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Gas Liquid

and
Gas- Liquid Solid Reactions

A. Gas Liquid Systems
Proper Approach to Gas-Liquid Reactions
References
Mass Transfer theories
Gas-liquid reaction regimes
Multiphase reactors and selection criterion
Film model: Governing equations, problem
complexities
Examples and Illustrative Results
Solution Algorithm (computational concepts)
Theories for Analysis of Transport
Effects in Gas-Liquid Reactions
Two-film theory
1. W.G. Whitman, Chem. & Met. Eng., 29 147 (1923).
2. W. K. Lewis & W. G. Whitman, Ind. Eng. Chem., 16, 215 (1924).
Penetration theory
P. V. Danckwerts, Trans. Faraday Soc., 46 300 (1950).
P. V. Danckwerts, Trans. Faraday Soc., 47 300 (1951).
P. V. Danckwerts, Gas-Liquid Reactions, McGraw-Hill, NY (1970).
R. Higbie, Trans. Am. Inst. Chem. Engrs., 31 365 (1935).

Surface renewal theory
P. V. Danckwerts, Ind. Eng. Chem., 43 1460 (1951).

Rigorous multicomponent diffusion theory
R. Taylor and R. Krishna, Multicomponent Mass Transfer,
Wiley, New York, 1993.
Two-film Theory Assumptions
1. A stagnant layer exists in both the gas and the
liquid phases.

2. The stagnant layers or films have negligible
capacitance and hence a local steady-state exists.

3. Concentration gradients in the film are one-
dimensional.

4. Local equilibrium exists between the the gas and
liquid phases as the gas-liquid interface

5. Local concentration gradients beyond the films are
absent due to turbulence.
Two-Film Theory Concept
W.G. Whitman, Chem. & Met. Eng., 29 147 (1923).
Bulk Liquid Bulk Gas
p
A
p
Ai
C
Ai


C
Ab
x = 0
x
x + Ax
o
L
Liquid Film Gas Film
x = o
L
x = o
G
p
Ai
= H
A
C
Ai
Two-Film Theory
- Single Reaction in the Liquid Film -
A (g) + b B (liq) P (liq)
R
A

kg-moles A
m
3
liquid - s



(

(
= - k
mn
C
A
m
C
B
n
Closed form solutions only possible for linear kinetics
or when linear approximations are introduced
B & P are nonvolatile
Film Theory Model for a Single Nonvolatile
Gas-Liquid Reaction
2
*
2
2
2
( ) ( ) ( )
0
0 0
A L
B L
A g bB l P l
d A
D r at x A A at x A A
dx
d B dB
D br at x at x B B
dx dx
o
o
+
= = = = =
= = = = =
Diffusion - reaction equations for a single reaction in the liquid film are:
In dimensionless form, the equations become dependent on two
dimensionless parameters, the Hatta number Ha and q
*
:
( )
1/ 2
1
* *
*
2
1
m n
mn
m
n
D L B
A mn L
R A
For r k A B
t B D
Ha D k A B q
t m bA D

=
(
= =
(
+

=
Diffusion - reaction equations for a
single reaction in the liquid film are:
A
A
A
A
R
x
C
D
t
C
+
c
c
=
c
c
2
2
B
B
B
B
R
x
C
D
t
C
+
c
c
=
c
c
2
2
Penetration Theory Model
Comparison Between Theories
Film theory:
k
L
D, o - film thickness
Penetration
theory:
k
L
D
1/2

Higbie model
t
*
- life of surface liquid
element

Danckwerts model
s - average rate of
surface renewal
'
*
A
L
R D
k
C C o
=

'
* *
2
A
L
R D
k
C C t t
=

'
*
A
L
R
k Ds
C C
=

=
=
=
Gas-Liquid Reaction Regimes
Very Slow
Rapid pseudo
1st or mth order
Instantaneous Fast (m, n)
General (m,n) or Intermediate Slow Diffusional
Instantaneous & Surface
Characteristic Diffusion &
Reaction Times
Diffusion time


Reaction time


Mass transfer time

2
D
L
D
t
k
=
E
R
C C
t
r

=
1
M
L B
t
k a
=
Reaction-Diffusion Regimes Defined
by Characteristic Times
Slow reaction regime t
D
<<t
R
k
L
=k
L
0

Slow reaction-diffusion regime: t
D
<<t
R
<<t
M


Slow reaction kinetic regime: t
D
<<t
M
<<t
R


Fast reaction regime: t
D
>>t
R
k
L
=E
A
k
L
0
>k
L
0


Instantaneous reaction regime: k
L
= E
A
k
L
0

For reaction of a gas reactant in the liquid with liquid reactant with/without assistance of a
dissolved catalyst
( ) ( ) ( ) P b g A = + |

The rate in the composition region of interest can usually be approximated as

n
B
m
A A
C C k
s m
A mol k
R =
|
|
.
|

\
|

3


Where
B A
C C , are dissolved A concentration and concentration of liquid reactant B in the liquid.
Reaction rate constant k is a function of dissolved catalyst concentration when catalyst is involved.

For reactions that are extremely fast compared to rate of mass transfer form gas to liquid one
evaluates the enhancement of the absorption rate due to reaction.

