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 onedimensional.
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).

pA

pAi

Bulk Gas

pAi = HA CAi

Gas Film Liquid Film

CAi

Bulk Liquid

CAb

x
x + x
L
x = G

x=0

x = L

Two-Film Theory
- Single Reaction in the Liquid Film A (g)

b B (liq)

P (liq)

B & P are nonvolatile

kg -moles A
m
n
RA
=
k
C
C
mn A
B
m3 liquid - s
Closed form solutions only possible for linear kinetics
or when linear approximations are introduced

Film Theory Model for a Single Nonvolatile

Gas-Liquid Reaction
Diffusion - reaction equations for a single reaction in the liquid film
are:

A( g ) bB (l ) P (l )

d2A
DA 2 r
dx
d 2B
DB 2 br
dx

at x 0 A A* at x A AL
dB
at x 0
0 at x B BL
dx

In dimensionless form, the equations become dependent on two

dimensionless parameters, the Hatta number Ha and q*:

For r kmn Am B n
tD 2
* m 1
n
Ha @

D
k
A
B

=
A mn
L

tR m 1

1/ 2

q*

BL DB
bA* DA

Penetration Theory Model

C A
2C A
DA
RA
2
t
x

C B
2C B
DB
RB
2
t
x

Diffusion - reaction equations for a

single reaction in the liquid film are:

Comparison Between Theories

Film theory:
kL D, - film thickness

Penetration theory:
kL D1/2
Higbie model
t* - life of surface liquid
element

Danckwerts model
s - average rate of surface
renewal

RA'
D
kL @

= *
C C

RA'
D
kL @
2
= *
*
C C
t
'
A

R
k L =@ *
Ds
C C

Gas-Liquid Reaction Regimes

Instantaneous

Fast (m, n)

Instantaneous & Surface

General (m,n) or Intermediate

Rapid pseudo
1st or mth order

Slow Diffusional

Very Slow

Characteristic
Reaction
Diffusion time

Reaction time

Mass transfer time

Diffusion &
Times

D
tD 2
kL
C CE
tR
r
1
tM
k L aB

Reaction-Diffusion Regimes Defined

by Characteristic Times

Slow reaction regime

tD<<tR kL=kL0

Slow reaction-diffusion regime:

tD<<tR<<tM

Slow reaction kinetic regime:

tD<<tM<<tR

Fast reaction regime:

Instantaneous reaction regime:

tD>>tR kL=EA kL0>kL0

kL= EA kL0

S30

Gas Absorption Accompanied by Reaction in the Liquid

Assume:

- 2nd order rate

Hatta Number :

Ei Number:
Enhancement Factor:

1
1
1

K L kL kg H
S31

S32

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.

D.

Rapid second order reaction in the film. No unreacted A penetrates into

bulk liquid

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 klaB and overall concentration driving force

Slow reaction-diffusion regime

Rate proportional to klaB and overall concentration driving force
Rate independent of liquid holdup and often of reaction rate

Fast reaction regime

Rate proportional to aB,square root of reaction rate and driving force to
the power (n+1)/2 (nth order reaction)
Rate independent of kl and liquid holdup

Instantaneous reaction regime

Rate proportional to kL and aB
Rate independent of liquid holdup, reaction rate and is a week function
of the solubility of the gas reactant

S29

Gas- liquid solid systems

S45

Gas Liquid Solid Catalyzed Reaction A(g)+B(l)=P(l)

Gas Limiting Reactant (Completely Wetted Catalyst)
KINETIC RATE

: k v A mol m 3 cat.s A

per unit catalyst volume

RATE IN CATALYST : k v p 1 B As mol m 3 react . s

per unit reactor volume

TRANSPORT RATE

mol

per unit reactor volume

m 3 react . s

Ag

: K 1 a B
A1
Ha

- Liquid - solid : k s a p Al As
- Gas - liquid

OVERALL (APPARENT) RATE mol m 3 react .s :

Ag
Ag
HA
R A o k v 1 B H A
1
1
1

K l a B k s a p 1 B k v p

S21

Dependence of Apparent Rate Constant (kapp) on

Transport (kls, p) and Kinetic Parameters (kv)
Reaction : A g B l P l
Liquid limiting reactant (nonvolati
le) -Case
(nonvolatile)
Caseof
of completely
completely wetted
wetted catalyst
catalyst

Kinetic rate
: kv B mol m 3 cat.s
(per unit catalyst volume)

