Chemical

Reac/on Engineering II
5. Design of Mul/phase
Cataly/c Reactor
Y.H.Yap

1. Introduction

Todays Topics

Introduc)on

Heterogeneous
Reac)ons

External
Diusion Eects

Diusion &
Reac)on in
Porous Catalyst

Design of
Mul)phase
Cataly)c Reactor

Resistance
Analysis

Data Analysis for

Reactor Design

Catalyst
Deac)va)on

Non-elementary
Reac)on Kine)cs

1. Introduction

Design of
Mul)phase
Cataly)c Reactor

Todays Topics

Areas covered

Introduc)on

Types of mul)phase
cataly)c reactor

Packed Bed Reactor

Dispersed catalyst Reactor

Strategies for selec)ng a

Mul)phase cataly)c reactor

Design Examples

Others

1. Introduction

Text

Levenspiel
Chemical Reac/on Engineering
Chapter 19 and 20

Fogler
Chapter 12.8 and 12.9

Ullmanns Encyclopedia of Chemical

Technology
R. Krishna, S.T. Sie (1994), Strategies for
Mul/phase Reactor Selec/on, Chemical
Engineering Science, 49, p. 4029 4065.
Various websites

1. Introduction

Multiphase Catalytic Reactor

Reactor in CRE1:

Design of reactor is a lot simpler without catalyst

1. Introduction

Multiphase Catalytic Reactor

A reactor is basically:
A unit opera)on with chemical reac)on taking
place in it
Unit opera)on could be mixing and separa)on
For example, Packed bed reactor is a mixing
opera)on
A mul)phase cataly)c reactor:
Usually implies a reactor that uses solid catalysts
with reactants in gas or liquid phase or both
This makes perfect sense since it is easier to
separate them aRer the reac)on

1. Introduction

Forms of catalyst

Some common catalysts:

1. Introduction

Multiphase Catalytic Reactor

Since heterogeneously catalyzed reactor is mainly

about the contact between reactants and catalyst:
The considera)on of contact paTern is very
important when designing a mul)phase
cataly)c reactor
Addi)onally, a process must:
Operate within technology feasible reac)on
coordinates of temperature, pressure, residence
)me
Safe opera)on and freedom from runaways
Environmental acceptability

1. Introduction

Multiphase Catalytic Reactor

Ideally, a process should also achieve:

Maximum possible conversion of feedstocks
Maximum selec)vity of reac)on to desired
products
Easy operability
Lowest capital and opera)ng costs, stemming
from:
Low pressure drop
Eec)ve u)liza)on of reactor space
Simple construc)on
Low catalyst usage

1. Introduction

Multiphase Catalytic Reactor

All these constraints imply that selec)ng and

designing a mul)phase cataly)c reactor is not a
trivial task, and
Most of the )me, the behaviour of the cataly)c
reac)on is unknown
This requires experiment to be performed at lab
scale, and then transferred into pilot scale before
it is ready for prime )me in the plant-scale
Which explains why it takes so long to develop a
process

2. Types of multiphase catalytic reactor

Types of mul)phase cataly)c reactors categorized

by contact paTerns:
Packed bed
Catalysts are ______________, e.g.:

Fixed bed reactor

Moving bed reactor
Fluidized bed reactor

Dispersed
Catalysts are ___________ in the uid, e.g.:

Bubble column reactor

Slurry reactor
Straight-Through-Transport reactor

2. Types of multiphase catalytic reactor

Types of mul)phase cataly)c reactors categorized

by contact paTerns:
Packed bed
Catalysts are closely packed, e.g.:

Fixed bed reactor

Moving bed reactor
Fluidized bed reactor

Dispersed
Catalysts are dispersed in the uid, e.g.:

Bubble column reactor

Slurry reactor
Straight-Through-Transport reactor

2. Types of MCR

Packed Bed

Fixed bed

2. Types of MCR

Packed Bed

Fixed bed

Fixed bed reactor

Most common type of mul)phase cat. reactor
Catalyst bed does not move

(a)

(b)

(c)

2. Types of MCR

Packed Bed

Fixed bed

Trickle bed

Fixed bed: Trickle-bed reactor

Liquid trickle down and surround
the catalyst
Gas surround the liquid lm
May have liquid maldistribu)on

(d)

2. Types of MCR

Packed Bed

Fixed bed

Fixed bed reactor

Advantage:
Simple and robust design no moving parts
Ecient contac)ng because )ghtly packed
Can achieve plug ow

