Catalytic Production of Chemicals from Waste Natural … · Catalytic Production of Chemicals from...

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

C12 diester

Thomas Seidensticker (Erasmus)

Marc Furst

Nu = OMe or NPh

CO

NuH

Conv 91 %, Sel 92 %

Chemicals from Castor Oil $ 0.9 kg-1

Thomas Seidensticker

Marc Furst

99 %

Methyl recinoleate

Nu = OMe or NPh


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 %

C16 diester

Conv 79 %, Sel 90 %

Isolated Yield 58 %

1 mol %

90 oC, 30 bar, 20 h

Marc Furst

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 %


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 %


DOI: 10.1002/ejlt.201200097

University of Greenwich

Metathesis of isomerised

cardanol

11% isolated yield

Juma Mmongoyo


DOI: 10.1002/ejlt.201200097

Alternative route to isocardanol

Pd/C H2

Ac2O

NBS/BzC(O)OOH

NaOH

Quintino Mgani

Trapping the conjugated

double bond ?

L. J. Gooßen, D. M. Ohlmann and M. Dierker, Green Chem., 2010, 12, 197

Isomerisation of anacardic

acid

James Mgaya

Mono unsaturated anarcardic acid

James Mgaya

S. Perdriau S. Harder , H. J. Heeres,

J.G. de Vries ChemSusChem, In the

press

Crystalline solid

Castor Oil

Polyesteramides?

MeO

Tsetse fly attractant Detergent precursor

Safe

replacement

for banned

detergent?

Polyethylene plasticiser

Bifunctional monomer

20-membered macrolactone

RO polymerisation precursor

Detergent

Possible route to unsaturated

benzolactone

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

Substrate scope

Added NH3 (aq)

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.


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 %

Critical Mass Grant

Clean catalysis for sustainable development

£ 2.7 M over 5 years

EaStCHEM

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

[Ru(acac)3]

Triphos, H2, H2OEt NH2

O

Et NH + Et OH

Et OPr Et NHPr

+O O

Et

M. Wood, S. P. Crabtree, D. Tyers, WO05/051875

No primary amine formed

Attempted primary amide

hydrogenation

Catalytic Production of Chemicals from Waste Natural … · Catalytic Production of Chemicals from...

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