ZSM-5 zeolites modified with Zn and their effect on the crystal size in the conversion of methanol to light aromatics (MTA)

被引:14
|
作者
Garcia Ruiz, Misael [1 ]
Solis Casados, Dora A. [2 ]
Aguilar Pliego, Julia [3 ]
Marquez Alvarez, Carlos [4 ]
Sastre de Andres, Enrique [4 ]
Sanjurjo Tartalo, Diana [4 ]
Sainz Vaque, Raquel [4 ]
Grande Casas, Marisol [4 ]
机构
[1] Univ Autonoma Estado Mexico, Fac Quim, Ciencia Mat, Paseo Colon Esquina Paseo Tollocan S-N, Mexico City 50000, DF, Mexico
[2] Univ Autonoma Estado Mexico, Ctr Conjunto Invest Quim Sustentable UAEM UNAM, Fac Quim, UAEMex, Mexico City, DF, Mexico
[3] UAM A, Dept Ciencias Basicas, Area Quim Aplicada, San Pablo 180, Mexico City 02200, DF, Mexico
[4] CSIC, Inst Catalisis & Petroleoquim, C Marie Curie 2,Campus Cantoblanco, Madrid 28049, Spain
关键词
ZSM-5; zeolite; MTA process; BTX fraction; Modified zeolites; Nanocrystalline zeolite; CATALYTIC PERFORMANCE; SELECTIVE CONVERSION; HZSM-5; CATALYSTS; PARTICLE-SIZE; PARA-XYLENE; AROMATIZATION; HYDROCARBONS; ACID; DEACTIVATION; MFI;
D O I
10.1007/s11144-019-01716-4
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
ZSM-5 zeolite catalysts modified with zinc were prepared by two forms of Zn incorporation the synthesis gel, and ion exchange techniques. The physico-chemical properties of zeolites were studied by XRD, N-2-adsorption, NH3 temperature-programmed desorption, Al-27 and Si-29 MAS NMR, SEM, TEM and TGA. ZSM-5 zeolite in its acid form was exchanged using an aqueous zinc salt solution and demonstrated a significantly higher selectivity for the aromatic products in comparison with the purely acidic catalysts. The samples with distribution of ZnOH+ species are more active than the samples with ZnO sites in the zeolites. The synthesis of zeolite ZSM-5 of nanometric size resulted to present high stability and selectivity towards light aromatics. The influence of the form of zinc incorporation, the acidity and the reaction temperature had a great influence on the catalytic activity. The MTA catalyst lifetime is increased by several times due to the enhanced mesoporosity and decreased acidity. In the present work the zeolite HZSM-5 exchanged with Zn with Si/Al 25 ratio presented conversions close to 100% methanol with 32% selectivity to the BTX fraction, however, this catalyst was deactivated after 8 h of reaction with a weight hourly space velocity of 4.74 h(-1) at 450 degrees C. On the other hand, a HZSM-5 zeolite with nanoscale crystals was found to be more stable in the MTA reaction. The nanometric catalyst showed conversions around 100% methanol after 8 h of reaction and 32.5% selectivity to the BTX fraction to 450 degrees C. These results clearly indicate that crystal size significantly influence the ZSM-5 lifetime and product distribution.
引用
收藏
页码:471 / 490
页数:20
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