Catalytic Chemistry in Industry

Premise: Catalysts are extremely important in industrial

organic synthesis.

Goal: Students should be able to

1) describe the nature of a catalyst

2) describe the important reaction types

involved in homogeneous catalysis

3) describe the important considerations

involved in heterogeneous catalyst design
 Importance of Catalysts

Bartholomew and Farrauto, Fundamentals of Industrial Catalytic Processes, Wiley, 2006.

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
 What is a Catalyst?
A catalyst is a substance that increases the rate at which a
chemical reaction approaches equilibrium, but is not consumed in
the process.

How Does a
Catalyst Work?
A catalyst provides an
alternative mechanism
for the chemical
reaction, with a lower
activation energy.
 Why are Catalysts Important?
It is estimated that catalysts contribute 1/6th of the value of ALL
manufactured goods in industrialized countries!
Catalysts can:
• make a reaction possible under achievable conditions

• reduce the necessity of expensive & dangerous conditions

• generate high yields and high product purity

• reduce the amount of side-product and waste created

• generate non-racemic mixtures of enantiomers

• make a chemical process “greener”

Synthetic chemical Rank Catalytic Process

Sulfuric acid (H2SO4) 1 SO2 oxidation to SO3 ; heterogeneous

Ethylene (CH2CH2) 2
Lime (CaO) 3
Ammonia (NH3) 4 N2 + H2 ; heterogeneous
Sodium hydroxide (NaOH) 5
Chlorine (Cl2) 6 Electrocatalysis; heterogeneous
Phosphoric acid (H3PO4) 7
Propylene (CH3CHCH2) 8
Sodium carbonate (Na2CO3) 9
1,2-Dichloroethane (ClCH2CH2Cl) 10 C2H4 + Cl2 ; homogeneous
Nitric acid (HNO3) 11 NH3 + O2 ; heterogeneous
Urea (CO(NH2)2) 12
Ammonium nitrate (NH4NO3) 13
Benzene (C6H6) 14 Petroleum refining; heterogeneous
Ethylbenzene (C6H5CH2CH3) 15 Alkylation of benzene; homogeneous
Carbon dioxide (CO2) 16
Vinyl chloride (CH2CHCl) 17 Chlorination of C2H4; heterogeneous
Styrene (C6H5CHCH2) 18 Dehydrogenation of ethylbenzene; heterog.
Terephthalic acid (1,4-(COOH)C6H4) 19 Oxidation of p-xylene; homogeneous
Methanol (CH3OH) 20 CO + H2; heterogeneous
 General Principles of Catalysis
• Homogeneous catalysts: in the same physical phase as reagents
• Heterogeneous catalysts: present in a different phase (solid state)

Catalytic efficiency

• Homogeneous catalysts: efficiency expressed as turnover freq., N

• Heterogeneous catalysts: rate of change of reagents is important

Selectivity

• a “selective” catalyst yields a high proportion of desired product

with a minimal amount of side-products.
 Homogeneous Catalysis
Homogeneous catalysts are more attractive for study in research labs
because:
a) the mechanism is accessible to detailed study
(i.e., the rate data is easier to interpret)
b) the species in solution are more easily characterized

Advantages of homogeneous catalysis on an industrial scale:

1. High selectivity
2. Ease of heat dissipation from exothermic reactions

Disadvantages of homogeneous catalysis on an industrial scale:

1. Scale-up can be costly, difficult, and dangerous

2. Separation is required
Nobel prizes for research in Catalysis

• 2010 Pd catalyzed cross coupling

Suzuki

Recognitions for science of catalysis

 Catalysis –Types
Heterogeneous- Reactant, catalyst & product in different phases
Metal clusters, Alloys, Metal oxides/sulfides/chlorides,
Zeolites, Clays
Homogeneous- Reactant, catalyst & product in the same phase
Metal complexes, mineral acids, bases
Heterogenized homogenous –To get the best of both proceses
Polymer supported,Tethered/functionalized on inorganic
supports
Enzymatic/Bio
Enzymes
Photo/Electro/Photo-electro-catalysis- Additional means
of activation
Semiconductors, metal complexes
Phase transfer catalysis- Quaternary ammonium salts, Ion-pairs
Catalysts-Key performance parameters
Activity - % Conversion per pass
Selectivity - Extent of formation of desired product
Minimum side products
Yield - Based on activity & selectivity
Life - Duration for which desired activity &
selectivity are maintained (Cycle/Total)
Regenerability- Ability to regain activity after one
life- cycle