( ) ( )
L A A L L A
H p E a k R
g o
c =
For not so fast reactions the rate is
( )
L
n
B
m
A
A
A
C
H
p
k R
g
c q
|
|
.
|

\
|
=

Where q effectiveness factor yields the slow down due to transport resistances.
S30
Gas Absorption Accompanied by Reaction in the Liquid
Assume:
- 2
nd
order rate
Hatta Number :
Ei Number:
Enhancement Factor:
H k k K
g L L
1 1 1
+ =
S31
S32
In this notation ( ) s m A mol k N
A
2

=
is the gas to liquid flux

( )
( )( ) s reactor m mol k R R
s liquid m mol k a N R
A L A
A A
3 '
3 '
=
=
c


S33
Eight (A H) regimes can be distinguished:
A. Instantaneous reaction occurs in the liquid film
B. Instantaneous reaction occurs at gas-liquid interface
High gas-liquid interfacial area desired
Non-isothermal effects likely
S34
C. Rapid second order reaction in the film. No unreacted A penetrates into
bulk liquid
D. Pseudo first order reaction in film; same Ha number range as C.
Absorption rate proportional to gas-liquid area. Non-isothermal effects still
possible.
S35
S36
Maximum temperature difference across film develops at complete mass
transfer limitations
Temperature difference for liquid film with reaction
Trial and error required. Nonisothermality severe for fast reactions.

e.g. Chlorination of toluene
S38
- Summary -
Limiting Reaction-Diffusion Regimes
Slow reaction kinetic regime
Rate proportional to liquid holdup and reaction rate and influenced by the
overall concentration driving force
Rate independent of k
l
a
B
and overall concentration driving force
Slow reaction-diffusion regime
Rate proportional to k
l
a
B
and overall concentration driving force
Rate independent of liquid holdup and often of reaction rate
Fast reaction regime
Rate proportional to a
B
,square root of reaction rate and driving force to the
power (n+1)/2 (nth order reaction)
Rate independent of k
l
and liquid holdup
Instantaneous reaction regime
Rate proportional to k
L
and a
B

Rate independent of liquid holdup, reaction rate and is a week function of the
solubility of the gas reactant
Key Issues
- Evaluate possible mechanisms and identify reaction pathways, key
intermediates and rate parameters
- Evaluate the reaction regime and transport parameters on the rate and assess
best reactor type
- Assess reactor flow pattern and flow regime on the rate
- Select best reactor, flow regime and catalyst concentration

Approximately for 2
nd
order reaction ( ) ( ) ( ) P B b g A +
( )
( )
reactor in fractin volume liquid local
reactor
liquid
factor t enhancemen ess dimensionl
ly. respective film, liquid and gas for t coefficien transfer mass volumetric 1 ,
A for constant s Henry'
phase gas in the A of pressure partial local
reactor of e unit volum per rate reaction local observed
1 1 1
3
3
3
3
=
|
|
.
|

\
|
=
=
=
|
|
.
|

\
|
=
=
|
.
|

\
|

+ +
=
m
m
E
E
s a k H a k
A mol k
liquid m atm
H
atm p
s m
A mol k
R
C k E a k H a k
H P
R
L
L
A A A
A
A
A
L L A A A
A A
A
L g
L g
c
|

S29
Gas- liquid solid systems

Gas-Liquid-Solid Reactions

Let us consider:
E B A
E
Catalyst
v v +


Reaction occurring in the pores of the catalyst particles and is gas reactant limited
A Reactant in the gas phase
B Non-volatile reaction in the liquid phase

Number of steps:
- Transport of A from bulk gas phase to gas-liquid interface
- Transport of A from gas-liquid interface to bulk liquid
- Transport of A&B from bulk liquid to catalyst surface
- Intraparticle diffusion in the pores
- Adsorption of the reactants on the catalyst surface
- Surface reaction to yield product

The overall local rate of reaction is given as
1
2
*
1 1 1

(
(

+ + =
l c p s
A
B k w a k a k
A R
L
q

S45
Gas Limiting Reactant (Completely Wetted Catalyst)
( )
( )
( ) ( )
( )
( )
( )
( )
( )
( )
( )
p v B p s B l
A
g
H
g
B v o A
s l p
a
g
B
s B p v
A v
k a k a K
H
A
A
k R
s react m mol
A A a
A
H
A
a
s react m mol
s react m mol A k
s cat m mol A k
A
q c
c q
c q

+ +
= =

|
|
.
|

\
|

O =
1
1 1 1
1
: . RATE (APPARENT) OVERALL
k : solid - Liquid -
K : liquid - Gas -
lume reactor vo unit per
. RATE TRANSPORT
lume reactor vo unit per
. 1 : CATALYST IN RATE
olume catalyst v unit per
. : RATE KINETIC
3
s
1 1
3
3
3
S21
Gas Liquid Solid Catalyzed Reaction A(g)+B(l)=P(l)
Dependence of Apparent Rate Constant (k
app
) on
Transport (k
ls
, q
p
) and Kinetic Parameters (k
v
)
( ) ( ) ( )
( )
( )( )
( ) ( ) s react m mol a B B k
s react m mol B k
s cat m mol B k
l P l B g A
p s l ls
B s p v
v
. :
lume) reactor vo unit (per
rate Transport
. 1 :
lume) reactor vo unit (per
catalyst in Rate
. :
olume) catalyst v unit (per
rate Kinetic
catalyst wetted completely of Case - le) (nonvolati reactant limiting Liquid
: Reaction
3
3
3

= +
c q
( )
( )
( )
B v p p ls
L
L app B v p
k a k
B
B k B k
s react m mol
c q
c q

+
=
1
1 1
1
. rate (apparent) Overall
1
3
Liquid limiting reactant (nonvolatile) Case of completely wetted catalyst

L
I
Q
U
I
D

F
I
L
M

B
U
L
K

L
I
Q
U
I
D

CATALYST
S
-
L

F
I
L
M

S
O
L
I
D

P
H
A
S
E

r
p

0
B
s
B
l


GAS
Clearly is determined by transport limitations and by
reactor type and flow regime.