Rate in catalyst
(per unit reactor volume)

: kv p Bs 1 B mol m 3 react .s

Transport rate
(per unit reactor volume)

: kls Bl Bs a p mol m 3 react .s

Overall (apparent) rate mol m 3 react .s

BL
p kv 1 B B1 k app BL
1
1

kls a p p kv 1 B

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
m
productivity versus vcatalyst concentration.
max

kg P
specific activity
S a
kg cat h
kg cat
x 3
catalyst concentration
m reactor

Sa

m v

m vmax

xmax

xmax

Clearly
is determined by transport limitations and
by
reactor type and flow regime.
m v
Sa
Improving
only improves
if we are not already transport S38

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)

S39

2-10
40-100
10-100
10-50
4000-104
150-800

S40

S41

Multiphase Reactor Types for Chemical,

Specialty, and Petroleum Processes

S42

Multiphase Reaction Engineering:

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

Starting References
1. P. A. Ramachandran and R. V. Chaudhari, ThreePhase 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

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
or solid catalyst

Gas-liquid-liquid with soluble

or solid catalyst (two liquid phases) Complex

Hierarchy of Multiphase Reactor Models

Model Type
Empirical

Implementation

Insight

Straightforward

Very little

Ideal Flow Patterns

Phenomenological
Volume-Averaged
Conservation Laws
Point-wise Conservation Very Difficult
or Impossible
Laws

Significant

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

Phenomena Affecting Fixed-Bed Reactor Performance

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

Elements of the Reactor Model

Micro or Local Analysis
Gas - liquid mass transfer

Macro or Global Analysis

Liquid - solid mass transfer

Flow patterns for the

gas, liquid, and solids

Interparticle and inter-phase

mass transfer

Dynamics of gas, liquid,

and solids flows

Intraparticle and intra-phase

diffusion

Macro distributions of
the gas, liquid and
solids

Intraparticle and intra-phase

heat transfer
Catalyst particle wetting

Heat exchange
Other types of transport
phenomena

Reactor Design Variables

Feed

Qin
Tin
Cin

Qout
Tout Product
Cout

Reactor

Reactor

Process

Reaction

Flow

Performance

Variables

Rates

Conversion

Flow rates

Kinetics

Selectivity

Inlet C & T

Transport Micro

Activity

Heat exchange

=f
Patterns
Macro

Idealized Mixing Models for Multiphase ( Three Phase) Reactors

Model Gas-Phase

Liquid Phase

Solid-Phase

Plug-flow

Fixed

Reactor Type

Plug-flow

Back mixed Back mixed

Back mixed

Mechanically
agitated

Plug-Flow

Back mixed

Bubble column
Ebullated - bed
Gas-Lift & Loop

Back mixed

Trickle-Bed
Flooded-Bed

Ideal Flow Patterns in Multiphase Reactors

Example: Mechanically Agitated Reactors
(t-g)
EG(t)

(t)
QG

XL(t)
QL
0

XG(t)

or

t
QL

1 = G + L + C
Vr G
QG

- t / L
e

EL(t)

QG

VR = vG + VL + VC
G

(t)

Vr (1 G L )
QL

First Absolute Moment of the

Tracer Response for Multi-phase Systems
For a single mobile phase in contact with p stagnant phases:
V1 +
1 =

K1j Vj

j=2

Q1

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

V1 +
1 =

K1j

C j
=
C1 equil.

Q1 +

K1j Vj

j= 2
p

K 1j Qj

j= 2

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:

- H (k ) t
p
c

1 - XA = e
Hp(kc) = pdf for the stagnant phase

= e
0

Eext ( t ) dt

- (k W W / Q1 ) t

Eext ( t ) dt

Illustrations of Ideal-Mixing Models

for Multiphase Reactors
Stirred tank

Trickle - Bed

Bubble Column

Flooded - Bed

Plug-flow of gas
Backmixed liquid & catalyst
Batch catalyst
Catalyst is fully wetted

Plug-flow of gas
Plug-flow of liquid
Fixed-bed of catalyst
Catalyst is fully wetted

Limiting Forms of Intrinsic Reaction Rates

Reaction Scheme: A (g) + vB (l)
(l)

Gas Limiting Reactant and Plug-Flow of Liquid

Reaction Scheme: A (g) + vB (l) C (l)

