Activated carbon (AC) and three graphite materials were studied as supports for Ru catalyzed glycerol hydrogenolysis to propanediols and 1-propanol. Structural characteristics of AC and graphite materials were found to greatly affect the reducibility and particle size of supported Ru and hence, the activity and product distribution in glycerol hydrogenolysis. XRD of graphite materials showed distinctly (002) plane having highly organized layered structure and the peak intensity decreased in the order of Ru/KS150 > Ru/HSAG100 > Ru/KS6 due to decrease in the graphite sheet thickness. In Raman, the intense D band in HSAG100 compared to that in KS6 and KS150 samples indicated its highly amorphous nature or mixed carbon hybridization. Glycerol conversion for Ru on AC was higher than that on graphite and among different graphites, it showed a descending activity order of Ru/KS6 > Ru/HSAG100 > Ru/KS150. The product distribution for AC and HSAG100 supported Ru was similar, giving 1-propanol (45%) alongwith 1,2-propanediol (1,2-PDO) (37%) and 1,3-propanediol (1,3-PDO) (9–11%). For graphite supports, availability of Ru although bigger in size (4–5 nm), would be higher on the surface than in case of AC which formed deep hydrogenolysis products like 1-, 2- propanol, ethanol etc.

Influence of carbon based supports on selectivity behavior of diols and propanol in Ru catalyzed glycerol hydrogenolysis

Selective Hydrogenolysis of Glycerol to 1,2-Propanediol over Highly Active and Stable Cu/MgO Catalyst in the Vapor Phase

A series of Cu/ZrO2 catalysts with nominal CuO loadings of 5, 10, 18 and 31 wt.% was synthesized by co‐precipitation, characterized and applied in the hydrodeoxygenation of glycerol under mild reaction conditions (200 °C, 25 bar H2). These catalysts were highly selective for the cleavage of C−O bonds while preserving C−C bonds leading to 95 % selectivity to 1,2‐propanediol. The conversion of glycerol was observed to be linearly correlated with the specific copper surface area derived from N2O frontal chromatography. The reaction was found to occur through the dehydration of glycerol to acetol followed by its hydrogenation to 1,2‐propanediol. Metallic copper was identified as the active site for both reactions suggesting the acid ZrO2 sites to be blocked by water. Reusability studies showed that the catalyst was relatively stable and the conversion decreased by only 18 % after three cycles.

The Role of Metallic Copper in the Selective Hydrodeoxygenation of Glycerol to 1,2‐Propanediol over Cu/ZrO2

In the last two decades, various glycerol value addition techniques have been developed and discussed in the literature. Among all these processes, conversion of glycerol to 1,2-propanediol (1,2-PDO) has been recognized as one of the promising and commercially attractive glycerol value addition routes. This review is an attempt to scan out the progress in catalysts design and development for liquid and vapor phase glycerol hydrogenolysis for the production of 1,2-PDO. The development of supported and mixed metal oxide catalysts with their novel catalytic characteristics for glycerol conversion and 1,2-PDO selectivity has been scrutinized systematically. It was observed that among the non-noble metal catalysts, Cu-based catalysts have shown promising activity toward 1,2-PDO; however, their stability is an issue. Among noble metals, Pt- and Ru-based catalysts were reported active for glycerol conversion. Comparatively, catalysts composed of Pt, Ru, Pd as a noble metal, and Cu as a non-noble metal have resulted in higher catalytic activity and 1,2-PDO selectivity. This review also summarizes different reaction pathways for hydrogenolysis of glycerol to 1,2-PDO, the effect of additives (solid acid and base), and methods of catalyst preparation on the catalyst performances. Further, glycerol hydrogenolysis with in situ H2 production by glycerol reforming or by chemical transfer hydrogen using various hydrogen donors and the effect of different solvents on the glycerol hydrogenolysis process are also discussed. Reaction kinetic models are also included at the end. 

Review of the Development of Heterogeneous Catalysts for Liquid and Vapor Phase Hydrogenolysis of Glycerol to Propylene Glycol (1,2-Propanediol): State-of-the-Art and Outlook

Direct thermo-catalytic transformation of pine wood into low oxygenated fuel: Influence of the support

Three alkysulfonic resins were obtained by co-polymerization of 2-acrylamido-2-methyl-propansulfonic acid with N,N-dimethylacrylamide and ethylene dimethacrylate (the cross-linker), with respectively 4, 20 and 40 mol% cross-linking degree (DAE26-4, DAE26-20, DAE26-40). These resins were employed as acidic components in physical mixtures with Ru/C (5 %, w/w) or as supports for bifunctional ruthenium and copper catalysts, to be used in the hydrogenolysis of glycerol (20 %, w/w, in water). The physical mixtures were more efficient than the bifunctional catalysts, but temperatures as high as 200 °C are required to obtain an appreciable activity. However, in view of their relatively high thermal stability in comparison with the sulfonated polystyrene-divinylbenzene ion-exchange catalysts employed so far they can withstand this temperature, while Amberlyst 70 cannot be employed above 180–190 °C. Interestingly, the catalytic systems based on physical mixtures of DAE with Ru/C resins at 200 °C are much more selective towards propylene glycol than those containing A70 are at 180 °C.

Resin-Based Catalysts for the Hydrogenolysis of Glycerol to Propylene Glycol

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Resin-Based Catalysts for the Hydrogenolysis of Glycerol to Propylene Glycol