Reactor Design and Analysis (MHU)

EKC338: REACTOR DESIGN & ANALYSIS
Core Course for

B.Eng.(Chemical Engineering)
Semester II (2014/2015)
Mohamad Hekarl Uzir
(chhekarl@usm.my)
School of Chemical Engineering

Engineering Campus, Universiti Sains Malaysia
Seri Ampangan, 14300 Nibong Tebal, Seberang Perai Selatan, Penang
EKC338-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, and effectiveness factor,
Falsified kinetics
EKC338-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
EKC338-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
EKC338-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.
Diffusionspontaneous 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.
EKC338-SCE p. 5/164
CA,b
External
diffusion
Porous catalyst
pellet
CA,s
CA(r)
Internal
diffusion
External
surface
EKC338-SCE p. 6/164

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 )
EKC338-SCE p. 7/164

(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 )
EKC338-SCE p. 8/164

(d) defining the dimensionless parameters;
CA
k
x=
Da =
CA,b
kA
thus;
1x
Da =
x
(e) where Da is defined as the ratio of reaction rate
with the convective/diffusive mass transfer rate.
EKC338-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 neglectedthe reactor contents
can be treated as a single phase.
Useful for preliminary designtruly homogeneous
system.
For heterogeneous modelused when temperature
and concentration need to be distinguished between
the phases.
EKC338-SCE p. 10/164

For real reactor: (multiphasesMulti-Phase Reactors)
Should be heterogeneous type
Normally used for systems involving fluid-fluid
interactions [liquid-liquid or gas-liquid]
EKC338-SCE p. 11/164

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
temperaturetherefore reduce surface area for
reaction hence reducing rate constant [sintering]
EKC338-SCE p. 12/164

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. could also be used in turbular reactor packed with
catalyst through which the fluid species flow
EKC338-SCE p. 13/164

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
EKC338-SCE p. 14/164

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
EKC338-SCE p. 15/164
Interfacial gradient effects: Reaction at catalyst surface

Concentration at the
catalyst surface
Bulk concentration
CsAs
CA
CAs
Concentration within
the catalyst
NA
Transfer flux
Boundary layer
Active centres
z
FLUID
SOLID
EKC338-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)
s
NA = kmc (CA CAs
)
(3)
where
EKC338-SCE p. 17/164

the mass-transfer coefficient can also be expressed
in terms of mole fraction & pressure:
kmy
NA
=
s
(yA yAs
)
kmp
NA
=
(pA psAs )
and
and kmc = kmp = kmy
EKC338-SCE p. 18/164

substitute (3) into (1):
s
NA = ks CAs
s
s
ks CAs
= kmc (CA CAs
)
kmc CA
s
CAs =
ks + kmc
(4)
EKC338-SCE p. 19/164

substitute into (1) and upon rearrangement gives;
1
1
1
=
+
ko
kmc ks
(5)
where ko is the overall rate constant.

Limiting cases:
1. kmc >> ks [rapid mass transfer]
ko ks
and
s
CAs
CA
EKC338-SCE p. 20/164

Limiting cases:
2. ks >> kmc [rapid reaction]
ko kmc
and
s
CAs
0
EKC338-SCE p. 21/164

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
s 2
ks CAs
+ 2kmc CA CAs
kmc CAs
= kmc CA2
EKC338-SCE p. 22/164

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
EKC338-SCE p. 23/164

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]
EKC338-SCE p. 24/164

For Complex reactions (analytical SOLUTION not
usually possible):
can work under conditions:
2. diffusion controlled:
ks >> kmc
[increase temperature]
EKC338-SCE p. 25/164

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
dz
(7)
EKC338-SCE p. 26/164

and km
1. since
NT = NA + NB = 0
thus
dyA
NA = CDAB
dz
(8)
EKC338-SCE p. 27/164

and km
1. upon integration of this leads to;
CDAB
s
(yA yAs
)
NA =
l
(9)
since
CDAB
=
l
and for equimolar counter diffusion;
kmy
kmy
= kmy
EKC338-SCE p. 28/164

relationship between kmy

and kmy
1. which then gives;
kmc
kmy
DAB
=
=
C
l
(10)
2. For reaction in which total moles are not

conserved
aA bB
EKC338-SCE p. 29/164


and kmy
2. which gives;
b
NB = NA
a
substitute into Equation (7) leads to;
yA
a
NA l = CDAB ln s
b yAs
(11)
(12)
EKC338-SCE p. 30/164


and kmy
s
2. for NA = kmy (yA yAs
) where
kmy
kmy
=
yf A
and
yf A
s
(1 + A yA ) (1 + A yAs
)