Key Assumptions

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

CB0 / C Al 1

DBL C B /D AL C Al 1

Concentration or Axial Height

Gas Reactant Limiting and Plug Flow of Liquid

Constant gas phase
concentration valid for pure
gas at high flow rate

Relative distance from catalyst particle

(Net input
(Input by Gas- - (Loss by Liquid- = 0
+
by
Liquid
solid Transport)
convection)
Transport)

Ql Al z Ql Al

k
a
A
Al Ar dz- k s a p Al As Ar dz= 0
l B
z dz

(1)

(2)

Dividing by Ar.dz and taking limit dz

(3)
(4)

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

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

Key Assumptions

Stirred Tank
Bubble Column

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

Concentration or Axial Height

Gas Reactant Limiting and Backmixed Liquid

Relative distance from catalyst particle

-Concentration of dissolved gas in the liquid bulk is constant [f(z)] [

-Concentration of liquid reactant in the liquid bulk is constant [f(z)]

A in liquid bulk:
bulk Analysis is similar to the previous case

Gas Reactant Limiting and Backmixed

Liquid

A at the catalyst surface:

For Reactant B:
(Net input
=
by flow)

(Rate of rxn of B
at the catalyst
surface)

(Note: No transport to
gas since B is nonvolatile)

Gas Reactant Limiting and Backmixed

Liquid
Solving the Model Equations

Flow Pattern Concepts

for Various Multiphase Systems
A

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

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 liquidphase 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, densephase or dilute-phase riser transport

Strategies for Multiphase Reactor

Selection

R. Krishna and S.T. Sie, CES, 49, p. 4029 (1994)

Two-Film Theory: Mass and Heat

Transfer

C ig ( j ), T g ( J )

Gas Bulk

C iL ( j ), T L ( J )

Gas Film
N if,( j )

qif,( j )

Liquid Film

Cell Jth
X 0

N if,( j )

NR
d 2 Ci f
f
Di

ji
j
dx 2
j 1

d 2T f NR f

R j (H R )
2
dx
j 1

X 1

qif,( j )

X 0

C ig ( j 1 ), T g ( J 1 )

Liquid Bulk

Heat
Film

X 1

C iL ( j 1 ), T L ( J 1 )

Gas-Liquid Film Model: Mass

Transfer
pg,i

Gas Film Liquid FilmBulk Liquid

Nif,Z0
Nif,Z m
g
pg,i Z0

Cif,Z0 C f Cb
i
i,Z m

Z 0 Z Z m

B.C.1D dC
i

NR
d 2 Ci f
Di
ji R j
2
dZ
j 1

f
i , z 0

dZ

k g (C C
g
i

g
i , z 0

Bim ,i c

*
g ,i

Bim ,i

Hi C
f

f
i , z 0

hi

f
0

dcif

p g ,i
m k g H ref ,i c *
g ,i

H ref ,i Cref ,i
Di

Solubility or Violability

B.C.2: Dirichlet conditions

g
i , z 0

ci

Hi H
f

ref
i

H Si
1
1
exp
( f
) H ref h f0
R
TZ 0 Tref

Gas-Liquid Film Model: Heat

Transfer
Gas-Liquid film

d 2T f
L
2
dZ

f
dT
B.C.1
L
dZ

dT f
B.C.2 L
dZ

hg T

g
out

Z 0

L
Z h

(T L TZf m )

h m

f
z 0

NR

j 1

( H r , j )( R j )

dCi f
( H s ,i )( Di )
dZ
i 1
NS

Z 0

Bubble Column Mixing Cell Model

Cells in series:
G plug flow, L mixed flow

Cells in series:
G and L mixed flow

Cell N

Cell j

Cells in
series-parallel
combination
Exchange
between
Upward and
downward
moving liquid

Cell 1

Liquid

Gas

Liquid

Gas

Prototype cell

- Cells arranged in different modes to simulate the averaged flow

patterns

Mixing Cell Model for gas-liquid

systems
Prototype Gas Cell

Novel features
Non-isothermal effects in the gasliquid film and in the bulk liquid
Effect of volatility of the liquid phase
reactant on the interfacial properties

Prototype Liquid Cell

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)

