lecture slides chapter1
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Catalysis: Concepts and Green ApplicationsLecture 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 [email protected]
Catalysis/ Rothenberg, ISBN 978-3-527-31824-7.
www.catalysisbook.org
The big picturePractical 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 chemistryEconomic 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 OHdiphenyl methanol
+ 2CrO3 + 3H2SO4
3 Obenzophenone
+ 2Cr2(SO4)3 + 6H2Owaste
Catalysis/ Rothenberg, ISBN 978-3-527-31824-7.
www.catalysisbook.org
Relative efficiency of various engine types100 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.
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The traditional propene oxide route
+ HOClpropylene
OH Clchlorohydrin
O + HClpropylene oxide
O
+ HCl + NaOH
O
+ NaCl + H2O
Catalysis/ Rothenberg, ISBN 978-3-527-31824-7.
www.catalysisbook.org
The SMPO processZeolite
+ CH2=CH2ethylbenzene
+ O2 OOHethylbenzene hydroperoxide
+ OOHAlumina
Ti/SiO2 OH + H2Ostyrene
+
O
OH
Catalytic oxidation of propene+ OOHMo catalyst
O
+
OH
OCH3MTBE
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 catalystsH F F B F
homogeneous acid catalysts
N H
CO2HL-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 + + Overbenone
Regioselectivity+ CO + H2 C5H11
Rh complex
O + C5H11iso-nonanal nonanal
O
EnantioselectivityMeO N + H2 MeOIr 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 triglyceridesR2 O O R1 O O O Otriglycerides OH catalyst
OH
R1COOMe
+ 3MeOH R3
OH + R2COOMe OHglycerol
R3COOMefatty acid methyl esters (FAME) used as biodiesel
Catalysis/ Rothenberg, ISBN 978-3-527-31824-7.
www.catalysisbook.org
Figure 1.11
2x Ligand
base:HXbase
Pd0L4
Ligand
L L Pd H X RLigand
R Ar X Ar X basecatalyst
Pd L L
Ar L Pd X Ar L Pd R XLigand
R
L
Ar Ar
R
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 On
O +
O + CO225 oC
trans
cis 98%
(R)-limonene oxide
Catalysis/ Rothenberg, ISBN 978-3-527-31824-7.
www.catalysisbook.org
Figure 1.13
metal crystallite
CH3CH2CH3oxide support
CH3CH=CH2 H H3C CH2
H H3C CH3 H
H
H H3C CH2 HH 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
HZeolite Y
Lewis acid
Lewis acid
OH H
OH
Catalysis/ Rothenberg, ISBN 978-3-527-31824-7.
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Figure 1.15
Nacrylonitrile
+ H2O
Rhodococcus (nitrile hydratase)
NH2 Oacrylamide
Catalysis/ Rothenberg, ISBN 978-3-527-31824-7.
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Figure 1.16E. coli cell
OH OH2 5000 KPaNi/Al2O3
OH H2O3PO OH
OH O H OH
OH OHD-glucose
HO OO2 900 KPaCo, 160 oC
CO2H
HO O
CO2H
CO2H O O O OH OH OH
OH H2O3PO OH
OH
OH +
O
HO2C CO2H OHconc. HNO3catechol
OH
cis,cismuconic acid
OHCu, 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 Raryl iodide
+ Cu Rbiaryl
+ CuI2 R
Catalysis/ Rothenberg, ISBN 978-3-527-31824-7.
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Figure 1.18X 2 Raryl halide
+ Pd0
Rbiaryl
+ PdIIX2 R
PdIIX2 + H2Pd0 PdII
Pd0 + 2HX
X 2 Rwhere X = Cl, Br, I
+ H2
R
+ 2HX R
Catalysis/ Rothenberg, ISBN 978-3-527-31824-7.
www.catalysisbook.org
Figure 1.19
+ 2benzene benzyne biphenyl
+ 1/2O2Pd0 PdII
2
+ Pd Cl2
II
AcOH
+ PdIIH2 + 2Cl+ H2OCo(OAc)3 AcOH
PdIIH2 + 2Cl- + 1/2O2
PdCl2 + 2H2O
Catalysis/ Rothenberg, ISBN 978-3-527-31824-7.
www.catalysisbook.org
Figure 1.20O O O
AlCl3
12-methylpropylbenzene
2NaOEt
OO Cl
1HF
O O
O
OEt
O H4
H3O+
H2O
3
O O
OEt
2Raney Nickel
OH2
NH2OH
N5
OH C6
N7Pd
OHCO
COOHIbuprofen
Catalysis/ Rothenberg, ISBN 978-3-527-31824-7.
www.catalysisbook.org
Figure 1.21Activity 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 1.24NH2 2aniline
+ 4MnO2 + 5H2SO4 O 2 Obenzoquinone
+ (NH4)2SO4 + 4MnSO4 + 4H2O
O + Fe + H2O O
OH + Fe + H2O OHhydroquinone
Catalysis/ Rothenberg, ISBN 978-3-527-31824-7.
www.catalysisbook.org
Figure 1.25Raw 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 1.26O
O CH3 + H2 R
Fe Ph2P
N
OH CH3 R8599% ee
Rutoluene, 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 1.27O CNacrylonitrile hydroformylation
+ CO + H2
H
CN
NH4CN
-cyanopropionaldehyde 93% yield
NH2 NC CNStrecker intermediate 95% yield
2H2O NaOH NH2 HOOC COOH + 2NH3glutamic acid (racemate) > 99% yield
Catalysis/ Rothenberg, ISBN 978-3-527-31824-7.
www.catalysisbook.org