TOPIC 10

Gas-liquid Systems
Considerations for chemists & engineers
working in process development

Contents

1. Gas-liquid Systems: dispersing gas as bubbles ......................................................... 1

Radial flow impellers ................................................................................................. 1
Example ..................................................................................................................... 3
Axial flow impellers ................................................................................................... 3
Case study: Steam Stripper Improvement ................................................................ 5
2. Gas-liquid reaction systems: lab-scale protocol ........................................................ 7
Definitions of reaction regimes (also see 'Multi-phase Fundamentals') ................... 7
Exponents on variables affecting r ............................................................................ 8
1. Fully-baffled stirred tank ...................................................................................... 9
2. Constant interfacial area cell or ‘model stirred contactor’ .................................. 10
Note on drawdown of gas from the vessel headspace ............................................. 11
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1. Gas-liquid Systems: dispersing gas as bubbles

For turbulent flow systems (Re > 10,000) a whole range of equipment can be used to disperse a
gas phase in a liquid: bubble columns, plate columns, stirred tanks, static mixers, ejectors (or
inductors), plunging jets…

The most common equipment is a stirred tank reactor. In stirred tanks the dispersion of gas into
fine bubbles is possible through the correct design of vessel, sparger and agitator. If the gas is not
dispersed well, a low mass transfer and reaction rate will result this can extend the batch time and
possibly cause a loss in selectivity (from competing side reactions).

Key requirements are:

-The vessel should have baffles
-The gas should be sparged underneath the agitator (at lab-scale use a small diameter, ca. 1 mm,
nozzle just below the stirrer near the center of the flask)
-The agitator should be a radial discharge turbine (or in some cases an up-pumping impeller)

Radial flow impellers

At low impeller speeds, any turbine sparged from beneath will be in the so-called ‘flooded’
condition (figure (a) above). The gas is not well dispersed and the liquid flows around the outer
parts of the blades undisturbed by the gas. The flooding condition should always be avoided.

As the speed is increased the gas will begin to fill the upper part of the vessel (figure (b) above).
When the gas is dispersed to the wall from the plane of the impeller this is called the ‘loaded’
condition. The gas begins to be captured by the vortices behind the blades and form
‘streamlining’ cavities. This results in a loss of power input with respect to the ungassed
condition. The loaded condition is suitable for many commercial scale processes as it
corresponds to good utilization of the liquid volume and relatively high mass transfer at low
power input.

The transition to the ‘completely dispersed’ condition (figure (c) above) is defined as the point at
which gas is dispersed throughout the vessel, including the region below the impeller. This
condition is usually achieved quite easily at the lab-scale but is often not required at the
commercial scale unless. To operate at this condition at commercial scale requires a high power
input and is not a necessary unless the reaction scheme has fast, competing by-product reactions.

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The Rushton turbine is the most common radial flow impeller. In fully coalescing (e.g. air-water)
systems the transitions from flooding-to-loading and loading-to-complete dispersion can be
estimated from:

Flooding-loading transition

Fl  30 Fr (d/T)3.5 (1)

Rearranging for N

N  (Qg.g.T3.5)/(30.d7.5)1/3 (1a)

Loading-complete dispersion transition

Fl  0.2 Fr0.5 (d/T)0.5 (2)

Rearranging for N

N  4.T0.25.Qg0.5/d2 (2a)

Where: gas flow number, Fl = Qg/Nd3

Froude number, Fr = N2d/g.
Qg is the volumetric flow rate of the gas [m3/s].
Reference: Nienow, A.W., Proc. 5th Euro. Conf. Mixing, 1985.

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Example

Could a chlorination reaction requiring 0.167 m3/s of gas be carried out successfully in a 10 m3
(2.34 m diameter) reactor with a 1.17 m diameter agitator at 60 rpm (1 rps)?

Eqtn (1)

Fr = N2d/g = (12 x 1.17)/ 9.81 = 0.12

30 Fr (d/T)3.5 = 30 x 0.12 x 0.53.5 = 0.318 is Fl less than this?

Fl = Qg/Nd3 = 0.167/(1 x 1.17)3 = 0.104 Yes, reactor will work

Eqtn. (2)

0.2 Fr0.5 (d/T)0.5 = 0.2 x 0.120.5 x 0.50.5 = 0.049 < Fl, gas will not be fully dispersed

Or

From Eqtn. (1a)

Minimum speed to overcome flooding:

0.7 rps x 60 = 42 rpm < N, reactor will work

From Eqtn. (2a)

Minimum speed to achieve complete dispersion

1.5 rps x 60 = 90 rpm > N, i.e. between loaded and complete dispersion

Axial flow impellers

Axial flow impellers pumping downwards are not recommended as over a large range of
operating conditions the upward buoyancy forces of the bubbles and downward pumping force of
the impeller compete. This results in a poor gas dispersion and low mass transfer. Over this
range of conditions the loading put on the impeller shaft is also fluctuating and this can cause
shaft failure.

