Aqueous-Phase Hydrogenolysis of Glycerol to 1,3-propanediol Over Pt-H4SiW12O40/SiO2

Abstract

Hydrogenolysis of glycerol to 1,3-propanediol in aqueous-phase was investigated over Pt-H 4 SiW 12 O 40 / SiO 2 bi-functional catalysts with different H 4 SiW 12 O 40 (HSiW) loading. Among them, Pt-15HSiW/SiO 2 showed superior performance due to the good dispersion of Pt and appropriate acidity. It is found that Brønsted acid sites facilitate to produce 1,3-PDO selectively confirmed by Py-IR. The effects of weight hourly space velocity, reaction temperature and hydrogen pressure were also examined. The optimized Pt-HSiW/SiO 2 catalyst showed a 31.4% yield of 1,3-propanediol with glycerol conversion of 81.2% at 200°C and 6 MPa.

Evidence for the Bifunctional Nature of Pt–Re Catalysts for Selective Glycerol Hydrogenolysis

“…The results from experiments with the homogenous acids and supported Pt, considered together with the work conducted by Li and co-authors, [43][44][45][46] suggest that intimate contact of the Brønsted acid site and a Pt metal site is required to produce 1,3-PDO at a high rate from glycerol. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 Figure 1 shows rate of glycerol hydrogenolysis measured over a wide range of glycerol concentrations (15 to 550 mM) after 1 h of reaction.…”

A review: Conversion of bioglycerol into 1,3-propanediol via biological and chemical method

“…These liquid acids which were used as additives for solid catalyst will cause the corrosion problem in reactor and catalyst separation. Another drawback is that the reaction required high pressure (5.0-32.0 MPa) system [75,79,80,82,84,85,87,88], thus increase the production cost whereby money will be spent on high pressure equipment, as well as increase the hazardous risk such as explosions which can be due to overpressurization in the reactor and sudden arise of reaction temperature.…”

“…Kurosaka [74]. The selectivity of 1,3-PDO was increased significantly to 38.7% and the glycerol conversion was 81.2% [85]. Due to that good thermal stability and high Bronsted acid sites of heteropolyacids, HSiW which attached on metal catalyst had improved the selectivity of 1,3-PDO [86].…”

Advances in selective catalytic transformation of ployols to value-added chemicals

“…38% yield of 1,3-PG was obtained with 81% conversion of glycerol. In addition, the combination of a heteropoly acid with a metal catalyst was applied to the conversion of glycerol to 1,3-PG, such as Cu-H4SiW12O40/SiO2 [202], Pt-H4SiW12O40SiO2 [203] and Pt/H3PW12O40/ZrO2 [205]. The heteropoly acid provides the appropriate acid sites and acid strength, and a supported heteropoly acid avoids a separation process and reduce the use of corrosive liquids.…”