Catalytic Hydrogenation of Renewable Methyl Esters of Vegetable Oils in Organic Solvents

Postgraduate Thesis uoadl:1318058 458 Read counter

Κατεύθυνση Ομογενής Κατάλυση
Library of the School of Science
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Καΐκα Νίκη
Supervisors info:
Παπαδογιαννάκης Γεώργιος Αναπλ. Καθηγητής
Original Title:
Καταλυτική Υδρογόνωση Ανανεώσιμων Μεθυλεστέρων Φυτικών Ελαίων σε Οργανικούς Διαλύτες
Translated title:
Catalytic Hydrogenation of Renewable Methyl Esters of Vegetable Oils in Organic Solvents
In this thesis we study the full hydrogenation of polyunsaturated methyl esters
of palm kernen oil (EDENOR), sunflower oil (MESO) and soybean oil (MESBO) to
their saturated counterpart methyl stearate (MS) catalyzed by rhodium and
ruthenium complexes modified with the hexasulfonated o-phenylendiphosphite
(HSPDP) ligand in homogeneous system.
The full hydrogenation of the C18 polyunsaturated methyl esters of EDENOR
proceeds with quantitative selectivity to MS in the presence of complexes of
Rh/HSPDP at the temperature of 90 oC, pressure of 40 bar and a molar ratio of
C=C units/Rh = 50. As well as at a molar ratio of C=C units/Rh = 100 and
pressure 60 bar in methanol. In contrast to Rh/HSPDP catalytic systems of
Ru/HSPDP exhibited low catalytic activity in the hydrogenation of EDENOR and
the yield to MS was only up to 40.4%.
Full hydrogenation of MESO with a quantitative selectivity towards MS with an
activity of 3800 TOF’s per hour was achieved with Rh/HSPDP catalysts at 80oC,
40 bar and a molar ratio of C=C units/Rh=2000 and a rhodium concentration of 10
ppm in the methanol solution. Higher catalytic activities (TOF=8680 h-1) were
obtained in the partial hydrogenation of MESO with Rh/HSPDP under mild
conditions ( 90oC, 40 bar).
The highest yield of 50.6 % MS was observed in the Ru/HSPDP-catalyzed
hydrogenation of MESBO at a reaction temperature of 110oC, 50 bar dihydrogen
pressure, a molar ratio C=C units / Ru=50, at [Ru]= 60 ppm within 60 min in
Full Hydrogenation, Methyl Esters of Vegetable Oils, Methyl Stearate, Transition metals, Sulfonated phosphites as ligands
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