Advanced Chemical Reaction

Engineering
Topic 3A
Solid-Catalyzed Reactions
(Catalysis and
Catalytic Reactors
Chapter 10 Fogler’s Essentials)

1
 CLO3. Determine the rate limiting
step between mass transfer and
kinetics in solid-catalyzed reactions,
and design packed-bed, fluidized bed
and other reactors for various
applications.

2
 CLO3 - Catalysis and
Catalytic Reactors- Contents
• Catalysts, Steps in a Catalytic Reaction, Synthesizing a
Rate Law, Mechanism, and Rate-Limiting Step, Solid-
catalyzed reaction Data Analysis, Reactor Design, Model
Discrimination, Catalyst Deactivation Reaction Engineering
in Microelectronic Fabrication, Chapter 10: Essentials of
CRE by Fogler;
• External Mass Transfer- Chapter 11: Elements of CRE by
Fogler;
• Internal Diffusion and Reaction- Chapter 12: Elements of
CRE by Fogler;

3
 Topic Learning Outcomes
• Describe the steps in a catalytic mechanism and how one
goes about deriving a rate law and a mechanism and rate
limiting step consistent with the experimental data.
• Use Regression to discriminate between reaction rate
laws and mechanisms.
• Size isothermal reactors for reactions with Langmuir-
Hinschelwood kinetics.
• Discuss the different types of catalyst deactivation and the
reactor types and describe schemes that can help offset
the deactivation.
• Analyze catalyst decay and conversion for CSTRs and
PFRs with temperature-time trajectories, moving bed
reactors, and straight through transport reactors.
• Describe the steps in Chemical Vapor Deposition(CVD).
4
 Contents of this Presentation

• Basic Catalysis & Reaction Mechanisms

• Steps in a Heterogeneous Catalytic Reaction
• Adsorption, Surface Reaction and Desorption
• Derive a Rate Law for Catalytic Rxn
• Evaluating a Catalytic Reaction Mechanism
• Collecting and Analyzing Data
• Solid-catalyzed Reactor Design
• Catalyst Deactivation

5
 L18-6

Types of Catalysts

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 Importance Of Catalysis

 90% of all chemical processes use

catalysts
 Changes in catalysts have a giant
influence on rates and selectivity’s of
reactions.
More than anything else
 Most real reactor design associated with
optimizing performance of catalyst

7
 Catalysis Definition

Ostwald defined a catalyst as a substance

which changed the rate of reaction
without itself being consumed in the
process

Not being consumed  catalyst does change

8
Catalytic Reaction Occurs Via A
Catalytic Cycle:

reactants + catalyst  complex

complex  products + catalyst

9
 Example: Rhodium Catalyzed
CH3OH+COCH3COOH
CH3COOH CH3OH
HI

H2O

CH3COI CH3I
[Rh(CO)2I2]-

C
O CH3
I I I I
H3C Rh Rh
C I I

C
O C C
O
O O
CO
Figure 12.1 A schematic of the catalytic cycle for Acetic acid production via the
Monsanto process.

Printing press analogy

10
 The Rate Enhancement Of A Number Of
Reactions In The Presence Of A Catalyst

Reaction Catalyst Rate Temperature

Enhancement
Ortho H2  Para H2 Pt (solid) 1040 300K
2NH3N2 + 3H2 Mo (solid) 1020 600K
C2 H4 + H2  C2 H6 Pt (solid) 1042 300K
H2 +Br2  2HBr Pt (solid) 1  108 300K
2NO + 2H2 N2 + 2H2 O Ru (solid) 3  1016 500K
CH3COH  CH4 + CO I2 (gas) 4  106 500K

CH3CH3  C2H4 +H2 NO2 (gas) 1  109 750K

(CH3)3 COH  HBr (gas) 3  108 750K

(CH3)2CH2CH2+H2O

11
 Examples Of Effects Of Solvent

Table 13.2 The rate of the SN2 reaction NaCl + CH3I  NaI + CH3Cl
at 350 K
______________________________________________________________
Rate Constant, Rate Constant,
Solvent liter/(mol-second) Solvent liter/(mol-second)
______________________________________________________________
Gas phase ~10-45 ______ _______

Water 3.5 x 10-6 Methylcyanide 0.13

Methanol 3.1 x 10-6 Dimethylformamide 2.5

______________________________________________________________

12
 Types Of Catalysts

• Homogeneous catalysts:
Soluble compounds that go in
solutions

• Heterogeneous catalysts:
Solids that sit in reactors

13
 Common Examples Of Catalysts

Homogeneous
Enzymes (detergents,
digestion, tears)

Heterogeneous
Catalytic converter

14
 Effects Of Surface Area

Consider a platinum catalyzed reaction.