=
1+A yA
ln 1+
s
Ay
As
where A =
(ba)
a
EKC338-SCE p. 31/164


and kmy
2. for general equation of the form;
aA + bB + . . . qQ + rR + . . .
therefore;
(q + r + . . .) (a + b + . . .)
A =
a
for
A 0, yf A 1
EKC338-SCE p. 32/164


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
EKC338-SCE p. 33/164

the j-factor:
1. for a flow in a packed-bed with spherical particles
and b = 0.37;
jD = 1.66Re0.51 ,
for Re < 190
jD = 0.983Re0.41 ,
for Re > 190
2. jH -factor:
defined as;
2
hf
jH =
Pr 3
Cp G
EKC338-SCE p. 34/164

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
EKC338-SCE p. 35/164

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;

kmy
km
=
yf A
EKC338-SCE p. 36/164

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;
T = Hr
jD
jH

Pr
Sc
23
yA
yf A

1
Mm Cp
(15)
T increases with the increase of yA . when

mass-transfer resistances is HIGH.
EKC338-SCE p. 37/164

1. for gaseous flow in a packed-beds;

Hr yA
T 0.7
M m cp y f A
(16)
s
for maximum T T |max occurs when yAs
=0
(for irreversible reaction)
and for reversible reaction,
s
yAs
= yAequilibrium
and
yf A
A yA
=
ln (1 + A yA )
EKC338-SCE p. 38/164

1. for maximum temperature difference, substitute the
above terms into Equation (17) then, T |max gives;

Hr ln (1 + A yA )
T |max = 0.7
(17)
M m cp
A
EKC338-SCE p. 39/164
Mass Transfer on Metallic Surfaces:

for a packed bed, concentration gradient, C variation
is SMALLusually 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)
EKC338-SCE p. 40/164
Intra-Particle Gradient Effects:

Catalyst internal structure:
reaction rate catalyst surface area
area range: 10 200 m2 /g
activated carbon: 800 m2 /g
sand: 0.01 m2 /g
EKC338-SCE p. 41/164

high areas through highly porous structure give high
surface area to volume ratio
pore sizes are not uniformpore 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 catalystshave bimodal distribution of pore
sizes ZEOLITE CATALYST
EKC338-SCE p. 42/164

non-ZEOLITE catalystsactive 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,
the ratio determines whether OR not pore wall
affects the diffusion behaviour
EKC338-SCE p. 43/164
dpore
where is the distance between the two molecules of gas

for collision.
for dpore >> :
1. molecular diffusion dominatesFickian Diffusion
2. for example; gases at HIGH pressure or liquids
EKC338-SCE p. 44/164

for dpore << and dmolecule < :
1. molecular interaction with pore wall dominates
2. diffusion described by Knudsens Law of Diffusion
3. for example; gases at LOW pressure but NOT
liquids (molecular structure of liquid is too high)
for dpore << and dmolecule :
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
EKC338-SCE p. 45/164

for dpore << and dmolecule :
4. for example:
(a) large hydrocarbon molecules [petroleum
desulphurisation]
(b) pores of VERY SMALL size [zeolite crystals and
biological cell walls]
EKC338-SCE p. 46/164
dpore
when dpore << and dmolecule < :
dpore
when dpore << and dmolecule :

EKC338-SCE p. 47/164
Correlations for Diffusion Coefficient:

For binary molecular diffusion; (for gases)
Dmi,k
3
2
Diffusion coefficient for the key component through a

mixture of the other components, Dmi,m
Nc
X
dyi
Ni = y i
Nk CDmi,m
dz
k=1
EKC338-SCE p. 48/164

With the Stefan-Maxwell equation for diffusion, Dmi,m
can be calculated from the actual binary diffusion data
using;
PNc
vk
1
(y
y
)
k
i
k=1 Dmi,k
vi
1
=
PNc vk
Dmi,m
1 yi k=1 vi
where v is the stoichiometric coefficient.
The Knudsen diffusion coefficient, DK can be

calculated using;
Dki
T
Mmi
12
dpore
EKC338-SCE p. 49/164

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
EKC338-SCE p. 50/164

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

Dp = Dm
dpore
< 0.2
(Knudsen diffusion controlling) thus,

Dp = Dk
EKC338-SCE p. 51/164

For intermediate values, both diffusion types are
important.
Use the Bosanquet Equation to estimate Dp where;
1
1
1
=
+
Dp
Dk Dm
EKC338-SCE p. 52/164

