L -23 : Multiphase Reactors

Prof. K.K.Pant
Department of Chemical Engineering
IIT Delhi.
kkpant@chemical.iitd.ac.in

Trickle Bed Reactors

Trickle-bed reactors are the most widely
used type of three-phase reactors. The
gas and liquid co-currently flow downward
over a fixed bed of catalyst particles.
Concurrent down-flow of gas and liquid
over a fixed-bed of catalyst. Liquid trickles
down, while gas phase is continuous
In a trickle-bed, various flow regimes are
distinguished, depending on gas and liquid
flow rates, fluid properties and packing
characteristics.

 Approximate dimensions of commercial trickle-bed reactors

are a height of 10 m and a diameter of 2 m.

Comparison of Three Phase

Trickle- Bed and Bubble Fixed Bed
Reactors

Overall or Apparent reaction rate (gas limiting)

Kinetic Factors

Theory of Catalytic Gas- Liquid

Reactions
A(G) + B(L)

Gaseous reactant A reacts with non-volatile liquid

reactant B on solid catalyst sites.
Mechanism Of Three- Phase Reactions:Mass Transfer of component A from bulk gas to
gas-liquid interface
Mass transfer of component A from gas-liquid
interface to bulk liquid
Mass transfer of A& B from bulk liquid to catalyst
surface

Intraparticle diffusion of species A& B

through the catalyst pores to active sites.
Adsorption of both or one of the reactant
species on catalyst active sites.
Surface reaction involving at least one or
both of the adsorbed species.
Desorption of products, reverse of forward
steps .

Three-Phase Gas-Liquid Catalytic Reactor- Design

Model
(Trickle-Bed, Fixed-upflow Bubble-Bed, Bubble Slurry
Bed, 3-Phase Fluidized Bed)

Non-Volatile Liquid-phase mass balance:

rA= kg ai (CA(g-C Ai(g)/(1-) c = kl ai (CAi(g - C Ab )/(1-) c

=

kc ac (CAb CAs ) = k CAs CBs

Moles/gcat.s

ai= interfacial area/ vol. of bed., = bed void fraction

Eliminate intermediate concentrations

-r =
A
'

CAg

H
H
H
A +
A
+ A +
k a k a k ac k ' C f
Ag i
Al i
Ac
A B s
1

First order rate constant for A

-r ' =k vgC
A
Ag

Mole balance for A

-r ' =
B

dF
A =r' =-k C g
vg A
dW A

1
1
+
k c ap nKC
AS

mol
C
B gcat.s

-r
=k
C
B
vl
B

Mole balance for B

dF
dC
B =v
B =-r' =k C
dW 1 dW B vg B

REACTOR MODEL
In kinetic models for trickle beds, the reaction is often
assumed to be first order to both reactants
For the ideal case of plug flow and completely wetted
catalyst, the conversion for a first-order reaction is
given by:

Conversion may be given as a function of the liquid

hourly space velocity (LHSV), and the apparent rate
constant, kapp, includes the effect of partial wetting as
well as the effect of internal concentration gradients.

where

CRITERIA FOR SELECTION OF CONTACTOR

The selection of a good contactor depends on:
where the controlling resistance lies in the rate expression,
the advantages of one contacting pattern over another, and the
difference in auxiliary equipment needed.
The overall economics which accounts for these three factors
will determine which set up and reactor type is best.
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The Rate:

Select the contactor which favors the weakest step in the

rate. (RDS)

For example,
if the main resistance lies in the G/L film, use a contactor
with large interfacial surface area.(bubble column/spray)
if the resistance lies at the L/S boundary, use a large
exterior surface of solid, thus large fs, or small particles.

if the resistance to pore diffusion intrudes, use tiny

particles.
Boosting the weakest step in the rate by a proper choice of
particle size, solid loading and reactor type can strongly affect
the overall economics of the process.
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Example : HYDROGENATION OF ACETONE IN A PACKED BUBBLE COLUMN

