Latin American Applied Research

31:433-439 (2001)

OXYGEN TRANSFER IN A STIRRED REACTOR IN LABORATORY SCALE

P. JUREZ and J. OREJAS Universidad Nacional de Ro Cuarto, Facultad de Ingeniera Ruta Nacional 36, Km 601,(5800) Ro Cuarto. Argentina. Keywords: Oxygen absorption, Mass-transfer coefficient, Dynamic method, Stirred-tank reactor, Stirred vessel
The main objective of this work was to find expressions for the prediction of the oxygen -transfer volumetric coefficient (kLa) in a laboratory -scale stirred-tank reactor. Different experiments were carried out, varying the agitation and aeration conditions. Dangs dynamic method was applied, only modifying the numerical processing of the experimental data. Some authors think that the evaluation of the La using this method as k an experimental technique leads to wrong expressions for the k a, especially when the liquid phase is a non L coalescent batch. It could be shown that the employment of the numerical technique for data processing nd developed in this work gives almost the same ka values as those fou with the approach by Koizumi and L Aiba (1984). Besides, the expressions for the ka are similar to those estimated through other measurement L techniques. These facts prove the efficacy of the dynamic method within the experimental range under study.

Abstract

1. Introduction Mass transfer in stirred-tank reactors is a very important process in the chemical and biochemical industry. The oxygen-transfer capacity in a specific reactor fundamentally depends on its mechanical design, the geometry of the air distributor and impellers, and the operating conditions, such as the agitation velocity and the aeration rate. All these variables, together with the physicochemical and rheologic properties of the absorption medium, are synthetised in a unique parameter, called volumetric gas-liquid mass-transfer coefficient (kLa). This parameter is essential in the analysis of the design and scale-up of chemical and biological reactors. In this work the standard dynamic method (Dang et al., 1977) was applied to the experimental determination of the volumetric gas-liquid masstransfer coefficient based on the liquid-phase volume (kLa). A new technique that takes into account the dynamics of both the oxygen sensor and the liquid phase was developed for the analysis and interpretation of the experimental data. This technique was compared with the one proposed by Koizumi and Aiba (1984). The resulting values for the kLa were correlated with the specific power and the superficial gas rate and the expressions were compared with data from the literature. It was demonstrated that the kLa expressions obtained through Dangs method are similar to those found using other measurement techniques.

two six-blade Rushton turbines. The main dimensions (in meters) of the reactor and the agitator are report in Fig.1 (for one turbine, H = 0.13 m and l = 0.065 m). Gas was fed into the system through an open-ended tube, which has 7 orifices (diameter: 0.001 m) situated below the bottom impeller. 2.1.2 Experimental conditions The reactor was operated in batch mode for the
Gas input

0.013

0.011 0.011 H=0.17 0.125

l= 0.04 0.045 0.13 0.015

2. Method 2.1 Materials and Operating Conditions Fig. 1. Schematic diagram of the reactor 2.1.1 Reactor The experiments were carried out in a reactor liquid phase and in continuous mode for the gas phase (Applikon Instruments) equipped with controllers for (air and nitrogen). The liquids employed in the temperature and agitation speed, using either one or 433

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experiments were distilled water (coalescing system) and a non-coalescing aqueous solution of Na2SO4 3 0.5M. The liquid volume was 0.0015 m for one 3 impeller and 0.002 m for two impellers. The temperature was controlled with a thermostatic bath at a set point of 20 C. The rotation speed of the impeller was varied between 5 and 15 r.p.s. at intervals of 1.667 r.p.s. The velocity controller was an ADI 1012 (Applikon Instruments). Its output signal, which is proportional to the torque, was used to evaluate the power transmitted from the agitation system to the fluid. The gas flow rates, which were recorded with an AALBORG GFM317 mass flowmeter, were 2.5, 3.75 -5 3 -1 and 5x10 m .s . The dissolved oxygen concentration was measured with an electrode YSI 5750, whose signal was amplified with a meter YSI 51B and modified with an output signal connected to a register. The electrode was placed so that its membrane remained parallel to the position of the disk in the lower agitator. The time required to do the experiments varied between 200 and 700 seconds (depending on both the impellers rotation speed and the superficial gas rate). 2.2 Experimental Technique and Interpretation of the Results There is a wide variety of proposals in the literature for the implementation of the experimental techniques for kLa evaluation. By way of illustration, we can mention the dynamic method, developed by Dang et al. (1977), the start-up dynamic method, the dynamic pressure method (Linek et al., 1989, 1994) and the dynamic method for fermentator systems (Bandyopadhyay et al., 1967). All of them consist in the measurement of the oxygen concentration in the reactor after a step change in the input gas. In this work the volumetric mass transfer coefficient, referred to the liquid volume (kLa) was determined using the dynamic method proposed by Dang et al. (1977). This technique consists in reducing the concentration of the dissolved oxygen by sweeping it with nitrogen, simultaneously interrupting the air input. Afterwards, the aeration is re-established and the increase in the dissolved oxygen concentration is registered. For the absorption process, the same authors developed a dynamic model that considers the behaviour of the gas and liquid phases. They also described how to apply this model to the evaluation of kLa from experimental data. In contrast with Dang et al. (1977), only the dynamics of the liquid phase is considered in this work. Assuming a well mixed model, the evolution of the dissolved oxygen concentration can be expressed as: d CO2 dt = k La C* 2 - CO 2 O

