Endothermic Reforming of <i>n</i>‑Hexane on Metal (Pt, Ga) Containing H‑ZSM‑5 at High Pressures

The supercritical, high-pressure reaction of <i>n</i>-hexane over H-ZSM-5, with and without the addition of Pt and Ga, has been studied for application to endothermic reforming in scramjet engines. The endothermicities of the reactions were determined from the product distributions. For unpromoted H-ZSM-5, the product distribution indicated that the endothermicity is low and decreases with increasing pressure. The addition of Ga to H-ZSM-5 has a relatively small effect on <i>n</i>-hexane conversion but significantly increases the endothermicity of the reaction by increasing the selectivity to form small aromatics. The H­(Ga)-ZSM-5 catalyst showed no deactivation for at least 5 h at 633 K and 137 bar of <i>n</i>-hexane. By contrast, the addition of Pt had a minor effect on both the rate and the reaction endothermicity

Diels–Alder and Dehydration Reactions of Biomass-Derived Furan and Acrylic Acid for the Synthesis of Benzoic Acid

Routes to benzoic acid starting from furanobtained from hemicellulose in high yieldand methyl acrylate are reported. These routes involve Diels–Alder and dehydration reactions of furan and acrylic acid (or methyl acrylate) in a two-step reaction protocol that minimizes side reactions. The Diels–Alder reaction of furan and methyl acrylate (or acrylic acid) was run at 298 K and was catalyzed by Lewis acidic (Hf-, Zr-, and Sn-Beta) zeolite catalysts, and achieving a high turnover frequency (∼2 h^–1) and no side reactions were observed. The oxanorbornene product was dehydrated at low temperatures (298 to 353 K) in mixtures of methanesulfonic acid and acetic anhydride in 96% yield. This is compared to an only 1.7% yield of methyl benzoate obtained for the dehydration of the oxanorbornene in neat methanesulfonic acid. The effect of oxanorbornene concentration and stereochemistry was found not to decrease the yield of aromatics, while dehydration of the carboxylic acid form of the oxanorbornene led to a decrease in selectivity to 43% at complete conversion in mixtures of methanesulfonic acid and acetic anhydride. This reaction sequence could be an important entry point for selectively directing high-yield, hemicellulose-derived furans to aromatic products used in the existing chemical process industry