Effect of Tungsten Species on Selective Hydrogenolysis of Glycerol to 1,3‐Propanediol

Abstract

Glycerol, as the major byproduct of biodiesel industry, is a cheap and green chemical feedstock. Following the expanded production of biodiesel, the oversupply of glycerol has led to increasing research of the catalytic conversion of glycerol. The selective hydrogenolysis of glycerol is an economical and sustainable way to produce 1,3‐propanediol, which experiences a global growing demand, and valorize glycerol. However, the secondary hydroxy group of glycerol is sterically hindered by two primary hydroxy groups. As a result, 1,2‐propanediol is the preferential product rather than 1,3‐propanediol during conventional hydrogenolysis of glycerol. Currently, tungsten‐containing bifunctional catalysts with metal and Brønsted acid sites are considered as a highly effective and atom‐economical catalytic system for the selective hydrogenolysis of glycerol to 1,3‐propanediol. Therefore, this Minireview summarized various tungsten‐containing bifunctional catalysts for the hydrogenolysis of glycerol in detail and deeply discussed the relationship between tungsten species, metal active sites, and glycerol for selectively producing 1,3‐propanediol.

The Promotional Effect of Sulfates on TiO2 Supported Pt‐WOx Catalyst for Hydrogenolysis of Glycerol

“…Glycerol is available as a byproduct in surplus amounts owing to the rapid growing of biodiesel production, and thus requires efficient transformation to value-added chemicals. [1][2][3] The renewability and unique structure of glycerol make it a versatile platform molecule for producing a variety of fine chemicals via catalytic reactions, such as hydrogenolysis, oxidation, dehydration, esterification and others. [4][5][6][7][8] 1,3-propanediol (1,3-PDO) is an important chemical from glycerol hydrogenolysis with wide applications in the manufacture of polytrimethylene terephthalate, polyurethanes, and cyclic compounds.…”

“…So far, the efficient hydrogenolysis of glycerol in aqueous phase are mostly conducted over a bifunctional catalyst including a noble metal (Ir, Rh, or Pt) and a transition metal oxide (such as ReO x or WO x ). [2,3,[13][14][15][16][17][18] Among them, Ir-ReO x based catalysts were mainly studied by Tomishige's group and 38 % yield of 1,3-PDO with 81 % conversion of glycerol was achieved over IrÀ Re/SiO 2 catalyst. [17] Pt-WO x based catalysts were widely investigated and showed high industrial application potential owing to their superior selectivity to 1,3-PDO.…”

“…[17] Pt-WO x based catalysts were widely investigated and showed high industrial application potential owing to their superior selectivity to 1,3-PDO. [2,3] The interface between the Pt and WO x species is regarded as the active sites for glycerol hydrogenolysis, which can be optimized through the increase of Pt and WO x loading. [19,20] However, high Pt and WO x content usually lead to the inactive polymerized WO x species or large Pt particles, resulting in undesired catalytic activity.…”

“…Glycerol is available as a byproduct in surplus amounts owing to the rapid growing of biodiesel production, and thus requires efficient transformation to value‐added chemicals [1–3] . The renewability and unique structure of glycerol make it a versatile platform molecule for producing a variety of fine chemicals via catalytic reactions, such as hydrogenolysis, oxidation, dehydration, esterification and others [4–8] .…”

“…Among them, Ir‐ReO x based catalysts were mainly studied by Tomishige's group and 38 % yield of 1,3‐PDO with 81 % conversion of glycerol was achieved over Ir−Re/SiO 2 catalyst [17] . Pt‐WO x based catalysts were widely investigated and showed high industrial application potential owing to their superior selectivity to 1,3‐PDO [2,3] . The interface between the Pt and WO x species is regarded as the active sites for glycerol hydrogenolysis, which can be optimized through the increase of Pt and WO x loading [19,20] .…”