Heat and Mass Transfer Resistances

Ch E 542 - Intermediate Reactor Analysis & Design
Heat and Mass

Transfer Resistances
Mass Transfer & Reaction
When convection dominates, the boundary
condition expressing steady state flux continuity
at z= o is used;

k
c
is the convection mass transfer coefficient

( )
As A c As
C C k = W

for flow around a sphere (roughly the geometric
shape of a catalyst particle), the convective heat
transfer coefficient can be found from correlation
such as the following:
t
p
k
d h
Nu

=
=
p
d v
Re
t
Pr
o
v
=
3 1 2 1
Pr Re 6 . 0 2 Nu + =
( )
As A c As
C C k = W
By the heat/mass transfer analogy:

for flow around a sphere, the convective heat transfer
coefficient can be found from:
Pr Sc
Nu Sh
AB t
c
D k
k h
AB
p c
D
d k
Sh

=
=
p
d v
Re
AB
D
Sc
v
=
3 1 2 1
Sc Re 6 . 0 2 Sh + =
" r W
As As
=
As r
C k =
molar flux to catalyst surface = reaction rate on surface
( )
As r As A c
C k C C k =
( ) =
As A c
C C k
r c
A c
As
k k
C k
C
+
=
r c
A r c
As
k k
C k k
" r
+
=
Fast Reaction Kinetics
fast reaction kinetics
A c
r
A r c
r c
A r c
As
C k
k
C k k
k k
C k k
" r = ~
+
=
c r
k k >>
3 1 2 1
p
AB
c
Sc Re
d
D
6 . 0 k
|
|
.
|
\
|
=
|
|
.
|
\
|
|
|
.
|
\
|
v
=
2 1
p
2 1
6 1
3 2
AB
c
d
v D
6 . 0 k
3 1
AB
2 1
p
p
AB
c
D
vd
d
D
6 . 0 k
|
|
.
|
\
|
v
|
|
.
|
\
|
v
|
|
.
|
\
|
=
Frssling Correlation
Fast Reaction Kinetics
fast reaction kinetics
A c As
C k " r ~
c r
k k >>
|
|
.
|
\
|
|
|
.
|
\
|
v
=
2 1
p
2 1
6 1
3 2
AB
c
d
v D
6 . 0 k
( ) T f
D
6 1
3 2
AB
=
|
|
.
|
\
|
v
| D
AB
| v
gas
+ v
liquid
| T as
( ) T f
d
v
2 1
p
2 1
=
|
|
.
|
\
|
to increase k
c
| v
+ d
p
Slow Reaction Kinetics
slow reaction kinetics
A r
c
A r c
r c
A r c
As
C k
k
C k k
k k
C k k
" r = ~
+
=
c r
k k <<
k
r
is independent of
fluid velocity
particle size
k
c
vd
p
( )
vd
p
0.5
:= r
As
vd
p
( )
k
r
k
c
vd
p
( )
C
A

k
r
k
c
vd
p
( )
+
:=
0 5 10 15
0
0.02
0.04
0.06
0.08
0.1
r
As
vd
p
( )
vd
p
0.5
Reaction and Mass Transfer
reaction
rate limited
mass
transfer
limited
Rate Units for Catalytic Reaction
for single pellets
for packed beds
a
c
surface area / gram
c A A
a " r ' r =
p c
c
d
6
a
=
( )
p p B
c
d
1 6
d
6
a
|
=
=
Example Calculation
The irreversible gas-phase reaction AB is carried out in a PBR. The
reaction is first order in A on the surface.
The feed consists of 50%(mol) A (1.0 M) and 50%(mol) inerts and enters
the bed at a temperature of 300K. The entering volumetric flow rate is
10 dm3/s.
The relationship between the Sherwood Number and the Reynolds
Number for this geometry is
Sh = 100 Re

Neglecting pressure drop, calculate catalyst weight necessary to achieve
60% conversion of A for
isothermal operation
adiabatic operation
Example Calculation

