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= δ is used;

W As = k c ( C A − C As )
– kc is the convection mass transfer coefficient
Mass Transfer & Reaction
W As = k c ( C A − C As )
– 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:
Nu = 2 + 0.6 ⋅ Re ⋅ Pr
12 13

h ⋅ dp v ⋅ dp ν
Nu = Re = Pr =
kt µ αt
Mass Transfer & Reaction
• By the heat/mass transfer analogy:
Sh → Nu h → kc
Sc → Pr k t → D AB

– for flow around a sphere, the convective

heat transfer coefficient can be found from:
Sh = 2 + 0.6 ⋅ Re ⋅ Sc 12 13

k c ⋅ dp v ⋅ dp ν
Sh = Re = Sc =
D AB µ D AB
Mass Transfer & Reaction
molar flux to catalyst surface = reaction rate on surface

k c ( C A − C As ) = WAs = −rAs " = k r C As

k cCA
k c ( C A − C As ) = k r C As C As =
kc + kr
k ck r C A
− rAs " =
kc + kr
Fast Reaction Kinetics
fast reaction kinetics k r >> k c

k ck r C A k ck r CA
− rAs " = ≅ = k cCA
kc + kr kr

 D AB  1 2 1 3
k c = 0.6  Re Sc Frössling Correlation
 d 
 p 
12 13
 D AB  vdp   ν 
k c = 0.6 
   
 d  ν
 p    D AB 
 D2AB3  v 1 2 
k c = 0.6 1 6  1 2 
 
 ν  dp 
Fast Reaction Kinetics
fast reaction kinetics k r >> k c
− rAs " ≅ k c C A
D 23

 AB
 = f ( T )  D2AB3  v 1 2 
ν
16
 k c = 0.6 1 6  1 2 
 
 ν  dp 
as T ↑
 v1 2 
D AB ↑   ≠ f ( T) to increase kc
d 
1 2
 p 
ν gas ↑ v↑

ν liquid ↓ dp ↓
Slow Reaction Kinetics
slow reaction kinetics k r << k c

k ck r C A k ck r CA
− rAs " = ≅ = k r CA
kc + kr kc

kr is independent of
• fluid velocity
• particle size
Reaction and Mass Transfer
( )
k r ⋅ kc vdp ⋅ CA
( )
kc vdp := vdp
0.5
( )
rAs vdp :=
k r + kc(vdp)

0.1

0.08
reaction
rate limited
0.06

rAs (vdp)
0.04

0.02
mass
transfer
limited
0
0 5 10 15
0.5
vd p
Rate Units for Catalytic Reaction
− rA ' = −rA " ac ac ≡ surface area / gram

6
ac =
ρc dp for single pellets

6 6( 1 − φ )
ac = = for packed beds
ρB dp dp
Example Calculation
• The irreversible gas-phase reaction A→B 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 Re½
• Neglecting pressure drop, calculate catalyst weight
necessary to achieve 60% conversion of A for
– isothermal operation
– adiabatic operation
Example Calculation
Mole Balance Mass Transfer Coefficient

dX
FAo = −rA ' Sh = 100 Re½
dW
12
 k c dp   vd 
Rate Law   = 100 p 
 D AB   ν 
− rAs ' = k r ' C As 12
 D AB  vdp  cm3
WA = k c ( C A − C As ) k c = 100   = 4242
 d  ν  s⋅g
 p  
k ck r ' CA
− rAs ' =
kc + kr '
assume reaction is mass transfer limited − rAs = WA
Example Calculation
Mole Balance Stoichiometry gas-phase, ε = 0, T = T0, P = P0.

FAo
dX
= −rA ' C A = C Ao (1 − X )
dW

Rate Law Energy Balance

k k 'C Reaction is being carried

− rAs ' = c r A out isothermally. Thus,
kc + kr '
• energy balance not needed
cm3 • and kr ≠ f(T)
k c = 4242
s⋅g
Example Calculation
Mole Balance Stoichiometry gas-phase, ε = 0, P = P0.

dX To
FAo = −rA ' C A = C Ao (1 − X )
dW T

Rate Law Energy Balance

− rAs ' =
k ck r ' C A X( − ∆Hr )
T= + Tio
kc + kr ' ∑ FioCpi
E 1 1 
 − 
k r ' ( T ) = k ro ' e
R  TR T 

cm3
k c = 4242
s⋅g
Multicomponent Diffusion

• Exact form of the flux equation for

multicomponent mass transport:
N−1 N
Nj = − ∑ C D ∇y − y ∑ N
k=1
t jk k j
k=1
k , j = 1,2, ,N− 1

• A simplified form uses a mean effective

binary diffusivity, N
Nj = −CtDjm∇yj − yj ∑N
k=1
k
Multicomponent Diffusion

• The Stefan-Maxwell equations (Bird, Stewart,

Lightfoot) are given for ideal gases:
N
− Ct∇yj = ∑
1
( ykNj − yjNk )
k=1 Djk
k≠ j

