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Norges teknisk-naturvitenskapelige universitet

Institutt for kjemisk prosessteknologi

EKSAMEN I EMNE TKP 4155 / KP 8903

REAKSJONSKINETIKK OG KATALYSE
REACTION KINETICS AND CATALYSIS

Contact person / Faglig kontakt:

Professor Magnus Rønning tlf.: 918 97 585

Eksamensdato: Onsdag 5. desember 2012

Eksamenstid: 0900 - 1300
Hjelpemidler: D - Ingen trykte eller håndskrevne hjelpemidler tillatt.
Bestemt, enkel kalkulator tillatt.

Date: Wednesday December 5. 2012

Time: 0900 - 1300
Helping aids: D – No written or typed documentation is allowed.
Simple, defined calculator is allowed.

Language: English. Answers can be submitted in English or Norwegian

Number of pages: 4 (starting on page 2)
Appendix: 2 pages (starting on page 6)

Sensurfrist: Mandag 7. januar 2013

Evaluation deadline: Monday January 7. 2013
___________________________________________________________________________
Merk! Studentene må primært gjøre seg kjent med sensur ved å oppsøke sensuroppslagene. Evnt. telefoner om sensur må
rettes til instituttet eller sensurtelefonene. Eksamenskontoret vil ikke kunne svare på slike telefoner.
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Problem 1. (25%)

Hydrogenation of CO (the Fischer-Tropsch synthesis) is carried out in a standard fixed-bed

laboratory reactor over a series of Co/Al2O3 catalysts at the following conditions: Temperature
and pressure at the outlet of the reactor are 220ºC and 1 bar. The molar ratio between H2 and CO
in the feed is 2. GHSV = 30000 cm3 (STP)(CO+H2)/g cat. hour. It is assumed 1. order kinetics
and spherical particles.

CO + 2H2 → -CH2- + H2O (1)

a) For one of the catalysts (12 weight% Co) a conversion of CO of 6 % was obtained.
The dispersion of Co was determined to be 3.1%. Calculate the reaction rate for the
conversion of CO.

b) Calculate the turnover frequency (specific reaction rate) for the catalyst above.

c) The activity can be increased by promoting the catalyst with Re. For a Co-Re/Al2O3
catalyst (12 weight% Co) with particle diameter 0.5 cm and average particle density
1.33 g/ cm3 the conversion is 15% at otherwise identical conditions as stated for the
unpromoted catalyst above. Use the Weisz-Prater criterion to evaluate if intra-particle
diffusion limitations are present. Deff = 6.5·10-2 cm2/sec. Given: Molar weight of Co:
58.9, and 1 mol = 22414 cm3 (STP, that is, at 25ºC and 1 bar). Gas constant, R = 82.05
cm3 atm/mol K.

d) Briefly discuss the product distribution in Fischer-Tropsch synthesis and how this is
optimised for fuel production in modern GTL plants.
Anderson–Schulz–
Product distribution in GTL Fischer-Tropsch synthesis: Flory (ASF)

– The product distribution follows the ASF-distribution except for C 1 and C 2

– Only methane and wax (C 20+ ) can be produced with high selectivity

– Modern F-T technology is therefore based on high yield of wax which

Problem 2. (25%) subsequently can be decomposed (cracked) to diesel and petrol fuel

The catalytic cracking of cumene (isopropylbenzene) over silica-alumina has been studied at
510˚C:

Cumene (C)  Propene (P) + Benzene (B) (1)

It is suggested that this reaction either can involve one active site (single site):

∗⇌ ∗ (2)

or two active sites (dual site):

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∗ ∗⇌ ∗ ∗ (3)

where * represents an active site on the catalyst surface.

a) Derive the Langmuir-Hinshelwood rate expression for the single site mechanism by
assuming that reaction (2) is the rate determining step.

b) Derive the Langmuir-Hinshelwood rate expression for the dual site mechanism by
assuming that reaction (3) is the rate determining step.

c) The feed contains not only cumene, but also a component A. Co-cracking of A and C over
the same catalyst may be described by the following reactions:

→ (4)

→ (5)

Show how the selectivity for the formation of benzene (B) depends on the diffusion
conditions in the porous silica-alumina catalyst. Both reactions are of 1. order and you can
assume isothermal conditions. For large values of the Thiele modulus (s) the following
relation is valid for the effectiveness factor ():

(6)

d) Diffusion in porous materials can take place through bulk diffusion or through
Knudsen diffusion. What are the principal differences between the two diffusion
modes?