' r
dW
dX
F
A Ao
=
Mole Balance
Rate Law
As r As
C ' k ' r =
assume reaction is mass transfer limited
( )
As A c A
C C k W =
A As
W r =
' k k
C ' k k
' r
r c
A r c
As
+
=
Re 100 Sh =
2 1
p
AB
p c
vd
100
D
d k
|
|
.
|
\
|
v
=
|
|
.
|
\
|
g s
cm
4242
vd
d
D
100 k
3
2 1
p
p
AB
c
=
|
|
.
|
\
|
v
|
|
.
|
\
|
=
Mass Transfer Coefficient
Example Calculation

' r
dW
dX
F
A Ao
=
Mole Balance
Rate Law
gas-phase, c = 0, T = T
0
, P = P
0
. Stoichiometry
( ) X 1 C C
Ao A
=
' k k
C ' k k
' r
r c
A r c
As
+
=
g s
cm
4242 k
3
c
=
Energy Balance
Reaction is being carried
out isothermally. Thus,
energy balance not needed
and k
r
= f(T)
Example Calculation

gas-phase, c = 0, P = P
0
. Stoichiometry
( )
T
T
X 1 C C
o
Ao A
=
' k k
C ' k k
' r
r c
A r c
As
+
=
g s
cm
4242 k
3
c
=
( )
|
|
.
|
\
|
=
T
1
T
1
R
E
ro r
R
e ' k T ' k
' r
dW
dX
F
A Ao
=
Mole Balance
Rate Law
Energy Balance
( )
io
pi io
r
T
C F
H X
T +
A
=
Multicomponent Diffusion
Exact form of the flux equation for multicomponent
mass transport:

A simplified form uses a mean effective binary
diffusivity,
1 N , , 2 , 1 j , N y y D C N
N
1 k
k j
1 N
1 k
k jk t j
= V =

=
=
V =
N
1 k
k j j jm t j
N y y D C N
The Stefan-Maxwell equations (Bird, Stewart, Lightfoot)
are given for ideal gases:

For binary system:
( )
=
=
= V
N
j k
1 k
k j j k
jk
j t
N y N y
D
1
y C
( ) | |
2 1 1 1
12
1 t
N N y N
D
1
y C + = V
Solved for flux

Simplified for
assumed equimolar
counter-diffusion
( ) | |
2 1 1 1
12
1 t
N N y N
D
1
y C + = V
( )
2 1 1 1 12 t 1
N N y y D C N + + V =
1 12 t 1
y D C N V =
The effective binary diffusivity for species j can then be
defined by equating the driving force terms of the
expression containing D
jm
and the Stefan-Maxwell
( )
=
=
= V
N
j k
1 k
k j j k
jk
j t
N y N y
D
1
y C
=
V =
N
1 k
k j jm j t j
N y D y C N
The effective binary diffusivity for species j can then be
defined by equating the driving force terms of the
expression containing D
jm
and the Stefan-Maxwell
( )

=
=
=

(
(
(
=
N
1 k
k j
N
j k
1 k
k j j k
jk
jm j
N y N y N y
D
1
D N

use for diffusion of species 1 through stagnant 2, 3, (all
flux ratios are zero for k=2,3,) reduces to
the "Wilke equation"
( )
=
=
=
=
N
1 k
k j j
N
j k
1 k
k j j k
jk
jm
N y N
N y N y
D
1
D
1
=
N
3 , 2 k k 1
k
1 m 1
D
y
y 1
1
D
1
For reacting systems where steady-state flux ratios are
determined by reaction stoichiometry,
=
=
=
|
|
.
|
\
|
o
o
+
o +
=
o
o
|
|
.
|
\
|
o
o
=
N
j k j
k
j k
jk j j
N
1 k
k
k
j
N
j k
j
k
j k
jk
jm
y y
D
1
y 1
1
y 1
y y
D
1
D
1
constant
N
j
j
=
o
Diffusion/Rxn in Porous Catalysts
Effective Diffusivity (D
e
) is a measure of
diffusivity that accounts for the following:
Not all area normal to flux direction is available for
molecules to diffuse in a porous particle (|
P
)
Diffusion paths are tortuous (t)
Pore cross-sections vary (o)
Internal void fraction, c
s
= |
P
o
t
o |
=
~
D
D
P A
e
Extended Stefan-Maxwell

