Determination of Oxygen Absorption Rate To estimate the design parameters for oxygen uptake in a fermenter, the correlations can

n be used which can be applicable to a wide range of gas liquid systems in addition to the air water system. However, the calculation procedure is lengthy and the predicted value from those correlations can vary widely. Sometimes, it may be unable to find suitable correlations which will be applicable to type and si e of fermenters of the choice. !n such cases, one can measure the oxygen transfer rate or use correlations based on those experiments. The oxygen absorption rate per unit volume qa " # can be estimated by
qa = K L a &C % L C L $ = k L a &C % L C L $

Since the oxygen is sparingly soluble gas, the overall mass transfer coefficient ' ( is equal the individual mass transfer coefficient k(. )ur ob*ective in fermenter design is to maximi e the oxygen transfer rate with the minimum air flow rate . To maximi e the oxygen absorption rate, we have to maximi e k ( , a, +%( ,+( . However , the concentration difference is quite limited for us to control because the value of +% ( is limited by its very low maximum solubility. Therefore, the main parameters of interest in design are the mass transfer coefficient and the interfacial area. Table Solubility of )xygen in -ater at . atm .a Temperature Solubility / + mmol )0" l / 0..2
./ .6 0/ 06 8/ 86 7/
a

1g )0"l 34.2 67.6 74.8 77.0 7/.8 85.. 87.4 88./

..5/ ..67 ..82 ..03 ...3 ../4 ../8

9ata from international +ritical Tables , :ol.!!!, ;ew <ork = 1c>raw Hill ?ook +o., .402 , p.05.. Table lists the solubility of oxygen at . atm in water at various temperatures. The value is the maximum concentration of oxygen in water when

Table Solubility of )xygen in Solution of Salt or @cid at 06/+.a +onc. Solubility, mmol)0"l 1ol"l H+l H0S)7 ;a+l /./ ..03 ..03 ..03 /.6 ..0. ..0. ../5 ../ ...3 ...0 /.24 0./ ...0 ../0 /.5. a 9ata from A. Todt, Blectrochemishe Sauerstoffmessunge, ?erlin= -.de >uy C +o., .462. !t is in equilibrium with pure oxygen . This solubility decreases with the addition of acid or salt as shown. ;ormally, we use air supply the oxygen demand of fermenters. The maximum concentration of oxygen in water which is in equilibrium with air +%( at atmospheric pressure is about one fifth of the solubility listed, according to the HenryDs law

C %L =

po 0 H o 0 &T $
&T$

HenryDs constant of oxygen at a temperature ,T. The value of HenryDs law constant can be obtained from the solubilites listed in table. Aor example, at 06 /+ , +%( is ..03 mmol"l and po0 is . atm because it is pure oxygen.
-here po0 is the partial pressure of oxygen and Ho 0
is / ?y substituting these values into Bq. we obtain Ho0 &06 +$ is /.548 atm l"mmol. Therefore

The equilibrium concentration oxygen for the air water contact at 06/+ will be
/.0/4atm = /.037mmolO0 " l = 2.78mg " l /.548atml " mmol

C %L =

!deally, oxygen , transfer rates should be measured in fermenter which contains the nutrient broth and microorganisms during the actual fermentation process. However, it is difficult to carry out such a task due to the complicated nature of the medium and the ever changing rheology during cell growth. @ common strategy is to use a synthetic system which approximates fermentation conditions.

Sodium Sulfite Oxidation Method

The sodium sulfite oxidation method &+ooper et al., .477$ is based on the oxidation of sodium sulfite to sodium sulfate in the presence of catalyst &+uEE or +oEE $as
. + + orCO + + Na 0 SO8 + O0 Cu Na 0 SO7 0

This reaction has following characteristics to be qualified for the measurement of the oxygen transfer rate= .. The rate of this reaction is independent of the concentration of sodium sulfite within the range of /./7 to . ;. 0. The rate of reaction is much faster than the oxygen transfesr rate F therefore the rate of oxidation is controlled by the rate of mass transfer alone. To measure the oxygen transfer rate in a fermenter,fill the fermenter with a . ; solution containing at least,/.//8 1 +uEEion.Turn on the air and start a timer when the first bubbles of air emerge from the sparger. @llow the oxidation to continue for 7 to 0/ minutes, after which, stop the air stream, agitator, and timer at the same instant. @nd take a sample. 1ix each sample with an excess of freshly pipetted standarad iodine reagent. Titrate with standard sodium thiosulfate solution &;a 0S0)8$ to a starch indicator end point. )nce the oxygen uptake is measure, the k (G may be calculated by using Bq. where +( is ero and +%( is the oxygen equilibrium concentration. The sodium sulfite oxidation technique has its limitation in the fact that the solution cannot approximate the physical and chemical properties of a fermentation broth. @n additional problem is that this technique requires high ionic concentrations & . to 0 mol " l$ , the presence of which can affect the interfacial area and, in a lesser degree, the mass transfer coefficient &:anDt Hiet, .454$. However, this technique is helpful comparing the performance of fermenters and studying the effect of scale up and operation conditions.

