L -24 : External Mass Transfer

Effects

Prof. K.K.Pant
Department of Chemical Engineering
IIT Delhi.
kkpant@chemical.iitd.ac.in
Mass transfer and reaction in a
packed bed
Steady state mole balance on reactian A

3
• Mole balance in flux form, where Ac is
constant and FA = AcWAz

dWAz
- + rA' ρb = 0
dz
where
dC Ab
WAz = -D AB + C AbU and
dz
U = superficial velocity
hence
d2C Ab dC Ab
A ρb = 0
'
D AB 2
- U + r
dz dz
 For mass transfer controlled reaction CA>>CAS

=>
 Therefore variation of reaction rate along the length

To investigate the effect of flow rate and T on conversion correlation for mass
transfer coefficient.

For flow through packed bed: Thoenes and Kramers relation ( modified
numbers)

6
7
Monolith Reactors/ Wire Gauge

8
EX.: A mass transfer limited reaction is being carried out in two reactors of equal
volume and packing, connected in series. The conversion is 86.5 at this condition. If
the reactors are placed in parallel and flow rate is divided equally in to two to
decrease the pressure drop. What will be conversion in this case?

For a mass transfer controlled reaction

Z=0, CA= CA0

9
Solve for X2

10
 Diffusion and Reaction in a Porous Catalyst
Effective Diffusivity: Bulk diffusion ( Large pore)and
Knudsen diffusion(small pore) Dk(cm2/s)=9.7 *103 r (cm) (TK/M)1/2

D c φpσ c
De =

where
Actual distance a molecule travels btw 2 points
τ = tortousity =
S hortest distance btw 2 points
Volume of void space
φp = pellet porosity =
Total volume( voids and solids)
σ c = Constriction factor, f(  )
Effective Diffusivity: Pores are not straight cylindrical.
These are a series of Tortuous, interconnecting paths of
varying cross sectional area.

Pellet porosity = volume of void space/ total volume

(voids and solids)

Constriction factor , (ϭ )accounts for the variation in the

cross sectional area that is normal to the diffusion. It is a
function of the ratio of maximum to minimum pore areas
(β).

Ϭ= f(β), ϭ=1 if β=1. Ϭ=0.5 if β= 10. Typical Ϭ value=0.8.

tortuosity, t = 3.0
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 Derivation of the Differential Equation
~ Diffusion and Reaction in a spherical pellet

d (WAr r )2 Moles = WAr (4 πr2)r

 rA c r 2  0
dr
dy A dC A
WAr  cDe   De Molar flux
dr dr
In – out – disappearance =0
WAr (4 πr2)r - WAr (4 πr2)r+∆ r - rA’ (4 πr2 c ∆r) =0
Dividing by -4 π ∆ r

Boundary
d [ De (dC A / dr )r 2 ]
 rA c r 2  0 conditions
dr =r+Δr

Order of r=0, CA finite, r=R, CA=CAS

-rA=c(-r’A)
reaction?
 Let’s simply consider 1st order
d[ De (dC A / dr )r ]
2

 rA c r  0
2

dr
c(-r’A) =-rA volumetric
-rA=kCA
d [ De (dC A / dr )r 2 ] 2
 r k1C A  0
dr Differentiation &
Divide by –r2De

What about n-th order ?

d [ De (dC A / dr )r 2 ] 2
 r knC An  0 Differentiation &
Divide by –r2De
dr
Let’s simply consider 1st order
d C A 2  dC A  k1
2
    CA  0
dr 2
r  dr  De

What about n-th order ?

