Effect of surfactants on liquid-side mass transfer coefficients in gas-liquid systems: A first step to modeling

This paper focuses on the effect of surfactants on the mass transfer parameters (volumetric mass transfer coefficient k_La and liquid-side mass transfer coefficient k_L). Tap water and aqueous solutions with surfactants (anionic, cationic and non-ionic at concentrations up to are used as liquid phases. The bubbles are generated into a small-scale bubble column having an elastic membrane with a single orifice as gas sparger. To understand the effects of the surfactants on the mass transfer, not only the static surface tension is used, but also the characteristic adsorption parameters like the surface coverage ratio at equilibrium Se. The liquid-side mass transfer coefficient is obtained from the ratio of the volumetric mass transfer coefficient (measured by a chemical method) and the specific interfacial area. These two parameters are obtained simultaneously. The methods used to obtain these parameters are described in Painmanakul et al. [2005. Effects of surfactants on liquid-side mass transfer coefficients. Chemical Engineering Science 60, 6480-6491].Whatever the liquid phase, three zones are found on the liquid-side mass transfer coefficient variation with the bubble diameter. For bubble diameters less than 1.5 mm, whatever the liquid phases, the k_L values are roughly constant at . For bubble diameters greater than 3.5 mm, the k_L values do not vary much with the bubble diameter, but depend on the surfactant concentration. For bubble diameters between 1.5 and 3.5 mm, the k_L values increase from to the value reached at 3.5 mm. This increase depends on the surfactants. Higbie's model does not represent the k_L values for bubble diameters greater than 3.5 mm, even though there is a small amount of surfactant in the liquid phase. Thus, a model is proposed for each zone described above. Explanations are also proposed for the effect of the surfactant on the k_L values for each of the above zones.     

Interfacial area and volumetric mass transfer coefficient in a bubble reactor at elevated pressures

The present study deals with the pressure effects on mass transfer parameters within a bubble reactor operating at pressures up to . The gas-liquid systems are N₂/CO₂-aqueous solution of Na₂CO₃-NaHCO₃ and N₂/CO₂-aqueous solution of NaOH. A sintered powder plate is used as a gas distributor. Three parameters characterizing the mass transfer are identified and investigated with respect to pressure: the gas-liquid interfacial area a, the volumetric liquid side mass transfer coefficient k_La and the volumetric gas side mass transfer coefficient k_Ga. The gas-liquid absorption with chemical reaction is used and the mass transfer parameters are determined by using the model reaction between CO₂ and the aqueous solutions of Na₂CO₃-NaHCO₃ and NaOH. For a given gas mass flow rate, the interfacial area as well as the volumetric liquid mass transfer coefficient decrease with increasing operating pressure. However, for a given pressure, a and k_La increase with increasing gas mass flow rates. The mass transfer coefficient k_L is independent of pressure. Furthermore, the pressure increase results in a decrease of k_G and k_Ga for a given gas mass flow rate. The values of the interfacial area, which are obtained from both chemical systems are found to be different. These discrepancies are attributed to the choice of the liquid system in the absorption reaction model.     

Gas–liquid interfacial area and mass transfer coefficient in a co‐current down flow contacting column

The gas–liquid interfacial area and mass transfer coefficient for absorption of oxygen from air into water, aqueous glycerol solutions up to 1.5% (w/w) and fermentation medium containing glucose up to a 3% concentration were determined in a co‐current down flow contacting column (CDCC; 0.05 m i.d. and 0.8 m length). Experimental studies were conducted using various nozzle diameters at different gas and re‐circulation liquid rates. Specific interfacial area (a) is determined from the fractional gas hold‐up (ε_G) and the average bubble diameter (d_b). Once the interfacial area is determined, the volumetric mass transfer coefficient (k_La) is then used to evaluate the film mass transfer coefficient in the CDCC. The effects of operating conditions and liquid properties on the specific interfacial area were investigated. The values of interfacial area in air–aqueous glycerol solutions and fermentation media were found to be lower than those in the air–water system. As far as experimental conditions were concerned, the values of interfacial area obtained from this study were found to be considerably higher than those of the literature values of conventional bubble columns. The penetration theory is used to interpret the film mass transfer coefficient and results match the experimental k_L data reasonably well. Copyright © 2006 Society of Chemical Industry     

Theoretical prediction of gas-liquid mass transfer coefficient, specific area and hold-up in sparged stirred tanks

