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).

pA pAi
pAi = HA CAi
•
Bulk Gas Gas Film Liquid Film Bulk Liquid
• CAi

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


m 3
liquid - s 

mn A B

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 at x  0 A  A* at x   A  AL
dx
d 2B dB
DB 2  br at x  0  0 at x   B  BL
dx dx
• In dimensionless form, the equations become dependent on two
dimensionless parameters, the Hatta number Ha and q*:

For r  kmn Am B n
1/ 2
tD  2 
DA kmn  A  BLn 
* m 1 BL DB
Ha =   q* 
tR  m  1  bA* DA
 Penetration Theory Model

C A  2C A
 DA  RA
t x 2

CB  2C B
 DB  RB
t x 2

• Diffusion - reaction equations for a

single reaction in the liquid film are:
 Comparison Between Theories

• Film theory:
RA' D
– kL D,  - film thickness kL = * 
• Penetration C C 
theory:
– kL D1/2 RA' D
Higbie model kL = 2
t* - life of surface liquid
C C
*
t *

element
'
R
Danckwerts model kL = A
 Ds
s - average rate of C C
*

surface renewal
 Gas-Liquid Reaction Regimes

Instantaneous Fast (m, n) Rapid pseudo

Instantaneous & Surface
1st or mth order

General (m,n) or Intermediate Slow Diffusional

Very Slow
 Characteristic Diffusion &
Reaction Times
D
• Diffusion time tD  2
kL
C  CE
• Reaction time tR 
r
1
• Mass transfer time 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: tD>>tR kL=EA kL0>kL0

– Instantaneous reaction regime: kL= EA kL0

For reaction of a gas reactant in the liquid with liquid reactant with/without assistance of a
dissolved catalyst
Ag   b    P

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

 k mol A 
 RA  3

  k C A
m
C B
n

 m s 

Where C A , CB 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.

 RA   k L a EL
o
p Ag 
HA L
For not so fast reactions the rate is
m
 p Ag 
 RA    k   CBn  L
 HA 

Where  effectiveness factor yields the slow down due to transport resistances.

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 k g H

S31
S32
 
In this notation   N A k mol A m 2 s 
is the gas to liquid flux


 R A'  N A a k mol m 3 liquid s 
 
 R A   L  R A' k mol m3 reactor s 

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 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
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 2nd order reaction Ag   b B  P

PA H A
 RA 
1 1 1
 
k Ag a H A k AL a EL k C  L
 k mol A 
 RA    observed local reaction rate per unit volume of reactor
 ms  3

p A atm   local partial pressure of A in the gas phase

 atm m3 liquid 
H A    Henry's constant for A

 k mol A 
k Ag a H A , k AL a1 s   volumetric mass transfer coefficient for gas and liquid film, respectively.
EL  dimensionl ess enhancement factor
 m3 liquid 
EL  3   local liquid volume fractin in reactor

 m reactor  S29
Gas- liquid – solid systems
 Gas-Liquid-Solid Reactions

A  B  
  E E
Catalyst
Let us consider:
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
 1 1 1 
RA  A*    
 L
k a k a
s p  c w k 2 l
B 
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 v olume 

RATE IN CATALYST : k v  p 1   B  As mol m 3 react. s 
per unit reactor vo lume 

TRANSPORT RATE mol m 3 react. s 
per unit reactor vo lume 
 Ag 
- Gas - liquid : K 1 a B   A1 
 Ha 
- Liquid - solid : k s a p  Al  As 

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
Liquid limiting reactant
reactant (nonvolati le) -–Case
(nonvolatile) Caseofofcompletely
completelywetted
wettedcatalyst
catalyst

Kinetic rate 
: kv B mol m3 cat.s 
(per unit catalyst v olume)

Rate in catalyst 
: kv p Bs 1   B  mol m3 react.s 
(per unit reactor vo lume)

Transport rate 
: kls Bl  Bs a p mol m3 react.s 
(per unit reactor vo lume)

CATALYST

 
GAS

Overall (apparent) rate mol m3 react.s

 p kv 1   B B1  kapp BL 
Bl
BL
Bs
1 1

LIQUID FILM

kls a p  p kv 1   B 
PHASE
SOLID

LIQUID
BULK

S-L FILM

rp 0
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.
m vmax
Sa  kg P 
m v S a    specific activity
 kg cat h 
 kg cat 
x 3   catalyst concentration
 m reactor 

xmax x
Clearly m vmax is determined by transport limitations and xmax by
reactor type and flow regime.

