CHEN30041/30051/30251

One hour + One hour technical time

THE UNIVERSITY OF MANCHESTER

Catalytic Reaction Engineering

[29th January 2021]

[09:00 – 11:00]

Answer both questions in this exam paper

Total 50 marks

Electronic calculators may be used in accordance with the University regulations.

Tables of mathematical formulae may be used without restriction.

You may use your notes and other material related to the course.

© The University of Manchester, 2021

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Potentially Useful Equations

Symbols have their usual meanings.

𝑑𝐶𝐴 𝐷𝐴𝐵
𝑁𝐴 = 𝐷𝐴𝐵 = (𝐶𝐴𝑏 − 𝐶𝐴𝑠 ) = 𝑘𝑐 (𝐶𝐴𝑏 − 𝐶𝐴𝑠 )
𝑑𝑥 𝛿
𝑈𝑑𝑝 𝜈 𝐷𝐴𝐵
𝑅𝑒 = 𝑆𝑐 = 𝑘𝑐 = 𝑆
𝜈 𝐷𝐴𝐵 𝑑𝑝 ℎ

𝑑𝐶𝐴 𝑑𝐶 𝜀𝑝 𝐷𝐴𝐵
−𝑈 + 𝑟"𝐴 𝑎𝑐 = 0 𝑁𝐴 = −𝐷𝑒 𝐷𝑒 =
𝑑𝑧 𝑑𝑥 𝜏

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𝑑 𝑑𝐶𝐴 2
[−𝐷𝑒 𝑟 ] + 𝑟 "𝐴 ρ𝑐 𝑆𝑎 𝑘"𝑛 𝐶𝐴 𝑛 = 0
𝑑𝑟 𝑑𝑟
1 1
𝜂= (𝑐𝑜𝑡ℎ3𝜙𝐿 − )
𝜙𝐿 3𝜙𝐿

C𝐴 1 sinhϕ λ
1
= ( ) For a 1st order reaction
C𝐴𝑠 λ sinhϕ 1

−𝑟′𝐴(𝑜𝑏𝑠) ρ𝑐 𝑅2
𝐶𝑤 = ηϕ12 =
𝐷𝑒 𝐶𝐴𝑆

Paper continues/…

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Question 1 [25 marks in total].

1.
a. Oxidation of carbon monoxide on platinum group metals (PGMs) surfaces is
one of the most widely studied subjects in surface chemistry as a model
system of heterogeneously catalyzed reactions:
CO+ ½ O2 → CO2
There are several mechanisms that one can imagine for such a reaction on a
metal surface. One particular interesting mechanism is the Mars van Krevelen
mechanism:
zO2 + 2Pd  2PdOz
PdOz + zCO → zCO2 + Pd
In simplistic symbolic form with z = 1, the reaction mechanism is:
O2 + 2S  2O•S
O•S + CO → CO2 + S
If the surface reaction is rate limiting, by using an available site balance derive
the rate law that describes the overall rate of this system.
[15 marks]

b. An aqueous NaOH solution was used to absorb CO2 in a packed bed tower.
The rate of the reaction can be written as
−𝑟𝐴 = 𝑘2 ∙ 𝐶𝐴 ∙ 𝐶𝐵
where CA and CB are the concentrations of CO2 and NaOH, respectively.
At the interface of a specific location inside the tower, the partial pressure of CO2
is 2.0310–3 MPa, the concentration of NaOH is 0.5 mol L–1 and the temperature
is 20 C. Assuming pseudo first order kinetics, determine the Hatta number,
enhancement factor and absorption rate at this point.

Given:
kL = 110–4 m s–1,
k2 =10 m3 s–1 mol–1,
the solubility constant of CO2 HA = 3.8510–7 kmol m–3 Pa–1, and
the diffusion constant of CO2 in the solution DAL = 1.810–9 m2 s–1.

[10 marks]

End of Question 1.
Paper continues/…

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Question 2 [25 marks in total].

2.
The catalytic isomerization of n-butane to isobutane is carried out in an industrial
packed bed reactor with solid catalyst particles at 460 °C and 3 bar with an initial
n-butane concentration of 49.2 mol m–3. Pure n-butane with a molar feed of
5 000 mol h–1 n-butane is fed to the reactor and the rate law is given by:

2
−𝑟′𝑛−𝑏𝑢𝑡𝑎𝑛𝑒 = 0.2 ∙ 𝐶𝑛−𝑏𝑢𝑡𝑎𝑛𝑒

Where −𝑟′𝑛−𝑏𝑢𝑡𝑎𝑛𝑒 units is mol kg–1 h–1

𝐶𝑛−𝑏𝑢𝑡𝑎𝑛𝑒 unit is mol m–3

a. Calculate the amount of catalyst (kg) needed if the amount of n-butane at the
outlet of the reactor is 30 mol m–3. Show your full working. Assume isothermal
and isobaric operation with no external or internal mass transfer effect.
[7 marks]

b. Independent from question 2(a), it was decided to use 1 000 kg of catalyst.

The catalyst deactivates by sintering (second order decay). The value of the
decay constant at 460 °C is known to be 3 day–1. Calculate how many days
this catalyst can be used, if the highest accepted amount of n-butane at the
outlet of the reactor is 30 mol m–3. Show your full working. Assume isothermal
and isobaric operation with no external or internal mass transfer effect.
[10 marks]

c. Independent from question 2(a) and 2(b), assume isothermal operation, with
no external or internal mass transfer effect and no catalyst deactivation.
Calculate the amount of catalyst (kg) needed if the amount of n-butane at the
outlet of the reactor is 30 mol m–3 and the effect of pressure drop is taken into
account with a pressure drop parameter α = 0.0085 kg–1. Show your full
working.

[8 marks]

End of Question 2.

END OF EXAMINATION PAPER

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