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Chemical Reac/on Engineering II

5. Design of Mul/phase Cataly/c Reactor

Y.H.Yap

1. Introduction Today’s Topics
1. Introduction
Today’s Topics

Introduc)on

Diffusion & Reac)on in Porous Catalyst

Data Analysis for Reactor Design

Heterogeneous

Reac)ons

Design of Mul)phase Cataly)c Reactor

Catalyst

Deac)va)on

External Diffusion Effects

Resistance

Analysis

Non-elementary Reac)on Kine)cs

1. Introduction Today’s Topics Areas covered
1. Introduction
Today’s Topics
Areas covered
Introduc)on Design of Mul)phase Cataly)c Reactor Packed Bed Reactor Dispersed catalyst Reactor Types of mul)phase
Introduc)on
Design of
Mul)phase
Cataly)c Reactor
Packed Bed Reactor
Dispersed catalyst Reactor
Types of mul)phase
cataly)c reactor
Others
Strategies for selec)ng a
Mul)phase cataly)c reactor
Design Examples
1. Introduction Text
1. Introduction
Text

Levenspiel

Chemical Reac/on Engineering Chapter 19 and 20

Fogler

Chapter 12.8 and 12.9

Ullmann’s 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
1. Introduction

Multiphase Catalytic Reactor

Reactor in CRE1:

Design of reactor is a lot simpler without catalyst

1. Introduction
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
1. Introduction
Forms of catalyst
1. Introduction Forms of catalyst •   Some common catalysts:

Some common catalysts:

1. Introduction Forms of catalyst •   Some common catalysts:
1. Introduction Forms of catalyst •   Some common catalysts:
1. Introduction Forms of catalyst •   Some common catalysts:
1. Introduction Forms of catalyst •   Some common catalysts:
1. Introduction Forms of catalyst •   Some common catalysts:
1. Introduction
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
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 Effec)ve u)liza)on of reactor space Simple construc)on Low catalyst usage

1. Introduction
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

Fixed bed reactor Moving bed reactor Fluidized bed reactor

Dispersed Catalysts are

, e.g.:

in the fluid, 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 fluid, 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
2. Types of MCR Packed Bed Fixed bed
2. Types of MCR Packed Bed Fixed bed
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

Fixed bed reactor •   Most common type of mul)phase cat. reactor •   Catalyst bed

(a)

(b)

Fixed bed reactor •   Most common type of mul)phase cat. reactor •   Catalyst bed

(c)

2. Types of MCR Packed Bed Fixed bed Trickle bed
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 film May have liquid maldistribu)on

down and surround the catalyst •   Gas surround the liquid film •   May have

(d)

2. Types of MCR Packed Bed Fixed bed
2. Types of MCR
Packed Bed
Fixed bed

Fixed bed reactor Advantage:

Simple and robust design – no moving parts Efficient contac)ng because )ghtly packed

Can achieve plug flow

Shortcomings:

Poor heat conduc)vity --> difficult temp control

Hot spots might developed in highly exothermic reac/ons

Cannot use small sizes of catalyst

Cause plugging and high pressure drop

Very difficult to unload and regenerate catalyst

2. Types of MCR Packed Bed Fixed bed
2. Types of MCR
Packed Bed
Fixed bed

Shortcomings:

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

of packed bed •   Leads to non-uniform product forma)on Non-isothermal field in packed bed for

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

2. Types of MCR Packed Bed Fixed bed
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 fluid, e.g.:

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

2. Types of MCR Packed Bed Moving bed
2. Types of MCR
Packed Bed
Moving bed

Moving bed reactor

2. Types of MCR Packed Bed Moving bed •   Moving bed reactor (g) Screw conveyor

(g)

2. Types of MCR Packed Bed Moving bed •   Moving bed reactor (g) Screw conveyor

Screw conveyor system to transport catalysts

2. Types of MCR Packed Bed Moving bed
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 flow Require large par)cle size like fixed 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 fluid, e.g.:

