David Cole-Hamilton
EaStCHEM,
University of St. Andrews
Catalytic Production of Chemicals
from Waste Natural Oils
Oil - what next?
• UK Oil consumption 2 x 1011 gallons
• Yield per hectare 1330 gallons
• Land area required 15.4 M hectares
• UK land area 24 M hectares
• Cultivated area 18.7 M hectares
BP Energy statistics
Fuels ?
http://www.telecoms.com
Oil - What next? Fuels
Chemicals ?
Demand is too high
Land use, fuel vs food
Contribution
10 % biodiesel in UK
diesel
?
Using waste streams is best
Tall Oil (paper) Cashew nut shell liquid (food) Kraft
Process
H2SO4
4 %
Uses of a,w-difunctionalised
compounds
Fibres Elastomers
Thermoplastics Melt adhesives
Coatings Engineering plastics,
Nylons (2 M tonnes per year).
Overall 3 M tonnes per year
Polyethylene replacement
Polyamide (nylon)
M. Kilner, D. V. Tyers, S. P. Crabtree and M. A. Wood, WO, 2003, 03/09328.
S. P. Crabtree, D. V. Tyers, M. Sharif, WO 2005, 05/051907A1
M. Wood, S. P. Crabtree, D. V Tyers, WO 2005, 05/051875
Difunctional materials from
methyl oleate
J. O. Metzger and U. Biermann, ACS Symp. Ser., 2004, 921, Chapter 2
Germany 1 M tonnes of natural oils / year → 3 M tonnes?
Major component of Tall Oil (waste from paper production)
2 M tonnes per year. (up tp 45 % oleic acid)
+
Self metathesis C18
CO/MeOH
Detergent
CO/MeOH
C19
C19
Cross metathesis
C11
C12 CO/MeOH
A. Behr, A. Westfechtel and J. Pérez Gomes, Chem. Eng. Technol, 2008, 37, 700
B. U. Biermann, U. Bornscheuer, M. A. R. Meier, J. O. Metzger and H. J. Schaefer, Angew. Chem. Int. Ed., 2011,
50, 3854.
Max 33 %
Max 50 %
Max 50 %
Max 100 %
Tandem isomerisation-carbonylation of
unsaturated esters
Cristina Alberto
Jiménez Rodriguez Núñez Magro
Graham Eastham
PBut2
PBut2
Bis(ditertiarybutylphosphino-
methyl)benzene
Very large steric bulk
Large ring
Highly electron donating
Semi rigid backbone
Protonation prevents quaternisation
Lucite Singapore Plant
120,000 tonnes per year
TOF = 12,000 h-1 TON = > 1,000,000 Selectivity = 99.9 %
Methoxycarbonylation of alkenes
[Pd2(dba)3] (0.05 mmol)
CH3SO3H (1 mmol), alkene (12.7 mmol), methanol (10 cm3),
CO (1-4 bar) 20 oC, 3 h
(0.5 mmol)
C. Jiménez Rodriguez, D. F. Foster, G. R. Eastham, and D. J. Cole-Hamilton
Chem. Commun., 2004, 1720-1721
97 % terminal
Tandem methoxycarbonylation of
unsaturated esters Conv Sel
% %
100 96.3
100 99
100 97.3
17.3 100 1 bar, 20 oC
30 bar 80 oC
C. Jiménez Rodriguez, G. R. Eastham and D. J. Cole-Hamilton, Inorg. Chem. Commun., 2005, 8,
878
See also: E. Drent, R. Ernst, W. W. Jager, C. A. Krom, T. M. Nisbet and J. A. M. van Broekhoven,
WO 2006, 125801; 2004, 103942; E. Bunel and D. A. Clark, US 2003, 105348, WO 2002,
048094; M. Slany, M. Schaefer and M. Roeper, WO 2002, 046143.
