An investigation of activities and selectivities of HZSM-5 and H-ferrierite zeolites modified by different methods in N-butene isomerization

Abstract

In this study the synthesis and preparation of active and selective zeolite catalysts for the skeletal isomerization of 1-butene to iso-butene reaction were investigated. Since this reaction occurs on the acid sites, acidity of the catalyst plays important role on catalyst activity and isobutene selectivity. The acidity of synthesized HZSM-5, commercial Ferrierite (H-FER) and HZSM-5-C zeolite catalysts were modified by chemical liquid deposition (CLD) using tetraetyhyl orthosilicate (TEOS), SiCl4 and triaminopropyltriethoxysilane (3-amino), alkali, acid and ammoniumhexafluorosilicate treatment methods. Reaction tests were performed in a fixed bed reactor at 375 0C at weight hour space velocities of 22 h-1. SiCl4 deposition dramatically decreased the total acidity and surface area, both conversion and selectivity of the catalysts whereas TEOS increased selectivity. The highest selectivity (81.2 %) among CLD agents, were obtained by H-FER modified by TEOS 1 hour 1 cycle. Mild alkali treatment slightly decreased the acidity, which increased selectivity for H-ZSM5 from 57 to 60. However severe alkali treatment decreased the selectivity of the catalysts since some acid sites increased after this treatment. Acid treatment significantly decreased the surface area, acidity and caused dealumination. As a result catalyt activity decreased by 10 %. However, selectivity to isobutene changed slightly. Pre-alkali treatment before acid treatment decreased the dealumination effect, so this increased the selectivity; for H-ZSM5 from 57 to 66. AHFS treatment decreased the acidity slightly without affecting other properties. This increased the selectivity of H-ZSM5 from 58 to 87. The highest selectivity values were obtained for AHFS treatment among all modifications.