If given Dp , the approximation of Deff is given by;
Deff
Dp
=
p
where Deff is the effective diffusion coefficient, p is the

intraparticle void fraction and p is the tortuosity factor.
EKC338-SCE p. 53/164

Comparing diffusion in a single pore, (a) & diffusion in
a porous pellet, (b):
tortuous path
NA = -Dp dCA/dz
CA,1
(a)
CA,2
(b)
EKC338-SCE p. 54/164

The cross-sectional area available for diffusion = Ap ,
thus, lower NA .
Tortuous molecules path and changing pore
cross-sectional area due to constrictions, thus
reduced.
dCA
dz
is
Therefore;
Dp dCA
NA =
p dz
For zeolite;
p = 3 10
EKC338-SCE p. 55/164

NOTE:
tortuosity
p =
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 surfacediffusion & reaction take place
simultaneously rather than consecutively.
EKC338-SCE p. 56/164
Diffusion and Reaction within a Catalyst Pellet:

Concentration profile for porous catalyst pellet:
concentration
on the surface
CA
bulk concentration
external
film
Concentration
rp
CA,s
CATALYST
CsA,s
concentration
within the catalyst
0
central axis of pellet
negligible external mass

transfer
significant external mass
transfer
Position
EKC338-SCE p. 57/164

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
=
rA
EKC338-SCE p. 58/164

< 1 for ISOTHERMAL or ENDOTHERMIC reaction.
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.
EKC338-SCE p. 59/164

For packed-bedexternal 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
= s
rAs
EKC338-SCE p. 60/164

Pseudo-First Order Reaction: [A Product]
consider material balance through the incremental
section of a catalyst SLAB of area, a;
r
rp
NA
r + r
r
Incremental
section
r=0
EKC338-SCE p. 61/164

IN OUT = CONSUMPTION
(NA a)|r+r (NA a)|r = rAs ar
dividing by ar and let limr0 gives;

dNA
= rAs = kv CAs
dr
EKC338-SCE p. 62/164

For no convective flow in pellet, Ficks Law is
obeyed;
dCAs
NA = D e A
dr
upon substitution gives;
d2 CAs
= kv CAs
De A
2
dr
(18)
for constant DeA with respect to radius, r.

EKC338-SCE p. 63/164

integrating Equation (18) using the following
boundary conditions;
s
r = rp : CAs = CAs
r=0 :
dCAs
dr
gives;
CAs
s
CAs

q
cosh r Dkev
A

=
q
cosh rp Dkev
(19)
EKC338-SCE p. 64/164

where Thiele Modulus can be defined as;
s
kv
slab = rp
De A
EKC338-SCE p. 65/164

slab = 0
CAs/CsAs
1.0
As slab increases - the rate

constant becomes SMALLER
slab = rp(kv/DeA)1/2
INCREASING
1.0
r/rp
0.0
EKC338-SCE p. 66/164

for spherical pellet, asphere = 4r2
applying the same method as for SLAB; the final
equation leads to;
q

kv
sinh
r
D eA
rp
CAs
q

=
(20)
s
kv
CAs
r sinh r
p
D eA
EKC338-SCE p. 67/164

for cylindrical-shaped pellet, acylinder = 2r(L + r)
applying the same method as for SLAB; the ratio
gives;
q
kv
r
D eA
I1
CAs
q
=
(21)
s
k
CAs
I0 rp
v
D eA
where I is the Bassel function given by;
m 2m
(1)
r
n
In (r) = r
2m+n m!(n + m)!
2
m=0
EKC338-SCE p. 68/164

GENERALLY;
1 d m
(r NA ) = rAs
rm dr
(22)
where;
1. for SLAB; m = 0
2. for CYLINDER; m = 1
3. for SPHERE; m = 2
EKC338-SCE p. 69/164

Effectiveness Factor, e (for First-order reaction)
It is given by;
observed reaction rate
e =
reaction rate at pellet surface conditions
rA
e =
rAs
(23)
EKC338-SCE p. 70/164

s
Isothermal and Endothermic reactions; rAs
gives a
maximum reaction rate
since;
s
CAs
> CAs
AND
s
s
[rAs
= kv CAs
] [rA = kv CAs ]
AND therefore;
e 1
EKC338-SCE p. 71/164