Oleochemicals
Methyl linoleate
(2 double bonds)
Methyl linolenate
(3 double bond)
C. Jimenez-Rodriguez, G. R. Eastham and D. J. Cole-Hamilton, Inorg. Chem. Commun., 2005, 8, 878.
[Pd] = 0.008 mol dm-3, [DTBPMB] = 0.04 mol dm-3, [MSA] = 0.08 mol dm-3, substrate (2 cm3, 6 mmol),
methanol (10 cm3), pCO = 30 bar, 80 °C, 22 h,
CO + MeOH
Oleochemicals
Methyl ester Yield (sat diester)/% linear selectivity / % Other prods (%)
oleate 95 > 95
linoleate 80 82 Unsat prods (20)
linolenate 80 83 Unsat prods (20)
25 g
Methoxycarbonylation of natural oils
Methyl oleate
(Aldrich)
Olive
(Tesco)
Rapeseed
(Tesco)
Sunflower
(Tesco)
Oleate / % >90 73 64 38
Linoleate / % 2 19 50
Linolenate / % 3 10 2
Diester / g from
10 mL oil
9.0 6.9 6.4 3.4
Yield / %
(from oleate)
74.7
102.3
69.3
108.3
36.8
96.8
Cost of diester
/ kg-1
$ 6500 (>99
%)
$ 50 (70 %)
$ 4.3 $ 1.3
Marc Furst
M. R. L. Furst, R. le Goff, D. Quinzler, S. Mecking and D. J. Cole-Hamilton, Green. Chem. 2012, 14, 472
Methyl linolenate
<10 % saturated
diester formed
28 %
31 %
45 %
20 %
Isolated 8 % Cross linking agent
Tall Oil Fatty Acids (TOFA)
Marc Furst
28 % 72 %
Cross linking agent
9 %
37 %
Isolated 32 %
8 %
25 %
Isolated 18 %
29 %
8 %
SILP metathesis of methyl oleate
CO2
CO2
Cat
Cat IL
IL
IL
Cat
Expanded liquid phase
Ruben Duque Eva Öschner
Steve Nolan Hervé Clavier
Marc Mauduit, ENSC, Rennes
SILP-CO2 metathesis methyl
oleate
20 oC 90 ppm Ru on SiO2
100 bar
50 oC, 240 ppm
0.05 cm3 min-1
0
2000
4000
6000
8000
10000
12000
0 2 4 6 8 10
Cu
mu
lati
ve
TO
N
Time on stream / h
Ru = 7-9 ppm
R. Duque, E. Öschner, H. Clavier, F. Cajo, S. P. Nolan, M. Mauduit and D. J. Cole-Hamilton, Green Chemistry, 2011, 13, 1187
Ru = < 0.5 ppm
Methyl oleate cross metathesis (batch)
0
20
40
60
80
100
120
0 0.5 1 1.5 2
time (h)
X (
%)
total
cross
self
+ + 0.2 mol %
[BMIM] [(CF3SO2)2N]
R. Duque, E. Öschner, H. Clavier, F. Cajo, S. P. Nolan, M. Mauduit and D. J. Cole-Hamilton, Green Chemistry,
2011, 13, 1187
1 mol % 100 % conversion in < 10 min
Chemicals from Castor Oil $ 0.9 kg-1
Thomas Seidensticker
Marc Furst
99 %
Methyl recinoleate
Nu = OMe or NPh
Difunctional materials from
methyl oleate
+
Self metathesis C18
CO/MeOH
Detergent
CO/MeOH
C19
C19
Cross metathesis
C11
C12 CO/MeOH
Max 33 %
Max 50 %
Max 50 %
Max 100 %
Cascade double carbonylations
Entry Substrate Pd
(%)
t(h) Ester
yield
(%)
a, b-
unsaturated
ester (%)
Diester
yield (%)
a, w-
diester
(%)
1 Butyne 0.1 0.5 100 83 0 0
2 Butyne 0.1 3 0 0 > 99 >99
3 Pentyne 0.1 3 90 73 0 0
4 Pentyne 0.5 3 0 0 100 92
5 Octyne 0.1 3 87 75 0 0
6 Octyne 0.5 3 34 29 66 61
7 Octyne 1 3 0 0 100 85
8 Octyne 0.5 14 0 0 100 87
80 oC, 30 bar A. Núñez Magro,, L.M. Robb, P J. Pogorzelec, A. M. Z. Slawin, G. R. Eastham and D. J. Cole-
Hamilton, Chem. Sci, 2010, 1, 723
Alberto Nunez Lynzi Robb
Linear Semicrystalline Polyesters from Fatty Acids by Complete Feedstock Molecule
Utilization D. Quinzler and S. Mecking, Angew Chem. 2010, 49, 4306; F. Stempfle, D.
