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Monoliths as G-L-S reactors

Book:
Structured Catalysts and Reactors (2nd edition) - 2006
A. Cybulski and J.A. Moulijn, Taylor and Francis Boca Raton

Multiphase Reactors 6PE20

Monolith reactors - 1

History

Mono = one, single

Lithos = stone
Concise Oxford (1995)

Webster (1991)

Introduction
Multiphase Reactors 6PE20

Monolith reactors - 2

History
Automotive Catalytic Converters

pellet filled catalytic converter

Monolith Key Features:

no attrition
high surface area
low pressure drop
rapid light-off

Multiphase Reactors 6PE20

monolith catalytic converter

Monolith reactors - 3

History
Air Purification

Matsumoto et al., 1993


US 5266543

Multiphase Reactors 6PE20

Monolith reactors - 4

Structured Reactors
Driving forces

Pressure drop
Mass transfer
Counter Current operation
Surface area
Catalyst Efficiency
Fluid distribution
Catalyst Separation

Multiphase Reactors 6PE20

Monolith reactors - 5

Structured Packings-Appearance
Sulzer
Packing

Foams

Monoliths
Ceramics: Cordierite, alumina, titania, silica
Metal

Multiphase Reactors 6PE20

Monolith reactors - 6

Monoliths - Cell density


200 cpsi

400 cpsi

600 cpsi

1 cm

1.80/0.27 mm
1934 m2/m3
= 0.74

Multiphase Reactors 6PE20

1.27/0.16 mm
2678 m2/m3
= 0.75

1.04/0.11 mm
3348 m2/m3
= 0.79

Monolith reactors - 7

Specific Surface Area


Sphere
6
aS S
dS

; S 0.6

Monolith
4
aM V
dc

100000

aa

(m2/m3)

10000

1000

; V 0.75
100

V S 1
void

solid

Multiphase Reactors 6PE20

(mm)

10
0.1

10

dd
100

Monolith reactors - 8

Geometric surface area and diffusion length


for catalytic reactors
Acat/Vbed (m2/m3)
10000

Diffusion length D (m)

Cylinder
10-3

Sphere
Quadrulobe

Estimated diffusion time

Monolith
10-4

l D2
D
2D

1000

300
0

10-5
10

D (mm)

diffusion length
2

No longer a fixed ratio


between catalyst particle
size and diffusion length!!
Multiphase Reactors 6PE20

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

Geometric surface area and diffusion length


for catalytic reactors
Acat/Vbed (m2/m3)
10000

Diffusion length D (m)

Cylinder
10-3

Sphere
Quadrulobe

Conventional (nonstructured) packings:

Monolith
10-4
1000

300
0

D (mm)

Multiphase Reactors 6PE20

10-5
10

The price you pay


for shorter diffusion
distances is the
pressure drop
(=energy costs)!

Monolith reactors - 10

Diffusion time scales in catalytic reactors


in
zeolite
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

Diffusion length D (m)


Multiphase Reactors 6PE20

Monolith reactors - 11

Structure in catalyst application


Dimensions in catalytic reactor
m

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

Multiphase Reactors 6PE20

Monolith reactors - 13

Flow regimes in Monoliths


Co current

Counter current

us,G

liquid
gas
us,L
Multiphase Reactors 6PE20

Monolith reactors - 14

Hydrodynamic regimes in monoliths


Liquid

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

Multiphase Reactors 6PE20

Taylor flow
co-current
low pressure drop
high surface area
high mass transfer
plug flow behaviour
egg-shell catalyst

Monolith reactors - 15

Hydrodynamic regimes in monoliths


Monolith
Reactor
Liquid

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

Multiphase Reactors 6PE20

Taylor flow
co-current
low pressure drop
high surface area
high mass transfer
plug flow behaviour
egg-shell catalyst

Monolith reactors - 16

Gas-liquid-solid system - monolith


porous support

monolith wall
gases
zeolite
liquids
active
component

Multiphase Reactors 6PE20

Monolith reactors - 17

Catalyst preparation
Cordierite

washcoating

polymer coating

Alumina
Silica
Carbon

Multiphase Reactors 6PE20

Monolith reactors - 18

Co-Current Applications
(Taylor Flow)

Multiphase Reactors 6PE20

Monolith reactors - 19

Mass Transfer in Taylor Flow


Four mass-transfer steps
thin walls

L/S

G/L

G/S

thin liquid film


liquid circulation

S r
Internal mass transfer

Assume liquid in slugs = ideally mixed


Multiphase Reactors 6PE20

Monolith reactors - 20

Mass Transfer in Taylor Flow


Gas-Solid
G/S

Lslug

Lbubble

Film thickness d

Direct fast supply of gas to catalyst

uTP=uL,s+uG,s
Monolith reactors - 21

Mass Transfer in Taylor Flow


Gas-Liquid
G/L

Saturation of liquid slugs with gas


LUC Lbubble Lslug
Ub

U L , s Lg , s
OFA

(OFA=open frontal area)


For gas absorption mass transfer via film is also important!