1
− Ct∇y1 =
• For binary system: [N1 − y1( N1 + N2 ) ]
D12
Multicomponent Diffusion

• Solved for flux N1 = −CtD12∇y1 + y1( N1 + N2 )

• Simplified for
assumed equimolar N1 = −CtD12∇y1
counter-diffusion

1
− Ct∇y1 = [N1 − y1( N1 + N2 ) ]
D12
Multicomponent Diffusion

• The effective binary diffusivity for species j

can then be defined by equating the driving
force terms of the expression containing Djm
and the Stefan-Maxwell
N
Nj = −Ct∇yjDjm − yj ∑N
k=1
k

N
− Ct∇yj =
1
∑ ( ykNj − yjNk )
k=1 Djk
k≠ j
Multicomponent Diffusion

• The effective binary diffusivity for species j

can then be defined by equating the driving
force terms of the expression containing Djm
and the Stefan-Maxwell
N  N
Nj = Djm ∑
1
 k=1 Djk
( ykNj − yjNk )  − yj Nk
 ∑ k=1
 k≠ j 
Multicomponent Diffusion
N

∑
1
( ykNj − yjNk )
1 k=1 Djk
k≠ j
= N
Djm
Nj − yj ∑N
k=1
k

• use for diffusion of species 1 through

stagnant 2, 3,… (all flux ratios are zero for
N
k=2,3,…) reduces to 1 1 yk
the "Wilke equation" D = 1− y
1m D
∑
1 k=2,3 1k
Multicomponent Diffusion
• For reacting systems where steady-state flux
ratios are determined by reaction N
j
stoichiometry, = constant
αj
N
1  α k 
1
∑ D 
yk − yj
α  1 N
1  α k 
 
∑
k≠ j jk j
= = yk + yj
Djm N
αk 1+ δ jyj 
k≠ j Djk  α j 
1− yj ∑
k=1 α k
Diffusion/Rxn in Porous
Catalysts
• Effective Diffusivity (De) 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 (φ P)
– Diffusion paths are tortuous (τ )
– Pore cross-sections vary (σ ) D A φP σ
– Internal void fraction, ε s = φ P σD e = ~
τ
Diffusion/Rxn in Porous
Catalysts
• Extended Stefan-Maxwell
N(jD)
( )
N
−1 1
RT
∇pj = ∑
k=1 De,jk
ykN(jD) − yjNk( D) +
De,Kj

• Solved for binary, steady-state, 1D

diffusion
CD  1− ( 1+ N N ) y ( L) + D D 
t e,AB B A A e,AB e,KA
NA = ln 
L( 1+ NA NB )  1− ( 1+ NB NA ) yA0 + De,AB De,KA 
Diffusion/Rxn in Porous
Catalysts
• Define effective binary diffusivity
for use in single reaction
multicomponent systems:
dCj
Nj = −De,jm
dz
1 N
1  α k  1
= ∑
De,jm k=1 De,jk 
yk − yj +
α j  De,Kj
Quantify De

• 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
Diffusion/Rxn in Porous Catalysts
rate in at r rate of generation within shell
WAr 4πr 2 rA' ρc 4πrm2 ∆r
r
reaction rate catalyst mass
× × shell volume
rate out at r + ∆ r catalyst mass shell volume

WAr 4πr 2
r + ∆r
steady state mass balance
R
r+∆ r
r WAr 4πr 2 − WAr 4πr 2
r r + ∆r

+ rA' ρC 4πrm2 ∆r = 0

(
d WAr r 2 )
− rA' ρCr 2 = 0
A →
 B
cat dr
Diffusion/Rxn in Porous Catalysts
(
d WAr r 2)− rA' ρCr 2 = 0
rate equation
dr definitions

substitute Fick’s Law − rA" = k nC2A

dC A
WAr = −De − rA' = Sak nC2A
dr
− rA = ρCSak nC2A
d dC A 2  '
 − De r  − rA ρCr 2 = 0
dr  dr 

d dC A 2  " n 2 2
 − De r  − rkAnSCaAρSCraρC=r 0 = 0
dr  dr 
Diffusion/Rxn in Porous Catalysts
d2 ϕ
 2d ϕ A 2knSaρCRn 2CnAs−1 2 n
dC dimensionless
2 −+De − r  − k nC A SaρCrϕ= =
00
dλ λ ddr
dr λ   De  CA r
ϕ= λ=
C As R
d2C A 2  dC A   k nS a ρ C  n
+   −  C A = 0
dr 2
r  dr   De  dC A
= C As
dϕ
identify boundary conditions dr 1
=
symmetry C A r =0 = finite dλ R