For a very HIGH diffusional resistances within
catalyst, NEGLIGIBLE penetration of reactant into
pellet;
CAs = 0, rAs = 0, e = 0
thus, the range of e ;
0 e 1
EKC338-SCE p. 72/164

With the value of e , rA can be determined using;
s
rA = e rAs
s
rA = e (kv CAs
)
rA = e (kv CA )
NOTE: This is only for NEGLIGIBLE external film
mass transfer resistances!
EKC338-SCE p. 73/164

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 e
Final solution for SLAB-type catalyst;
tanh slab
e =
slab
(24)
EKC338-SCE p. 74/164

FOR SLAB:
NOTE:
slab 0, e 1
slab , e
slab
EKC338-SCE p. 75/164

FOR SPHERE:
By applying Equation (20), the Effectiveness factor
for spherical shape is given by;

3
1
1
e =
(25)
sphere tanh sphere sphere
NOTE:
sphere 0, e 1
sphere , e
3
sphere
EKC338-SCE p. 76/164

FOR CYLINDER:
I1 (2cylinder )
1
e =
I0 (2cylinder ) cylinder
(26)
NOTE:
cylinder 0, e 1
cylinder , e
2
cylinder
For a very SMALL , e will always converge to

UNITY (1)!
EKC338-SCE p. 77/164

The Effectiveness Factor for First Order Reaction:
1.0
sphere
cylinder
slab
10
20
30
EKC338-SCE p. 78/164

The equations (e and ) 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 e and curve coincide
EKC338-SCE p. 79/164

Curve for sphere and cylinder coincide with slab
curve such that a relatively simple expression
reduces into;
tanh
e =
where is generally given by;

r
Vp
kv
=
Ap DeA
(27)
EKC338-SCE p. 80/164

Effectiveness Factor, e (General Order Reactions)
For general order & reversible reactions;
s
Vp rAs
=
Ap 2
(Z
s
CAs
DeA rAs dCAs
CAs
) 12
(28)
where CAs
is the equimolar concentration of the
limiting reactant (= 0 for an irreversible reaction)
The above equation accounts for DeA varies with
CAs
EKC338-SCE p. 81/164

Effectiveness Factor, e (General Order Reactions)
It also assumes HIGH differential resistances such
that within the region of e 1
ELSE, CAs
in the above equation needs to be
calculated using;
rp =
s
CAs
CAs
DeA dCAs
i
h R
C
2 C A DeA rAs dCA
(29)
As
EKC338-SCE p. 82/164

Criteria for Intraparticle Diffusional Limitations:
For known reaction kinetics e can be calculated
(e < 1 indicates diffusional limitation)
The Weisz-Prater Criteria:
Using;
s
Vp
kv
=
A p De A
EKC338-SCE p. 83/164

upon rearrangement gives;
Ap
Vp
2
DeA = kv
for First-order reaction;

s
s
= kv CAs
rA = e rAs
EKC338-SCE p. 84/164

eliminating kv gives;
rA
=
s
DeA CAs
Vp
Ap
2
= e 2
(30)
is the Weisz-Prater Parameter

s
CAs
CA under typical conditions.
EKC338-SCE p. 85/164

The RHS of Equation (30) is measurable, then;
1. NEGLIGIBLE diffusional limitations; when;
1, e 1
therefore;
1
EKC338-SCE p. 86/164

The RHS of Equation (30) is measurable, then;
2. CONSIDERABLE diffusional limitations; when;
1
1, e
therefore;
1
The above method can be generalised to any

reaction scheme where appropriate for the Thiele
Modulus.
EKC338-SCE p. 87/164
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
De A
r
= rAs
2
r
dr
dr
similarly for energy balance;

1
d
2 dTs
e
r
= rAs Hr
2
r
dr
dr
(31)
EKC338-SCE p. 88/164

Equation (31) is known as Fouriers Law where e is
the effective thermal conductivity of the pellet.
By eliminating rAs and integrating twice leads to;
Ts = (Ts
Tss )
Hr DeA
s
(CAs CAs
)
=
e
(32)
For irreversible reaction, Ts is maximum when
CAs = 0 (OR CAs

for an equimolar reversible reaction)
thus;
Hr DeA s
Ts |max =
CAs
(33)
e
EKC338-SCE p. 89/164

Equation (33) is applicable to all pellet catalyst
geometries.
For many industrial applications;
Ts |max
< 0.1
s
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 e is complex since, it will
influence DeA as well as kv .
EKC338-SCE p. 90/164

Consider the First-order non-isothermal reaction on a
pellet; the mass balance is given by;