Aqueous acetone (CB0, = 1000 mol/m3 1, vl = 10-4 m3 l /s) and

hydrogen (1 atm, vg = 0.04 m3 g /s, HA = 36845 Pa.m3 l /
mol) are fed to the bottom of a long, slender column (5-m
high, 0.1-m2 cross section) packed with porous Raney nickel
catalyst (dp, = 5 x 10-3m cat, ps = 4500 kg/m3 cat, fs = 0.6, De
= 8 X 10-10 m2 / s based on vol of l /m of cat) and kept at 140C.
At these conditions acetone is hydrogenated to propanol
according to the reaction

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What will be the conversion of acetone in this unit?

Additional Data:
The mass transfer rate constants are estimated to be the

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-r =
A
'

CAg

H
H
H
A +
A
+ A +
k a k a k ac k ' C f
Ag i
Al i
Ac
A B s
1

First order rate constant for A

-r ' =k vgC
A
Ag

19

CBo = 1000, mol/m3

CA is given by Henry's law as

CB >> CA
Since pure hydrogen; p A is constant throughout the packed column. And since
the rate is only dependent on CA and not on CB, this means that the rate of
reaction is constant throughout the column.
Thiele Modulus MT or

= 1/ = ~0.01
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L 24: Fluid- Fluid Reactions (Non

catalytic)

Prof. K.K.Pant
Department of Chemical Engineering
IIT Delhi.
kkpant@chemical.iitd.ac.in

Setting up the rate equation for straight mass transfer based

on the two film theory.

The Rate Equation for Straight Mass Transfer (Absorption) of A

Here two resistances in series, of the gas film and of the liquid
film. The rate of transfer of A from gas to liquid is given by the rate
expressions, for the gas film

In the liquid film

Combining the two eqns and using Henrys law

PAi= H CAi

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All sorts of special forms of the rate equation can result depending
on the relative values of the rate constants k, kg, and k,, the
concentration ratio of reactants pA /CB, and Henry's law constant HA.
There are eight cases to consider, going from the extreme of
infinitely fast reaction rate (mass transfer control) to the other
extreme of very slow reaction rate (no mass transfer resistance
need be considered)
Case A: Instantaneous reaction with low CB,
Case B: Instantaneous reaction with high CB
Case C: Fast reaction in liquid film, with low CB
Case D: Fast reaction in liquid film, with high C,
Case E and F: Intermediate rate with reaction in the film and in the
main body of the liquid
Case G: Slow reaction in main body but with film resistance
Case W: Slow reaction, no mass transfer resistance

Figure : Concentration of reactants as visualized by the twofilm theory for an infinitely fast irreversible reactions of any
order, A + bB products. Case A-low CB, Case B high CB,

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General rate expression

The absorption of A from gas is larger when reaction occurs within the
liquid film than for straight mass transfer.
Thus for the same concentrations at the two boundaries of the liquid film
we have
E >1

Instantaneous Reaction with Respect to Mass Transfer. : Since an

element of liquid can contain either A or B, but not both, reaction will occur
at a plane between A-containing and B-containing liquid.
Also, since reactants must diffuse to this reaction plane the rate of diffusion of
A and B will determine the rate, so that a change in p, or C, will move the
plane one way or the other

kAg, and kAl ,: mass transfer coefficients in gas and liquid

phases. The liquid side coefficients are for straight mass transfer
without chemical reaction and are therefore based on flow
through the whole film of thickness x0.
In addition, since the movement of material within the film is
visualized to occur by diffusion alone, the transfer coefficients
for A and B are related by

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General rate expression

The absorption of A from gas is larger when reaction occurs within the
liquid film than for straight mass transfer.
Thus for the same concentrations at the two boundaries of the liquid film
we have

E >1

Can be correlated with HATTA MODULUS/ NUMBER (MH)