A prediction method for calculating the volumetric mass transfer coefficient, k_La, in gas-liquid sparged stirred tanks is proposed. A theoretical equation based on Hibie's penetration theory and the isotropic turbulence theory of Kolmogoroff is used for k_L determination. The values of the interfacial area have been calculated from a hold-up theoretical equation and the mean size of the gas bubble. Both Ostwald-De Waele and Casson models are used to describe the rheological properties of the fluid. The model predicts the mass transfer coefficient and the interfacial area values in stirred tank reactors, analysing the influence of different variables. The values of the volumetric mass transfer coefficient can be calculated for different geometries of the reactor, different physicochemical properties of the liquid and under different operational conditions. The capability of prediction has been examined using experimental data available in the literature for Newtonian and non-Newtonian fluids, for very different vessel sizes, different numbers and types of stirrers and a wide range of operational conditions, with very good results.     

Mass Transfer Characteristics of Syngas Components in Slurry System at Industrial Conditions

The gas‐liquid mass transfer behavior of syngas components, H₂ and CO, has been studied in a three‐phase bubble column reactor at industrial conditions. The influences of the main operating conditions, such as temperature, pressure, superficial gas velocity and solid concentration, have been studied systematically. The volumetric liquid‐side mass transfer coefficient k_La is obtained by measuring the dissolution rate of H₂ and CO. The gas holdup and the bubble size distribution in the reactor are measured by an optical fiber technique, the specific gas‐liquid interfacial area aand the liquid‐side mass transfer coefficient k_L are calculated based on the experimental measurements. Empirical correlations are proposed to predict k_L and a values for H₂ and CO in liquid paraffin/solid particles slurry bubble column reactors.     

Using image analysis in the study of multiphase gas absorption

For the air-water-calcium alginate beads system, the effect of the presence of solids on the mass transfer characteristics in a bubble column was experimentally studied.Volumetric liquid side mass transfer coefficient, k_La, specific interfacial area, a, and hence liquid side mass transfer coefficient, k_L, were determined under different solid concentrations (0, 5, and 10 vol%), superficial gas velocities (up to 0.27 cm/s) and solid sizes (1.2 and 2.1 mm diameter). The bubble characteristics, namely the interfacial area, were obtained using an image analysis technique.This technique proved to be a suitable and practical method to characterize mass transfer phenomena in bubble columns for the range of operating conditions used. The solids affect negatively k_La, decreasing both a and k_L, the effect being more pronounced for the smaller particles. For these particles the variation of k_La is due to the variation of its two components, while for larger particles k_La variation is due, essentially, to changes in k_L as no significant differences in a were observed.     

Oxygen mass transfer coefficient in bubble column slurry reactor with ultrafine suspended particles and neural network prediction

The gas–liquid volumetric mass transfer coefficient was determined by the dynamic oxygen absorption technique using a polarographic dissolved oxygen probe and the gas–liquid interfacial area was measured using dual‐tip conductivity probes in a bubble column slurry reactor at ambient temperature and normal pressure. The solid particles used were ultrafine hollow glass microspheres with a mean diameter of 8.624 µm. The effects of various axial locations (height–diameter ratio = 1–12), superficial gas velocity (u_G = 0.011–0.085 m/s) and solid concentration (ε_S = 0–30 wt.%) on the gas–liquid volumetric mass transfer coefficient k_La_L and liquid‐side mass transfer coefficient k_L were discussed in detail in the range of operating variables investigated. Empirical correlations by dimensional analysis were obtained and feed‐forward back propagation neural network models were employed to predict the gas–liquid volumetric mass transfer coefficient and liquid‐side mass transfer coefficient for an air–water–hollow glass microspheres system in a commercial‐scale bubble column slurry reactor. © 2012 Canadian Society for Chemical Engineering     

Interfacial Area and Liquid‐Side Volumetric Mass Transfer Coefficient in a Downflow Bubble Column

An experimental investigation was made to measure interfacial area, a, and liquid‐side volumetric mass transfer coefficient, k_La, in a downflow bubble column by chemical methods viz., absorbing CO₂ in aqueous sodium hydroxide and sodium carbonate/bicarbonate buffer solution respectively. The effect of gas and liquid flowrate and nozzle sizes on a and k_La were investigated. The experimental data obtained in the present system were analyzed and correlations were developed to predict a and k_La in terms of superficial gas velocity. The variation of a and k_La with specific power input were shown in graphical plot and compared with other gas‐liquid systems.     

