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University of Dortmund – Chemical Engineering Department – Chair for Reaction Engineering
Gas - LiquidReaction Engineering
David W. Agar
Short Course
16th-25th June 2003
Chemical Engineering Department
IISc Bangalore
University of Dortmund
University of Dortmund – Chemical Engineering Department – Chair for Reaction Engineering
University of Dortmund
1997- Chair for Reaction Engineering,TCB Dortmund, D
1956 Danbury, England, GB
Curriculum Vitae
1980 Postdoctoral work Pasadena, CA, USA
1977-1980 PhD Chemical Engineering Houston, TX, USA
1981-1986 Central Research, BASF AG Ludwigshafen, D
1987-1990 Caprolactam plant, BASF AG Ludwigshafen
1990-1993 Coordinator for Isocyanate LudwigshafenResearch, BASF AG
1993-1995 Coordinator for Reaction LudwigshafenEngineering Research, BASF AG
1995-1996 Technical Support, Amine sales, Calgary, CDNBASF AG
1977 BSc Biochemical Engineering Swansea, Wales, GB
Ludwigshafen
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
25.06.03 Design problem
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
University of Dortmund – Chemical Engineering Department – Chair for Reaction Engineering
University of Dortmund
Solid
Gas
(2nd Liquid)
Liquid
Catalyst
Heterogeneous reaction systems
University of Dortmund – Chemical Engineering Department – Chair for Reaction Engineering
University of DortmundModelling analogies
• Non-catalytic gas-solid reactions- instantaneous reaction ⇔ shrinking core model- bulk phase reaction ⇔ homogenous conversion model
• Differences- heat effects slight- minimal changes in physical properties- fluid dynamics instead of porous solid structures- importance of phase equilibria- high separation factors
• Heterogeneously catalysed reactions- Ha ⇔ φ- E ⇔ h
• Reactor engineering- surface renewal ⇔ residence time distribution- M or Ha ⇔ Da
University of Dortmund – Chemical Engineering Department – Chair for Reaction Engineering
University of Dortmund
Gas Liquid
Two film model
Boundary layers
Pha
sein
terfa
ce
Bulkphase
Bulkphase
A
CA0
pA0 CA*
pA*
• mass transferlocalised insurface films
• CA* & pA* at equilibrium
• continuity ofinterfacialflux
• no reaction ⇒const. slope
δLδG
University of Dortmund – Chemical Engineering Department – Chair for Reaction Engineering
University of Dortmund
Gas LiquidSurface film
Pha
sein
terfa
ce
A
CA0
pA0
CA*
pA*
• very slow reaction
CB0
A(g) + B(aq) → C(aq)δL
University of Dortmund – Chemical Engineering Department – Chair for Reaction Engineering
University of Dortmund
Gas Liquid
A
CA0
pA0
CA*
pA*
• moderate reaction
CB0
A(g) + B(aq) → C(aq)δL
University of Dortmund – Chemical Engineering Department – Chair for Reaction Engineering
University of Dortmund
Gas Liquid
A
CA0=0
pA0
CA*
pA*
• fast reaction
CB0
A(g) + B(aq) → C(aq)
δL
University of Dortmund – Chemical Engineering Department – Chair for Reaction Engineering
University of Dortmund
Gas Liquid
ApA0
CA*
pA*
• very fast reaction
CB0
A(g) + B(aq) → C(aq)
Rea
ctio
nfr
ont
δL
δR
University of Dortmund – Chemical Engineering Department – Chair for Reaction Engineering
University of Dortmund
Gas Liquid
ApA0
CA*
pA*
• instantaneousreaction
CB0
A(g) + B(aq) → C(aq)
Reaction front =Phase interface
δL
δG
University of Dortmund – Chemical Engineering Department – Chair for Reaction Engineering
University of DortmundCO2(g) + 2 RNH2(aq) →
RNHCOO-(aq) + RNH3+(aq)
δL
CA [kmol/m³]1x10-5
0.6x10-5
0.2x10-5
CB [kmol/m³]
2
1
0.8x10-3
0.4x10-3
P[bar]
δG
δL
CA [kmol/m³]0.03
0.02
0.01
CB [kmol/m³]P[bar]
δG
2
1
0.5
0.3
0.1
δL
CA [kmol/m³]0.5x10-3
0.3x10-3
0.1x10-3
CB [kmol/m³]
2
1
P[bar]
δG
0.05
0.03
0.01
MonoethanolamineMEA: R=HOCH2CH2-
University of Dortmund – Chemical Engineering Department – Chair for Reaction Engineering
University of Dortmund
Relative conversion as a function ofvolumetric utilisation factor & Hatta-number
reactive volume fraction
BC
Xrel
ATPC JR
BC: bubble column
AT: aerated tank
PC: packed column
JR: jet reactor
Ha =Reaction in film
Penetration thru‘ film
University of Dortmund – Chemical Engineering Department – Chair for Reaction Engineering
University of Dortmund
Heat transport
Gas-Liquid reactors:problems & solutions
Phase interface
Homogenisation
Proprietary agitators
Extruder
Evaporative coolingFalling film reactor
Bubble column Spray tower Packed column
University of Dortmund – Chemical Engineering Department – Chair for Reaction Engineering
University of Dortmund
Interfacial area
Heat exchangeHomogenisation
• two-phase pipe flow• venturi scrubber• spray tower• segmented reactor with gas injection• stirred tank with gas injection• packed column• tray column• loop reactor• bubble column• ….