Solved for binary, steady-state, 1D diffusion
( ) ( )
( )
( )
Kj , e
D
j
N
1 k
D
k j
D
j k
jk , e
j
D
N
N y N y
D
1
p
RT
1
+ = V
=
( )
( ) ( )
( )
(
(
+ +
+ +
+
=
KA , e AB , e 0 A A B
KA , e AB , e A A B
B A
AB , e t
A
D D y N N 1 1
D D L y N N 1 1
l n
N N 1 L
D C
N
Define effective binary diffusivity for use in
single reaction multicomponent systems:
dz
dC
D N
j
jm , e j
=
Kj , e
N
1 k j
k
j k
jk , e jm , e
D
1
y y
D
1
D
1
+
|
|
.
|
\
|
o
o
=
=
Quantify D
e
Random Pore Model
Parallel Cross-linked Pore Model
Pore Network Model of Beeckman & Froment
Tortuosity factor using Wicke-Kallenbach cell
Pore diffusion with
Adsorption
Surface Diffusion
steady state mass balance
rate in at r
r
2
Ar
r 4 W t
rate out at r + Ar
r r
2
Ar
r 4 W
A +
t
rate of generation within shell
c
mass catalyst
rate reaction
volume shell
mass catalyst
volume shell
r
r + Ar
R

r r 4
2
m
A t
'
A
r
0 r r 4 r
r 4 W r 4 W
2
m C
'
A
r r
2
Ar
r
2
Ar
= A t +
t t
A +
( )
0 r r
dr
r W d
2
C
'
A
2
Ar
=
B A
cat

( )
0 r r
dr
r W d
2
C
'
A
2
Ar
=
dr
dC
D W
A
e Ar
=
0 r r r
dr
dC
D
dr
d
2
C
'
A
2
A
e
=
|
.
|
\
|
0 r S r r
dr
dC
D
dr
d
2
C a
"
A
2
A
e
=
|
.
|
\
|
2
A n a C A
2
A n a
'
A
2
A n
"
A
C k S r
C k S r
C k r
=
=
=
0 r S C k
2
C a
n
A n
=
rate equation
definitions
substitute Ficks Law
0 r S C k r
dr
dC
D
dr
d
2
C a
n
A n
2
A
e
=
|
.
|
\
|
identify boundary conditions

finite C
0 r
A
=
=
symmetry
As
R r
A
C C =
=
surface
dimensionless
As
A
C
C
=
R
r
=
As
A
C
d
dC
=
R
1
d
dr
=
R
C
d
d
dr
dC
As A
=
0 C
D
S k
dr
dC
r
2
dr
C d
n
A
e
C a n A
2
A
2
=
|
|
.
|
\
|

|
.
|
\
|
+
0
D
C R S k
d
d 2
d
d
n
e
1 n
As
2
C a n
2
2
=
|
|
.
|
\
|

define Thiele modulus (|
n
)
0
D
C R S k
d
d 2
d
d
n
e
1 n
As
2
C a n
2
2
=
|
|
.
|
\
|

e
1 n
As
2
C a n
2
n
D
C R S k

= |
0
d
d 2
d
d
n 2
n
2
2
= |
understand the Thiele modulus

( ) R 0 C D
RC S k
As e
n
As C a n
2
n
= |
reaction rate
diffusion rate
large |
n
- diffusion controls
small |
n
- kinetics control
first order
kinetics
(n = 1)
define y =
0
d
d 2
d
d
2
1
2
2
= |
2
e
C a n
2
1
R
D
S k
= |
3 2 2
2
2
2
y 2
d
dy 2
d
y d 1
d
d
+
|
.
|
\
|

|
|
.
|
\
|

=
2
y
d
dy 1
d
d
|
.
|
\
|

=
0 y
d
y d
2
1
2
2
= |
| + | =
1 1 1 1
sinh B cosh A y
| + | =

1
B
1
A
sinh cosh
1 1
differential has the solution apply boundary conditions
1 , 1
finite is , 0
= =
=
first order
kinetics
(n = 1)
0
d
d 2
d
d
2
1
2
2
= |
2
e
C a n
2
1
R
D
S k
= |
0 y
d
y d
2
1
2
2
= |
| + | =
1 1 1 1
sinh B cosh A y
| + | =

