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Effect of Electrolytes in Aqueous Solution on Bubble Size in GasLiquid Bubble Columns

 Jos E. Botello-A lvarez,*, Sergio A. Baz-Rodrguez, Ral Gonzlez-Garca, Alejandro Estrada-Baltazar, e u a Jos A. Padilla-Medina, Guillermo Gonzlez-Alatorre, and Jos L. Navarrete-Bola~os e a e n

Departamento de Ingeniera Qumica Ingeniera Bioqumica Ingeniera Electrnica, Instituto Tecnolgico de Celaya, o o Av. Tecnolgico y Garca Cubas s/n, Celaya, Gto 38010, Mxico o e Facultad de Ciencias Qumicas, Universidad Autnoma de San Luis Potos, Av. Dr. M. Nava No. 6, San Luis Potos, SLP 78210, Mxico o e ABSTRACT: The eects of three inorganic electrolytes (CaCl2, MgCl2, and NaCl) in aqueous solutions on the bubble size in a gasliquid bubble column under a homogeneous bubbling regime were investigated. The concentration of electrolytes and the supercial gas velocity at the entrance of the column were varied. The average bubble diameter in the main section of the equipment was estimated using digital image analysis. From an analysis of variance, it was found that the electrolyte concentration is the main reason for bubble size variation. Moreover, it was found that the coalescent and noncoalescent behaviors in the bubble column are separated by the transition concentrations of coalescence. The ratio between the electrolyte concentrations and the transition concentration of coalescence (reduced concentration) was used to modify an empirical correlation that describes the experimental behavior of the Sauter mean diameter within an absolute percentage deviation of 10.47%.

1. INTRODUCTION Interfacial mass transfer in gasliquid systems has many important applications in chemical and biochemical industries. When considering the design and operation of bubble columns, bubble size is an important parameter because it denes the available area for mass transfer, the gas hold up, and other hydrodynamic variables. The amount, size, shape, and motion conditions for the bubbles depend on variables such as the supercial gas velocity at the entrance, diuser design, frequency of bubble coalescence and break up, and physicochemical properties of the liquid phase. In this sense, the presence of solutes can be important because they can signicantly aect the liquid properties and the bubble coalescence behavior; thus, the interfacial area availability can be aected too. In particular, the electrolytes are present in many biotechnological processes that are carried out using bubble columns, and their eects on bubble size are a relevant matter to research. It has been reported in the literature that the average bubble size in bubble columns is smaller in electrolyte aqueous solutions than in pure water.13 It is possible that the increment of the liquid surface tension due to the presence of inorganic electrolytes causes the reduction in the bubble volume when they are generated in the diuser.4,5 Moreover, an important eect of electrolytes is the inhibition of bubble coalescence.13 This allows the maintenance of bubbles as single elements during the approach or collision with other bubbles. There are several attempts to explain why the presence of electrolytes causes the inhibition of bubble coalescence. Some authors claim that coalescence occurs because the liquid is drained from the space between two approaching bubbles until a minimum lm thickness is reached; then, the lm ruptures and the bubble coalesces. If the formation of ordered structures
r 2011 American Chemical Society

among ions and water molecules in aqueous electrolyte solutions prevents the critical liquid draining, coalescence is inhibited.6,7 Other authors have proposed that the inhibition of bubble coalescence above a minimum lm thickness can be explained in terms of the change of surface tension with concentration.2 The amount of dissolved air that is aected by the electrolyte concentration also has been suggested as an important factor in the inhibition of bubble coalescence.8,9 In this context, a transition concentration of coalescence has been dened as the concentration of electrolyte in aqueous solution from which the air bubbles reduce their coalescence above 50%, with respect to that observed in pure water.7 The eects of the presence of electrolytes in aqueous solutions on the average size of air bubbles in a bubble column were studied. For this purpose, the average bubble size was related with the transition concentration of coalescence. The relevance of the reduced concentration (ratio between the electrolyte concentration and the transition concentration of coalescence) as a reference for assessing the average bubble size was investigated.

2. EXPERIMENTAL PROCEDURE Experiments were carried out in a Pyrex glass bubble column with an internal diameter of 0.095 m and 1.2 m height. A schematic diagram is shown in Figure 1. A porous glass plate with a nominal porous diameter of 160250 m was used as a diuser. Temperature was maintained at 30 C inside the bubble column using a recirculating bath (PolyScience, 9100 series). Six supercial air velocities at the bottom of the bubble column were
Received: March 7, 2011 Accepted: September 19, 2011 Revised: September 15, 2011 Published: September 19, 2011
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Figure 1. Experimental setup.