Improving only improves if we are not already transport
limited.
Our task in catalytic reactor selection, scale-up and design is to
either maximize volumetric productivity, selectivity or product
concentration or an objective function of all of the above. The key
to our success is the catalyst. For each reactor type considered
we can plot feasible operating points on a plot of volumetric
productivity versus catalyst concentration.
v
m

a
S
v
m
max
v
m
max
x
x
max
x
max
v
m
a
S
ion concentrat catalyst
activity specific
3
=
|
.
|

\
|
=
|
|
.
|

\
|
reactor m
cat kg
x
h cat kg
P kg
S
a
S38
Chemists or biochemists need to improve S
a
and together with engineers work on
increasing
max
x .

Engineers by manipulation of flow patterns affect
max
v
m .

In Kinetically Controlled Regime
v
m

a
S x,


max
x
limited by catalyst and support or matrix loading capacity for cells or
enzymes

In Transport Limited Regime
v
m

p
p
a
x S ,

2 / 1 0 s s p


Mass transfer between gas-liquid, liquid-solid etc. entirely limit
v
m
and set
max
v
m
.
Changes in
,
a
S
do not help; alternating flow regime or contact pattern may help!

Important to know the regime of operation

S39
Key Multiphase Reactors
Bubble Column in different modes
Key Multiphase Reactor Parameters
Trambouze P. et al., Chemical Reactors From Design to
Operation, Technip publications, (2004)
Depending on the reaction regime one should select reactor type

- For slow reactions with or without transport limitations choose reactor with large
liquid holdup e.g. bubble columns or stirred tanks
- Then create flow pattern of liquid well mixed or plug flow (by staging) depending on
the reaction pathway demands

This has not been done systematically

- Stirred tanks
- Stirred tanks in series
- Bubble columns &
- Staged bubble columns

Have been used (e.g. cyclohexane oxidation).

One attempts to keep gas and liquid in plug flow, use small gas bubbles to increase a and
decrease gas liquid resistance.

Not explained in terms of basic reaction pathways.
Unknown transport resistances.
S39
2-10
40-100
10-100
10-50
4000-10
4

150-800
S40
S41
Multiphase Reactor Types for Chemical,
Specialty, and Petroleum Processes
S42

3. Basic Design Equations for
Multiphase Reactors
P.A. Ramachandran, P. L. Mills and M. P. Dudukovic
rama@wustl.edu; dudu@wustl.edu
Chemical Reaction Engineering Laboratory
Multiphase Reaction Engineering:
Starting References
1. P. A. Ramachandran and R. V. Chaudhari, Three-Phase
Catalytic Reactors, Gordon and Breach Publishers, New York,
(1983).

2. Nigam, K.D.P. and Schumpe, A., Three-phase sparged
reactors, Topics in chemical engineering, 8, 11-112, 679-
739, (1996)

3. Trambouze, P., H. Van Landeghem, J.-P. Wauquier,
Chemical Reactors: Design, Engineering, Operation,
Technip, (2004)

4. Dudukovic, Mills and Ramachandran, Course Notes (1990s
and 2000s)
Types of Multiphase Reactions
Gas-liquid without catalyst
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)
Straightforward
Complex
Reaction Type
Degree of Difficulty
Hierarchy of Multiphase Reactor Models
Empirical

Ideal Flow Patterns

Phenomenological

Volume-Averaged
Conservation Laws

Point-wise Conservation
Laws
Straightforward
Implementation Insight
Very little
Very Difficult
or Impossible
Significant
Model Type
Basic Reactor Types for Systems With Solid
Catalyst ( three or four phase systems)
Systems with moving catalysts
- stirred tank slurry systems
- slurry bubble columns
- loop slurry reactors
- three phase fluidized beds (ebulated beds)
Systems with stagnant catalysts
-packed beds with two phase flow: down flow,
up flow, counter-current flow
- monoliths and structured packing
- rotating packed beds

Phenomena Affecting Slurry Reactor Performance
Flow dynamics of the multi-phase dispersion
- Fluid holdups & holdup distribution
- Fluid and particle specific interfacial areas
- Bubble size & catalyst size distributions
Fluid macro-mixing
- PDFs of RTDs for the various phases
Fluid micro-mixing
- Bubble coalescence & breakage
- Catalyst particle agglomeration & attrition
Heat transfer phenomena
- Liquid evaporation & condensation
- Fluid-to-wall, fluid-to-internal coils, etc.
Energy dissipation
- Power input from various sources
(e.g., stirrers, fluid-fluid interactions,)
Reactor
Model
Fluid dynamics of the multi-phase flows
- Flow regimes & pressure drop
- Fluid holdups & holdup distribution
- Fluid-fluid & fluid-particle specific interfacial areas
- Fluid distribution
Fluid macro-mixing
- PDFs of RTDs for the various phases
Heat transfer phenomena
- Liquid evaporation & condensation
- Fluid-to-wall, fluid-to-internal coils, etc.
Energy dissipation
- Pressure drop
(e.g., stirrers, fluid-fluid interactions,)
Reactor
Model
Phenomena Affecting Fixed-Bed Reactor Performance
Elements of the Reactor Model
Micro or Local Analysis Macro or Global Analysis
Gas - liquid mass transfer
Liquid - solid mass transfer
Interparticle and inter-phase
mass transfer
Intraparticle and intra-phase
diffusion
Intraparticle and intra-phase
heat transfer
Catalyst particle wetting
Flow patterns for the
gas, liquid, and solids
Dynamics of gas, liquid,
and solids flows
Macro distributions of
the gas, liquid and solids