Bubble size and mass transfer coefficients in dual-impeller agitated reactors

The study relates to the mass transfer and the bubble size in a non standard vessel equipped with various dual-impeller combinations. The effects of the rotational speed, gas flow rate, impeller type and diameter are investigated. The volumetric mass transfer coefficient k_La and the bubble size d_bs were studied. The liquid side mass transfer coefficient k_L and the volumetric interfacial area a were estimated separately. A comparison has been made with some existing correlations.     

Gas-Liquid mass transfer in a three-phase fluidized bed with floating bubble breakers

The effects of liquid and gas velocities, particle size and volume ratio of floating bubble breakers to solid particles (V_f/V_s) on both the volumetric mass transfer coefficient, k_la, and the gas-liquid interfacial area, a, have been determined in three-phase fluidized beds with floating bubble breakers. Beds having a volume ratio (V_f/V_s) of about 0.15 showed a maximum increase in both k_la and a of about 30% in comparison to that in the corresponding bed without floating bubble breakers. The volumetric mass transfer coefficient in three-phase fluidized beds with or without floating bubble breakers can be estimated from the surface renewal frequency of liquid microeddies and the particle size.     

Bubble size and mass transfer characteristics of sparged downwards two-phase flow

When gas is continuously fed through a sparger into a downflowing liquid in a pipe a ventilated cavity is often formed. The cavity remains attached to the sparger even in the presence of high liquid flow rates that would wash away a free slug bubble. Small bubbles are shed from the base of this cavity by the falling liquid film at the wall of the pipe and these bubbles are swept downwards forming a bubbly flow that is highly effective for mass transfer. The ventilated cavity is undesirable since it reduces the driving force for liquid circulation when the pipe is the downcomer of an external air loop fermenter or analogous gas/liquid reactors. The cavity also reduces the available interfacial area for mass transfer. It has been shown [Thorpe et al., 1997. Proceedings of the Fourth International Conference on Bioreactor and Bioprocess Fluid Dynamics; Lee, 1998. Ph.D Thesis, University of Cambridge, UK], that the length of the cavity can be reduced by replacing the common industrial design of a horizontal sparger (HS) with two novel spargers; a peripheral sparger (PS) and a plunging jet sparger (PJS) (Fig. 3). In this paper we investigate the effect of PS and PJS on mass transfer and the resulting bubble size.Experiments were carried out with air and water in a large circulating rig with a 0.105 m diameter test section. The local average bubble size in the bulk two-phase flow region below the ventilated cavity was determined using photography for three combinations of liquid and gas volumetric flow rates. The average bubble size was essentially the same (differences within 10%) for the PS, central spranger (CS) and HS. The PS created the largest bubble in all cases examined. The PJS created smaller bubbles than all the other spargers and did not allow the formation of cavities, which suggests that it has the superior performance. The estimated increase in k_La due to the smaller bubble size for the PJS was by a factor of 1.3.In order to check this result, the effects of sparger type on the volumetric mass transfer coefficient (k_La) were also measured. The k_La was determined with a dynamic method, by using unsteady state absorption of oxygen. The results confirmed the apparent superiority of PJS over the other spargers. An average increase of 19% in the k_La was observed when the PJS was used instead of the industrial design (HS). The CS and PS showed similar k_La values again within 10% of the HS.However the power consumption is larger when the PJS is used instead of the industrial design HS. Hence an attempt was made to adjust the bubble size and mass transfer coefficients of the PJS to account for the differences in energy consumption. When this is done the PJS and HS produce roughly the same bubble size and have the same mass transfer performance. Still the PJS had the important operational advantages of producing shorter cavities and having the greater resistance to stall at low liquid flow rates.     

Revisiting Basics of kLa Dependency on Aeration in Bubble Columns: a Is Surprisingly Stable

A comprehensive experimental characterization of a small-scale bubble column bioreactor (60 mL) is presented. Bubble size distribution (BSD), gas holdup, and k_La were determined for different types of liquids, relevant fermentation conditions and superficial gas velocities u_G. The specific interfacial area a and liquid mass transfer coefficient k_L have been identified independent of each other to unravel their individual impact on k_La. Results show that increasing u_G leads to larger bubbles and higher gas holdup. As both parameters influence a in opposite ways, no increase of a with u_G is found. Furthermore, k_L increases with increasing bubble size outlining that improved oxygen transfer is not the result of higher a but of risen k_L instead. The results build the foundation for further simulative investigations.     