Quinzler, I. Heckler, S. Mecking, Macromolecules 2011, 44, 4159-4166
Nature’s polyethylene
n = 13 or 18 Polyamides?
Hydrogenation of carboxylic
acids
O
OH
Ru/TriphosOHH2, H2O
164 oC
H. T. Teunissen, C. J. Elsevier, Chem. Commun, 1997, 667, 1998, 1367;
S. P. Crabtree, D. V. Tyers, M. Sharif, WO05/051907A1
M. Wood, S. P. Crabtree, D. Tyers, WO05/051875
F. Stempfle, D. Quinzler, I. Heckler, S. Mecking, Macromolecules 2011, 44,
4159
G. Walther, J. Deutsch, A. Martin, F.-E. Baumann, D. Fridag and A. Köckritz,
ChemSusChem, 2011, 4, 1052
Reduction of oleoderived diester
Ru/triphos, 1,4-dioxane
220 oC, 40 bar, 16 h
H2 / H2O
96 %
Ronan le Goff Marc Furst
M. R. L. Furst, R. le Goff, D. Quinzler, S. Mecking and D. J. Cole-Hamilton, Green. Chem, 2012, 14, 472
Amines from amide hydrogenation
Alberto Núñez Magro
Graham Eastham
Debbie Dodds
ACS Green Chemistry
Round Table
Jacorien Coetzee
Secondary amide hydrogenation
Ru(acac)3Triphos, H2Oct NH
O
Ph Oct NHPh
+ Oct OH
H2O
/ % v/v
10 93 7
0 99 1
A. A. Núñez Magro, G. R. Eastham and D. J. Cole-Hamilton
Chem. Commun, 2007, 3154
THF, 200-220 oC
10-40 bar
Poor reproducibility
Effect of added acid on amide hydrogenation
97%
83%
25%
12%
J. Coetzee, D. L. Dodds, S. Brosinski, J. Klankermeyer, W. Leitner and D. J. Cole-Hamilton, J. Amer. Chem.
Soc., to be submitted
Jacorien Coetzee
Reactions at RWTH
Entry triphos
/ mol % MSA / mol %
pH2 / barb
Time / h
Conv. / %
Sel. / %
1 2 1.5 10 16 51 91 2 2 1.5 30 16 90 90 3 2 1.5 50 16 97 88 4 2 1.5 75 24 >99 92 5 2 1.5 75 16 >99 90 6 1 1 75 24 87 87