C A r =R = C As dC A dϕ C As
surface =
dr dλ R
Diffusion/Rxn in Porous Catalysts
d2 ϕ 2 dϕ  k nSaρCR 2CnAs−1  n
+ −  ϕ = 0
d λ λ dλ 
2
De 
2 n −1
k S ρ R C As
define Thiele modulus (φ n) φn =
2 n a C
De
d2 ϕ 2 dϕ
+ − φ nϕ = 0
2 n

dλ λ dλ
2

understand the Thiele modulus

k nSaρCRCnAs reaction rate large φ - diffusion controls

φ =
2 n

De ( C As − 0 ) R
n
diffusion rate small φ n - kinetics control
Diffusion/Rxn in Porous Catalysts
first order d2 ϕ 2 d ϕ k nS a ρ C 2
kinetics + − φ1ϕ = 0
2 φ =
2
1 R
(n = 1) dλ λ d λ
2
De

dϕ 1  dy  y
define y = ϕ λ =  − 2
dλ λ  dλ  λ d2 y
− φ1y = 0
2

d2ϕ 1  d2 y  2  dy  2y dλ 2

=  2  − 2   + 3
dλ2
λ  dλ  λ  d λ  λ

differential has the solution apply boundary conditions

y = A 1 cosh φ1λ + B1 sinh φ1λ λ = 0, ϕ is finite
A1
ϕ= λ
cosh φ1λ + Bλ1 sinh φ1λ λ = 1, ϕ = 1
Diffusion/Rxn in Porous Catalysts
first order d2 ϕ 2 d ϕ k nS a ρ C 2
kinetics + − φ1ϕ = 0
2 φ =
2
1 R
(n = 1) dλ λ d λ
2
De

1  sinh φ1λ  C A d2 y
ϕ =   = − φ1y = 0
2
λ  sinh φ1  C As dλ 2

differential has the solution apply boundary conditions

y = A 1 cosh φ1λ + B1 sinh φ1λ λ = 0, ϕ is finite
A1
ϕ= λ
cosh φ1λ + Bλ1 sinh φ1λ λ = 1, ϕ = 1
Thiele Modulus
ϕ

CA
=ϕ
C As
Internal Effectiveness Factor
(η )
• The internal effectiveness factor (η ) is
a measure of the relative importance of
diffusion to reaction limitations:
actual overall reaction rate
η≡
rate if entire surface were exposed to C As , Ts

− rA − rA' − rA" MA
η= = ' = " = M ≡ mol / time
r ≡ mol / time / mass cat
− rAs − rAs − rAs MAs
Internal Effectiveness Factor
(η )
• Determine MAs (rate if all surface at CAs)
 surface area 
MAs = ( rate per unit area ) ×   × ( mass catalyst )
 mass catalyst 

MAs = − rAs
'
x VρC

k 1C As x Sa

MAs = k1C AsSa 34 πR 3ρc

Internal Effectiveness Factor
(η )
• Determine MA (actual rate is equal to
reactant diffusion rate at outer surface)
dϕ
MA = 4πRDeC As
dλ λ =1
MA = 4πRDeC As ( φ1 coth φ1 − 1)

dϕ  φ1 cosh λ φ1 1 sinh λ φ1 
=  − 2  = φ1 coth φ1 − 1
dλ λ =1  λ sinh φ1 λ sinh φ1  λ =1
Internal Effectiveness Factor
(η )
• Substitute results into definition of η
MA 4πRDeC As ( φ1 coth φ1 − 1)
η= =
MAs k1C AsSa × 34 πR 3ρc
De
=3 ( φ1 coth φ1 − 1)
k1SaR ρc
2

3
η = 2 ( φ1 coth φ1 − 1)
φ1
Internal Effectiveness Factor (η )
φ1 → 0 small dp

η →1

η
φ1 > 2
η ≈ φ32 ( φ1 − 1)
1

φ1 > 20
3
η≈ 3
= 3 De η = 2 ( φ1 coth φ1 − 1)
φ12 R k 1ρc S a φ1
Internal Effectiveness Factor (η )
φ1 → 0
internal
η →1 diffusion
reaction limited
rate
η limited

φ1 > 2
η ≈ φ32 ( φ1 − 1)
1

φ1 > 20
3
η≈ 3
= 3 De η = 2 ( φ1 coth φ1 − 1)
φ12 R k 1ρc S a φ1
Revisit φ and η

• Thiele modulus - φ
– Derived for spherical particle geometry
– Derived for 1st order kinetics
12
• For large φ , approximately  2  3
η= 
 n + 1 φ12

