Graduate

Seminars on

Chemical Reac4on Engineering and Kine4cs

October 12- Nov 4, 2010

Lecture 5:
Fixed Bed Catalytic Reactors!
Brian G. Higgins
Department of Chemical Engineering and
Materials Science
University of California, Davis

Email: bghiggins@ucdavis.edu
Lecture notes posted at
hNp://www.ekayasolu4ons.com

Multiple Scales for Reactor Analysis

xed bed reactor

inters>>al pores

catalyst pellet

From: Rawlings and Ekerdt: Chemical Reactor Analysis and Design Fundamentals, 2002

Catalyst Pellet
catalyst support
(alumina)

catalyst site
(Pt, Ni, Ru)

pores

void volume
support volume
pellet volume: V = Vs + Vg

Ms
Vs

bulk density of pellet:

Vg
porosity of pellet: =
V

b
=1
s

density of support: s =

or

Surface area of support from 0.5 m2/g to 100 m2/g

b =

Ms
V

Transport/Reaction Sequence for Catalyst Pellet

(Step 1) Transport of reactants/energy up to catalyst exterior surface

(Step 2) Transport of reactants from surface to interior of pellet

Transport/Reaction Sequence for Catalyst Pellet

cont.

species O2 CO
adsorp>on

species
surface reac>on

desorp>on

(Step 3) Adsorp>on, reac>on, desorp>on at cataly>c surface

Transport/Reaction Sequence for Catalyst Pellet

cont.
(Step 4) Transport of products from catalyst surface to external surface of pellet

(Step 5) Transport of products into the bulk uid

Coupling of transport
and chemical reac>on
lead to concentra>on
and temperature
gradients in pellet

Rates of individual steps determine overall rate of reac>on in pellet

Rate Limiting Steps

(i) Intrapar>cle transport controlled - Step (2):

If this is the slow step in process, then system said to be diusion limited.

(ii) Kine>c or reac>on controlled- Step (3)

If surface reac>on is the slow step in process , then system is reac>on limited.

(iii) External transport controlled Step (1)

If transport of bulk reactants to catalyst pellet surface is the slow step, then system
is external transport limited.

Diffusion Limited versus Reaction Limited

z
CA ()

JA

JsA

CA (z)
CA (0)

A
B

Diusion ux:
Reac>on ux:

dCA
CA () CA (0)
JA = D
D
dz

JsA = k CA (0)

Thiele modulus:

reaction rate
=
=
diusion rate

Diusion limited:

>> 1

Reac4on limited

<< 1

CA (0) 0

k 2
D

CA (0) = 0

First-Order Reaction in Catalyst Pellet

RA = k CA

A
B
1 d
D 2
r dr
dCA
= 0, r = 0
dr

Solu>on:

k(R/3)2
D

2 dCA

dr

kCA = 0

CA = CAs , r = R

CAs sinh( r)
CA (r) =
r sinh(3 )

Thiele modulus

3r
r =
R

Concentration Profiles in Catalyst Pellet

1.0

A C A s

0.8

Out[42]=

0.2

reactant can penetrate par>cle,

i.e., reac>on limited

0.5

0.6
0.4

0.2

0.0
0.0

0.5

1.0

r 3 r R
1.5

2.0

2.5

3.0

reactant concentra>on nearly

zero except near surface
i.e., diusion limited

As

0 , diusion is very fast rela>ve to reac>on kine>cs, thus reactant
molecule can diuse to center of par>cle before being consumed.

Effectiveness Factor for Catalyst Pellet

Volume average rate of produc>on:

R AP

1
=
V

RA (r)4r2 dr

Rate of produc>on at surface concentra>on:

RAS = k CAS
Eec>veness factor:

R AP
=
R AS

For =
1 , en>re volume of pellet is reac>ng at the same high rate
For

0
, pellet reacts at low rate; reactant unable to penetrate into pellet

Effectiveness Factor versus Thiele Modulus

1
1
1
=

tanh(3) 3

1.00
0.50

=1

0.20
0.10

Out[52]=

0.05
0.02
0.01
0.01

0.1

10

100

For =
1 , en>re volume of pellet is reac>ng at the same high rate
For

0
, pellet reacts at low rate; reactant unable to penetrate into pellet

RA = k CA

A
B

R = 0.3 cm

DA = 0.007 cm2 /s

PA = 0.7 atm

p = 0.85 g/cm2

T = 450 K
pellet produc>on rate species A:

A = 2.5 105 mol/(g s)

R

What is the rate constant?