By means of Eqn. 1, the kLa can be evaluated from * the slope of E(t) vs [dE(t)/dt], with E(t)=CO2/CO2 , * considering that CO2 is known. However, the deviations of the experimental data with respect to a linear dependence show the influence of the dynamics of the oxygen sensor. In consequence, it is necessary to take into account the sensors own characteristics when processing the experimental data. Figure 2 shows the dynamic behaviour of the sensor employed in the experiments. The experimental data were obtained using a modification of the dynamic method developed by Dang et al. (1977). In this technique first the electrode is first placed in a nitrogen-saturated medium; so, the electrodes signal is zero. After that, a step input is generated by placing the electrode in the reactor, which has the same medium, but saturated with air. The agitation speed should be fast enough to generate high turbulence, so that the diffusion resistance is negligible. In the same Fig., it can be observed that the electrodes dynamics can be represented with a firstorder system, as stated in Eqn. 2.
1.1 1.0 0.9 0.8 0.7 63.21%

Experimental value Theoretical response

CE/CE

0.6 0.5 0.4 0.3 0.2 0.1 0.0 0

tE=8.6 seg
5

16.67 rps Time (sec)

10 15 20 25 30 35 40 45 50 55 60 65 70 75 80

Fig. 2. Determination of the electrodes time constant d C E C O2 - C E (2) = tE dt The time constants found at 16.67 rps were 8.6 seconds with water and 9 seconds with Na2SO4. Equations 1 and 2 constitute the model proposed in this work to interpret the experimental data, with the objective of obtaining kLa values. The analytical solution for these equations is Eqn. 3: CE = C* 2 + O B e- k La t + C e- t / t E 1 - k La t E (3)

(1)

where B and C are integration constants. To evaluate the experimental data, Eqn. 3 was used to approximate the registered oxygen composition values, considering the variables C * 2 , B, C and kLa as O

434

P. JUREZ and J. OREJAS adjusting parameters to minimize the function given in Eqn. 4:
* Exp Pr ed Y CO 2 , B, C, k La = CE - CE i =1

Ei ( t - t) = E( t ) +

1 d E( t) f dt
i

(7)

Equation 7 means that the ideal response E at t= (t-tE), can be estimated from the real response E at The relationships between the adjusting parameters and either the oxygen composition or its first-order t=t. The differentiation of both sides of Eqn. 7 with respect to t gives: derivative are given by Eqns. 5 and 6 respectively: d EO 2 dt B k La e- k Lat C* 2 O d Ei ( t - t ) d E( t ) 1 d2E( t ) = + dt dt f dt 2 Applying this to the mass balance leads to: (6) d Ei E i ( t ) = - ( k L a ) -1 +1 dt (9)

) (
m

(4)

(5)

(8)

E O2 = 1 +

B e- k L at C* 2 O

It was found that the parameter fitting carried out with this technique was strongly dependent on the time intervals associated to the experimental data, the biggest differences arising when the data included the first 10 or 15 seconds after the gas exchange. This generates composition profiles with curvatures that do not correspond to the real ones. The best results were obtained when using the values in the following range, which has been recommended by Merchuk et al. (1990): 0.3 C < CE < C . C  is the final stabilized E E E oxygen concentration value read from the electrode. Figure 3 shows the experimental composition profile resulting after applying the fitting and the proposed correction, using Na2SO4 as liquid medium.

