EKC337: REACTOR DESIGN & ANALYSIS

Core Course for

B.Eng.(Chemical Engineering)
Semester II (2009/2010)
Mohamad Hekarl Uzir, DIC.,MSc.,PhD.
([email protected])

School of Chemical Engineering

Engineering Campus, Universiti Sains Malaysia
Seri Ampangan, 14300 Nibong Tebal, Seberang Perai Selatan, Penang
EKC314-SCE – p. 1/164
 Syllabus

1. External Diffusion:
External diffusion effects
Mass Transfer Coefficient
Diffusion with chemical reaction
2. Internal Diffusion:
Internal diffusion effects
Effective diffusivity
Diffusion and chemical reaction in a cylindrical pore
Thiele Modulus, φ and effectiveness factor, η
Falsified kinetics

EKC314-SCE – p. 2/164
 Syllabus

3. Bioreactor Analysis and Operation:

Mixing and transfer of masses: Oxygen transfer and
Kla
Bioreactor kinetics: substrate consumption,
biomass production, product formation and kinetics
models
Design of bioreactors
Role of transport processes in bioreactor design

EKC314-SCE – p. 3/164
 Syllabus

4. Design of Multiple-Phase Reactors

Gas-liquid-solid reaction
Trickle-bed reactor
Slurry reactor
Three-phase fluidised-bed reactors
5. Projects on COMPUTER APPLICATIONS (MATLABr )
in REACTOR DESIGN

EKC314-SCE – p. 4/164
 External & Internal Diffusion

1. Diffusion Fundamentals
Consider a tubular-typed reactor, where the molar
flow rate of reaction mixture in the z-direction is
given by;
F A z = A c WA z
where WAz is the flux and Ac is the cross-sectional
area.
Diffusion–spontaneous mixing of atoms or
molecules by random thermal motion which gives
rise to the motion of the species relative to the
motion of the mixture.

EKC314-SCE – p. 5/164
 External & Internal Diffusion

CA,b
CA,s Porous catalyst
External pellet
diffusion
CA(r)
Internal
diffusion

External
surface

EKC314-SCE – p. 6/164
 External & Internal Diffusion

1. Diffusion Fundamentals
Molecules of a given species within a single phase
will diffuse from regions of higher concentrations to
regions of lower concentrations (this gives a
concentration gradient per unit area between the 2
regions).
External mass transfer:
(a) Consider a non-porous particle where the entire
surface is uniformly accessible.
(b) The average flux of reactant, CA to the fluid-solid
interface can be written as;
NA = kA (CA,b − CA )

EKC314-SCE – p. 7/164
 External & Internal Diffusion

1. Diffusion Fundamentals
External mass transfer:
(b) where CA,b is the bulk concentration of reactant A
and CA is the concentration at the solid-liquid
interface and kA is the mass-transfer coefficient.
(c) let the reaction rate, rA follows first order reaction;

rA = kCA
where k is the first order rate constant. Therefore,
at steady-state;

kCA = kA (CA,b − CA )

EKC314-SCE – p. 8/164
 External & Internal Diffusion

1. Diffusion Fundamentals
External mass transfer:
(d) defining the dimensionless parameters;

CA k
x= Da =
CA,b kA

thus;
1−x
Da =
x
(e) where Da is defined as the ratio of reaction rate
with the convective/diffusive mass transfer rate.

EKC314-SCE – p. 9/164
 Heterogeneous Reaction

Introduction to Heterogeneous and Multiphase Reactions

For pseudo-homogeneous assumption:
Mass and heat transfer resistances between
different phases are neglected–the reactor contents
can be treated as a single phase.
Useful for preliminary design–truly homogeneous
system.
For heterogeneous model–used when temperature
and concentration need to be distinguished between
the phases.

EKC314-SCE – p. 10/164
 Heterogeneous Reaction

Introduction to Heterogeneous and Multiphase Reactions

For real reactor: (multiphases–Multi-Phase Reactors)
Should be heterogeneous type
Normally used for systems involving fluid-fluid
interactions [liquid-liquid or gas-liquid]

EKC314-SCE – p. 11/164
 Heterogeneous Reaction

Introduction to Heterogeneous and Multiphase Reactions

For solid state:
solid as porous catalyst pellet:
1. not being consumed during reaction BUT
changes in physical & chemical states
2. pore blocking due to deposits of carbonaceous
by-products [coking]
3. metal particles [active catalyst]–coalesce at high
temperature–therefore reduce surface area for
reaction hence reducing rate constant [sintering]

EKC314-SCE – p. 12/164
 Heterogeneous Reaction

Introduction to Heterogeneous and Multiphase Reactions

For solid state:
solid as non-catalyst:
1. dissolution of solid through reaction with fluid
2. burning off coke in catalyst pellet for its
regeneration
3. most common utilisation of solid catalyst in
fixed-bed catalytic reactor -FBCR
4. it is a turbular reactor packed with catalyst
through which the fluid species flow

EKC314-SCE – p. 13/164
 Heterogeneous Reaction

Introduction to Heterogeneous and Multiphase Reactions

For solid state:
Advantages of FBCR:
1. no solids handling
2. little solids attribution
3. high surface area through use of porous catalyst
4. plug flow operation can be achieved
5. no separation of catalyst from reaction products
needed

EKC314-SCE – p. 14/164
 Heterogeneous Reaction

Introduction to Heterogeneous and Multiphase Reactions

For solid state:
Disadvantages of FBCR:
1. pressure drop
2. complex arrangement (e.g. multitubular) for
reactions requiring high heat-exchange duties
3. large down-time for catalyst which deactivate
rapidly

EKC314-SCE – p. 15/164
 Heterogeneous Reaction

Interfacial gradient effects: Reaction at catalyst surface

Concentration at the
catalyst surface

Bulk concentration CsAs

CA

Concentration within
CAs the catalyst
NA
Transfer flux

Boundary layer Active centres

z
FLUID 0 SOLID EKC314-SCE – p. 16/164
 Transport Processes in
Heterogeneous Catalysis

Interfacial gradient effects

For first order reaction:
reaction rate at the catalyst surface:
s s
rAs = ks CAs (1)

where ks is the rate constant at the catalyst surface

s
and CAs is the concentration at the active surface at
z=0
at steady-state:
s
rAs = NA = rA (2)

where
s
NA = kmc (CA − CAs ) (3)
EKC314-SCE – p. 17/164
 Transport Processes in
Heterogeneous Catalysis

Interfacial gradient effects

For first order reaction:
the mass-transfer coefficient can also be expressed
in terms of mole fraction & pressure:
NA
kmy = s
(yA − yAs )

and
NA
kmp =
(pA − psAs )
and kmc = kmp = kmy

EKC314-SCE – p. 18/164
 Transport Processes in
Heterogeneous Catalysis

Interfacial gradient effects

For first order reaction:
substitute (3) into (1):
s
NA = ks CAs
s s
ks CAs = kmc (CA − CAs )
s kmc CA
CAs = (4)
ks + kmc

EKC314-SCE – p. 19/164
 Transport Processes in
Heterogeneous Catalysis

Interfacial gradient effects

For first order reaction:
substitute into (1) and upon rearrangement gives;
1 1 1
= + (5)
ko kmc ks
where ko is the overall rate constant.
Limiting cases:
1. kmc >> ks [rapid mass transfer]

ko ∼ ks
and
s
CAs ∼ CA
EKC314-SCE – p. 20/164
 Transport Processes in
Heterogeneous Catalysis

Interfacial gradient effects

For first order reaction:
Limiting cases:
2. ks >> kmc [rapid reaction]

ko ∼ kmc
and
s
CAs ∼0

EKC314-SCE – p. 21/164
 Transport Processes in
Heterogeneous Catalysis

Interfacial gradient effects

For Second order reaction:
the rate of reaction is expressed by;
s s 2
rAs = ks CAs (6)

at steady-state;
s 2
ks CAs = kmc (CA − CAs )2
s 2 s 2
ks CAs s
+ 2kmc CA CAs − kmc CAs = kmc CA2

EKC314-SCE – p. 22/164
 Transport Processes in
Heterogeneous Catalysis

Interfacial gradient effects

For Second order reaction:
Limiting cases:
1. kmc >> ks :
rA ∼ ks CA2
[second order dependent] overall is reaction
rate controlled
2. ks >> kmc :
rA ∼ kmc CA
[first order dependent] overall is diffusion
controlled regime