What is the Thiele modulus?
What is the eec>veness factor for pellet?

rate constant

pellet radius

k(R/3)2
Thiele Modulus:
=
D
diusivity

1
1
1

Eec>veness factor: =
tanh(3) 3
Volume rate of produc>on:

RAP = RAS
surface rate of produc>on

Goal: for given data determine

, k,

RAP = RAS

RAS = k CAf

RAP = k CAf

1
1
1
=

tanh(3) 3

k(R/3)2
D

1
1
RAP R2 /9

=
tanh 3 3
DA CAs
Solve for

(Thiele modulus)

CAS

0.7 atm
5
3
=
=
1.90

10
mol/cm
3 atm
(82.06 cm
mol K )(450 K)

RAP = (2.5 10

5 mol

g
mol
)(0.85 3 ) = 2.125
gs
cm
cm3 s

1
1

= 1.60
tanh 3 3
=

k(R/3)2
D

1
1
1
=

tanh(3) 3

=1 .93
k = 2.61 s1
= 0.685

Mass Transfer Eects

External ow round pellet can impede transport of
reactants/products to and from catalyst pellet

CA
CAf

region of external mass

transfer resistance

ux from uid to pellet surface

dCA
JA = D
= km (CAf CA )
dr

mass transfer coecient

km a
Biot Number: Bi =
D
Bi

No mass transfer resistance!

radius of catalyst pellet

Mass Transfer Eects cont.

Concentra>on proles

CA

decreasing Biot number

CAf

Eec>veness factor

Mass transfer resistance in

external phase makes catalyst
less ecient

Controlling Mechanism in Catalyst Pellet

Mechanisms:
CA

(i) Reac>on controlled

(ii) Internal diusion controlled
(iii) External mass transfer controlled

CAf

Controlling mechanisms for pellet reactions

Biot Number
Bi < 1

Thiele modulus
< Bi
Bi < < 1
1<

1 < Bi

<1
1 < < Bi
Bi <

Mechanism controlling rate

reaction controlled
external mass transfer controlled
both external mass transfer
and internal diusion controlled
reaction controlled
internal diusion controlled
both internal diusion
and external mass transfer controlled

First-order, isothermal fixed bed reactor

k

N Af

A
B

volume of catalyst /volume reactor:

Species balance:

RA = k CA

(1 b )

dNA
= RA
dV

Mass transfer resistance unimportant

RA = (1 b ) k CA
porosity of bed

eec>veness factor

Find catalyst mass to convert 97% of reactant A

First-order, isothermal fixed bed reactor

k

N Af

A
B

RA = k CA

Addi>onal Data
Feed pure A:

MA = 12 mol/s

Inlet pressure:

P = 1.5 atm

Pellet radius:

R = 0.3 cm

Reactor temperature: T = 450 K

Bed density:

b = 0.6 g/cm3

First-order, isothermal fixed bed reactor

RA = k CA

A
B

N Af
Solu>on Strategy:

Step 1: Determine Thiele Modulus:

0.3 cm
k(R/3)2
=
3
D

2.6 s 1
= 1.93
0.007 cm2 /s

Step 2: Determine Eec>veness factor:

1
1
1

tanh(3) 3

1
1
=
[1
] = 0.49
1.93
5.78

Step 3: Concentra>on of A in terms of molar ows:

CA =

P
RT

NA
NA + NB

ideal gas approxima>on

N A + N B = N Af
from stoichiometry

First-order, isothermal fixed bed reactor

k

A
B

N Af

RA = k CA

dNA
= (1 b ) k CA
dV

Species balance:

97% conversion

Integrate:

VR = (1 b )
VR =
Catalyst weight:

0.6
0.85

R T N Af
kP

0.03NAf

NAf

dNA
NA

(82.06)(450)(12)
ln(0.03) = 1.32 106 cm3
(0.429)(2.6)(1.5)

0.6
W c = b V R =
(1.32 106 ) = 789 kg
1000