If a downward pumping impeller is to be used the following calculation gives a rough estimate of
the minimum impeller speed for a 4-bladed downward pumping 45º pitched blade turbine.

Nmin = 11.7 Qg / d1.63

For the above example Nmin = 220 rpm i.e. not suitable for example above

Upward pumping impellers have been found to be suited to gas dispersion as they give a more
stable gas dispersion profile. Similar regimes existed as for the radial impellers, i.e. flooded,
loaded and complete dispersion.

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For a 6-bladed upward pumping 45º pitched blade turbine

Minimum speed to overcome flooding is given by:

N  (0.08.Qg / (d5.7.T1.55))0.156

Minimum speed to achieve complete dispersion is given by:

N  ((0.76.Qg)/(d8.T2.8))1/11

For the example above, the minimum speed to overcome flooding is 22 rpm and the minimum
speed to achieve complete dispersion is 36 rpm, i.e. this could be a good impeller type to use for
this application.

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Case study: Steam Stripper Improvement

- Specialty Chemicals Manufacturer with sites in the US and Ireland - dedicated plant
- Bottleneck was a glass-lined stripping vessel - batch cycle time 19 hours
- Customer considered retro-fitting agitator ($ 28,000) - each batch worth $100,000.

The sparge pipe (2" NB) discharges radially straight into a Turbofoil impeller.

Steam mass flow = 1 te/h = 0.278 kg/s

Steam @ 2 barg, T = 120 C, vg = 0.88 m3/kg (from steam tables)
Volumetric flow rate, Qg  0.244 m3/s = 14.64 m3/min, this is equivalent to 3 vvm (vessel
volumes per minute)
Note: vessel headspace is at just above atmospheric pressure.

These calculations would normally indicate that the agitator is completely 'flooded' with steam.
However, this would only be the case if the sparge point was positioned beneath the agitator.
Measurements showed that the power draw of the agitator remains constant whether under gassed
or ungassed conditions. Hydrofoil-type impellers always show a reduction of power draw under
gassed conditions and, further, a down pumping hydrofoil would show significant power draw
fluctuations due to uneven loading.

The strong indication is that the agitator is being largely by-passed by the steam plume.

1. Existing Stripper
This supposition was confirmed by CFD
simulations representative of the
stripping vessel (see left). The steam
plume largely by-passes the agitator and
gives rise to high local velocities at the
liquid surface.

Observation of the liquid/foam surface

showed that there is localised surging of
steam breaking through in one part of the
tank. The disruption of the liquid surface
due to high local steam velocities may be
largely responsible for the unwanted
generation of foam.

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2. The wrong way to retro-fit

Simply retro-fitting a new sparge point beneath
the existing agitator is not recommended. As
shown in the figures (left) using down-pumping
axial flow turbines is an inefficient method for
dispersing gas.

CFD simulation of down-pumping turbine at 100

rpm with a single sparge point of steam at 1 te/h
retro-fitted beneath the agitator. Plot shows
vessel flow patterns; velocity vectors are coloured
with speed. The steam flow overwhelms the
impeller flow below the hub and high local
velocities are predicted near the shaft.

CFD simulation representative of existing CE

stripping vessel operation except that the sparge
point is beneath the agitator. Plot shows steam
volume fraction in the vessel. The impeller is
flooded and does not disperse gas effectively.

Potential torque fluctuations could damage glass-

lined impeller and shaft.

3. Recommended retro-fit
CFD animation representative of existing
stripping vessel operation except that the
sparge point is beneath the agitator and the
impeller rotation has been reversed (so
now it is up-pumping). Plot shows
increased uniformity of steam volume
fraction in the vessel.

Recommended solution - move sparge

point, reverse agitator rotation - cycle time
8 hours (also predicted by DynoChem, see
steam stripper model).