Example To measure k(a a fermenter was filled with ./ l of /.6 1 sodium sulfite solution containing /.//8 1 +uEE ion and the air sparger was turned on. @fter exactly ./ minutes, the air flow was stopped and a ./ ml sample was taken and titrated. The concentration of the sodium sulfite in the sample was found to be /.0. mol "l . The experiment was carried out at 06/+ and . atm . +alculate the oxygen uptake and k(a

Solution:

The amount sodium sulfite reacted for ./ minutes is /.6 , /.0. I /.04 mol "l @ccording to the stoichiometric relation, Bq. the amount of oxygen required to react /.04 mol"l is
/.04 . = /..76 mol"l 0

Therefore, the oxygen uptake is

&/..76moleO0 " l $ &80 gO0 " mol $ = 5.58 ./ 8 g " ls &3// s $

The solubility of oxygen in equilibrium with air can be estimated by Bq. @s

C %L =

pO 0 &.atm$&/.0/4molO0 " molair $ = = 2.78 ./ 8 g " l H O 0 &T $ &548atml " mol $&.mol " 80 g $

Therefore, the value of k(a is, according to the Bq.

KLa = q a " 5.58 ./ 8 g " ls = = /.4.5 s . C % L C L &2.78 ./ 8 g " l /$

Dynamics

assing out Techni!ue

This technique &:anDt Hiet, .454$ monitors the change of the oxygen concentration while an oxygen rich liquid deoxygenated by passing nitrogen through it. Jolarographic electrode is usually used to measure the concentration. The mass balance is a vessel gives
dC L &t $ = k L a[ C % L CL&T $] dt

!ntegration of the preceding equation between t. and t0 results in

[ C %L CL&t. $]
kLa = C % L CL &t 0 $ t 0 t.

Arom which k(G can be calculated based on the measure values of +(&t.$ and +(&t0$ Direct Measurement !n this technique, we directly measure the oxygen content of the gas stream entering and leaving the fermenter by using gaseous oxygen analy er. The oxygen uptake can be calculated as
qa = &Qin C O 0 , in Qout C O 0 , out

-here K is the gas flow rate. )nce the oxygen uptake is measured, the k(G can be calculated by using Bq. where +( is the oxygen concentration of the liquid in a fermenter and +% ( is the concentration of the oxygen which would be in equilibrium with the gas stream. The oxygen concentration of the liquid in a fermenter can be measured by an on,line oxygen sensor. !f the si e of the fermenter is rather small &less than 6/ l $ , the variation of the +% (,+( of the inlet and outlet of the gas stream can be used us

&C % L C L $ LM =

&C % L C L $ in &C % L C L $ out ln[ &C % L C L $ in "&C % L C L $ out ]

Dynamic Techni!ue ?y using the dynamics technique &Taguchi and Humphrey,.433$,we can estimate the k (G value for the oxygen transfer during an actual fermentation process with real culture medium and microorganisms. This technique is based on the oxygen material balance in an aerated batch fermenter while microorganisms are actively growing as
dC L k L a &C % L C L $ rO 0 CX dt

-here r)0 is cell respiration rate Lg)0 "g cell hM. -hile the dissolved oxygen level of the fermenter is steady, if you suddenly turn off the air supply, the oxygen concentration will be decreased with the following rate

dC L = rO 0 C X dt

Since k(a in Bq. is equal to ero . Therefore, by measuring the slope of the + ( vs. t curve, we can estimate r)0 +N.!f you turn on the air flow again, the dissolved oxygen concentration will be increased according to Bq. which can be rearranged to result in a linear relationship as
C L = C %L . dCL + rO 0 CX kLa dt

"orrelation for #$a

%ubble "olumn @kita and <oshida &.458$ correlated the volumetric mass transfer coefficient k(a for the absorption of oxygen in various aqueous solutions in bubble columns, as follows=
k L a = /.3 D AB
/.6

/..0

/.56

-hich applies to columns with less effective spargers. !n bubble columns, for /O:sO/..6m"s and .// OJg"#O..//-"m 8, ?otton et al.&.42/$ correlated the k(a as
g " kLa = /./2 2//
/.56

-here Jg is the gas power input, which can be calculated from

!s = 2// /..
g /.56

Mechanically Agitated &essel Aor aerated mixing in aqueous solution, the mass transfer coefficient is proportional to the power consumption &(opes 9e Aigueiredo and +alderbank, .452$ as
k L (
m

" )

/.88

Therefore, k(a will be

m k L a
/.55

!s /.6

;umerous studies for the correlations of k(a have been reported and their results have the general form as
k L a = ". m !s " 8
"0

-here b., b0 and b8 vary considerably depending on the geomentry of the system, the range of variable covered, and the experimental method used. The values of b0 and b8 are generally between / to . and /.78 to /.46, respectively, as tabulated by Sideman et al. &.433$.

:anDt Hiet &.454$ reviewed the data obtained by various investigator sand correlated them as follows= .. Aor PcoalescingD air water dispersion,
k L a = /./03 m !s /.6
/.7

0. Aor PnoncoalescingQ air electrolyte solution dispersions,

k L a = /.//0 m !s /.0
/.5

?oth of which are applicable for the volume up to 0.3 m8F for a wide variety of agitator types, si es, and 9!"9T rations= and 6// O Jm"# O./,/// -"m8. These correlations are accurate within approximately 0/ percent to 7/ percent.

Example Bstimate the volumetric mass transfer coefficient k(a for the gas liquid contactor using the correlation for k(a. The reactor volume # is ..78 m8, the superficial gas velocity :s is /.//863 m"s and power consumption Jm is 325 -

Solution: ?y substituting these values into Bq.

325 k L a = /./03 ..78
/.7

/.//863 /.6 = /./.2 s .