Shortcomings:
Poor heat conduc)vity --> dicult temp control
Hot spots might developed in highly exothermic
reac/ons

Cannot use small sizes of catalyst

Cause plugging and high pressure drop

Very dicult to unload and regenerate catalyst

2. Types of MCR

Packed Bed

Fixed bed

Shortcomings:
Nonisothermal behavior of packed bed
Leads to non-uniform product forma)on

Non-isothermal eld in packed bed for exothermic reac/on

2. Types of MCR

Packed Bed

Fixed bed

Fixed bed reactor

Hot spots can be reduced
By increasing the cooling surface like in (b)
With further intercooling (via heat exchange)
like in (c)

2. Types of multiphase catalytic reactor

Types of mul)phase cataly)c reactors categorized

by contact paTerns:
Packed bed
Catalysts are closely packed, e.g.:

Fixed bed reactor

Moving bed reactor
Fluidized bed reactor

Dispersed
Catalysts are dispersed in the uid, e.g.:

Slurry reactor
Con)nuous bubble column reactor
Straight-Through-Transport reactor

2. Types of MCR

Packed Bed

Moving bed

Moving bed reactor

(g)

Screw conveyor system

to transport catalysts

2. Types of MCR

Packed Bed

Moving bed

Moving bed reactor

The catalyst bed is moving in the reactor
Typically used for system with catalysts that are
deac)vated very quickly
Advantage:
Catalysts can be removed and regenerated
Shortcoming:
Catalyst size have to be uniform for smooth ow
Require large par)cle size like xed bed
Could also cause hot spot
Limited to low pressure system

2. Types of multiphase catalytic reactor

Types of mul)phase cataly)c reactors categorized

by contact paTerns:
Packed bed
Catalysts are closely packed, e.g.:

Fixed bed reactor

Moving bed reactor
Fluidized bed reactor (semi-dispersed)

Dispersed
Catalysts are dispersed in the uid, e.g.:

Slurry reactor
Con)nuous bubble column reactor
Straight-Through-Transport reactor

2. Types of MCR

Packed Bed

Fluidized bed

Fluidized bed reactor

In this type of reactor, an upward-owing stream
of uid (gas or liquid) is passed through a granular
solid material (usually a catalyst) at high
enough __________ to suspend the solid and cause
it to behave as though it were a uid.
This process is known as ______________
The uid velocity is sucient to suspend the
par/cles but not enough to carry them out of vessel
Almost all commercial applica/ons for uidized bed
reactor involves gas-solid

2. Types of MCR

Packed Bed

Fluidized bed

Fluidized bed at dierent gas velocity

Gas-solid contac)ng regimes, from low to very high gas velocity

2. Types of MCR

Packed Bed

Fluidized bed

Main applica)on:
___________________
__________ (FCC)
To convert high-boiling
point, high molecular
weight frac)ons of
crude oil to more
valuable gasoline and
gases
BeTer than thermal
cracking because it can
generate higher octane
fuel

2. Types of MCR

Packed Bed

Fluidized bed

Fluidized bed reactor

Advantage:
Uniform temperature gradient good control
From rapid mixing of solids (like CSTR)
High mass and heat transfer

Can use small sizes of catalyst

Good for very fast reac/ons when pore and lm
diusion may inuence the rate

Can be unloaded and regenerated easily

Good for system with catalysts that are
deac/vated easily

2. Types of MCR

Packed Bed

Fluidized bed

Fluidized bed reactor

Shortcoming:
Flow is complex with considerable bypassing
Requires much more catalyst for high conversion
and bigger reactor

Pumping requirement and pressure drop

Erosion of internal components
result in wear of reactor vessel

2. Types of MCR

Packed Bed

Fluidized bed

Dierent types of uidized bed reactor:

(d)

(e)

(f)

2. Types of MCR

Packed Bed

Fluidized bed

Dierent types of uidized bed reactor:

Type (d)
No regenera)on
Heat exchangers are immersed in bed
Type (e)
Catalysts are con)nually removed and
regenerated
Type (f)
Like (e) but with three-stage counter-current
unit to overcome poor contact

2. Types of MCR

Packed bed

Fluidized

Dierent types of uidized bed

reactor:
Gas-solid vortex reactor
Also known as rota)ng uidized
bed reactor
Replace gravita)onal force by
centrifugal force
Probably beTer than conven)onal
uidized bed due to beTer
external mass and heat transfer