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2. Gas-liquid reaction systems: lab-scale protocol

Definitions of reaction regimes (also see 'Multi-phase Fundamentals')

"Very slow" reaction - rate of reaction between dissolved A and B is very much slower than rate
of transfer of A into B. B phase (the reaction phase) is saturated with A at any moment and
product formation is determined by kinetics of homogeneous chemical reaction.

"Slow" reaction - rate of reaction between A and B is faster than the rate at which A is transferred
to the B phase. The reaction occurs uniformly throughout the phase containing B, but the rate is
controlled by the transfer of A into the phase containing B. The concentration of dissolved A in
the bulk B phase is zero.

"Fast" reaction - reaction of the solute A with reactant B occurs while the solute is diffusing in the
film; that is diffusion and chemical reaction occur simultaneously and are therefore parallel steps.

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Exponents on variables affecting r

Regime cAi cB l k kL a
1. Very slow 1 1 1 1 0 0
2. Slow* 1 0 0 0 1 1
3. Fast 1 ½ 0 ½ 0 1
4. Instantaneous 0-1 0-1 0 0 1 1
* limiting case for slow reactions, see ‘Multi-phase Fundamentals’, eqtn (3b).

A simple protocol involves just two experimental techniques to identify reaction regime [1]:
 a fully baffled stirred tank,
 a constant interfacial area cell.

An experimental protocol to identify the reaction regime in a liquid-liquid system illustrates the
application of some of the results in the ‘exponents on r’ table above.
(i) Sensitivity to agitation = sensitivity to changes in interfacial area, a.
(ii) Sensitivity to phase volume = sensitivity to changes in l. Where l is the volume fraction of
the bulk liquid within which reaction takes place (= VB/Vtot).

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1. Fully-baffled stirred tank

Typical capacity 2-6 litres; with 6-bladed (Rushton-type) disc turbine of diameter 30-40% of tank
diameter; sparge point beneath agitator (link to drawdown systems); range of agitator speeds 400-
2000 rpm.

If gas-side resistance can be neglected, the concentration of A (species originating from gas-
phase) can be varied by changing the ratio of gas reactant flow to inert gas flow. If B
concentration in the liquid can be changed without affecting interfacial properties (i.e. a and kLa),
the order of reaction on species B can be determined.

Regime 1: will show no affect of agitator speed on rate of absorbtion per unit volume of liquid
phase above a certain speed.

Regimes 2, 3 and 4: rate of absorbtion will vary linearly with agitator speed.

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2. Constant interfacial area cell or ‘model stirred contactor’

The model stirred contactor is

characterized by a flat gas-liquid
interface of fixed area and has provision
for independent control of gas-side mass
transfer coefficient. The apparatus is
similar to the Lewis cell used in step 3
of the liquid-liquid protocol. Regimes 3
& 4 are indicated by insensitivity to
changes in the volume of B used if
concentration is unchanged; experiments
at a larger scale may be required to gain
confidence in a scaled-up reactor design.
Regime 2 (slow) will show sensitivity.

Note: for reactions are in the fast

regime, the reaction rate, r will be:
- independent of kL. Therefore,
decreasing N in the constant area cell
apparatus will cause kL to drop which
will influence an instantaneous reaction
but not a fast one.
- proportional to cB1/2 [see refs. 9, 11 &
13 from ‘Multi-phase Fundamentals’].
This is another method of identifying a
reaction in the fast regime.

Note: For a more detailed dissection of

reaction regime the jet apparatus can
also be employed. Ref.: L. K.
Doraiswamy and M .M. Sharma,
“Heterogeneous Reactions” Vol. 2,
Wiley (1984). Contains theoretical
background to multi-phase protocols,
examples of industrial processes and
equipment used, plus references for
further reading.

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Note on drawdown of gas from the vessel headspace

For gas-liquid mixing in the pharmaceutical industry it is common for the gas phase not to be
sparged but to be drawndown from the headspace. The rate vs. agitator speed schematics for
identifying reaction regime are shown below for drawdown systems and differ somewhat to those
shown previously for sparged systems. A major difference is that the rate of gas entrainment is
determined by the agitator speed rather than being metered in. A minimum critical speed (N crit) is
required to start drawing-down gas whichever method is used (vortexing, surface gassing or self-
inducing impeller). Although largely neglected to date, an increasing amount of design data is
currently being generated for drawdown systems that rely on vortexing.

Gas-liquid Systems 11 ©PFD 2001