Professional Documents
Culture Documents
Book:
Structured Catalysts and Reactors (2nd edition) - 2006
A. Cybulski and J.A. Moulijn, Taylor and Francis Boca Raton
Monolith reactors - 1
History
Lithos = stone
Concise Oxford (1995)
Webster (1991)
Introduction
Multiphase Reactors 6PE20
Monolith reactors - 2
History
Automotive Catalytic Converters
no attrition
high surface area
low pressure drop
rapid light-off
Monolith reactors - 3
History
Air Purification
Monolith reactors - 4
Structured Reactors
Driving forces
Pressure drop
Mass transfer
Counter Current operation
Surface area
Catalyst Efficiency
Fluid distribution
Catalyst Separation
Monolith reactors - 5
Structured Packings-Appearance
Sulzer
Packing
Foams
Monoliths
Ceramics: Cordierite, alumina, titania, silica
Metal
Monolith reactors - 6
400 cpsi
600 cpsi
1 cm
1.80/0.27 mm
1934 m2/m3
= 0.74
1.27/0.16 mm
2678 m2/m3
= 0.75
1.04/0.11 mm
3348 m2/m3
= 0.79
Monolith reactors - 7
; S 0.6
Monolith
4
aM V
dc
100000
aa
(m2/m3)
10000
1000
; V 0.75
100
V S 1
void
solid
(mm)
10
0.1
10
dd
100
Monolith reactors - 8
Cylinder
10-3
Sphere
Quadrulobe
Monolith
10-4
l D2
D
2D
1000
300
0
10-5
10
D (mm)
diffusion length
2
D(m /s)
unconfined gas
unconfined liquid
liquid in catalyst pore
liquid in zeolite pore
-5
10
10-9
10-10
10-11
10 mm 1 mm 0.1 mm
0.5 s
50 ks
500 ks
5 Ms
50 ms
500 s
5 ks
50 ks
0.5 ms
5s
50 s
500 s
0.01 mm 0.001 mm
0.005 ms
50 ms
0.5 s
5s
50 ns
0.5 ms
5 ms
50 ms
Monolith reactors - 9
Cylinder
10-3
Sphere
Quadrulobe
Monolith
10-4
1000
300
0
D (mm)
10-5
10
Monolith reactors - 10
Diffusion
8
time (s)
liquid
in pore liquid
Monolith
(washcoated)
Slurry
reactor
Fixed bed
reactor
2
gas
0
10 -6
10 -5
10 -4
10 -3
Monolith reactors - 11
dm
cm
mm
10-1
10-2
10-3
mm
10-4
10-5
10-6
10-7
10-8
nm
10-9
10-10
zeolite crystals
monoliths
metal crystallites
monolith channels
washcoat thickness
macropores
mesopores
Regular arrangement
zeolite pores
decoupling
optimal reactor performance
Multiphase Reactors 6PE20
Monolith reactors - 12
Monolithic Reactors
Advantages
No filtering of catalyst necessary
No attrition of catalyst
Low pressure drop
High geometric surface area
Efficient mass-transfer
In the case of internal diffusion limitations:
more efficient use of catalyst due
to thin catalytic layer
Disadvantage
Little practical experience in multi-phase applications
Monolith reactors - 13
Counter current
us,G
liquid
gas
us,L
Multiphase Reactors 6PE20
Monolith reactors - 14
Monolith
Reactor
Flooding
Gas
Film flow
counter- and co-current
operation
high gas throughputs
low pressure drop
high catalyst load
high S/V ratio
short diffusion length
Taylor flow
co-current
low pressure drop
high surface area
high mass transfer
plug flow behaviour
egg-shell catalyst
Monolith reactors - 15
Liquid
Liquid
Flooding
Gas
Gas
Film flow
counter- and co-current
operation
high gas throughputs
low pressure drop
high catalyst load
high S/V ratio
short diffusion length
Taylor flow
co-current
low pressure drop
high surface area
high mass transfer
plug flow behaviour
egg-shell catalyst
Monolith reactors - 16
monolith wall
gases
zeolite
liquids
active
component
Monolith reactors - 17
Catalyst preparation
Cordierite
washcoating
polymer coating
Alumina
Silica
Carbon
Monolith reactors - 18
Co-Current Applications
(Taylor Flow)
Monolith reactors - 19
L/S
G/L
G/S
S r
Internal mass transfer
Monolith reactors - 20
Lslug
Lbubble
Film thickness d
uTP=uL,s+uG,s
Monolith reactors - 21
U L , s Lg , s
OFA
Monolith reactors - 22
Sh
k d
D
Monolith reactors - 23
k
Deff
S r
Monolith reactors - 24
G/L
G/S
S r
Monolith reactors - 25
Pressure drop
(mm)
(Pa/m)
Monolith
p
1
4
16
f V 2 ; f
L
2
d
Re
Laminar Channel Flow
Sphere
packed bed
(m/s)
p 150 mV (1 V ) 2 1.75 V 2 (1 V )
2
3
L
dS
V
dS
V2
Ergun Equation
(single phase water flow)
Monolith reactors - 26
0.6
0.5
p
0
L
0.4
p
0
L
0.3
0.2
0.1
0
Unstable !