1
d
2 dCAs
De A
r
= rAs
2
r
dr
dr
and
rAs = kv CAs
where
kv = A0 e

E
RT
0
EKC338-SCE p. 91/164

Upon substitution gives;

E
1
d
dC
RT
As
2
0 C
De A
r
= A0 e
As
2
r
dr
dr
putting into dimensionless form leads to;
d2 C
(1T)
= Ce
2
d
r
where
Ts
r
CAs
C = s T = s r =
CAs
Ts
rp
EKC338-SCE p. 92/164

and both and is defined as;
2
r
A
e
0
p
=
De A
and
E
=
RTss
EKC338-SCE p. 93/164

Similarly, for energy balance;
d2 T
2 (1T)
= Ce
2
d
r
where
s
(Ts )max
Hr DeA CAs
=
=
s
Ts
e Tss
EKC338-SCE p. 94/164
1.0
> 0: Exothermic
= 0: Isothermal
< 0: Endothermic
0.001
0.1
EKC338-SCE p. 95/164
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;

dCAs
s

r = rp : kmc (CA CAs ) = DeA
dr rp
EKC338-SCE p. 96/164

Resistances:
and;
r=0:

dCAs

=0
dr
0
For slab pellet with a First-order reaction, the solution

with the above boundary conditions gives;
CAs =
CA cosh r
rp
cosh +
D eA
rp kmc
sinh
EKC338-SCE p. 97/164

Resistances:
Therefore, the Global Effectiveness Factor can be
defined as;
rate observed
G =
rate at bulk fluid concentration
rA
G =
rAs CA
EKC338-SCE p. 98/164

Resistances:
Which then gives;
1
1
2
= +
G
Bim
(34)
where Bim is Biot number for mass-transfer given by;

kmc rp
Bim =
De A
For Bim 1.0, G = e .
EKC338-SCE p. 99/164

Resistances:
For the region of strong intraparticle diffusional
limitations, where;
and
1
e =
thus,
1
2
=+
G
Bim
(35)
EKC338-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 b =
rA b
dV
|vA |
(36)
EKC338-SCE p. 101/164

when ni = uaCi and dV = adz, thus, the equation
reduces into;
d
vi
(uCi ) = ri b =
rA b
dz
|vA |
(37)
since u 6= constant, therefore momentum equation

is required.
EKC338-SCE p. 102/164

Using the Ergun equation of the form;
dp
= E1 u E2 u2
dz
(38)
to find the pressure along the bed, where;

180(1 b )2
E1 =
d2p 3b
and
1.8(1 b )g Mm
E2 =
dp 3b
EKC338-SCE p. 103/164

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
i
P
Ci =
= g
RT
For non-isothermal operation, energy balance is

required to describe T z variation
EKC338-SCE p. 104/164

Energy balance across a fix-bed reactor is given as;
X
dT
=(
ni cpi ) + b rA
r Qav = 0
dV
i
(39)
where
Q = U (Tc T )
(J/m2 s)
and av is the surface area per unit reactor volume,

(m1 ), therefore;
X
dT
r Qav = 0
= (U
ni cpi ) + b rA
dz
i
(40)
EKC338-SCE p. 105/164

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;
i
ni = nio +
(nAo nA )
|nA |
EKC338-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 bedno relative
movement between particles
1. P u for LAMINAR flow
2. P u2 for TURBULENT flow
EKC338-SCE p. 107/164
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 flowresults 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!
EKC338-SCE p. 108/164
When superficial velocity > umf ;
1. LIQUID fluidisation;
bed continues to EXPAND with u
it maintains a uniform character
and AGITATION of particle
increasesparticulate fluidisation
EKC338-SCE p. 109/164
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 phaseaggregation 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
bedbubbles coalesce forming slugs of gas
that occupy the entire cross-section of the bed.
EKC338-SCE p. 110/164
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 fluidhydrostatic 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 (s g )
EKC338-SCE p. 111/164
WHY Fluidisation?
Can achieve a GOOD control of TEMPERATURE
Can work with VERY FINE particles for which
e 1
As catalyst improvesthe rates of reaction
INCREASE resulted form higher kv BUT;
s
rp
kv
=
3 De A
when fv , the ONLY way to keep SMALL and e
close to 1 is to decrease rp
EKC338-SCE p. 112/164
WHY Fluidisation?
NOTE: an increase of kv will increase , therefore it
will be MASS TRANSFER controlling and NOT
kinetics (reaction) the possible way is to REDUCE
rp
EKC338-SCE p. 113/164
P versus uo for fluidised bed:
log P
hysterisis due to
pressure different
blown out particles

