Efficient C–C coupling of bio-based furanics and carbonyl compounds to liquid hydrocarbon precursors over lignosulfonate derived acidic carbocatalysts

Abstract

This paper demonstrates the catalytic potential of novel Na-lignosulfonate (LS) derived meso/macroporous solid protonic acids upon C–C coupling of bio-based furanics and carbonyl compounds. The materials demonstrated catalytic activity for solventless hydroxyalkylation/alkylation (HAA) of 2-methylfuran with furfural, acetone, butanal, cyclohexanone, levulinic acid and α-angelica lactone under mild reaction conditions (50–60 °C) producing branched-chain C12–C16 hydrocarbon precursors in yields approaching 96%. Moreover, the carbon materials exhibiting high total acidity (6–6.4 mmol g⁻¹) outperformed sulfonic acid resins (Amberlyst®70, Amberlite®IR120 and LS resin), zeolites and liquid acids (p-toluenesulfonic acid, acetic acid and phenol). In fact, the most active carbocatalyst (60LS40PS350H⁺) exhibited the same turnover frequency as p-toluenesulfonic acid (186 h⁻¹) upon furfural conversion but with an improved HAA product yield (up to 88%) and reusability, maintaining 98% of its original activity up to seven reaction cycles. The observed catalytic activity and operational stability of the LS derived acidic carbocatalysts were attributed to the strongly Brønsted acidic –SO₃H groups covalently incorporated into their structural carbon framework and the promotional effects of hydrophilic surface functional groups (–COOH and –OH) favoring adsorption of oxygenated reactant molecules.