Catalysts-Performance materials
Turnover frequency (TOF) & Turnover number (TON)

Turnover Frequency-TOF
No.of molecules converted or no.of catalytic cycles per second per site

Turnover number- TON

TON- No.of catalytic cycles in the life time of catalyst
TON = TOF X Time
For industrial applications TON- 106 -107
 Catalysis- Heterogeneous Vs Homogeneous
Aspect Heterogeneous Homogeneous
Activity Comparable Comparable
Reproducibility Difficulty in reproducibility Reproducible results
Selectivity Heterogeneous sites. Difficult to control Relatively higher selectivity, easy to
selectivity optimize, various types of selectivity
Reaction conditions Higher temp. & pressure, better thermal Lower temp. (<250ºC), Higher pressure,
stability lower thermal stability
Catalyst cost & High volume –low cost. Easy catalyst Low volume, high value. Recovery
recovery recovery difficult. Major drawback
Active sites, nature Not well- defined, heterogeneous, Molecular active sites, very well defined,
& accessibility but tunable, limited accessibility uniform, tunable & accessible
Diffusion limitations Susceptible, to be eliminated with proper Can be overcome easily by optimization
reaction conditions of stirring
Catalyst life Relatively longer, regeneration feasible Relatively shorter, regeneration may/may
not be feasible
Reaction kinetics Complex kinetics & mechanism, Difficult Reaction kinetics ,mechanism & catalytic
mechanism & to establish & understand unequivocally l, activity could be established &
catalytic activity at but days are not far-off understood with relative ease
molecular level
Susceptibility to Highly susceptible Relatively less susceptible. Sensitive to
poisons water & oxygen
Industrial Bulk/Commodity products manufacture Pharma, fine & specialty chemicals
Application ~ 85% manufacture, ~15%
Homogeneous catalysis-Major industrial processes

Processes/Products Production (Milln.MTA)

Terephthalic acid -PTA 50
Acetic acid & acetyl chemicals 7
Aldehydes and alcohols- Hydroformylation 6
Adiponitrile- Hydrocyanation 1
Detergent-range alkenes- SHOP- Oligomerization 1
Alpha Olefins (C4- C20)- Dimerization & 4
Oligomerization
Total fine chemicals manufacture <1
Olefins Polymerization (60% uses Ziegler-Natta) 60
Wilkinson’s catalyst: Oxidative addition of H2
H2 adds to the catalyst before the olefin.
The last step of the catalytic cycle is irreversible. This is very useful because a kinetic product
ratio can be obtained. S-Solvent

Tris (triphenylphosphine) Rh (I) chloride

Homogeneous Vs Heterogeneous
Functional similarities

Homogeneous Functions Heterogeneous

Dissociation Metal-ligand bond breaking Desorption
Association Metal-ligand bond formation Adsorption
Oxidative addition Fission of bond in substrate Dissoc. Adsorption
Reductive elimination Bond formation towards product Association
Important Homogeneous Catalytic Processes
1. Oxo process: Hydroformylation of alkenes
O
Co(I) or Rh(I)
RHC CH2 + CO + H2
R H
Important Homogeneous Catalytic Processes
2. Wacker-Hoechst process: Oxidation of alkenes
O
Pd(II) + Cu(II) R = H, aldehyde
RHC CH2 + O2 H3C R R = CnHn+2, ketone
Important Homogeneous Catalytic Processes
3. Monsanto process: Carbonylation of methanol to acetic acid
O
[RhI2(CO)2]
CH3OH + CO H3C OH

4. Hydrocyanation of butadiene to adiponitrile

Ni(P(OR)3)4 N
+ 2 HCN
N

5. Oligomerization of ethylene
NiHL
n H2C CH2 H2C CH(CH2CH2)n-2CH2CH3
Important Homogeneous Catalytic Processes
6. Olefin metathesis: Alkene dismutation
WOCl4/AlCl2Et
2 H2C CHCH3 H2C CH2 + H3CHC CHCH3

7. Asymmetric hydrogenation of prochiral alkenes

H COOR [Rh(DiPAMP)2]
COOR
+ H2 RH2CC* H
R NHCOR NHCOR

8. Cyclotrimerization of acetylene

Ni(acac)2
3 HC CH
 Homogeneous Catalysis:
5 Important Reaction Steps
There are 5 types of reactions (and their reverse) which, in
combination, account for most homogeneous catalytic cycles
involving hydrocarbons.