Figure 4 shows a comparison between the kLa values obtained with Koizumi and Aiba (1984) - a method that requires evaluations of the first and second order derivatives of the experimental data - and the coefficients resulting from this work (Eqns.1 to 6). It can be observed that the values resemble each other because the plots generated with both techniques have similar slopes.
1 .0

Water. 1.5 vvm Two turbin es 300 r.p.m. Ko izumi and Aiba (1984) (Eqn . 9)

0.8

E=CExp/C* O2

0.6

(-k a)-1
L

This work (Eqn . 6)

0.4

CEx103 [kg.m-3]

Prediction (Eqn. 3) Experimental data

experimental value
0.2 0.000 0.001 0.002 0.003 0.004 0.005 0.006

dE /d t

SO 4 Na 2 1.5 vvm. 800 rpm. Two turbines

20 40 60 80 1 00 1 20 1 40

Fig. 4. Comparison between correction techniques for the evaluation of kLa 3. Results Different authors have analysed the validity of the dynamic method developed by Dang et al. (1977) for the experimental evaluation of the kLa (Linek et al. (1987) and Moucha et al. (1995)). As established in the literature, the dynamic models that assume ideal mixing in both phases fail to describe the gas mixing when Dangs method is used, producing lower or higher kLa values with non-coalescent or coalescent mediums, respectively.

O2

Time (sec)

Fig. 3. Composition profile of oxygen There are other alternatives to evaluate the experimental data. Koizumi and Aiba (1984) proposed to include the effects of the electrodes response over i E(t), by defining a new function E (t), and considering i i E (t) equal to E(t) if the sensor was an ideal one. E (t) is defined as shown in Eqn. 7:

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3.1 kLa as a Function of (PG/VL) and <vG>: As shown in Table 1, the exponents of the specific 3.1.1 Coalescent liquid (water) power (n1) and the superficial gas rate (n2) are similar The expressions found for the kLa as a function of to the values found in the bibliography when working the superficial air rate and the specific power are: with the same medium. For one turbine: P k L a = 1.11x10 -3 G V L For two turbines: k L a = 9.954x10
-4

0.9504

< v G > 0.6282

(10)

Table 1. Constants for

P k L a = n0 G V L
Author This work : E (10) qn.

< vG > n
Nt n0 x 10 1 2 1 1 3 1.11 4.95 3.84 1.76 14.60 14.41 10.36 43.31 5.3 15 10.40 26.0
3

n1

PG V L

1.0006

< v G > 0.6532

(11)

n1

n2

0.9504 0.6282 0.593 0.654 0.726 0.4 0.611 0.606 0.67 0.58 0.55 0.59 0.475 0.4 0.4 0.4 0.4 0.35 0.554 0.556 0.56 0.7 0.32 0.55 0.4 0.5

Figures 5 and 6 show the results obtained for one Eqn. (11) and two impellers, respectively. As is clear from the plots, kLa depends on both variables, bearing a close Linek et al. (1987) resemblance to the correlations found in the Linek et al. (1991) bibliography. Linek et al. (1994)
Wu et al . (19 95) ( k=0.56 ) Mouc ha et al . (19 95) ( k=0.55 4)

0.9954 1.0006 0.6532

1
Thi s w ork (k=0 .628 2) Ex peri m e nta l val ue

Robinson and W ilke 1 (1973) M oucha et al. (1995) 1 2 Wu (1995) Wu et al. (1998) 1 2

kLa/<vG>

Li nek et al . (19 91) (k =0.4) Li nek et al . (19 87) (k =0.4)

Stenberg and Andersson 1 (1987) Nocentini et al. (1993) 4 Smith et al. (1977) 1 1 van Rieth (1979)

0.1

1000

PG /VL [W/m ]

-3

Fig. 5. Comparison of kLa values with correlations obtained by other methods, using water and one turbine
T his w ork: Experi m ent al valu e ( k=0.6 532)
Mo uch a et al. (19 95) (k =0 .556)

) 3.1.2 Non-coalescent liquid (Na2SO4 0.5 M Following the same lines that had been taken for water, relationships between the kLa and both the superficial gas velocity and the specific power were obtained: For one impeller: P k L a = 1.09x10 3 G V L For two impellers: P k L a = 8.12 x10 4 G V L
1.0775

kLa/<vG>

No cen tini et al . (1 99 3 ) (k =0 .55) Lin ek et al. (19 9 4) (k =0 .4 0 )

1.029

< vG > 0.723

(12)

0.1
G

1000 P /V [W.m ]
L -3

< vG >0.6875

(13)

Fig. 6. Comparison of kLa values with correlations obtained by other methods using water and two turbines 436

