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ChE 553 Lecture 22

Introduction To Catalysis
1
Importance Of Catalysis
90% of all chemical processes use
catalysts
Changes in catalysts have a giant
influence on rates and selectivitys of
reactions.
More than anything else
Most real reactor design associated with
optimizing performance of catalyst
2
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
3
Catalytic Reaction Occurs Via
A Catalytic Cycle:
reactants + catalyst complex

complex products + catalyst
4
Example: Rhodium Catalyzed
CH
3
OH+COCH
3
COOH

5

HI
H O
2
CH OH
3
CH I
3
CH COOH
3
CH COI
3
[Rh(CO) I ]
2 2
-
Rh
I
H C
3
C
I
I
O
Rh
I
CH
3
C
O
I
I
C
O
C
O
C
O
CO

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

Printing press analogy
The Rate Enhancement Of A Number Of
Reactions In The Presence Of A Catalyst

6
Reaction Catalyst Rate
Enhancement
Temperature
Ortho H
2
Para H
2
Pt (solid) 300K
2NH
3
N
2
+ 3H
2
Mo (solid) 600K
C
2
H
4
+ H
2
C
2
H
6
Pt (solid) 300K
H
2
+Br
2
2HBr
Pt (solid)
1 10
8
300K
2NO + 2H
2
N
2
+ 2H
2
O
Ru (solid)
3 10
16
500K
CH
3
COH CH
4
+ CO I
2
(gas)
4 10
6
500K
CH
3
CH
3
C
2
H
4
+H
2
NO
2
(gas)
1 10
9
750K
(CH
3
)
3
COH
(CH
3
)
2
CH
2
CH
2
+H
2
O
HBr (gas)
3 10
8
750K
10
40

10
20

10
42

Catalysts Do Not Work Over A
Broad Temp Range

Gas Phase -- No
Wall Reactions
Catalyst Alone
Approximate
Effect Of Walls
0 500 1000 1500 2000 2500
Temperature, K
1E-15
1E-12
1E-9
1E-6
0.001
1
1000
R
a
t
e
,

M
o
l
e
s
/
l
i
t

s
e
c

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
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Types Of Catalysts:
Homogeneous Catalysts
Heterogeneous Catalysts
8
Homogeneous Catalysts:
Acids or Bases
Metal salts
Enzymes
Radical initiators
9
Table 12.2-Some Reactions Commonly
Catalyzed By Acids And Bases

10
Reaction Example Typical Application
Isomerization
(Rearranging the
structure of a molecule)
CH
2
=CHCH
2
CH
3

CH
3
CH=CHCH
3

Octane Enhancement
Monomer Production
Paraxylene Production
Alkylation
(Making too little
molecules into a bigger
one)
CH
3
CH=CHCH
3
+
CH
3
CH
2
CH
2
CH
3

(CH
3
CH
2
)CH(CH
3
)(C
4
H
9
)
Pharmaceutical
Production
Monomer Production
Fine Chemicals
Butane + olefin
octane
Cracking
(Taking a big molecule
and making it into two
littler ones).
C
12
H
24
C
7
H
14
+ C
5
H
10
Crude Oil Conversion
Digestion
Some Reactions Commonly Catalyzed By
Acids And Bases Continued

11
Reaction Example Typical Application
Esterfication Soap Production
(Attaching an acid to a base
eliminating water)
Fragrance Production
2 CH
3
CH
2
CH
2
CHO
Fine Chemicals
+ H
2
O
Pharmaceutical
production
Alcohol Dehydration
(removing a hydrogen and
an OH from an alcohol,
producing a double bond)
Cationic Polymerization Propylene
polypropylene
Polymer Production
Aldol Condensation
Reactions (combining two
aldehydes by eliminating
water)
CH
3
CH
2
OH +CH
3
COOH
CH
3
COOCH
2
CH
3
+
H
2
O
CH
3
CH
2
OH CH
2
=CH
2
+ H
2
O
Alternative fuels
Acids And Bases As Catalysts

