ChE426 Final Exam 2005

King Saud University
College of Engineering
Chemical Engineering Department
ChE 426: Heterogeneous Reaction Engineering
:
Summer 1425/1426 (2005) Final Exam Prof. Ibrahim S. Al-Mutaz
1-a Derive the Langmuir isotherm for adsorption of species A in a non-reacting system. State all
the necessary assumptions in your derivation.
1-b Carbon monoxide (CO) oxidation can be illustrated by the following two steps:
O2 + 2S 2O.S
O.S + CO → CO2 + S
If the surface reaction is rate limiting, derive the rate law that described the overall rate.
1-c To remove oxides of nitrogen (assumed to be NO) from automobile exhaust, a scheme has been
proposed that uses unturned carbon monoxide (CO) in the exhaust to reduce the NO over a
solid catalyst, according to the reaction: CO + NO → products (N2, CO2)
Experimental data for a particular solid catalyst indicate that the reaction rate can be well
represented over a large range of temperatures by:
k PN PC
− rN =
(1 + K 1 PN + K 2 PC ) 2
PN = gas phase partial pressure of NO, PC = gas phase partial pressure of CO and k, K1 and K2 are
coefficients depending only on temperature. Develop an adsorption-surface reaction-desorption
mechanism that will fit the experimentally observed kinetics.
2-a Catalyst deactivation can be very costly in industrial processes and complicates operation of
full-scale fixed-bed reactors. Describe how catalyst deactivation can be accounted for in a
catalytic process by defining the general expression for a reaction rate law for a gas-phase
reaction with separable kinetics. Also explain the various parameters included in this rate law.
2-b A product is manufactured by the following reversible isomerization reaction: A (g)  B  (g)
The reaction is carried out over a supported metal catalyst in an isothermal fixed-bed flow reactor.
The reaction is elementary. The equilibrium constant for the reaction is 8.5 at 350°C and 6.0 at
380°C. The activation energy is 75x103 kJ/kmol. Side reactions have a negligible effect on yield,
but they slowly deactivate the catalyst. To increase the reaction rate and to partly offset
deactivation, the temperature is raised from 350°C to 380°C. At the end of an operating cycle, the
catalyst is dumped and replaced.
Alternatively the catalyst is to be regenerated in place by treatment with a special chemical of
proprietary composition. The cost seems to be attractively low compared to catalyst replacement.
This option guarantees to achieve:
1) at least 90% of fresh catalyst activity, or
2) at least 2 times the activity of spent catalyst.
The catalyst regeneration procedure was tested in the laboratory using a plug-flow reactor which is
a down-scaled version of the reactor in the plant. This test was compared to earlier tests for fresh
and spent catalysts. The volumetric flow was 1.2 m3/h (at 350 °C) in all cases. Review the
following data and determine whether the guarantee described above was met assuming that the
pressure drop and the influence of temperature on flow rate in the temperature interval 350-380°C
can be neglected.
Case Catalyst Temp., °C Conversion of A at reactor outlet, %
1 Fresh 350 75
2 Spent 380 65
3 Regenerated 350 70
3-a Gaseous reactant diffuses through a gas film and reacts on the surface of a solid according to a
reversible first order rate, -r” = ks (Cs - Ce). Develop an expression for the rate of reaction
accounting for both the mass transfer and reaction steps. What would be the rate of reaction if the
rate of surface reaction has the form of the Langmuir-Hinshelwood adsorption equation?
k C
−r " = 1 s
1+ k 2 C s
3-b In the kinetic investigation of a hydrogenation catalyst the following normalized reaction rates
were observed under identical reaction conditions.
Characteristic catalyst core dimension (cm) 0.445 0.0635

Reaction rate [µmol/g.cat.s] 4.5 7.0
The catalyst particles have the same geometric shapes in both the cases the void fraction of the fixed
bed is identical. Is there a limitation of reaction rate by pore diffusion:
a) In the 0.445 cm catalyst particle?
b) In the 0.0635 cm particle?
If yes, estimate the value of the effectiveness factor.
4-a The irreversible, first-order reaction of gaseous A → B occurs in spherical catalyst pellets with
a radius of 2 mm. The molecular diffusivity of A is 1.2 x 10-1 cm2 s-1 and the Knudsen diffusivity
is 9 x 10-3 cm2 s-1. The intrinsic first-order rate constant determined from detailed laboratory
measurements was found to be 5.0 s-1. The concentration of A in the surrounding gas is 0.01
mol/L. Assume the porosity and the tortuosity of the pellets are 0.5 and 4, respectively.
(a) Determine the Thiele modulus for the catalyst pellets.

(b) Find a value for the internal effectiveness factor.
(c) For an external mass-transfer coefficient of 32 s-1 (based on the external area of the
pellets), determine the concentration of A at the surface of the catalyst pellets.
(d) Find a value for the overall effectiveness factor.
4-b .Cyclohexane decomposes to benzene and hydrogen by the first order reaction
C6H12 → C6H6 + H2 − rC"6 H 12 = k c C C 6 H 12 , gmole/cm2 s
the reaction is external mass transfer limited at high temperature and carried out in 5-cm ID
pipe packed with cylindrical pellets 0.5 cm in diameter and 0.5 cm in length. The pellets are
coated with the catalyst only on the outside. The bed porosity is 40%. The entering volumetric
flow rate is 600 liter/min. Calculate the length of the pipe necessary to achieve 95%
conversion.
Additional Data:
DAB = 0.856 cm2/s, ρ= 0.00019 g/cm3, µ=0.00017 g/cm.s
Thoenes-Kramers correlations for mass transfer coefficient is given by:
1/ 2
k cd p φ 1  Ud p ρ 1 1  µ 1/ 3
( )( )( ) = ( )( )( )  ( )
DAB 1 − φ γ  µ 1−φ γ  ρDAB
Good Luck

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King Saud University

Characteristic catalyst core dimension (cm) 0.445 0.0635

(a) Determine the Thiele modulus for the catalyst pellets.

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