Abstract
Direct C-O hydrogenolysis of bioglycerine to produce 1,3-propanediol selectively is a vital technology that can expand the scope of biodiesel industry and green chemical production from biomass. Herein we report sulphuric acid-activated montmorillonite clay supported platinum nanoparticles as highly effective solid acid catalysts for the selective production of 1,3-propanediol from glycerol. The catalytic performances of the catalysts were investigated in the hydrogenolysis of glycerol with a fixed bed reactor under ambient pressure. The results were found promising and showed that the activation of montmorillonite by sulphuric acid incorporated Brønsted acidity in the catalyst and significantly improved the selectivity to 1,3-propanediol. The catalytic performance of different platinum loaded catalysts was examined and 2 wt% Pt/S-MMT catalyst presented superior activity among others validating 62% 1,3-propanediol selectivity at 94% glycerol conversion. The catalytic activity of 2Pt/S-MMT was systematically investigated under varying reaction parameters including reaction temperature, hydrogen flow rate, glycerol concentration, weight hourly space velocity, and contact time to derive the optimum conditions for the reaction. The catalyst stability, reusability and structure-activity correlation were also elucidated. The high performance of the catalyst could be ascribed to well disperse Pt nanoparticles immobilized on acid-activated montmorillonite, wider pore-structure and appropriate acid sites of the catalyst.
Highlights
Focused on the utilization of biodiesel waste glycerol as a versatile building block and its transformation into high value-added specialty chemicals
The diffraction profiles of montmorillonite, sulfuric acid-treated montmorillonite and various loadings (0.5–3 wt%) of Pt/S-MMT catalysts are shown in Figs 2 and S2 (Supplementary)
The other characteristic reflections at 2θ 12.5°, 17.7°, 19.7°, 22.08°, 23.7°, 26.54°, 29.94°, 36.56°, 50.01°, 62.0° assigned to the crystal lattice planes of d 060 (0.502 nm), 080 (0.451 nm), 020 (0.378 nm), 060 (0.303 nm), 030 (0.171 nm), 050 (0.151 nm) and 050 (0.148 nm) respectively[24], remained clearly identified in both MMT and S-MMT
Summary
Focused on the utilization of biodiesel waste glycerol as a versatile building block and its transformation into high value-added specialty chemicals. Supported noble metal (Pt, Ir) catalysts with a co-catalyst (WO3, ReOx) especially high in Brønsted acid sites have been proven to be the more efficient catalytic materials for the selective production of 1,3-PDO from glycerol hydrogenolysis[10,11,12,13,14,15,16,17] (Fig. 1). To achieve an improved catalytic activity and selectivity to 1,3-PDO in hydrogenolysis of glycerol, the present work focused on the development of highly efficient, eco-friendly and recyclable sulfuric acid-activated MMT supported platinum nanoparticles as a potential catalyst promoting selective production of 1,3-PDO. The research work reported is unique and to the best of our understanding, platinum supported on sulfuric acid-activated montmorillonite has not been explored so far as a catalyst for glycerol conversion to 1,3-PDO by hydrogenolysis
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