Table 1. Electrolyte Concentrations in Aqueous Solution

concentration in electrolyte NaCl CaCl2 MgCl2 aqueous solution (M) 0.05, 0.13, 0.21, 0.29, 0.37 0.02, 0.04, 0.06, 0.08, 0.10 0.02, 0.04, 0.05, 0.08, 0.11, 0.14 transition concentration of coalescence (Ctc, M) 0.175 0.055 0.055

evaluated: 0.0005, 0.0045, 0.0085, 0.0125, 0.0160, and 0.0196 m/s. These velocities were measured and controlled with a rotameter (112-02-GL, Aalborg Instruments and Controls, Inc.). Table 1 shows the molarities of NaCl, CaCl2, and MgCl2 in aqueous solutions, which were used as liquid phase; the transition concentrations of coalescence are indicated too.2 Deionized water was used to prepare the solutions. Geometric measures of the bubbles were determined using digital image analysis. A 0.15 m height glass cube was placed concentrically on the column around the location where the image acquisition was carried out (0.40 m above the diuser). The cube was lled with water in order to avoid the optical distortion of the images due to the column curvature. The negligibility of the optical distortion was veried by looking at rigid spheres of known dimensions. Image acquisition was carried out using a video camera (Sony Handycam DVCVTR730), and it was zoomed manually for a better focusing of the bubbles. A couple of incandescent lamps (60 W) were used to enhance the clarity of the bubbles. These lamps were placed at the lateral sides of the cube, with respect to the camera location, in order to highlight the bubble contours; clear and dark backgrounds were placed outside of the cube (see Figure 1). At the wall, inside the column, a transparent band with a graduated distance scale in millimeters was placed to establish a pixel/ distance relationship.

Figure 2. Eects of supercial gas velocity on the average bubble diameter in NaCl aqueous solutions: (a) concentration below the transition concentration of coalescence (0.05 M) and (b) concentration above the transition concentration of coalescence (0.37 M).

Video sequences were captured at an average rate of 25 frames/s and then sent to a personal computer. A script of the Image Acquisition Toolbox of Matlab 7.0 (The MathWorks, Inc.) was used to monitor the capture. The resolution of video frames was 240 320 pixels, and the average of the pixel/distance ratio was 100 pixels/cm. Images were extracted and processed from the video sequences by using a script performed in the Image Processing Toolbox of Matlab 7.0. By enhancing the contrast among the dark and clear zones of the images, the contours of the bubbles could be traced. At least 150 bubbles were isolated from the images for each experimental condition (electrolytecomposition supercial gas velocity). The bubble shape was assumed to be oblate ellipsoidal. The geometric properties of each bubble was measured, and its diameter associated with an equivalent sphere was calculated using the following equation: p 3 1 dbi dH 2 dL where dH and dL are the major and minor axis of each bubble, respectively. In order to obtain a representative diameter for each experimental condition, the Sauter mean diameter was calculated
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Industrial & Engineering Chemistry Research Table 2. Analysis of Variance

sum of degrees of source model A supercial gas velocity B electrolyte concentration C electrolyte species AB AC BC residual total 0.047 0.210 0.017 0.094 0.015 1.61 2 20 10 8 37 86 0.024 0.010 1.653 103 0.012 0.0004 1.020 4 0.260 squares 1.600 0.190 freedom 49 5 mean square 0.033 0.038

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F-value P-value 78.61 <0.0001 90.76 <0.0001 615.14 <0.0001 56.75 <0.0001 25.07 <0.0001 3.9 <0.0001 28.44 <0.0001

Figure 3. Eects of concentration in aqueous solution on the average bubble diameter in NaCl aqueous solutions at (a) Usg = 0.0005 m/s and (b) Usg = 0.0196 m/s.

as follows:

ni dbi 3 i d32 ni dbi 2 i

where ni is the number of bubbles with a dbi diameter.

3. RESULTS AND DISCUSSION In Figure 2, the cumulative frequencies of the bubble equivalent diameters formed in aqueous solutions of NaCl at two dierent molarities are plotted. Each data series in the gure depicts a constant supercial gas velocity. The lowest composition (0.05 M) depicts coalescing conditions, whereas the highest composition (0.37 M) is the opposite. The equivalent bubble diameter increases as the supercial gas velocity increases, and it decreases as the electrolyte concentration increases. It was found that the size distribution dispersion is lower at high concentration values. At the lowest supercial gas velocity, bubble coalescence does not occur even if medium properties are propitious; therefore, the bubble diameter does not change, and it is independent of the salt content in the solution. This is shown in Figure 3a, where

