Activity and Selectivity of Platinum–Copper Bimetallic Catalysts Supported on Mordenite for Glycerol Hydrogenolysis to 1,3-Propanediol

Abstract

Biomass derived glycerol is considered an ideal feedstock with a prospective to be converted into a number of valuable compounds. Catalytic glycerol hydrogenolysis to produce 1,3-propanediol is one of the pioneering biosustainable pathways. Bimetallic Pt−Cu catalysts supported on H-mordenite were synthesized with various copper loadings and applied in the selective glycerol hyrogenolysis to 1,3-propanediol in a continuous fixed bed reactor performed in vapor phase under atmospheric pressure. Several techniques such as XRD, ICP-AES, NH 3 -TPD, Pyr FTIR, BET, TPR, HR-TEM, XPS, and solid state NMR were employed to characterize the physical and chemical properties of Pt−Cu/Mor catalysts. A detailed reaction parametric study has been carried out. The results designated that well dispersed Pt−Cu catalysts with small particle size, supported on a Brønsted acidic H-mordenite with a multiple pore system and strong bimetallic phase-support interaction, promote the selectivity to 1,3-propanediol. Over the Pt−Cu/Mor catalyst of optimum composition (2% Pt and 5% Cu by weight) and under the optimum reaction conditions (210 °C, H 2 flow rate of 80 mL min −1 , and gly concentration of 10 wt %), the glycerol conversion and 1,3-PD selectivity reached 90% and 58.5%, respectively. Structural characterizations and reusability of the Pt-5Cu/Mor catalyst were also performed. With evident advantages of selective C−O hydrogenolysis with low C−C cleavages, the bimetallic Pt−Cu/Mor catalysts hold great potential as high-performance catalysts for glycerol conversion to 1,3propanediol.

Toward the Sustainable Synthesis of Propanols from Renewable Glycerol over MoO3-Al2O3 Supported Palladium Catalysts

“…Glycerol hydrogenolysis is a complex reaction (Scheme 2) and is generally believed to proceed via dehydration-hydrogenation route in two distinct pathways, which involve the formation of intermediates (acetol and 3-hydroxypropanaldehyde (3-HPA)) by acid-catalyzed dehydration and subsequent formation of propanediols (1,2-PDO and 1,3-PDO) over metal sites [35][36][37][38][39]. Thereafter, C-O hydrogenolysis of 1,2-PDO results in the formation of 1-propanol (1-PrOH), while C-O hydrogenolysis of 1,3-PDO gives rise to 2-propanol (2-PrOH).…”

Nanostructured Metal Catalysts for Selective Hydrogenation and Oxidation of Cellulosic Biomass to Chemicals

“…Controlling WO 3 density on catalyst surface by obtaining highly dispersed polytungstate species is also important in producing more Bronsted acid sites . The addition of Cu restrains C−C cleavage but promotes C−O cleavage reactions on Pt catalyst surface, therefore 1,3‐PDO selectivity (X: 90 %, S: 58.5 %) can be improved on bimetallic PtCu catalysts …”

Catalytic glycerol hydrogenolysis to 1,3-propanediol in a gas–solid fluidized bed

“…The maximum 1,3-PDO selectivity was 58.5%. 20,21 Selectivity of 1,3-PDO reached 32% with Pt/WO 3 /ZrO 2 at 130 C and 40 bar 16 but the highest selectivity to date was 66% (Table 1) with a Pt/WO 3 / AlOOH catalyst. 22 Recent studies show that acrolein in an aqueous solution reacts to form 3-hydroxypropanal in a yield of 20%.…”