University of Dortmund

David W. Agar

Gas - Liquid
Reaction Engineering

Short Course
16th-25th June 2003
Chemical Engineering Department
IISc Bangalore

University of Dortmund Chemical Engineering Department Chair for Reaction Engineering

 University of Dortmund
Curriculum Vitae
1956 Danbury, England, GB

1977 BSc Biochemical Engineering Swansea, Wales, GB

1977-1980 PhD Chemical Engineering Houston, TX, USA

1980 Postdoctoral work Pasadena, CA, USA

1981-1986 Central Research, BASF AG Ludwigshafen, D

1987-1990 Caprolactam plant, BASF AG Ludwigshafen

Ludwigshafen

1990-1993 Coordinator for Isocyanate Ludwigshafen

Research, BASF AG
1993-1995 Coordinator for Reaction Ludwigshafen
Engineering Research, BASF AG
1995-1996 Technical Support, Amine sales, Calgary, CDN
BASF AG
1997- Chair for Reaction Engineering,TCB Dortmund, D

University of Dortmund Chemical Engineering Department Chair for Reaction Engineering

 University of Dortmund

Course content:
A survey of the most important gas-liquid reactions and the reactors
employed together with appropriate modelling & design fundamentals,
with special emphasis being placed on acid gas removal from syngas
& natural gas.

Recommended Reading:
1. Gas-Liquid Reactions P.V. Danckwerts, McGraw-Hill, 1970

2. Gas treating with chemical solvents G. Astarita, D.W. Savage &

A. Bisio, Wiley, 1982
3. Gas Purification A.L. Kohl & R.B. Nielsen, Gulf Publishing Co.,
1997

University of Dortmund Chemical Engineering Department Chair for Reaction Engineering

 University of Dortmund

Course schedule:
16.06.03 Introduction to gas-liquid reactor

17.06.03 Chemistry of gas-liquid reactions

18.06.03 Reaction & diffusion

19.06.03 Reaction, diffusion & convection

20.06.03 Modelling of gas-liquid reactors

23.06.03 Determination of parameters

24.06.03 Exercises

25.06.03 Design problem

University of Dortmund Chemical Engineering Department Chair for Reaction Engineering

 University of Dortmund

Heterogeneous reaction systems

Gas
(2nd Liquid)

Catalyst Solid

Liquid

University of Dortmund Chemical Engineering Department Chair for Reaction Engineering

 University of Dortmund
Modelling analogies

Non-catalytic gas-solid reactions

- instantaneous reaction shrinking core model
- bulk phase reaction homogenous conversion model

Heterogeneously catalysed reactions

- Ha
-Eh
Reactor engineering
- surface renewal residence time distribution
- M or Ha Da

Differences
- heat effects slight
- minimal changes in physical properties
- fluid dynamics instead of porous solid structures
- importance of phase equilibria
- high separation factors

University of Dortmund Chemical Engineering Department Chair for Reaction Engineering

 University of Dortmund

Two film model

Bulk Bulk
phase Boundary layers phase
mass transfer
A localised in
pA0 CA* surface films
CA* & pA*
at equilibrium
pA*
continuity of
interface interfacial
flux
Phase

CA0
no reaction
const. slope
Gas G L Liquid

University of Dortmund Chemical Engineering Department Chair for Reaction Engineering

 University of Dortmund

A(g) + B(aq) C(aq)

L
A
pA0 pA*
CB0

very slow reaction CA*

CA0

interface
Gas Phase
Surface film Liquid

University of Dortmund Chemical Engineering Department Chair for Reaction Engineering

 University of Dortmund

A(g) + B(aq) C(aq)

L
A
pA0 pA*
CB0

moderate reaction CA*

CA0

Gas Liquid

University of Dortmund Chemical Engineering Department Chair for Reaction Engineering

 University of Dortmund

A(g) + B(aq) C(aq)

L
A
pA0 pA*
CB0

fast reaction CA*

CA0=0
Gas Liquid

University of Dortmund Chemical Engineering Department Chair for Reaction Engineering

