Regulating the Acidity and Pore Structure of Hβ Zeolite with Citric Acid Concentration for Optimized Aniline Condensation Catalysis

Diphenylamine is an important organic chemical intermediate, and its industrial synthesis is mainly achieved through the continuous condensation of aniline. In this study, Hβ zeolite was modified with citric acid, and its catalytic performance in the aniline condensation reaction for diphenylamine synthesis was systematically investigated. The crystal structure, acidic characteristics, pore properties, and Si/Al composition of the catalysts were comprehensively characterized by means of XRD, SEM, BET, Py-IR, ICP, and 27Al MAS NMR. The catalytic activities of Hβ zeolites modified with different concentrations of citric acid were evaluated in a micro fixed-bed reactor, and the structure–activity relationship was systematically discussed in combination with the characterization results. The results demonstrate that the Hβ zeolite modified with 1.5 mol/L citric acid achieves precise matching with the aniline condensation reaction in terms of crystal structure integrity, pore channel parameters, acid property distribution, and Si/Al ratio regulation. Compared with the unmodified catalyst, its catalytic activity is improved by approximately 28%, with a diphenylamine selectivity of 100%. This study proposes a modification mechanism of Hβ zeolite by citric acid.