• Internal effectiveness factor - η

– Assumed ε =0, correction applied when ε ≠ 0
– Assumed isothermal conditions
Non-Isothermal Behavior
• For exothermic reactions, η can be > 1 as internal
temperature can exceed Ts.
• The rate internally is thus larger than at the surface
conditions where η is evaluated.
• The magnitude of this effect is dependent on
∆ Hrxn , Ts, Tmax , and kt (thermal conductivity of the pellet)
∀ γ and β are used to quantify this effect:
E Tmax − Ts ∆HrxnDeC As
γ= ≡ ( Arrhenius Number ) β= =
RTs Ts k t Ts
– can result in mulitple steady states
β γ< 4(1 + β )
– No multiple steady states exist if Luss criterion is fulfilled
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 actual conditions, rather
overall reaction rate
Ω≡
than surface conditions:
rate if entire surface were exposed to C A,bulk
Overall Effectiveness Factor
• Accounting for reaction both on and within the pellet, the
molar rate becomes:

MA = −rA" ⋅ [ ac + Saρc (1 − φ) ] ∆V
ρb

WA ac = −rA" ⋅ [ ac + Saρb ]
• For most catalyst, internal surface area is significantly
higher than the external surface" area:
WA ac = −rA Saρb
Overall Effectiveness Factor
reaction rate WA ac = −r Saρb
"
A
(internal & external surfaces)

internal surfaces not

all exposed to CAs
mass transport rate

WAr ac ∆V = k c ( C A,bulk − C As ) ⋅ ac ∆V
Relation between CAs and CA − rA" = −rAs
"
η = ηk 1C As
defined by the η as:

WA ac ∆V = ηk 1C AsSaρb ∆V

k c ( C A,bulk − C As ) ⋅ ac = ηk 1C AsSaρb
Overall Effectiveness Factor
reaction rate WA ac = −r Saρb
"
A
(internal & external surfaces)

mass transport rate

WAr ac ∆V = k c ( C A,bulk − C As ) ⋅ ac ∆V
Relation between CAs and CA − rA" = −rAs
"
η = ηk 1C As
defined by the η as:

ac k c C A,bulk
Solving for CAs : C As =
ac k c + ηk 1Saρb
Overall Effectiveness Factor
reaction rate WA ac = −r Saρb
"
A
(internal & external surfaces)

mass transport rate

WAr ac ∆V = k c ( C A,bulk − C As ) ⋅ ac ∆V
ηk1k c ac C A,bulk
Substitution into the rate law: − rA =
"

ac k c + ηk1Saρb
ac k c C A,bulk
Solving for CAs : C As =
ac k c + ηk 1Saρb
Overall Effectiveness Factor
summary of factor relationships:
− rAs
"
= k1C As
(
− rA" = Ω − rA" ,bulk = η − rAs
"
) ( ) −r "
= k 1C Ab
Ab

Rearranging the expression:

η ηk1k c ac C A,bulk
k 1C A,bulk = − rA =
"
1 + ( ηk 1Saρb k c ac ) ac k c + ηk1Saρb

η
−r = Ω −r
"
A ( "
A ,bulk ) Ω=
1 + ( ηk1Saρb k c ac )
Overall Effectiveness Factor (Ω )
Weisz-Prater Criterion
• Weisz-Prater Criterion is a method of determining if a given
process is operating in a diffusion- or reaction-limited regime
– CWP is the known as the Weisz-Prater parameter. All
quantities are known or measured.

− r '
R 2
ρc
C WP = η φ1 =
2 A ,obs

DeC As
– CWP << 1, no ∇ C in the pellet (kinetically limited)
– CWP >> 1, severe diffusion limitations
Mears’ Criterion
• Mass transfer effects negligible when it is true that
− rA' Rρbn
< 0.15
k c C Ab
– n is the reaction order, and the transfer coefficients kc 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
( )
− ∆Hrxn − rA' ρbRE
< 0.15
2
hR gTb
Application to PBRs
• Shell balance on dWAz
volume element A∆ z − rA' ρb = 0
dz
dC A
• Mole flux of A WAz = −D AB + C AbU
dz
• First order reaction − rA' = −rAb
'
Ω = ΩkS aC Ab

2
d C Ab dC Ab
D AB 2
− U + Ω
rAρA
'
=0
bkS a C Ab = 0
dz dz
Application to PBRs

• Axial dispersion negligible

(relative to forced axial − r ρb dp
'
A Uo dp
<<
convection) when… UoC Ab Da
– dp is the particle diameter
– Uo is the superficial velocity of the gas
– Da is the effective axial dispersion coefficient

Which can be rewritten as:

d2C Ab dC Ab
D AB 2
−U + ΩρbkS aC Ab = 0
dz dz
Application to PBRs
Entrance condition: C Ab z =0
= C Abo

Integrating and applying boundary condtion yields:

 ΩρbkS a z 
C Ab = C Abo exp − 
 U 
Which can be rewritten as:

dC Ab  ΩρbkS a 
= − C Ab
dz  U 