EKC314-SCE – p. 23/164
 Transport Processes in
Heterogeneous Catalysis

Interfacial gradient effects

For Complex reactions (analytical SOLUTION not
usually possible):
mass-transfer can lead to difficulties in
experimentally determining rate coefficient & orders
can work under conditions:
1. reaction controlled:
kmc >> ks
[reduce TEMPERATURE (lower rate), increase
fluid turbulence]

EKC314-SCE – p. 24/164
 Transport Processes in
Heterogeneous Catalysis

Interfacial gradient effects

For Complex reactions (analytical SOLUTION not
usually possible):
can work under conditions:
2. diffusion controlled:
ks >> kmc
[increase temperature]

EKC314-SCE – p. 25/164
 Transport Processes in
Heterogeneous Catalysis

Interfacial gradient effects

Determining the km value:
usually defined as the mass-transfer coefficient of
◦
equimolar counter diffusion, km
◦
relationship between km and km
1. Equimolar counter diffusion:
NA = −NB
the total mass flux of component A:

dyA
NA = NT yA + CDAB (7)
dz

EKC314-SCE – p. 26/164
 Transport Processes in
Heterogeneous Catalysis

Interfacial gradient effects

Determining the km value:
◦
relationship between km and km
1. since
NT = NA + NB = 0
thus
dyA
NA = CDAB (8)
dz

EKC314-SCE – p. 27/164
 Transport Processes in
Heterogeneous Catalysis

Interfacial gradient effects

Determining the km value:
◦
relationship between km and km
1. upon integration of this leads to;

CDAB s
NA = (yA − yAs ) (9)
l
since
◦ CDAB
kmy
=
l
and for equimolar counter diffusion;
◦
kmy = kmy
EKC314-SCE – p. 28/164
 Transport Processes in
Heterogeneous Catalysis

Interfacial gradient effects

Determining the km value:
◦
relationship between kmy and kmy
1. which then gives;

kmy DAB
kmc = = (10)
C l
2. For reaction in which total moles are not
conserved
aA ⇋ bB

EKC314-SCE – p. 29/164
 Transport Processes in
Heterogeneous Catalysis

Interfacial gradient effects

Determining the km value:
◦
relationship between kmy and kmy
2. which gives;
b
NB = − NA (11)
a
substitute into Equation (7) leads to;
a yA
NA l = CDAB ln s (12)
b yAs

EKC314-SCE – p. 30/164
 Transport Processes in
Heterogeneous Catalysis

Interfacial gradient effects

Determining the km value:
◦
relationship between kmy and kmy
s
2. for NA = kmy (yA − yAs ) where
◦
kmy
kmy =
yf A

and
s
(1 + δA yA ) − (1 + δA yAs )
yf A =  
1+δA yA
ln 1+δ Ay
s
As

(b−a)
where δA = a
EKC314-SCE – p. 31/164
 Transport Processes in
Heterogeneous Catalysis

Interfacial gradient effects

Determining the km value:
◦
relationship between kmy and kmy
2. for general equation of the form;

aA + bB + . . . ⇋ qQ + rR + . . .

therefore;
(q + r + . . .) − (a + b + . . .)
δA =
a
for
δA −→ 0, yf A −→ 1
EKC314-SCE – p. 32/164
 Transport Processes in
Heterogeneous Catalysis

Interfacial gradient effects

Determining the km value:
◦
relationship between kmy and kmy
◦
2. thus; kmy = kmy
the j-factor:
1. jD -factor:
defined as;
◦
km Mm 2
jD = Sc 3
G
◦ ◦ ◦
km can be taken as kmy /kmp , as long as;
◦
km = kmy yf A = kmp P yf A = kmp Pf A
EKC314-SCE – p. 33/164
 Transport Processes in
Heterogeneous Catalysis

Interfacial gradient effects

the j-factor:
1. for a flow in a packed-bed with spherical particles
and εb = 0.37;

jD = 1.66Re−0.51 , for Re < 190

jD = 0.983Re−0.41 , for Re > 190
2. jH -factor:
defined as;
hf 2
jH = Pr 3
Cp G

EKC314-SCE – p. 34/164
 Transport Processes in
Heterogeneous Catalysis

Interfacial gradient effects

Concentration partial pressure differences across
external film:
1. if ∆CA /∆PA ∼ 0 that is (yA ∼ 0) where the mass
transfer is very fast, therefore, rA can be expressed
as function of bulk CA or PA
s
rA = rAs = ks CA
s
since CA ∼ CAs
2. using differential definition of rA , thus;
 
′ mol
rA
kgcat · s
EKC314-SCE – p. 35/164
 Transport Processes in
Heterogeneous Catalysis

Interfacial gradient effects

Concentration partial pressure differences across
external film:
2. with the correction factor for area, am given by;
′ s
rA = kmc am (CA − CAs ) (13)

but in terms of concentration (mole fraction);

′
rA = am kmy (∆yA )

and upon rearrangement gives;

◦
km
kmy =
yf A
EKC314-SCE – p. 36/164
 Transport Processes in
Heterogeneous Catalysis

Interfacial gradient effects

Temperature differences across the external film:
1. taking energy balance at steady-state;
′
rA (−∆Hr ) = hf am (Tss − T ) (14)

′
but it is known that, rA = kmy am ∆yA upon
substitution gives;
   23   
jD Pr ∆yA 1
∆T = −∆Hr (15)
jH Sc yf A Mm Cp

∆T increases with the increase of ∆yA . → when

mass-transfer resistances is HIGH.
EKC314-SCE – p. 37/164
 Transport Processes in
Heterogeneous Catalysis

Interfacial gradient effects

Temperature differences across the external film:
1. for gaseous flow in a packed-beds;
 
∆Hr ∆yA
∆T ≈ 0.7 − (16)
M m cp y f A
s
for maximum ∆T → ∆T |max occurs when yAs =0
(for irreversible reaction)
and for reversible reaction,

s δA yA
yAs = yAequilibrium and yf A =
ln (1 + δA yA )

EKC314-SCE – p. 38/164
 Transport Processes in
Heterogeneous Catalysis

Interfacial gradient effects

Temperature differences across the external film:
1. for maximum temperature difference, substitute the
above terms into Equation (17) then, ∆T |max gives;
 
∆Hr ln (1 + δA yA )
∆T |max = 0.7 − (17)
M m cp δA

EKC314-SCE – p. 39/164
 Transport Processes in
Heterogeneous Catalysis

Mass Transfer on Metallic Surfaces:

for a packed bed, concentration gradient, ∆C variation
is SMALL–usually negligible
mass transfer may be significant when catalyst is a
METALLIC SURFACE
1. catalyst monolith/honeycomb–[e.g. catalytic
converter]
2. wire gauze–[oxidation of NH3 ]
advantages of this unit:
1. LOW ∆P (due to porous structure)
2. particulate in feed (NO clog-up bed)

EKC314-SCE – p. 40/164
 Transport Processes in
Heterogeneous Catalysis

Intra-Particle Gradient Effects:

Catalyst internal structure:
reaction rate α catalyst surface area
area range: 10 – 200 m2 /g
activated carbon: 800 m2 /g
sand: 0.01 m2 /g

EKC314-SCE – p. 41/164
 Transport Processes in
Heterogeneous Catalysis

Intra-Particle Gradient Effects:

Catalyst internal structure:
high areas through highly porous structure give high
surface area to volume ratio
pore sizes are not uniform–pore sizes distribution
exists
pore size classifications:
1. Micropores: dpore < 0.3nm
2. Mesopores: 0.3nm < dpore < 20nm
3. Macropores: dpore > 20nm
IN CALCULATION → use MEAN PORE SIZE!!
some catalysts–have bimodal distribution of pore
sizes ZEOLITE CATALYST
EKC314-SCE – p. 42/164
 Transport Processes in
Heterogeneous Catalysis

Intra-Particle Gradient Effects:

Catalyst internal structure:
non-ZEOLITE catalysts֌active metal dispersed
and supported within a macroporous support matrix
such as SILICA and ALUMINA
FURTHER COMPLICATION: DIFFUSION RATE
AND MECHANISMS VARY WITH PORE SIZE!
Pore diffusion:
for a gas diffusion through a single cylindrical pore
⇒ ratio of dpore to mean free path, λ
the ratio determines whether OR not pore wall
affects the diffusion behaviour

