Lecture Slides Chapter1

Catalysis: Concepts and Green Applications
Lecture slides for Chapter 1: Introduction to catalysis, green chemistry, and sustainable development. Most of the graphics here were drawn using PowerPoint and Chemdraw (version Ultra 9.0). Feel free to modify and/or add your own pyrotechnics. Please send any feedback to feedback@catalysisbook.org
Catalysis/ Rothenberg, ISBN 978-3-527-31824-7.
www.catalysisbook.org
The big picture

Practical approaches Green chemistry Strategic goal Sustainable development Green engineering Industrial ecology Renewable energy Operational tools Catalysis
Waste management Process intensification
Monitoring tools Life-cycle assessment E-factor, atom economy
The drivers of green chemistry

Economic benefit Lower capital investment Lower operating costs
Societal pressure Improved public image Safer and smaller plants
Government legislation Less hazardous materials
Green chemistry
High fines for waste
Pollution control
Producer responsibility
Oxidation of diphenylmethanol to benzophenone
stoichiometric reagents
3 OH
diphenyl methanol
+ 2CrO3 + 3H2SO4
3 O
benzophenone
+ 2Cr2(SO4)3 + 6H2O
waste
Relative efficiency of various engine types

100 90 80 70 % Efficiency 50 50 40 30 20 10 Gas electric Diesel electric Microturbine Hydrogen fuel cell Costs of obtaining hydrogen
The traditional propene oxide route
+ HOCl
propylene
OH Cl
chlorohydrin
O + HCl
propylene oxide
+ HCl + NaOH
+ NaCl + H2O
The SMPO process

Zeolite
+ CH2=CH2
ethylbenzene
+ O2 OOH
ethylbenzene hydroperoxide
+ OOH
Alumina
Ti/SiO2 OH + H2O
styrene
OH
Catalytic oxidation of propene

+ OOH
Mo catalyst
OH
OCH3
MTBE
t-butyl hydroperoxide
The four stages of life-cycle assessment
Life-cycle assessment
Stage 1 Defining the scope
Stage 2 Inventory analysis
Stage 3 Impact analysis
Stage 4 Improvement analysis
Different types of catalysts

H F F B F
homogeneous acid catalysts
N H
CO2H
L-proline (organocatalyst)
enzyme (biocatalyst)
zeolite (crystalline
aluminosilicate)
OMe P P OMe
Rh
(R,R)-DiPAMP-Rh (organometallic complex)
copper-zinc crystallites on silica
Examples of chemo- and diastereoselectivity

-pinene oxide diastereomers
O + O2
-pinene CrCl3
O + + O
verbenone
Regioselectivity
+ CO + H2 C5H11
Rh complex
O + C5H11
iso-nonanal nonanal
Enantioselectivity
MeO N + H2 MeO
Ir complex
MeO * NH + * NH
prochiral imine
(R)-enantiomer
(S)-enantiomer
Base-catalysed transesterification of triglycerides

R2 O O R1 O O O O
triglycerides OH catalyst
OH
R1COOMe
+ 3MeOH R3
OH + R2COOMe OH
glycerol
R3COOMe
fatty acid methyl esters (FAME) used as biodiesel
Figure 1.11
2x Ligand
base:HX
base
Pd0L4
Ligand
L L Pd H X R
Ligand
R Ar X Ar X base
catalyst
Pd L L
Ar L Pd X Ar L Pd R X
Ligand
Ar Ar
Pd L X Ar R
base:HX
Figure 1.12
catalyst:
N O Zn N O O O O
n
O +
O + CO2
25 oC
trans
cis 98%
(R)-limonene oxide
Figure 1.13
metal crystallite
CH3CH2CH3
oxide support
CH3CH=CH2 H H3C CH2
H H3C CH3 H
H H3C CH2 H
H H3C CH2 H
H3C
CH2
H2 H H
Figure 1.14
OH
Y-zeolite
OH +
-cyclogeraniol
OH
-cyclogeraniol
geraniol
H
Zeolite Y
Lewis acid
Lewis acid
OH H
OH
Figure 1.15
N
acrylonitrile
+ H2O
Rhodococcus (nitrile hydratase)
NH2 O
acrylamide
Figure 1.16
E. coli cell
OH O
H2 5000 KPa
Ni/Al2O3
OH H2O3PO OH
OH O H OH
OH OH
D-glucose
HO O
O2 900 KPa
Co, 160 oC
CO2H
HO O
CO2H
CO2H O O O OH OH OH
OH H2O3PO OH
OH
OH +
HO2C CO2H OH
conc. HNO3
catechol
OH
cis,cismuconic acid
OH
Cu, NH4NO3
OH
CO2H
O HO O OH
Adipic acid
Figure 1.17
I 2 R
aryl iodide
+ Cu R
biaryl
+ CuI2 R
Figure 1.18
X 2 R
aryl halide
+ Pd0
R
biaryl
+ PdIIX2 R
PdIIX2 + H2
Pd0 PdII
Pd0 + 2HX
X 2 R
where X = Cl, Br, I
+ H2
+ 2HX R
Figure 1.19
+ 2
benzene benzyne biphenyl
+ 1/2O2
Pd0 PdII
+ Pd Cl2
II
AcOH
+ PdIIH2 + 2Cl+ H2O

