Epoxidation with hydrogen peroxide of

unsaturated FAMEs
over Nb
Nb(V)
(V)--silica catalysts

Bernardino Cesari (1571-1622)

The Destruction of Niobe’s Children

Vladimiro Dal Santo, Alessandro Gallo, Rinaldo Psaro,

Cristina Tiozzo, Matteo Guidotti
CNR - Istituto di Scienze e Tecnologie Molecolari, Dip. Chimica IMA, MILANO – ITALY

ISTM
 Vegetable oils for non
non--food purposes

Constant increase of
100%
non-food use of vegetable oil
75%
per person worldwide
50%

Share
non-Food
with a global increase of production 25% Food
(over 9 main veg oils)
0%
from 80 Mt (1998) to 133 Mt (2009)
year

Gunstone, Eur. J. Lip. Sci. Techn. (2011)

and an increase of population

from 5.91 billions (1998)
to 6.75 billions (2009)
 Fatty acids – epoxidised derivatives
In such trend, derivatization by epoxidation is a
powerful and versatile tool

• Stabilizers and Plasticizers in plastics

(PVC, polyurethane foams, etc.)
• Components in lubricants
lubricating resins and films
• Precursors
of bio-
bio-based polymers
of polyols and alkoxyalcohols

Epoxides of unsaturated FAMEs as precursors

OH OH O RCONH2 OH NHCOR
H2O
CH CH HC CH CH CH

ROH RNH2

RCOOH
OH OR OH NHR

CH CH OH OCOR CH CH
CH CH
 Fatty acids – epoxidised derivatives

Industrial pathway: Prilezhaev process

Use of peroxoacids acid

H15 C 7 (C 6H12) OR
Drawbacks
• organic acidic by-
by-products O O
• (over) stoichiometric amounts R'(C=O)OOH
R' OOH
• low selectivity
• troublesome separation O
• high concentration H2O2 H15 C 7 (C 6H12) OR

• environmentally unfriendly
O
R = Me, Et, diglyceride, etc.
 FAME epoxidation : heterogeneous alternatives

Supported Rh and Ru H2O2 oxidant

Conventional process
highly active, BUT
high cost of metal, use of chlorinated solvents

Sepulveda et al., Appl. Cat. А: Gen., 2007, 318, 213 Al2O3 – high yields, BUT
relatively oxidant/substrate ratio
Suarez et al., Ind. Eng. Chem. Res. 2009, 48, 3268

Soybean oil Ti/SiO2+t-BuOH –yield Campanella, et al., Green Chem., 2004, 6, 330
87%
BUT separation of highly-boiling alcoholic solvent

Nb-PMO – periodic mesoporous organosilica

excellent yields and selectivity
BUT complex and costly systems

Nowak et al., Catal. Today, 2009, 140, 23. Nb

water tolerant
 from Titanium to Niobium
after contact with H2O2 Ti-SiO2 systems are
irreversibly modified and deactivated J. Phys. Chem. C, 111 (2007) 5083

250
A DRS-UV-Vis A
210
225

of Ti-MCM-41

210
b

Kubelka-Munk function
a
Kubelka-Munk function

350 400 450

a: fresh catalyst

b: after
 TBHP H2O2 
adsorption at RT
c b b
a c
a

250 300 350 400 450

c: after
W a v e len g th / n m
re-activation 250 300 350 400 450 500 550 600
in O2 500°C Wavelength/ nm

irreversible agglomeration leading to deactivation

Nb and Ti
 from Titanium to Niobium

Epoxidation of methyl oleate with H2O2

C (%) Y (%) S monoepox

Catalyst Oxidant
24 h 24 h 24 h (%)

optimized *Ti/MCM-41 TBHP 100 98 >98

non-optimized Ti/MCM-41 H2O2 50% very poor performance

methyl oleate

Slow dropwise
Ti/MCM--41
Ti/MCM addition of H2O2
(0.01 mL min-1)

methyl 9,10-epoxystearate

slow addition = slower agglomeration leading to deactivation

up to 91% yield in epoxide

Green Chem., 13 (2011) 1806
 from Titanium to Niobium

Liquid-phase epoxidation of limonene O

with TBHP or aqueous H2O2 oxidant
+

endocyclic exocyclic
after 1 h
Catalyst Oxidant
Conv Sel epox endo/exo epox
Nb/SiO2 H2O2 64 99 24:76
TBHP 29 80 76:24
Ti/SiO2 H2O2 10 40 n.d.
TBHP 44 94 98:02
dry CH3CN; 100 mg cat; 1 mmol limonene; 1.1 mmol dry TBHP or 2.0 mmol aq. H2O2; 80°C; batch reactor

