Open Access

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.

Hydroxybenzene, commonly known as phenol, is one of the most important organic commodity chemicals. To produce phenol, the cumene process is the most used process worldwide. A crucial step in this process is the Hock rearrangement, which has a major impact on the overall cumene consumption rate and determines the safety level of the process. The most used catalyst for the cleavage of cumene hydroperoxide (CHP) is sulfuric acid. Besides its strong corrosive property, which increases plant investment costs, it also requires neutralization after the decomposition step to prevent side reactions. In this study, we show that high-temperature-treated Linde Type X (LTX) zeolites exhibit a high activity for the peroxide cleavage step. In addition, the structure–activity relationship responsible for this good performance in the reaction system of the HOCK rearrangement was investigated. XRPD analyses revealed the formation of a new phase after temperature treatment above 900 °C. The Si/Al ratio determined by EDX suggested the formation of extra-framework aluminum, which was confirmed by solid-state NMR analysis. The newly formed extra-framework aluminum was found to be responsible for the high catalytic activity. BET analyses showed that the surface area drops at higher calcination temperatures. This leads to a lower catalytic activity for most known reactions. However, for this study, no decrease in activity has been observed. The newfound material shows extraordinarily high activity as a catalyst in the HOCK cleavage and has the potential to be a heterogeneous alternative to sulfuric acid for this reaction.