D.

of
Journal Moutafchieva, D. Popova,
Chemical Technology M.Metallurgy,
and Dimitrova, 48,
S. Tchaoushev
4, 2013, 351-356

EXPERIMENTAL DETERMINATION
OF THE VOLUMETRIC MASS TRANSFER COEFFICIENT
D. Moutafchieva, D. Popova, M. Dimitrova, S. Tchaoushev

University of Chemical Technology and Metallurgy Received 16 April 2013
8 Kl. Ohridski, 1756 Sofia, Bulgaria Accepted 15 May 2013
E-mail: dmoutaf@uctm.edu

ABSTRACT

The volumetric mass transfer coefficient (kLa) is often used in order to compare the efficiency of bioreactors
and as an important scale-up factor. In bioreactors, a number of methods are available for estimation the overall
volumetric oxygen mass transfer coefficient: the dynamic method, the steady-state method based on a preliminary
determination of the oxygen uptake rate, the gaseous oxygen balance, the carbon dioxide balance. Each method
provides a different estimation of the value of kLa. We examined the sensitivity of the various methods and compare
the kLa values obtained in order to select the most suitable method as a function of the type of bioreactor used. In
this work we applied dynamic gassing-out method for measuring the volumetric mass transfer coefficient kLa in
three type gas-liquid reactors (stirred tanks, bubble columns and airlift). Тhe aim of this work is on the basis of our
experimental data to obtain several correlations for evaluation of kLa.
Keywords: volumetric oxygen transfer coefficient, bubble columns, CSTR, airlift reactors.

INTRODUCTION biocatalyst’s properties [3].
In aerated systems the critical limiting factor in pro�
Aeration and agitation are important variables to viding the optimal environment is the oxygen transfer
provide effective oxygen transfer rate during aerobic rate (OTR). The mass balance for the dissolved oxygen
bioprocesses. Hence, the knowledge of the volumetric in the well-mixed liquid phase can be written as:
mass transfer coefficient (kLa) is required.�����������
The deter�
dC L
mination of kLa in a bioreactor is essential in order to = k L a (C L∗ − C L ) − rO2 = OTR − OUR (1)
establish its aeration efficiency and to quantify the effects dt
of operating variables on oxygen supply. When oxygen uptake rate, OUR = 0, the oxygen
Oxygen transfer in aerobic bioprocesses is essential mass balance in the liquid phase can be simplified to:
and any shortage of oxygen vastly affects the process
dCL
performance. Therefore, oxygen mass transfer is one = k L a (CL∗ − CL=
) OTR (2)
of the most important phenomena in the design and dt
operation of mixing-sparging equipment for bioreactors or
[4]. It can be described and analyzed by means of the the oxygen mass transfer rate can be described as
volumetric mass transfer coefficient, kLa. The values of proportional to the concentration gradient. For aerobic
kLa are affected by many factors, such as geometrical and fermentation the maximum value of the concentration
operating characteristics of the reactor (type of impeller,
gradient is limited due to the low solubility of oxygen.
the geometry of the bioreactor, the agitation speed and
Therefore, the maximum mass transfer rate from the gas
the air flow rate), media composition and properties,
concentration and microorganism’s morphology and
to the liquid in the bioreactor can be estimated by kL a.CL∗,