2. Types of multiphase catalytic reactor

Types of mul)phase cataly)c reactors categorized

by contact paTerns:
Packed bed
Catalysts are closely packed, e.g.:

Fixed bed reactor

Fluidized bed reactor
Moving bed reactor

Dispersed
Catalysts are dispersed in the uid, e.g.:

Bubble column reactor

Slurry reactor
Straight-Through-Transport reactor

2. Types of MCR

Dispersed

Bubble column reactor

Jet Reactor

Loop Reactor

Dierent congura)on of bubble

column reactors:
Single Stage

Multi Staged

Multi Channel

8'8'
Stage

Multi

Loop Reactor

Single Stage
Single Stage

Multi Staged
Multi Staged

Multi Channel
Multi Channel

Loop

Staged

Multi

3- Phase Fluidized Bed

Slurry Reacto
Reactor
Figure 1.1. Bubble column reactors and modlflcatlon

Reactor

Jet

Reactor

Downfl

LO
fluid-fluid interfacial areas, and interphase mass and heat transfer
holdup of 66%, wh
L
O
I
coefficients depend strongly on the prevailing flow regime. Many
stagnant liquid
theT
1
larger thanL 11
about G
investigators (Govier and Aziz, 1972; Lockett and Kirkpatrick,
T
1975; Wallis, 1969 Kawagoe et al., 1976 Hills, 1976; Miller,Go
1980,
1971).
3- Phase Fluidiz
etc.) have proposed different criteria to differentiate flow regimes.
2.
Churn Turbu
React
Wallis (1969) has characterized the upward movement of the
higher gas velocitie
interfacial areas, and interphase mass and heat transfer
holdup
66%,
wh
Figure
1.1. Bub
bubblefluid-fluid
swarms into
threestrongly
separate
regimes.flow
These
regimes
cannot
beofliquid
maintain
coefficients
depend
on flow
the prevailing
regime.
Many
stagnant
the
larger than about
investigators (Govier and Aziz, 1972; Lockett and Kirkpatrick,
1975;
Wallis,
1969 Kawagoe
et
1 9 7 6 Hills, 1976; Miller, 1980,
1971).
occur in
order
of increasing
gas flow
rate.
neling
occurs. This h
etc.) have proposed different criteria to differentiate flow regimes.
2. Churn Turbu
Wallis (1969) has characterized the upward movement of the
higher gas velociti
1. Bubbly
or Quiescent
regime
is characbubbles
movin
bubbleFlow
swarms
into three separate
flow
regimes.
These
regimes
IBubbling:
T This
Suspension
1 large
cannot
be maintain
occur in order of increasing gas flow rate.
neling occurs. This h
terizedterized
by1.
almost
uniformly
sized
bubbles
with
equal
radial
dissmall
bubbles
Bubbly
Flow or Quiescent
Bubbling:
This
regime
is characlarge
bubbles(Hills
movi
Downflow
Bubble Column
fluid-fluid
areas,
anddisinterphase
mass
and (Hills
heat
by almost uniformly
sized bubbles
with equal
radial
small
bubbles
L1
Gointerfacial
GO
tribution.
This regime
occurs
if superficial
the superficial
gas
velocity
is less
form
ofspherical
spherical ca
c
tribution.
This
regime
occurs
if
the
gas
velocity
is
less
form
of
coefficients
depend
strongly
on
the
prevailing
flow
regime
than
0
.
0
5
m
/
s
(Fair,
1967)
and
the
rise
velocity
of
the
bubbles
lies
These
large
bubble
Downflow Bubble Column
between 0.18 and 0.30m / s (Levich, 1962). However, these data
3. Slug Flow: In
than 0.05
m/sonly
(Fair,
1967)
the
rise velocity
ofarethe
bubbles
lies 1972;
These
bubbles
large large
bubbles
are s
be regarded
a investigators
guideline
which
valid
for Aziz,
aeration
should
3- and
Phase
Fluidized
Bed
Slurry
Reactor
(Govier
and
Lockett
and
Kirk
formation of bubble
of water.
Suspension

3 - Phase

G O

Fluidized
Reactor

Figure 1.1.

al.,

Jet Reactor
Jet Reactor

Channel

Downflow Bubble
G O Col

L 1

Loop Reactor
Loop Reactor

Suspension

Go

Jet Reactor
L1

With Static
With
Static
Mixers
Mixers

With Static
Mixers

Loop Reactor

8'