P. JUREZ and J. OREJAS Equations (12) and (13) are shown in Figs. (7) and (8), respectively. In the same figure, Moucha and Lineks correlations, calculated for sulphate solutions and geometrically similar reactors, were plotted. As revealed in the figures, the results from Linek with both the start-up and the dynamic pressure methods could be compared with those from this work, where Dangs method was used. Author This work : Eqn. (12) Eqn. (13) Linek et al. (1987) Linek et al. (1991) Linek et al. (1994) Robinson and Wilke (1973) Moucha et al. (1995) vant Riet (1979) Smith et al. (1977) Nt 1 2 1 1 3 1 1 2 1 1 n0 x 10 1.09 0.812 1.35 0.311 0.416 0.579 0.440 2.0 20.0
3

This work: experimental value

kLa/<vG>

0.723

=1.09x10 (PG/VL)

-3

1.029

n1 1.029 1.0775 0.946 1.24 1.21 0.9 1.2 1.188 0.7 0.475

n2 0.723 0.6875 0.4 0.4 0.4 0.39 0.439 0.3895 0.2 0.4

Linek et al. (1991)

kLa/<vG>

Moucha et al. (1995)

3.2 Analysis of the kLa Values Obtained in Both Mediums

Linek et al. (1987) Na2 SO 4, (Eqn. 12)

PG/VL [W.m ]

-3

kLa/<vG>

1000

Fig. 7. Comparison of kLa values with correlations obtained by other methods (Na2SO4, 1 turbine)

Water, (Eqn. 10)

1000 Moucha et al. (1995)

PG /VL [W.m ]

-3

Linek et al. (1994)

Fig. 9. Comparison of kLa values measured in both mediums In Fig. 9 the influence of the medium properties over the kLa value when using one turbine is shown. Some authors have studied this effect (Robinson et al. (1973) and Linek et al. (1987)). They found that by adding a small amount of solute to the water, the bubbles size is reduced, even if the other properties are kept constant. For electrolytic solutions, this behaviour is attributed to the electric effect of the concentration gradient of the ionic species on the gasliquid interface, which causes a decrease in the coalescent rate of the bubbles and an increase in the kLa for the same specific power. Identical results were obtained with two impellers.

kLa/<vG>

1
This work: experimental value

kLa/<vG>0.687=8.12 x 10-4 (PG/VL)1.077

1000

Fig. 8. Comparison of kLa values with correlation obtained by other methods (Na2SO4, 2 turbines)

PG/VL [W.m ]

-3

In table 2, there is a summary of the results from different sources, always using Na2SO4 solutions. In 3.3 Analysis of the kLa Values Obtained Using One this table one can notice the similarities between these and Two Impellers In turn, the influence of the number of impeller reports and this work for n1 and n2. was also analysed for each liquid, i.e. water and sulphate solutions. Table 2. Constants for A significant difference between the mediums could be observed. In water there is an increment of n P 1 the kLa value calculated with two turbines (Fig. 10), n k L a = n 0 G < vG > 2 V but if the liquid is sulphate solutions, the almost the L same values are obtained (Fig. 11). This can be explained assuming that the upper turbine is used to 437

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disperse the bubbles from the lower impeller (Wu et al., 1998). In coalescent solutions, such as water, the upper turbine breaks the bubbles and produces an increase in the kLa, while in sulphate solutions there is no change in the bubble size and as result, the second turbine has no effect.
Experimental value (1 turbine) Experimental value (2 turbines)

those obtained by Moucha and Linek, especially for sulphate solutions. The influence of the medium properties and the number of impellers were analysed. It was found that the kLa augments with two turbines and this increase is greater in a coalescent liquid (e.g. water). The same effect is produced when the bubble size is decreased, that is, when there is a raise in the capacity of the medium to inhibit the coalescence of the bubbles. Nomenclature B integration constant C integration constant -3 C E theoretical oxygen concentration, kg.m

kLa/<v G>

2 turbines 1 1 turbine

CE CE
1000

Exp Pr e

experimental oxygen concentration, kg.m predicted oxygen concentration, kg.m

-3

-3

Fig. 10. Comparison of kLa values measured in water for one and two turbines

P G/V L [W.m-3]

CE CO
CO
*

final stabilized oxygen concentration, kg.m liquid phase oxygen concentration, kg.m
2
2

-3

-3

Experimental vlaue (1 turbine) Experimental value (2 turbines)

2 turbines

1 turbine 1

1000

P G/VL [W.m-3]