EKC314-SCE – p. 43/164
 Transport Processes in
Heterogeneous Catalysis

Intra-Particle Gradient Effects:

λ dpore

where λ is the distance between the two molecules of gas

for collision.
for dpore >> λ:
1. molecular diffusion dominates–Fickian Diffusion
2. for example; gases at HIGH pressure or liquids

EKC314-SCE – p. 44/164
 Transport Processes in
Heterogeneous Catalysis

Intra-Particle Gradient Effects:

for dpore << λ and dmolecule < λ:
1. molecular interaction with pore wall dominates
2. diffusion described by Knudsen’s Law of Diffusion
3. for example; gases at LOW pressure but NOT
liquids (molecular structure of liquid is too high)
for dpore << λ and dmolecule ≃ λ:
1. complex interaction of diffusing molecules with
force-fields of molecules making up the wall
2. referred to Configurational Diffusion OR activated
diffusion
3. very difficult to predict
EKC314-SCE – p. 45/164
 Transport Processes in
Heterogeneous Catalysis

Intra-Particle Gradient Effects:

for dpore << λ and dmolecule ≃ λ:
4. for example:
(a) large hydrocarbon molecules [petroleum
desulphurisation]
(b) pores of VERY SMALL size [zeolite crystals and
biological cell walls]

EKC314-SCE – p. 46/164
 Transport Processes in
Heterogeneous Catalysis

Intra-Particle Gradient Effects:

dpore

when dpore << λ and dmolecule < λ:

dpore

when dpore << λ and dmolecule ≃ λ:

EKC314-SCE – p. 47/164
 Transport Processes in
Heterogeneous Catalysis

Correlations for Diffusion Coefficient:

For binary molecular diffusion; (for gases)
3
T2
Dmi,k α
P

Diffusion coefficient for the key component through a

mixture of the other components, Dmi,m

Nc
X dyi
Ni = y i Nk − CDmi,m
k=1
dz

EKC314-SCE – p. 48/164
 Transport Processes in
Heterogeneous Catalysis

Correlations for Diffusion Coefficient:

With the Stefan-Maxwell equation for diffusion, Dmi,m
can be calculated from the actual binary diffusion data
using;
PNc 1 vk
1 k=1 Dmi,k (y k − y i vi
)
= PNc vk
Dmi,m 1 − yi k=1 vi
where v is the stoichiometric coefficient.
The Knudsen diffusion coefficient, DK can be
calculated using;
  12
T
Dki α · dpore
Mmi
EKC314-SCE – p. 49/164
 Transport Processes in
Heterogeneous Catalysis

Correlations for Diffusion Coefficient:

And
Dki 6= f (P )
when P ↑: transport regime can switch from
Knudsen to molecular diffusion.
Micropore diffusion coefficient – difficult to predict –
and always relies on experimental measurement
For NON-zeolite catalysts – molecular & Knudsen
diffusion dominate and the pore diffusion coefficient,
Dp is a function of Dm and Dk

EKC314-SCE – p. 50/164
 Transport Processes in
Heterogeneous Catalysis

Correlations for Diffusion Coefficient:

Where Dp ⇒ the pore diffusion coefficient for a single
pore
dpore
→ > 20
λ
(molecular diffusion controlling) thus,

Dp = Dm

dpore
→ < 0.2
λ
(Knudsen diffusion controlling) thus,

Dp = Dk
EKC314-SCE – p. 51/164
 Transport Processes in
Heterogeneous Catalysis

Correlations for Diffusion Coefficient:

For intermediate values, both diffusion types are
important.
Use the Bosanquet Equation to estimate Dp where;

1 1 1
= +
Dp Dk Dm

EKC314-SCE – p. 52/164
 Transport Processes in
Heterogeneous Catalysis

Correlations for Diffusion Coefficient:

If given Dp , the approximation of Deff is given by;

εDp
Deff =
τp

where Deff is the effective diffusion coefficient, εp is the

intraparticle void fraction and τp is the tortuosity factor.

EKC314-SCE – p. 53/164
 Transport Processes in
Heterogeneous Catalysis

Correlations for Diffusion Coefficient:

Comparing diffusion in a single pore, (a) & diffusion in
a porous pellet, (b):
tortuous path

NA = -Dp dCA/dz A

CA,1 z CA,2
(a) (b)
EKC314-SCE – p. 54/164
 Transport Processes in
Heterogeneous Catalysis

Correlations for Diffusion Coefficient:

The cross-sectional area available for diffusion = Aεp ,
thus, lower NA .
Tortuous molecules path and changing pore
dCA
cross-sectional area due to constrictions, thus dz
is
reduced.
Therefore;
εDp dCA
NA = −
τp dz
For zeolite;
τp = 3 ∼ 10

EKC314-SCE – p. 55/164
 Transport Processes in
Heterogeneous Catalysis

Correlations for Diffusion Coefficient:

NOTE:
tortuosity
τp =
constriction factor
where;
actual diffusion path length
tortuosity =
shortest radial pellet length

If Deff is given, then the combined diffusion & reaction

within a catalyst pellet can be considered.
Reaction at the surface–diffusion & reaction take place
simultaneously rather than consecutively.
EKC314-SCE – p. 56/164
 Transport Processes in
Heterogeneous Catalysis

Diffusion and Reaction within a Catalyst Pellet:

Concentration profile for porous catalyst pellet:
concentration
on the surface

CsA,s CA,s concentration

CA
within the catalyst

CATALYST
bulk concentration
external
film

Concentration rp 0
r
central axis of pellet

negligible external mass

transfer
significant external mass
transfer

Position EKC314-SCE – p. 57/164

 Transport Processes in
Heterogeneous Catalysis

Diffusion and Reaction within a Catalyst Pellet:

The rate of reaction is measured under conditions
where external and internal mass-transfer resistances
∗
are negligible; ⇒ rA [use small particle!]
When mass-transfer is important;
CA > CAs
1. CANNOT use bulk concentration to calculate the
actual (observed) reaction rate.
∗
2. NEED to relate rA to rA using the Effectiveness
Factor:
rA
η= ∗
rA
EKC314-SCE – p. 58/164
 Transport Processes in
Heterogeneous Catalysis

Diffusion and Reaction within a Catalyst Pellet:

η < 1 for ISOTHERMAL or ENDOTHERMIC reaction.
η is useful for DESIGN CALCULATION
For rigorous calculations, particularly for COMPLEX
REACTION KINETICS and NON-ISOTHERMAL
operation, BETTER to solve the simultaneous
equations governing diffusion and reaction.

EKC314-SCE – p. 59/164
 Transport Processes in
Heterogeneous Catalysis

Diffusion and Reaction within a Catalyst Pellet:

For packed-bed–external film mass-transfer
resistances ⇒ SMALL
ASSUME: situation depicted by the solid line in
previous graph
∗
rA is the reaction rate measured if all of the pellets
s
give concentration of CAs , thus;
∗ s s
rA = rAs [CAs ] = rAs

and
rA
η= s
rAs

EKC314-SCE – p. 60/164
 Transport Processes in
Heterogeneous Catalysis

Diffusion and Reaction within a Catalyst Pellet:

Pseudo-First Order Reaction: [A → Product]
consider material balance through the incremental
section of a catalyst SLAB of area, a;
∆r r

rp

NA r + ∆r

r=0
Incremental
section EKC314-SCE – p. 61/164
 Transport Processes in
Heterogeneous Catalysis

Diffusion and Reaction within a Catalyst Pellet:

Pseudo-First Order Reaction: [A → Product]

IN − OUT = CONSUMPTION
(NA · a)|r+∆r − (NA · a)|r = rAs a∆r
dividing by a∆r and let lim∆r→0 gives;

dNA
= rAs = kv CAs
dr

EKC314-SCE – p. 62/164
 Transport Processes in
Heterogeneous Catalysis

Diffusion and Reaction within a Catalyst Pellet:

Pseudo-First Order Reaction: [A → Product]
For no convective flow in pellet, Fick’s Law is
obeyed;
dCAs
NA = D e A
dr
upon substitution gives;

d2 CAs
De A 2
= kv CAs (18)
dr
for constant DeA with respect to radius, r.

