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Lecture Slides Chapter1

This document provides an introduction to catalysis, green chemistry, and sustainable development. It discusses key concepts like green chemistry, catalytic processes, and life-cycle assessment. Various examples of catalytic reactions are presented along with figures illustrating reaction schemes. The overall goals of the document are to introduce principles of catalysis and green chemistry and to provide a strategic framework for achieving sustainable development through these approaches.

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John Beveridge
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120 views

Lecture Slides Chapter1

This document provides an introduction to catalysis, green chemistry, and sustainable development. It discusses key concepts like green chemistry, catalytic processes, and life-cycle assessment. Various examples of catalytic reactions are presented along with figures illustrating reaction schemes. The overall goals of the document are to introduce principles of catalysis and green chemistry and to provide a strategic framework for achieving sustainable development through these approaches.

Uploaded by

John Beveridge
Copyright
© Attribution Non-Commercial (BY-NC)
Available Formats
Download as PDF, TXT or read online on Scribd
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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

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

www.catalysisbook.org

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

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

www.catalysisbook.org

Oxidation of diphenylmethanol to benzophenone

stoichiometric reagents

3 OH
diphenyl methanol

+ 2CrO3 + 3H2SO4

3 O
benzophenone

+ 2Cr2(SO4)3 + 6H2O
waste

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

www.catalysisbook.org

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

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

www.catalysisbook.org

The traditional propene oxide route

+ HOCl
propylene

OH Cl
chlorohydrin

O + HCl
propylene oxide

+ HCl + NaOH

+ NaCl + H2O

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

www.catalysisbook.org

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

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

www.catalysisbook.org

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

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

www.catalysisbook.org

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

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

www.catalysisbook.org

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

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

www.catalysisbook.org

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

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

www.catalysisbook.org

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

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

www.catalysisbook.org

Figure 1.12

catalyst:

N O Zn N O O O O
n

O +

O + CO2
25 oC

trans

cis 98%

(R)-limonene oxide

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

www.catalysisbook.org

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

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

www.catalysisbook.org

Figure 1.14

OH

Y-zeolite

OH +
-cyclogeraniol

OH
-cyclogeraniol

geraniol

H
Zeolite Y

Lewis acid

Lewis acid

OH H

OH

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

www.catalysisbook.org

Figure 1.15

N
acrylonitrile

+ H2O

Rhodococcus (nitrile hydratase)

NH2 O
acrylamide

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

www.catalysisbook.org

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

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

www.catalysisbook.org

Figure 1.17

I 2 R
aryl iodide

+ Cu R
biaryl

+ CuI2 R

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

www.catalysisbook.org

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

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

www.catalysisbook.org

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

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

www.catalysisbook.org

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

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

www.catalysisbook.org

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

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

www.catalysisbook.org

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

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

www.catalysisbook.org

Figure 1.23

+ CrO3

O + CrO + H2O

valencene 1 mol% OsO4

nootkatone, 85% yield

O + 2NaCl + H2O

+ 2NaOCl

65% yield

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

www.catalysisbook.org

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

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

www.catalysisbook.org

Figure 1.25
Raw materials

Carton paperboard Aluminium foil

Carton filling

Consumer

Waste management

LDPE

Carton manufacturing

Landfill disposal

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

www.catalysisbook.org

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

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

www.catalysisbook.org

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

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

www.catalysisbook.org

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