(initiation of
particle entrainment)
umf
log uo
EKC338-SCE p. 114/164
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
EKC338-SCE p. 115/164
Calculation of P across fluidised bed: Consider a
diagram below;
uo = superficial velocity
at bed inlet
ut = terminal velocity
when pellet are
blown out of the
L
bed
A
P2
F2
P1
F1
uo
EKC338-SCE p. 116/164
Resolving forces on the bed;
F1
P1 A
(P1 P2 )
P
=
=
=
=
F2
P2 A + (s g )(1 )ALg
(s g )(1 )Lg
(s g )(1 )Lg
(41)
As P1 , P also , and therefore, as the bed

expends
OR resistance as the gas by-pass through
bubbling and P remains the same.
EKC338-SCE p. 117/164
Calculation of the minimum fluidisation velocity, umf ;
For LAMINAR flow;
Using the previously defined Ergun equation
[Equation (38)];
Pmf
= E1 umf
Lmf
umf
(1 mf )(s g )g
=
E1
(42)
where
180(1 mf )2
E1 =
d2p 3mf
EKC338-SCE p. 118/164
For LAMINAR flow;
Substitute into Equation (40) and simplify gives;
umf
1 3mf d2p (s g )g
=
180 (1 mf )
(43)
For mf 0.4 the bed is packed with isometric

particles.
EKC338-SCE p. 119/164
For TURBULENT flow [usually for coarse particles];
Similarly, applying the Ergun equation;
Pmf
= E1 umf E2 u2mf = (1 mf )(s g )g
Lmf
and solving for umf explicitly gives;
(1 mf )
1.75 2
Remf + 3 Remf
Ga = 180
3
mf
mf
(44)
EKC338-SCE p. 120/164
For TURBULENT flow [usually for coarse particles];
where
g (s g )gd3p
Ga =
2
is the Galileos Number and
Remf
g umf dp
=
is the Reynolds Number for minimum fluidisation.

in reality, expect Darcys Law and Ergun equation
to overestimate Pmf .
EKC338-SCE p. 121/164
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.
EKC338-SCE p. 122/164
Calculation of terminal 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!
EKC338-SCE p. 123/164
this can be shown by;
Fdrag = Vp (s g )g
but (FROM FLUID FLOW NOTES);
Fdrag
1
= g u2t CD Ap
2
where CD is the drag coefficient. with Ap =

Fdrag
d2p
4
thus;
d2p
=
g u2t CD
8
EKC338-SCE p. 124/164
upon rearrangement gives;
s
4dp (s g )g
ut =
3CD g
(45)
for spherical particles and Re < 0.4 where

g ut dp
Re =
EKC338-SCE p. 125/164
and the Drag coefficient is given by;
24
CD =
Re
and Equation (43) reduces into Stokes Law of the
form;
(s g )gd2p
ut =
(46)
18
EKC338-SCE p. 126/164
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 (s g )g
ut =
g
EKC338-SCE p. 127/164
Fluidisation regimes:
For COARSE PARTICLES:
bubbles appear as soon as umf is exceeded.
in TURBULENT regimesbubbles life time is
SHORT due to bubbles burst. Bed is quite
uniformshort circuiting of gas through bubbles is
less likely.
umf and particle blow-out coincide.
in FAST fluidisation regimethere is the net
entrainment of solids.
in TRANSPORT regimethere is solid flow in the
direction of gas flow.
carry-over (entrainment) separates particles by
size.
EKC338-SCE p. 128/164
Fluidisation regimes:
For FINE PARTICLES:
bubbles DO NOT appear as soon as minimum
fluidisation is reachedinstead, 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
sizea more cohesive bed.
EKC338-SCE p. 129/164
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 bedlittle 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 ).
EKC338-SCE p. 130/164
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.
EKC338-SCE p. 131/164
Modelling of fluidised-bed reactors:
Two-phase model:
the model is based on the interchange between
the two phases;
CA
CAb|out
Bubble
phase
CAe|out
Emulsion
phase
ub
ue
CAb
CAe
uo, CAo
EKC338-SCE p. 132/164
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
dz
(47)
for emulsion-phase:
dCAe
d2 CAe
fe ue
fe Dze
k
(C
C
)+(1f
)g
r
I
Ab
Ae
b e A = 0
2
dz
dz
(48)
EKC338-SCE p. 133/164
Two-phase model:
also;
uo CA = fb ub CAb + fe ue CAe
(49)
and the boundary conditions are;