10 cm3 stainless steel reactor with glass liner
J. Coetzee, D. L. Dodds, S. Brosinski, J. Klankermeyer, W. Leitner and D. J. Cole-Hamilton, J.
Amer. Chem. Soc., to be submitted
Primary amine synthesis
Jacorien Coetzee
In the absence of NH3
0 % 94 % 6% 100 % conversion
In the presence of NH3
61 % 19 % 20% 100 % conversion
J. Coetzee, D. L. Dodds, S. Brosinski, J. Klankermeyer, W. Leitner and D. J. Cole-Hamilton, J.
Amer. Chem. Soc., to be submitted
Cascade reductive amination
49
37
5
9
NH3 (aq) : THF = 0.5
164 oC. 40 bar, 14 h
G. R. Eastham, A. A. Nunez Magro and D.J. Cole-Hamilton, Chem. Commun. 2007,
3154
Reductive amination of
1,19-nonadecanedioate
H2 / NH3 (aq)
Ru/triphos, 1,4-dioxane
220 oC, 40 bar, 16 h
Ronan le Goff
For more information: www.st-andrews.ac.uk/euchems/
Materials
Industry
Homogeneous Catalysis
Green Chemistry
Photochemistry
Organic Synthesis
Biological Systems
Reaction Mechanisms Supramolecular Chemistry
L. Carlucci E. Hevia E. Meggers
F. Mongin E. Zuidema
P. Arnold E. Carmona
P.Kalck W. Leitner
M. Putala M.Tilset
Young Plenary Lecturers
Keynote Lecturers
Maurice Brookhart University of North
Carolina
Kyoko Nozaki University of
Tokyo
Ei-ichi Negishi Purdue
University
Bruno Chaudret INSA, CNRS, Toulouse
Michael Grätzel Ecole Polytechnique de
Fédéral de Lausanne
Distinguished Plenary Lecturers
Chemicals from Cashew nut shell liquid
Royal Society, Leverhulme Trust
Solvent extraction
60 10 15 tr
Roasting
10 85 2
(10 % polymer)
R = C15 H32-n n = 0, 2, 4, 6
heat
600,000Tonnes per year
Polymer precursors from
cardanol
Mr = 330
Loss of MeO and OH
Signals in NMR
James Mgaya
Egid Mobufo
Mr = 362
?
4-nonylphenol
Large scale production as detergent (100 k tonnes per year)
Endocrine disrupter – banned in Europe
Chemicals from cardanol
Safe detergent?
Less foaming
polymer additive
4
2
3?
Yeast assay for endocrine
distrupton
E. J. Routledge and J. P. Sumpter,
J. Biol. Chem., 1997, 272, 3280
Juma Mmongoyo
600,000 tonnes
$1.2 Bn per year
J
J. Mmongoyo, Q. Mgani, S. Mdachi, P. J. Pogorzelec and D. J. Cole-Hamilton, Eur. J. Lipid Sci.Technol., 2012,
DOI: 10.1002/ejlt.201200097
1-octene • Commodity additive for polyethylene
• Demand 608, 500 tonnes in 2006 $2 per kg crude oil $0.8 per kg
Sources
• Petroleum refining
• Fischer Tropsch process
• Ethene tetramerisation
• Cashew Nut Shell Liquid
– 60,000 tonnes per year in Tanzania
– 10,000 tonnes per year of 1-octene
$20 M per year
Metathesis of cardanol
Juma Mmongoyo
76 % isolated 65 %
J. Mmongoyo, Q. Mgani, S. Mdachi, P. J. Pogorzelec and D. J. Cole-Hamilton, Eur. J. Lipid Sci.Technol., 2012,
DOI: 10.1002/ejlt.201200097
Clean metathesis
Jenni Julis
EPSRC
10.00 15.00 20.00 25.00 30.00 35.00
10000
20000
30000
40000
50000
60000
70000
80000
90000
100000
110000
120000
130000
140000
Time-->
Abundance
JJ15-2.D\FID1A
10.00 15.00 20.00 25.00 30.00 35.00
50000
100000
150000
200000
250000
300000
350000
400000
450000
500000
Time-->
Abundance
JJ13-2.D\FID1A
and isomers
cardanol
saturated
B
B
C
C
Triene 28.9
Diene 18.3
Monoene 52.6
Saturated 1.1 %
Substrate: catalyst
5000:1
P = 8 bar, T = 40 oC
J. Julis, D. J. Cole-Hamilton, C. S. J. Cazin, GB Pat Appl, 2012, PE955409
Phenols in metathesis
G. S. Forman, A. E. McConnell, R. P. Tooze, W. J. van Rensburg, W. H. Meyer, M. M. Kirk, C. L. Dwyer and D.
W. Serfontein, Organometallics, 2005, 24, 4528
• altering the relative rates of phosphine loss and rebinding
• activating the carbene carbon for reaction with olefinic substrate
• hemilabile stabilization of the key 14-electron intermediate species.