Single

Downflo

as

Bed

Slurry

React

Bubble column reactors and modlflcatlo

2. Types of MCR

Dispersed

Slurry reactor

Slurry reactor 1:
Gas feed from boTom
Gas sparger
Temperature control
through internal coil
Catalyst in solu)on

Sasols Fischer Tropsch process to

produce wax

2. Types of MCR

Dispersed

Slurry reactor

Slurry reactor 2:
Comes with s)rrer like
CSTR
Gas sparger
Temperature control
through hea)ng jacket
Catalyst in solu)on
Bae and impeller to
promote mixing

Par)al hydrogena)on of edible

oil

2. Types of MCR

Dispersed

Slurry reactor

Slurry reactor:
Catalyst is _________ in the liquid (small) and gas is
bubbled through the liquid
The solu)on may:
Act as reactant e.g. Hydrogena)on of methyl linoleate
Act as product e.g. Produc)on of HC wax
Inert e.g. Fischer Tropsch synthesis of methane

May be operated in either semibatch or con)nuous

mode
Advantage:
Temperature control and heat recovery is easy to
achieve
Flexibility in changing feed rate and residence )me

2. Types of MCR

Dispersed

Slurry reactor

Slurry reactor:
Shortcomings:
Dicult to achieve high degree of conversion because
reactant and product is well mixed like CSTR
Catalyst removal by ltra)on cause plugging
Higher consump)on of catalyst than packed bed

2. Types of multiphase catalytic reactor

Types of mul)phase cataly)c reactors categorized

by contact paTerns:
Packed bed
Catalysts are closely packed, e.g.:

Fixed bed reactor

Fluidized bed reactor
Moving bed reactor

Dispersed
Catalysts are dispersed in the uid, e.g.:

Bubble column reactor

Slurry reactor
Straight-Through-Transport reactor

2. Types of MCR

Dispersed

Straight-Through-Transport Reactor

Straight-Through Transport Reactor:

For system with catalysts that
are deac)vated very quickly
Catalyst pellets and reactant
enter together and are
transported __________ through
the reactor (usually travel at
same velocity)
Bulk density of catalyst pellets
are signicantly smaller than in
moving-bed reactors

2. Types of MCR

Other

Cataly)c reactors can also be congured to

incorporate other unit opera)on, for example
Cataly)c membrane reactor
Reac)ve dis)lla)on

Or comes in other forms:
Spinning basket reactor
Monolithic reactor
Rotary bed reactor
With thrus)ng capability

2. Types of MCR

Other

Other reactors:
Cataly)c membrane reactor
Comes with membrane for ltra)on

2. Types of MCR

Other

Other reactors:
Reac)ve dis)lla)on
Combine both dis)lla)on
and reac)on in single step
Lower capital cost
Especially useful for
equilibrium limited
reac)on such as
esterica)on
Conversion can be higher
due to con)nuous removal
of products from the
reac)ve zone
Dicult to design

2. Types of MCR

Other

Other reactors:
Monolithic reactor
Emission control

1 mm

Extremely good for system that require low pressure

drop, rapid startup and transient opera/on

2. Types of MCR

Other

Other reactors:
Spinning basket reactor

2. Types of MCR

Other

Other reactors:
Rotary bed reactor

(b)

C0 2, H20
N2, 02, H20

CO2 capture in power

at the top without diluting the other zone. Due to rotation, some steam from the fuel
plant
air (or fuel) sector.

ctor, a feed steam continuously flushes the residual fuel (or unburned air) into the

ging sector may also end up entering the following

(a)

exit
chamber

view, and (b) the isometric p

Figure 3-4 Schematic
driving drawing of rotary CLC system design with (a) bottom

engine

the wireframe.

fuel

recirculated CO2

reactor
diluted fuel
H20+CO2C0

feeding
chamber

ambient air

69

Flue gas (N 2,0 2, H20)

2. Types of MCR

Other

Other reactors:
Space propulsion thruster
Small rocket engine for spacecraR to alter path & al)tude

Usually hydrazine (N2H4)

propellant is used
Noble metals such as Pt, Ir
are used as catalyst

3. Strategies for selecting a Multiphase Catalytic Reactor

We have:
Seen the design of dierent types of mul)phase
cataly)c reactor in the previous subchapter