d C A 2  dC A  kn n
2
    CA  0
dr 2
r  dr  De
 Dimensionless Form of the Equation
• Dimensionless symbol was normally introduced to
– Reduce complexity in equation
– Simplify operation of calculation
– Scale-up the reactor
Let = CA/CAs and =r/R
dCA/dr= (dCA/dλ)(dλ/dr)= (d/d λ)(dCA/d) x
(dλ/dr)
=> dCA/dr = (d/d λ)(CAS /R)
d2CA/dr2= d/dr(dCA/dr)= (d2/d λ2)(CAS /R2)
When
CA=CAs at r=R,  =1 and =1
CA=finite at r=0,  =finite and =0
 Dimensionless eq. – 1st order

d 2C A 2  dC A  k1 d 2 2  d  2
    CA  0     1   0
dr 2
r  dr  De d r  dr 
2

Thiele
Module k1 R 2
De
About for n-th order ?
d C A 2  dC A  kn n
2
d 2
 2  d  2 n
    CA  0     n  0
dr 2
r  dr  De d r  dr 
2

n 1
Thiele k n R 2C As
Module De
 Thiele Modulus, n
2 n-1 n
k R C k RC "a" surface reaction rate
φn =
2 n As
= n As
=
De De [(CAs - 0)/R] "a" diffusion rate
•If n is large – internal diffusion limits the
overall rate
•If n is small – the surface reaction limits the
overall rate C 1  sinhφ λ 
ψ= A
= 
1

CAs λ  sinhφ1 
y=  
d2y/d 2 - ø2y=0
y= A Cosh ø  + B Sinh ø 
A=0 as φ must be finite
at the centre
 (B. C =0, cos h ø  1;
1/ ∞, and Sinh ø 0.
 Calculation of Catalytic Effectiveness Factor
Catalytic Effectiveness Factor:

  1 (Coth3  1 )
where  3
- Thiele Modulus
1st order reaction rate:
  R kSap / De
Spherical Pellet 3
Cylindrical Pellet  R kSap / De
2
Slab Pellet

  L kSap / De
 Internal Effectiveness Factor
Actual overall rate of reaction
η=
Rate of reaction that would result if entire
interior surface were exposed to the external
pellet surface conditions C As ,Ts
• Internal
effectiveness -rA -rA' -rA"
η= = ' = "
Factor,  is: -rAs -rAs -rAs
ranged 0 – 1
•  for a first-order 3
η = 2  φ1cothφ1 -1
reaction in a φ1
spherical catalyst
pellet
Internal Effectiveness Factor
 Falsified Kinetics
• Measurement of the apparent reaction order
and activation energy results primarily when
internal diffusion limitations are present.

• This becomes serious if the catalyst pellet

shape and size between lab (apparent) and
real reactor (true) regime were Too different.

• Smaller catalyst pellet  reduces the diffusion

limitation  higher activation energy  more
temperature sensitive 
• RUNAWAY REACTION CONDITIONS!!!!
 Falsified Kinetics
• Apostrophe/ prime sign denotes the
apparent parameter vice versa
• With the same rate of production, reaction
order and activation energy to be measured
 Rate of reaction, -rA’
= (Actual overall rate of reaction) divided by
(rate that would result if the entire surface
were exposed to the bulk conditions, CAb, Ts)

η
Ω=
1+ηk1Saρb /k c ac
"

-r = Ω(-r ) = Ωk CAb
"
A
"
Ab
"
1

-rA = -r ρ = -r Saρb = Ωk CAbSaρb

'
A b
"
A
"
1
Mass transfer and reaction in a packed bed –
cont.
d2CAb
• Axial diffusion,Da can be neglected when
dz 2
U0 dp -rA' ρb dp
Da
>>
U0CAb
FA is very large

dCAb  Ωρbk "Sa 

• so = -  CAb
Remember the
forced
dz  U 
convection in
• Finally, the conversion for binary external
diffusion, JA is
1st order reaction in PBR is also neglected

CAb
X =1- =1- e-(ρbk"SaΩL)/U
CAb0
 Determination of limiting situation from
reaction data

Type of Variation of Reaction Rate with:

Limitatio
Particle
n
Velocity Size Temperature
External
U½ (dp)-1/2  Linear
diffusion
Internal
Independent (dp)-1 Exponential
Diffusion
Surface Independe
Independent Exponential
Diffusion nt