Gas- Liquid and Gas –Liquid –

Solid Reactions
Basic Concepts
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
 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   kLa 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.

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 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 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

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S32
 
In this notation   N A k mol A m2 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 m 3 reactor s 

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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.

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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

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 - 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 volum e of reactor
 m 3
s 
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 coefficien t for gas and liquid film, respective ly.
EL  dimensionl ess enhancemen t factor
 m3 liquid 
EL  3   local liquid volume fractin in reactor

 m reactor  S29
 Gas-Liquid-Solid Reactions

A  B  
  E E
Catalyst
Let us consider:
Reaction occurring at the surface of the catalyst
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 
R A  A*    
 L
k a k a
s p  c w k 2 l
B 
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 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 m 3
react. s 
per unit reactor volume
 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  HA

1 1 1
 
K l a B k s a p 1   B  k v p

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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

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Comparison Between Gas-Solid and Gas-Liquid-Solid Catalytic Converters
Category Gas-Solid Catalytic Gas-Liquid-Solid Catalytic
Design and engineering Simple More elaborate

Material Often expensive material can be used Corrosion problems can be critical

Catalyst Possible poisoning by non-volatile Resistance to corrosion is required

byproducts
Thermal control Low thermal stability and low heat Better stability and higher heat capacity;
capacity require internal heat exchange or partial vaporization is possible; better heat
low conversion exchange coefficient
Reactant recycling Often important Stoichiometric ratio can generally be
achieved; hydrodynamics can require gas
recycling
Safety Temperature run-away and ignition can Better stability
occur. Gas mixture must lie outside the
explosive range Operation within the inflammability or
explosion limits sometimes possible
Dissipated power Higher pressure drop Low pressure drop but sometimes stirring
is required

Reactant preheating Always important Less important or unnecessary

Heat recovery Generally at a high level but low heat At a lower level but high heat transfer
transfer rate rate; high efficiency
 Key Multiphase Reactor Types
• Mechanically agitated tanks
• Multistage agitated columns Soluble catalysts
• Bubble columns &
• Draft-tube reactors Powdered
catalysts
• Loop reactors

• Packed columns
• Trickle-beds
• Packed bubble columns
• Ebullated-bed reactors
Soluble catalysts
&
Tableted catalysts
 Classification of Multiphase
Gas-Liquid-Solid Catalyzed Reactors
1. Slurry Reactors
Catalyst powder is suspended in the liquid
phase to form a slurry.

2. Fixed-Bed Reactors

Catalyst pellets are maintained in place as

a fixed-bed or packed-bed.

K. Ostergaard, Adv. Chem. Engng., Vol. 7 (1968)

 Modification of the Classification for
Gas-Liquid Soluble Catalyst Reactors

1. Catalyst complex is dissolved in the liquid

phase to form a homogeneous phase.

2. Random inert or structured packing, if used,

provides interfacial area for gas-liquid contacting.
Multiphase Reactor Types for Chemical,
Specialty, and Petroleum Processes

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 Multiphase Reactor Types at a Glance

Middleton (1992)
Key Multiphase Reactor
 Comparison Between Slurry and Fixed-Bed Gas-Liquid-Solid Catalytic Converters

Category Slurry Reactors Trickle-Bed Reactors

Specific reaction rate High or fast reactions Rel. high for slow reactions

Catalyst Highly active Supported; high crushing strength, good

thermal stability and long working life
needed
Homogeneous side reactions Poor selectivity Good selectivity
Residence time distribution Perfect mixing Plug flow
Pressure drop Low or medium Low except for small particles
Temperature control Isothermal operation Adiabatic operation
Heat recovery Easy Less easy
Catalyst handling Technical difficulties None
Maximum volume 50 m3 300 m3
Maximum working pressure 100 bar high pressure possible
Process flexibility Batch or continuous Continuous
Investment costs High Low
Operating costs High Low
Reactor design and Well known difficult
extrapolation
Bubble Column in different modes
 Slurry and Fixed Bed Three Phase Catalytic Reactors

Typical Properties

Slurry Trickle-bed Flooded bed

Catalyst loading 0.01 0.5 0.5

Liquid hold-up 0.8 0.05-0.25 0.4

Gas hold-up 0.2 0.25-0.45 0.1

Particle diameter 0.1 mm 1 – 5 mm 1 – 5 mm

External catalyst area 500 m-1 1000 m-1 1000 m-1

Catalyst 1 <1 <1

effectiveness
G/L Interfacial area 400 m-1 200 m-1 200 m-1

Dissipated power 1000 Wm-3 100 Wm-3 100 Wm-3

 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.

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

150-800

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