UGs / m s-1
Multiphase Reactors 6PE20
Monolith reactors - 27
Gas-liquid distribution
no gas supply
inlet
maldistribution
gas bubbles
proper distribution
clear liquid
exit
Monolith reactors - 28
a-Methylstyrene hydrogenation
CH2
CH3
+
H2
CH3
CH3
200
400
600
400
Monolith (only liquid)
5
4
Trickle bed
3
2
1
0
3
mreactor
2
mext.
cat.
gcatalyst
*1000
*100
gNi
Selectivity Improvement
Benzaldehyde hydrogenation
H
H2
O
+ H2
OH
CH3
+
H2
Ni/g-Al2O3
410 K
15 bar
Batch
slurry , monoliths or extrudates
slurry < 50 m, monolith 4 cm , extrudates 1.7x 5
mm
Pilot
monoliths 1 cm - variation cell density
trickle bed 4.7 cm , extrudates 1.7x 5 mm
Monolith reactors - 30
Concentration (a.u.)
35
30
25
benzaldehyde
20
benzylalcohol
15
toluene
10
5
0
0
100
200
300
400
Time (min)
Multiphase Reactors 6PE20
Monolith reactors - 31
160
benzaldehyde
benzylalcohol
120
toluene
80
40
0
0
Time (h)
99.5
100
Pilot
Industrial
97.5
96
94
Selectivity
at 50% conversion
400
94
600
Monolith
90
90
Trickle bed
80
Slurry
73
70
diluted feed
pure feed
Monolith reactors - 33
Taylor-flow - Summary
Only co-current
Very high mass transfer rates
Stable operation only at high superficial
velocities
Gas-liquid ratio between 1:3 and 3:1
Monolith reactors - 34
Counter-Current Applications
(Film Flow)
Monolith reactors - 35
Co-current, counter-current?????
gas
cocurrent
countercurrent
liquid
Flooding !
Countercurrent:
Equilibrium reaction with gas phase reactant / product
Inhibition by gas phase product
Multiphase Reactors 6PE20
Monolith reactors - 36
products
liquid
gas
Gas
Liquid
Catalyst
Multiphase Reactors 6PE20
Monolith reactors - 37
uLs (m/s)
entrance
flooding
0.03
slug
flow
0.02
a=50o
a=70o
a=70o
exit
flooding
0.01
annular
0.00
0.0
a=70o
Typical
region TBR
1.0
2.0
3.0
uGs (m/s)
Monolith reactors - 38
Monolith
Comparison
Flooding
Sulzer Mellapak
0.08
0.06
special IFM
us,L
special square
70o tapered
Sulzer Mellapak
125 Y
0.05
0.03
0.02
250 Y
0.00
0.00
us,G
170 Y
0.50
1.00
1.50
2.00
Monolith reactors - 39
Low liquid
velocity
2uF ,z 2uF ,z
p
g F
2
x 2
L
y
0.45
0.30
High liquid
velocity
0.15
0.60
0.00
Monolith reactors - 40
Hydrodynamic model
uLS = 0.57 cm/s
Liq. = 5.5%
Pwet = 50%
2.0
1.0
0.45
0.0
0.30
Gas
Liquid
0.15
Velocity [m/s]
0.60
0.00
Monolith reactors - 41
2.0
water
Et (1/s)
0.2
1.5
0.3
1.0
0.1
0.5
0.0
0.0
0
10
t (s)
20
0.0
W AVE/
MALDISTRIBUTION
1.0
2.0
3.0
LAMINAR
FILM SUBSTRATE
Monolith reactors - 42
Sh
10
0
0.00
Sh 104
. 0.35 0.63
0.05
0.10
k Ld Fm
zDL
Sh
; 2
DL
d FmuLm
Monolith reactors - 43
HO
(calculated)
O
O
+ H 2O
450
Ester
Water
Countercurrent
Cocurrent
No Stripping
400
Concentration (mol/m 3)
350
300
250
200
150
100
50
0
0
Length (m)
Monolith reactors - 44
8m
10 wt%
5 cm/s
1 cm/s
Results:
Conversion (%)
Selectivity (%)
Counter-current
98.7
95.2
Co-current
94.8
94.7
No stripping
82.1
94.6
Monolith reactors - 45
Laminar flow
Mass transfer relatively slow (diffusion)
Residence time distribution
Low liquid superficial velocities
Flooding risk at exit
Monolith reactors - 46
Monolith reactors - 47
Gas
Exothermal systems
High rates - Low conversions
Multiphase Reactors 6PE20
Monolith reactors - 48
vertical mode:
Staging possible
Cross-, co- and countercurrent
Multiphase Reactors 6PE20
Monolith reactors - 49
H2O2 decomposition
in a rotating monolith reactor
Monolith reactors - 50
Novel Monolithic
reactor designs
Cross-Flow
module
Monolith reactors - 51
Monoliths - Summary
Small Channel
Co-Current
Plug flow (Taylor flow)
High velocities
High mass transfer
rates
Low catalyst amount
Low P
Fast reactions
Multiphase Reactors 6PE20
Large Channels
Counter-current
possible
Film flow
Low velocities
Higher amount of
catalyst
Low P
Slow(er) reactions
Monolith reactors - 52