You can run the reaction
1) Run the reaction on the wire
2) Take the wire and smash it with a
hammer and then run the reaction.

The rate will be higher on the wire you

smashed with a hammer!

15
 Why Does Smashing A Wire
Change The Rate?

• When you squashed the platinum you

created more surface area.
• You also changed the shape of the
surface which can affect the rate.

16
 Turnover Numbers

Rates of catalytic reactions often expressed

as turnover number

RA
TN =
NS
RA = Rate per unit area (molecules/cm2-sec)
NS = Number of exposed metal atoms /
unit area (Atoms/cm2)
17
Turnover Numbers For Some Typical
Reactions

Dehydrogenation

-1
2 Hydrogenation
10
Turnover Number, sec
0 Silicon
10
Deposition
GaAs
Deposition
-2
10

-4
10 Olefin
Isomerization
Alkane
-6
Hydrogenolysis
10 Cyclization
200 400 600 800 1000 1200 1400
Reaction Temperature, K

18
 Typical Catalytic Kinetics

13
10
Rate, Molecules/cm -sec

450 K 450 K
2

12
10 440 K
440 K
425 K
410 K
415 K
390 K
11
10 -8 -7 -6 -8 -7 -6
10 10 10 10 10 10
CO pressure, torr O 2 pressure, torr

Figure 2.15 The influence of the CO pressure on the rate of CO

oxidation on Rh(111). Data of Schwartz, Schmidt, and Fisher

19
 Typical Catalyst Kinetics

k1PCO PO 2
R CO 
1  K 2PCO  2

Called a Langmuir-Hinshelwood rate

law. Also called Monod rate law.

20
 Temperature Dependence

PO2=2.5E-8 torr PCO=2.E-7 torr

Rate, Molecules/cm 2-sec

1E+13

C
1E+12
F
B E
D
1E+11
A
400 600 800 400 600 800
Temperature, K Temperature, K

Figure 2.18 The rate of the reaction CO

+ 2 O2  CO2 on Rh(111). Data of
Schwartz, Schmidt and Fisher[1986].

21
Catalysts Do Not Work Over A Broad Temp
Range

1000

1
Rate, Moles/lit sec

Catalyst Alone Gas Phase -- No

0.001 Wall Reactions

1E-6
Approximate
1E-9 Effect Of Walls

1E-12

1E-15
0 500 1000 1500 2000 2500
Temperature, K

Figure 12.2 The rate of hydrogen oxidation on a platinum coated pore calculated
with a) only heterogeneous (catalytic) reactions, b) only radical reactions, and c)
combined radical, homogeneous reactions

22
 Types Of Catalysts:

Homogeneous Catalysts
Heterogeneous Catalysts

23
 Homogeneous Catalysts:

 Acids or Bases
 Metal salts
 Enzymes
 Radical initiators

24
 Table 12.2-Some Reactions Commonly
Catalyzed By Acids And Bases

Reaction Example Typical Application

Isomerization CH2=CHCH2CH3  Octane Enhancement

(Rearranging the CH3CH=CHCH3 Monomer Production
structure of a molecule) Paraxylene Production
Alkylation CH3CH=CHCH3 + Pharmaceutical
(Making too little CH3CH2CH2CH3  Production
molecules into a bigger (CH3CH2)CH(CH3)(C4H9) Monomer Production
one) Fine Chemicals
Butane + olefin
octane
Cracking C12H24 C7H14 + C5H10 Crude Oil Conversion
(Taking a big molecule Digestion
and making it into two
littler ones).