1
B
1
A
sinh cosh
1 1
differential has the solution apply boundary conditions
1 , 1
finite is , 0
= =
=
|
|
.
|
\
|
|
|
=
1
1
sinh
sinh 1
As
A
C
C
=
Thiele Modulus
d |
1
, ( )
1
sinh |
1
( )
sinh |
1
( )
|
\
|
|
.
:=
0 0.5 1
0
0.5
1
d 1 ,
( )
d 2 ,
( )
d 5 ,
( )
d 20 ,
( )
=
As
A
C
C
Internal Effectiveness Factor (q)

The internal effectiveness factor (q) is a measure
of the relative importance of diffusion to reaction
limitations:
s As
T , C to exposed were surface entire if rate
rate reaction overall actual
q
As
A
"
As
"
A
'
As
'
A
As
A
M
M
r
r
r
r
r
r
=
= q
M mol / time
r mol / time / mass cat
Determine M
As
(rate if all surface at C
As
)
( ) ( ) catalyst mass
catalyst mass
area surface
area unit per rate M
As

|
|
.
|
\
|
=
'
As
r
a
S
C
V =
As
M
x
x
As 1
C k
c
3
3
4
a As 1 As
R S C k M t =
Determine M
A
(actual rate is equal to reactant
diffusion rate at outer surface)
1
As e A
d
d
C RD 4 M
=
t =
1
1
1
2
1
1 1
1
sinh
sinh 1
sinh
cosh
d
d
=
=
|
|
.
|
\
|
|
|
|
| |
=
1 coth
1 1
| | =
( ) 1 coth C RD 4 M
1 1 As e A
| | t =
Substitute results into definition of q
As
A
M
M
= q
( )
c
3
3
4
a As 1
1 1 As e
R S C k
1 coth C RD 4
t
| | t
=
( ) 1 coth
R S k
D
3
1 1
c
2
a 1
e
| |
=
( ) 1 coth
3
1 1
2
1
| |
|
= q
( ) 1 coth
3
1 1
2
1
| |
|
= q
q |
( )
3
|
2
| coth |
( )
1
( )
:=
0.1 1 10 100
0.1
1
q |
( )
|
q
( ) 1
2
1
3
1
2
1
| ~ q
> |
|
1
0
1
q
|
a c 1
e
2
1
S k
D
R
3 3
1
20
|
= ~ q
> |
small d
p
( ) 1 coth
3
1 1
2
1
| |
|
= q
q |
( )
3
|
2
| coth |
( )
1
( )
:=
0.1 1 10 100
0.1
1
q |
( )
|
q
( ) 1
2
1
3
1
2
1
| ~ q
> |
|
1
0
1
q
|
a c 1
e
2
1
S k
D
R
3 3
1
20
|
= ~ q
> |
reaction
rate
limited
internal
diffusion
limited
Revisit | and q
Thiele modulus - |
Derived for spherical particle geometry
Derived for 1
st
order kinetics
For large |, approximately

Internal effectiveness factor - q
Assumed c=0, correction applied when c=0
Assumed isothermal conditions
2
1
2 1
3
1 n
2
|
|
.
|
\
|
+
= q
Non-Isothermal Behavior
For exothermic reactions, q can be > 1 as internal
temperature can exceed T
s
.
The rate internally is thus larger than at the surface
conditions where q is evaluated.
The magnitude of this effect is dependent on
AH
rxn
, T
s
, T
max
, and k
t
(thermal conductivity of the pellet)
and | are used to quantify this effect:

can result in mulitple steady states
No multiple steady states exist if Luss criterion is fulfilled
( ) Number Arrhenius
s
RT
E
=
s t
As e rxn
s
s max
T k
C D H
T
T T A
=
= |
( ) | + < | 1 4
Overall Effectiveness Factor
When both internal AND external diffusion
resistances are important (i.e., the same order of
magnitude), both must be accounted for when
quantifying kinetics.
It is desired to express the kinetics in terms of the
bulk conditions, rather than surface conditions:
bulk A,
C to exposed were surface entire if rate
rate reaction overall actual
O
Accounting for reaction both on and within the pellet, the molar rate
becomes:

