Hydrogenation of Renewable Levulinic Acid to γ-Valerolactone catalyzed by Ruthenium Complexes in Aqueous Medium

Postgraduate Thesis uoadl:1592644 408 Read counter

Κατεύθυνση Ομογενής Κατάλυση
Library of the School of Science
Deposit date:
Moustani Chrysavgi
Supervisors info:
Νικόλαος Ψαρουδάκης, Επίκουρος Καθηγητής ΕΚΠΑ
Μαρίνος Πιτσικάλης, Καθηγητής ΕΚΠΑ
Γεώργιος Παπαδογιαννάκης, Αναπληρωτής Καθηγητής ΕΚΠΑ
Original Title:
Υδρογόνωση Ανανεώσιμου Λεβουλινικού Οξέος προς γ-Βαλερολακτόνη καταλυόμενη από Σύμπλοκα του Ρουθηνίου σε Υδάτινο Περιβάλλον
Translated title:
Hydrogenation of Renewable Levulinic Acid to γ-Valerolactone catalyzed by Ruthenium Complexes in Aqueous Medium
In this thesis we study the selective hydrogenation of renewable levulinic acid to γ-valerolactone catalyzed by water-soluble ruthenium complexes modified with nitrogen-containing and phosphine ligands in aqueous monophasic systems. The best results regarding activity, selectivity and stability of the catalyst were obtained with RuCl3.3H2O/Taurine complexes under mild reaction conditions in the aqueous solvent to achieve a high catalytic activity of TOF=2560h-1 with a high selectivity towards the desired product γ-valerolactone of 98.4% with a low formation (1.6%) of the byproduct 1.4-pentanediol. Good results were also obtained with the catalytic system RuCl3.3H2O modified with the sodium salt of disulfonated bathophenanthroline to give high rates (TOF=1200h-1) and a high selectivity towards γ-valerolactone of 99.2% with quantitative conversion of the starting material. High catalytic activities (TOF>1400h-1) were observed with the precursors Ru(NO)(OAc)3, Ru(NO)(NO3)3 and Ru(acac)3 whereas with [Ru(NO)]2(SO4)3 and RuO2•H2O the activities were lower (TOF<900h-1) applying taurine ligands under mild conditions with the catalyst to keep its high selectivity and stability. Water-soluble phosphines such as sodium salt of trisulfonated triphenylphosphine and other bidentate and monodentate nitrogen-containing ligands such as the tetrasodium salt of ethylenediaminetetraacetic acid, sodium salt of disulfonated bathocuproine and 3-pyridine sulfonic acid efficiently modified the precursor salt RuCl3.3H2O to afford high catalytic activity (>800h-1 TOF’s per hour) and nearly quantitative selectivity towards γ-valerolactone under mild reaction conditions at a ruthenium concentration of only 24ppm in the aqueous medium. γ-Valerolactone’s applications are in the industrial production of food, chemicals, pharmaceuticals and of anvironmentally friendly biofuels.
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Other subject categories:
Hydrogenation, renewable levulinic acid, water-soluble ruthenium complexes, nitrogen-containing ligands and phosphines, γ-Valerolactone
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