for bubble-phase:
z = 0 : CAb = CAo
EKC338-SCE p. 134/164
Two-phase model:
for emulsion-phase:
dCAe
= ue (CAo CAe )
z = 0 : Dze
dz
z=L:
dCAe
=0
dz
EKC338-SCE p. 135/164
Model simplification:
If ub ue , that is when ub umf , then the
emulsion-phaseclosed (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.
EKC338-SCE p. 136/164
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 = db g
EKC338-SCE p. 137/164
two-phase model:
1. ub : bubble velocity:
where = 0.64 for dt < 0.1m OR = 1.6d0.4
t for
0.1m < dt < 1.0m OR = 1.6 for dt > 1.0m
2. fb : bubble friction:
this is given by;
uo umf
fb =
ub
EKC338-SCE p. 138/164
two-phase model:
2. fb : bubble friction:
BUT for ub umf
uo
fb
ub
3. fe : emulsion friction:
This is given by
fe + fb = f
where f is the VOIDAGE of a fluidised-bed.
EKC338-SCE p. 139/164
two-phase model:
4. Lf and f : length of bed and bed voidage:
Given that the volume of solids constant, where;
Lf (1 f ) = Lmf (1 mf ) = L(1 b )
1 f
Lmf
=
= 1 fb
1 mf
Lf
given that fb and mf 0.4, then Lf and f can be
calculated.
EKC338-SCE p. 140/164
two-phase model:
5. Dze : diffusion coefficient of emulsion phase:
Using;
Dze = f (uo , dt )
6. ue : emulsion velocity:
Using
umf
ue =
mf
EKC338-SCE p. 141/164
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 modelskI often used as a fitting
parameter such that model agrees with plant
data.
EKC338-SCE p. 142/164
Three-phase model:
ub
ue
emulsion
bubble
cloud
EKC338-SCE p. 143/164
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;
cloud
bubble
emulsion
kI,b
kI,e
CA,b
CA,b
CA,e
EKC338-SCE p. 144/164
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
EKC338-SCE p. 145/164
Example: k-L Model for First-order reaction
Consider the material balances:
Bubble phase:
dCAb
+ kIb (CAb CAc ) + fb gb kCAb = 0
fb ub
dz
Emulsion phase:
kIe (CAc CAe ) = (1 fb fc )ge kCAe
Cloud phase:
kIb (CAb CAc ) = kIe (CAc CAe ) + fc gc kCAc
EKC338-SCE p. 146/164
fc is with the units
gc is in the form of
m3cloud
of m3
bed
kg
which
m3cloud
is approx. equal to
b
ge =
1 fb
and fc is normally given by;
fc
1.17
fb =
1.17 + uueb
EKC338-SCE p. 147/164
using equations for emulsion and could phases
and substitute into the bubble phase equation
gives;
dCAb
ub
= kCAb
(51)
dz
EKC338-SCE p. 148/164
and K is given by;
1
K = k gb + kfb
1
+
1
kIb
gc fc + kf
1
b+
kI
ge (1fb fc )
e
fb
which is the effective rate constant for a

three-phase fluidised-bed model k-L rate
constant.
EKC338-SCE p. 149/164
Integration of Equation (49) with boundary
conditions;
z = 0; CAb = CAo
leads to;
CAb
CA
=
= eKb
CAo
CAo
where b =
(52)
Lf
ub
EKC338-SCE p. 150/164
Modelling of Transport Reactor (Riser):
Example: Fluid Catalytic Crackingfast reactions
(small required) and rapid catalyst deactivation.
Velocity of SOLIDS velocity of GAS. That is, NO
SLIP VELOCITY
Usually employed FINE SOLIDS such that e 1
For NO catalyst DEACTIVATION, riser is very much
like pseudo-homogeneous Plug-Flow reactor (PFR)
but
> b
EKC338-SCE p. 151/164
Calculation of :
Given that;
3
mg
Auo
=
3
mb
Auo + mps
where p is the pellet density with units of
(53)
kg
m3pellet
Upon simplification of Equation (51) gives;

3
mg
1
=
3
mb
1 + umosAp
(54)
EKC338-SCE p. 152/164
Calculation of :
The diagram is given;
gas
solid
uo (m/s)
ms (kg/s)
EKC338-SCE p. 153/164
Calculation of :
From Equation (52);
m
s uo :
m
s uo :
for Packed-Bed reactor; b 0.4