Heat exchange

Other types of transport
phenomena
Reactor Design Variables
Reactor Process Reaction Flow
= f
Performance Variables Rates Patterns

Conversion Flow rates Kinetics Macro

Selectivity Inlet C & T Transport Micro

Activity Heat exchange

Feed
Reactor
Q
in

T
in

C
in
Product
Q
out

T
out

C
out
Idealized Mixing Models for Multi-
phase ( Three Phase) Reactors
Model Gas-Phase Liquid Phase Solid-Phase Reactor Type

1 Plug-flow Plug-flow Fixed Trickle-Bed
Flooded-Bed

2 Back mixed Back mixed Back mixed Mechanically
agitated

3 Plug-Flow Back mixed Back mixed Bubble column
Ebullated - bed
Gas-Lift & Loop

Ideal Flow Patterns in Multiphase Reactors
Example: Mechanically Agitated Reactors
t
c c
L
r G L
L
V
Q
=
( ) 1
t
c
G
r G
G
V
Q
=
V
R
= v
G
+ V
L
+ V
C

1 = c
G
+ c
L
+ c
C
or
First Absolute Moment of the
Tracer Response for Multi-phase Systems
For a single mobile phase in contact with p stagnant phases:

1
=
V
1
+ K
1j
V
j
j = 2
p

Q
1
For p mobile phases in contact with p - 1 mobile phases:

1
=
V
1
+ K
1j
V
j
j = 2
p

Q
1
+ K
1j
Q
j
j = 2
p

K
1j
=
C
j
C
1
|
\

|
.
|
equil.
is the partition coefficient of the tracer
between phase 1 and j
Relating the PDF of the Tracer Impulse
Response to Reactor Performance
For any system where the covariance of sojourn times is zero
(i.e., when the tracer leaves and re-enters the flowing stream at
the same spatial position), the PDF of sojourn times in the reaction
environment can be obtained from the exit-age PDF for a
non-adsorbing tracer that remains confined to the flowing phase
external to other phases present in the system.

For a first-order process:
}

0
H -
A
p
e = X - dt ) t ( E 1
ext
t ) (k
c
}

0
( -
e = dt ) t ( E
ext
t ) Q / W k
1 W
H
p
(k
c
) = pdf for the stagnant phase
Illustrations of Ideal-Mixing Models
for Multiphase Reactors
Az
G L
Plug-flow of gas
Backmixed liquid & catalyst
Batch catalyst
Catalyst is fully wetted
Az
G L
Plug-flow of gas
Plug-flow of liquid
Fixed-bed of catalyst
Catalyst is fully wetted
Stirred tank

Bubble Column
Trickle - Bed

Flooded - Bed


























Limiting Forms of Intrinsic Reaction Rates
Reaction Scheme: A (g) + vB (l) C (l)
Az
G L
Gas Limiting Reactant and Plug-Flow of Liquid
1. Gaseous reactant is limiting

2. First-order reaction wrt dissolved gas

3. Constant gas-phase concentration

4. Plug-flow of liquid

5. Isothermal operation

6. Liquid is nonvolatile

7. Catalyst concentration is constant

8. Finite gas-liquid, liquid-solid,
and intraparticle gradients
Key Assumptions
Reaction Scheme: A (g) + vB (l) C (l)

1 /
0
>>
l
A B
C C 1 / >>
l
L
L
A
A
B B
C D C D v
Gas Reactant Limiting and Plug Flow of Liquid
Constant gas phase concentration
valid for pure gas at high flow rate
C
o
n
c
e
n
t
r
a
t
i
o
n

o
r

A
x
i
a
l

H
e
i
g
h
t

Relative distance from catalyst particle
( ) ( ) 0 dz= A A A a dz- k A A A a k A Q A Q
r s l p s r l
*
B l
dz z
l l
z
l l
+
+
(Net input by
convection)
(Input by Gas-
Liquid Transport)
(Loss by Liquid-
solid Transport)
+
- = 0
(1)
(2)
(3)
(4)
Dividing by Ar.dz and taking limit dz
Gas Reactant Limiting and Plug Flow of Liquid
Gas Reactant Limiting and Plug Flow of Liquid
Solving the Model Equations
Concept of Reactor Efficiency
=
R
q
Rate of rxn in the Entire Reactor with Transport Effects
Maximum Possible Rate
Conversion of Reactant B
(in terms of Reactor Efficiency)
Gas Reactant Limiting and Backmixed Liquid
Az
G L
1. Gaseous reactant is limiting