Tsetse fly attractant
+
Kairomone
Tsetse fly attractant
Quintino Mgani
Juma Mmongoyo
Detergent
precursor
metathesis
Pd/C H2 CO
MeOH
Pd/H+/
40 %
J. Mmongoyo, Q. Mgani, S. Mdachi, P. J. Pogorzelec and D. J. Cole-Hamilton, Eur. J. Lipid Sci.Technol., 2012,
DOI: 10.1002/ejlt.201200097
Metathesis of isomerised
cardanol
11% isolated yield
Juma Mmongoyo
J. Mmongoyo, Q. Mgani, S. Mdachi, P. J. Pogorzelec and D. J. Cole-Hamilton, Eur. J. Lipid Sci.Technol., 2012,
DOI: 10.1002/ejlt.201200097
Trapping the conjugated
double bond ?
L. J. Gooßen, D. M. Ohlmann and M. Dierker, Green Chem., 2010, 12, 197
Mono unsaturated anarcardic acid
James Mgaya
S. Perdriau S. Harder , H. J. Heeres,
J.G. de Vries ChemSusChem, In the
press
Crystalline solid
Tsetse fly attractant Detergent precursor
Safe
replacement
for banned
detergent?
Polyethylene plasticiser
Bifunctional monomer
20-membered macrolactone
RO polymerisation precursor
Detergent
Origin of unwanted products in
amide hydrogenation
A. A. Núñez Magro, G. R. Eastham and D. J. Cole-Hamilton, Chem. Commun, 2007, 3154
Mechanism of heterocycle
formation
Amidation Hydrogenation
Hydrogenation
Cyclisation
Cyclisation
Acid speeds up cyclisaton reactions
Heterocycle formation
Lactams: S. P. Crabtree, D. V. Tyers, M. Sharif, WO05/051907A1
O-heterocycles: F. M. A. Geilen, B. Engendahl, A. Harwardt, W. Marquardt, J. Klankermayer
and W. Leitner, Angew. Chem. Angew. Chem. 2010, 122, 5642
Michelle Harvie Peter Pogorzelec
Emma Baxter Kate Lim
Heterocycle or linear products?
n % % % % Ring
size
1 80 20 5
2 87 13 6
3 70 9 11 4 7
4‡ 2 27 43 8
4* 27 32 37 8
* With MSA (0.068 mmol)
Emma Baxter
Substrate : PhNH2 : [Ru(acac)3] : triphos; dioxane, H2 (40 bar), 220 oC, 20 h
mmol 20 20 0.068 0.17 20 cm3
(27 % also formed) ‡
Effect of acid
MSA = MeSO3H
Substrate : PhNH2 : [Ru(acac)3] : triphos; dioxane, H2 (40 bar), 220 oC, 20 h
mmol 20 20 0.068 0.17 20 cm3
0,00%
10,00%
20,00%
30,00%
40,00%
50,00%
60,00%
70,00%
80,00%
90,00%
0 0,25 0,5 0,75 1 1,25 1,5 2
MSA:Ru
Hydrogenation of adipic acid (not stirred)
caprolactone
hexanediol
azepane
caprolactam
hydroxy amine
di-amine
Methoxycarbonylation of
unsaturated esters and acids
C. Jiménez Rodriguez, G. R. Eastham and D. J. Cole-Hamilton, Inorg. Chem. Commun., 2005, 8, 878.
Difunctional materials from
methyl oleate
+
Self metathesis C18
CO/MeOH
Detergent
CO/MeOH
C19
C19
Cross metathesis
C11
C12 CO/MeOH
Max 33 %
Max 50 %
Max 50 %
Max 100 %
Cascade alkyne dicarbonylation
BUT
E. Drent, P. Arnoldy and P. H. M. Budzelaar, J. Organomet Chem, 1994, 475, 57
T. Hayima, N. Wakasa, T. Ueda and T. Kusumoto, Bull. Chem. Soc. Japan, 1990, 63, 640