Selectivity control through fundamental mechanistic insight in the conversion of methanol to hydrocarbons over zeolites

被引:137
作者
Teketel, Shewangizaw [1 ]
Olsbye, Unni [1 ]
Lillerud, Karl-Petter [1 ]
Beato, Pablo [2 ]
Svelle, Stian [1 ]
机构
[1] Univ Oslo, Dept Chem, InGAP Ctr Res Based Innovat, N-0315 Oslo, Norway
[2] Haldor Topsoe Res Labs, DK-2800 Lyngby, Denmark
关键词
Alkenes; Reaction mechanism; Methanol-to-gasoline; Zeolites; ZSM-22; CATALYZED METHYLATION REACTIONS; TO-HYDROCARBONS; CO-REACTION; MEDIUM-PORE; H-ZSM-5; SAPO-34; ZSM-22; ETHENE; CAVITIES; ACIDITY;
D O I
10.1016/j.micromeso.2010.07.013
中图分类号
O69 [应用化学];
学科分类号
081704 ;
摘要
In this paper, the methanol to hydrocarbon (MTH) reaction mechanism is studied over H-ZSM-22 zeolite catalyst. The H-ZSM-22 catalyst is chosen due to its narrow one-dimensional 10-ring straight channels which are likely to suppress the space demanding hydrocarbon pool type mechanism and favor product formation from alkene cracking and methylation. The study was performed using isotope switch experiments from C-12 to C-13 methanol at different times on stream. The reactivity of the gas phase products and hydrocarbons trapped in the channels of H-ZSM-22 is determined. The result obtained for the H-ZSM-22 catalyst is compared with other zeolite/zeotype topologies. The study shows that the aromatics based hydrocarbon pool mechanism, which produces sizable amounts of light alkenes including ethene is suppressed over H-ZSM-22 catalyst. The methanol conversion and selectivity is controlled by the alkene cracking and methylation pathway, yielding an aromatics free product, rich in branched alkenes. This contribution addresses the possibility of controlling product selectivity based on intimate knowledge about the MTH reaction mechanisms over zeolite/zeotype materials. Reaction mechanism is shown to be one parameter that determines the selectivity in the MTH reaction, and this hint could be useful in rational design of catalysts based on mechanistic insight, thereby enhancing the selectivity for the desired products to the ultimate goal of 100%. (C) 2010 Elsevier Inc. All rights reserved.
引用
收藏
页码:33 / 41
页数:9
相关论文
共 42 条
[1]   CATALYTIC CRACKING AND SKELETAL ISOMERIZATION OF NORMAL-HEXENE ON ZSM-5 ZEOLITE [J].
ABBOT, J ;
WOJCIECHOWSKI, BW .
CANADIAN JOURNAL OF CHEMICAL ENGINEERING, 1985, 63 (03) :451-461
[2]   INSITU SOLID-STATE NMR-STUDIES OF THE CATALYTIC CONVERSION OF METHANOL ON THE MOLECULAR-SIEVE SAPO-34 [J].
ANDERSON, MW ;
SULIKOWSKI, B ;
BARRIE, PJ ;
KLINOWSKI, J .
JOURNAL OF PHYSICAL CHEMISTRY, 1990, 94 (07) :2730-2734
[3]   The reactivity of molecules trapped within the SAPO-34 cavities in the methanol-to-hydrocarbons reaction [J].
Arstad, B ;
Kolboe, S .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (33) :8137-8138
[4]   Methanol-to-hydrocarbons reaction over SAPO-34. Molecules confined in the catalyst cavities at short time on stream [J].
Arstad, B ;
Kolboe, S .
CATALYSIS LETTERS, 2001, 71 (3-4) :209-212
[5]  
BAERLOCHER C, 2001, ATLAS ZEOLITE FRAMEW, P266
[6]   Methanol to gasoline over zeolite H-ZSM-5: Improved catalyst performance by treatment with NaOH [J].
Bjorgen, Morten ;
Joensen, Finn ;
Holm, Martin Spangsberg ;
Olsbye, Unni ;
Lillerud, Karl-Petter ;
Svelle, Stian .
APPLIED CATALYSIS A-GENERAL, 2008, 345 (01) :43-50
[7]   Conversion of methanol to hydrocarbons over zeolite H-ZSM-5: On the origin of the olefinic species [J].
Bjorgen, Morten ;
Svelle, Stian ;
Joensen, Finn ;
Nerlov, Jesper ;
Kolboe, Stein ;
Bonino, Francesca ;
Palumbo, Luisa ;
Bordiga, Silvia ;
Olsbye, Unni .
JOURNAL OF CATALYSIS, 2007, 249 (02) :195-207
[8]   The mechanisms of ethene and propene formation from methanol over high silica H-ZSM-5 and H-beta [J].
Bjorgen, Morten ;
Joensen, Finn ;
Lillerud, Karl-Petter ;
Olsbye, Unni ;
Svelle, Stian .
CATALYSIS TODAY, 2009, 142 (1-2) :90-97
[9]   The Effect of Acid Strength on the Conversion of Methanol to Olefins Over Acidic Microporous Catalysts with the CHA Topology [J].
Bleken, Francesca ;
Bjorgen, Morten ;
Palumbo, Luisa ;
Bordiga, Silvia ;
Svelle, Stian ;
Lillerud, Karl-Petter ;
Olsbye, Unni .
TOPICS IN CATALYSIS, 2009, 52 (03) :218-228
[10]   On the reaction mechanism for hydrocarbon formation from methanol over SAPO-34 .2. Isotopic labeling studies of the co-reaction of propene and methanol [J].
Dahl, IM ;
Kolboe, S .
JOURNAL OF CATALYSIS, 1996, 161 (01) :304-309