With this knowledge:
We can select and design the most appropriate
cataly)c reactor for a cataly)c process
We will follow a set of strategies or heuris)c for
our design and selec)on process

3. Strategies for selecting a Multiphase Catalytic Reactor

Strategies:
Level 1:
__________________________
Level 2:
_____________________________
Level 3:
__________________________
Combina)on of individual decisions at each
strategy level will yield the nal, ideal reactor
congura)on

3. Strategies for selecting a Multiphase Catalytic Reactor

Level 1

Level 1: Catalyst Design strategy

Involves determining the:
Par)cle size
Spa)al distribu)on of cataly)c agent
Par)cle shape / geometry
Porous structure
HaTa number
Does not involve:
Choosing the type of ac)ve catalyst and the
chemistry for the reac)on

on rates as apply to most processes,

vities in gas- or liquid-filled pores
ion limitation will generally occur
ng a diameter of a few millimeters_
ast reactions or very slow diffusion,
of so-called conformational-type
lite pores, pore diffusion limitation
particles of even much smaller

values close to unity.

Another example of the occurrence of diffusion
limitation caused by the presence of liquid in the
catalyst pores is depicted in Fig. 7. This figure shows
the effectiveness factor as a function of the Thiele
modulus for a number of Fischer-Tropsch catalysts
operated under different conditions. The experimental
results are in very good agreement with the theoretical
curve calculated for the case that the reaction rate
obeys first-order kinetics in hydrogen (as has been
verified experimentally), while the limiting factor is
the rate of diffusion of hydrogen as reactant in the
liquid hydrocarbon product which fills the pores. The
excellent fit demonstrates that as far as catalyst
effectivity is concerned, its dependence on catalyst
morphology may be established on the basis of first

3. Strategies for selecting a Multiphase Catalytic Reactor

Level 1

Level 1: Catalyst Design strategy

Par)cle size:

s effectiveness factors of some

hase reactions as a function of
n be seen that in these processes
n is far from complete for fixed
ctical sizes, i_e. above 3 mm_ In such
s the diffusivity inside the catalyst
y a Knudsen-type diffusion or a

Important for diusion-limited reac/on

Reactant molecules might not reach interior if
par/cles size is large
Big par/cle also decreases the space velocity
We can employ _____________
and ___________________ to
determine the op/mum pellet
size

ammon!a
0.8

0.4

(~
0

\
~
Dehydrogenation
Cumene'~
'~.~cyclohexane
cracking D""B.~__ffi
I

I
4

dp/ [mm]

I
8

I.

12

3. Strategies for selecting a Multiphase Catalytic Reactor

Level 1

Level 1: Catalyst Design strategy

Par)cle size:
Usually, we do not want pellet that is too small as this
will result in high pressure drop and plugging
But if small size has to be used, the only reactor choice
would be _______________ or slurry reactor
For bigger sizes of catalyst par/cles, we can consider
packed bed and uidized bed reactor

3. Strategies for selecting a Multiphase Catalytic Reactor

Level 1

Level 1: Catalyst Design strategy

Spa)al distribu)on of cataly)c agent:
In the case that par/cle size cannot be changed, we
can change the spa/al distribu/on of cataly/c agent
to suit the R.reac/on
KRISHNAand S. T. SIE
For example, egg-shell for high Thiele modulus and
for reac/ons that are highly exothermic which will
cause local hotspot in the inner core
Egg-white and egg-yolk are for catalyst with
Uniform
Outer Egg Shell
aeri/on problem

4038

8000

Predicted
catalyst
life/[h]

KRISHNAand S. T. SIE
0

'

'

t- - I

0 0
I

-3
Base
3
Average pore diameter/[nm]

Fig. 17. "Computer-aided design" of catalyst porous texture.

Predicted life as a function of the average pore diameter of
Uniform
Shell
tail-end catalyst in the
hydroconversionOuter
of an Egg
Arabian

Middle Egg White

Inner Egg Yolk

3. Strategies for selecting a Multiphase Catalytic Reactor

Level 1

Level 1: Catalyst Design strategy

Par)cle geometry:
Aect the surface to volume ra/o, strength and heat
conduc/vity between the pellet
4034

R. KRISHNAand S. T. SIE

50

-~-.x dp 10 '

hollowextrul

tr"ob ql
~1~ spheres
2

I
0

I
L / dp

~~'~"~-~i~
:liscs
--J
10

rings

quadrulobes
cylindrical
extrudates

Fig. 8. Surface area over volume ratio of shaped catalyst particles.