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

2. Types of MCR Packed Bed Fluidized bed
2. Types of MCR
Packed Bed
Fluidized bed

Fluidized bed reactor

In this type of reactor, an upward-flowing stream of fluid (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 fluid. This process is known as The fluid velocity is sufficient to suspend the par/cles but not enough to carry them out of vessel Almost all commercial applica/ons for fluidized bed reactor involves gas-solid

2. Types of MCR Packed Bed Fluidized bed
2. Types of MCR
Packed Bed
Fluidized bed

Fluidized bed at different gas velocity

bed •   Fluidized bed at different gas velocity Gas-solid contac)ng regimes, from low to very

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

2. Types of MCR Packed Bed Fluidized bed
2. Types of MCR
Packed Bed
Fluidized bed
2. Types of MCR Packed Bed Fluidized bed •   Main applica)on: •   (FCC) •

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
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 film diffusion may influence 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
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
2. Types of MCR
Packed Bed
Fluidized bed

Different types of fluidized bed reactor:

2. Types of MCR Packed Bed Fluidized bed •   Different types of fluidized bed reactor:

(d)

2. Types of MCR Packed Bed Fluidized bed •   Different types of fluidized bed reactor:

(e)

(f)

2. Types of MCR Packed Bed Fluidized bed
2. Types of MCR
Packed Bed
Fluidized bed

Different types of fluidized 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
2. Types of MCR
Packed bed
Fluidized
2. Types of MCR Packed bed Fluidized •   Different types of fluidized bed reactor: •

Different types of fluidized bed reactor:

Gas-solid vortex reactor

fluidized bed reactor: •   Gas-solid vortex reactor •   Also known as rota)ng fluidized bed

Also known as rota)ng fluidized bed reactor Replace gravita)onal force by centrifugal force Probably beTer than conven)onal fluidized 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 fluid, e.g.:

Bubble column reactor Slurry reactor Straight-Through-Transport reactor

2. Types of MCR Dispersed
2. Types of MCR
Dispersed
Bubble column reactor T I Suspe Go L1 3- Phase Fluidized Reactor Bed
Bubble column reactor
T
I
Suspe
Go
L1
3- Phase Fluidized
Reactor
Bed
T I Suspe Go L1 3- Phase Fluidized Reactor Bed •   Different configura)on of bubble

Different configura)on of bubble column reactors:

8' Single Stage Multi Staged Multi Channel With Static Mixers
8'
Single Stage
Multi Staged
Multi
Channel
With
Static
Mixers
LO Loop Reactor Jet Reactor Downflow Bubble Column
LO
Loop Reactor
Jet
Reactor
Downflow
Bubble Column

Suspension 1

GO

Slurry

Reactor

2. Types of MCR Dispersed Slurry reactor
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

control through internal coil •   Catalyst in solu)on Sasol’s Fischer Tropsch process to produce wax

Sasol’s Fischer Tropsch process to produce wax

2. Types of MCR Dispersed Slurry reactor
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 Baffle and impeller to promote mixing

jacket •   Catalyst in solu)on •   Baffle and impeller to promote mixing Par)al hydrogena)on

Par)al hydrogena)on of edible oil

2. Types of MCR Dispersed Slurry reactor
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
2. Types of MCR
Dispersed
Slurry reactor

Slurry reactor:

Shortcomings:

Difficult to achieve high degree of conversion because reactant and product is well mixed like CSTR Catalyst removal by filtra)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 fluid, e.g.:

Bubble column reactor Slurry reactor Straight-Through-Transport reactor

2. Types of MCR Dispersed
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 significantly smaller than in moving-bed reactors

2. Types of MCR Other
2. Types of MCR
Other
2. Types of MCR Other •   Cataly)c reactors can also be configured to incorporate other

Cataly)c reactors can also be configured 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
2. Types of MCR
Other

Other reactors:

Cataly)c membrane reactor

of MCR Other •   Other reactors: •   Cataly)c membrane reactor •   Comes with

Comes with membrane for filtra)on

of MCR Other •   Other reactors: •   Cataly)c membrane reactor •   Comes with
2. Types of MCR Other
2. Types of MCR
Other
2. Types of MCR Other •   Other reactors: •   Reac)ve dis)lla)on •   Combine

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 esterifica)on Conversion can be higher due to con)nuous removal of products from the reac)ve zone Difficult to design

  Conversion can be higher due to con)nuous removal of products from the reac)ve zone •
2. Types of MCR Other
2. Types of MCR
Other
2. Types of MCR Other •   Other reactors: •   Monolithic reactor •   Emission

Other reactors:

•   Monolithic reactor •   Emission control 1 mm
•   Monolithic reactor
•   Emission control
1 mm
•   Monolithic reactor •   Emission control 1 mm Extremely good for system that require

Extremely good for system that require low pressure drop, rapid startup and transient opera/on

2. Types of MCR Other
2. Types of MCR
Other

Other reactors:

Spinning basket reactor

2. Types of MCR Other •   Other reactors: •   Spinning basket reactor
2. Types of MCR Other •   Other reactors: •   Spinning basket reactor
2. Types of MCR Other •   Other reactors: •   Spinning basket reactor
2. Types of MCR Other
2. Types of MCR
Other
2. Types of MCR Other •   Other reactors: •   Rotary bed reactor •  

Other reactors:

Rotary bed reactor

CO 2 capture in power plant

(a)

exit

chamber

(b) C0 2 , H 2 0 N2, 02, H20
(b)
C0 2 , H 2 0
N2, 02, H20

reactor

feeding

chamber

driving

engine

fuel recirculated CO2 diluted fuel H20+CO2C0 ambient air Flue gas (N 2 ,0 2 ,
fuel
recirculated CO2
diluted fuel
H20+CO2C0
ambient air
Flue gas (N 2 ,0 2 , H 2 0)
2. Types of MCR Other
2. Types of MCR
Other

Other reactors:

Space propulsion thruster

  Other reactors: •   Space propulsion thruster •   Small rocket engine for spacecraR to

Small rocket engine for spacecraR to alter path & al)tude

rocket engine for spacecraR to alter path & al)tude Usually hydrazine (N 2 H 4 )

Usually hydrazine (N 2 H 4 ) propellant is used Noble metals such as Pt, Ir are used as catalyst

& al)tude Usually hydrazine (N 2 H 4 ) propellant is used Noble metals such as

3. Strategies for selecting a Multiphase Catalytic Reactor

We have:

Seen the design of different 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 final, ideal reactor configura)on

3. Strategies for selecting a Multiphase Catalytic Reactor

Level 1
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

3. Strategies for selecting a Multiphase Catalytic Reactor

Level 1
Level 1

Level 1: Catalyst Design strategy Par)cle size:

Important for diffusion-limited reac/on Reactant molecules might not reach interior if par/cles size is large Big par/cle also decreases the space velocity

0.8

ammon!a

0.4 \ Cumene'~ cracking D""B.~

~

ffi

We can employ and

to

determine the op/mum pellet size

Dehydrogenation

'~.~cyclohexane

(~ 0

I

I

I

I

4

I

I

I

8

I

dp/[mm]

I

I

I .