⇒ scale-up⇒ bubble & solid⇒ distribution⇒ shearing⇒ stirrer power⇒ stirrer type
• evaporative cooling• falling film reactor• internal / externalheat exchangers
• ….
• three-phasefluidised beds
• fixed bed reactors- trickle- flooded
• slurry reactors- bubble column- stirred tank
• extruder reactor• jet mixer• loop reactor• …
Critical design features of gas-liquid-reactors
University of Dortmund – Chemical Engineering Department – Chair for Reaction Engineering
University of DortmundMixing of gas-liquid-reactors
Viscosity [Pas]<0.5 0.5-5 5-50
tang
entia
l -ra
dial
flow
axia
l flo
w
Types of agitator:
a) disc turbine
b) radial impellor
c) cross blade
d) gate paddle
e) flat blade paddle
f) anchor
g) axial impellor
h) propellor
i) MIG (Ekato)
j) spiral
University of Dortmund – Chemical Engineering Department – Chair for Reaction Engineering
University of DortmundCharacteristic mixing times
Re =
j n.t m
ρ.N.Di2
µ
e,es
f i
is
habs
b
e esis
i
bsa
c,cs=1.8e
d,ds=1.25e
tm<< τ
Types of agitator:a) disc turbine d) gate paddle g) axial impeller j) spiralb) radial impeller e) flat blade paddle h) propellerc) cross blade f) anchor i) MIG (Ekato) .s) baffled
tank
University of Dortmund – Chemical Engineering Department – Chair for Reaction Engineering
University of Dortmund
Re
Ne
=P/
ρN3 D
i5
Mixing power requirements
Pg Qg N2Di4
P N.VL gWiVB2/3
-0.20 -0´25
= 0.1 ( ) ( )
Wi
N
us, Qg
Di
VB
(µ/ρ)³P/ρVR
0.25
δ = ( )
j
f c,cs,d,ds,e,es
i(s)b(s)
ashs es
asdscs
c,de hs
isbs
if,j
b
PgVR
0.4
kLa = 0.0026 us0.5( )Mass
transfercoefficient
δ << √(DAtm)
KolmogorovEddy size
University of Dortmund – Chemical Engineering Department – Chair for Reaction Engineering
University of DortmundHeat exchange in gas-liquid-reactors
a) Cooling/heatingjacket
b) Internalheatexchanger
c) Externalheatexchanger
d) Evaporativecooling
• facile maintenance• low external hold-up• flexible design
• intensive cooling• uniform T-profile• large reactors
University of Dortmund – Chemical Engineering Department – Chair for Reaction Engineering
University of DortmundHeat exchange ingas-liquid-reactors
e) Falling film reactor
University of Dortmund – Chemical Engineering Department – Chair for Reaction Engineering
University of DortmundHeat 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 DortmundCreating interfacial area in gas-liquid-reactors
Gas-liquidcontactors
G = gas flow
L = liquid flow
Driving forces:
• pressure drop
• gravity
• mechanicalenergy
University of Dortmund – Chemical Engineering Department – Chair for Reaction Engineering
University of DortmundTaxonomy of bubble columns
a) Single stagebubble column
b) Multistagebubble column(sieve plate cascade)
c) Airlift reactors
upflow downflow jet-stream
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 DortmundTaxonomy of three phase reactors
a) Three phasefixed-bed reactor
b) Trickle bed reactor(or flooded operation)
c) Slurry reactors
bubblecolumn
stirredtank
fluidisedbed
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
• Catalyst in wire gauze envelopes avoids flooding• Catalyst in wire gauze envelopes avoids floodingReactive DistillationReaction requires:
• high liquid hold-up• bubbly flow / froth regime• low gas velocities• small catalyst particles• high catalyst loading
Reactive DistillationReaction requires:
• high liquid hold-up• bubbly flow / froth regime• low gas velocities• small catalyst particles• high catalyst 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
pure gas
raw gas
pure gas
Absorbentmake-up
raw gas with
solventvapours
Strippingcolumn
Absorber
recoveredsolvent
rich absorbentabsorbent liquid distributor
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