Gas-Liquid Reactor
Model
Non-Dimensionalized parameters
Variables
Cig
c g
Ci ,ref
g
i

and

Ci f
ci
Ci ,ref
f

TL

Tref

Tg

Tref

Qg
g
Qref

fi

L
uref
g
uref
H i ,ref

Effective G/L ratio

Reaction based
Bj

V ( a m ) ref
M j cell LL
Rj
Q C ref

H r , j C ref
L C pL Tref

Heat of reaction
parameter

Bulk reaction number

Ha
2
j

2
R ref
j m

D ref C ref
Hatta number

E aj

RTref

Arrhenius
number

( H r , j ) Dref Cref

LTref

Heat of reaction
parameter

Mass transfer based

gL

aV k
Lcell L
u ref A r

BiM ,i

Damkohler number

H k
m i ,ref g
Di

i C i , ref C ref

C i ,ref C ig,ref / H i ,ref

si

Di
D ref

Diffusivities
ratio

Biot number

Heat transfer based

BiH

hg m

Biot number

S ,i

(H S ,i ) Di Ci ,ref

LTref

Heat of solution
parameter

S
L

a glVcell L
mL C p , L m

Liquid heat
transfer number

S
g

a glVcell L
mg mC p , g

Gas heat
transfer number

Le L L C pL Dref
Lewis number

Studies for Complex Gas-Liquid

Reactions
- 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)

Types of Heat Generation

1. Heat of solution (Hs), which is generated at the gasliquid interface due to the physical process of gas
dissolution
2 Heat of vaporization (Hv), of volatile reactants due to
evaporative cooling in oxidation reaction
3. Heat of reaction (Hr), which is generated in the film
near the gas-liquid interface (for fast reactions), or in
the bulk liquid
(forgeneration
slow reactions).
Uncontrolled
heat
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

Case 1: Single non-isothermal reaction

Reaction Scheme: A + vB
C
2
2

GL second order reaction

d B
d A
D
vk 2 A B
DA
k2 A B
B
2
2
dx
dx

Non-dimensionlizing
2

d b Ha

ab
2
dy
q

d a
2

Ha
ab
2
dy

where y x

D B
q B 0*
zD A A

2 k 2 B0
Ha
DA
2

d 2a
d 2b
q 2
2
dy
dy
E
E

Ha
tanh Ha
Ha bi

tanh Ha bi

For no depletion of B (interface concentration=

bulk,
2
first order reaction

k 2 Bi
Ha bi
1
2

Ha

For depletion of B bi q q 1
DA
tan( Ha bi )

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,
BiHg= 1

Temp
.

Vaporization of B

Conc.

(Bim=1.5)
(Bim=0)

No vaporization

Case 1: Single non-isothermal reaction

BiHg

Temp
Ha Rxn Temp.

BiHg

2 b
k

m hg
ref mCB
2
Ha

DA

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 gasliquid reactions involving a volatile product, Chem. Eng. Sci., 29, 1601-1612, (1974)

Axial Dispersion Model (Single Phase)

C
2C
C
Dax
u
R
2
t
z
dz
@z=0

Let

u0C0 uC Dax

Peax

uL
Dax

C
z

Basis: Plug flow with

superimposed diffusional or
eddy transport in the
direction of flow

@z=L

C
0
z

C
1 2C C

R
2
t
Peax
d
@ = 0

1 C
C0 C
Peax

@ = 1

C
0

Axial Dispersion Model

C
1 2C C

R
2
t
Peax
d
@ = 0

1 C
C0 C
Peax

@ = 1

C
0

Axial Dispersion Model for the Liquid with

Constant Gas-Phase Concentration - 1
Mass Balance of A in the liquid phase
(Net input
(Net input by + (input by gas(Loss by Liquid-= 0
+
liquid
by
axial
solid Transport)
transport)
convection)
dispersion)
<Al> = 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

d 2 Al
dAl
*

Dax

k
a
A
Al k s a p Al As
l
l B
2
dz
dz
k s a p Al As c k1wAs

@z=0

dAl
ul Ali ul Al Dax
dz

@z=L

dAl
0
dz

Comments regarding axial dispersion model

(ADM)
The model is very popular because it has only a single
parameter, axial dispersion coefficient, Dax, 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:

L / Dax characteristic axial dispersion time

Peax U L / Dax

L /U
characteristic convection time
2

Peax

plug flow

Peax0

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 Dax 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, 39583997 (2000).
2. Froment, G.F. and Bischoff, K.B., Chemical Reactor
Analysis and Design, Wiley (1990).
3. Levenspiel, O., Chemical Reaction Engineering, Wiley,
3rd Edition (1999).

S50

References
1.

Dudukovic, M.P., Larachi, F., Mills, P.L., Multiphase

Reactors Revisited, Chem. Eng. Science, 541, 19751995 (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, 3rd

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