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CHAPTER 2

MULTIPHASE
REACTORS

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CPE624 FACULTY OF CHEMICAL ENGINEERING
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
catalyst
Gas-liquid-liquid with
solid catalyst 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.
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:
u
**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

Aj as
The mass transfer can be regarded

A reversible
j surface reaction:

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

Cont
A
At steady state C A 0 C A r
k m (C
A C
A)
V

Mass transfer to or from an unmixed


phase.
Mass balance at steady state in PFTR:

dC j A
u
dz
ij ri V
k m (C j C j )

Or for reactant A in phase:

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Summary of Multiphase Reactor
Equations
If species A is a reactant, r will have
In mixed phase (at steady state): a +ve value. Refer to page 88-89
Schmidt to understand why.
A
C A 0 C A
r

k m (C
A C
A)
V

In unmixed phase:

Can be +ve or can be ve.


Can be +ve or can be ve. So, when is +ve and when
So, when is +ve and when is ve?
is ve?
Flow configurations
Four flow configurations of two-phases reactors:

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Reaction only in one
phase
Only in one phase? Whats the use of another phases then??
Another phase serves to: supply reactant, remove product and provide
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.
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:
C Aeq
Aj A j ;
K eq
C Aeq
a.k.a. partition coefficient or
distribution coefficient
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.
or
Pj = H j x j 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 (counter- L
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.
Falling Film Reactor (FFR)(cont.)
The gas will occupy a cross sectional area:
Ri2
The liquid will occupy a cross-sectional area:
(R02 Ri2 )
The volumes occupied by the phases are:

V (R R )L
l 2
0 i
2

V R L
g
i
2

The residence time for each phase is:


L

L V l
( R 2
R 2
i )L
l l
l 0
u l
L V g
R 2
i L
g g g
g

u
Falling Film Reactor (FFR)(cont.)
Consider the following reaction: A B C D
g l g l L
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
l A B
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
g 2Ri g gl l
u 0 k m (C A K C A)
dz R i
2

dC Al
l l l l 2Ri g gl l
u k C ACB k m (C A K C A)
dz (R0 - R i )
2 2
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.
Practice Questions for FFR (cont.)
5) Question 5 Final Paper Dec 2014
CHE625
Practice Questions for FFR
6) (cont.)
Question 2 b) Final Paper Dec 2013
CPE624

12 m

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

dRb
4Rb2 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
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

air which contains 9 mol% H2


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.