25
 Acids And Bases As Catalysts

Benzene  ethylene  ethylbenzene

(12.2)

a proton reacts with the ethylene to form an

ethyl ion:

H   CH 2CH 2   CH 3CH 2 
(12.3)

26
 Acids As Catalysts Continued

The ethyl ion reacts with benzene to yield

and ethylbenzene ion:

  C H  CH CH C H 
 3 2
CH CH 6 6  3 2 6 6
(12.4)

Then the ethylbenzene ion loses a proton:

CH 3CH 2C6H 6   CH 3CH 2C6H5  H 

(12.5)

27
 Solid Acids And Bases As
Catalysts

Table 12.9 Some common solid acids and bases

Material Type Material Type
silica/alumina solid acid Mordenite zeolite
alumina solid acid ZSM-5 zeolite
Y-zeolite zeolite VFI large pore
Faugasite zeolite
Sodalite zeolite Offretite zeolite
HF-SbF5 superacid HSO3F superacid
H2[Ti6O4(SO4)4( superacid Sulfated superacid
OEt)10] Zirconia
MgO solid base Na2O base

28
Very Complex Pore Structure

Figure 12.4 A diagram of the pore structure in Faugasite.

29
 Enzymes As Catalysts

Oxidoreductases (promote Transferases

oxidation reduction reactions) (promote transfer of functional groups)

NADH NADH + H2O2 Dimethylallylcis- Dimethylallyl diphosphate +

peroxidase NAD(+)+2 transferase (Transfer isopentenyl
(Oxidizes H2O. dimethylallyl groups) disphosphatediphosphate +
NADH with dimethylallylcis-
peroxides isopentenyldiphosphate
Ferroxidase 4 Fe2+ + 4 H+ + Glycoaldehyde Sedoheptulose 7-phosphate + D-
(oxidizes O2  4 Fe3+ + 2 transferase glyceraldehyde 3-phosphate  D-
Iron) H2 O (Transfer’s ribose 5-phosphate + D-xylulose
Glucoaldeydes) 5-phosphate
Also called
Transketolase
Glucose -D-Glucose + Alanine L-Alanine + 2-oxoglutarate 
oxidase O2  D- aminotransferase pyruvate + L-glutamate
(oxidizes glucono-1,5- (Transfer amino
Glucose) lactone + H2O2 groups from alanine)

30
Solvents: As Catalysts

CH 3I  NaCl  CH 3Cl + NaI

(12.17)

Table.12.6 The rate of reaction (12.17) in

several solvents. All measurements have
been extrapolated to 25 C
Solvent Rate const,
lit/mole sec
Gas Phase about 10-45
Water 3.5  10-5
Methol 3  10-6
Methyl 0.13
Cyanide
DMF 2.5
31
Next: Heterogeneous Catalysis

Examples of heterogeneous catalysts

include:

 Supported Metals
 Transition Metal Oxides and Sulfides
 Solid Acids and Bases
 Immobilized Enzymes and Other
Polymer Bound Species

32
 Supported Metal Catalysts

Use support because platinum

very expensive and only the
surface is active.

Spread platinum out on cheap

support.

Support also provides strength

Figure.12.3 A picture of a
supported metal catalyst.

33
 Advantage Of Heterogeneous Catalysts
Compared To Homogeneous:
 Cheaper separation
 More selective
 Generally cheaper

Disadvantage
 Not quite as active or a per metal atom
basis

34
Typical Mechanism Of Heterogeneous
Catalysis (H2+C2H4C2H6)

H 2 + 2S  2 H(ad)
(12.18)

C 2 H 4  S  C 2 H 4 ad 
(12.19)

C2 H 4 ad   H ad   C2 H5ad   S

(12.20)

C2 H5ad   H ad   C2 H 6  2S
(12.21)
35
 Summary

 Catalysts make a tremendous difference to

rates
 1013 enhancement average 1040 possible
 Kinetics change – rarely linear
 Optimum conditions often at max rate
 Zero order kinetics

 Two types of catalysts

 Homogeneous
 Heterogeneous
 Homogeneous more active
 Heterogeneous less expensive to use/control

36
 Catalysts Open Up New Reaction Pathways

O−

C + H2O
CH2 CH3
OH− −OH−

Base catalyzed
O OH
rate = k[OH−][acetone]
C C
CH3 CH3 CH2 CH3

propanone propenol
‡ ‡

propenol
intermediate
propanone
● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○

W. F. Schneider CBE 40445

 Catalysts Open Up New Reaction Pathways
‡ ‡

propenol
different
propanone intermediate
propenol
O OH
propanone rate = k[H3O+][acetone]
C C
Acid catalyzed
CH3 CH3 CH2 CH3