bubble size distribution has almost the same behavior at dierent NaCl molarities. This happens when the supercial gas velocity is low because the bubbles tend to behave as isolated bodies; when the volumetric gas fraction is low, the possibility of collisions decreases, and then the coalescence falls.10 On the other hand, at higher supercial gas velocities, a clearly dierent behavior exists. Figure 3b shows that at concentrations lower than 0.21 M, there are coalescent conditions, whereas at equal or higher concentrations, this does not occur signicantly. The hydrodynamic conditions allow the bubble interactions due to spatial proximity to be conducted. Thus, the eects of the increase in electrolyte concentration on the coalescence behavior can be observed. It was found that the transition concentration (0.175 M for NaCl aqueous solutions) separates the coalescence occurrence in the bubble column. While the concentration is lower than transition concentration, the bubble coalescence occurrence decreases as the content of electrolyte increases. Once the transition concentration is reached, the occurrence of coalescence is no longer signicant, and the bubble size is essentially the same for higher concentrations. The experimental data of the equivalent bubble diameter for each of the cases studied have a log-normal distribution, given that their distribution frequency is not symmetrical. A slant toward the right occurred because no bubble size could equal or be less than zero. This is in agreement with the results of Lage and Espsito11 for bubbling a homogeneous regime in bubble o columns. From each distribution, the Sauter mean diameter (d32) was calculated as a representative parameter. Using a BoxCox test, it was determined that the Sauter mean diameter data follows a normal distribution function. Using an analysis of variance, it was found that the supercial gas velocity at the entrance, the concentration, and the chemical nature of the salt have signicant eects on the Sauter mean diameter. However, the salt concentration is the most sensitive variable and the largest source of variation, as shown in Table 2. Salt composition gradually generates noncoalescence behavior.6 From this result, it is advisible to suggest that a good correlative variable can be a reduced concentration, Cr: the ratio between the concentration of the salt (Ci) and the transition concentration of coalescence (Ctc). Cr
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Ci Ctc

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must be taken into account. Even if the physicochemical properties do not vary signicantly with a moderate change in the electrolyte concentration, the bubble coalescence behavior does. This is relevant because the interfacial area availability, related to the average bubble size, is crucial for the mass transfer achievement in many biotechnological processes, in which electrolytes are present as source of mineral nutrients.13 Previously, Pohorecki et al14 correlated the Sauter diameter using the Froude number (Fr): !   Usg 2 FL Usg 4 L Usg k 4 Fr d32 g g where k, , and are adjustment parameters; Usg is gas supercial velocity; g is gravity; FL and L are the liquid density and viscosity, respectively, and they were measured by Baz-Rodrguez;13 and is the liquid surface tension and was obtained from the literature.9 It is reasonable to propose that the adjustment parameters should be a function of the reduced concentration. These parameters were estimated using the subroutine GREG:15 k 0:138 3:345Cr 0:712Cr 2 0:412 0:059Cr 0:013Cr
2

Figure 4. Reduced concentration (Cr) against Sauter mean diameter for Usg = 0.0125 m/s.

5 6

The parameter is almost constant and equal to 0.1. Figure 5 shows a comparison between the experimental results and the prediction of the proposed correlation. The correlation agrees within an absolute average percentage deviation of 10.42, 9.47, and 11.53% for CaCl2, MgCl2, and NaCl aqueous solutions, respectively. Data used to t eqs 46 are encompassed within a homogeneous bubbling regime (0.0005 m/s e Usg e 0.0196 m/s; 0.034 e g e 0.1443, where g is the volumetric gas fraction), and 0 e Cr e 2.545. This is a rst attempt to obtain a general correlation for the Sauter mean diameter using the critical concentration of coalescence in a bubble column.

Figure 5. Experimental vs calculated data of reduced concentration (Cr) for three inorganic electrolytes.

This variable was used previously by Ribeiro and Mewes.12 They found that gas hold up and ow regime in bubble columns can be related to the ratio of the electrolyte concentration and the transition concentration of coalescence in the aqueous electrolyte solution. Figure 4 shows bubble Sauter diameter behavior for the three dierent salts against the reduced concentration, Cr, at supercial gas velocity Usg = 0.0125 m/s. The data trend allows the assumption that the coalescence may follow a behavior similar to the principle of corresponding states of single uids. Once the transition concentration is reached (Cr > 1), the Sauter mean diameter no longer varies signicantly. As mentioned above, this can be explained by the almost total inhibition of bubble coalescence. This leads to the conclusion that the experimental data of transition concentration obtained from experiments addressed to force the contact of bubble pairs7 are good references to assess the average bubble size in bubble columns, where there are interactions between multiple bubbles. Provided that the hydrodynamic conditions are favorable for a homogeneous bubbling regime that ensures that the bubbles interact, the eects of electrolyte concentration on bubble size

4. CONCLUSION In this work, it was found that the coalescence and the average diameters of bubbles in electrolyte aqueous solutions in bubble columns are inuenced mainly by the solute concentrations and the hydrodynamic conditions. The experimental data of transition concentrations of coalescence2 obtained from experiments addressed to force the contact of bubble pairs are good references to assess the average bubble size in bubble columns. The transition concentrations marked the point where the bubble coalescence was drastically inhibited. A new correlation was developed that is a function of the reduced concentration (the ratio between the electrolyte concentration and the transition concentration of coalescence); the estimated data of this work were used to t the proposed equation. The new correlation is based upon the Froude number and predicts the Sauter mean diameter within an absolute average percentage deviation of 10.47%.
AUTHOR INFORMATION
Corresponding Author

*E-mail: joseb@itc.mx. Tel.: +52 (461)6117575 ext. 415.