For NO catalyst deactivation:
dCA
= rA
(1 )p
uo
dz
(55)
EKC338-SCE p. 154/164
Calculation of :
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)
A =
= f (t)
rA (0)
(56)
EKC338-SCE p. 155/164
Calculation of :
The function can be of the form;
= 1 t
OR
= et
Therefore Equation (53) becomes;
dCA
uo
= rA
A (1 )p
dz
(57)
EKC338-SCE p. 156/164
Calculation of :
Where t = uzo (NO SLIP) and it represents the
time for a particular catalyst to have spent in the
riser.
Sometimes, 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
Cc
kgcatalyst
EKC338-SCE p. 157/164
Calculation of :
And the rate of formation of coke is given by;

kgcoke
rc
kgcatalyst s
where rc can itself be deactivated as the coke is
being produced!
The balances for coke deposition is given by;
m
s dCc
= rc c p (1 )
A dz
(58)
EKC338-SCE p. 158/164
Calculation of :
The energy balances for the ADIABATIC riser can
be written as;
m
g cpg + m
s cps dT
A
dz
= [rA
A (HA ) + rc c (Hc )]
p (1 )
(59)
where cpg and cps are the specific heat capacities

kJ
of gas and solid respectively in kgK
and m
g is the
mass flow rate of gas in
kg
s
EKC338-SCE p. 159/164
Calculation of :
And m
g is given by;
Auo po
m
g=
Mg
RTo
EKC338-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)
EKC338-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
GAS: disperse
LIQUID: disperse
GAS: continuous
LIQUID: continuous
GAS: continuous
LIQUID
LIQUID
LIQUID
GAS
Bubble reactor
Slurry reactor
Fermentation vessel
GAS
Spray tower
Trickle-bed reactor
Packed-bed reactor
GAS
Wetted-wall reactor
(falling film)
EKC338-SCE p. 162/164
Multiphase Reactors
If mass-transfer resistance located in the liquid-film,

use DISPERSEgas phase and CONTINUOUSliquid
phase.
If mass-transfer resistance located in the gas-film,
use CONTINUOUSgas phase and DISPERSEliquid
phase.
Residence time, 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
EKC338-SCE p. 163/164
Multiphase Reactors
Residence time, 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.
EKC338-SCE p. 164/164

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Reactor Design and Analysis (MHU)

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EKC338: REACTOR DESIGN & ANALYSIS

Core Course for

School of Chemical Engineering

3. Bioreactor Analysis and Operation:

4. Design of Multiple-Phase Reactors

External & Internal Diffusion

External & Internal Diffusion

External & Internal Diffusion

External & Internal Diffusion

External & Internal Diffusion

Introduction to Heterogeneous and Multiphase Reactions

Introduction to Heterogeneous and Multiphase Reactions

Introduction to Heterogeneous and Multiphase Reactions

Introduction to Heterogeneous and Multiphase Reactions

Introduction to Heterogeneous and Multiphase Reactions

Introduction to Heterogeneous and Multiphase Reactions

Interfacial gradient effects: Reaction at catalyst surface

Interfacial gradient effects

where ks is the rate constant at the catalyst surface

Interfacial gradient effects

and kmc = kmp = kmy

Interfacial gradient effects

Interfacial gradient effects

where ko is the overall rate constant.

Interfacial gradient effects

Interfacial gradient effects

Interfacial gradient effects

[second order dependent] overall is reaction

Interfacial gradient effects

Interfacial gradient effects

Interfacial gradient effects

equimolar counter diffusion, km

Interfacial gradient effects

Interfacial gradient effects

Interfacial gradient effects

relationship between kmy

2. For reaction in which total moles are not

Interfacial gradient effects

relationship between kmy

Interfacial gradient effects

relationship between kmy

Interfacial gradient effects

relationship between kmy

Interfacial gradient effects

relationship between kmy

2. thus; kmy = kmy

Interfacial gradient effects

for Re < 190

for Re > 190

Interfacial gradient effects

Interfacial gradient effects

but in terms of concentration (mole fraction);

and upon rearrangement gives;

Interfacial gradient effects

but it is known that, rA

T increases with the increase of yA . when

Interfacial gradient effects

Interfacial gradient effects

Mass Transfer on Metallic Surfaces:

Intra-Particle Gradient Effects:

Intra-Particle Gradient Effects:

Intra-Particle Gradient Effects:

Intra-Particle Gradient Effects: