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L -33 -34 : Multiphase Reactors

Prof. K.K.Pant
Department of Chemical Engineering
IIT Delhi.
kkpant@chemical.iitd.ac.in
2
Packed Bed Reactor : Differential equation describing
diffusion for a first order reaction in a packed bed
Z=0 , C
Ab
= C
Ab0
Axial diffusion, can be neglected when

F
A
is very large

so


Finally, the conversion for
1
st
order reaction in PBR is
'
0 p A b p
a 0 Ab
U d -r d
>>
D U C
2
Ab
a
2
d C
D
dz
| |
|
\ .
"
Ab b a
Ab
dC k S
=- C
dz U
Remember the
forced
convection in
binary external
diffusion, J
A
is
also neglected
b a
-( k"S L)/U
Ab
Ab0
C
X=1- =1- e
C
Mass transfer and reaction in a packed bed
Ind engg. Chem res. 12, 412, 1973
4
Overall Rate with in the pellet (-r
A
= (r
Ab
)

For first order reaction

: (-r
Ab;
= (r
Ab
)Sa= k
s
S
a
C
Ab

=>
(-r
A
)= (r
Ab
)

= S
a

b
k C
Ab

2
2
0 s b b
Ab Ab
A
d C dC
Da U k SaC
dz dz

| |
O =
|
\ .
Neglecting Axial Dispersion




( )
s a
Ab
Ab
dC k S
C
dz U
O
| |
=
|
\ .
C
Ab
= C
Ab0
exp(- Sa
b
ks Z/U)


X=1- C
Ab
/ C
Ab0

For design, Calculate and then to calculate rate.
Determination of limiting situation from
reaction data
Type of
Limitatio
n
Variation of Reaction Rate with:
Velocity
Particle
Size
Temperature
External
diffusion
U


(d
p
)-
3/2
Rate= k
c
ac CA

~ Linear
Internal
Diffusion
Independent
(d
p
)
-1

Exponential
Surface
Reaction
Independent
Independe
nt
Exponential
6
Multiphase Reactors
Reactors in which Two or more phases are
involved in Reactions.

Majority of reactions are : Gas liquid reactions
involving catalyst as solid material.

Hydrotreating, FT reaction, Hydrogenation
Reaction etc.
Reactor Types
Two-Phase Reactors:
8
Sasol slurry reactor for CO
hydrogenation Dia 5 m, height
22m ,T240
o
C, P 22 atm.
FT synthesis
Three-Phase Reactors:
10
Three-phase reactors
Multi-phase Reactors- Advantages and Disadvantages
Advantages Disadvantages
Catalytic Fixed
Bed Reactor
+
The fluid flow regimes
approach plug flow, so
high conversion can be
achieved.
+
Pressure drop is low.
+
Owing to the high hold-
up there is better radial
mixing and channeling
is not encountered.
+
High catalyst load per
unit of reactor volume
+
The intra-particle
diffusion
resistance is very
high.
+
Comparatively low
Heat and mass
transfer rates
+
Catalyst
replacement is
relatively hard and
requires shut
down.
Multi-phase Reactors- Advantages and Disadvantages
Advantages Disadvantages
Catalytic
Fluidized-bed
Reactor
+
The smooth, liquid-like flow of particles
allows continuous controlled operations
with ease of handling.
+
Near isothermal conditions due to the rapid
mixing of solids.
+
Small Intra-Particle resistance leads to a
better heat and mass transfer rate.
+
This violent particle motion of
particles tends to homogenize all
intensive properties of the bed.
Thus it is not generally possible to
provide an axial temperature
gradient which might be highly
desirable in some instances.
+
Erosion by abrasion of
particles can be serious.
+
Particle attrition
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.
Three-phase Reactors- Advantages and Disadvantages
Advantages Disadvantages
Trickle-
Bed
Reactor
+
Gas and liquid flow regimes
approach plug flow; high
conversion may be achieved.
+
Large catalyst particle, therefore,
catalyst separation is easy.
+
Low liquid holdup, therefore liquid
homogenous reactions are
minimized.
+
Low pressure drop
+
Flooding problems are not
encountered.
+
High catalyst load per unit reactor
volume.
+
Poor distribution of the
liquid-phase
+
Partial wetting of the catalyst
+
High intra-particle resistance
+
Poor radial mixing
+
Temperature control is
difficult for highly exothermic
reactions
+
Low gas-liquid interaction
decreases mass transfer
coefficients.
Three -phase Reactors- Advantages and
Disadvantages
Advantages Disadvantages
Bubble
Fixed- Bed
Reactor
+
High liquid holdup,
therefore, catalyst are
completely wetted, better
temperature control, and no
channeling problems.
+
Gas-liquid mass transfer is
higher than in Trickle bed
due to higher gas-liquid
interaction.
+
Axial back mixing is
higher than trickle-
beds, conversion is
lower.
+
Feasibility of liquid side
homogeneous
reactions
+
Pressure drop is high
+
Flooding problems may
occur.
16
17
Steps in Slurry Reactors
Catalytic Fixed-Bed Reactor - Design Model
Mass Balance around the catalyst