2. First-order reaction wrt dissolved gas

3. Constant gas-phase concentration

4. Liquid and catalyst are backmixed

5. Isothermal operation

6. Liquid is nonvolatile

7. Catalyst concentration is constant

8. Finite gas-liquid, liquid-solid,
and intraparticle gradients
Stirred Tank

Bubble Column


























Key Assumptions
Gas Reactant Limiting and Backmixed Liquid
C
o
n
c
e
n
t
r
a
t
i
o
n

o
r

A
x
i
a
l

H
e
i
g
h
t

Relative distance from catalyst particle
-Concentration of dissolved gas in the liquid bulk is constant [f(z)] [=A
l,0
]
-Concentration of liquid reactant in the liquid bulk is constant [f(z)] [=B
l,0
]
A in liquid bulk: Analysis is similar to the previous case
Gas Reactant Limiting and Backmixed Liquid
A at the catalyst surface:
For Reactant B:
(Note: No transport to gas
since B is non-volatile)
(Net input by
flow)
(Rate of rxn of B at
the catalyst surface)
=
Gas Reactant Limiting and Backmixed Liquid
Solving the Model Equations
Flow Pattern Concepts
for Various Multiphase Systems
A
B
A - Single plug flow phase flow of
gas or liquid with exchange between
the mobile phase and stagnant phase.
Fixed beds, Trickle-beds, packed
bubble columns

B - Single phase flow of gas or
liquid with exchange between a
partially backmixed stagnant phase.
Semi-batch slurries, fluidized-beds,
ebullated beds
Flow Pattern Concepts
for Various Multiphase Systems
C D
E
C, D - Co current or
countercurrent two-phase
flow (plug flow or dispersed
flow) with exchange
between the phases and
stagnant phase.
Trickle-beds, packed or
empty bubble columns

E - Exchange between two
flowing phases, one of
which has strong internal
recirculation.
Empty bubble columns and
fluidized beds
Strategies for Multiphase Reactor Selection
Strategy level I: Catalyst design strategy
gas-solid systems: catalyst particle size, shape, porous structure,
distribution of active material
gas-liquid systems: choice of gas-dispersed or liquid-dispersed
systems, ratio between liquid-phase bulk volume and liquid-phase
diffusion layer volume
Strategy level II: Injection and dispersion strategies
(a) reactant and energy injection: batch, continuous, pulsed,
staged, flow reversal
(b) state of mixedness of concentrations and temperature: well-
mixed or plug flow
(c) separation of product or energy in situ
(d) contacting flow pattern: co-, counter-, cross-current
Strategy level III: Choice of hydrodynamic flow regime
e.g., packed bed, bubbly flow, churn-turbulent regime, dense-
phase or dilute-phase riser transport
Strategies for Multiphase Reactor Selection
R. Krishna and S.T. Sie, CES, 49, p. 4029 (1994)
) J ( T ), j ( C
g g
i
1 1
Gas Film
Liquid Bulk
) J ( T ), j ( C
g g
i
) J ( T ), j ( C
L L
i
) J ( T ), j ( C
L L
i
1 1
Gas Bulk

=
A =
NR
j
R
f
j
f
H R
dx
T d
1
2
2
) ( k

=
=
NR
j
f
j ji
f
i
i
R
dx
C d
D
1
2
2
u
Liquid Film
Cell J
th

0 = X
f
) j ( , i
N
1 = X
f
) j ( , i
N
1 = X
f
) j ( , i
q
0
) ( ,
= X
f
j i
q
m
o
h
o
Two-Film Theory: Mass and Heat Transfer
Heat
Film
Gas-Liquid Film Model: Mass Transfer
j
NR
j
ji
f
i
i
R
dZ
C d
D

=
=
1
2
2
u
) (
0 ,
0 , g
z i
g
i g
f
z i
i
C C k
dZ
dC
D
=
=
=
B.C.1
f
z i
f
i
g
z i
C H C
0 , 0 , = =
=
m
Z Z Z o = =0








Gas Film
f
Z i
N
0 , =
Liquid Film
f
Z i
m
N
o = ,
i g
p
,
g
Z
i g
p
0
,
=
f
Z i
C
0 , =
b
i
f
Z i
C C
m
=
=o ,
Bulk Liquid
( )
f
ref
ref
f
Z
Si ref
i
f
i
h H
T T R
H
H H
0
0
)
1 1
( exp
=
=
=
(
(

A
=

u
Solubility or Violability
( ) | |
0
0
0
*
, ,
=
=
=
=


u
d
dc
h c c Bi
f
i
f
i
f
i i g i m
i
i ref g m
i m
D
H k
Bi
,
,
o
=
i ref i ref
i g
i g
C H
p
c
, ,
, *
,
=
B.C.2: Dirichlet conditions

=
A =
|
|
.
|

\
|
NR
j
j j r
f
L
R H
dZ
T d
1
,
2
2
) )( (
B.C.1
B.C.2
( )
0
1
, 0
0
) ( ) (
=
=
=
=
A + =

Z
f
i
i
NS
i
i s
f
z
g
out g
Z
f
L
dZ
dC
D H T T h
dZ
dT

( )
m h
f
Z
L
L
Z
f
L
m
h
T T
dZ
dT
o o

o
o

=
=
=
) (






g
T
f
T
g
A
C
g
B
C
f
B
C
f
A
C
h
o
b
A
C
b
B
C
Z
Gas Film Liquid Film
Liquid Bulk
Heat Transfer Film
Mass Transfer Film
b
T
m
o
Gas-Liquid film
Gas-Liquid Film Model: Heat Transfer
Bubble Column Mixing Cell Model
- Cells arranged in different modes to simulate the averaged flow patterns
- These averaged flow patterns can be obtained from the CFD simulations
Cells in series:
G and L mixed flow
Cells in
series-parallel
combination