Benzene ethylene ethylbenzene +
(12.2)

a proton reacts with the ethylene to form an
ethyl ion:


| |
H CH
2
CH
2
CH
3
CH
2
+
+
+

(12.3)

12
Acids As Catalysts Continued
The ethyl ion reacts with benzene to yield
and ethylbenzene ion:

| | | |
CH
3
CH
2
C
6
H
6
CH
3
CH
2
C
6
H
6
+
+
+

(12.4)

Then the ethylbenzene ion loses a proton:


| |
CH
3
CH
2
C
6
H
6
CH
3
CH
2
C
6
H
5
H
+
+
+

(12.5)

13
Metal Atoms: As Catalysts

( )
H
2
2S 2H ad +
(12.6)

( )
C
2
H
4
+ S C
2
H
4
ad

(12.7)


C
2
H
4
(ad) + H(ad) C
2
H
5
(ad) + S

(12.8)


( ) ( )
C
2
H
5
ad H ad C
2
H
6
2S + +

(12.9)
14
Examples Of Reactions Catalyzed By
Homogeneous Transition Metal Catalysts

15
Reaction Catalyst
Olefin Polymerization [TiCl
2
(C
5
H
5
)
2
]
2+
or
TiCl
2
/Al(C
2
H
5
)
3
(Ziegler-Natta Catalyst)
Olefin Hydrogenation Rh(P(C
6
H
5
)
3
)
3
Cl
Wilkinson Catalyst
C
2
H
4
+H
2
OAcetaldehyde
(Wacker Process)
PdCl
2
(OH)
2

C
2
H
4
+H
2
+CO propylaldehyde
(Hydroformylation)
HCo(CO)
4

CH
3
OH + CO CH
3
COOH
(Monsanto Carbonylation
Process)
[Rh(CO)
2
I
2
]
1-

H
2
O
2
+CH
3
CH
2
OH
CH
3
CHO+2 H
2
O
Fe
2+


Enzymes As Catalysts
Oxidoreductases (promote
oxidation reduction reactions)
Transferases
(promote transfer of functional groups)
NADH
peroxidase
(Oxidizes
NADH with
peroxides
NADH + H
2
O
2

NAD(+)+2
H
2
O.
Dimethylallylcis-
transferase (Transfer
dimethylallyl groups)
Dimethylallyl diphosphate +
isopentenyl
disphosphatediphosphate +
dimethylallylcis-
isopentenyldiphosphate
Ferroxidase
(oxidizes
Iron)
4 Fe
2+
+ 4 H
+
+
O
2
4 Fe
3+
+ 2
H
2
O
Glycoaldehyde
transferase
(Transfers
Glucoaldeydes)
Also called
Transketolase
Sedoheptulose 7-phosphate + D-
glyceraldehyde 3-phosphate D-
ribose 5-phosphate + D-xylulose
5-phosphate
Glucose
oxidase
(oxidizes
Glucose)
|-D-Glucose +
O
2
D-
glucono-1,5-
lactone + H
2
O
2