maximum

- - J/

/10

extrudates

cylindrical extrudates need not

wagon wheels in a certain rang
0
L
/
dp
3. Strategies for selecting a Multiphase Catalytic Reactor Trilobe
Level
1 of a speci
extrudates
i:~Opsab.~
applicable for this case. The
Fig. 8. Surface area over volume ratio of shaped catalyst particles.
wheel and trilobe extrudates ov
with respect to the reaction
relation
caused
by theproduc
higher
drop isand
reactor
Pressure drop, reactor productivity and strength of relation between pressure
ratio of the
former
of
acceptable
of different
shape
and types
size_ Th
catalyst particles. As discussed above, the problem of ivity for extrudates
these types of extrudates also
figure shows trends rather than quantitative da
diffusion limitation can be alleviated by choosing
so that they may not be the p
since the latter dependscircumstances_
on several factors such
smaller catalyst particles of a shape that has a high
rate per
aspect
ratio the
of the
be
(SA/F) ratio_ The main limiting factor for reduction properties of reactant fluids,
Figure
10 shows
relatio
Fig. 9. Relation between reactor productivity and pressure
axial
etc. costs
The and
demand
for
of particle size in a fixed bed reactordrop
is generally
theof fixed
facturing
surface-to
for some types
bed versus
catalysts. radial flow,

PressurAm
edro/p,

!~?.m

r~Rtm

Level 1: Catalyst Design strategy

Par)cle geometry:
~ reactionrate

Also aect the Overall

pressure
reaction drop
kgcalalyst
Dierent shapes of pellets have dierent costs

minimum desired reaction rate within a maximu

allowable pressure drop determines suitable sizes a
shapes of catalyst particles for a given case. F
instance, for the case depicted, it can be seen th
cylindrical extrudates need not be considered, but th
wagon wheels in a certain range of sizes can
use
maxibe
mum
Trilobe extrudates of / a specific
size are almarginal
i/
lowable
~/ case./ .:The ...............
~
cost
i:~Opsab.~
manufacturi
ng ........................
applicable
for this
superiority
of wag
wheel and trilobe extrudates over cylindrical extrudat
with respect to the reaction rate-pressure dr
relation is caused by the higher surface area to volum
ratio of the former types of extrudates. Howev
acceptable
these types of extrudates also have their drawbac
so that they may not be the preferred type under
SA IV
rate per
circumstances_
Fig. tO. Relation between reactor
manufacturing
surface/volumebetween
ratio of some
Figure
10 shows cost
theandrelationship
manfi
Fig. 9. Relation between reactor productivity and pressure

pressure drop over the bed. Figure 9 shows the general

maximum

PressurAm
edro/p,

/ /

!~?.m

Overallreaction

r~Rtm

~ reactionrate
kgcalalyst

3. Strategies for selecting a Multiphase Catalytic Reactor

Level 1

Level 1: Catalyst Design strategy

Porous structure:
Pore size can aect the ac/vity as well as ___________
For example, big molecules could not enter small pore,
as in the case for hydrogena/on of edible oils
Or it could aect the selec/vity of a reac/on say


A ! B ! C

Where B is the desired product but small pore size
force B to stay in the pore longer and convert to C
Where C is the desired product and B conver/ng to C
will be a good thing

3. Strategies for selecting a Multiphase Catalytic Reactor

Level 1: Catalyst Design strategy

Porous structure:

Activity

Level 1

Metal storage
Sulfur removal

Pore size can also aect __________________

For example in hydrodesulfuriza/on of residual oil
4037
Strategies for multiphase reactor selection
Catalyst ac/vity drops as

pore size is increased
b
because ac/ve inner core
b..9
becomes smaller for
0
0"-.. -.
..41..............'.,,...

sulfur removal
.......Q
~
Useful
However, catalyst life
becomes longer because a
1 nm
larger propor/on of pores
I
I
becomes storage for
metal deposits
pore diameter/[nm]
....

. D

life

.................

