Gas-liquid mass transfer

Gas-liquid mass transfer

Chapter 10 (Section 10.1)

Why is gas-liquid mass transfer important? The kla concept

theory measurements correlations

Oxygen obviously needs to be transported in aerobic cultivations

1.

Oxygen requirements
Organism Specific oxygen requirement (mmol/g h)

For direct energetic reasons

Respiratory chain oxidation of NADH coupled to ATP synthesis XNADH + 0.5 O2 + ADP H2O + XNAD+ ATP

Aspergillus niger

2.

To maintain desired metabolism and avoid fermentation

e.g. in E. coli / S. cerevisiae

Penicillin chrysogenum

3.9

Klebsiella aerogenes

3.

To avoid induction of undesired enzymes

Saccharomyces cerevisiae 8

Solubilities of gases
Table 10.1. Henry's constant for some gases in water at 25 C. Compound A HA (atm L mole-1) Ammoniaa 17.1 10-3 Methane 745.5 Ethane 545.1 Carbon dioxide 29.7 Oxygen 790.6 Hydrogen 1270.0 a At a concentration of 0.2 g L-1 in the aqueous phase.

Example
Typical aerobic process
C 6 H 12 O6 + 2.16O2 + 0.7316 NH 3 3.658CH 1.8 O0.5 N 0.2 + 2.342CO2

YXO 0.77

g/g

For a biomass concentration of 10 g/l and a specific growth rate of 0.2 h-1 we have qO = 1.54 g/l h = 48 mmol/l h. In an oxygen saturated water solution the oxygen will be consumed within 12 sec!

Minimum desirable oxygen concentrations

Organism Critical oxygen concentration (mg/l)

Gas-liquid mass transfer

Gas bubble Well mixed Bulk fluid Liquid film Cell

E. coli

0.3

Penicillin chrysogenum

0.4

S. cerevisiae

0.6

O2

Candida utilis

How does oxygen transfer occur?

pA Gas film pA,i
Gas bubble

Liquid film

pA

Gas film pA,i

Liquid film

cA,i

Bulk liquid cA

Gas bubble
Gasbubbla Vtskefilm Vlomblandad vtskefas Cell

cA,i

Bulk liquid cA
Interface

O2

Interface

Diffusion
Ficks (first) law of diffusion
Gradient for Compound i (mol/m4) ji

Mass flux through a surface

n Normal vector

ji = Di ci

Flux vector Diffusivity for compound i (m2/ s) Flux vector for compound i (mol/m2 s) Transfer through the surface A

Surface A

j
A

ndA

One-dimensional case
Direction of transport

Conceptual models for kl,

Film theory (Nernst, 1904)
kl D the film thickness is typically 0.1 mm

dc ci = i dz

Penetration theory (Higbie, 1935)

kl D0.5

Film thickness =

Surface renewal theory (Danckwerts, 1951)

kl D0.5

ji = Di

c c dci = Di i , sat i ,bulk dz

Alternative description
ji = kl (ci.sat ci.bulk )
Mass transfer coefficient (m/s) Comparsion with the diffusion equation gives:

kLa consists of kL and a..

qO 2 = kl a(C * Cb )
mt
specific surface area (m2/m3)

saturation conc.

bulk conc.

kl =

Di

mass transfer coefficient (m/s)

He 6 a= Henrys law db i.e. a depends on bubble diameter and gas hold-up

Ci =
*

pi

Gas hold up,

Two possible definitions; gas volume divided by liquid volume or divided by total volume

How big is a bubble?

Bubble break-up

Bubble break-up

Vg Vl

d =

Vg Vl + V g

Coalescence

Coalescence

How big is a bubble?

Two competing processes:
Bubble break-up and coalescence

Bubble size is determined by a balance of surface tension forces and shear forces
s = k1
Shear stress Surface tension stress
1 2 3

d b ,max

What factors can be expected to influence?

viscosity, surface tension, power dissipation, gas flow rate

Balance between surface tension forces and shear stress (turbulent shear) gives the maximum stable bubble diameter

s = k 2 l3

Pg Vl

2 d b3
d b ,max = k

From Kolmogorovs theory of turbulence

(P

Vl ) l0.2
0.4

0.6

The specific surface area (based on total volume) is given by:

ad =

6 d mean

0.4

Typical correlation for estimation of kla

Pg kl ad = kus V l

We therefore get the following expression for the specific surface area

ad =

6 l Pg k 0.6 Vl

Since the gas-hold up can be expected to be a function of the gas flow rate or superficial gas velocity, we get:

Pg a d = ku s V l

Superficial gas velocity Specific power dissipation

Surface tension is affected by the ionic strength

Mean Sauter diameter (mm)
5 4 3 2 1 0 0,01

Correlations for kla

Medium Coalescing k 0.025 0.00495 0.01 0.026 0.0018 0.02

0.5 0.4 0.4 0.5 0.3 0.4 0.2

0.4 0.593 0.475 0.4 0.7 0.475 0.7

Agitator Six-bladed Rushton turbine Six-bladed Rushton turbine Various agitators Not specified Six-bladed Rushton turbine Various agitators Not specified

Reference MooYoung and Blanch (1981) Linek et al. (1987) Moo-Young and Blanch (1981) van't Riet (1979) Moo-Young and Blanch (1981) Moo-Young and Blanch (1981) van't Riet (1979)

Noncoalescing

0,1

1
-1

0.002

Ionic strength (moles L )

Measuring kla
Direct method Dynamic method Indirect methods using model chemical reactions (e.g. sulphite method) Radioactive tracers

The direct method

Partialtryck av syre i ingende och utgende gas

poin vgas
Fldeshastighet av gas

poout

co
Lst syre i vtskan

t qO =

1 Vl

in in out out pO v g pO v g RT in RT out

kl a =

t qO c cO * O

The dynamic method

Luft/Kvve

The sulphite method

Tillstt initialt sulfitlsning Provtagning

ndring av ingende gas

co
Flj ndringen av lst syre som funktionav tiden

1 2 SO 2 SO 3 O 2 = 0 4 2

dcO * = kl a(cO cO ) + qO dt

kl a =

qso3 qo = * * co co 2(co co )

The hydrogen peroxid method

partialtryck av syre i ingende och utgende gas Vteperoxidlsning

vH2O2

poin vgas

poout

Fldeshastighet av gas

co
Lst syrehalt

2 H 2 O2 catalase 2 H 2 O + O2

kl a =

f f vH 2 O 2 cH 2 O2 * 2Vl (co co )