Solid Acid Catalysts for the Hock Cleavage of Hydroperoxides

The oxidation of cumene and following cleavage of cumene hydroperoxide (CHP) with sulfuric acid (Hock rearrangement) is still, by far, the dominant synthetic route to produce phenol. In 2020, the global phenol market reached a value of 23.3 billion US$ with a projected compound annual growth rate of 3.4% for 2020–2025. From ecological and economical viewpoints, the key step of this process is the cleavage of CHP. One sought-after way to likewise reduce energy consumption and waste production of the process is to substitute sulfuric acid with heterogeneous catalysts. Different types of zeolites, silicon-based clays, heteropoly acids, and ion exchange resins have been investigated and tested in various studies. For every type of these solid acid catalysts, several materials were found that show high yield and selectivity to phenol. In this mini-review, first a brief introduction and overview on the Hock process is given. Next, the mechanism, kinetics, and safety aspects are summarized and discussed. Following, the different types of heterogeneous catalysts and their performance as catalyst in the Hock process are illustrated. Finally, the different approaches to substitute sulfuric acid in the synthetic route to produce phenol are briefly concluded and a short outlook is given.

Chemoenzymatic Conversion of Biomass-Derived D-Xylose to Furfuryl Alcohol with Corn Stalk-Based Solid Acid Catalyst and Reductase Biocatalyst in a Deep Eutectic Solvent–Water System

In this work, the feasibility of chemoenzymatically transforming biomass-derived D-xylose to furfuryl alcohol was demonstrated in a tandem reaction with SO42−/SnO2-CS chemocatalyst and reductase biocatalyst in the deep eutectic solvent (DES)–water media. The high furfural yield (44.6%) was obtained by catalyzing biomass-derived D-xylose (75.0 g/L) in 20 min at 185 °C with SO42−/SnO2-CS (1.2 wt%) in DES ChCl:EG–water (5:95, v/v). Subsequently, recombinant E.coli CF cells harboring reductases transformed D-xylose-derived furfural (200.0 mM) to furfuryl alcohol in the yield of 35.7% (based on D-xylose) at 35 °C and pH 7.5 using HCOONa as cosubstrate in ChCl:EG–water. This chemoenzymatic cascade catalysis strategy could be employed for the sustainable production of value-added furan-based chemical from renewable bioresource.