Improving S a only improves m v if we are not already transport

limited. S38
Chemists or biochemists need to improve Sa and together with engineers work on
increasing xmax .

Engineers by manipulation of flow patterns affect m vmax .

In Kinetically Controlled Regime

m v  x, Sa

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

In Transport Limited Regime

 Sa , x p
p
m v
0  p  1/ 2

Mass transfer between gas-liquid, liquid-solid etc. entirely limit m v and set m vmax .
Changes in S a , 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
4000-104

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 Laboratory

 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
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
Complex
or solid catalyst (two liquid phases)
Hierarchy of Multiphase Reactor Models

Model Type Implementation Insight

Empirical Straightforward Very little

Ideal Flow Patterns

Phenomenological

Volume-Averaged
Conservation Laws

Point-wise Conservation Very Difficult Significant

Laws or Impossible
 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
- PDF’s of RTDs for the various phases

Fluid micro-mixing
Reactor
- Bubble coalescence & breakage
- Catalyst particle agglomeration & attrition Model

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,…)
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
- PDF’s of RTDs for the various phases
Reactor
Heat transfer phenomena Model
- Liquid evaporation & condensation
- Fluid-to-wall, fluid-to-internal coils, etc.

Energy dissipation
- Pressure drop
(e.g., stirrers, fluid-fluid interactions,…)
 Elements of the Reactor Model
Micro or Local 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
Macro or Global Analysis
• 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
Qin Qout
Feed Tin Reactor Tout Product
Cin Cout

Reactor Process Reaction Flow

=f
Performance Variables Rates Patterns

• Conversion • Flow rates • Kinetics • Macro

• Selectivity • Inlet C & T • Transport • Micro

• Activity • Heat exchange

 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

VR = vG + VL + VC
or
1 = G + L + C
Vr G Vr (1   G   L )
G  L 
QG QL
 First Absolute Moment of the
Tracer Response for Multi-phase Systems
For a single mobile phase in contact with p stagnant phases:
p
V1 +  K1j V j
j=2
1 =
Q1

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

p
V1 +  K1j V j
j= 2
1 = p
Q1 +  K 1j Q j
j= 2

C j 
K1j =   is the partition coefficient of the tracer
C1 equil.
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
1 - XA =  e p c
Eext ( t ) dt
0
Hp(kc) = pdf for the stagnant phase 
- (k W W / Q1 ) t
= e Eext ( t ) dt
0
 Illustrations of Ideal-Mixing Models
for Multiphase Reactors
Stirred tank
Trickle - Bed
Bubble Column  

  Flooded - Bed

 
 
 


z z
 

 


 









G L G L
• Plug-flow of gas • Plug-flow of gas
• Backmixed liquid & catalyst • Plug-flow of liquid
• Batch catalyst • Fixed-bed of catalyst
• Catalyst is fully wetted • Catalyst is fully wetted
Limiting Forms of Intrinsic Reaction Rates
Reaction Scheme: A (g) + vB (l)  C (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
z 5. Isothermal operation
6. Liquid is nonvolatile
7. Catalyst concentration is constant
8. Finite gas-liquid, liquid-solid,
and intraparticle gradients
G L CB0 / CAl  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 by (Input by Gas- - (Loss by Liquid- =0 (1)
+
convection) Liquid Transport) solid Transport)

Ql Al z  Ql Al z  dz
 k a
l B 
A*

 Al Ar dz- k s a p  Al  As Ar dz= 0 (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
Rate of rxn in the Entire Reactor with Transport Effects
R 
Maximum Possible Rate
 Conversion of Reactant B
(in terms of Reactor Efficiency)
Gas Reactant Limiting and Backmixed Liquid
Stirred Tank Key Assumptions
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
z
 

 


5. Isothermal operation
 




6. Liquid is nonvolatile





7. Catalyst concentration is constant
8. Finite gas-liquid, liquid-solid,
and intraparticle gradients
G L
 Gas Reactant Limiting and Backmixed Liquid
Concentration or Axial Height

