Controllable transformation of biomass-derived diols over an ammonia-modified H-Beta zeolite

Abstract

For the controllable transformation of C_3–6 diols in ethylene glycol (EG), a H-Beta zeolite catalyst was modified with NH₃via incomplete desorption. 60.8% of acid sites on the zeolite were deactivated, but the ratio of strong acid sites was obviously increased. With 1,2-pentanediol (PDO) as a representative large-carbon-number diol, the undesirable acetalization and oligomerization reactions of EG were suppressed in the EG-PDO reaction system over the modified catalyst due to their dependency on total acid sites. NH₃-TPD and FTIR results proved that Lewis acid sites on the modified zeolite were eliminated after modification, resulting in the suppression of acetalization and oligomerization reactions. In contrast, a portion of strong Brønsted acid sites still remained, ensuring the catalytic transformation of PDO. Only 8.2% of EG was consumed after 8 h reaction, and the conversion of PDO could reach 84.3%. The loading of NH₃ on the surface of zeolite pores led to diffusion resistance, slightly decreasing the reaction rate of PDO without affecting the reaction selectivity. The catalytic reactions of other C_3–6 diols in EG followed similar principles, and the selectivity to aldehydes or ketone was improved over this modified catalyst. Non-diol biomass hydrogenation products such as glycerol had a negative influence on the selectivity, so these components should be isolated before the reactions. This catalyst could be reused at least 5 times, and the conversion of PDO slightly decreased. This work sheds light on the relationships between the acid properties of the catalyst and different reactions of diols.