Gas‐Liquid Mass Transfer in Fibrous Bed Reactor with Counter‐Current Liquid Recycle

In this work, the gas‐liquid mass transfer in a lab‐scale fibrous bed reactor with liquid recycle was studied. The volumetric gas‐liquid mass transfer coefficient, k_La, is determined over a range of the superficial liquid velocity (0.0042–0.0126 m.s^–1), gas velocity (0.006–0.021 m.s^–1), surface tension (35–72 mN/m), and viscosity (1–6 mPa.s). Increasing fluid velocities and viscosity, and decreasing interfacial tension, the volumetric oxygen transfer coefficient increased. In contrast to the case of co‐current flow, the effect of gas superficial velocity was found to be more significant than the liquid superficial velocity. This behavior is explained by variation of the coalescing gas fraction and the reduction in bubble size. A correlation for k_La is proposed. The predicted values deviate within ± 15 % from the experimental values, thus, implying that the equation can be used to predict gas‐liquid mass transfer rates in fibrous bed recycle bioreactors.     

Effect of electrolytes in aqueous solutions on oxygen transfer in gas–liquid bubble columns

The effects of inorganic electrolytes (NaCl, MgCl₂, CaCl₂) in aqueous solutions on oxygen transfer in a bubble column were studied. Electrolyte concentrations (c) below and above the critical concentrations for bubble coalescence (c_tc), and six superficial gas velocities (v_sg), were evaluated. The volumetric mass transfer (k_La) and the mass transfer (k_L) coefficients were experimentally determined. It was found that the concentration of electrolytes reduced the k_L, but the interfacial area (a) increased enough to result in a net increase of k_La. Using as independent variable a normalizing variable (c_r = c/c_tc), and maintaining fixed v_sg, similar values of k_La were observed regardless the kind of electrolyte; the same happened for k_L. This suggests that c_r quantifies the structural effects that these solutes exert on mass transfer. Also, once c_r = 1 was reached, no significant variations were found in k_La and k_L for constant v_sg. It is concluded that the gradual inhibition of bubble coalescence (c_r < 1) governs the significant changes in hydrodynamics and mass transfer via the reduction of bubble size and the consequent increment of a and gas holdup (?_g). Finally, regarding the effects of v_sg on mass transfer, transition behaviors between those expected for isolated bubbles and bubble swarms were observed.     

Mass transfer characteristics in a gas–liquid reciprocating plate column. II. Interfacial area

This paper is the second part of a continuing study on mass transfer in a reciprocating plate column. The first part dealt with k_La. The bubble size distribution, the Sauter mean diameter and the interfacial area are the subject of this paper. The bubble size increases slightly with gas flow rate and decreases with agitation intensity above a “critical” level. The interfacial area increases with increasing agitation and aeration intensities, while the liquid flow rate and coalescing properties of the liquid have no significant effect. The specific interfacial area is correlated in terms of the superficial gas velocity and the maximum power consumption. The correlations obtained for k_La and a were used to calculate k_L. It was found that k_L depends on the agitation intensity and the bubble size.     

Effect of contaminants on mass transfer coefficients in bubble column and airlift contactors

In this work, the effects of surface-active contaminants on mass transfer coefficients k_La and k_L were studied in two different bubble contactors. The oxygen transfer coefficient, k_L, was obtained from the volumetric oxygen transfer coefficient, k_La, since the specific interfacial area, a, could be determined from the fractional gas holdup, ε, and the average bubble diameter, d₃₂. Water at different heights and antifoam solutions of 0.5- were used as working media, under varying gas sparging conditions, in small-scale bubble column and rectangular airlift contactors of 6.7 and capacity, respectively. Both the antifoam concentration and the bubble residence time were shown to control k_La and k_L values over a span of almost 400%. A theoretical interpretation is proposed based on modelling the kinetics of single bubble contamination, followed by sudden surface transition from mobile to rigid condition, in accordance with the stagnant cap model. Model results match experimental k_L data within ±30%.     

