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771 IMPACT OF STRUCTURED PACKING ON BUBBE COUMN MASS TRANSFER CHARACTERISTICS EVAUATION. Part 3. Sensitivity of ADM Volumetric Mass Transfer Coefficient evaluation Ana akota Faculty of Chemistry and Chemical Technology, University of jubljana, Aškerčeva 5, SI-1000 jubljana, Slovenia Received 13-10-2003 Abstract Based on the available concentration profiles the present work discusses the sensitivity of volumetric mass transfer coefficient on axial dispersion coefficient. The calculations were performed for a bubble column without internals, the parameters of ADM were determined with nonlinear regression. The volumetric mass transfer coefficient shows a slight dependence on the axial dispersion coefficient which leads to the conclusion that ADM provides reasonable values for k a whenever more or less reliable correlation for E is available. Nevertheless, the exact concentration profile evaluation requires E to be determined with caution. Introduction An extensive experimental study of hydrodynamic and mass transfer characteristics of bubble column, with or without internals, is described in details in Part 1 1 and Part 2. 2 The experiments were performed in the Plexiglas column with a high length to diameter ratio. The column operated in the cocurrent upflow mode, tap water and oxygen were employed as the flowing phases. Both hydrodynamic regimes, the homogeneous and heterogeneous, were partly covered. The perforated plate served as the gas distributor. A significant deviation from the ideal plug flow of the liquid phase was experimentally confirmed 1 and validated in the form of axial dispersion number, E. For the evaluation of mass transfer characteristics the measurement of oxygen concentration in the liquid phase were taken under stationary conditions 2 at four different axial positions along the column. The data were then interpreted with the use of axial dispersion model (ADM) and plug flow model (PFM). The resulting values for the volumetric mass transfer coefficients clearly showed the more realistic response of ADM against PFM.

772 Axial dispersion model (Part 1, 1 equation 3 to equation 11) involves two parameters, the Stanton number, St, and the Bodenstein number, Bo. At the given operating conditions k a and E may be explicitly expressed and used instead. The ADM concentration curves are extremely sensitive to the Stanton number, while the Bo number shows minor effect. 3 In the present work the sensitivity of the calculated volumetric mass transfer coefficient based on the available concentration profiles, on axial dispersion coefficients is shown. The calculations were performed on the experimental data for a bubble column without internals, the parameters of the ADM were determined with nonlinear regression procedure by means of the Mathematica. Results and discussion The deviation of the calculated profile from the experimental one is expressed as the sum of the differences between the measured and calculated values of the concentration to the square, in all cases. In Table 1 the k a values as an average along the column were obtained from the adaptation to the measured concentration profiles. For the second parameter of the model, E, the experimental values 1 best represented with the following equation: E 0.191 = 129.05 ug (1) were put into the model. In the above equation E is in cm 2 s -1 and u G in cms -1 (with e y =8.89% and σ =9.37%). The calculated profiles seems to be very close the experimental ones, the sums of the squares lie between 0.74 and 12. At the u =1.81 cms -1 some irregularities may be observed, the k a values are evidently too high. The examination of the measured profiles was made. Extremely high values of the concentration at the first measuring point were found what could easily corrupt the results. For comparison the k a evaluated from the last measured concentration in the column 2 are also presented. Except for the first set of data at the lowest liquid velocity the k a values are very close to those from the profile adaptation, but the deviations of the calculated profiles from the measured ones are about doubled.

773 In spite of insufficient number of the experimental data for liquid concentration along the column an attempt to optimise both parameters from the concentration profiles was also made. These results are shown in Table 2. In this case the summations of squares are lower than 1 in all runs. The values of the axial dispersion coefficients do not match with the measured coefficients (equation 1). Because the concentration profile is rather insensitive to E 3 these values are very uncertain. Surprisingly, the volumetric mass transfer coefficients are nearly identical to those based on the one parameter concentration profile adaptations (within 5%). Table 1. Results of ADM k a values based on the measured concentration profiles. u G E * ADM k a optimized from the concentration profile k a Σ (s -1 ) ADM k a adjusted to the last measured concentration Σ ( s -1 ) ( c ) 2 Run No u (cm s -1 ) (cm s -1 ) (cm 2 s -1 ) ( c ) 2 k a 1 1.81 1.81 144.5 0.03116 2.60 0.02795 5.47 2 3.61 165.0 0.08216 9.41 0.05242 38.22 3 5.41 178.2 0.1199 10.87 0.06911 42.68 4 9.0 196.3 0.1817 11.17 0.08247 60.05 5 3.61 1.81 144.5 0.02307 0.74 0.02372 1.026 6 3.61 165.0 0.05080 1.60 0.04850 2.45 7 5.41 178.2 0.07547 4.11 0.06752 7.80 8 9.0 196.3 0.11561 9.60 0.09250 20.42 9 5.41 1.81 144.5 0.02128 1.12 0.02104 1.16 10 3.61 165.0 0.04667 0.90 0.04525 1.98 11 5.41 178.2 0.06739 1.02 0.06485 1.65 12 9.0 196.3 0.10617 4.88 0.09537 9.05 * Equation 1. For comparison the volumetric mass transfer coefficients evaluated from the PFM are also included in Table 2. These values are adjusted to the last measured concentration in the column. As one can see the coefficients are lower then those from ADM, the summations of squares are between 10 and 100. In order to test the sensitivity of k a on the axial dispersion coefficient the experimental data points from run No. 7 were employed. In these calculations E was varied from 1 cm 2 s -1 to 1500 cm 2 s -1. The values of the mass transfer coefficient were then optimised to the measured concentration profile (Figure 1).