Exchange
between
Upward and
downward
moving liquid
Liquid
Gas
Liquid
Gas
Cell 1
Cell N
Cell j
Cells in series:
G plug flow, L mixed flow
Prototype cell
Mixing Cell Model for gas-liquid systems
Novel features
Non-isothermal effects in the gas-liquid film
and in the bulk liquid
Effect of volatility of the liquid phase
reactant on the interfacial properties
Interfacial region modeled using film theory
and solved using integral formulation of the
Boundary Element Method (BEM)
Model validity over a wide range of
dimensionless numbers like Hatta, Arrhenius,
solubility parameter, Biot, Damkohler
Application to oxidation reactions like
cyclohexane, p-xylene, etc. in stirred tank and
stirred tank in series
(Ruthiya et al. under progress)
(Kongto, Comp.&Chem.Eng., 2005)
Prototype Gas Cell
Prototype Liquid Cell
Non-Dimensionalized parameters
Variables
Reaction based
ref i
f
i f
i
g
ref i
g
i g
i
C
C
c and
C
C
c
, ,
= =
ref i
g
ref i ref i
H C C
, , ,
/ =
r
L
ref
L cell
gL
A u
k aV
= o
ref ref , i i
C C = e
ref
j
ref
L
m L cell
j
R
C Q
a V
M
) ( o c
=
ref
aj
j
RT
E
=
ref
L
p L L
D C Le =
ref
L
p L
ref j , r
j
T C
C H
B

A
=
ref ref
2
m
ref
j 2
j
C D
R
Ha
o
=
i
g ref i m
i M
D
k H
Bi
,
,
o
=
Mass transfer based
ref L
ref ref
j
r
j
T
C D H

|
) (
,
A
=
L
m g
H
h
Bi

o
=
ref L
ref i i i S
i S
T
C D H

|
, ,
,
) ( A
=
ref i
g
ref
L
ref
fi
H u
u
,
=
ref
i
i
D
D
s =
g p m g
L cell gl g
C m
V a
S
,
o

=
m L p L
L cell gl L
C m
V a
S
o

,
=
Heat transfer based
Gas-Liquid Reactor Model
m
Z
o
=
g
ref
g
g
Q
Q
f =
ref
L
L
T
T
= u
ref
g
g
T
T
= u
Heat of reaction
parameter
Bulk reaction number
Hatta number
Arrhenius
number
Heat of reaction
parameter
Damkohler number Biot number
Biot number
Heat of solution
parameter
Liquid heat
transfer number
Gas heat
transfer number
Lewis number
Diffusivities
ratio
Effective G/L ratio
- Vas Bhat R.D., van Swaaij W.P.M., Kuipers, J.A.M., Versteeg,G.F., Mass transfer with
complex chemical reaction in gas-liquid , Chem. Eng. Sci., 54, 121-136, (1999)

- Vas Bhat R.D., van Swaaij W.P.M., Kuipers, J.A.M., Versteeg,G.F., Mass transfer with
complex chemical reaction in gas-liquid , Chem. Eng. Sci., 54, 137-147, (1999)

- Al-Ubaidi B.H. and Selim M.H. (1992), Role of Liquid Reactant Volatility in Gas
Absorption with an Exothermic Reaction, AIChE J., 38, 363-375, (1992)

- Bhattacharya, A., Gholap, R.V., Chaudhari, R.V., Gas absorption with exothermic
bimolecular (1,1 order) reaction, AIChE J., 33(9), 1507-1513, (1987)

- Pangarkar V.G., Sharma, M.M., Consecutive reactions: Role of Mass Transfer
factors, 29, 561-569, (1974)

- Pangarkar V.G., Sharma, M.M., Simultaneous absorption and reaction of two
gases, 29, 2297-2306, (1974)

- Ramachandran, P.A., Sharma, M.M., Trans.Inst.Chem.Eng.,49, 253,(1971)
Studies for Complex Gas-Liquid Reactions
Types of Heat Generation
1. Heat of solution (H
s
), which is generated at the gas-liquid
interface due to the physical process of gas dissolution

2 Heat of vaporization (H
v
), of volatile reactants due to
evaporative cooling in oxidation reaction

3. Heat of reaction (H
r
), which is generated in the film near the
gas-liquid interface (for fast reactions), or in the bulk liquid
(for slow reactions).
Uncontrolled heat generation can lead to:
1. Undesired production of by-products
2. Thermally-induced product decomposition
3. Increased rate of catalyst deactivation
4. Local hot spots and excess vapor generation
5. Reactor runaway and unsafe operation

Modeling of simultaneous mass and heat transport effects in
the film is necessary for accurate predictions
How Heat Generation Can Affect Mass
Transfer Rates in Gas-Liquid Reactions
1. Physical, transport, and thermodynamic
properties of the reaction medium exhibit
various degrees of temperature dependence

