CHE505

Reaction Engineering II

TOPIC 2
Multiphase Reactor

SITI WAHIDAH BINTI PUASA

PHONE NO: 03-55436404
019-6694190

Credit to: Dr Norhidayah, Pn. Norhasyimi,

Pn. Sharmeela, Cik Siti Khatijah & Cik Faeqah
CHE505: REACTION ENGINEERING II
Mass transfer steps between phases accompany reaction
steps, frequently control the overall rate of chemical
reactions

Mass & energy balance must be written & solved for each
species in each phase

Gravity is important in controlling patterns (lighter phase

will rise, denser phase to fall)

Mixing within phases & between phases has

dominant effect

Solubility & phase distributions of species

between phases require careful application
principles

CHE505: REACTION ENGINEERING II

Type of multiphase reactors:

 Gas liquid and Liquid-liquid reactors

 Gas-Solid and Liquid-Solid reactors

 Three Phases

Why the need to use 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.

CHE505: REACTION ENGINEERING II

 Reaction Type Degree of Difficulty

Straightforward
• Gas-liquid without catalyst

• Gas-liquid with soluble catalyst

• Gas-liquid with solid catalyst

• Gas-liquid-liquid with soluble catalyst

• Gas-liquid-liquid with solid catalyst Complex

CHE505: REACTION ENGINEERING II

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Bubble column reactor
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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.

Solubility and phase distributions of species between phases

require careful application principles.

CHE505: REACTION ENGINEERING II

Chemical species can transfer between phases and represents the
coupling between the mass balance equations

Resembles a membrane reactor in which permeable area Aαβ

which 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 for α phase if the fluid is unmixed (i.e in PFR):
dC j
u   ij ri  [gain or loss to other phases]
dz

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

dC j
V    (C j  C j 0 )  V   ij ri  [gain or loss to other phases]
dz

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

  (C j  C j 0 )  V   ij ri  [gain or loss to other phases]  0

CHE505: REACTION ENGINEERING II

Residence time in α and β phase:

V V
  ;  
 

In PFR:

V L
   
 u

**All equations valid for no density change system reactor

CHE505: REACTION ENGINEERING II

Three combinations of two phases:

CHE505: REACTION ENGINEERING II

Other phase serving to:
 supply reactant, removing
product and providing catalyst

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

CHE505: REACTION ENGINEERING II

Breakup of liquids into drops and bubbles

Interfacial area between phases Aαβ 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, therefore 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

CHE505: REACTION ENGINEERING II

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

also flow pattern caused

by gravity controls the
interfacial area
IMPELLER
DESIGN
Mass transfer to or from a mixed phase

 Mass transfer for α phase in contact with β phase in

CSTR

dC j
V    (C j  C j 0 )  V   ij ri  [gain or loss to other phases]
dz

dC j
V    (C j  C j 0 )  V   ij ri  A k m (C j  C j )
dz

Mass transfer rate of

species j from phase β A k m (C j  C j )  A x J j
to α:

CHE505: REACTION ENGINEERING II

 The mass transfer can be regarded as reversible surface
reaction:
A j  A j

 Thus, the pseudohomogeneous rate:

A A A
r  r"   r"   k m (C j  C j )
V V V

 At steady state

A
C A0  C A    r     k m (C A  C A )
V

CHE505: REACTION ENGINEERING II

Mass transfer to or from an unmixed phase.

 Mass balance at steady state in PFTR:

dC j A
u 
  ij ri  k m (C j  C j )
dz V

 Or for reactant A in α phase:


 dC A
u A
  r  k m (C A  C A )
dz V

CHE505: REACTION ENGINEERING II

In mixed phase:


A
C A0  C A    r     k m (C A  C A )
V

In unmixed phase:

dC A
 A
u   r  k m (C A  C A )
dz V

CHE505: REACTION ENGINEERING II

An equilibrium distribution of species A between phases α
and β if the phases are in contact for long time:

C Aeq
A j  A j ; K eq 
C Aeq
a.k.a. partition coefficient
or distribution coefficient

Mass transfer between phases:

r"  k m(C Aβ  K eq C A )

Concentration gradient in the

vicinity of the interface is the
driving force of the mass transfer

CHE505: REACTION ENGINEERING II

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 Henry’s

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

For gases, Henry’s Law constant:

Pj  H j x j

CHE505: REACTION ENGINEERING II

? ? ?