3. Strategies for selecting a Multiphase Catalytic Reactor

Level 1

Level 1: Catalyst Design strategy

Porous structure:
Pore size can also aect catalyst deac)va)on
For example in hydrodesulfuriza/on of residual oil
To get best result, we can use a combina/on of catalysts:
Metal tolerant catalyst at upstream
Highly ac/ve catalyst at downstream

storage
Metal
Metal storage
Sulfur removal
Bigger pore at
Upstream

Sulfur removal
Smaller pore at
Downstream

to be active.
The perspectives for use of monoliths in heterogeneous
catalysis are
by aCybulski
and
3. Strategies
foranalyzed
selecting
Multiphase
Moulijn (1994).

summarized in the Enhancement factor-Hatta number diagram of Fig. 26, which is equivalent to the
EffectivenessReactor
factor-Thiele modulus
diagram
Catalytic
Level
1

of Fig.
4. The overall aim is to choose the value of ,8
such that the reactor volume is effectively utilized.
Thus, for slow liquid-phase r~actions the aim should
Gas-liquid systems
For a gas-liquid system with reaction within the be to increase the bulk liquid volume at the expense
liquid phase there are fundamentally three different of interfacial area. A high value of ,8 is achieved by
modes of gas-liquid contact: (1) gas bubbles dispersed dispersing the gas in the form of bubbles (e.g. bubble
in liquid (as encountered in bubble columns), (2) liquid columns and tray columns operating in the froth
droplets dispersed in gas (e.g. tray operating in the regime). To give an example, air oxidation of cyclospray regime), and (3) a thin flowing liquid film in hexane (in the liquid phase) is a slow reaction usually
contact with a gas (e.g. gas-liquid contacting in a carried out in bubble contactors.
packed column or wetted-wall column); see Fig. 25.
In the fast pseudo-first-order reaction regime, the
reaction occurs predominantly in the diffusion film
close to the gas-hquid interface and a contactor with
Dispersion Modes
a low value of ,8 should be chosen (e.g. spray towers
4
and packed columns). Furthermore,
the fast
Rate of rin
eac/on
gas bubbles
liquid drops
gas and
pseudo-first-order reaction regime, the rate of transfer
dispersed in
dispersed in
liquid in
through
liquid lm
is independent of the liquid-phase
hydrodynamics;
liquid
gas
film contact there is no need to spend energy for increasing
turbulence in the liquid
An example
of process
of diusion
phase.Rate
operating in the fast pseudo-first-order reaction
through
he aqueous
lm
regime is absorption of carbon
dioxide tin
caustic solutions; this is usually carried out in packed
columns_ The liquid phase flows down the column in
thin liquid rivulets. If the gas-liquid reaction correfl = 103-104
/3 = 1 0 - 40
sponds to the instantaneous reaction rate regime, once
Fig. 25. Three fundamental procedures for contacting gases again efforts should be made to maximize the
beta)
and liquids, fl is the ratio
of(the
liquid-phase volume to the interracial area at the expense of bulk liquid volume.
volume of the diffusion layer within the liquid phase.
In contrast to the fast pseudo-first-order reaction

Level 1: Catalyst Design strategy

HaTa number:
Probably the most important factor for choosing
between packed bed, slurry or uidized reactor

HaTa
number

dispersed in
liquid

dispersed in
gas

3. Strategies for selecting

liquid in
is independent of the liquid-phase hydrodynamics;
film contact there is no need to spend energy for increasing
a Multiphase Catalytic Reactor
Level 1

turbulence in the liquid phase. An example of process

operating in the fast pseudo-first-order reaction
regime is absorption of carbon dioxide in aqueous
caustic solutions; this is usually carried out in packed
columns_ The liquid phase flows down the column in

thin liquid rivulets. If the gas-liquid reaction correfl = 103-104
/3
=
1
0
40
instantaneous reaction rate regime, once
Choice of depends on sponds
Haea tonthe
umber
ig. 25. Three fundamental procedures for contacting gases again efforts should be made to maximize the
The
im is to volume
choose
such
that
reactor
volume
is liquid volume.
interracial
area
at the expense
of bulk
nd liquids, fl is theratio
of thealiquid-phase
to the
volume of the diffusion layer within the liquid phase.
In contrast to the fast pseudo-first-order reaction
eec/vely u/lized

Level 1: Catalyst Design strategy

HaTa number:

Prefer bulk 1000'

volume over
interfacial
area
100

Enhancement
factor, E

slow reaction;
choose high value
of I~ (e.g. bubble
columns)

Fast pseudo
first order reaction;
choose low I~
(e.g. packed columns,
spray towers)
instantaneous
reaction; choose
low [~with high
degree of gas phase
turbulence

10

0.1

10
100
Hatta number, Ha

1000

Prefer interfacial area

over bulk volume