2. Kinetic parameters exhibit exponential
dependence on the local temperature

3. Instabilities at the gas-liquid reaction
interface that are driven by surface tension effects
(Marangoni effect) and density effects
Typical Systems with Notable Heat Effects
Shah & Bhattacharjee, in Recent
Advances, 1984.
Properties and Interfacial Temperature
Rise for Some Practical Systems
Shah & Bhattacharjee, in Recent Advances in the Engineering Analysis
of Multiphase Reacting Systems, Wiley Eastern, 1984.
Laboratory Reactors for
Gas - Liquid Reaction Kinetics
GL second order reaction
B A k
dx
A d
D
A 2
2
2
=
A
D
B k
Ha
0 2
2
2
o
=
Non-dimensionlizing
o
x
y =
Reaction Scheme: A + vB C
B A vk
dx
B d
D
B 2
2
2
=
b a Ha
dy
a d
2
2
2
=
ab
q
Ha
dy
b d
2
2
2
=
where
*
0
A zD
B D
q
A
B
=
2
2
2
2
dy
b d
q
dy
a d
=
( ) Ha
Ha
E
tanh
= For no depletion of B (interface concentration= bulk,
first order reaction
( )
i
i
b Ha
b Ha
E
tanh
=
For depletion of B
|
|
.
|

\
|
+ =
) tan(
1
1
i
i
i
b Ha
b Ha
q
q
b
A
i
D
B k
Ha
2
2
2
o
=
Case 1: Single non-isothermal reaction
Dimensionless Film Thickness
D
i
m
e
n
s
i
o
n
l
e
s
s

C
o
n
c
e
n
t
r
a
t
i
o
n

A
c
B
c
P
c
0
.
0
0
.
2
0
.
4
0
.
6
0
.
8
1
.
0
0 0
.
2 0
.
4 0
.
6 0
.
8 1
1
.
035
1
.
040
1
.
045
1
.
050
1
.
055
D
i
m
e
n
s
i
o
n
l
e
s
s

T
e
m
p
e
r
a
t
u
r
e

Non-volatility (Bi
m
=0)
Volatility (Bi
m
=1.5)


(Bim=1.5)
(Bim=0)
Temp.
Conc.
Case 1: Single non-isothermal reaction
Reaction Scheme:
A + vB C
Ha = 10, q = 0.05, = 22,
s = -7.5, vap = 2, |s=0.001,
|
vap
= -0.005, B
iHg
= 1
No vaporization
Vaporization of B
6.7 13.0 Enhancement
0.31 0.42 Product (C)
0.33 0.58 Reactant (B)
0.76 0.70 Gas (A)
Volatile Non-
volatile
6.7 13.0 Enhancement
0.31 0.42 Product (C)
0.33 0.58 Reactant (B)
0.76 0.70 Gas (A)
Volatile Non-
volatile

Bi
Hg
= 0.75
Bi
Hg
= 1.5
Bi
Hg
= 10
Ha
D
i
m
e
n
s
i
o
n
l
e
s
s


T
e
m
p
e
r
a
t
u
r
e

1
.
00
1
.
02
1
.
04
1
.
06
1
.
08
1
.
10
1
.
12
1
.
14
1
.
16
0 5 10 15 20 25 30 35
m g
Hg
h
Bi
o
k
=
Bi
Hg
Temp
A
b
B m ref
D
C k
Ha
2
2
o
=
Ha

Rxn Temp.
Case 1: Single non-isothermal reaction
Case 2: Local Supersaturation in the film
No C reaction here
Shah, Y.T., Pangarkar, V.G. and Sharma, M.M., Criterion for supersaturation in gas-liquid reactions
involving a volatile product, Chem. Eng. Sci., 29, 1601-1612, (1974)
Axial Dispersion Model (Single Phase)
Basis: Plug flow with superimposed
diffusional or eddy transport in
the direction of flow
R
dz
C
u
z
C
D
t
C
ax
+
c

c
c
=
c
c
2
2
@ z = 0
z
C
D uC C u
ax
c
c
=
0 0
@ z = L
0 =
c
c
z
C
Let
L
z
=
ax
ax
D
uL
Pe =
u
L
=
R
d
C

C
Pe t
C

ax
+
c

c
c
=
c
c
2
2
1
@ q = 0

C
Pe
C C
ax
c
c
=
1
0
@ q = 1 0 =
c
c

C
Axial Dispersion Model
R
d
C

C
Pe t
C

ax
+
c

c
c
=
c
c
2
2
1
@ q = 0

C
Pe
C C
ax
c
c
=
1
0
@ q = 1 0 =
c
c

C
Axial Dispersion Model for the Liquid with
Constant Gas-Phase Concentration - 1
Mass Balance of A in the liquid phase
(Net input by
convection)
(Net input by
axial dispersion)
(Loss by Liquid-
solid Transport)
+
+ = 0
(input by gas-
liquid transport)
-
<A
l
> = mean X-sectional area occupied by liquid at z
Axial Dispersion Model for the Liquid with
Constant Gas-Phase Concentration - 2
Axial Dispersion Model for the Liquid with
Constant Gas-Phase Concentration - 3
ADM Model: Boundary Conditions
Axial Dispersion Model - Summary
( ) ( )
s l p s l
*
B l
l
l
l
ax
A A a k A A a k
dz
dA
u
dz
A d
D = +
2
2
( )
s c s l p s
wA k A A a k
1
=
@ z = 0
dz
dA
D A u A u
l
ax l l li l
=
@ z = L
0 =
dz
dA
l
Comments regarding axial dispersion model
(ADM)
The model is very popular because it has only a single
parameter, axial dispersion coefficient, D
ax
, the value of
which allows one to represent RTDs between that of a
stirred tank and of a plug flow. The reactor model is usually
written in dimensionless form where the Peclet number for
axial dispersion is defined as:

time convection stic characteri
time dispersion axial stic characteri
/
/
/
2
= = =
U L
D L
D L U Pe
ax
ax ax
Pe
ax
plug flow

