Toluene Alkylation to Selective Formation of p-Xylene over Co-Crystalline ZSM-12/ZSM-5 Catalyst

The alkylation of toluene with methanol to selective formation of p-xylene has been systematically studied. ZSM-12 （MTW）/ZSM-5 co-crystalline zeolite in 40：60 proportions have been synthesized by the same molar gel composition, but at different temperatures and periods than that of ZSM-12 and ZSM-5, separately. All the prepared samples are characterized by XRD, SEM, BET, and XRF. The activity of toluene alkylation was investigated with a mixture of toluene and methanol as a feed over the ZSM-12, ZSM-12/ZSM-5 co-crystalline, ZSM-5, and physical mixture of ZSM-12/ZSM-5. From characterization, it is observed that the ZSM-12/ZSM-5 co-crystalline material is different from that of ZSM-12, ZSM-5, and their physical mixture. Further, the ZSM-12/ZSM-5 co-crystalline zeolite produces the highest content of xylene and has better selectivity for p-xylene than ZSM-12, ZSM-5, and their physical mixture.

Synthesis and Characterization of ZSM-5/β Co-Crystalline Zeolite

ZSM-5/β co-crystalline zeolites with different content of ZSM-5 have beensynthesized by adding different amount of ZSM-5 to the synthetic system of β zeolite with NaAlO_2,silica sol as the source of aluminum and silica, respectively, and TEA^+ as the template undercontrolled condition of the synthesis. The ZSM-5/β co-crystalline zeolite was studied by XRD, SEM,BET and NH_3-TPD. The reaction activity of toluene alkylation was investigated with a mixture oftoluene-methanol as the feedstock in a pulse micro-reactor over the ZSM-5/β co-crystalline zeolite.It is found that ZSM-5/β co-crystalline zeolite has two kinds of zeolite structure including ZSM-5and β zeolite, not in the form of a physical mixture. The pore structure of ZSM-5/βco-crystalline zeolites is different from that for β zeolite, ZSM-5 and their physical mixture. Inaddition, the peaks of both high and low temperature desorption of ammonia over the ZSM-5/βco-crystalline zeolite shift 23℃ to lower temperatures and the acid amount of its strong acid is 3%more than the physical mixture. So the ZSM-5/β co-crystalline zeolite produces the highest contentof xylene, which is 10.4% higher than the physical mixture. And the ZSM-5/β co-crystalline zeolitehas better selectivity for toluene alkylation and weaker de-methylation than β zeolite, ZSM-5 andtheir physical mixture.

AIO_(3)·H_(6)TeO_(6)(A=NH_(4)^(+),Rb^(+)):Two telluric acid and iodate Co-crystalline compounds with second harmonic generation response

Two co-crystalline compounds containing telluric acid and iodate,namely AIO_(3)·H_(6)TeO_(6)(A=Rb^(+),NH_(4)^(+)),were investigated as potential nonlinear optical materials.They crystallize into isostructural and consist of isolated[IO_(3)]group and[H_(6)TeO_(6)]molecule linked by hydrogen bonds and charge interactions of Rb^(+)/NH_(4)^(+).They show phase-matching second harmonic generation responses with moderate intensity of 1.2×KDP(Rb^(+))and 1.1×KDP(NH_(4)^(+)).They also possess large optical band gaps over 4.25 eV and can be easily grown from aqueous so-lutions.The local dipole moment calculations based on the structures of AIO_(3)·H_(6)TeO_(6)(A=K+,Rb^(+),NH_(4)^(+))series of compounds indicate that the change of A+cation in their structural frame causes a slight change in the arrangement directions of[IO_(3)]and[Te(OH)_(6)]groups,and further induces their SHG responses of different in-tensities at the macroscopic level.