EKC314-SCE – p. 63/164
 Transport Processes in
Heterogeneous Catalysis

Diffusion and Reaction within a Catalyst Pellet:

Pseudo-First Order Reaction: [A → Product]
integrating Equation (18) using the following
boundary conditions;
s
r = rp : CAs = CAs

dCAs
r=0 :
dr
gives;
 q 
CAs cosh r · Dkev
A
s
=   (19)
CAs
q
cosh rp · Dkev
A
EKC314-SCE – p. 64/164
 Transport Processes in
Heterogeneous Catalysis

Diffusion and Reaction within a Catalyst Pellet:

Pseudo-First Order Reaction: [A → Product]
where Thiele Modulus can be defined as;
s
kv
φslab = rp
De A

EKC314-SCE – p. 65/164
 Transport Processes in
Heterogeneous Catalysis

Diffusion and Reaction within a Catalyst Pellet:

Pseudo-First Order Reaction: [A → Product]

1.0 φslab = 0
CAs/CsAs

As φslab increases - the rate

constant becomes SMALLER

φslab = rp(kv/DeA)1/2
INCREASING

1.0 r/rp 0.0

EKC314-SCE – p. 66/164
 Transport Processes in
Heterogeneous Catalysis

Diffusion and Reaction within a Catalyst Pellet:

Pseudo-First Order Reaction: [A → Product]
for spherical pellet, asphere = 4πr2
applying the same method as for SLAB; the final
equation leads to;
 q 
kv
CAs rp sinh r D eA
s
=  q  (20)
CAs r sinh r kv
p D eA

EKC314-SCE – p. 67/164
 Transport Processes in
Heterogeneous Catalysis

Diffusion and Reaction within a Catalyst Pellet:

Pseudo-First Order Reaction: [A → Product]
for cylindrical-shaped pellet, acylinder = 2πr(L + r)
applying the same method as for SLAB; the ratio
gives;
q
kv
CAs I1 r D eA
s
= q (21)
CAs I0 rp kv
D eA

where I is the Bassel function given by;

∞ m 2m
X
n (−1) r
In (r) = r 2m+n m!(n + m)!
m=0
2
EKC314-SCE – p. 68/164
 Transport Processes in
Heterogeneous Catalysis

Diffusion and Reaction within a Catalyst Pellet:

Pseudo-First Order Reaction: [A → Product]
GENERALLY;
1 d m
(r NA ) = rAs (22)
rm dr
where;
1. for SLAB; m = 0
2. for CYLINDER; m = 1
3. for SPHERE; m = 2

EKC314-SCE – p. 69/164
 Transport Processes in
Heterogeneous Catalysis

Diffusion and Reaction within a Catalyst Pellet:

Effectiveness Factor, ηe (for First-order reaction)
It is given by;

observed reaction rate

ηe =
reaction rate at pellet surface conditions

rA
⇒ ηe = (23)
rAs

EKC314-SCE – p. 70/164
 Transport Processes in
Heterogeneous Catalysis

Diffusion and Reaction within a Catalyst Pellet:

Effectiveness Factor, ηe (for First-order reaction)
s
Isothermal and Endothermic reactions; rAs gives a
maximum reaction rate
since;
s
CAs > CAs
AND
s s
[rAs = kv CAs ] ≥ [rA = kv C̄As ]
AND therefore;
ηe ≤ 1

EKC314-SCE – p. 71/164
 Transport Processes in
Heterogeneous Catalysis

Diffusion and Reaction within a Catalyst Pellet:

Effectiveness Factor, ηe (for First-order reaction)
For a very HIGH diffusional resistances within
catalyst, NEGLIGIBLE penetration of reactant into
pellet;
C̄As = 0, rAs = 0, ηe = 0
thus, the range of ηe ;
0 ≤ ηe ≤ 1

EKC314-SCE – p. 72/164
 Transport Processes in
Heterogeneous Catalysis

Diffusion and Reaction within a Catalyst Pellet:

Effectiveness Factor, ηe (for First-order reaction)
With the value of ηe , rA can be determined using;
s
rA = ηe · rAs
s
⇒ rA = ηe (kv CAs )
⇒ rA = ηe (kv CA )
NOTE: This is only for NEGLIGIBLE external film
mass transfer resistances!

EKC314-SCE – p. 73/164
 Transport Processes in
Heterogeneous Catalysis

Diffusion and Reaction within a Catalyst Pellet:

Effectiveness Factor, ηe (for First-order reaction)
FOR SLAB:
The rate of reaction is given as;

rAs = kv CAs
substitute into the average rate of reaction gives rA
which can be used to obtain ηe
Final solution for SLAB-type catalyst;

tanh φslab
ηe = (24)
φslab

EKC314-SCE – p. 74/164
 Transport Processes in
Heterogeneous Catalysis

Diffusion and Reaction within a Catalyst Pellet:

Effectiveness Factor, ηe (for First-order reaction)
FOR SLAB:
NOTE:
φslab → 0, ηe → 1
1
φslab → ∞, ηe ∼
φslab

EKC314-SCE – p. 75/164
 Transport Processes in
Heterogeneous Catalysis

Diffusion and Reaction within a Catalyst Pellet:

Effectiveness Factor, ηe (for First-order reaction)
FOR SPHERE:
By applying Equation (20), the Effectiveness factor
for spherical shape is given by;
 
3 1 1
ηe = − (25)
φsphere tanh φsphere φsphere

NOTE:
φsphere → 0, ηe → 1
3
φsphere → ∞, ηe ∼
φsphere
EKC314-SCE – p. 76/164
 Transport Processes in
Heterogeneous Catalysis

Diffusion and Reaction within a Catalyst Pellet:

Effectiveness Factor, ηe (for First-order reaction)
FOR CYLINDER:

I1 (2φcylinder ) 1
ηe = (26)
I0 (2φcylinder ) φcylinder
NOTE:
φcylinder → 0, ηe → 1
2
φcylinder → ∞, ηe ∼
φcylinder
For a very SMALL φ, ηe will always converge to
UNITY (1)!
EKC314-SCE – p. 77/164
 Transport Processes in
Heterogeneous Catalysis

Diffusion and Reaction within a Catalyst Pellet:

The Effectiveness Factor for First Order Reaction:

1.0

cylinder sphere
η

slab

10 20 30
φ
EKC314-SCE – p. 78/164
 Transport Processes in
Heterogeneous Catalysis

Diffusion and Reaction within a Catalyst Pellet:

Effectiveness Factor, ηe (for First-order reaction)
The equations (ηe and φ) for sphere and cylinder
are rather complex
From the previous plot, the trend is similar only the
line shift in the x-axis
Thiele Modulus can be redefined for any pellet
geometry such that ηe and φ curve coincide

EKC314-SCE – p. 79/164
 Transport Processes in
Heterogeneous Catalysis

Diffusion and Reaction within a Catalyst Pellet:

Effectiveness Factor, ηe (for First-order reaction)
Curve for sphere and cylinder coincide with slab
curve such that a relatively simple expression
reduces into;
tanh φ
ηe =
φ
where φ is generally given by;
r
Vp kv
φ= (27)
Ap DeA

EKC314-SCE – p. 80/164
 Transport Processes in
Heterogeneous Catalysis

Diffusion and Reaction within a Catalyst Pellet:

Effectiveness Factor, ηe (General Order Reactions)
For general order & reversible reactions;
(Z s
)− 12
s CAs
Vp rAs
φ= √ DeA rAs dCAs (28)
Ap 2 ∗
CAs

∗
where CAs is the equimolar concentration of the
limiting reactant (= 0 for an irreversible reaction)
The above equation accounts for DeA varies with
CAs

EKC314-SCE – p. 81/164
 Transport Processes in
Heterogeneous Catalysis

Diffusion and Reaction within a Catalyst Pellet:

Effectiveness Factor, ηe (General Order Reactions)
It also assumes HIGH differential resistances such
that within the region of ηe ∼ φ1
∗
ELSE, CAs in the above equation needs to be
calculated using;
s
CAs
DeA dCAs
Z
rp = h R ′
C
i (29)
∗
CAs 2 C ∗A DeA rAs dCA′
As

EKC314-SCE – p. 82/164
 Transport Processes in
Heterogeneous Catalysis

Diffusion and Reaction within a Catalyst Pellet:

Criteria for Intraparticle Diffusional Limitations:
For known reaction kinetics ⇒ ηe can be calculated
(ηe < 1 indicates diffusional limitation)
The Weisz-Prater Criteria:
Using;
s
Vp kv
φ=
A p De A

EKC314-SCE – p. 83/164
 Transport Processes in
Heterogeneous Catalysis

Diffusion and Reaction within a Catalyst Pellet:

Criteria for Intraparticle Diffusional Limitations:
upon rearrangement gives;
 2
2 Ap
φ DeA = kv
Vp

for First-order reaction;

s s
rA = ηe rAs = ηkv CAs

EKC314-SCE – p. 84/164
 Transport Processes in
Heterogeneous Catalysis

Diffusion and Reaction within a Catalyst Pellet:

Criteria for Intraparticle Diffusional Limitations:
eliminating kv gives;
 2
rA Vp
Φ= s
= ηe φ 2 (30)
DeA CAs Ap

Φ is the Weisz-Prater Parameter

s
CAs ∼ CA under typical conditions.