774 Table 2. Results of both ADM parameters optimized from the measured concentration profiles and k a values from PFM. ADM E and k a optimized from the concentration profile PFM k a adjusted to the last measured concentration Σ (s -1 ) ( c ) 2 Run No u (cm s -1 ) u g (cm s -1 ) E (cm 2 s -1 ) k a (s -1 ) Σ ( c ) 2 k a 1 1.81 1.81 200.1 0.0308 0.0735 0.01938 100.1 2 3.61 396.1 0.0848 0.969 0.02819 166.3 3 5.41 566.7 0.1217 0.276 0.0329 166.3 4 9.0 849.6 0.1730 0.640 0.03522 200.2 5 3.61 1.81 116.6 0.02377 0.089 0.0231 20.54 6 3.61 220.5 0.05125 0.391 0.0394 34.70 7 5.41 330.4 0.0797 0.009 0.0478 56.61 8 9.0 557.0 0.1311 0.162 0.0592 74.70 9 5.41 1.81 107.0 0.02224 0.539 0.0234 10.27 10 3.61 152.9 0.04676 0.872 0.04258 13.54 11 5.41 229.8 0.06801 0.651 0.05591 18.45 12 9.0 470.5 0.1168 0.046 0.07469 35.32 ka (s -1 ) 0,10 0,09 0,08 0,07 0,06 0,05 Series1 k a (s -1 ) Series2 ( c ) 2 80 70 60 50 40 30 20 10 ( c) 2 0,04 0 1 10 100 1000 10000 E (cm 2 s -1 ) Figure 1. Volumetric gas-liquid mass transfer coefficient and the summation of squares as a function of axial dispersion coefficient (experimental concentration data points from run No. 7). From Table 1 it can be seen that at these operating conditions the experimental value of E (equation 1) is 178.2 cm 2 s -1 and the k a value adjusted to the measured profile is equal to 0.07547 s -1. The sum of the squares is about 4. When E is nearly doubled (to 330.4 cm 2 s -1 ) the change in the volumetric mass transfer coefficient is within

775 5% (to 0.0797 s -1 ). These two values are taken from the two-parameter fit from Table 2. In fact for values of axial dispersion coefficient from 1 to 1000 cm 2 s -1 the volumetric mass transfer coefficients lie within 0.06 s -1 and 0.08 s -1 (Figure 1). However, the deviation of the calculated concentration profile from the measured one does change significantly, the sum of the squares is first minimised and then goes up to 50, increasing rapidly. In Figure 2 the calculated dimensionless concentration profile at different values of E are drawn together with the experimental data points. It is obvious that the k a determination is quite insensitive to the value of E, while the prediction of the reliable concentration profile along the column requires both parameters to be determined with caution. C 1 0,9 0,8 0,7 0,6 0,5 0,4 0,3 0,2 0,1 0 experimental el=1 E = 1 cm 2 s -1 el=100 E = 100 cm 2 s -1 el=400 E = 400 cm 2 s -1 el=1000 E =1000 cm 2 s -1 0 0,2 0,4 0,6 0,8 1 z Figure 2. Calulated concentration profiles at different values of axial dispersion coefficient (experimental concentration data points from run No. 7). Conclusion The sensitivity of the volumetric mass transfer coefficient on the axial dispersion coefficient was examined. The experimental data were taken from the previous studies. 1,2 The use of axial dispersion model in k a evaluation based on the measured concentration profile, or even one single measured concentration, gives the satisfactory result as long as more or less reliable correlations for E are available. Nevertheless, the estimation of the exact concentration profile requires also E to be determined with caution.

776 Acknowledgements This work was supported by the Slovenian Ministry of Science and Technology through Grant PO-0510-0103. Nomenclature C dimensionless oxygen concentration, c/c*, / c oxygen concentration, mgl -1 E dispersion coefficient, m 2 s -1 e y mean relative error, 100 N = i = N 1 y () i y () i y k a volumetric gas-liquid mass transfer coefficient, s -1 column length, m N number of experimental data Pe St modified Peclet number in the liquid phase, Stanton number, k a, / u u superficial velocity, ms -1 z dimensionless length of a column, / E () PRED i u ( 1 ε ) G,/, % Greek letters ε phase hold-up, / σ standard deviation, Subscripts G gas phase liquid phase * in equilibrium measured value PRED predicted value 2 1 N y () () PRED i y i = 100 i () = e 1 y, N 1 y i References 1. A. akota, M. Jazbec, J. evec, Acta Chim. Slov. 2001, 48, 453 468. 2. A. akota, M. Jazbec, J. evec, Acta Chim. Slov. 2002, 49, 587 604. 3. W. D. Deckwer, Bubble Column Reactors; J. Wiley & Sons td., Chicester (GB), 1992. Povzetek Dvoparametrski aksialno disperzni model je primeren za določitev volumetričnega koeficienta snovnega transporta na osnovi eksperimentalno posnetih koncentracijskih krivulj. Sama vrednost k a kaže rahlo odvisnost od vrednosti aksialno disperznega koeficienta, tako da E lahko ocenimo iz razpoložljivih korelacij. V primeru, ko nas zanima eksakten koncentracijski profil vzdolž kolone, nenatančnost v oceni aksilno disperznega koeficienta doprinese k znatni napaki.