Multiphase Reactors 6PE20

Monolith reactors - 22

Mass Transfer in Taylor Flow


Liquid-Solid
L/S

Transfer from liquid slugs to solid

Sh

k d
D

Mass transfer of both liquid reactant (product) AND dissolved gas


Multiphase Reactors 6PE20

Monolith reactors - 23

Mass Transfer in Taylor Flow


Internal Mass Transfer

Internal mass transfer

k
Deff

S r

Approximate using Thiele modulus (calculate efficiency) recommended


Or calculate concentration profile in wall
Multiphase Reactors 6PE20

Monolith reactors - 24

Mass Transfer in Taylor Flow


L/S

G/L

G/S

Simplify by assuming ideal plug flow behavior (no


mixing between slugs)
Assume equal distribution over channels
Complexing factor:
Change in bubble volume by pressure
differences or consumption of gas
More details:
Kreutzer et al.

Multiphase Reactors 6PE20

S r

Chem.Eng.Sci. 56 (2001) 6015-6023


Chem.Eng.Sci. 60 (2005) 5895-5916

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)

Multiphase Reactors 6PE20

Monolith reactors - 26

Flow map for Taylor flow


ULs / m s-1
1

L= 0.9 0.8 0.7

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

High gas and


liquid
velocities
required for
stable
operation !!!

Check you are in a


stable operating regime
when designing a
monolithic reactor!!

Monolith reactors - 27

Gas-liquid distribution
no gas supply
inlet

maldistribution
gas bubbles

proper distribution
clear liquid

exit

Foam layer crucial


Multiphase Reactors 6PE20

Monolith reactors - 28

Mass Transfer limited reaction:

a-Methylstyrene hydrogenation
CH2

CH3
+

H2

CH3

CH3

200

Reaction rate (mol/s/X)

400

600

Monolith (Taylor flow)

400
Monolith (only liquid)

5
4

Trickle bed

3
2
1
0

3
mreactor

Multiphase Reactors 6PE20

2
mext.
cat.

gcatalyst

*1000

*100

gNi

Efficient catalyst use


Excellent mass transfer
Monolith reactors - 29

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

Multiphase Reactors 6PE20

Monolith reactors - 30

Batch reactor - monolith

Concentration (a.u.)

35
30

25

benzaldehyde

20

benzylalcohol

15

toluene
10

Little mass transfer


effect: high
selectivity possible

5
0
0

100

200

300

400

Time (min)
Multiphase Reactors 6PE20

Monolith reactors - 31

Pilot reactor - trickle bed


Concentration (mol/m3)

160

benzaldehyde
benzylalcohol

120

toluene
80

40

0
0

Time (h)

Multiphase Reactors 6PE20

Internal mass transfer


Stagnant zones
Non-ideal plug flow
Monolith reactors - 32

Benzaldehyde hydrogenation selectivities


Batch CSTR
99.5

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

rates up to 2.5 mol / mR3 s


Multiphase Reactors 6PE20

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

Most suited for fast reactions


Multiphase Reactors 6PE20

Monolith reactors - 34

Counter-Current Applications
(Film Flow)

Multiphase Reactors 6PE20

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

Counter-current gas/liquid flow; how to avoid


flooding???
Wavy Annular
Film Flow
reactants

products

liquid
gas

liquid exit phenomena

Gas
Liquid
Catalyst
Multiphase Reactors 6PE20

Monolith reactors - 37

Flooding - influence outlet geometry


Finned Unfinned

uLs (m/s)

Liquid superficial velocities are low!


0.04

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

Multiphase Reactors 6PE20

Typical
region TBR

1.0

2.0

3.0

uGs (m/s)

Monolith reactors - 38

Monolith
Comparison
Flooding
Sulzer Mellapak

Data from Lebens (1999) and Heibel (1999)

0.08

0.06

special IFM

us,L

special square
70o tapered
Sulzer Mellapak

125 Y

0.05

0.03

0.02

, air/decane, 25 cpsi IFM,


air/water, 50 cpsi square

Multiphase Reactors 6PE20

250 Y

0.00
0.00

us,G

170 Y

0.50

1.00

1.50

2.00

Monolith reactors - 39

Hydrodynamics - velocity profiles


Momentum balance for:
developed laminar flow in both phases
Newtonian rheology
no slip at all interfaces (G-L, L-S, G-S)
corner-flow due to surface tension forces

Low liquid
velocity

2uF ,z 2uF ,z
p

g F
2
x 2
L
y

0.45

0.30

High liquid
velocity

0.15

Axial velocity [m/s]

0.60

0.00

Significant velocity profile !


