Week 5 – Workshop (Solutions)

Heterogeneous catalysis
CHEE3005
 Why Catalysis?
• Q1. 1Worldwide, more than ______% of all chemical products are manufactured with
the help of catalysts?
a) 50

b) 40

c) 85

d) 95

• Q2. 2The value of goods produced with the help of catalysts amounted to ___billion
US$ in 2005
a) ~ 9 billion

b) ~ 90 billion

c) ~ 900 billion

1 J. Chem. Educ. 2012, 89, 1530-1536 2

2 U.S. Climate Change Technology Program − Technology Options for the Near and Long Term. http://www.climatetechnology.gov/library/2005/tech-options/tor2005-143.pdf, accessed May 16, 2012.
Exercise 2
Catalyst X is used in reactor 1 where the rate-determining step is a
surface reaction. It is also loaded into reactor 2 operating at the same
temperature, but where external mass transfer is slow and limits the
reaction. The reaction rate in reactor 1 is ___________ that in reactor 2.

A. greater than
B. less than
C. equal to
Reactant A diffuses to the surface of a non-porous catalyst pellet where the
reaction A → B takes place. The reaction is at steady-state and is limited by
diffusion. If the reaction is so fast that CA at the surface is essentially zero,
what is the rate of reaction at the catalyst surface? The mass transfer
coefficient is kM.
CA

A. 4πR2kMCA R
B. 4/3πR3kMCA
C. 4πR2kMCA2
D. kMCA
Two reactors have the same volumes and feed flow
rates, but reactor 1 has 60% void volume and reactor 2
has 35% void volume. Both reactors contain the same
amount of catalyst. Which reactor has the higher
conversion for an isothermal reaction?
60% void volume
Reactor 1:
35% void volume
Reactor 2:
A. Reactor 1
B. Reactor 2
C. Same conversion in both
Exercise 3
Hydrogenation of ethylene

R1 (kf1,kb1): C2H4 + X ⇌ 𝐶2𝐻4. 𝑋 Rate controlling step

R2 (kf2,kb2): H2 + C2H4.X ⇌ 𝐶2𝐻4. 𝑋. 𝐻2
R3 (kf3,kb3): C2H4.X.H2 ⇌ 𝐶2𝐻6 + X

Determine a rate expression for the reaction assuming that each of the steps above is
elementary.
 ⎯⎯ → C2 H 4 . X
k
( A  C2 H 4 . X )
f1
R1: C 2 H 4 + X ⎯⎯
kb1

⎯⎯→
k
( B  C 2 H 4 . X .H 2 )
f2
R2: H 2 + C 2 H 4 . X ⎯⎯ C 2 H 4 . X .H 2
kb 2

⎯⎯→
f3 k
R3: C 2 H 4 . X .H 2 ⎯⎯ C2 H 6 + X
kb 3

r1 = k f 1CC 2 H 4 Cv − kb1 C A
 1 
r2 = k f 2CH 2 C A − kb 2 C B = k f 2  CH 2 C A − CB 
 K2 
 1 
r3 = k f 3 C B − kb 3CC 2 H 6 C v = k f 3  C B − CC 2 H 6 C v 
 K3 
R 1 as rate determining step → R 2 and R 3 are relatively fast (quasi-steady)
1
r2 k f 2  0  CH 2 C A − C B = 0  C B = K 2C H 2 C A
K1
1 K CB
r3 k f 3  0  C B − CC 2 H 6 C v = 0  C v = 3
K3 CC 2 H 6
Use active site balance: C m = C v + C A + C B
K3 C B
C m = + C A + K 2C H 2 C A
CC 2 H 6
K 2 K 3CH 2 C A
C m = + C A + K 2C H 2 C A
CC 2 H 6
Cm K 2C H 2 C m K 2 K 3CH 2 C m
→ CA = ; CB = ; Cv =
 K 2 K 3CH 2   K 2 K 3CH 2  K K C 
 C + K C
2 H2 + 1  C + K C
2 H2 + 1 CC 2 H 6  2 3 H 2 + K 2CH 2 + 1
 C 2H 6   C 2H 6   CC 2 H 6 

These relationships can be used to formualte rate expression for any species, i.e. for C2 H 4 :
rC 2 H 4 = − r1 = − k f 1CC 2 H 4 Cv + kb1 C A
K K C C Cm Cm 
 rC 2 H 4 = − k f 1  2 3 C 2 H 4 H 2 + 
 EC C 2H 6 K1 
E
K K C 
where E   2 3 H 2 + K 2CH 2 + 1
 CC 2 H 6 

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Exercise 4
Exercise 4
A packed bed reactor uses catalyst for a first order irreversible reaction of reactant A (g). The catalyst are non-
porous spherical particles with a solid density of 2,500 kg/m3 and Sg=0.06 m2/kg. The packed bed of catalyst has
a voidage of 0.4. The reactor is fed with 1 m3/s of gas. The reactor is cylindrical with an internal diameter of 25
cm and a length of 1 m. The diffusivity of A in the inert gas is 0.3 cm2/s. The mass transfer coefficient is 0.48 m/s.
The conversion of A at the exit of the reactor is 0.78.

What is the k” for the catalyst? Assume that the adsorption/desorption, and internal transport are fast and do not
impact reaction kinetics and that the surface reaction is first order.

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Exercise 5
A stream contains small amounts of butane is catalytically oxidized in a fluidized bed
reactor. The catalyst comprises of nonporous particles of density 3.0 g/cm3 and
diameter 3.0 mm. The reaction is effectively first order in butane concentration, with
air being far in excess. The reactor is maintained isothermal at 450 K, and there are
no heat transfer resistances. At this temperature the effective surface reaction rate
constant has the value ks = 0.05 m/s.

Determine the conversion of butane if the design flow rate of the butane air mixture
at 450 K is 7.0 lit/s, with 3 kg of catalyst in the reactor. Assume the fluid phase is
completely micro mixed as in a CSTR.

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 Solution
Assume: - Isothermal - Constant volumetric flow rate - Steady State
Assume: - Completely micro-mixed
dN A
= 0 = FA0 − FA + rAV
dt
rAV = rA  ( Total catalyst area )
Total catalyst area = S g mc
0 = vC A0 − vC A − k sC A S g mc
vC A0
CA =
v + k s S g mc

where Sg is surface area per unit mass, and mc is mass of catalyst. For nonporous
particles of radius rp and density p, the surface area per unit mass is given as:
4 rp2 3
Sg = =
(4 r / 3)  p
3
p rp  p
CA 1
 =
C A0 1 + 3k s mc ( v  p rp )  For v = 7.0 lit/s, and substitution of the values of ks, mc,
 
ρp and rp yields CA/CA0 = ???

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Thanks!