Modelling of oxygen transfer in water through emulsified organic liquids

Notation: interfacial active area, m2 immersed electrode area,m interfacial gaseous area, m interfacial vector area, m oxygen concentration in air, mol m oxygen concentration in vector, mol m Saturation oxygen concentration in vector, mol m CW oxygen concentration in water, mol m Satuartion oxygen concentration in vector, mol m Steady-state oxygen concentration in water, mol m dG Sauter mean bubble diameter, m dV Sauter mean droplet diameter, m ev vector film thickness, m F Faradays number, C mol-1 HVW equilibrium constant for oxygen partition at vector-water interface HGW equilibrium constant for oxygen partition at gas-water interface i current intensity, A kL mass transfer coefficient, m s-1 kL GW , kL GV , kL VW mass transfer coefficients for gas-water, gas-vector and vector-water interfaces, ms-1 (kLa)GW, (kLa)GV, (kLa)VW volumic mass transfer coefficients for gas-water, gas-vector and vector-water interfaces referred to water volume, s-1 A AE AG AV CO2 CV volumic mass transfer coefficient without vector, s-1 overall volumic mass transfer coefficient in presence of vector and referred to water volume and water concentration gradient, s-1 NGW, NGV NVW gas-water, gas-vector and vector-water mass fluxes, mol s-1 NO oxygen mass flux in absence of vector, mol s-1 NT total oxygen mass flux in presence of vector, mol s-1 RW oxygen consumption in the aqueous phase, mol s-1 SP spreading coefficient, dyn cm-1 t time, s VG gas volume, m3 VV vector volume, m3 VW water volume, m3 Greek letters number of electrons involved in the electrochemical reaction V total volume fraction of vector G gaseous retention referred to water volume G surface fraction of bubble covering V volume fraction of covering vector volume WG interfacial water-gas tension, dyn cm-1 VG interfacial vector-gas tension, dyn cm-1 VW interfacial vector-water tension, dyn cm-1 (kLa)O (kLa)T

Description: The basic idea of the model is that, when a bubble is submerged in the emulsion, the organic liquid will cover more or less totally the gas bubble surface and the film formed will then be loaded with oxygen as long as the bubble has not exploded. When the spreading coefficient SP defined as Sp=
WG-( VG+ VW)

is positive, it has been found that the static cover up is effective. This phenomenon has been extended to the dynamic behaviour of the bubbles in the emulsion. The total aeration process is divided into three steps as presented in Fig.1. Step 1: As soon as the gas bubble is generated in the organic emulsion, numerous collisions between bubbles and droplets are caused by agitation and the bubble surface becomes enveloped by an unbroken organic film. The more favourable the environmental conditions to the draining of the boundary layers around bubbles and droplets, the faster is the gas-liquid pseudo-coalescence process. Step 2: When the bubble is rising, oxygen is transferred from the bubble to the organic film, the greater the oxygen solubility in the organic phase, the greater the transfer. Step 3: After the bubble explosion, either at the liquid free surface or by contact with the agitation device, the vector film is re-dispersed into droplets. This fraction of vector volume will then discharge its oxygen by liquid-liquid contact; the more the organic phase is finely dispersed, the greater is the transfer efficiency.

During this process, oxygen solubility in the organic liquid, the dispersion level of the emulsion and bubble-droplet pseudo-coalescence have to be taken into account. Compared to the conventional gas-liquid system, the oxygen vector will act, in the triphasic system, by a concentration gradient increase for the gas-liquid transfer due to high oxygen solubility and by an enhanced redistribution of oxygen through a larger liquid-liquid interfacial area than the formatter gas-water interface. Explanation of enhanced transfer may be found in these combined effects.