ACKNOWLEDGMENT The authors respectfully acknowledge the Consejo Nacional de Ciencia y Tecnologa (National Council for Science and
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Industrial & Engineering Chemistry Research Technology) (CONACyT), Mxico, for their nancial support e through a Graduate Scholarship (SABR). They thank Dr. Gustavo Iglesias for some interesting remarks.

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NOMENCLATURE Ci = electrolyte concentration in aqueous solution (M) Cr = reduced concentration Ctc = transition concentration of coalescence (M) d32 = Sauter mean diameter (m) dbi = bubble diameter associated with an equivalent sphere (m) dH = major axes of the bubble (m) dL = minor axes of the bubble (m) Fr = Froude number based on Sauter mean diameter and supercial gas velocity g = acceleration of gravity (m/s2) k = tting paramenter in eq 4 Usg = supercial air velocity at the entrance of the bubble column (m/s) GREEK LETTERS = tting paramenter in eq 4 = tting paramenter in eq 4 g = volumetric gas fraction L = viscosity of liquid (Pa 3 s) FL = density of liquid (kg/m3) = surface tension of liquid (N/m) REFERENCES
(1) Kluytmans, J. H. J.; van Wachem, B. G. M.; Kuster, B. F. M.; Schouten, J. C. Gas Holdup in a Slurry Bubble Column: Inuence of Electrolyte and Carbon Particles. Ind. Eng. Chem. Res. 2001, 40, 5326. (2) Prince, M. J.; Blanch, H. W. Transition Electrolyte Concentrations for Bubble Coalescence. AIChE J. 1990, 36, 1425. (3) Zieminski, S. A.; Whittemore, R. C. Behavior of Gas Bubbles in Aqueous Electrolyte Solutions. Chem. Eng. Sci. 1971, 26, 509. (4) Martin, M.; Montes, F. J.; Galn, M. A. On the Inuence of the a Physical Properties on Bubble Volumes and Generation Times. Chem. Eng. Sci. 2006, 61, 5196. (5) Martin, M.; Montes, F. J.; Galn, M. A. Oxygen Transfer for a Growing Bubbles: Eect of the Physical Properties of the Liquid. Chem. Eng. J. 2007, 128, 21. (6) Chan, B. S.; Tsang, Y. H. A Theory on Bubble Size Dependence of the Critical Electrolyte Concentration for Inhibition of Coalescence. J. Colloid Interface Sci. 2005, 286, 410. (7) Lessard, R. R.; Zieminski, S. A. Bubble Coalescence and Gas Transfer in Aqueous Electrolytic Solutions. Ind. Eng. Chem. Fundam. 1971, 10, 260. (8) Weissenborn, P. K.; Pugh, R. J. Surface Tension and Bubble Coalescence Phenomena of Aqueous Solutions of Electrolytes. Langmuir 1995, 11, 1422. (9) Weissenborn, P. K.; Pugh, R. J. Surface Tension of Aqueous Solutions of Electrolytes: Relationships with Ion Hydration, Oxygen Solubility, and Bubble Coalescence. J. Colloid Interface Sci. 1996, 184, 550. (10) Martn, M.; Montes, F. J.; Galn, M. A. Mass Transfer from a Oscillating Bubbles in Bubble Column Reactors. Chem. Eng. J. 2009, 151, 79. (11) Lage, P. L. C.; Espsito, R. O. Experimental Determination of o Bubble Size Distribution in Columns: Prediction of Mean Bubble Diameter and Gas Holdup. Powder Technol. 1999, 101, 142. (12) Ribeiro, C. P., Jr.; Mewes, D. The Inuence of Electrolytes on Gas Holdup and Regime Transition in Bubble Columns. Chem. Eng. Sci. 2007, 62, 4501.

(13) Baz-Rodrguez, S. A. The Eect of Electrolytes in Aqueous Solution on Oxygen Transfer in Bubble Columns (in Spanish). M.Sc. Thesis, Instituto Tecnolgico de Celaya: Celaya, Mxico, 2008. o e (14) Pohorecki, R.; Moniuk, W.; Bielski, P.; Sobieszuk, P.; Dabrowiecki, G. Bubble Diameter Correlation via Numerical Experiment. Chem. Eng. J. 2005, 113, 35. (15) Stewart, W. E. GREG: A FORTRAN Subroutine for Nonlinear Regression and Experimental Design; Users Manual; University of Wisconsin-Madison: Madison, WI, 1995.

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