Pe
ax
0 complete back mixing
ADM comments continued-1
Use of ADM was popularized by the work of
Danckwerts, Levenspiel, Bischoff, j. Smith and
many others in the 1960s through 1970s.
Since D
ax
encompasses the effects of the
convective flow pattern, eddy as well as
molecular diffusion, prediction of the Axial Peclet
Number with scale up is extremely difficult as a
theoretical basis exists only for laminar and
turbulent single phase flows in pipes.
Moreover use of ADM as a model for the reactor
is only advisable for systems of Peclet larger
than 5 (preferably 10).
ADM comments continued -2
However, ADM leads to the boundary value
problem for calculation of reactor performance
with inlet boundary conditions which are needed
to preserve the mass balance but unrealistic for
actual systems. Since at large Peclet numbers
for axial dispersion the RTD is narrow, reactor
performance can be calculated more effectively
by a tanks in series model or segregated flow
model.
ADM comments continued -3
ADM is not suitable for packed beds, since there is
really never any dispersion upstream of the point of
injection (Hiby showed this conclusively in the
1960s); a parabolic equation does not describe the
physics of flow in packed beds well. A hyperbolic
equation approach (wave model) should be used as
shown recently by Westerterp and coworkers (AICHE
Journal in the 1990s).
ADM is not suitable for bubble column flows as the
physics of flow requires at least a two dimensional
convection- eddy diffusion model for both the liquid
and gas phase (Degaleesan and Dudukovic, AICHEJ
in 1990s).
ADM is clearly unsuitable for multiphase stirred tanks
Final Comments
To improve predictability of multiphase reactor
models and reduce the risk of scale-up, they
should be increasingly developed based on
proper physical description of hydrodynamics in
these systems.
Improved reactor scale descriptions coupled
with advances on molecular and single eddy
(single particle) scale will facilitate the
implementation of novel environmentally benign
technologies by reducing the risk of such
implementations.
Return to Systems Approach in
selecting best reactor for the task
Expansion in capacity of a best selling
herbicide provides an opportunity to
assess the current reactor and suggest a
better solution
Detailed chemistry is kept proprietary
Reaction System
S46
Disadvantages of Semi-Batch Slurry Reactor
Batch nature variable product
Low volumetric productivity (due to low catalyst loading
and limited pressure)
Pressure limitation (shaft seal)
High power consumption
Poor selectivity (due to high liquid to catalyst volume
ratio and undesirable homogeneous reactions)
Catalyst filtration time consuming
Catalyst make-up required
Oxygen mass transfer limitations
S47
Potential Advantages of Fixed Bed System
S48
Slurry vs Fixed Bed
With proper design of catalyst particles a packed-bed
reactor with co-current down-flow of gas and liquid both
in partial wetting regime and in induced pulsing regime
can far surpass the volumetric productivity and
selectivity of the slurry system, yet require an order of
magnitude less of the active catalyst component.

Undesirable homogenous reactions are suppressed in
the fixed bed reactor due to much higher catalyst to
liquid volume ratio

Father advantage is accomplished in fixed beds by
operation at higher pressure (no moving shafts to seal).

Fixed bed operation requires long term catalyst stability
or ease of in situ regeneration .
S49
References
1. Suresh, A.K., Sharma, M.M., Sridhar, T., Engineering
Aspects of Liquid-Phase Air Oxidation of
Hydrocarbons, Ind. Eng. Chem. Research, 39, 3958-
3997 (2000).
2. Froment, G.F. and Bischoff, K.B., Chemical Reactor
Analysis and Design, Wiley (1990).
3. Levenspiel, O., Chemical Reaction Engineering, Wiley,
3
rd
Edition (1999).
S50
References
1. Dudukovic, M.P., Larachi, F., Mills, P.L., Multiphase
Reactors Revisited, Chem. Eng. Science, 541, 1975-
1995 (1999).
2. Dudukovic, M.P., Larachi, F., Mills, P.L., Multiphase
Catalytic Reactors: A Perspective on Current Knowledge
and Future Trends, Catalysis Reviews, 44(11), 123-246
(2002).
3. Levenspiel, Octave, Chemical Reaction Engineering, 3
rd

Edition, Wiley, 1999.
4. Trambouze, P., Euzen, J.P., Chemical Reactors From
Design to Operation, IFP Publications, Editions TECHNIP,
Paris, France (2002).
S45
For any process chemistry involving more
than one phase one should :
Select the best reactor flow pattern based on the
kinetic scheme and mass and heat transfer
requirements of the system,
Assess the magnitude of heat and mass transfer
effects on the kinetic rate
Assess whether design requirements can be met
based on ideal flow assumptions
Develop scale-up and scale-down relations
Quantify flow field changes with scale if needed
for proper assessment of reactor performance
Couple physically based flow and phase
contacting model with kinetics

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