Objectives: Prediction of the potential of oxygen transfer intensification in a gas-liquid-liquid system. To describe the process in oxygen transfer in water through emulsified organic liquid and its modelling. Mathematical Model:

Assumptions: Organic vector used is insoluble in water. Their utilization in an emulsified form can significantly increase the oxygen transfer coefficient between gas and aqueous phases. Isothermal operation Stirring speed must be constant Surface tension effect is not there. Direct oxygen supply to microorganisms by adhesion to droplets, are not involved in the transfer enhancement

Model formation and experiments performed to validate of the transfer process: Overall properties of each phase are considered as shown in Fig.2. Two parameters, to describe the covering of the gas bubble by vector film, have been defined:

G is the fraction of bubble surface covered by the organic film. V is the fraction of vector volume participating in the bubble covering (active vector
volume fraction).

G and V simultaneously increase with V. (G AG) is surface encapsulated by a vector film with a thickness V, and that [( 1 - G)AG] surface is free to generate direct gas-water transfer. At steady state, the volume (V AV) of vector participating in the liquid-liquid transfer is the same as the one involved in the bubble covering. This steady state is allowed by the reaction of oxygen consumption from the microorganisms in the aqueous phase. The equations for oxygen fluxes may be written as:

NGW= kL GWAG( 1 - G)(

-CW)

(1) (2) (3)

NGV= kL GVAG G(HVWCW-CV) NGV= kL VWAV V[(CW/HVW)-CW] with AG= 6VG/dG, and AV= 6VV/dV,

being total areas of bubbles and droplets, respectively. The total flux transferred to the aqueous phase NT is then NT = NGW + NVW (4)

Because of the oxygen transfer steady state [NGW = NVW in the active vector volume (2VVV)], an average oxygen concentration is obtained as CV =( kL GVAG GCWHVW + kL VW6 VCWVV/dV)/( kL GVAG G + kL VW6VV V/HVWdV) (5)

The transfer fluxes in the conventional diphasic system (NO) and in the oxygen vector system (NT) are compared by means of the ratio of overall volume transfer coefficients (kLa) with reference to the same concentration gradient in the aqueous phase. The equations are: NT= (kLa)TVW( NO= (kLa)OVW( - CW) - CW). (6) (7)

The ratio (kLa)L/(kLa)O quantifies the transfer enhancement generated by the oxygen vector. Experiment: Specific mass transfer experiments are performed in conditions allowing an easier evaluation of the three interphasic volumic transfer coefficients (kLa)GW, (kLa)GV, (kLa)VW and to investigate their evolution in respect of the total volume fraction of the vector V. An electrochemical reactoris used to carry out these experiments. These experiments are performed in a transient state and measurement of a limiting diffusion current at one electrode gives the oxygen concentration of the aqueous phase.

Experimental apparatus

The electrochemical reactor is presented in Fig. 3. The cathodic compartment consists of a transparent PVC cylinder of volume 1.5 x 10-4 m3. It is equipped with four anti-vortexes baffles and a platinised rotating propeller acting simultaneously as a disperser and as a working electrode with an immersed active surface AE= 8.5 x 10-4m2. It is separated from the anodic compartment by a Nafion 427 membrane (area = 50.3 x 10-4 m2) at the bottom. This membrane is not impermeable to molecular oxygen (Ogumi et al., 1984) and the leak has been evaluated by specific measurements and included in the equation of the mode1 in the oxygen consumption term: RW = kEAE + leak. Operating conditions are described as follows: Total liquid volume: 0.7 x 10-3 m3 Agitation speed: 1000 rpm Aeration rate: 0.48 vvm Temperature: 25C Applied potential: - 0.55 V Electrolytic aqueous solution of NaOH: 0.1 M. Mass-transfer coefficient at the electrode surface k, has been determined by preliminary experiments through the electrochemical reduction of ferricyanide ion Fe(CN)i- (Kreysa and Woebken, 1985). For the operating conditions, its value has been evaluated as kE = 2.25 x 10-4 m s-1.