EKC314-SCE – p. 85/164
 Transport Processes in
Heterogeneous Catalysis

Diffusion and Reaction within a Catalyst Pellet:

Criteria for Intraparticle Diffusional Limitations:
The RHS of Equation (30) is measurable, then;
1. NEGLIGIBLE diffusional limitations; when;
φ ≪ 1, ηe ∼ 1

therefore;
Φ≪1

EKC314-SCE – p. 86/164
 Transport Processes in
Heterogeneous Catalysis

Diffusion and Reaction within a Catalyst Pellet:

Criteria for Intraparticle Diffusional Limitations:
The RHS of Equation (30) is measurable, then;
2. CONSIDERABLE diffusional limitations; when;
1
φ ≫ 1, ηe ∼
φ

therefore;
Φ≫1
The above method can be generalised to any
reaction scheme where appropriate for the Thiele
Modulus.
EKC314-SCE – p. 87/164
 Transport Processes in
Heterogeneous Catalysis

Temperature Gradient Within Catalyst Pellet:

Temperature gradient, ∆T can be calculated by
considering simultaneously the intraparticle mass and
energy balances.
For spherical pellet; the mass balance is given by;
 
1 d 2 dCAs
2
De A r = rAs
r dr dr

similarly for energy balance;

 
1 d 2 dTs
2
λe r = rAs · ∆Hr (31)
r dr dr
EKC314-SCE – p. 88/164
 Transport Processes in
Heterogeneous Catalysis

Temperature Gradient Within Catalyst Pellet:

Equation (31) is known as Fourier’s Law where λe is
the effective thermal conductivity of the pellet.
By eliminating rAs and integrating twice leads to;

∆Hr DeA
∆Ts = (Ts − Tss ) = s
(CAs − CAs ) (32)
λe

For irreversible reaction, ∆Ts is maximum when

∗
CAs = 0 (OR CAs for an equimolar reversible reaction)
thus;
−∆Hr DeA s
∆Ts |max = CAs (33)
λe
EKC314-SCE – p. 89/164
 Transport Processes in
Heterogeneous Catalysis

Temperature Gradient Within Catalyst Pellet:

Equation (33) is applicable to all pellet catalyst
geometries.
For many industrial applications;

∆Ts |max
s
< 0.1
Ts

that is for small ∆Ts , ∆T (external film) can be large.

EXCEPT for HIGHLY exothermic reactions such as
some oxidation and hydrogenation reactions.
The effect of ∆Ts on ηe is complex since, it will
influence DeA as well as kv .
EKC314-SCE – p. 90/164
 Transport Processes in
Heterogeneous Catalysis

Temperature Gradient Within Catalyst Pellet:

Consider the First-order non-isothermal reaction on a
pellet; the mass balance is given by;
 
1 d 2 dCAs
2
De A r = rAs
r dr dr

and
rAs = kv CAs
where  
E
− RT
kv = A0 e 0

EKC314-SCE – p. 91/164
 Transport Processes in
Heterogeneous Catalysis

Temperature Gradient Within Catalyst Pellet:

Upon substitution gives;
 
1 d dC
 
E
2 As − RT
2
De A r = A0 e 0 C
As
r dr dr

putting into dimensionless form leads to;

d2 Ĉ ′ γ(1−T̂ )
= φ Ĉe
dr̂2
where
CAs Ts r
Ĉ = s T̂ = s r̂ =
CAs Ts rp
EKC314-SCE – p. 92/164
 Transport Processes in
Heterogeneous Catalysis

Temperature Gradient Within Catalyst Pellet:

and both φ′ and γ is defined as;
2 −γ
rp A 0 e
φ′ =
De A

and
E
γ=
RTss

EKC314-SCE – p. 93/164
 Transport Processes in
Heterogeneous Catalysis

Temperature Gradient Within Catalyst Pellet:

Similarly, for energy balance;

d2 T̂ ′2 γ(1−T̂ )
= −βφ Ĉe
dr̂2
where
s
(∆Ts )max −∆Hr DeA CAs
β= s
=
Ts λe Tss

EKC314-SCE – p. 94/164
 Transport Processes in
Heterogeneous Catalysis

Temperature Gradient Within Catalyst Pellet:

η

1.0

β > 0: Exothermic

β = 0: Isothermal

β < 0: Endothermic

0.001
0.1 φ’

EKC314-SCE – p. 95/164
 Transport Processes in
Heterogeneous Catalysis

Combined Interfacial [External] and Intraparticle [Internal]

Resistances:
s
In the solution of intraparticle diffusional equation, CAs
was assumed known;
s
CAs = CA

and it remains constant.

When the external-film resistances are important, the
BOUNDARY CONDITIONS for the solution of the
intraparticle diffusion equation become;
 
s
 dCAs 
r = rp : kmc (CA − CAs ) = DeA  
dr rp
EKC314-SCE – p. 96/164
 Transport Processes in
Heterogeneous Catalysis

Combined Interfacial [External] and Intraparticle [Internal]

Resistances:
and;  
 dCAs 
r=0: 
 dr 
 =0
0

For slab pellet with a First-order reaction, the solution

with the above boundary conditions gives;

CA cosh φr
rp
CAs = D eA φ
cosh φ + rp kmc
sinh φ

EKC314-SCE – p. 97/164
 Transport Processes in
Heterogeneous Catalysis

Combined Interfacial [External] and Intraparticle [Internal]

Resistances:
Therefore, the Global Effectiveness Factor can be
defined as;
rate observed
ηG =
rate at bulk fluid concentration
rA
ηG =
rAs CA

EKC314-SCE – p. 98/164
 Transport Processes in
Heterogeneous Catalysis

Combined Interfacial [External] and Intraparticle [Internal]

Resistances:
Which then gives;

1 1 φ2
= + (34)
ηG η Bim

where Bim is Biot number for mass-transfer given by;

kmc rp
Bim =
De A

For Bim ≫ 1.0, ηG = ηe .

EKC314-SCE – p. 99/164
 Transport Processes in
Heterogeneous Catalysis

Combined Interfacial [External] and Intraparticle [Internal]

Resistances:
For the region of strong intraparticle diffusional
limitations, where;
φ→∞
and
1
ηe =
φ
thus,
1 φ2
=φ+ (35)
ηG Bim

EKC314-SCE – p. 100/164
 Fixed-Bed Catalytic Reactor Design

Describing the homogeneous models and models

accounting for interfacial and intrafacial gradients
using;
1. Effectiveness factor
2. Actual pellet phase mass and energy balances
PLUG-FLOW REACTOR (PFR) model:
the simplest PFR model is given by;

dni ′ vi ′
= −ri = −ri ρb = rA ρb (36)
dV |vA |

EKC314-SCE – p. 101/164
 Fixed-Bed Catalytic Reactor Design

PLUG-FLOW REACTOR (PFR) model:

when ni = uaCi and dV = adz, thus, the equation
reduces into;
d ′ vi ′
(uCi ) = −ri ρb = rA ρb (37)
dz |vA |

since u 6= constant, therefore momentum equation

is required.