Guidotti et al., submitted

Opposite behaviour of Nb and Ti catalysts

Good robustness of Nb catalysts to water-containing media

 from Titanium to Niobium
Our catalysts Nb-SiO2
by deposition of
Nb(Cp)2Cl2 onto mesoporous SiO2

Organometallic
Liquid-phase Chemical
grafting Vapour
Deposition

Use of chlorinated solvents

time-consuming
Simpler, cheaper
less time-consuming

O2 O
OH
NEt3 500°C
Ti Nb
OH OH OH
+ M
Cl O O O O O O
Cl deposition calcination

SiO2 SiO2 SiO2

M = Ti, Nb
CHCl3
 from Titanium to Niobium
Our catalysts Nb-SiO2
by deposition of
Nb(Cp)2Cl2 onto mesoporous SiO2

Organometallic
Chemical
Vapour
Deposition

Simpler, cheaper
less time-consuming


solventless mixture of
stirred overnight
mesoporous SiO2
at room temperature
and Nb(Cp)2Cl2
under reduced pressure
 Characteristics of silica supports

S BET Dp Vpores
Support
(m2 g-1) (nm) (mL g-1)

MCM-41 1350 1.13 2.7

SBA-15 705 1.12 8.5

SiO2
Grace Davisil 529 5.4 0.88

SiO2
333 n.d. n.d.
Aerosil 380

silica materials
with various morphology
ordered/non-ordered
porous/non-porous
 Niobium--silica materials
Niobium

Calcination at 500°C prior to use  Nb(V)

Nb content between 1 and 2 wt.%

SEM micrograph and EDS mapping for Nb on the 2% Nb/SiO2-CVD RT sample

Good dispersion of Nb sites by CVD technique

 Niobium--silica materials
Niobium

DR UV-vis spectra of representative

dry Nb/SiO2 catalysts after calcination

no presence of
large Nb2O5 domains (>380 nm)

maxima located around 210 nm

most of sites as tetrahedral Nb(V)

shoulders around 350 nm

presence of oligomeric Nb(V) sites
on samples obtained by CVD

Satisfying dispersion of Nb sites

CVD not fully comparable to liquid-phase grafting technique
over non-ordered silicas
 Epoxidation of pure FAMEs
Oleate O

MeO

Linoleate O

MeO

Ricinoleate
OH
M eO (C 6H 12) (C 5H 11)

O
 Reaction conditions

• Glass Batch Reactor, 85°C, 6h

• Catalyst pretreated at 500°C in air
• Substrate: FAME 1 mmol
• Oxidant aq. H2O2 (50%)
• H2O2 : FAME ratio = 2:1
• Solvent CH3CN

No slow dropwise addition of H2O2

No large excess of oxidant

 Epoxidation of methyl oleate
C C Specific
Nb S epox Y epox
Catalyst MeOLE MeOLE activity
(wt.%) 1 h (%) 1 h (%)
1 h (%) 6 h (%) (h-1)

Nb-SiO2 CVD 1.75 35 38 >98 34 18

Nb-SiO2 CVD 0.92 25 41 >98 25 25

Nb-SiO2 liq 0.76 62 64 >98 62 75

Nb-Aerosil 1.59 17 17 96 16 10

Nb-SBA-15 1.96 48 62 96 46 24

Nb-MCM-41 1.21 28 47 95 27 23
Conditions: 1 mmol methyl oleate, 2 mmol aq. H2O2 (50%), 100 mg catalyst, 85°C, CH3CN
C: conversion of substrate, S: selectivity, Y: yield, SA (molconv/[molNb h])