Relative distance from catalyst particle

-Concentration of dissolved gas in the liquid bulk is constant [≠f(z)] [=Al,0]

-Concentration of liquid reactant in the liquid bulk is constant [≠f(z)] [=Bl,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:
(Net input by (Rate of rxn of B at (Note: No transport to gas
= since B is non-volatile)
flow) 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 - Co current or E
C D
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)

Two-Film Theory: Mass and Heat Transfer
C ig ( j ), T g ( J ) C iL ( j ), T L ( J )

Gas Bulk Gas Film Liquid Film Heat Liquid Bulk

Film
Cell Jth
N if,( j ) N if,( j )
X 0 X 1
d 2Ci f NR
Di
dx 2
  
j 1
 R
ji j
f

d 2T f NR f
 2
  R j (H R )
dx j 1
qif,( j ) qif,( j )
X 0 X 1

m
h

Cig ( j  1 ), T g ( J  1 ) CiL ( j  1 ), T L ( J  1 )
 Gas-Liquid Film Model: Mass Transfer
Gas Film Liquid Film Bulk Liquid
Nif,Z0 d 2Ci f NR
Nif,Z m Di 2
  ji R j
dZ j 1

pg,i
Cif,Z0
g Cif,Z m  Cib
pg,i
Z0
Z 0 Z Z  m

B.C.1 D
dC f
i , z 0
 k g (C  C
g g
)

Bi m ,i c *
g ,i  ci f
 0

hi  f
 0  
dcif
d
i i i , z 0  0
dZ
 m k g H ref ,i c *  p g ,i
Bi m ,i  g ,i
Di H ref ,i C ref ,i

B.C.2: Dirichlet conditions Solubility or Violability

  H Si 1 
C g
i , z 0  Hi C f f
i , z 0
Hi  H
f
i
ref
exp 
1
( f  )   H ref h f0  
 R TZ 0 Tref 
 Gas-Liquid Film Model: Heat Transfer
Gas Film Liquid Film Liquid Bulk
f
T

Tg Tb

C Ag
C Af Gas-Liquid film
C Ab
 d 2T f  NR
C Bb L  2
   (H r , j )( R j )
 dZ  j 1
C Bg
CBf
Z m
Mass Transfer Film h
Heat Transfer Film

dT f
  dCi f
NS
B.C.1  L  hg T g
out T f
z 0   (H s ,i )( Di )
dZ Z 0 i 1 dZ Z 0

dT f (T L  TZf m )
B.C.2  L  L
dZ Z  h
 h   m 
 Bubble Column Mixing Cell Model
Cells in series: Cells in series: Cells in
G and L mixed flow G plug flow, L mixed flow series-parallel
combination
Cell N
Exchange
between
Upward and
Cell j
downward
moving liquid

Cell 1

Liquid Gas
Liquid Gas

Prototype cell
- Cells arranged in different modes to simulate the averaged flow patterns
- These averaged flow patterns can be obtained from the CFD simulations
 Mixing Cell Model for gas-liquid systems
Prototype Gas Cell 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)
Prototype Liquid Cell
• 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)
 Gas-Liquid Reactor Model
Non-Dimensionalized parameters
Variables
L
Cig Ci f Z Tg TL Qg uref
c  g
g
and ci 
f
   g
 
L
f g
 g  fi 
m
i g
Ci ,ref Ci ,ref Tref Tref Qref uref H i ,ref
Effective G/L ratio
Reaction based
H r , j C ref V (  a m ) ref (H r , j ) Dref Cref
j m
R ref 2 E aj
Bj   M j  cell LL Rj Ha  2 j  j 
 L CpL Tref Q C ref
j
D ref C ref RT ref LTref
Heat of reaction Hatta number Arrhenius Heat of reaction
Bulk reaction number
parameter number parameter

Mass transfer based

aV k  m H i ,ref k g Ci ,ref  Cig,ref / H i ,ref i  C i ,ref C ref si 
Di
 gL  Lcell L Bi M ,i  D ref
u ref A r Di
Biot number Diffusivities
Damkohler number
ratio

Heat transfer based

hg  m (H S ,i ) Di Ci ,ref a glVcell L a glVcell L Le  L  LC pL Dref
Bi H   S ,i  S 
L
S 
g

