Dimethyl ether synthesis via methanol dehydration: Effect of zeolite structure

被引:88
作者
Catizzone, Enrico [1 ]
Aloise, Alfredo [1 ]
Migliori, Massimo [1 ]
Giordano, Girolamo [1 ]
机构
[1] Univ Calabria, Dept Environm & Chem Engn, I-87036 Arcavacata Di Rende, CS, Italy
关键词
Methanol-to-DME; Zeolite structure effect; Coke formation; Catalyst deactivation; SOLID-ACID; HYBRID CATALYSTS; TO-HYDROCARBONS; SYNTHESIS GAS; DME; CONVERSION; RATIO; H-ZSM-5; COKE; DEACTIVATION;
D O I
10.1016/j.apcata.2015.06.017
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
In this paper, the effects of either pore size or topology of zeolites were studied in the methanol dehydration to dimethyl ether reaction by comparing catalytic performances of BEA, MFI and FER structures in the temperature range 180 degrees C-300 degrees C. The aim of this study was to investigate how the zeolite catalyst characteristics affect the process performances in terms of methanol conversion and DME selectivity. It was found that the largest-pore 3-D framework zeolite (BEA) was very effective in converting methanol but the channel size and topological connection spaces allowed the fast formation of coke precursors that rapidly decreases the catalyst performances at higher temperatures. Even if lower in intensity, the same phenomenon was observed for MFI structure (medium pores 3-D framework) confirming stable performances in the temperature range used in the real processes. On the contrary, the 2-D small pores FER zeolite showed a very good selectivity at high temperature also exhibiting a promising conversion rate for an industrial application. Continuous catalytic tests at 300 degrees C, followed by coke deposition analysis, confirmed that BEA rapidly deactivates and exhibited the higher coke formation rate, on the contrary, FER structure exhibited a great stability (conversion and selectivity) as well as a reduced coke formation tendency. (C) 2015 Elsevier B.V. All rights reserved.
引用
收藏
页码:215 / 220
页数:6
相关论文
共 35 条
[21]   Catalytic dehydration of methanol to dimethyl ether over modified γ-Al2O3 catalyst [J].
Liu, Dianhua ;
Yao, Chunfeng ;
Zhang, Jianqiang ;
Fang, Dingye ;
Chen, Dasheng .
FUEL, 2011, 90 (05) :1738-1742
[22]   Kinetic Analysis of Methanol to Dimethyl Ether Reaction over H-MFI Catalyst [J].
Migliori, Massimo ;
Aloise, Alfredo ;
Catizzone, Enrico ;
Giordano, Girolamo .
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH, 2014, 53 (38) :14885-14891
[23]   Methanol to dimethylether on H-MFI catalyst: The influence of the Si/Al ratio on kinetic parameters [J].
Migliori, Massimo ;
Aloise, Alfredo ;
Giordano, Girolamo .
CATALYSIS TODAY, 2014, 227 :138-143
[24]   Acidity of β zeolite with different Si/Al2 ratio as measured by temperature programmed desorption of ammonia [J].
Miyamoto, Y ;
Katada, N ;
Niwa, M .
MICROPOROUS AND MESOPOROUS MATERIALS, 2000, 40 (1-3) :271-281
[25]  
Ogawa T., 2003, J NAT GAS CHEM, V12, P219
[26]   Conversion of Methanol to Hydrocarbons: How Zeolite Cavity and Pore Size Controls Product Selectivity [J].
Olsbye, Unni ;
Svelle, Stian ;
Bjorgen, Morten ;
Beato, Pablo ;
Janssens, Ton V. W. ;
Joensen, Finn ;
Bordiga, Silvia ;
Lillerud, Karl Petter .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2012, 51 (24) :5810-5831
[27]   IR study on methanol-to-olefin reaction over zeolites with different pore structures and acidities [J].
Park, Ji Won ;
Seo, Gon .
APPLIED CATALYSIS A-GENERAL, 2009, 356 (02) :180-188
[28]   Selective dehydration of methanol to dimethyl ether on ZSM-5 nanocrystals [J].
Rownaghi, Ali A. ;
Rezaei, Fateme ;
Stante, Matteo ;
Hedlund, Jonas .
APPLIED CATALYSIS B-ENVIRONMENTAL, 2012, 119 :56-61
[29]   "Coking" of zeolites during methanol conversion: Basic reactions of the MTO-, MTP- and MTG processes [J].
Schulz, Hans .
CATALYSIS TODAY, 2010, 154 (3-4) :183-194
[30]   Methanol-to-hydrocarbons:: catalytic materials and their behavior [J].
Stöcker, M .
MICROPOROUS AND MESOPOROUS MATERIALS, 1999, 29 (1-2) :3-48