Development of High Performance Heterogeneous Catalysts for Selective Cleavage of C−O and C−C Bonds of Biomass‐Derived Oxygenates

Abstract

The environmental impact of CO emissions via the use of fossil resources as chemical feedstock and fuels has stimulated research to utilize renewable biomass feedstock. The biogenic compounds such as polyols are highly oxygenated and their valorization requires the new methods to control the oxygen to carbon ratio of the chemicals. The catalytic cleavage of C-O bonds and C-C bonds is promising methods, but the conventional catalyst systems encounter the difficulty to obtain the high yields of the desired products. This review describes our recent development of the high performance heterogeneous catalysts for the valorization of the biogenic chemicals such as glycerol, furfural, and levulinic acid via selective cleavage of C-O bonds and C-C bonds in the liquid-phase. Selective C-O bond cleavage by hydrogenolysis enables production of various diols useful as engineering plastics, antifreeze, and cosmetics in high yields. The success of the selective C-C bond scission of levulinic acid can be applied to a wide range of the biogenic oxygenates such as carboxylic acids, esters, lactones, and primary alcohols, in which the selective C-C bond scission at adjacent to the oxygen functional groups are achieved. Furthermore, valorization of glycerol by selective acetylation and acetalization, and of levulinic acid by hydrogenation is described. Our catalysts show excellent performance compared to the reported catalysts in the aforementioned valorization.

Recent Advances in Ruthenium-Catalyzed Hydrogenation Reactions of Renewable Biomass-Derived Levulinic Acid in Aqueous Media

“…At a higher temperature of 140 • C the yields of both 2-butanol and 2pentanol were increased to 63.6 and 15.2 mol%, respectively, with, however, a low yield of 1,4-PDO of 0.9 mol%. Mizugaki et al (2017) and Mizugaki and Kaneda (2019) investigated the one-pot hydrogenative C-C bond cleavage reaction of LA catalyzed by RuNPs with an average particle diameter of 3 nm supported on CeO 2 to achieve almost an quantitative conversion of LA and a yield of 85 mol% 2-butanol and of 5 mol% 2-pentanol at 150 • C under 30 bar dihydrogen pressure within 12 h reaction time in aqueous media. The presence of the aqueous solvent is indispensable in the Ru/CeO 2catalyzed hydrogenative C-C cleavage reaction of LA toward 2butanol, because in organic solvents such as 2-propanol, THF or dimethoxyethane the yield to 2-butanol was only up to 5 mol% and the major products were GVL of 70 mol% and 1,2-PDO of 23 mol%.…”

Progress in Production of 1, 3-propanediol From Selective Hydrogenolysis of Glycerol

“…Priya and his group (Priya et al, 2015) first used the hydrothermally stable molecular sieve SBA-15 as a carrier to support Pt-W to prepare a Pt-W-SBA15 catalyst. It is believed that in Pt-Wbased catalysts, the selectivity of 1,3-PDO is positively correlated with the concentration of the Brønsted acid site (Sun et al, 2016;da Silva Ruy et al, 2020;Nakagawa et al, 2014;Lee et al, 2015;Kandasamy et al, 2019;Mizugaki and Kaneda, 2019;Nakagawa and Tomishige, 2011). However, there is an exception, Fan et al prepared a Pt NPS-W-SBA15 catalyst with the tetrahedral phase WO 4 , which only showed Lewis acidity, but the selectivity of 1,3-PDO was up by 70.8%.…”

“…The secondary hydroxyl group in glycerol is replaced by hydrogen to produce 1,3-PDO, and the primary hydroxyl group is replaced by hydrogen to produce 1,2-propanediol (1,2-PDO) (Kandasamy et al, 2019). Since propylene glycol also contains C-OH bonds, hydrogenolysis will continue during the reaction to produce n-propanol (n-PO), isopropanol (i-PO), propane, and other products (Figure 1) (Mizugaki and Kaneda, 2019).…”

“…At present, most reviews described in detail the reaction mechanism and chemical route of glycerol hydrogenolysis, but there are few reviews that focus on the refined classification of catalysts in the reaction of glycerol hydrogenolysis to 1,3-PDO (Rao and Rathod, 2019;Sun et al, 2016;Gerardy et al, 2018;da Silva Ruy et al, 2020;Nakagawa et al, 2014;Lee et al, 2015;Kandasamy et al, 2019;Mizugaki and Kaneda, 2019;Nakagawa & Tomishige, 2011;Tong et al, 2017). In this paper, the main catalytic reaction mechanisms on selective hydrogenolysis of glycerol to 1,3-PDO are summarized and discussed.…”

An Efficient Acetalization Method for Biomass‐Derived Furfural with Ethanol Using γ‐Al2O3‐Supported Catalysts

“…The large generation of residues during the steps of products purification, catalyst recovery and equipment corrosion make these processes environmentally unfriendly. To overcome these drawbacks focus has recently shifted to the development of environmentally benign heterogeneous catalyst systems instead …”