An experimental study of air-water Taylor flow and mass transfer inside square microchannels

Flow and mass transfer properties under air-water Taylor flow have been investigated in two square microchannels with hydraulic diameters of 400 and 200 μm. Experimental data on Taylor bubble velocity, pressure drop and liquid side volumetric mass transfer coefficient (k_La) have been presented. It was shown that the measured Taylor bubble velocity in square microchannels could be well interpreted based upon an approximate measurement of the liquid film profile therein. Then, the obtained two-phase frictional pressure drop values in both microchannels were found to be significantly higher than the predictions of the correlation proposed by Kreutzer et al. [2005b. Inertial and interfacial effects on pressure drop of Taylor flow in capillaries. A.I.Ch.E. Journal 51, 2428-2440] when the liquid slug was very short, which can be explained by the inadequacy of their correlation to describe the excess pressure drop caused by the strong inner circulation in such short liquid slugs. An appropriate modification has been made to this correlation in order to improve its applicability in microchannels. Finally, the experimental (k_La) values in the microchannel with hydraulic diameter of 400 μm were found to be in poor agreement with those predicted by the existing correlations proposed for capillaries with diameters of several millimeters. The observed deviation was mainly due to the fact that mass transfer experiments in this microchannel actually corresponded to the case of short film contact time and rather poor mixing between the liquid film and the liquid slug, which was not in accordance with mass transfer assumptions associated with these correlations. A new empirical correlation has been proposed to describe mass transfer data in this microchannel.     

Gas Holdup and Volumetric Mass Transfer Coefficient in a Slurry Bubble Column

The gas holdup, ?, and volumetric mass transfer coefficient, k_La, were measured in a 0.051 m diameter glass column with ethanol as the liquid phase and cobalt catalyst as the solid phase in concentrations of 1.0 and 3.8 vol.‐%. The superficial gas velocity U was varied in the range from 0 to 0.11 m/s, spanning both the homogeneous and heterogeneous flow regimes. Experimental results show that increasing catalyst concentration decreases the gas holdup to a significant extent. The volumetric mass transfer coefficient, k_La, closely follows the trend in gas holdup. Above a superficial gas velocity of 0.04 m/s the value of k_La/? was found to be practically independent of slurry concentration and the gas velocity U; the value of this parameter is found to be about 0.45 s^–1. Our studies provide a simple method for the estimation of k_La in industrial‐size bubble column slurry reactors.     

Numerical simulations of gas-liquid mass transfer in bubble columns with a CFD-PBM coupled model

Gas-liquid mass transfer in a bubble column in both the homogeneous and heterogeneous flow regimes was studied by numerical simulations with a CFD-PBM (computation fluid dynamics-population balance model) coupled model and a gas-liquid mass transfer model. In the CFD-PBM coupled model, the gas-liquid interfacial area a is calculated from the gas holdup and bubble size distribution. In this work, multiple mechanisms for bubble coalescence, including coalescence due to turbulent eddies, different bubble rise velocities and bubble wake entrainment, and for bubble breakup due to eddy collision and instability of large bubbles were considered. Previous studies show that these considerations are crucial for proper predictions of both the homogenous and the heterogeneous flow regimes. Many parameters may affect the mass transfer coefficient, including the bubble size distribution, bubble slip velocity, turbulent energy dissipation rate and bubble coalescence and breakup. These complex factors were quantitatively counted in the CFD-PBM coupled model. For the mass transfer coefficient k_l, two typical models were compared, namely the eddy cell model in which k_l depends on the turbulent energy dissipation rate, and the slip penetration model in which k_l depends on the bubble size and bubble slip velocity. Reasonable predictions of k_la were obtained with both models in a wide range of superficial gas velocity, with only a slight modification of the model constants. The simulation results show that CFD-PBM coupled model is an efficient method for predicting the hydrodynamics, bubble size distribution, interfacial area and gas-liquid mass transfer rate in a bubble column.     

Comparison of Hydrodynamics and Mass Transfer in Airlift and Bubble Column Reactors Using CFD

Computational Fluid Dynamics (CFD) is used to compare the hydrodynamics and mass transfer of an internal airlift reactor with that of a bubble column reactor, operating with an air/water system in the homogeneous bubble flow regime. The liquid circulation velocities are significantly higher in the airlift configuration than in bubble columns, leading to significantly lower gas holdups. Within the riser of the airlift, the gas and liquid phases are virtually in plug flow, whereas in bubble columns the gas and liquid phases follow parabolic velocity distributions. When compared at the same superficial gas velocity, the volumetric mass transfer coefficient, k_La, for an airlift is significantly lower than that for a bubble column. However, when the results are compared at the same values of gas holdup, the values of k_La are practically identical.