For most catalyst, internal surface area is significantly higher than the
external surface area:
( ) | | V 1 S a r M
c a c
"
A A
A | + =
b
| |
b a c
"
A c A
S a r a W + =
b a
"
A c A
S r a W =
b a
"
A c A
S r a W =
reaction rate
(internal & external surfaces)
( ) V a C C k V a W
c As bulk , A c c Ar
A = A
mass transport rate
internal surfaces not
all exposed to C
As
As 1
"
As
"
A
C k r r q = q =
Relation between C
As
and C
A

defined by the q as:

V S C k V a W
b a As 1 c A
A q = A
( )
b a As 1 c As bulk , A c
S C k a C C k q =
b a
"
A c A
S r a W =
reaction rate
( ) V a C C k V a W
A = A
mass transport rate
As 1
"
As
"
A
C k r r q = q =
Relation between C
As
and C
A

defined by the q as:

b a 1 c c
bulk , A c c
As
S k k a
C k a
C
q +
=
Solving for C
As
:

b a
"
A c A
S r a W =
reaction rate
( ) V a C C k V a W
A = A
mass transport rate
b a 1 c c
bulk , A c c 1 "
A
S k k a
C a k k
r
q +
q
=
Substitution into the rate law:

b a 1 c c
bulk , A c c
As
S k k a
C k a
C
q +
=
Solving for C
As
:

summary of factor relationships:
b a 1 c c
bulk , A c c 1 "
A
S k k a
C a k k
r
q +
q
=
Rearranging the expression:

( )
=
q +
q
bulk , A 1
c c b a 1
C k
a k S k 1
( )
"
bulk , A
"
A
r r O =
( )
c c b a 1
a k S k 1 q +
q
= O
( ) ( )
"
As
"
bulk , A
"
A
r r r q = O =
As 1
"
As
C k r =
Ab 1
"
Ab
C k r =
Overall Effectiveness Factor (O)
Weisz-Prater Criterion
Weisz-Prater Criterion is a method of determining if a given
process is operating in a diffusion- or reaction-limited regime
C
WP
is the known as the Weisz-Prater parameter. All
quantities are known or measured.

C
WP
<< 1, no VC in the pellet (kinetically limited)
C
WP
>> 1, severe diffusion limitations
As e
c
2 '
obs , A 2
1 WP
C D
R r
C

= q| =
Mears Criterion
Mass transfer effects negligible when it is true that

n is the reaction order, and the transfer coefficients k
c
and h (below) can
be estimated from an appropriate correlation (i.e., Thoenes-Kramers for
packed bed flow)
Heat transfer effects negligible when it is true that
15 . 0
C k
n R r
Ab c
b
'
A
<

( )
15 . 0
T hR
RE r H
2
b g
b
'
A rxn
<
A
0 r
dz
dC
U
dz
C d
D
A
'
A
Ab
2
Ab
2
AB
= +
Application to PBRs
Shell balance on
volume element AAz

Mole flux of A

First order reaction
0 r
dz
dW
b
'
A
Az
=
U C
dz
dC
D W
Ab
A
AB Az
+ =
Ab a
'
Ab
'
A
C kS r r O = O =
0 C kS
Ab a b
= O
0 C kS
dz
dC
U
dz
C d
D
Ab a b
Ab
2
Ab
2
AB
= O +
Application to PBRs
Axial dispersion negligible
(relative to forced axial
convection) when
d
p
is the particle diameter
U
o
is the superficial velocity of the gas
D
a
is the effective axial dispersion coefficient
a
p o
Ab o
p b
'
A
D
d U
C U
d r
<<

Which can be rewritten as:
Application to PBRs
Which can be rewritten as:
Ab
a b Ab
C
U
kS
dz
dC
|
.
|
\
|
O
=
Entrance condition:
o
Ab
0 z
Ab
C C =
=
Integrating and applying boundary condtion yields:
|
.
|
\
|
O
=
U
z kS
exp C C
a b
Ab Ab
o

Heat and Mass Transfer Resistances

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Heat and Mass Transfer Resistances

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Ch E 542 - Intermediate Reactor Analysis & Design

Heat and Mass

identify boundary conditions

understand the Thiele modulus

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