351

Hence a plot of of Integrating:  C∗ − CL1  ln  ∗L   CL − CL 2  CL 2 t 1 ∫( CL1 ∗ CL − CL dC = kL a ∫ dt ) 0 (3) vs.0. Nongassing period must be short and Biological OUR independent of DO concentration. and 0 .5 Minutes Pilot plant oxidation chemical enhancement.1 Minutes >100 ml response time of the electrode.1 Minutes Any scale method with necessary and response time must be high OUR considered For large scales. Hydrodynamic changes may disturb the microbial metabolism. Biological OUR is independent from DO Biological dynamic concentration. catechol A nonrespiring system can be employed to simulate the fermentation broth. where 0 . the assumptions of well- mixed gas and liquid phase may not be valid. Change of the coalescence behavior. Salt addition does not alter the hour pH mass transfer rate of CO2. This method is fairly labor intensive.0. No 0-0.102 Assay Scale method Assumptions/Drawbacks [s-1] time applied The rate of reaction is assumed to be zero order in sulfite.1 Minutes Any scale Invasive probes are necessary and gassing out response time must be considered.3 Hours >100 ml analysis the difference between Fin and Fout may be very small because of the short contact time The accuracy depends on the precision of oxygen analyzer 352 .8 Minutes < 100ml small scales.0. limited to oxidation of < 0. τr.t C  L − CL2  depending on whether the determination is made in the Table 1.3 Hours oxidation scale coalescence properties. diffusion coefficient. t should result in a straight line of slope kL a . Possible alteration of the Chemical 0 . Gassing time can be significant at larger scales High DO concentration is necessary. Assumptions about kinetic reaction must Absorption Laboratory be made. Invasive probes are 0 . Methods for volumetric mass transfer coefficient determination [2]. 48.1 Minutes of CO2 scale driving force. (4) METHODS ∗  CL − CL1  The methods for measuring the kLa can be classified ln  ∗  = kL a.0. is a critical parameter.0.0. Measurement kLa. 2013 as CL∗ is the saturation concentration in the liquid phase. Hydrazine Hydrazine does not accumulate. 4. complex kinetics boundary layer reduction. Alteration of driving Sulfite Laboratory force. The Physical Dynamic 0 . Bio- Available of oxidative enzyme. Journal of Chemical Technology and Metallurgy. Dynamic Assumptions about kinetic reaction must Half an measure of 0 -0 . This method may not be the best Gas phase choice in case of small bioreactors.03 Any scale be made. Dynamic 0 .

761 −0. method as described by Benyahia and Jones [14]. gas flow during absorption/desorption process. Moutafchieva. integration of equation with CL= 0 at t = 0 gives: in the gas used.82 [7] column water Hikita et al Bubble Air- k L a = 14.1 −2 External = [10] water loop Airlift Karimi et al Air- k L a 0. The air flow and from biological methods . 79 [1 + Ad /Ar ] U G0. measured until equilibrium was reached.971 Air- Mirόn et al Internal k L a = 0.02 µ L−0. In Table 1 are summarized methods for the The k La was determined by physical dynamic volumetric mass transfer coefficient determination.1107 [1 + Ad /Ar ] U G0.0U G2/3 µ −2/3 = −4 Akita and Bubble Air- k L a = d c0.76 [8] column water Bubble 0. 0296U G0.10−3 ( Ptot /VL ) 1.7 Yoshida [6] column water Deckwer et al Bubble Air- k L a = 0.60σ −1.17U G0. and concentration to a level below saturation.cellular respiration. 081.08 µG0.8979 −2 Internal = [11] water loop Sánchez Airlift 0. CL ( t ) = C*L    t  353 . Corellations for volumetric mass transfer coefficient calculation in the literature.75U G0.c f ( solution) column water Airlift Bello et al Air- k L a 0. Then.85 g 0. The Chemical and biological methods require a reaction in activated sludge liquid was deoxygenated by stripping the liquid phase to reduce the dissolved oxygen (DO) with nitrogen. S.6 Garcia-Ochoa P k= La а 6. D. D.86 Air- Sada et al [9] k L a cU = = G . M.9 DL0.19 Rushton U G0.176U Gr water loop absence of microorganisms (chemical and physical EXPERIMENTAL methods) or in the presence of biomass (biological methods). 66 ×10−4   U G2/3 µ −2/3 Air- and Gomez STR V  water [2] k аL a 17. The was uninterrupted during the switch from nitrogen to physical methods are based on the measurement of the air so that the consistent fluid dynamic conditions were oxygen concentration in the liquid or in the exhaust maintained in the reactor throughout the experiment.24 ρ L0. and in the model for the gas-phase  1 − exp ( −kL a )  description [2]. The When kL a is considered to be independent of time.35 ( rpm/rpmmin ) 1.8+ 0.19 Rushton U G0.168 [13] Internal k L a = 0.549 al [5] water impeller 0.6 Heindel [3] V  water impeller STR Moucha et al Air- k L a = 1.47 Kapic and P Air- Rushton k L a = 0. The most the dissolved oxygen concentration in the liquid was often used chemical method is chemical oxidation. Popova. methods differ in the procedure of gas interchange. Dimitrova. 20 ×10 N 2.549 [4] water impeller STR Yawalkar1 et Air- k L a = 3.056 ( Lc Lh ) 0. Tchaoushev Table 2.837U GR water [12] loop Choi et al Airlift Air- ( Ad Ar ) −0. 04   U G0. nitrogen was replaced by air. Authors Type Corellation System STR 0.

2096.68 1 0.68 1 0.U G0.72 pinched 0. k L a = 0. Stirred tank.06 . d/D ratio = 0.062 m3. 3 m height (Hr). . and dissolved oxygen concentration. 4496.09. Journal of Chemical Technology and Metallurgy.102 0.09 loop 354 .375 k L a = 0.785 0. Experimental results. This method for evaluation of kLa is Bubble columns reactors: the experiments were applicable when assuming a well-mixed liquid phase.2 m and downcomer with Stirred tank reactor: measurements were performed Hd = 2.rps 0.031 0. b) external circulation.5 0. The first one – constant air concentration along the column height and with total volume 50 l and 35 l work volume.8 m and diameter dd = 0.028 0. against the time.375) and 1300 of the straight line obtained from a plot of ln ( C*L − CL ) l (1000 l work volume. a made with 3 different bubble columns. 4637.8858 turbine 50 35 0.rps 0. 4.72 . 48.19 0.8414 Bubble 85 58 3 0.5 0. 0638.6 . where Ad and Ar are downcomer Table 3. d. Ad/Ar = 0.2 0.06 m. the second a fast response of oxygen electrode to a change in the – with 85 l total volume and 58 l working volume.U G1. working volume V = in six pitched turbine stirred fermentors with total volume 0. .165 turbine Stirred tank Six 1300 1000 1. A volume volume d/H Impeller da/d Estimated values for type [l] [l] [m] [m] [m2] kLa Six 50 35 0. d/D ratio = 0. k L a = 0.785 0. The values of kL a were determined from the slope 50 l (35 l working volume.7661 column 1300 1000 1. 2 – manometers. 2013 Fig.U G0.1708 external 0.6 pinched 0. bubble column and airlift reactor were respectively. [m] Ad/Ar with 92 62 3 0. riser with of a dynamic gassing-out method.06 k L a = 1.36 0. Total Work Derived correlation/ Reactor H. 4 – DO probe. 3 – liquid circulation velocity measure.102 0. 1.U G0.8802 Airlift dd.3 k L a = 0. Airlift reactor: measurements have been used to conduct experiments for kLa determination using carried out in the pilot-plant size airlift reactor.1458. k L a = 0. 0147. the third – 1300 l and 1000 l total and work volume. c) bubble column: 1 –air distributor. .36 0. diameter dr = 0.6). Schematic diagram of the airlift reactors with a) internal circulation.06 0.

. Garcia-Ochoa. Gomez. editors. D. Eng. J. Correlating gas–liquid mass dynamic oxygen method is the most widely used. Popova. Experimentally obtained values of kLa��������� �������� in bub� r riser ble column with work volume 1000 l and 35 l are 0. T�������������������������� heir applicability�������� for me� Chem.s-1] numerical results from model solution and the experi� V volume [l] mental data for dissolved oxygen concentration [15]. Chem.m-3] or [-] d diameter [m] The experiments were carried out in STR at 300 rpm kLa volumetric mass transfer coefficient [s-1] stirring speed and gas phase flow rate 0. pitched blade and The steady state sulfite method is not recommended techmix impeller and their combinations. E. other methods are available with a sufficient degree of 840-848. 76 . Kapic. Gas hold- bioreactors with errors less than 10 %. G. D. are given in Table 3. especially in small oxygen probe and a 703P polarographic oxygen meter scale stirred tank reactors. It desalted water and tylozin as a liquid phase. M. Gomez. volume and type of the overview. The most suitable method selectiоn for kLa meas� 2. In: Flickinger C. 12. Zoll. Akita. The probe was located at 300 mm from Nomenclature the bottom of the column at an angle of 450. E. Yawalkar1. Heesink. especially in large L liquid reactors.069 s-1 and 0. W. Deckwer. Can. This method is suitable for large scale 4. M.80. J. 6. F. Biotech. More details media have to be tested.1640. Moutafchieva. over the entire up. Dev. pure oxygen for accurate estimation of the volumetric Pangarkar1. F. The use of 5. Bioreactor scale-up urement requires to take into account the range of and oxygen transfer rate in microbial processes: An the variables as power input. accuracy.25 l/s. reactor. Mixing and 355 . The value H length of the reactor [m] of kLa = 0.245. v. 2009. Tchaoushev and riser cross-sectional area. A. R. Chem. 84. with transfer in a stirred-tank reactor. Proc. as it gives inaccurate values in comparison with the Sci. New York: John Wiley & Sons. 2010. 2002. Burckart. B. Garcia-Ochoa. F. S. G. 27..1846. Versteeg. 58. 153 . V. in the reactor.066 s-1. V. Eng.. and a small degree of approximations for gas–liquid mixing Des. when applied to stirred vessels.176. The 3. 239 . Ind. It Subscripts is obvious that the values of kLa are not so sensible to d downcomer the variation of the input air flow rate in comparison G gas with variation of the agitation speed. E. REFERENCES In Table 3 are presented experimentally obtained correlations for evaluation of kLa. On the base of our experimental data empirical cor� In all experiments as a gas phase was used air and relations were developed for calculation of kLa values. G. Res.M. A3. Prokopova. confgurations-: rushton turbine. Gas hold-up and volumetric The response methods are also found to be satisfactory mass transfer coefficient in bubble columns. Linek. F. 1. mixing time and gas–liquid volumetric mass range of the operating conditions encountered in the transfer coeffcient of various multiple-impeller industrial fermentor operations. 1973. 80. Ad downcomer cross-sectional area [m2] Ar riser cross-sectional area [m2] RESULTS AND DISCUSSION C oxygen concentration [kg. A. other methods applied in industrial scale. respectively [16]. Chem.. T. The oxygen was found that the predicted kLa values were sufficiently concentration is followed with a P2 – type dissolved well comparable with the observed.. A.076 s-1 was obtained by comparison of the U velocity [m. 2003. 1607 . 1839 . respectively. 7. Heindel. dia with high viscosity and non-coalescing fermentation 7. from Uniprobe. Eng. 2006. Gas–liquid mass transfer coefficient in mass transfer coefficient is highly uneconomical when stirred tank reactors. D. K. Yoshida. Encyclopedia of Industrial Biotechnology: CONCLUSIONS Bioprocess. Dimitrova. Bioseparation. characteristics of gas and liquid phase. p. Adv. Moucha. Eng. Des. T. and Cell Technology.

Chem.H.308. Chem. R. 2000. 1993. Kitao. 2013 mass transfer in tall bubble column. 2007. Sci.. 69.J. D. 27-33. Moutafchieva. Chem. I. Des. Lee.. Asai. I. Ind. Chem. Techn. H. K. Т. Fujiwara. D. 3. Comp. airlift reactors. E. 10. H. Karimi. Robinson. Jolodar. 49. D. Techn. and 9. H. M. 73 .. 356 . Petroleum&Coal. Chem. Popova. Bubble column Anal. C. Popova. 1974. Sanchez Miron. RajabPour. D. Тsolov. 22.. Dev. Tchaoushev. Journal of Chemical Technology and Metallurgy. S. Proc. 51 . Sci. The volumetric mass transfer coefficient in gas hold-up. 53-58. 255–261. 1985. Kumazawa. 49. Chisti. A. Chem. Biotech. 4.81. Scale effects on hydrodynamic with suspended sparingly soluble fine particles. García Camacho. and airlift photobioreactors for algal culture. 1. Gas– Biotechn. Choi.58. of Comp. Pentchev. and mass transfer characteristics of external loop Eng. Y. 24. liquid mass transfer characteristics in a bubble column 14. C. 46.1887. N. Sada. 2003.R. F.A. J. 61–67. Hikita. K. 1. Gómez.2188.K. 1. 13. Molina Grima. Lee. Circulation liquid velocity. Moo-young.12. Int. K. Tanigawa.. Eng. W. Contreras a bubble column bioreactor. J.. 2177 . S. A. A. F. J. Eng. 301 . 1985.. investigation of stirred tank bioreactor. 56. Appl. Num. Moutafchieva. Segawa. A. 48. Benyahia. 8. 1981. A. Bakhtiary�������������������������������������� . A theoretical and experimental 11. volumetric oxygen transfer coefficient bubble columns. Тsolov. tion” reactor for H2S removal of acid gas streams. Т. Bello. Jones. Int. AIChE 29. in external-loop airlift reactors. 3. Prediction of 1997. Appl. K. J. the Volumetric Mass Transfer Coefficient in Pneumatic 15. Mass transfer investigations in 12. Tchaoushev. Contactors. 16.. 40. 2008. 1 . 11. Mass ������������������������������������ t������������������������������ ������������������������������� ransfer s��������������������� ���������������������� tudy i��������������� ���������������� n “������������ a����������� utocircula� Num. Eng. Pentchev.. L. Anal. J. J. 1872 . E.W.A.