1. Ligand Coordination and Dissociation

2. Insertion and Elimination

3. Nucleophilic attack on coordinated ligands

4. Oxidation and Reduction

5. Oxidative addition and Reductive elimination

 1. Ligand Coordination and Dissociation
Homogeneous catalysis requires that:
• reagents be easily coordinated to the metal center
• products be easily lost from the coordination sphere

THEREFORE, a metal catalyst must be:

• a highly labile metal complex
• coordinatively unsaturated

Many square-planar 16e- complexes E.g., Wilkinson’s catalyst

meet these criteria.
Ph3P Cl
Thus, ML4 complexes of Pd(II), Rh
Pt(II) and Rh(I) are commonly used Ph3P PPh3
as catalysts.
 2. Insertion and Elimination
Insertion : the migration of alkyl (R) or hydride (H) ligands
from the metal center to an unsaturated ligand
R L H
O
CH2
L + M C O M C R M M CH2CH3
CH2

Elimination: the migration of alkyl (R) or hydride (H) ligands

from a ligand to the metal center
e.g., β-hydride elimination
H CH2 H H
-C2H4
CH2
M CH2 CH3 M CH2 M M Sol
CH2 +Sol
 3. Nucleophilic Attack on
Coordinated Ligands
A (+)ve charge on a metal-ligand complex tends to activate the
coordinated C atom toward attack by a nucleophile.

H H 2+ +
OH2 H H
L C L
L Pd L Pd C C OH + H+
L C L H R
H R
 4. Oxidation and Reduction
During a catalytic cycle, metal atoms frequently alternate between
two oxidation states:
Cu2+/Cu+ Co3+/Co2+ Mn3+/Mn2+ Pd2+/Pd

Catalytic Oxidation: generating alcohols and carboxylic acids

The metal atom 1) initiates the formation of the radical R•

2) contributes to the formation of R-O-O• radical
R H + Co(III) R + H + Co(II)

+ O2 R H
R R O O R O O H + R

R O O H + Co(II) R O + Co(III)OH R O O H + Co(III) R O O + H + Co(II)

AND
 5. Oxidative Addition
& Reductive Elimination
Oxidative Addition of a molecule AX to a complex:
• dissociation of the A—X bond
• coordination of the two fragments to the metal center
A
L L
L M L + AX L M X
L L
L

Reductive Elimination is the reverse process:

• formation of a A—X bond
• dissociation of the AX molecule from the coordination sphere
 Heterogeneous Catalysts: Active Sites
The active sites of heterogeneous catalysts are NOT uniform.

Many types of sites are exposed on the surface of a material.

Each type of site may serve a unique function in the catalysis.
e.g., crystalline solids

Irregularities (e.g., steps) Many exposed planes

 Heterogeneous Catalysis
Heterogeneous catalysts are more widely used in industry because:

1) Solid catalysts are robust at

high T, P.

2) No solvents are required.

3) No separation of the product

from the catalyst is required.
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
 Classes of Heterogeneous Catalyst
There are 2 classes of Heterogeneous catalyst:

1. Uniform catalyst is a high surface area material.

e.g., ZSM-5
Na3(AlSi31O64)3•16H2O

2. Multiphasic catalyst is deposited on a high surface area material.

Typical inert supports

Silica gel, SiO2
microcrystalline γ-alumina, Al2O3
 Heterogeneous Catalysis: Considerations
A. Surface area and porosity

Special measures must be taken to ensure that reagent molecules

achieve contact with catalytic sites.

B. Surface acidic and basic sites

Surface OH groups act as weak Brønsted acids.

Exposed Al3+ acts as a Lewis acid site.
Exposed O2- acts as a Lewis base site.
 Heterogeneous Catalysis: Considerations
C. Surface metal sites
A supported metal particle (25 Å diameter) has ~40% of its atoms
exposed on the surface.
The metal atoms are capable of forming a variety of bonds.
CH3
H O O
H H
N C C H H H2C H N N

Al Pt Pt Pt Pt Pt Pt Pt Fe Fe Fe Fe Fe

D. Chemisorption and desorption

“Activation”: desorption of H2O, reduction of M with H2(g), etc.