EKC314-SCE – p. 102/164
 Fixed-Bed Catalytic Reactor Design

PLUG-FLOW REACTOR (PFR) model:

Using the Ergun equation of the form;

dp
= −E1 u − E2 u2 (38)
dz
to find the pressure along the bed, where;

180µ(1 − εb )2
E1 =
d2p ε3b

and
1.8(1 − εb )ρg Mm
E2 =
dp ε3b
EKC314-SCE – p. 103/164
 Fixed-Bed Catalytic Reactor Design

PLUG-FLOW REACTOR (PFR) model:

If the flow is highly TURBULENT, E1 can be
neglected.
If the flow is LAMINAR, E2 can be omitted.
While for a perfect gas;
X P
Ci = = ρg
i
RT

For non-isothermal operation, energy balance is

required to describe T –z variation

EKC314-SCE – p. 104/164
 Fixed-Bed Catalytic Reactor Design

PLUG-FLOW REACTOR (PFR) model:

Energy balance across a fix-bed reactor is given as;

dT X
′
=( ni cpi ) + ρb rA ∆r − Qav = 0 (39)
dV i

where
Q = U (Tc − T ) (J/m2 s)
and av is the surface area per unit reactor volume,
(m1 ), therefore;

dT X
′
= (U ni cpi ) + ρb rA ∆r − Qav = 0 (40)
dz i
EKC314-SCE – p. 105/164
 Fixed-Bed Catalytic Reactor Design

PLUG-FLOW REACTOR (PFR) model:

where; U is the overall heat transfer coefficient,
(J/m2 s.K)
and Tc is the temperature of cooling fluid (K)
For no-separation of reactor species due to different
rates of axial dispersion OR intra-particle diffusion,
Ci can be related to CA using the reaction
stoichiometry;

(nAo − nA ) → mol A reacted

thus;
νi
ni = nio + (nAo − nA )
|nA |
EKC314-SCE – p. 106/164
 Fluidised-Bed Reactors

These involve catalyst beds which are not packed in

rigid but either suspended in fluid (for fluidised-bed
reactor) or flowing with the fluid (transport reactor)
Fluidisation Principles (Overview):
Downward flow in packed bed–no relative
movement between particles
1. ∆P α u for LAMINAR flow
2. ∆P α u2 for TURBULENT flow

EKC314-SCE – p. 107/164
 Fluidised-Bed Reactors

Fluidisation Principles (Overview):

Upward flow through bed ⇒ ∆P is the same as
downward flow at LOW flow rate:
when frictional drag on particles become equal to
their apparent weight (actual weight LESS
buoyancy)–particle rearrange and offer LESS
resistance to flow–results in bed EXPANSION.
as u increases, process continues until bed
assumes its “loosest” stable form of packing.
MINIMUM fluidisation velocity, umf –is the velocity at
a point where fluidisation occurs!

EKC314-SCE – p. 108/164
 Fluidised-Bed Reactors

Fluidisation Principles (Overview):

When superficial velocity > umf ;
1. LIQUID fluidisation;
bed continues to EXPAND with u
it maintains a uniform character
and AGITATION of particle
increases–particulate fluidisation

EKC314-SCE – p. 109/164
 Fluidised-Bed Reactors

Fluidisation Principles (Overview):

When superficial velocity > umf ;
2. GAS fluidisation;
gas bubble formation within a continuous
phase consisting of fluidised solids.
continuous phase refers to as the
dense/emulsion phase–aggregation fluidisation
at HIGH inlet flow rate: flow in emulsion phase
to particulate remains approx. constant but
bubbles may be more rigorous.
at HIGH inlet flow rate and a deep
bed–bubbles coalesce forming slugs of gas
that occupy the entire cross-section of the bed.

EKC314-SCE – p. 110/164
 Fluidised-Bed Reactors

Fluidisation Principles (Overview):

An increase of bubbles within the bed gives ↑ V and
this lowers the transfer area.
HIGH volume of bubbles also gives high residence
time.
It behaves like fluid–hydrostatic forces are
transmitted and solid objects FLOAT when;
densities of objects < density of bed
Intimate mixing and rapid heat transfer → easy to
control the TEMPERATURE (even for highly
EXOTHERMIC reaction)
Type of fluidisation depends on [i] the particle size
and [ii] relative density of the particles (ρs − ρg )
EKC314-SCE – p. 111/164
 Fluidised-Bed Reactors

WHY Fluidisation?
Can achieve a GOOD control of TEMPERATURE
Can work with VERY FINE particles for which
ηe ∼ 1

As catalyst improves–the rates of reaction

INCREASE resulted form higher kv BUT;
s
rp kv
φ=
3 De A

when fv ↑, the ONLY way to keep φ SMALL and ηe

close to 1 is to decrease rp
EKC314-SCE – p. 112/164
 Fluidised-Bed Reactors

WHY Fluidisation?
NOTE: an increase of kv will increase φ, therefore it
will be MASS TRANSFER controlling and NOT
kinetics (reaction) the possible way is to REDUCE
rp

EKC314-SCE – p. 113/164
 Fluidised-Bed Reactors

∆P versus uo for fluidised bed:

log ∆P
hysterisis due to blown out particles
pressure different (initiation of
particle entrainment)

umf
log uo EKC314-SCE – p. 114/164
 Fluidised-Bed Reactors

∆P versus uo for fluidised bed:

NOTE:
1. LAMINAR FLOW:
∆P
= −E1 uo
L
→ log (∆P ) = C + log uo
2. TURBULENT FLOW:
∆P
= −E2 u2o
L
→ log (∆P ) = C + 2 log uo

EKC314-SCE – p. 115/164
 Fluidised-Bed Reactors

∆P versus uo for fluidised bed:

Calculation of ∆P across fluidised bed: Consider a
diagram below;

uo = superficial velocity A
at bed inlet
P2
ut = terminal velocity
when pellet are
blown out of the
L
bed

F2
P1
F1

uo
EKC314-SCE – p. 116/164
 Fluidised-Bed Reactors

∆P versus uo for fluidised bed:

Resolving forces on the bed;

F1 = F2
P1 A = P2 A + (ρs − ρg )(1 − ε)ALg
(P1 − P2 ) = (ρs − ρg )(1 − ε)Lg
−∆P = (ρs − ρg )(1 − ε)Lg (41)

As P1 ↑, ∆P also ↑, and therefore, ↑ ε as the bed

expends
OR ↓ resistance as the gas by-pass through
bubbling and ∆P remains the same.

EKC314-SCE – p. 117/164
 Fluidised-Bed Reactors

Calculation of the minimum fluidisation velocity, umf ;

For LAMINAR flow;
Using the previously defined Ergun equation
[Equation (38)];
∆Pmf
= −E1 umf
Lmf

(1 − εmf )(ρs − ρg )g
⇒ umf = (42)
E1
where
180µ(1 − εmf )2
E1 =
d2p · ε3mf
EKC314-SCE – p. 118/164
 Fluidised-Bed Reactors

Calculation of the minimum fluidisation velocity, umf ;

For LAMINAR flow;
Substitute into Equation (40) and simplify gives;

1 ε3mf · d2p (ρs − ρg )g

umf = (43)
180 (1 − εmf ) µ

For εmf ∼ 0.4 ⇒ the bed is packed with isometric

particles.

EKC314-SCE – p. 119/164
 Fluidised-Bed Reactors

Calculation of the minimum fluidisation velocity, umf ;

For TURBULENT flow [usually for coarse particles];
Similarly, applying the Ergun equation;

∆Pmf
= −E1 umf − E2 u2mf = −(1 − εmf )(ρs − ρg )g
Lmf
and solving for umf explicitly gives;

(1 − εmf ) 1.75 2
Ga = 180 3
Remf + 3 Remf (44)
εmf εmf

EKC314-SCE – p. 120/164
 Fluidised-Bed Reactors

Calculation of the minimum fluidisation velocity, umf ;

For TURBULENT flow [usually for coarse particles];
where
ρg (ρs − ρg )gd3p
Ga =
µ2
is the Galileo’s Number and
ρg umf dp
Remf =
µ

is the Reynold’s Number for minimum fluidisation.

in reality, expect Darcy’s Law and Ergun equation
to overestimate ∆Pmf .
EKC314-SCE – p. 121/164
 Fluidised-Bed Reactors

Calculation of the minimum fluidisation velocity, umf ;

For LAMINAR flow, many investigations have
shown that it is more accurate to use a value of 120
rather than 180 in Equation (41).
Equation (42) for TURBULENT flow DOES NOT
account for;
1. Channeling of fluid
2. Electrostatic forces between particles
3. Agglomeration of particles
4. Friction between fluid and vessel walls.