Problem 3. (25%)

Isomerisation of 1-butene to 2-butene can be performed using specific nickel hydride complexes.
The figure below presents a likely mechanism for the reaction using a 16-electron [HNiL3]+
catalyst. The ligand L is a neutral ligand:
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a 7

a) Iddentify the type

t of reacction in the reactions I to IV in thhe cycle.

mber of valence electrons and thee oxidation state of Nii in the mettal complex
b) Sttate the num xes
innvolved.

Which step in the catalyytic cycle determines

c) W d i isomerization will take
if t place, or
o simply a
ree-productionn of the 1-bbutene?

d) Exxplain why
y an 18-elecctron metal hydride coomplex is not able to catalyse
c thiss reaction.

Problem 4. (25%)

Michel Boudart
B statted that ‘thee steady-staate approxim
mation (SS SA) can be considered
c as the mosst
important general teechnique off applied chhemical kinnetics.’ It caan be applieed both for
homogenneous and heterogeneo
h ously catalyysed reactioons.

The folloowing mechhanism has been propoosed for thee water-gas shift reactiion (WGS)) over Cu-
based cattalysts:
W
WGS: →

∗ ⇌ ∗ (1)

∗→ ∗ (2)

∗→ ∗ (3)

∗ ∗→ 2∗ (4)
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a) Derive a rate expression which is consistent with the above mechanism. Use the steady-state
approximation on the reactive surface intermediates. It can be assumed that the surface
concentration of O atoms is negligible.

b) Make a sketch of how the heat of adsorption depends on the surface coverage of an adsorbate
on a typical metal catalyst surface. Give a possible explanation for the dependency.

c) The decomposition of acetaldehyde:

proceeds via methyl radicals, CH3:

 
→ (5)

 
→ (6)
 
→ (7)

2 → (8)

Derive the rate expression for the formation of CH4 by using the steady state assumption.

d) Pt-Re/Al2O3-Cl catalysts are used in catalytic reforming of naphtha. Catalysts used for
increasingly longer periods at the Mongstad refinery have been analysed. Sample R401 has
been used for a short time, whereas sample R404 has been used for the longest period.

The naphtha reforming catalysts used in industrial units are exposed to several deactivation
mechanisms. Use the table below to discuss the deactivation mechanisms that can be
identified from the data.

Analyses of used reforming catalysts from the Mongstad refinery:

R401 R402 R403 R404
Surface area (m /g) 155
2
130 123 117
Pore size r (Å) 50 62 70 72
Sulphur (wt%) 0.01 0.02 0.02 0.08
Cl (wt%) 1.07 0.75 0.63 0.41
Coke (wt%) 0.59 1.06 2.25 4.23
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Appendix 1: Equation and formula chart, TKP 4155

dC
Ficks’ law: N   Dp [mol/s cm2]
dx
3 1
0, 001858T 2 [( M 1  M 2 ) / M 1M 2 ] 2
D12   cm 2 / s 
Bulk diffusion: Ps122 WD

D12q
Effective bulk diffusivity: Deff  cm 2 / s 
t 
T
Knudsen diffusion: DK ,1  9700re cm 2 / s 
M 
1
q2  T  2
Effective Knudsen diffusivity: DK ,eff  19400   cm 2 / s 
tK Sr p  M 

(H ) Deff
Damköhler equation: T  T  TS  (Cs  C )
keff

T (H ) Deff CS
Prater number:  b
TS keff Ts

3  1 1
Effectiveness factor: h   
fs  tanh fs fs 

Mass transfer rate: r  k g a (Cb  Cs )  mole  s 1cm 3 

Constants:

Molar gas volume: 22414 cm3/mol (STP, at 25ºC and 1 bar)

The gas constant, R: 82.05 cm3 atm/mol K

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Transition metals and their number of d electrons in various oxidation states:

Ligands with their typical charges and coordination numbers: