Chemical and Catalytic Reaction Engineering

EXERCISES (PART I: CATALYSIS)

1. List the most important scientific journals in catalysis.

2. How would you best explain catalysis to friends who know nothing about
chemistry and chemical engineering?

3. Can a catalyst change the composition of a gas mixture in equilibrium?

4. Nickel metal successfully catalyzes the hydrogenation of double bonds in

unsaturated hydrocarbons such as propylene and butene. Can this metal also
catalyze the dehydrogenation of alkanes such as propane and butane?

5. Define an elementary step and point out how it differs from an overall reaction.

6. Can a catalytic reaction be an elementary step?

7. Under what conditions may reactions start to oscillate? Give one example of
oscillating reaction.

8. What are the aims of catalyst characterization in the context of (a) industrial
catalysis and (b) fundamental research?

9. The outlet of an industrial reactor for the production of biogas contains 0.4 mol/s
CH4, 5 g/s CO2, 120 L/min H2 and 12% (molar basis) H2O steam. Calculate (a)
the selectivity of each product, (b) the selectivity on a dry basis, and (c) the
selectivity of carbon-containing compounds. If the process can yield up to 72%
methane on a dry basis, which is the efficiency of the reactor?

10. Demonstrate that the specific surface area of a spherical particle (in m2/g) is
S=3000/(R), where  is density (g/cm3) and R is radius (nm).

11. For each of the following techniques, give a description of the principles, the sort
of information yielded about a supported catalyst, and a brief assessment of
strengths and weaknesses. (a) X-ray diffraction, (b) X-ray photoelectron
spectroscopy, (c) Temperature-programmed reduction and temperature-
programmed oxidation, (d) Transmission electron microscopy. Which of the
techniques listed above requires a vacuum as a measurement environment, and
why?

12. For an oxide material the TPD profile of ammonia desorption as a function of
temperature is given below. What information can you derive from it?
13. What are the major requirements of a solid catalyst that is to be applied in an
industrial process?

14. How does a gas environment affect the surface composition of alloys?

15. What determines the shape of a metal particle in a vacuum? What determines
the shape of a metal particle on a substrate?

16. Propose a simple recipe for preparing the reduced form of a 2 wt% Pd on SiO 2
catalyst. For what type of reaction(s) can this catalyst be used?

17. Why catalyst powders are usually pressed into bodies of particular shapes?

18. What is the purpose of a calcination step in solid catalyst preparation?

19. State the major advantages of supercritical drying for the preparation of
catalysts.

20. Describe qualitatively the consequences of transport limitations on the apparent

activation energy of a catalytic process by using an Arrhenius plot. What is the
best temperature to run a reaction in an industrial application?

21. What is the difference between the intrinsic and extrinsic rate of a catalyst?

22. What is the most important property to consider when designing a catalyst for an
industrial process: (a) the rate per catalytically active site; (b) the rate per unit
weight of catalyst; or (c) the rate per unit volume of catalyst? Explain your
answer.

23. What is the essential difference between physisorption and chemisorption?

24. How does the chemical reactivity of a metal atom depend on its coordination
number?
25. Why do many catalytic reactions exhibit a “volcano” behavior as a function of
adsorption strength of products and/or reactants?

26. Give a number of sources for the production of synthesis gas, and also a number
of applications of synthesis gas.

27. Describe the potential of the Fischer–Tropsch process as a source of

transportation fuels.

28. Give a short description of the methanol synthesis, and answer the following: (a)
What are the dominant surface species? (b) Can methanol be synthesized from
CO2 and why would that be of interest?

29. Summarize the key points of the water-gas shift reaction. What are the dominant
surface species?

30. Why are the methanol and water gas shift process always coupled?

31. What is the difference between electronic and structural promoters?

32. Explain the Mars–van Krevelen mechanism and give one example of its
occurrence.

33. Why is the automotive exhaust catalyst called a three-way catalyst?

34. Why does an automotive exhaust catalyst have a control system to regulate the
composition of the air–fuel mixture? How is this control performed?

35. Under what driving conditions does a car emit the most polluting exhaust?

36. Describe the SCR-process for the removal of NOx from stationary power plants.
Which reactants are usually used for the SCR process?

37. Is SCR technology suitable for application in mobile sources of NOx such as
trucks and ships?

38. Dehydrogenation of n-hexane is carried out on a PtSn/SiO2 catalyst at 200°C

and atmospheric pressure. The rate constant of the reaction under these
conditions is 0.5 s-1. Taking into account that the pores in the silica support have
a mean radius of 15 nm and that the diffusion constant of n-hexane is DAB=0.065
cm2 s-1, estimate the dimensions of the pellets of this catalyst to attain an
efficiency of 75%.

39. We have to choose between two different catalysts in a chemical plant to run the
Bazarov process, which is the industrial production of urea from ammonia and
carbon dioxide at 110 atm and 160°C:

CO2 + 2 NH3  NH2CONH2 + H2O.

 The two catalysts are Pt/MgO (2% wt. Pt) and Fe/SiO2 (15% wt. Fe) and their
performance during the first month of operation is reported in the following table.

Pt/MgO Fe/SiO2
Time (days) kgurea/(day x kgcatalyst) molurea/(day x gcatalyst)
2 355 6.3
4 305 6.1
6 270 6
8 245 5.8
10 230 5.7
12 220 5.5
14 210 5.3
16 205 5.2
18 200 5
20 197 4.8
22 195 4.7
24 193 4.5
26 192 4.3
28 191 4.2
30 191 4

Before starting operation in the plant, an ammonia conversion (%) vs. temperature
(in °C) graph was recorded over each catalyst. The same curves were repeated after
the first month of operation, and the results are provided below:

fresh fresh
1 month 1 month

a) Which catalyst would you use to operate the catalytic reactor for, at least, half a
year?
b) What is the reason of the deactivation of each catalyst?
c) How would you reactivate the catalyst you have chosen?
40. A process occurring in biorefineries is xylose dehydration into furfural:

Two acid catalysts have been tested: Al2O3 y ZrO2, with specific surface areas of 118
and 81 m2/g, respectively. Their behavior at atmospheric pressure and 150°C in an
identical packed bed reactor is:

catalyst gcat kg/h xylose furfural

Al2O3 20 0.1 0.9
0.2 0.9
0.4 0.475
0.8 0.25
1.6 0.125
ZrO2 24 0.1 0.3
0.2 0.3
0.4 0.3
0.8 0.3
1.6 0.15

a) Which catalyst is more active?

b) Which catalyst shows more severe mass transport problems?
c) If cost and stability are similar, which catalyst would you use?

41. Two catalysts were used for the production of dimethylcarbonate (DMC) from the
reaction between CO2 and methanol (CO2 + 2CH3OH  (CH3O)2CO + H2O).
Table 1 reports the yield (%) of DMC obtained at different temperatures over 10
g of each catalyst in a packed bed reactor with exactly the same geometry by
using a feed stream of 400 g/h of methanol and 20 mol/h of CO 2. Catalyst A is
constituted by copper nanoparticles of 6 nm in diameter supported over zinc
oxide (10% Cu weight). Catalyst B contains ruthenium nanoparticles of 2 nm in
diameter over aluminum oxide (8% Ru weight). The same tests performed over
the catalysts after 4 months of continuous operation yielded different results
(Table 1). Which of these catalysts would you choose for practical application?
Explain in detail your answer and provide details on which characterization
techniques would you use to support your conclusions.
Table 1. Yield of DMC

Catalyst A Catalyst B Catalyst A Catalyst B

T/K fresh fresh used used
300 2 2 0 2
350 8 5 4 4
400 16 12 8 10
450 60 40 18 38
500 85 88 55 58
550 100 95 80 75
600 100 99 95 86
650 100 100 100 94
700 100 100 100 98
750 100 100 100 100