Alanine
aminotransferase
(Transfer amino
groups from alanine)
L-Alanine + 2-oxoglutarate
pyruvate + L-glutamate
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Enzymes Continued
Hydrolases
(Promote hydrolysis/cleavage reactions)
Lyases
(promote addition of CO
2
, H
2
O and NH
3
to
double bonds or formations of double bonds
via elimination of CO
2
, H
2
O or NH
3
)
Carboxylesterase
(Promotes
hydrolysis of ester
linkages)
A carboxylic ester +
H
2
O an alcohol + a
carboxylic anion
Carbonate
dehydratase
(Dehydrates
carbonates)
H
2
CO
3
CO
2
+ H
2
O
1,4-ALPHA-D-
Glucan
glucanohydrolase
(also called ALPHA-
Amylase)
Hydrolysis of 1,4-
ALPHA-glucosidic
linkages in
oligosaccharides and
polyasaccharides.
Citrate dehydratase Citrate CIS-
aconitate + H
2
O
Interleukin 1-beta
converting enzyme
Release of interleukin
1-beta by specific
hydrolysis at 116-ASP-
|-ALA-117 and 27-
ASP-|-GLY-28 bonds
Pyruvate
decarboxylase
A 2-OXO acid an
aldehyde + CO
2
17
Enzymes Continued
18
Maleate isomerase
(promotes cis-trans
isomerization of Maleate)
Maleate
Fumarate
Leucine--trna
ligase
ATP + L-leucine
+ t-RNA(leu)
AMP +
diphosphate + L-
leucyl-t-
RNA(leu).
Cholestenol DELTA-
isomerase
5-Alpha-
cholest-7-en-3-
beta-ol 5-
Alpha-cholest-
8-en-3-beta-ol
Pyruvate
carboxylase
ATP + pyruvate +
(HCO
3
) ADP +
phosphate +
oxaloacetate
Mannose isomerase D-Mannose
D-fructose
Aspartate--
ammonia
ligase
ATP + L-aspartate
+ NH
3
AMP +
diphosphate + L-
asparagine
Isomerases (promote isomerization
reactions)
Ligases (promotes formation of
bonds - generally used to catalyze
endothermic reactions requiring
ATP)
Radical Initiators As Catalysts
Example:

19

C
2
H
6
C
2
H
4
H
2
+
(12.10)

X+ I
2
2I + X
(12.11)

Then the iodine can react with ethane to start
the reaction:

I CH
3
CH
3
HI CH
2
CH
3
+ +

(12.12)
Free Radical Polymerization
Catalysts:
R R R - O O 2 O

(12.13)

Then the radical reacts with the ethylene to
start the polymerization process:

R R O
2
CH
2
OCH
2
CH
2
- + - CH
(12.14)

20
Free Radicals Catalysts For
Ozone Destruction

Cl O
3
ClO O
2
+ +
(12.15)

The ClO can then react via a number of
processes to reduce the ozone layer. One
particular reaction is:

ClO O
3
Cl 2O
2
+ +
(12.16)
21
Some Examples Of Reactions Initiated Or Catalyzed By
Free Radicals And Similar Species

22
Reaction Initiator Reaction Catalyst
Olefin
Polymerization
Peroxides,
(Ph)
3
CC(Ph)
3

2SO
2
+O
2

SO
3

(Lead Chamber
Process)
NO/NO
2

Hydrocarbon
Dehydrogenatio
n
Iodine, NO
2

chlorine atoms
Ozone
Depletion
Cl
Hydrocarbon
Oxidations
( )
| |
| |
CH CH N I ,
3 2
4

( )
| |
| |
CH CH N C H COO
3 2
4
6 5



Solvents: As Catalysts

CH
3
I NaCl CH
3
Cl + 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
Cyanide
0.13
DMF 2.5
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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
24
Supported Metal Catalysts

25


Figure.12.3 A picture of a
supported metal catalyst.
Use support because platinum
very expensive and only the
surface is active.

Spread platinum out on cheap
support.

Support also provides strength
Pictures Of Some
Heterogenous Catalysts

26
Pores In Heterogeneous
Catalysts

27

Figure 14.3 A cross sectional diagram of a typical
catalyst support.
Advantage Of Heterogeneous Catalysts
Compared To Homogeneous:
Cheaper separation
More selective
Generally cheaper

Disadvantage
Not quite as active or a per metal atom
basis

28
A Selection Of The Reactions
Catalyzed By Supported Metals

29
Reaction Catalyst Reaction Catalyst
Hydrocarbon
Hydrogenation,
Dehydrogenation
Pt, Pd, Ni
CO + H
2

Hydrocarbons
(Fischer-
Tropsch)
Fe, Rh
CO oxidation,
total oxidation of
hydrocarbons
Pt, Pd, Cu, Ni,
Fe, Rh, Ru
Steam reforming
for
production of
hydrogen
Ni plus additives
CO + 2H
2

CH
3
OH
Cu/ZnO Reforming
(Isomerization of
oil)
Pt/Re/Al2O3


A Selection Of The Reactions
Catalyzed By Supported Metals
Reaction Catalyst Reaction Catalyst
2 CO + 2NO
2CO
2
+ N
2

