CHAPTER 4

MULTIPHASE
REACTORS

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Types of Multiphase Reactors

Types of multiphase reactor:

Gas - Liquid reactors
Liquid-Liquid reactors
Gas-Solid reactors
Liquid-Solid reactors
Three Phases reactors

Why multiphase reactors?

To react gases, liquids and solids with each other. Most solids processes

require reacting with gases or liquids and products may also be gases or
liquids.
To use multiple phases to attain conversions higher than attainable from
equilibrium constraints in a single phase process and to improve mixing
within in the reactor by allowing gravity to cause flows of phases relative
to each other.

Types of Multiphase Reactions

Reaction Type

Degree of Difficulty

Gas-liquid without catalyst

Straightforward

Gas-liquid with soluble catalyst

Gas-liquid with solid catalyst
Gas-liquid-liquid with soluble
or solid catalyst

Gas-liquid-liquid with soluble

or solid catalyst (two liquid phases) Complex

Key Multiphase Reactors

Common Multiphase
Reactors

Common Multiphase
Reactors

Middleton,1992

Bubble column reactor

Features that distinguish multiphase

reactors from single phase reactors

Mass transfer steps between phases which accompany the

reaction steps, frequently control the overall reaction rate.
Mass & energy balance must be written and solved for each
species in each phase.
Gravity is important in controlling patterns (lighter phase will
rise, denser phase to fall)
Mixing within phases and between phases has dominant effect.
Solubilities and phase distributions of species between phases
require careful application principles.

10

Mass Balance in Multiphase

Reactor
Chemical species can transfer between phases and represents

the coupling between the mass balance equations.

Resembles a membrane reactor in which permeable area A
separates the phases.

Clicker Questions:
i) What do , and represent?
ii) What do A and A represent?

Before we take a look at mass

balance equations for multiphase
reactors, I suggest you refresh
yourself on mass balance equations
for single-phase reactors. This will
give you better understanding on
the mass balance equation for
multiphase reactors. Refer to
Schmidt book:
i) Batch reactor (pg. 38-39)
ii) PFTR (pg. 51-52)
iii) CSTR (pg. 86-89)

Mass Balance in Multiphase Reactor

(cont.)

Mass balance for phase if the fluid is unmixed (i.e.: in PFR):

???

For mixed fluid (i.e.: in CSTR) at transient:

For mixed fluid (i.e.: in CSTR) at steady state:

???

Residence time in and phase:

???

V
V

V
L

In PFR:

**All equations valid for no density change system reactor

Mass transfer between

phases
Mass
transfer to or from a mixed phase
Mass transfer for phase in contact with phase in CSTR

Mass transfer rate of

species j from phase to

The mass transfer can be regarded

Aj as
A reversible
surface reaction:
j

A
A
A
r r " r " k m (C j C j )
V
V
V

Cont
At steady state

C A 0 C A r

k
(
C

C
m
A
A)

Mass transfer to or from an unmixed

phase.
Mass balance at steady state in PFTR:

dC j
dz

ij ri

A
k m (C j C j )
V

Or for reactant A in phase:

CPE624

dC A
A
r k m (C A C A )
dz
V

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15

Summary of Multiphase Reactor

Equations..

In mixed phase:
C A 0

If species A is a reactant, r will have

a +ve value. Refer to page 88-89
Schmidt to understand why.

C A

k
(
C

C
m
A
A)

In unmixed phase:
dC A
A
u
r k m (C A C A )
dz
V

Can be +ve or can be ve.

So, when is +ve and when
is ve?

Can be +ve or can be ve.

So, when is +ve and when
is ve?

Flow configurations

Four flow configurations of two-phases reactors:

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17

Reaction only in one

phase

Only in one phase? Whats the use of another phases then??

Eg. In catalytic reactor reaction occurs only at the boundary

with a solid phase.

In moving bed catalytic reactor or in a slurry or fluidized bed

catalytic reactor, catalyst phase is continuously added and
removed from the reactor and in multiphase reactor the
reaction occurs on the catalyst surface.

Interfacial surface area

Interfacial area between phases, A can change depending

on:
Conversion
Geometry
Flow conditions

Stirring with an impeller or the flow pattern caused by gravity

will also control the interfacial area.
Suitable design and positioning of impeller or propeller can provide very

efficient breakups of liquids into drops and bubbles, increasing the

interfacial area.

Surface tension can be very important in determining drop

and bubble sizes and shapes. The presence of surface active
agents that alter the interfacial tension between phases can
have enormous influences in multiphase reactors.

Suitable
design
and
positioning of impeller or
propeller can provide very
efficient breakups of liquids
into drops and bubbles,
increasing the interfacial
area.

flow pattern caused by

gravity also controls the
interfacial area

Impeller Designs:

Equilibrium between
Phases
An equilibrium distribution of species A between phases and if the

phases are in contact for long time:

Aj A j ; K eq

a.k.a. partition coefficient or

distribution coefficient

C Aeq

C Aeq

Mass transfer between phases (at equilibrium):

r" k m (C A K eq
CA )

Concentration gradient in the vicinity

of the interface is the driving force of
the mass transfer

However this driving force for mass transfer of a species disappears when
the partial pressure of the species in the gas is in equilibrium with the
concentration of the liquid phase. The equilibrium is conveniently expressed
as Henrys Law: At a constant temperature, the amount of a given gas that
dissolves in a given type and volume of liquid is directly proportional to the
partial pressure of that gas in equilibrium with that liquid.