 University of Dortmund

A(g) + B(aq) C(aq)

L
A
pA0 pA*
CB0

Reaction
front
very fast reaction CA*

Gas R Liquid

University of Dortmund Chemical Engineering Department Chair for Reaction Engineering

 University of Dortmund

A(g) + B(aq) C(aq)

L
A
pA0 pA*
CB0

instantaneous CA*
reaction

Gas G Reaction front = Liquid

Phase interface

University of Dortmund Chemical Engineering Department Chair for Reaction Engineering

 University of Dortmund
CB [kmol/m] CA [kmol/m]
CO2(g) + 2 RNH2(aq) P[bar] 1x10-5
RNHCOO-(aq) + RNH3+(aq) 0.8x10-3 2
Monoethanolamine 0.6x10-5
0.4x10-3 1
MEA: R=HOCH2CH2-
0.2x10-5

G L
CB [kmol/m] CA [kmol/m]
P[bar] 0.5x10-3
0.05
2
0.03 0.3x10-3
1

0.01 0.1x10-3

G L
CB [kmol/m] CA [kmol/m]
P[bar] 0.03
0.5
2
0.02
0.3
1
0.01
0.1

G L

University of Dortmund Chemical Engineering Department Chair for Reaction Engineering

 University of Dortmund

Relative conversion as a function of

volumetric utilisation factor & Hatta-number

Xrel
Reaction in film
Ha =
Penetration thru film

BC: bubble column

AT: aerated tank
AT PC: packed column
BC PC JR
JR: jet reactor

reactive volume fraction

University of Dortmund Chemical Engineering Department Chair for Reaction Engineering

 University of Dortmund
Falling film reactor Heat transport
Evaporative cooling
Gas-Liquid reactors:
problems & solutions

Phase interface

Homogenisation Bubble column Spray tower Packed column

Proprietary agitators

Extruder

University of Dortmund Chemical Engineering Department Chair for Reaction Engineering

 University of Dortmund
Critical design features of gas-liquid-reactors
Interfacial area
two-phase pipe flow
three-phase venturi scrubber
fluidised beds spray tower
fixed bed reactors segmented reactor with gas injection
- trickle stirred tank with gas injection
- flooded packed column
tray column
slurry reactors loop reactor
- bubble column bubble column
- stirred tank
.

Homogenisation
Heat exchange scale-up
evaporative cooling bubble & solid
extruder reactor
falling film reactor distribution
jet mixer
internal / external shearing
loop reactor
heat exchangers stirrer power

. stirrer type

University of Dortmund Chemical Engineering Department Chair for Reaction Engineering

 University of Dortmund
Mixing of gas-liquid-reactors
Viscosity [Pas]
Types of agitator: <0.5 0.5-5 5-50

tangential - radial flow

a) disc turbine
b) radial impellor
c) cross blade
d) gate paddle
e) flat blade paddle
f) anchor
g) axial impellor
axial flow

h) propellor
i) MIG (Ekato)
j) spiral

University of Dortmund Chemical Engineering Department Chair for Reaction Engineering

 University of Dortmund
Characteristic mixing times
Types of agitator:
a) disc turbine d) gate paddle g) axial impeller j) spiral
b) radial impeller e) flat blade paddle h) propeller
c) cross blade f) anchor i) MIG (Ekato) .s) baffled
tank
i a f h

e,es is bs

b
n.tm

i c,cs=1.8e
a is
j d,ds=1.25e
e es bs
tm<<

.N.Di2
Re =

University of Dortmund Chemical Engineering Department Chair for Reaction Engineering

 University of Dortmund
Mixing power requirements
Kolmogorov
Eddy size j

<< (DAtm) f c,cs,d,

ds,e,es

0.25 Di
= (
P/VR)
(/) Ne = P/N3Di5
as
i(s)
b(s)
VB
es
hs Wi
ds as
cs

N
bs is
f,j c,d
e hs
i
b us, Qg

Re
-0.20 -025 0.4
Mass
Pg
( )( Qg N Di
) ( )
Pg
2 4
= 0.1 transfer kLa = 0.0026 us0.5
P N.VL gWiVB2/3 VR
coefficient