Multiphase Reactors 6PE20

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

uLS = 2.9 cm/s


Liq. = 12 %
Pwet = 75%

0.15

Axial velocity [m/s]

Velocity [m/s]

0.60

0.00

Significant RTD for gas and liquid!!


Multiphase Reactors 6PE20

Monolith reactors - 41

Residence time distribution


0.4

2.0
water

Et (1/s)

0.2

1.5

uLs = 0.020 m/s


uLs = 0.025 m/s
uLs = 0.030 m/s

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

Laminar flow leads to strong tailing of the RTD


Short residence time, due to wave formation & maldistribution
Lower RTD expected for organic liquids at industrial conditions
Multiphase Reactors 6PE20

Monolith reactors - 42

Average G/L mass transfer results


15

Sh

10

uGs=0.24 - 0.47 m/s


uGs=0.71 - 0.95 m/s
model

0
0.00

a derived from hydrodynamic


model

Sh determined from kGL and


maximum film thickness (dFm)

Sh 104
. 0.35 0.63

0.05

Multiphase Reactors 6PE20

kGLa derived from experiments

0.10

k Ld Fm
zDL
Sh
; 2
DL
d FmuLm

Monolith reactors - 43

Effect of stripping in IFM reactor


O
OH

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

Multiphase Reactors 6PE20

Length (m)

Monolith reactors - 44

Reactive stripping - Modeling


Modeling of reactive stripping in monolithic configuration using Falling
Laminar Film Flow Model (Lebens et al, 1999) and obtained kinetic data:
Reactor Length
BEA loading
Gas (sup. vel.)
Liq (sup. vel.)

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

Multiphase Reactors 6PE20

Monolith reactors - 45

Film Flow - Summary

Laminar flow
Mass transfer relatively slow (diffusion)
Residence time distribution
Low liquid superficial velocities
Flooding risk at exit

Counter Current operation !!!

Multiphase Reactors 6PE20

Monolith reactors - 46

Film-Flow monoliths - References

Gas and liquid distribution in the monolith film flow reactor


A. K. Heibel, F. J. Vergeldt, H. van As, F. Kapteijn, J.A. Moulijn and T. Boger
AIChE Journal, Volume 49, (2003), Pages 3007-301
Flooding performance of square channel monolith structures
A. K. Heibel, F. Kapteijn and J. A. Moulijn - Ind.Eng.Chem.Res. 2002, 41, 6759-6771
Influence of channel geometry on hydrodynamics and mass transfer in the monolith film
flow reactor
A. K. Heibel, J. J. Heiszwolf, F. Kapteijn and J. A. Moulijn
Catalysis Today, Volume 69, Issues 1-4, 15 September 2001, Pages 153-163
Gasliquid mass transfer in an internally finned monolith operated countercurrently in the
film flow regime
P. J. M. Lebens, J. J. Heiszwolf, F. Kapteijn, S. T. Sie and J. A. Moulijn
Chemical Engineering Science, Volume 54, Issue 21, November 1999, Pages 5119-5125
Hydrodynamics and mass transfer issues in a countercurrent gas-liquid internally finned
monolith reactor
P. J. M. Lebens, M. M. Stork, F. Kapteijn, S. T. Sie and J. A. Moulijn
Chemical Engineering Science, Volume 54, Issues 13-14, July 1999, Pages 2381-2389
Potentials of internally finned monoliths as a packing for multifunctional reactors
P. J. M. Lebens, F. Kapteijn, S. T. Sie and J. A. Moulijn
Chemical Engineering Science, Volume 54, Issue 10, May 1999, Pages 1359-1365

Multiphase Reactors 6PE20

Monolith reactors - 47

Novel Monolithic reactor designs

Co-current Monolithic reactor


Liquid

Gas

External recycle - liquid


Internal recycle - gas

Exothermal systems
High rates - Low conversions
Multiphase Reactors 6PE20

Monolith reactors - 48

Novel Monolithic reactor designs

Monolithic Stirrer reactor


horizontal mode:

Liquid phase reactions

vertical mode:

Staging possible
Cross-, co- and countercurrent
Multiphase Reactors 6PE20

Monolith reactors - 49

H2O2 decomposition
in a rotating monolith reactor

Multiphase Reactors 6PE20

Monolith reactors - 50

Novel Monolithic
reactor designs

Cross-Flow
module

Multiphase Reactors 6PE20

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

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