Abstract

The catalytic process of glycerol hydrogenolysis to produce 1,2-propandiol (1,2-PD) in the absence of external hydrogen addition has been investigated. The methanol present in the crude glycerol from a biodiesel production process is used to provide in situ hydrogen produced via methanol steam reforming for the glycerol hydrogenolysis process. This process can reduce the additional cost for the transportation and storage of molecular hydrogen and also reduce the safety risks related to using high hydrogen pressure. It was found that the introduction of Pd onto a Cu/MgO/Al2O3 catalyst significantly improved the glycerol conversion and 1,2-PD selectivity. The pseudo-first-order kinetic results suggested that the promoting effect of Pd is primarily attributed to the enhanced activity for the hydrogenation of acetol, which is the intermediate formed via glycerol dehydration. A 27−3 fractional factorial design experiment was carried out to investigate the impacts of seven single factors and their binary effects on two responses, namely 1,2-PD selectivity and glycerol conversion. The results showed that the glycerol feed concentration has the most significant effect on the 1,2-PD selectivity, such that the 1,2-PD selectivity is lower if a more concentrated glycerol is used as the feedstock; stirring speed, inert gas pressure and water to methanol molar ratio have insignificant effects on the reaction system. The addition of Pd, higher temperature and higher catalyst loading are the essential factors in order to obtain a high selectivity of 1,2-PD and a high glycerol conversion.

Highlights

  • IntroductionPublisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affiliations

  • Cu with different other metals combinations, i.e., Zn, Al, Mg, Ni, Mg, Zr and La, have been investigated to discover the most active catalyst for the glycerol hydrogenolysis process with in situ hydrogen produced from methanol steam reforming

  • We have recently reported the process using a Cu/ZnO/Al2 O3 catalyst [32], the glycerol conversion and 1,2-PD selectivity were 87.1% and 70.7%, respectively, after an 8 h reaction time, which is significantly higher than the results using the Cu/ZnO/ZrO2, Cu/ZrO2 /Al2 O3 and

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Summary

Introduction

Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affiliations. In order to fight climate change and to achieve sustainable development for human life, the production of green chemicals from biomass-derived feedstocks has been of great interest in scientific research and industrial applications. As the major byproduct of the biodiesel production process, can be used to produce a number of important chemicals, such as 1,2-propanediol (1,2-PD), 1,3-propanediol, acrolein, acrylic acid and so on [1]. As the production of biodiesel is rapidly increasing, producing value-added chemicals from glycerol derived from biodiesel does reduce the biodiesel production cost and reduces the chemical wastes and environmental hazards caused by handling the large amount of surplus crude glycerol [2]

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