Mathematical modelling

The transfer scheme is presented in Fig. 4. Equilibrium relations at the interfaces are given by: = CO2/HGW = /HVW (10) (8) (9)

= (HVW/HGW)CO2

Mass transfer balances in transient state for the two liquid phases provide the following system of ordinary differential equations: VWdCW/dt = (kLa)GW ( VVdCV/dt = (kLa)GV ( - CW) +(kLa)VW [(CV/HVW)- CW] - RwCW - CV) +(kLa)VW [(CV/HVW)- CW] (11) (12)

We then obtain the second order differential equation d2CW/dr + PdCW/dt + QCW = U with P = (kLa)GW + (HVE/h) (kLa)GV +[(1+h)/h](kLa)VW + RW/VW Q = (HVW/h)[ (kLa)GW(kLa)GV +(kLa)GV(kLa)VW] + [(kLa)GW(kLa)VW/HVW] + (RW/VW)[ (kLa)GV +(kLa)VW/HVW] U = (HVW with h = HVWVV/VW Integration of the equation with the following boundary conditions: t = 0, CW = CV = 0 (dCW/dt)t=0 = (kLa)GW
,

(13)

(14)

(15)

/h)[ (kLa)GV(kLa)VW +(kLa)GV(kLa)GW + (kLa)GW(kLa)VW/HVW] (16) (17)

(18) (19)

yields: CW = C1 exp(r1t) + C2 exp(r2t) + (20)

In which r1 and r2 are the roots of the characteristic polynomial and C1 = [ C2 = [ (kLa)GW + (kLa)GW + r2]/(r1 r2) r1]/(r2 r1) ) aand is given by (21) (22)

is the aqueous concentration at steady state (t

= /{[1 + (RW/VW)[ (kLa)GV + (kLa)VW/HVW]/[ (kLa)GV(kLa)VW + (kLa)GW(kLa)GV + (kLa)GW(kLa)VW/HVW]} When there is no oxygen consumption, = .

Analytical expression of Cw(t) is used to compute the values of the intensity i(t)=kEAE(1V) EFCw(t) that are compared to experimental values in order to identify the interphasic volumic transfer coefficients. Solution and Model Validation:

Experimental kinetics of aeration of a dispersion of n-dodecane in water for different volume fractions are presented in Fig.5 through the time recording of the electrochemical current intensity characteristic of oxygen concentration by the equation: i(t)=kEAE(1V) EFCw(t) V)]

The term [AE(1-

accounts for the electrode active surface pollution by the organic phase.

This phenomenon is clearly revealed when considering the different final intensities obtained at t for the same equilibrium concentration. It must also be noticed from fig.5 that rapid visual study of the curves seems to indicate that the presence of the vector slightly increases the time of achieving the final equilibrium and is apparently in contradiction with the anticipated acceleration effect. The explanation is given by the fact that the saturation of the emulsified system requires the transfer of the quantity of oxygen necessary to saturate both phases and because of the high oxygen solubility in the organic phase, the additional transfer, even at low volume fractions, is not negligible and induces a delay in the kinetics. This effect, called here the reservoir effect, will only appear in the transient state. Parameters and variable used for validation: V and interphasic volumic coeffients Criterion Used: Graph is plotted between V and interphasic volumic coefficients From the analytical solution of the system of equations of the transient model developed above, we have calculated values of the interphasic volumic transfer coefficients by performing a numerical identification using a Gauss- Newton algorithm of minimization of deviations. Results are presented on Fig. 6.

It appears that (kLa)GW gradually decreases with increasing V and is divided by 2 for V = 0.25. In parallel (kLa)GV and (kLa)VW are increasing, the last one reaching high values (tenfold factor). These evolutions are a good illustration of the role of the vector that allows the gasvector-water pathway to prevail over the direct gas-water pathway. The numerical values of the interphasic volume coefficients may be introduced in a steady-state model in order to compute the (kLa)T/(kLa)O ratio at different vector volumic fractions. At steady state, it may be seen from Fig. 4 that: NGW= (kLa)GW VW( - CW) NGV= (kLa)GVVW( - CV) NGV= (kLa)VWVW[(CV/HVW)-CW] Total transferred flux toward aqueous phase is: NT = NGW + NVW = (kLa)T VW( - CW) (28) (25) (26) (27)

At steady state, NGV= NVW and if we assume sufficient oxygen consumption in the aqueous phase, we may consider CW 0. Then we obtain: (kLa)T = (kLa)GW + (29)

Computed values of the coefficients ratio (kLa)T/(kLa)O show a monotonic increase with increasing V (see Fig. 7) that is in qualitative agreement with the experimental evidence (Rols et al., 1990). These results cannot lead to quantitative comparison with conventional reactor operation because complete geometric similarity ts not achieved. Evolution of the parameters does however give good support to the assumptions of the mechanism concerning a transfer enhancement caused by the gas-vector-water pathway.