Highest activity for catalyst with ca. 1% Nb

among the best results over simple niobosilicate materials with H2O2
 good oxidant efficiency
 Epoxidation of methyl oleate : yield profiles

Maximum activity within first hour of reaction, then reaction “stops”

Better Nb isolation  higher activity and performance

Nb-SBA-15 vs. Nb-MCM-41 : accessible sites  easier epoxidation
 Epoxidation of methyl ricinoleate

OH

Nb-SiO2 CVD
0.92% Nb

Conditions: 1 mmol methyl ricinoleate, 2 mmol aq. H2O2 (50%), 100 mg catalyst, 85°C, CH3CN

Similar performance with ca. 1% Nb over C18-1 and C18-1-OH

No remarkable effect of allylic –OH group on epoxidation

 difference with Ti-SiO2 systems!
 Epoxidation of methyl linoleate
C C
H2O2:LIN S monoepox S diepox
Catalyst MeLIN MeLIN
ratio 1 h (%) 1 h (%)
1 h (%) 4 h (%)

Nb-SiO2
1%
2:1 52 63 89 8

Nb-SiO2
1%
4:1 83 89 81 16

Conditions: 1 mmol methyl linoleate, aq. H2O2 (50%), 100 mg catalyst, 85°C, CH3CN

H2O2:LIN ratio 2:1

Interesting selectivity
towards monoepoxide
by tuning oxidant amount
O
MeO (C6H12)
(C5H 11)
and isomer
O

 difference with Ti-SiO2

systems!
Tuning selectivity in methyl linoleate epoxides
Methyl linoleate

Methyl epoxyoleate Methyl diepoxystearate

(monoepoxide) (diepoxide)

Ti-SiO2 catalysts Nb-SiO2 catalysts

with tBuOOH with H2O2

100% H2O2:LIN ratio 2:1

80%

60%

40%

20%

0%
0 3 6 9 12 15 18 21 24
time (h)

 Conv  Sel MONO

MONO--epox  Sel DI
DI--epox

J. Mol. Catal
Catal.. A: Chem. 250 (2006) 218
 In Conclusion ...

Simple Nb-silica materials are suitable catalysts

for the epoxidation of unsaturated C-18 FAMEs

Nb-SiO2 systems are water tolerant and aqueous H2O2 can

be used as a direct oxidant (no dropwise additions)

High yields in epoxide are obtained

in short reaction times with excellent selectivities

Nb-silica materials show complementary behaviour

with respect to Ti-silica catalysts
broader set of catalysts
for selective epoxidation of oleochemicals
Acknowledgements
Milano – CNR ISTM
dr. Nicoletta Ravasio

Alessandria – Univ. Eastern Piedmont

dr. Chiara Bisio
dr. Fabio Carniato

Como – Univ. of Insubria

prof.. Sandro Recchia
prof

www.velica.org
From ancient crops
materials and products for the future
The main goal of VeLiCa project is to make again
gainful the growing of flax and hemp in Northern
Italy, by the exploitation of all parts of the plant to
make various products with different added value

€
 Thank you for your kind attention

... and have a nice dinner...

...maybe, with Italian oleochemicals !

Società Chimica Italiana
Divisione di Chimica Industriale
Gruppo Interdivisionale di Catalisi-GIC

11-15 September 2012

EFCATS Summer School – 2012
and
1st Italian-Spanish School
on Catalysis

“Recent Advances and New TOPICS

Trends in Catalysis”
Hotel Castagnola
Pallanza, Lake Maggiore, Italy
further info
http://gic.istm.cnr.it/EFCATS2012
•Fundamentals on homogeneous and
heterogeneous catalysis
•Catalyst characterization: approaches,
methods and techniques
•Mechanisms and reactivity: catalysts
under working conditions
•Catalysis role in Horizon 2020 challenges
DR UV-
UV-vis spectra of dry Nb
Nb/SiO
/SiO2-CVD
CVD--RT catalyst
before (blue) and after (purple) catalytic use