I

12

3. Strategies for selecting a Multiphase Catalytic Reactor

Level 1
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 fluidized bed reactor

3. Strategies for selecting a Multiphase Catalytic Reactor

Level 1
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 reac/on 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 aeri/on problem

Uniform

0

Outer Egg Shell

0

Middle Egg White

Inner Egg Yolk

3. Strategies for selecting a Multiphase Catalytic Reactor

Level 1
Level 1

Level 1: Catalyst Design strategy Par)cle geometry:

Affect the surface to volume ra/o, strength and heat conduc/vity between the pellet

50 ' hollowextrul •-~-.x dp 10 rings tr"ob ql v ~~'~"~-~i~ quadrulobes ~1~ spheres :liscs
50
'
hollowextrul
•-~-.x dp 10
rings
tr"ob
ql
v
~~'~"~-~i~
quadrulobes
~1~ spheres
:liscs
cylindrical
--J
extrudates
2
I
I
10
0
L/ dp

3. Strategies for selecting a Multiphase Catalytic Reactor

Level 1
Level 1

Level 1: Catalyst Design strategy Par)cle geometry:

Also affect the pressure drop Different shapes of pellets have different costs

maximum / / / i/ allowable maximum PressuAredmro/p, i:~Opsab.~ !~?.m r~Rtm manufacturing ~ ~ cost
maximum
/
/
/
i/
allowable maximum
PressuAredmro/p, i:~Opsab.~ !~?.m
r~Rtm
manufacturing
~
~
cost
/
/
.:
acceptable
~
Overallreactionrate per kgcalalyst
reactionrate
SA IV

3. Strategies for selecting a Multiphase Catalytic Reactor

Level 1
Level 1

Level 1: Catalyst Design strategy Porous structure:

Pore size can affect 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 affect 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
Level 1

Level 1: Catalyst Design strategy Porous structure:

Pore size can also affect

  Porous structure: •   Pore size can also affect Metal storage Sulfur removal •  

Metal storage Sulfur removal

For example in hydrodesulfuriza/on of residual oil

b b 9 0 0"- -. 41 '.,, • Activity Q ~ Useful •.D life
b
b
9
0
0"-
-.
41
'.,,
Activity
Q
~
Useful
•.D
life
1 nm
I
I
I
I
I
I
I
I
pore diameter/[nm]

Catalyst ac/vity drops as pore size is increased because ac/ve inner core becomes smaller for sulfur removal However, catalyst life becomes longer because a larger propor/on of pores becomes storage for metal deposits

3. Strategies for selecting a Multiphase Catalytic Reactor

Level 1
Level 1

Level 1: Catalyst Design strategy Porous structure:

Pore size can also affect 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

at upstream •   Highly ac/ve catalyst at downstream Metal storage Sulfur removal Bigger pore at

Metal storage Sulfur removal

Bigger pore at Upstream

at downstream Metal storage Sulfur removal Bigger pore at Upstream Metal storage Sulfur removal Smaller pore

Metal storage Sulfur removal

Smaller pore at Downstream

3. Strategies for selecting a Multiphase Catalytic Reactor

Level 1
Level 1

Level 1: Catalyst Design strategy HaTa number:

Probably the most important factor for choosing between packed bed, slurry or fluidized reactor

Dispersion Modes 4 gas bubbles liquid drops gas and dispersed in dispersed in liquid in
Dispersion Modes
4
gas bubbles
liquid drops
gas and
dispersed in
dispersed in
liquid in
liquid
gas
film contact
fl = 103-104
/3 = 10-
40

β (beta)

HaTa

number

contact fl = 103-104 /3 = 10- 40 β (beta) HaTa number Rate of reac/on through

Rate of reac/on through liquid film

fl = 103-104 /3 = 10- 40 β (beta) HaTa number Rate of reac/on through liquid

Rate of diffusion through the film

3. Strategies for selecting a Multiphase Catalytic Reactor

Level 1
Level 1

Level 1: Catalyst Design strategy HaTa number:

Choice of β depends on Haea number The aim is to choose β such that reactor volume is effec/vely u/lized

~j 1000' 100 Enhancement factor, E slow reaction; choose high value of I~ (e.g. bubble
~j
1000'
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)
10
instantaneous
reaction; choose
low [~with high
degree of gas phase
turbulence
0.1
1
10
100
1000
Hatta number, Ha
Prefer interfacial area
over bulk volume

Prefer bulk volume over interfacial area