Pt, Rh, Ru
(catalytic
converter)
2NH
3
+O
2

N
2
O
5
+3H
2
O
Pt
N
2
+ 3 H
2
2
NH
3

Fe, Ru, Rh
Alcohols + O
2

Aldehydes +
H
2
O e.g.
2 CH
3
OH + O
2


2 H
2
CO +H
2
O
Ag, Cu
2 C
2
H
4
+ O
2

2 ethylene oxide
Ag, Cu
R-R' + H
2

RH + HR'
(Hydrogenolysis)
Ni, Co, Rh, Ru

30
Typical Mechanism Of Heterogeneous
Catalysis (H
2
+C
2
H
4
C
2
H
6
)
H
2
+ 2S 2 H(ad)
(12.18)

( )
C
2
H
4
S C
2
H
4
ad +

(12.19)

( ) ( ) ( )
C
2
H
4
ad H ad C
2
H
5
ad S + +

(12.20)

( ) ( )
C
2
H
5
ad H ad C
2
H
6
2S + +

(12.21)
31
Transition Metal Oxides,
Nitrides, Sulfides:
Bond transition
Metal to O, N, S to reduce activity and to
increase selectivity
32
A Selection Of The Reactions Catalyzed By Transition
Metal Oxides, Nitrides, And Sulfides
Reaction Catalyst Reaction Catalyst
2 SO
2
+ O
2
2 SO
3
V
2
O
5
CO + H
2
O CO
2
+
H
2 (Water Gas Shift)
FeO, CuO, ZnO
Hydrodesulfurization CoS, MoS, WS 2(CH3)3COH
(CH3)3COC(CH
3)3 + H2O
TiO
2
CH
3
CH=CH
2
+ O
2
(Bi
2
O
3
)
x
(MoO
3
)
y
2 CH
3
CH=CH
2
+ 3
O
2
+ 2NH
3

CH
2
=CHCHO +
(Bismuth
molybate)
2CH
2
=CHCN +
H
2
O
Uranium
Antimonate
6 H
2
O
(aminoxidation)
(FeO)
x
(Sb
2
O
3
)
y
33
A Selection Of The Reactions Catalyzed By Transition
Metal Oxides, Nitrides, And Sulfides
Reaction Catalyst Reaction Catalyst
4 NH
3
+ 4 NO +O
2

4N
2
+ 6 H
2
O
benzene+O
2

maleic
anhydride +
water
(Selective catalytic
reduction)
naphthylene+O
2
phthalic
anhydride +
water
CH
3
CH
2
(C
6
H
5
) +O
2

CH
2
=CH(C
6
H
5
) + H
2
O
NiO, Fe
2
O
3
,
V
2
O
5
, TiO
2
(styrene production)
CuO, Co
3
, O
4
,
MnO
2
Aromatiztion
e.g. HeptaneTolvene
H
2
or H
2
O
Cr
2
O
3
/Al
2
O
3
Hydrodenitroge
nation
NiS,MoS
V
2
O
5
, TiO
2
(V
2
O
5
)
x
(PO
4
)
y
FeO Selective
oxidation of
hydrocarbons
34
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
Faugasite
zeolite VFI large pore
zeolite
Sodalite zeolite Offretite zeolite
HF-SbF
5
superacid HSO
3
F superacid
H
2
[Ti
6
O
4
(SO
4
)
4
(
OEt)
10
]
superacid Sulfated
Zirconia
superacid
MgO solid base Na
2
O base

35
Very Complex Pore Structure
36
Figure 12.4 A diagram of the pore structure in Faugasite.
Leads To Shape Selective
Catalysis
C
H
H
H
C
H
H
H
Diffusion
Channel
Cavity
37
Figure 12.27 An interconnecting pore structure which is
selective for the formation of paraxylene.
Summary
Two types of catalysts
Homogeneous
Heterogeneous
Homogeneous more active
Heterogeneous less expensive, easier
to use/control
38

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