L LTref m L C p , L m mg mC p , g Lewis number

Biot number Heat of solution Liquid heat Gas heat
parameter transfer number transfer 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)

- Ramachandran, P.A., Sharma, M.M., Trans.Inst.Chem.Eng.,49, 253,(1971)

 Types of Heat Generation
1. Heat of solution (ΔHs), which is generated at the gas-liquid
interface due to the physical process of gas dissolution

2 Heat of vaporization (ΔHv), of volatile reactants due to

evaporative cooling in oxidation reaction

3. Heat of reaction (ΔHr), 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
 Case 1: Single non-isothermal reaction
Reaction Scheme: A + vB  C
GL second order reaction
d2A d 2B
DA 2
 k 2 A B DB 2
 vk2 A B
dx dx
Non-dimensionlizing
2
d a
2
d b Ha 2
D B  2 k 2 B0
 Ha 2
ab  ab where y  x q  B 0* Ha 2

dy 2
dy 2
q  zD A A DA

d 2a d 2b
2
q 2
dy dy

Ha
E For no depletion of B (interface concentration= bulk,
tanh Ha  first order reaction
Ha bi 1  Ha bi 

 2
k 2 Bi
E For depletion of B bi  q  q  1 
2

 
Ha
tanh Ha bi  tan( Ha bi )  DA
 Case 1: Single non-isothermal reaction
Reaction Scheme:
Temp.
1 .055
A + vB  C

Dimensionless Temperature
Ha = 10, q = 0.05,  = 22, No vaporization
1 .050
s = -7.5, vap = 2, s=0.001,
vap = -0.005, BiHg= 1
1 .045

Non- Volatile Vaporization of B

1 .040
volatile
Gas (A) 0.70 0.76
1 .035
Reactant (B) 0.58 0.33
Product (C) 0.42 0.31
Dimensionless Concentration 1 .0
Conc. cB
0 .8
Enhancement 13.0 6.7
0 .6 Non-volatility (Bim=0)
การกระจายของความเข้มข้น
และอุณหภูมใิ นฟิ ล์มของเหลว 0 .4 cP Volatility (Bim=1.5)
สาหร ับการถ่ายโอนมวลของ
0 .2
ปฏิกริ ย
ิ าเดีย
่ วแบบ cA
 ผ ันกล ับไม่ได้สาหร ับระบบทีม
่ ี 0 .0
0 0 .2 0 .4 0 .6 0 .8 1
การระเหย (Bim=1.5) และ ไม่
Dimensionless Film Thickness
มีการระเหย (Bim=0)
 Case 1: Single non-isothermal reaction
1 .16
Dimensionless Temperature

1 .14 BiHg = 0.75

1 .12 BiHg = 1.5
BiHg = 10
1 .10
1 .08
1 .06 BiHg ↑
→ Temp ↓
1 .04
Ha ↑ → Rxn ↑ → Temp. ↑
1 .02
1 .00
0 5 10 15 Ha 20 25 30 35

 m hg k  2 b
ref mCB
BiHg  Ha 
2
 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 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
C  2C C
 Dax u R
t z 2
dz
C C
@z=0 u0C0  uC  Dax @z=L 0
z z
z uL L
Let η Peax  τ
L Dax u
C 1  2C C
τ    τR
t Peax η 2
dη
1 C C
C0  C  @  = 1 0
@  = 0 Peax η η
 Axial Dispersion Model
C 1  2C C
τ    τR
t Peax η 2
dη
1 C C
C0  C  @  = 1 0
@  = 0 Peax η η
 Axial Dispersion Model for the Liquid with
Constant Gas-Phase Concentration - 1
Mass Balance of A in the liquid phase
(Net input by (Net input by + (input by gas- (Loss by Liquid- = 0
+ liquid transport) -
convection) axial dispersion) solid Transport)

<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
Dax 2  ul
dz
dAl
dz
 
 kl aB A*  Al  k s a p  Al  As 

k s a p  Al  As   ηc k1wAs

dAl
@z=0 ul Ali  ul Al  Dax
dz
dAl
@z=L 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:
2
L / Dax characteristic axial dispersion time
Peax  U L / Dax  
L /U characteristic convection time
Peax →∞ plug flow

Peax→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 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, 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,
3rd 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, 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