M H, stands for the Hatta modulus,

M2H=

(k CAi CB x0 )/ kAl CAi

MH >1 ALL REACTION IN FILM and surface area is controlling factor. MH >2 ,
REAXN IN FILM, INSTANTANEOUS Reaction (BUBBLE COLUMN)
MH < 1, No Reaction in Film, and bulk liquid volume is controlling
MH < 0.02 INFINITELY SLOW REACTION ( BUBBLE COLUMN )

The enhancement factor for fluid-fluid reactions as a function of MH and Ei

modified from the numerical solution of van Krevelens and Hoftijzer

Role of the Hatta Number, MH

To identify whether reaction is fast or slow, we focus on unit
surface of gas-liquid interface, assume that gas-phase
resistance is negligible, and we define a film conversion
parameter

If MH >>1, all reaction occurs in the film, and surface area is the controlling rate
factor.
On the other hand, if MH <<1 no reaction occurs in the film, and bulk volume
becomes the controlling rate factor. More precisely, it has been found
that:

From Fig. 23.4, for

MH >1000

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To find the rate from the general expression, we need to first evaluate
Ei and MH. :
1. If MH > 2, reaction occurs in the film and we have Cases A, B, C, D.
2. If 0.02 < MH < 2, we then have the intermediate Cases E, F, G.
3. If MH < 0.02, we have the infinitely slow reaction of Case H.

(a) locate the resistance to reaction (what % is in the gas film, in the liquid
film, in the main body of liquid)
(b) locate the reaction zone
(c) determine the behavior in the liquid film (whether pseudo first-order
reaction,
instantaneous, physical transport, etc.)
(d) calculate the rate of reaction (mol/m3 hr)

35

Eliminating the unmeasured intermediates x, x0, pAi, CAi,

For the special case of negligible gas-phase resistance, for example, if you used
pure reactant A in the gas phase, then

= KAl CAi E ,

E = x0/x
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Case C: Fast Reaction; Low CW The plane of reaction for

case A now spreads
into a zone of reaction in which A and B are both present.
However, reaction is fast enough so that this reaction zone
remains totally within the liquid film.
Thus, no A enters the main body of liquid to react there.
Since the last resistance term in the general rate equation, Eq.
5, (I/kfl )is negligible (large k), the rate form for this case is

Case G: Slow Reaction with Respect to Mass Transfer. all

reaction occurs
in the main body of the liquid; however, the film still provides a
resistance to the transfer of A into the main body of liquid. Thus,
three resistances enter into the rate expression, Thus

Case H: Infinitely Slow Reaction.

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Slow reactions Case G still shows film resistance. Case H shows no film
resistance.

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Factors to Consider in Selecting a Contactor

(a) Contacting pattern.

Towers approximate plug G plug L.

Bubble tanks approximate plug G / mixed L.

Agitated tanks approximate mixed G / mixed L.

Towers have the largest mass transfer driving force and in this respect have an
advantage over tanks.

Agitated tanks have the smallest driving force.

(b) kg and kL. For liquid droplets in gas kg is high, kL, is low.
For gas bubbles rising in liquid, kg is low, kL is high.

(c) If the resistance is in the gas and or liquid films : Use a large interfacial
area "a," thus most agitated contactors and most columns. If the L film
dominates, stay away from spray contactors. If the G film dominates stay

away from bubble contactors.

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d) If the resistance is in the main body of the L you want

large fl = Vl/Vr. Stay away from towers. Use tank contactors.
(e) Solubility. For very soluble gases, those with a small

value of Henry's law constant H (ammonia, for example), gas

film controls, thus avoid bubble contactors.
For gases of low solubility in the liquid, thus high H value (O2,
N2, as examples) liquid film controls, so avoid spray towers.
(f) Reaction lowers the resistance of the liquid film, so

For absorption of highly soluble gases, chemical reaction is not

helpful. For absorption of slightly soluble gases, chemical

reaction is helpful and does speed up the rate.

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Fluid Solid non catalytic

Reactions

Substituting all values in the equation.

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