Fig. 11. Comparison of kLa values measured in Na2SO4 for one and two turbines 4. Conclusions

saturation concentration of dissolved oxygen, -3 kg.m E(t) dimensionless liquid phase oxygen concentration * E O 2 CO2/CO2 , experimental dimensionless liquid phase oxygen concentration (Eqns. 5 y 6) i E (t) ideal output for E(t) (Eqns. 7 y 8) -1 f electrode sensitivity, s H liquid height from the bottom, m kLa volumetric mass transfer coefficient for -1 oxygen, s l position of the first agitator from the bottom, m Nt turbines number power dissipated under aeration conditions, W PG t time, s. -1 <vG> superficial gas velocity, m.s 3 volume of liquid in the reactor, m VL Greek signs time constants, s tE objective function Y References

Bandyopadhyay, B., A.E. Humphrey and H. Taguchi, Dangs dynamic method was applied to determine Dynamic measurement of volumetric oxygen the kLa based on the liquid volume, using either water transfer coefficient in fermentation systems. or aqueous sulphate solutions (0.5M). The Biotechnol. Bioeng.IX, 533-544 (1967). concentration curves were corrected to take into Dang, N.D.P., D.A. Karrer and I.J. Dunn, Oxygen account the electrodes own dynamics, employing a transfer coefficients by dynamic model moment new technique which yielded almost the same values analysis, Biotechnol. Bioeng. XIX, 853-865 as Koizumi and Aiba (1984). The results were (1977). correlated with the superficial gas velocity and the Koizumi, J. and S. Aiba, Reassessment of the specific power and this correlation was compared to dynamic kLa method, Biotechnol. Bioeng., others from different authors. The expressions for the XXVI, 1131-1133 (1984). kLa estimated with these variables was very similar to Linek V., V. Vacek and P. Bene, A critical review and experimental verification of the correct use of 438

kLa/<v G>

P. JUREZ and J. OREJAS the dynamic method for the determination of oxygen transfer in aereated agitated vessels to water, electrolyte solutions and viscous liquids, Chem. Eng. J., 34, 11-34 (1987). Linek, V., P. Bene and V. Vacek, Dynamic pressure method for kLa measurements in large-scale bioreactors, Biotechnol. Bioeng. 33, 1406-1412 (1989). Linek, V., J. Sinkule and P. Bene, Critical assessment of gassing-in methods for measuring kLa in fermentors, Biotechnol. Bioeng., 38, 323330 (1991). Linek, V., T. Moucha, M. Douov and J. Sinkule, Measurement of kLa by dynamic pressure method in pilot-plant fermentor, Biotechnol. Bioeng., 43, 477-482 (1994). Merchuk, J.C., S. Yona, M.H. Siegel and A. Ben Zvi, On the first-order approximation to the response of dissolved oxygen electrodes for dynamic kLa estimation, Biotechnol. Bioeng. 35, 1161-1163 (1990). Moucha, T., V. Linek and J. Sinkule, Measurement of kLa in multiple impeller vessels with significant axial dispersion in both phases, Trans IChemE, 73, part A, 286-290, (1995). Nocentini, M., D. Fajner, G. Pasquali and F. Magelli, Gas-liquid mass transfer and holdup in vessels stirred with multiple Rushton turbines: water and water-glycerol solutions. Ind. Eng. Chem. Res. 32(1), 19-26 (1993). Robinson C.W. and C.R. Wilke, Oxygen absorption in stirred tanks: A correlation for ionic strength effects, Biotechnol. Bioeng. XV, 755-782 (1973). Smith, J.M., K. vant Riet and J.C. Middleton, Proc. 2nd Eur. Conf. on Mixing, St. Johns College, Cambridge, England, BHRA Fluid Eng., Cranfield, England, F4-51, (1977) Stemberg, O. and B. Andersson, Gas-liquid mass transfer in agitated vessels-II. Modelling of gasliquid mass transfer, Chem. Eng. Sci. 43(3) 725730 (1988). vant Riet, K., Review of measuring methods and results in non-viscous gas-liquid mass transfer in stirred vessels, Ind. Engng Chem. Process Des. Dev., 18, 357-364 (1979). Wu, H., An issue on applications of a disk turbine for gas-liquid mass transfer, Chem. Eng. Sci. 50, 2801-2811 (1995). Wu, H., V. Arcella and M. Malavasi, A study of gasliquid mass transfer in reactors with two disk turbines, Chem. Eng. Sci. 53(5), 1089-1095 (1998). Acknowledgements The authors wish to acknowledge the support given by the Secretara de Ciencia y Tcnica of the Universidad Nacional de Ro Cuarto (UNRC) and by the Agencia Crdoba Ciencia (ACC) - Argentina.

Received September 2, 1999. Accepted for publication March 27, 2001. Recommended by A. Bandoni. 439

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