Limitation: The model is compatible both with electrochemical and fermentation experiments. It is not able to predict the experimentally observed decay of performances for high vector concentrations (Rols et aI., 1990) that might be attributed to a dramatic increase of the emulsion viscosity. Prediction of aeration enhancement by oxygen vector is not yet possible because of the lack of important information concerning interface properties, frequency of bubble droplet collisions, coalescence time, etc. that appear mainly in the model through parameters G, V and the interphasic volumic transfer coefficients The use of a conventional membrane oxygen probe would have led to errors in a twoliquid system

Innovation: The above model is used as a reference in various areas like increased oxygen absorption into stirred emulsions of n-alkanes, mechanistic modelling of Increased oxygen transport using functionalized magnetic fluids in bioreactors,etc. Remarks: These results cannot lead to quantitative comparison with conventional reactor operation because complete geometric similarity ts not achieved. But, above results enable these parameters to be defined and provide experimental validation of the transfer process by specific mass-transfer experiments.

References Furiet, C., Storck, A. and Lapicque, F., 1987, Methode electrochimique transitoire de determination des conductances de transfert liquid-liquide. Recents progress en genie des procedes, 1, 386-391, Lvoisier, Paris. Hassan, I. T. M. and Robinson, C. W., 1977, Oxygen transfer in mechanically agitated aqueous systems containing dispersed hydrocarbon. Biocechnol Bioengng 19, 661-682. Kreysa, G. and Woebken, C., 1985, A new method for the investigation of fluid-fluid mass transfer: l-Mass transfer in gas-liquid systems. Chem. Engng Sci. 40, 1221-1227. Kreysa, G. and Woebken, C., 1986, A new method for the investigation of fluid-fluid mass transfer: 2-Mass transfer in liquid-liquid systems. Ckem. Engng Sci. 41,307-315. Linek, V. and Benes, P., 1976, A study of the mechanism of gas absorption into oil-water emulsions. Chem. Engng Sci. 31, 1037-1046. Maclean, G. T., 1977, Oxygen transfer in aerated systems with two liquid phases. Process Biochem. 12, 22-24. Macmillan, J. D. and Wang, D. 1. C., 1987, Enhanced oxygen transfer using oil in water dispersions. Ann. N. Y. Acad. Sci. 506, 569-582. Macmillan, J. D. and Wang, D. I. C., 1990, Enhanced oxygen transfer using oil in water dispersions. Ann. N. Y. Ad. Sci. 589, 283-300. Mattiasson, B. and Adlercreutz, P., 1987, Perfluorochemicais in biotechnology. Trends Biotechnol. 5, 250-254. Ogumi, Z., Takehara, Z. and Yoshizawa, S., 1984, Gas permeation in SPE method: 1. Oxygen permeation through NAFION and NEOSEPTA. J. eiectrockem. Sot. 131, 769-773. Rols, J. L. and Goma, G., 1989, Enhancement of oxygen transfer rates in fermentation using oxygen vectors. BiotechnoL Adv. 7, l-14. Rols, J. L., Condoret, I. S., Fonade, C. and Goma, G., 1990, Mechanism of enhanced oxygen transfer in fermentation using emulsified oxygen-vectors. Biotechnol. Bioengng 35, 427-435. Yoshida, F., Yamane, T. and Miyamoto, Y., 1970, Oxygen absorption into oil-in-water emulsions. A study on hydrocarbon fermentors. Ind. Engng Chem. Proc. Des. Dev. 9, 570577.