EKC314-SCE – p. 122/164
 Fluidised-Bed Reactors

Calculation of turbulent velocity, ut ;

Force exerted by flowing gas

mg

when the drag force exerted on a spherical particle

by the upflowing gas, the gravitational force (based
on the apparent density) on the particle, then the
particle will be BLOWN OUT of the bed! EKC314-SCE – p. 123/164
 Fluidised-Bed Reactors

Calculation of turbulent velocity, ut ;

this can be shown by;

Fdrag = Vp (ρs − ρg )g

but (FROM FLUID FLOW NOTES);

1
Fdrag = ρg u2t CD · Ap
2
πd2p
where CD is the drag coefficient. with Ap = 4
thus;

πd2p
Fdrag = · ρg u2t · CD
8
EKC314-SCE – p. 124/164
 Fluidised-Bed Reactors

Calculation of turbulent velocity, ut ;

upon rearrangement gives;
s
4dp (ρs − ρg )g
ut = (45)
3CD ρg

for spherical particles and Re < 0.4 where

ρg ut dp
Re =
µ

EKC314-SCE – p. 125/164
 Fluidised-Bed Reactors

Calculation of turbulent velocity, ut ;

and the Drag coefficient is given by;
24
CD =
Re
and Equation (43) reduces into Stoke’s Law of the
form;
(ρs − ρg )gd2p
ut = (46)
18µ

EKC314-SCE – p. 126/164
 Fluidised-Bed Reactors

Calculation of turbulent velocity, ut ;

for 1 < Re < 103 ;
the Drag coefficient is given by;
69.43
ln CD = −5.50 +
ln Re + 7.99
and for Re > 103 ;
the Drag coefficient CD = 0.43, which gives;
s
3.1dp (ρs − ρg )g
ut =
ρg

EKC314-SCE – p. 127/164
 Fluidised-Bed Reactors

Fluidisation regimes:
For COARSE PARTICLES:
bubbles appear as soon as umf is exceeded.
in TURBULENT regimes–bubbles life time is
SHORT due to bubbles burst. Bed is quite
uniform–short circuiting of gas through bubbles is
less likely.
umf and particle blow-out coincide.
in FAST fluidisation regime–there is the net
entrainment of solids.
in TRANSPORT regime–there is solid flow in the
direction of gas flow.
carry-over (entrainment) separates particles by
size.
EKC314-SCE – p. 128/164
 Fluidised-Bed Reactors

Fluidisation regimes:
For FINE PARTICLES:
bubbles DO NOT appear as soon as minimum
fluidisation is reached–instead, there is a uniform
expansion of bed.
bed is more coherent rather than particles
behaving independently.
TURBULENT regime sets in well after uo exceeds
ut of an individual particle, thus, operate at higher
uo .
carry-over DOES NOT separate particles by
size–a more cohesive bed.

EKC314-SCE – p. 129/164
 Fluidised-Bed Reactors

Fluidised-Bed Reactors: The Applications

It is useful for highly EXOTHERMIC systems
AND/OR systems requiring close temperature
control such as oxidation reactions.
In a classical fluidised-bed operation, catalyst
particles are retained in bed–little catalyst
entrainment.
Some of the systems of reactions that use
fluidised-bed include:
1. Oxidation of napthalene into phtalic anhydride.
2. Ammoxidation of propylene to acrylonitrile.
3. Oxychlorination of ethylene to ethylene dichloride.
4. Coal combustion (injection of limestone for the
in-situ capture of SO2 ).
EKC314-SCE – p. 130/164
 Fluidised-Bed Reactors

Fluidised-Bed Reactors: The Applications

Some of the systems of reactions that use
fluidised-bed include:
5. Roasting of ores
Even with classical fluidised-bed, region above the
surface of bed contains some solid concentration.
This concentration becomes constant as it is moved
away from the surface.

EKC314-SCE – p. 131/164
 Fluidised-Bed Reactors

Modelling of fluidised-bed reactors:

Two-phase model:
the model is based on the interchange between
the two phases;
CA

CAb|out CAe|out
Bubble Emulsion
phase phase

ub ue

CAb CAe

uo, CAo
EKC314-SCE – p. 132/164
 Fluidised-Bed Reactors

Modelling of fluidised-bed reactors:

Two-phase model:
for ISOTHERMAL fluidised-bed in emulsion
phase, the material balance is given by;
for bubble-phase:

dCAb ′
fb ub + kI (CAb − CAe ) + fb gb rA =0 (47)
dz
for emulsion-phase:

dCAe d2 CAe ′
fe ue −fe Dze 2
−kI (C Ab −C Ae )+(1−f b e A = 0
)g r
dz dz
(48)

EKC314-SCE – p. 133/164
 Fluidised-Bed Reactors

Modelling of fluidised-bed reactors:

Two-phase model:
also;
uo C̄A = fb ub CAb + fe ue CAe (49)
and the boundary conditions are;
for bubble-phase:

z = 0 : CAb = CAo

EKC314-SCE – p. 134/164
 Fluidised-Bed Reactors

Modelling of fluidised-bed reactors:

Two-phase model:
for emulsion-phase:

dCAe
z = 0 : −Dze = ue (CAo − CAe )
dz
dCAe
z=L: =0
dz

EKC314-SCE – p. 135/164
 Fluidised-Bed Reactors

Modelling of fluidised-bed reactors:

Model simplification:
If ub ≫ ue , that is when ub ≫ umf , then the
emulsion-phase∼closed (relatively negligible inlet
OR outlet flow). Thus Equation (46) reduces into;
′
kI (CAb − CAe ) = (1 − fb )ge rA (50)

also neglecting the DISPERSION.

The above equation assumes a stagnant
emulsion phase BUT, CAe varies with bed length
z.

EKC314-SCE – p. 136/164
 Fluidised-Bed Reactors

Modelling of fluidised-bed reactors:

Estimation of parameters appearing in the
two-phase model:
1. ub : bubble velocity:
this is given by;

ub = (uo − umf ) + ubr

where ubr is the bubble rise velocity when there is

a SWARM of bubbles. This is separately given by;
p
ubr = α db g

EKC314-SCE – p. 137/164
 Fluidised-Bed Reactors

Modelling of fluidised-bed reactors:

Estimation of parameters appearing in the
two-phase model:
1. ub : bubble velocity:
where α = 0.64 for dt < 0.1m OR α = 1.6d0.4
t for
0.1m < dt < 1.0m OR α = 1.6 for dt > 1.0m
2. fb : bubble friction:
this is given by;
uo − umf
fb =
ub

EKC314-SCE – p. 138/164
 Fluidised-Bed Reactors

Modelling of fluidised-bed reactors:

Estimation of parameters appearing in the
two-phase model:
2. fb : bubble friction:
BUT for ub ≫ umf
uo
fb ∼
ub
3. fe : emulsion friction:
This is given by

fe + fb = εf

where εf is the VOIDAGE of a fluidised-bed.

EKC314-SCE – p. 139/164
 Fluidised-Bed Reactors

Modelling of fluidised-bed reactors:

Estimation of parameters appearing in the
two-phase model:
4. Lf and εf : length of bed and bed voidage:
Given that the volume of solids constant, where;

Lf (1 − εf ) = Lmf (1 − εmf ) = L(1 − εb )

1 − εf Lmf
⇒ = = 1 − fb
1 − εmf Lf
given that fb and εmf ∼ 0.4, then Lf and εf can be
calculated.

EKC314-SCE – p. 140/164
 Fluidised-Bed Reactors

Modelling of fluidised-bed reactors:

Estimation of parameters appearing in the
two-phase model:
5. Dze : diffusion coefficient of emulsion phase:
Using;
Dze = f (uo , dt )
6. ue : emulsion velocity:
Using
umf
ue =
εmf

EKC314-SCE – p. 141/164
 Fluidised-Bed Reactors

Modelling of fluidised-bed reactors:

Estimation of parameters appearing in the
two-phase model:
7. gb and ge : mass of solid in bubble and
emulsion phases respectively:
Using;
m
fb gb + (1 − fb )ge =
A · Lf
8. kI : gas interchange coefficient:
For two-phase models–kI often used as a fitting
parameter such that model agrees with plant
data.