H3O+ −H3O+
OH

C
+
CH3 CH3

+ H2O
● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○

W. F. Schneider CBE 40445

 Types of Catalysts - Enzymes

 The “Gold Standard” of

catalysts
 Highly specific
 Highly selective
 Highly efficient
 Catalyze very difficult
reactions
 N2  NH3
 CO2 + H2O  C6H12O6
Triosephosphateisomerase
“TIM”  Works better in a cell
Cytochrome C Oxidase
than in a 100000 l
reactor
Highly tailored “active sites”
Often contain metal atoms
● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○

W. F. Schneider CBE 40445

 Types of Catalysts – Organometallic Complexes
 Perhaps closest man has
come to mimicking
nature’s success
 2005 Noble Prize in
Chemistry
 Well-defined, metal-based
active sites
 Selective, efficient
manipulation of organic
functional groups
 Various forms, especially
Polymerization: for polymerization
catalysis

 Difficult to generalize
Termination:
beyond organic
transformations
● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○

W. F. Schneider CBE 40445

 Types of Catalysts – Homogeneous vs.
Heterogeneous

Zeolite catalyst Catalyst powders

Homogeneous catalysis Heterogeneous catalysis

Single phase Multiphase
(Typically liquid) (Mostly solid-liquid and solid-gas)
Low temperature High temperature
Separations are tricky Design and optimization tricky

● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○

W. F. Schneider CBE 40445

 Types of Catalysts: Crystalline Microporous
Catalysts

 Regular crystalline structure

 Porous on the scale of molecular dimensions
 10 – 100 Å
 Up to 1000’s m2/g surface area
 Catalysis through
 shape selection
 acidity/basicity
 incorporation of metal particles

10 Å
100 Å

Zeolite (silica-aluminate) MCM-41 (mesoporous silica)

Silico-titanate
● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○

W. F. Schneider CBE 40445

 Types of Catalysts: Amorphous Heterogeneous
Catalysts
 Amorphous, high surface area supports
 Alumina, silica, activated carbon, …
 Up to 100’s of m2/g of surface area
 Impregnated with catalytic transition metals
 Pt, Pd, Ni, Fe, Ru, Cu, Ru, …
 Typically pelletized or on monoliths
 Cheap, high stability, catalyze many types of reactions
 Most used, least well understood of all classes

SEM micrographs of alumina and Pt/alumina

● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○

W. F. Schneider CBE 40445

 Important Heterogeneous Catalytic Processes

 Haber-Bosch process
 N2 + 3 H2 → 2 NH3
 Fe/Ru catalysts, high pressure and temperature
 Critical for fertilizer and nitric acid production

 Fischer-Tropsch chemistry
 n CO + 2n H2 → (CH2)n + n H2O , syn gas to liquid fuels
 Fe/Co catalysts
 Source of fuel for Axis in WWII

 Fluidized catalytic cracking

 High MW petroleum → low MW fuels, like gasoline
 Zeolite catalysts, high temperature combustor
 In your fuel tank!

 Automotive three-way catalysis

 NOx/CO/HC → H2O/CO2/H2O
 Pt/Rh/Pd supported on ceria/alumina
 Makes exhaust 99% cleaner
● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○

W. F. Schneider CBE 40445

 Heterogeneous Catalytic Reactors
 Design goals
 rapid and intimate contact
Packed Bed between catalyst and
(single or multi-tube) reactants
 ease of separation of
products from catalyst

Fluidized Slurry Catalyst

Bed Reactor Recycle
Reactor

● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○

W. F. Schneider CBE 40445

 Automotive Emissions Control System

“Three-way” Catalyst
CO  CO2
HC  CO2 + H2O
NOx  N2

Monolith reactor

Most widely deployed

heterogeneous catalyst in
the world – you probably Pt, Rh, Pd
own one! Alumina, ceria, lanthana, …
● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○

W. F. Schneider CBE 40445

 Length Scales in Heterogeneous Catalysis

Mass transport/diffusion Chemical adsorption

and reaction
● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○

W. F. Schneider CBE 40445

 Characteristics of Heterogeneous Supported
Catalysts
 Surface area:
 Amount of internal support surface accessible to a fluid
 Measured by gas adsorption isotherms
 Loading:
 Mass of transition metal per mass of support
 Dispersion:
 Percent of metal atoms accessible to a fluid

M M M

support
● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○ ● ○

W. F. Schneider CBE 40445