Lewis acid zeolites for tandem Diels–Alder cycloaddition and dehydration of biomass-derived dimethylfuran and ethylene to renewable p-xylene

Abstract

p-Xylene was synthesized by [4 + 2] cycloaddition of biomass-derived ethylene and dimethylfuran over Lewis acid zeolite catalyst, Zr-BEA, with 90% selectivity in products.

Production of renewable toluene from biomass-derived furans via Diels-Alder and dehydration reactions: A comparative study of Lewis acid catalysts

“…In addition to CI, other side products, i.e., AT, AC, and OLI, also formed in considerable amounts. Overall, Zr-Beta showed superior performance to Sn-Beta for the Diels-Alder reaction, which is in accordance with findings in the literature [25,26]; however, its activity was still poorer than that of Na-Y zeolite. Na-Y showed a lower conversion of MF (55%) than Zr-Beta, but the toluene selectivity (69%) was much higher than that of Zr-Beta (18%).…”

“…Specifically, Sn-and Zr-Beta zeolites have Lewis acid sites, which originate from tetrahedrally coordinated framework metal centers, unlike cationexchanged Y zeolites. It was recently shown that Sn-and Zr-Beta are fairly active for the Diels-Alder reaction of DMF and ethylene as well as for the Diels-Alder reaction of oxidized derivatives of DMF and ethylene [17,25,26]. Thus, these Lewis acid zeolites were also investigated for the reaction of MF and ethylene.…”

“…However, in the case of conversion of furans to aromatics, Lewis acids have received very little attention because they are not as effective as Brønsted acids for catalyzing the second dehydration reaction. Although successful application of the Lewis acid zeolites of Sn-and Zr-Beta to this cascade reaction with oxidized 5-hydroxymethylfufural (HMF) or DMF has recently been reported, the role of Lewis acids in the Diels-Alder and dehydration reactions of furans is not well understood [25,26]. A systematic study of the reactions with well-defined Lewis acid catalysts would help understand how Lewis acids affect the catalytic chemistry and help design improved catalysts for the conversion of furans such as MF to value-added aromatics.…”

cis,cis-Muconic acid isomerization and catalytic conversion to biobased cyclic-C6-1,4-diacid monomers

“…In the case of terephthalic acid (TPA), the common approach targets renewable p-xylene as a drop-in for oxidation in the AMOCO process (Scheme 1a). [10][11][12] However, oxidation-free routes through muconic acid (MA), a platform intermediate from sugar and lignin fermentation, [13][14][15][16][17][18][19] have also emerged (Scheme 1b). The MA route can be considered advantageous as this intermediate can be converted to a variety of commodity and specialty chemicals, including adipic acid, 14,19,20 TPA, 4,5,21 and 1,4-cyclohexanedicarboxylic acid (CHDA).…”

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“…[6][7][8][9][10][11][12][13] Selectivep roduction of p-xylene from dimethylfuran and ethylene with zeoliteB etac atalyst was developed by Chang et al [14] Here, we used similar chemistry to prepare precursors to p-methylstyrene and p-divinylbenzene. [6][7][8][9][10][11][12][13] Selectivep roduction of p-xylene from dimethylfuran and ethylene with zeoliteB etac atalyst was developed by Chang et al [14] Here, we used similar chemistry to prepare precursors to p-methylstyrene and p-divinylbenzene.…”