Co(OAc)3 AcOH
PdIIH2 + 2Cl- + 1/2O2
PdCl2 + 2H2O
Figure 1.20
O O O
AlCl3
1
2-methylpropylbenzene
2
NaOEt
O
O Cl
1
HF
O O
OEt
O H
4
H3O+
H2O
O O
OEt
2
Raney Nickel
O
H2
NH2OH
N
5
OH C
6
N
7
Pd
OH
CO
COOH
Ibuprofen
Figure 1.21
Activity testing Mechanistic studies
Synthesis tools
Characterisation tools
Modelling tools
Novel reactor concepts Parallel screening Process intensification
Spectroscopy
Quantum mechanics Molecular simulations
Surface science
Microscopy
Data mining
Kinetic studies
Process simulations
Figure 1.22
substrates infrared flow cell
pump substrate loop solvent reservoir catalyst loop micromixer air loop
waste
air bubble substrate pulse mixed substrate/ catalyst pulse
catalysts
Figure 1.23
+ CrO3
O + CrO + H2O
valencene 1 mol% OsO4
nootkatone, 85% yield
O + 2NaCl + H2O
+ 2NaOCl
65% yield
Figure 1.24
NH2 2
aniline
+ 4MnO2 + 5H2SO4 O 2 O
benzoquinone
+ (NH4)2SO4 + 4MnSO4 + 4H2O
O + Fe + H2O O
OH + Fe + H2O OH
hydroquinone
Figure 1.25
Raw materials
Carton paperboard Aluminium foil
Carton filling
Consumer
Waste management
LDPE
Carton manufacturing
Landfill disposal
Figure 1.26
O
O CH3 + H2 R
Fe Ph2P
OH CH3 R
8599% ee
Ru
toluene, 50 bar, 25 C
R Cl CH3O F
substrate:catalyst 50,000 20,000 500
time, h 78 1 1
conversion, % 99 92 100
Figure 1.27
O CN
acrylonitrile hydroformylation
+ CO + H2
CN
NH4CN
-cyanopropionaldehyde 93% yield
NH2 NC CN
Strecker intermediate 95% yield
2H2O NaOH NH2 HOOC COOH + 2NH3

glutamic acid (racemate) > 99% yield

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Catalysis: Concepts and Green Applications

Catalysis/ Rothenberg, ISBN 978-3-527-31824-7.

The big picture

Waste management Process intensification

Monitoring tools Life-cycle assessment E-factor, atom economy

Catalysis/ Rothenberg, ISBN 978-3-527-31824-7.

The drivers of green chemistry

Societal pressure Improved public image Safer and smaller plants

Government legislation Less hazardous materials

High fines for waste

Catalysis/ Rothenberg, ISBN 978-3-527-31824-7.

Oxidation of diphenylmethanol to benzophenone

Catalysis/ Rothenberg, ISBN 978-3-527-31824-7.

Relative efficiency of various engine types

Catalysis/ Rothenberg, ISBN 978-3-527-31824-7.

The traditional propene oxide route

Catalysis/ Rothenberg, ISBN 978-3-527-31824-7.

The SMPO process

Catalytic oxidation of propene

Catalysis/ Rothenberg, ISBN 978-3-527-31824-7.

The four stages of life-cycle assessment

Stage 1 Defining the scope

Stage 2 Inventory analysis

Stage 3 Impact analysis

Stage 4 Improvement analysis

Catalysis/ Rothenberg, ISBN 978-3-527-31824-7.

Different types of catalysts

homogeneous acid catalysts

(R,R)-DiPAMP-Rh (organometallic complex)

copper-zinc crystallites on silica

Catalysis/ Rothenberg, ISBN 978-3-527-31824-7.

Examples of chemo- and diastereoselectivity

Catalysis/ Rothenberg, ISBN 978-3-527-31824-7.

Base-catalysed transesterification of triglycerides

Catalysis/ Rothenberg, ISBN 978-3-527-31824-7.

Catalysis/ Rothenberg, ISBN 978-3-527-31824-7.

Catalysis/ Rothenberg, ISBN 978-3-527-31824-7.

CH3CH=CH2 H H3C CH2

Catalysis/ Rothenberg, ISBN 978-3-527-31824-7.

Catalysis/ Rothenberg, ISBN 978-3-527-31824-7.

Rhodococcus (nitrile hydratase)

Catalysis/ Rothenberg, ISBN 978-3-527-31824-7.

Catalysis/ Rothenberg, ISBN 978-3-527-31824-7.

Catalysis/ Rothenberg, ISBN 978-3-527-31824-7.

Catalysis/ Rothenberg, ISBN 978-3-527-31824-7.

+ PdIIH2 + 2Cl+ H2O

PdIIH2 + 2Cl- + 1/2O2

Catalysis/ Rothenberg, ISBN 978-3-527-31824-7.

Catalysis/ Rothenberg, ISBN 978-3-527-31824-7.

Novel reactor concepts Parallel screening Process intensification

Quantum mechanics Molecular simulations

Catalysis/ Rothenberg, ISBN 978-3-527-31824-7.

substrates infrared flow cell

air bubble substrate pulse mixed substrate/ catalyst pulse

Catalysis/ Rothenberg, ISBN 978-3-527-31824-7.

valencene 1 mol% OsO4

nootkatone, 85% yield

Catalysis/ Rothenberg, ISBN 978-3-527-31824-7.

+ (NH4)2SO4 + 4MnSO4 + 4H2O

Catalysis/ Rothenberg, ISBN 978-3-527-31824-7.

Carton paperboard Aluminium foil

Catalysis/ Rothenberg, ISBN 978-3-527-31824-7.

substrate:catalyst 50,000 20,000 500