Toward an Integrated Conversion of 5-Hydroxymethylfurfural and Ethylene for the Production of Renewable p-Xylene

Abstract

The use of biomass as a solution to satisfy the pressing needs for a fully sustainable biocommodity industry has been explored for a long time. However, limited success has been obtained. In this study, a highly effective two-stage procedure for the direct preparation of para-xylene (PX) from 5-hydroxymethylfurfural (HMF) and formic acid in one pot is described; these chemicals are two of the major bio-based feedstocks that offer the potential to address urgent needs for the green, sustainable production of drop-in chemical entities. The use of a robust, efficient heterogeneous catalyst, namely, bimetallic Pd-decorated Au clusters anchored on tetragonal-phase zirconia, is crucial to the success of this strategy. This multifunctional catalytic system can not only facilitate a lowenergy-barrier H 2 -free pathway for the rapid, nearly exclusive formation of 2,5-dimethylfuran (DMF) from HMF but also enable the subsequent ultraselective production of PX by the dehydrative aromatization of the resultant DMF with ethylene.

Formic Acid‐Assisted Selective Hydrogenolysis of 5‐Hydroxymethylfurfural to 2,5‐Dimethylfuran over Bifunctional Pd Nanoparticles Supported on N‐Doped Mesoporous Carbon

“…Tao et al also reported a DMF yield of 98% from HMF and FA over 1% Au^Pd0.2/t-ZrO2. 22 Nevertheless, the different roles of FA have not yet been elucidated in detail. Pd exhibits high catalytic activity in the hydrogenolysis of HMF to DMF using FA as the hydrogen source, and it is usually supposed to be the optimum metal for the decomposition of FA.…”

“…Tao et al. also reported a DMF yield of 98 % from HMF and FA over 1 % Au^Pd 0.2 /t‐ZrO 2 [22] . Nevertheless, the different roles of FA have not yet been elucidated in detail.…”

Catalytic Conversion of Biomass to Furanic Derivatives with Deep Eutectic Solvents

“…Among these bio‐based chemicals, several typical furanic derivatives, such as 5‐hydroxymethylfurfural (HMF) and furfural (FF), indeed appear in the list of the “TOP 10+4” described by the US Department of Energy [2] . These platform molecules can be employed as starting materials for the preparation of many value‐added products including fuel additives 2,5‐dimethylfuran (DMF) and 5‐ethoxymethylfurfural (EMF), [3] polymer monomers 2,5‐furandicarboxylic acid (FDCA) [4] and 2,5‐dihydroxymethylfuran (DHMF), [5] industrial solvent tetrahydrofuran (THF), [6] and the commodity chemical para ‐xylene (PX) [7] . Thus, it is promising and significant to produce platform components or chemicals from biomass.…”

Ameisensäure‐unterstützte selektive Hydrogenolyse von 5‐Hydroxymethylfurfural zu 2,5‐Dimethylfuran über bifunktionale Pd‐Nanopartikel auf N‐dotiertem mesoporösem Kohlenstoff als Träger

“…Tao et al. berichteten auch über eine DMF‐Ausbeute von 98 % aus HMF und FA über 1 % Au^Pd 0.2 /t‐ZrO 2 [22] . Dennoch sind die verschiedenen Rollen von FA noch nicht im Detail aufgeklärt.…”