Pj = H j x j

or

yjPT = H j x j

Gas-liquid multiphase reactors.

Falling Film Reactor (FFR)

Consider a vertical tube of length L and

diameter D0 with liquid admitted at the top
such that it forms a falling film that coats
the wall tube.
Gas was added into the top of the tube
(co-current) or into the bottom (countercurrent) wetted wall column.
Assume the liquid falls with a constant
average velocity (ul) and forms a liquid film
of thickness R0 Ri (Ri = radius in the tube
at the surface of the liquid film).
If the liquid film thickness is constant, the
cross section occupied by the gas is
constant and the velocity of the gas (ug) is
independent of position z if the density of
gas is constant.

Falling Film Reactor (FFR)

(cont.)
The gas will occupy a cross sectional area:
R

2
i

The liquid will occupy a cross-sectional area:

The volumes occupied by the phases are:

(R02 Ri2 )

V l (R02 Ri2 )L
V g Ri2L

The residence time for each phase is:

L
2
2
l

(
R

R
L
V
l
0
i )L
l l
u

l
L V g Ri2L
g
g g g
u

Falling Film Reactor (FFR)

(cont.)
Consider the following reaction:
A B C D

Lets assume the following:

Reactions are irreversible

Products can easily escape from the phases, so the spesific

products are not important to know.

the reaction occurs only in the liquid phase (no reaction in
gas phase): r l k C l C l ; r g 0

The rate of mass transfer per unit area is: rmA k mA (C Ag K gl C Al )

Area of interface: 2R L
i

Mass balance for the phases:

dC Ag
2Ri
g
gl
l
u
0
k
(
C

K
C
m
A
A)
2
dz
R i
g

dC Al
2Ri
l
l
l
g
gl
l
u
k C ACB
k
(
C

K
C
m
A
A)
2
2
dz
( R0 - R i )
l

Reactor volume is proportional to R02 while the surface area

for mass transfer is proportional to R, the falling film column
will be less efficient for larger reactor sizes.

The mass transfer coefficient is usually much lower in the

liquid phase and therefore CAl is a function of R (distance
from the wall to interface)

Practice Questions for FFR

1) Sketch and label a liquid-gas countercurrent falling film reactor
that is made from a vertical cylindrical tube of length L and
diameter Do.
2) Express the volumetric flow rate of each phase in the falling film
reactor sketched in Question 1 in terms of reactors length, L and
the residence time of each phase. Assume no density change in
the reactor.
3) Falling film reactors are widely used in industry particularly in
processes that involve hydrogenation, chlorination, ethoxylation
and sulfonation. Its main characteristics are the motion of liquid
film over a wetted surface under the effect of gravity. Assuming
there is no gas phase reaction in a falling film reactor, derive
mass balance equation for the gas and liquid phases for a
reaction stated as:
Ag + Bl Cg + Dl , rl = klCAlCBl
4) Answer all questions (a to g) in Example 12-1 page 490 Schmidt.
28

Practice Questions for FFR (cont.)

5) Question 5 Final Paper Dec 2014

CHE625

Practice Questions for FFR

(cont.)
Question 2 b) Final
Paper Dec 2013

6)
CPE624

Answer: film thickness = 0.2 cm

Falling Film Catalytic Wall

Reactor

Bubble Column Reactors

(BCR)
In falling film reactor, surface area increases as the perimeter of gas-liquid

interface increases. Volume increases as the cross sectional area

increases. Hence, FFR will be less efficient for larger reactor sizes.
To design efficient falling film reactor, small tubes in parallel are needed to
increase the interfacial area, which is difficult and not practical.
However, higher interfacial area can be accomplished with rising bubbles or
falling drops. This can be done by using bubble column reactor (BCR) or
spray tower.
BCR:

Normally used for reaction where the

gas-liq rxn is slow compared to the mass
transfer rate.
Widely used in oxidation, hydrogenation
and alkylation.
Gas bubbles introduced at the bottom
(normally using sparger).
The bubbles rise. Why?
The gas separated from the liquid in the
head space and pure liquid is withdrawn
at the bottom.

Figure below shows the concentration profile for reactant A

which must migrate from a bubble (in BCR) or a drop (in spray
tower) into the continuous phase to react.

Bubble columns rely on nozzles (spargers), mixing plates and

impellers within the reactor to control the bubble size.

Bubble phase volume occupying a fraction g:

V g gV

Volume of each bubble:

4
Rb3
3

Assume that all particles have the same size

Rb2

dRb

k m 4Rb2 (C A C As )
dt

Practice Questions for BCR

1) Answer all questions (a to d) in Example 12-2 page 496 Schmidt.
2) Question 3 c) Final Paper CPE624 June 2014

Answer: V = 137.5
m3
35

Practice Questions for BCR (cont.)

3) Question 2 c) Test 2 June 2015 CHE625

State your assumption(s).

Answer: vl = 1.56 x 10-4 m3s-1

Practice Questions for BCR

(cont.)
4) Question 3 b) Final Paper June 2013 CPE624

Answer: V = 56886 dm3

References

Schmidt, L.D. (2005). The Engineering of Chemical Reactions,

2nd edition, New York: Oxford University Press.
Pn. Hasyimi Rahmat, FKK UiTM Shah Alam.
Pn. Sharmeela Matali, FKK UiTM Shah Alam.
Pn. Siti Wahidah Puasa, FKK UiTM Shah Alam.