Selective hydrogenation of lactic acid to 1,2-propanediol over highly active ruthenium-molybdenum oxide catalysts.

Yasuyuki Takeda, Tomohiro Shoji, Hideo Watanabe, Masazumi Tamura, Yoshinao Nakagawa, Kazu Okumura, Keiichi Tomishige
Author Information
  1. Yasuyuki Takeda: Department of Applied Chemistry, School of Engineering, Tohoku University, 6-6-07, Aoba, Aramaki, Aoba-ku, Sendai 980-8579 (Japan).

Abstract

Modification of Ru/C with a small amount of MoOx (RuMoOx /C) enhanced the catalytic activity in the hydrogenation of L-lactic acid to form 1,2-propanediol and maintained high selectivity. The turnover frequency based on the amount of Ru over the optimized RuMoOx /C catalyst (Mo/Ru molar ratio=1:16) was 114 h(-1) at 393 K, which was about 4 times higher than that over Ru/C. The same effect of MoOx was obtained over RuMoOx /SiO2 , although RuMoOx /SiO2 showed slightly lower activity than that of RuMoOx /C. RuMoOx /C achieved a high yield of 95 % in 18 h at 393 K and was applicable to various carboxylic acids to provide the corresponding alcohols in high yields. Modification with MoOx also brought about suppression of racemization and (S)-1,2-propanediol was obtained in high enantiomeric excess at 353 K. Based on kinetic analysis and characterization data, such as XRD, TEM, CO adsorption by a volumetric method, FTIR spectroscopy, and X-ray absorption spectroscopy, for RuMoOx /C and RuMoOx /SiO2 , the catalyst structure and reaction mechanism are proposed.

Keywords

MeSH Term

Adsorption
Catalysis
Hydrogenation
Kinetics
Lactic Acid
Molybdenum
Oxides
Propylene Glycol
Ruthenium

Chemicals

Oxides
Lactic Acid
Propylene Glycol
Ruthenium
Molybdenum

Word Cloud

Created with Highcharts 10.0.0RuMoOx/ChighMoOxhydrogenation2-propanediol/SiO2ModificationRu/Camountactivityacid1catalyst-1393 KobtainedcarboxylicacidsspectroscopysmallenhancedcatalyticL-lacticformmaintainedselectivityturnoverfrequencybasedRuoptimizedMo/Rumolarratio=1:16114 h4timeshighereffectalthoughshowedslightlylowerachievedyield95 %18 happlicablevariousprovidecorrespondingalcoholsyieldsalsobroughtsuppressionracemizationSenantiomericexcess353 KBasedkineticanalysischaracterizationdataXRDTEMCOadsorptionvolumetricmethodFTIRX-rayabsorptionstructurereactionmechanismproposedSelectivelactichighlyactiveruthenium-molybdenumoxidecatalystsenantioselectivitymolybdenumruthenium

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