Technology development for the production of biobased products from biorefinery carbohydrates—the US Department of Energy’s “Top 10” revisited

http://www1.udel.edu/chem/polenova/PDF/Polyoxometalates/POMs_Catalysis_NMR_ChemRev1998.pdf

Catalysis by Heteropoly Acids and Multicomponent Polyoxometalates in Liquid-Phase Reactions

Advances in the development of novel cobalt Fischer-Tropsch catalysts for synthesis of long-chain hydrocarbons and clean fuels.

Conversion of Biomass into Chemicals over Metal Catalysts

Homogeneous catalysis by transition metal oxygen anion clusters

Production of acrolein from glycerol over silica-supported heteropoly acids

Applications of renewable biomass provide facile routes to alleviate the shortage of fossil fuels as well as to reduce the emission of CO2. Glycerol, which is currently produced as a waste in the biodiesel production, is one of the most attractive biomass resources. In the past decade, the conversion of glycerol into useful chemicals has attracted much attention, and glycerol is mainly converted by steam reforming, hydrogenolysis, oxidation, dehydration, esterification, carboxylation, acetalization, and chlorination. In this review, we focused on the catalytic hydrogenolysis of glycerol into C3 chemicals, which contain many industrially important products such as 1,2-propanediol, 1,3-propanediol, allyl alcohol, 1-propanol and propylene. In the hydrogenolysis of glycerol into propanediols, advantages and disadvantages of liquid- and vapor-phase reactions are compared. In addition, recent studies on catalysts, reaction conditions, and proposed pathways are primarily summarized and discussed. Furthermore, new research trends are introduced in connection with the hydrogenolysis of glycerol into allyl alcohol, propanols and propylene.

/pdf/glycerol-hydrogenolysis-into-useful-c3-chemicals-hezz67vslj.pdf

Glycerol hydrogenolysis into useful C3 chemicals

Basic properties of rare earth oxides (REOs) calcined at different temperatures were investigated. During the calcination process, the crystal structures of Lu, Yb, Tm, Er, Y, Ho, and Dy oxides transformed from monoclinic to cubic with increasing calcination temperature, while those of Sc, Ce, La, Pr, Nd, Sm, Eu, Gd, and Tb oxides showed no change at temperatures below 1100 °C. No acidic sites were observed in the measurement of NH 3 adsorbed on the REOs at 25 °C. CO 2 was adsorbed on the REOs: CO 2 desorption peaks were observed depending on the strength of the basic sites. Light REOs, such as La 2 O 3 , Pr 6 O 11 , Nd 2 O 3 , and Sm 2 O 3 , had surface basic sites from which CO 2 desorbed at temperatures below 500 °C, as well as structural carbonate that decomposed above 500 °C. Heavy REOs, such as Dy 2 O 3 , Ho 2 O 3 , Y 2 O 3 , Er 2 O 3 , Tm 2 O 3 , Yb 2 O 3 , and Lu 2 O 3 , had weak basic sites. The basic properties of REOs are attributed to lanthanide contraction: the strength of the basic sites decreases with decreasing radius of the rare earth cation.

Basic properties of rare earth oxides

X-ray photoelectron spectroscopy (XPS) is among the most powerful techniques to analyze defective structures of carbon materials such as graphene and activated carbon. However, reported assignments of defects, especially sp3C and sp2C, are questionable. Most reports assign sp3C peaks to be higher than sp2C peaks, whereas a few reports assign sp3C peaks to be lower than sp2C peaks. Our group previously reported that calculated binding energies of sp3C were basically lower than those of sp2C. This work clarified that one of the reasons for the prevailing ambiguous assignments of sp3C peaks is charging effects of diamond.

Origins of sp(3)C peaks in C1s X-ray Photoelectron Spectra of Carbon Materials.

The vapor-phase reaction of glycerol was performed over copper metal catalysts at ambient hydrogen pressure. Glycerol was converted into 1,2-propanediol (1,2-PDO) through the dehydration into hydroxyacetone, followed by the hydrogenation into 1,2-PDO. The yield of 1,2-PDO was limited up to 80% at a constant temperature of 190 °C because of a trade-off problem between the dehydration and the hydrogenation. The dehydration needs relatively high reaction temperatures, whereas the hydrogenation favors low temperatures and high hydrogen concentration. We developed an efficient process during which glycerol was converted into 1,2-PDO with yield higher than 96% in hydrogen flow at gradient temperatures; the dehydration into hydroxyacetone was catalyzed at ca. 200 °C, and the following hydrogenation into 1,2-PDO was completed at ca. 120 °C. The developed process controls the thermodynamic equilibrium of the second-step hydrogenation.

Satoshi Sato

Papers

Production of acrolein from glycerol over silica-supported heteropoly acids

Glycerol hydrogenolysis into useful C3 chemicals

Basic properties of rare earth oxides

Origins of sp(3)C peaks in C1s X-ray Photoelectron Spectra of Carbon Materials.

Dehydration–hydrogenation of glycerol into 1,2-propanediol at ambient hydrogen pressure