CHE505: REACTION ENGINEERING II

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
(counter-current)  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
CHE505: REACTION ENGINEERING II
The gas will occupy a cross sectional area  Ri2

The liquid will occupy a cross-sectional area   ( R0

2
 R 2
i )

The volumes occupied  V l   ( R02  Ri2 ) L

by the phases
V g  Ri2 L

The residence time of  L V l

 ( R 2
 R 2
i )L
  l  l 
l 0
each phase u  l
L V g
 R 2
i L
  g  g  g
g

u  
Consider the following reaction:

Ag  Bl  C g  Dl

Assumption:

 Reactions are irreversible.

 Products can easily escape from the phases, so
the specific products are not important to
know.
 The reaction occurs only in the liquid phase
(no reaction in gas phase).
 Rate equation for this reaction is:

r l  kl C Al C Bl ; r g  0

CHE505: REACTION ENGINEERING II

The rate of mass transfer per unit area is:

rmA  k mA (C Ag  K gl C Al )

Area of interface:
2Ri L

Mass balance for the phases:

dC g
2Ri
ug A
 0 k (C g
 K gl l
CA )
R i
2 m A
dz
dCAl 2Ri
u l
 k C ACB 
l l l
k (C g
 K gl l
CA )
 ( R0 - R i )
2 2 m A
dz

CHE505: REACTION ENGINEERING II

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)

CHE505: REACTION ENGINEERING II

In falling film reactor (FFR), 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

needed to large 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.
WHEN & HOW DOES BUBBLE COLUMN REACTOR WORKS??

• 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, mixing plates and impellers

within the reactor to control the bubble size
Bubble phase volume V g   gV
occupying a fraction εg:

4 3
Volume of each bubble: Rb
3

Assume that all particles have the same size

dRb
4R 2
b  k m 4Rb2 (C A  C As )
dt

CHE505: REACTION ENGINEERING II

CHE505: REACTION ENGINEERING II
 Example
• An aqueous solution containing 10 ppm by weight of an organic
contaminant of molecular weight 120 is to be removed by air oxidation
in a 1‐cm‐diameter falling film reactor at 25°C. The liquid flows at an
average velocity of 10 cm/sec and forms a film 1 mm thick on the wall,
while the air at 1 atm flows at an average velocity of 2 cm/sec. The
reaction in the liquid phase has the stoichiometry A + 2O2  products
with a rate l
r  k CACO2
l l l

– (a) What are the compositions when the reaction has gone to
completion?
– (b) Write the equation(s) that must be solved to find the reactor
length required for a given organic removal.
– (c) How many tubes in parallel are required to process 100 
liters/min of water? What will be the diameter of the tube bundle if 
the tubes are packed in a square array and the tube wall thickness is 
neglected?
CPE624 FACULTY OF CHEMICAL ENGINEERING 39
  (d) Estimate the reactor length needed to reduce the
organic concentration to 1 ppm if O2 mass transfer is
sufficiently fast that the liquid solution remains saturated
with O2 and the rate coefficient kl is 1 x 102 liter/mole sec.
The Henry’s Law constant for O2 in water is 1 x 105 atm.

 (e) Estimate the reactor length needed to reduce the

organic concentration to 1 ppm if the reaction actually
occurs on a catalyst on the wall of the reactor tube.
Assume that the reaction rate on the wall is infinite and
the process is limited by the diffusion of O2 through the
liquid, with DO2 = 10‐5 cm2/sec, and that the concentration
profile is linear.

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