Gas-Phase component mass balance (Plug Flow model)


Gas-Phase component mass balance (Dispersion model)


Energy Model

i net S G i c c R i C C a k ) ( ) ( ) ( = q
0 . 0 ) ( ) ( = i S G i c c
Gi
G C C a k
dz
dC
U
0 . 0 ) ( ) (
2
2
= i S G i c c
Gi
G
Gi
G C C a k
dz
dC
U
z d
C d
i D
) ( ) ( Ta T UA j H Rj
dz
dT
Cp U R G G G + A =

19
Reactions Steps in slurry reactors
20
Rate of gas absorptions
Transport to the Catalyst Pellet
21
Diffusion and Reaction in the Catalyst Pellet
m = mass of cata/vol of solution
Determination of RDS
22
23
24
Comparison of Three Phase
Trickle- Bed and Bubble Fixed Bed
Reactors
Comparison of Three Phase
Suspended Bed Reactors
Approximate dimensions of commercial trickle-bed
reactors are a height of 10 m and a diameter of 2 m.
Theory of Catalytic Gas- Liquid
Reactions
A
(G)
+ B
(L)
C
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 .
| |
|
\ .
1
m
-r =
A H H H
1
A A A
+ + +
k a k a k a m
k C Af
c
Ag i Al i Ac
s
A B
First order rate constant for A
( )
'
-r =k C g
vg
A A
Mole balance for A
Mole balance for B
( )
dF
'
A
=r =-k C g
vg
A A
dW
1 mol
'
-r = C
B B 1 1 gcat.s
+
k a nKC
c p
AS
-r =k C
B vl B
dF dC
'
B B
=v =-r =k C
vg
1 B B
dW dW
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
Calculation of Catalytic
Effectiveness Factor
Catalytic Effectiveness Factor:


where
|- Thiele Modulus
1
st
order reaction rate:

Spherical Pellet
Cylindrical Pellet
Slab Pellet



1 1
= (Coth3- )
3
R
= kSap/De
3
R
= kSap/De
2
=L kSap/De
Applications
Trickle-bed reactors are employed in
petroleum, petrochemical and chemical
industries, in waste water treatment and
biochemical and electrochemical
processing.
For Example:
Residuum and vacuum residuum
desulfurization
Catalytic dewaxing of lubestock cuts
Hydrogenation of methyl styrene to
cumene
Oxidation of glucose
Biochemical reactions and fermentations

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:
2
L, i L, i
L, i L c c i L, i S, i
2
d C dC
D -U -(K a )(C - C ) =0.0
dz
dz
Volatile Liquid-phase mass balance:
2
g, i L, i L, i
L, i L L g i L, i c c i L, i S, i
2
C d C dC
D -U +(K a )( - C ) -(K a )(C - C ) =0.0
dz Hi
dz