effects more or less cancel each other out. (ii) coalescence is enhanced and (iii) surface tension decreases. 4 from [58]. Basheva et al. According to these authors. and hence kL a starts to rise. acting as an antifoam agent. who found similar changes in kL a with silicone oil addition. S is “initially” positive (Table 2. Finally. the shuttle effect should range from 1 to 1. Meanwhile.59] have demonstrated that S becomes negative at equilibrium (S = −0. While contradictory results exist about the actual mechanisms of mass transfer in gas–water–organic systems [10]. S is calculated with the values of pure component surface tension). silicone oil lowers the surface tension between gas and liquid. the modelled kL a values calculated for all organic phases (0 ≤ φ ≤ 0. there is a critical concentration at which the gas–liquid mass transfer is minimal. In both cases. silicone oil tends to promote coalescence. Fig. which ultimately implies that silicone oil remains as discrete droplets. For the hydrodynamic effect. when the aqueous and organic phases are mutually saturated. reducing bubble size. ρ the density of the emulsion and ε corresponds to the energy dissipation rate of the system. oil–water and oil–air interfaces. For silicone oils. A positive value of S is considered to correspond to easy spreading of the oil droplet on gas bubbles. silicone oil. it appears that the use of an organic phase is a good strategy for enhancing the productivity of cultures by microorganisms or allowing the biodegradation of gaseous hydrophobic pollutants. According to this explanation. µφ=0 ρφ εφ µφ ρφ=0 εφ=0 1/4 (12) The first term of the right-hand side expression represents the influence of the shuttle effect on the enhancement. D is the diffusion coefficient of oxygen. surface tension keeps decreasing. φ = 0 and φ correspond to the binary air–water system and multiphase system. may however reach a limit. Calculations of µφ and ρφ are detailed in [58]. S is negative (Table 2). For dodecane and hexadecane. respectively. Thus.2. the addition of an organic phase has no significant positive influence on the volumetric mass transfer coefficient of oxygen for our experimental conditions. the second represents the hydrodynamic effect. the energy dissipation rate is assumed unchanged between each experiment. which implies that these organic phases should be able to spread on the gas–aqueous surface. Firstly.1 and mR < 10) and. discussed the influence of silicone oil on both kL and a. are within the maximum deviation of the experimental results. [60]. The first two effects. increasing the oxygen driving force between the air and the water–oil emul- . has two opposing effects on the interfacial area a. it appears that the hydrodynamic effect ranges from 1 to 0. On the one hand. On the other hand. µ the dynamic viscosity of the emulsion. Morao et al. (i) bubble surface mobility decreases. 3) can be explained by three effects. which implies that the organic solvent remains as discrete droplets and does not contact the gas bubbles.1). In summary. (12) and the data gathered in Table 2. as oil concentration increases. thus decreasing a.8 mN m−1 for silicone oil whose viscosity is 5 mPa s). it seems that the relationship between the mass transfer coefficient kL a and the physical–chemical properties of the emulsion are not sufficiently taken into account and should be reconsidered. OW and OA refer to air–water. [49. the variation in the relative kL a measurements (decreasing then increasing with oil addition. Morao et al. which depress kL a. and hence the most important effect is on the film coefficient kL . whatever the bioreactor design. the transfer is not affected by the presence of organic droplets and kL a remains roughly constant. thus decreasing the bubble diameter and consequently increasing a. For our system (φ ≤ 0. the organic phase acts as an oxygen reservoir. An assessment of the influence of the shuttle effect is difficult to calculate. As demonstrated experimentally. and taking into account both shuttle and hydrodynamic effects.95 when φ varies from 0 to 10%. The results obtained could be explained by the interfacial properties of the emulsions. However. according to Fig. According to Eq. namely when all contacting bubbles coalesce and mobility is suppressed. the change in kL a is due only to the change in the density and the dynamic viscosity of the emulsion with the addition of oil.

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