EKC314-SCE – p. 142/164
 Fluidised-Bed Reactors

Modelling of fluidised-bed reactors:

Three-phase model:

ub

ue

emulsion
bubble

cloud

EKC314-SCE – p. 143/164
 Fluidised-Bed Reactors

Modelling of fluidised-bed reactors:

Three-phase model:
there is an interchange of gas from bubble to
cloud, then from cloud to emulsion in sequential
step
this can be depicted in the diagram below;
bubble cloud emulsion

kI,b

kI,e

CA,b CA,b CA,e

EKC314-SCE – p. 144/164
 Fluidised-Bed Reactors

Modelling of fluidised-bed reactors:

Three-phase model:
different mixing regimes in different phases can
be assumed.
Kunnii-Levenspiel Model (k-L) assumes
emulsion phase with no net gas flow.
this is usually achieved for
uo
>6
umf

EKC314-SCE – p. 145/164
 Fluidised-Bed Reactors

Modelling of fluidised-bed reactors:

Example: k-L Model for First-order reaction
Consider the material balances:
Bubble phase:

dCAb
fb ub + kIb (CAb − CAc ) + fb gb kCAb = 0
dz
Emulsion phase:

kIe (CAc − CAe ) = (1 − fb − fc′ )ge kCAe

Cloud phase:

kIb (CAb − CAc ) = kIe (CAc − CAe ) + fc′ gc kCAc

EKC314-SCE – p. 146/164
 Fluidised-Bed Reactors

Modelling of fluidised-bed reactors:

Example: k-L Model for First-order reaction
m3cloud
fc is with the units of m3
bed
kg
gc is in the form of m3cloud
which is approx. equal to

ρb
ge =
1 − fb

and fc′ is normally given by;

1.17
fc′ · fb =
1.17 · + uueb

EKC314-SCE – p. 147/164
 Fluidised-Bed Reactors

Modelling of fluidised-bed reactors:

Example: k-L Model for First-order reaction
using equations for emulsion and could phases
and substitute into the bubble phase equation
gives;
dCAb
−ub = kCAb (51)
dz

EKC314-SCE – p. 148/164
 Fluidised-Bed Reactors

Modelling of fluidised-bed reactors:

Example: k-L Model for First-order reaction
and K is given by;
 

 


 

 1 
K = k gb + kfb 1

 kIb
+ gc fc′ + kf 1


1

 b+


 kI ge (1−fb −fc′ )

e
fb

which is the effective rate constant for a

three-phase fluidised-bed model ⇒ k-L rate
constant.

EKC314-SCE – p. 149/164
 Fluidised-Bed Reactors

Modelling of fluidised-bed reactors:

Example: k-L Model for First-order reaction
Integration of Equation (49) with boundary
conditions;
z = 0; CAb = CAo
leads to;
CAb C̄A
= = e−Kτb (52)
CAo CAo
Lf
where τb = ub

EKC314-SCE – p. 150/164
 Fluidised-Bed Reactors

Modelling of Transport Reactor (Riser):

Example: Fluid Catalytic Cracking⇒fast reactions
(small τ required) and rapid catalyst deactivation.
Velocity of SOLIDS ≈ velocity of GAS. That is, NO
SLIP VELOCITY
Usually employed FINE SOLIDS such that ηe ∼ 1
For NO catalyst DEACTIVATION, riser is very much
like pseudo-homogeneous Plug-Flow reactor (PFR)
but
ε > εb

EKC314-SCE – p. 151/164
 Fluidised-Bed Reactors

Modelling of Transport Reactor (Riser):

Calculation of ε:
Given that;
 3
mg Auo
ε = (53)
3
mb Auo + ṁρps

kg
where ρp is the pellet density with units of m3pellet
Upon simplification of Equation (51) gives;
 3
mg 1
ε 3
= (54)
mb 1 + uṁosρAp

EKC314-SCE – p. 152/164
 Fluidised-Bed Reactors

Modelling of Transport Reactor (Riser):

Calculation of ε:
The diagram is given;
A

gas solid
uo (m/s) ms (kg/s)

EKC314-SCE – p. 153/164
 Fluidised-Bed Reactors

Modelling of Transport Reactor (Riser):

Calculation of ε:
From Equation (52);
ṁs ≪ uo : ε→1

ṁs ≫ uo : ε→0
for Packed-Bed reactor; εb → 0.4
For NO catalyst deactivation:

dCA ′
uo = −rA (1 − ε)ρp (55)
dz

EKC314-SCE – p. 154/164
 Fluidised-Bed Reactors

Modelling of Transport Reactor (Riser):

Calculation of ε:
Catalyst deactivation in Fluid-Catalytic Cracking
is believed to arise from:
1. coke deposition
2. adsorption of certain species present in the
feed
Thus will give a reduction in the reaction rate(s)
and therefore with time, with Deactivation
Function given by;
′
rA (t)
ΦA = ′ = f (t) (56)
rA (0)

EKC314-SCE – p. 155/164
 Fluidised-Bed Reactors

Modelling of Transport Reactor (Riser):

Calculation of ε:
The function can be of the form;
Φ = 1 − αt
OR
Φ = e−αt
Therefore Equation (53) becomes;

dCA ′
uo = −rA ΦA (1 − ε)ρp (57)
dz

EKC314-SCE – p. 156/164
 Fluidised-Bed Reactors

Modelling of Transport Reactor (Riser):

Calculation of ε:
Where t = uzo (NO SLIP) and it represents the
time for a particular catalyst to have spent in the
riser.
Sometimes, Φ is given as a function of the coke
concentration on the catalyst pellets. It is practical
to express the concentration in the form of;
 
kgcoke
Ĉc
kgcatalyst

EKC314-SCE – p. 157/164
 Fluidised-Bed Reactors

Modelling of Transport Reactor (Riser):

Calculation of ε:
And the rate of formation of coke is given by;
 
kgcoke
r̂c
kgcatalyst · s

where r̂c can itself be deactivated as the coke is

being produced!
The balances for coke deposition is given by;

ṁs dĈc
· = r̂c Φc ρp (1 − ε) (58)
A dz

EKC314-SCE – p. 158/164
 Fluidised-Bed Reactors

Modelling of Transport Reactor (Riser):

Calculation of ε:
The energy balances for the ADIABATIC riser can
be written as;
ṁg cpg + ṁs cps dT ′
= [rA ΦA (−∆HA ) + rc Φc (−∆Hc )]
A dz
× ρp (1 − ε) (59)

where cpg and cps are the specific heat capacities

kJ
of gas and solid respectively in kg−K and ṁg is the
kg
mass flow rate of gas in s

EKC314-SCE – p. 159/164
 Fluidised-Bed Reactors

Modelling of Transport Reactor (Riser):

Calculation of ε:
And ṁg is given by;

Auo po
ṁg = Mg
RTo

EKC314-SCE – p. 160/164
 Multiphase Reactors

Involved GAS and LIQUID phases in contact with a

SOLID.
The SOLID may be of the form of;
1. catalyst particles dispersed in the liquid phase (Eg.
SLURRY REACTOR)
2. packing for liquid distribution (Eg. PACKED-BED
ABSORBER)
3. packing for liquid distribution and catalyst support
(Eg. TRICKLED-BED REACTOR and PACKED
BUBBLE REACTOR)
4. plates for liquid-gas contact (Eg. DISTILLATION
COLUMN)

EKC314-SCE – p. 161/164
 Multiphase Reactors

Reactors can also be classified in terms of which

phase is continuous and which is dispersed.
Referring to the diagram below:
LIQUID: continuous LIQUID: disperse LIQUID: continuous
GAS: disperse GAS: continuous GAS: continuous

LIQUID

LIQUID

LIQUID

GAS GAS GAS

Bubble reactor Spray tower Wetted-wall reactor
Slurry reactor Trickle-bed reactor (falling film)
Fermentation vessel Packed-bed reactor
EKC314-SCE – p. 162/164
 Multiphase Reactors

If mass-transfer resistance located in the liquid-film,

use DISPERSE–gas phase and CONTINUOUS–liquid
phase.
If mass-transfer resistance located in the gas-film,
use CONTINUOUS–gas phase and DISPERSE–liquid
phase.
Residence time, τ of reactant and heat transfer
consideration will also dictate the type of reactor;
1. plate columns can achieve long contact times
between gas and liquid, BUT poor TEMPERATURE
control

EKC314-SCE – p. 163/164
 Multiphase Reactors

Residence time, τ of reactant and heat transfer

consideration will also dictate the type of reactor;
2. stirred-tank (BUBBLE and SLURRY), will have large
LIQUID:GAS ratio, BUT yet, cope with HIGH GAS
flow rates and therefore GOOD TEMPERATURE
control.
Reactors can have co- OR counter- current flow of
GAS and LIQUID to utilise driving force for MASS and
HEAT transfers.
Where reactors are employed for GAS purification,
then it is referred to as ABSORBERS.

EKC314-SCE – p. 164/164