University of Dortmund Chemical Engineering Department Chair for Reaction Engineering

 University of Dortmund
Heat exchange in gas-liquid-reactors

a) Cooling/ b) Internal
heating heat
jacket exchanger

c) External d) Evaporative
heat cooling
exchanger intensive cooling
uniform T-profile
large reactors

facile maintenance
low external hold-up
flexible design

University of Dortmund Chemical Engineering Department Chair for Reaction Engineering

 University of Dortmund
Heat exchange in
gas-liquid-reactors

e) Falling film reactor

University of Dortmund Chemical Engineering Department Chair for Reaction Engineering

 University of Dortmund
Heat exchange vs. homogenisation

Heat removal (Qa) &

power dissipation (P)
of an anchor agitator
as a function of rota-
tional speed (n)

University of Dortmund Chemical Engineering Department Chair for Reaction Engineering

 University of Dortmund
Creating interfacial area in gas-liquid-reactors

Gas-liquid
contactors
G = gas flow
L = liquid flow

Driving forces:
pressure drop
gravity
mechanical
energy

University of Dortmund Chemical Engineering Department Chair for Reaction Engineering

 University of Dortmund
Taxonomy of bubble columns
a) Single stage b) Multistage c) Airlift reactors
bubble column bubble column
(sieve plate cascade)

upflow jet-stream
downflow

University of Dortmund Chemical Engineering Department Chair for Reaction Engineering

 University of Dortmund

University of Dortmund Chemical Engineering Department Chair for Reaction Engineering

 University of Dortmund

University of Dortmund Chemical Engineering Department Chair for Reaction Engineering

 University of Dortmund
Taxonomy of three phase reactors
a) Three phase b) Trickle bed reactor c) Slurry reactors
fixed-bed reactor (or flooded operation)

fluidised bubble stirred

bed column tank

University of Dortmund Chemical Engineering Department Chair for Reaction Engineering

 University of Dortmund

University of Dortmund Chemical Engineering Department Chair for Reaction Engineering

 University of Dortmund

Reactive
ReactiveDistillation
Distillation Catalyst
Catalystin
inwire
wiregauze
gauzeenvelopes
envelopesavoids
avoidsflooding
flooding

Reaction
Reactionrequires:
requires:
high
highliquid
liquidhold-up
hold-up
bubbly
bubblyflow
flow/ /froth
frothregime
regime
low
lowgas
gasvelocities
velocities
small
smallcatalyst
catalystparticles
particles
high
highcatalyst
catalystloading
loading
Distillation requires:
high interfacial areas
spray regime
open x-section for two phase flow

Compromise:
separate side-reactors
packing = 20-25% vol. of column

University of Dortmund Chemical Engineering Department Chair for Reaction Engineering

 University of Dortmund
Waste air purification: solvent recycling using absorption

Absorber Stripping
pure gas
Absorbent column
make-up
pure gas

recovered
solvent

raw gas
with
solvent
vapours
raw gas absorbent liquid distributor
rich absorbent packing

University of Dortmund Chemical Engineering Department Chair for Reaction Engineering

 University of Dortmund
Techniques for solvent regeneration

a) Flashing b) Inert stripping gas c) thermal stripping

University of Dortmund Chemical Engineering Department Chair for Reaction Engineering

 University of Dortmund

University of Dortmund Chemical Engineering Department Chair for Reaction Engineering

 University of Dortmund

University of Dortmund Chemical Engineering Department Chair for Reaction Engineering

 University of Dortmund

Course schedule:

16.06.03 Introduction to gas-liquid reactors

17.06.03 Chemistry of gas-liquid reactions

18.06.03 Reaction & diffusion

19.06.03 Reaction, diffusion & convection

20.06.03 Modelling of gas-liquid reactors

23.06.03 Determination of parameters

24.06.03 Exercises

25.06.03 Design problem

University of Dortmund Chemical Engineering Department Chair for Reaction Engineering