CHEN 30041/30051/64111-11

1 hours

The University of Manchester

Catalytic Reaction Engineering

For candidates taking
B.Eng. Chemical Engineering, Third Year
B.Eng (Ord). Chemical Engineering, Third Year
M.Eng. Chemical Engineering, Third Year
M.Eng. Chemical Engineering with Environmental Technology, Third Year
M.Eng. Chemical Engineering with Biotechnology, Third Year
M.Eng. Chemical Engineering with Industrial Experience, Third Year
M.Eng Chemical Engineering with Chemistry, Third Year
M.Eng Chemical Engineering (Business Management), Third Year
M.Eng. Chemical Engineering with Study in Europe, Fourth Year
B.Eng. Chemical Engineering with Industrial Experience, Fourth Year

???day ??th January 2011

?:?? ??:??
_____________________________________________________________________
Answer TWO questions
_____________________________________________________________________
Electronic calculators may be used, provided that they cannot store text.
All numerical working must be shown. Graph paper will be provided.
Tables of mathematical formulae are available and may be used without restriction.

Dr A Garforth

(0161 306 8850)

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CHEN 30041/30051/64111-11

CATALYTIC REACTION ENGINEERING

Answer any TWO questions
1.

Answer ALL parts (25 Marks in Total)

a)
i. Determine the equilibrium conversion for the elementary reaction,
AB
carried out in aqueous solution, between 0 oC and 100 oC.
Present your results in the form of a plot of conversion versus temperature. You
may assume no change in specific heat capacity and hence,
ln

H r 1 1
K

K 298
R T 298

where T is the temperature of reaction, K is the equilibrium constant and H r is

the enthalpy of reaction at temperature T K.
DATA for Question 1 part (a)
CpA

= CpB = constant

H 298
G 298
E
R

= 75.30 kJ mol1
= 14.13 kJ mol1
= 8.89 104 J mol1
= 8.314 J mol1 K1
[11 Marks]

ii. What restrictions will you need to place on the operation of the reactor to obtain
a conversion of 75% or higher?
[2 Marks]
b) Explain the following brief statements on the characteristics of heterogeneous
catalytic reactions:
i. Catalytic activity is dependent upon the physical state of the catalyst.
[2 Marks]
ii.

Chemisorption on a surface is responsible for catalytic activity

[4 Marks]

iii. Although catalysts do not change equilibria, they change the product
composition by influencing the reaction pathway. Exemplify your answer with
one example of a petrochemical reaction path where the yields of products have
been altered by a change in the catalyst used.
[6 Marks]
(End of Question 1)
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CHEN 30041/30051/64111-11

2.

Answer ALL parts (25 Marks in Total)

a) Name THREE zeolites commonly used in a refinery context stating the process in
which they are used.
[3 marks]
b) Name and discuss briefly FOUR techniques frequently used to characterise metalloaded catalysts and supports.
[4 marks]
c) Indicate how the volumetric rate of reaction in the fixed bed of catalyst is related to
surface rates of reaction.
[3 marks]
d)
i. A dual site mechanism for the reaction A + B C + D gives the following
expression for the rate of the surface reaction of A:

rA

k1s K A K B C AC B k 2 s K C K D CC C D
1 K AC A K B C B K C CC K D C D 2

Where;
k1s and k2s are the rate constants for the forward and reverse reaction,
Ki = the adsorption equilibrium constant, where i = A, B, C, D ,
Ci = the concentration of component i, where i = A, B,C, D.
With the aid of a sketch of the dual site mechanism, explain the meaning of the
symbols appearing in the above expression.
[5 marks]
ii.

Under what circumstances would the above complex rate equation

reduce to the simpler behaviour which is first order in reactant A and negative
first order in reactant B?
[4 marks]

iii. The dimensionality of the surface reaction kinetics expression shown in part d i)
above, can be reduced by performing initial rate measurements using equimolar
feeds of A and B, so that the total pressure can be used as a single discriminating
variable for identifying the correct surface reaction model.
Show how this approach is applied to the above example and deduce an
expression for the variation of the initial rate of surface reaction with total
pressure.
[6 marks]
(End of Question 2)

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CHEN 30041/30051/64111-11

3.

Answer ALL parts (a to f)

(25 Marks in Total)

a) Explain why catalysts tend to have an upper limit of surface area of around 1000
m2 g1.
[2 marks]
b) Sketch a Langmuir Adsorption isotherm and show how it alters with temperature.
[3 marks]
c) For a first order reaction, sketch the dimensionless concentration profile for the
idealized cylindrical pore model under conditions of strong diffusional resistance.
[3 marks]
d) Explain how the cylindrical pore model leads to the following expression for an
average pore diameter;
_
r = 2Vp / Sg
[2 marks]
e) The Table below shows data on specific surface area (Sg) and pore volume (Vp) for
a range of industrial catalysts samples. By making reference to this table, answer
the following.
i.

Which material has probably the lowest reactivity and why?

[2 marks]

ii.
iii.

Which material has probably the highest diffusional resistance?

[2 marks]
What is the least mass (g) of material (chosen from the Table below) that
would have a surface area equal to one football field (approximately 100 m
70m)?
[3 marks]

(Q3 continued on the next page)

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CHEN 30041/30051/64111-11

Q3. Continued.
f)

For a catalytic process, describe how the observed activation energy changes with
temperature for each of the following controlling regimes;
i.

mass transfer,
[2 marks]

ii.

pore diffusion
[2 marks]

iii.

surface reaction.

[2 marks]
In each case suggest how the overall reaction rate might be improved at a given
temperature.
[2 marks]

(End of Question 3)

End of paper

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