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REVIEW ARTICLE
Mesoporous zeolites as efficient catalysts for oil refining and natural gas conversion
Jie ZHU1,2, Xiangju MENG1, Fengshou XIAO1()
1. Department of Chemistry, Zhejiang University, Hangzhou 310028, C 2. College of Biological, Chemical Sciences and Engineering, Jiaxing University, Jiaxing 314001, China
(862 KB) &
Abstract Zeolites have been regarded as one of the most important catalysts in petrochemical industry due to their excellent catalytic performance. However, the sole micropores in zeolites severely limit their applications in oil refining and natural gas conversion. To solve the problem, mesoporous zeolites have been prepared by introducing mesopores into the zeolite crystals in recent years, and thus have the advantages of both mesostructured materials (fast diffusion and accessible for bulky molecules) and microporous zeolite crystals (strong acidity and high hydrothermal stability). In this review, after giving a brief introduction to preparation, structure, and characterization of mesoporous zeolites, we systematically summarize catalytic applications of these mesoporous zeolites as efficient catalysts in oil refining and natural gas conversion including catalytic cracking of heavy oil, alkylation, isomerization, hydrogenation, hydrodesulfurization, methane dehydroaromatization, methanol dehydration to dimethyl ether, methanol to olefins, and methanol to hydrocarbons.
Corresponding Authors:
XIAO Fengshou,Email:fsxiao@&&&
Issue Date: 05 June 2013
&Cite this article: &&
Jie ZHU,Xiangju MENG,Fengshou XIAO. Mesoporous zeolites as efficient catalysts for oil refining and natural gas conversion[J]. Front Chem Sci Eng,
): 233-248.
Articles by authors
Fig.1&&Schematic illustration of 3Dom-i zeolite templating from 3Dom carbon. Reproduced by permission of Ref []. Copyright 2011 American Chemical Society
Fig.2&&HRTEM of as-synthesized (a) and calcined (b) MFI nanosheet templated from C surfanctant. Reproduced by permission of Ref. []. (Copyright 2009 Nature Publishing Group)
Fig.3&&Proposed reaction of 1,3,5-triisopropylbenzene cracking
Fig.4&&Catalytic properties of conventional ZSM-5 and meso ZSM-5 employed in the cracking of TIPB (1,3,5-triisopropylbenzene) as a probe reaction: (a) deactivation behavior at 500°C, and (b) catalytic activities (conversions) at different temperatures. Reproduced by permission of Ref []. (Copyright 2011 American Chemical Society)
Fig.5&&Proposed reaction of benzene alkylation with ethylene
Fig.6&&Catalytic conversions (. Wt-%) and selectivities (. Wt-%) in the alkylation of benzene with 2-propanol with various zeolites samples as a function of reaction time (Reaction temperature: 200°C; 4 ∶ 1 benzene/2- reaction pressure: 2.0 MP, weight hourly spare velocity (WHSV): 10 h). Reproduced by permission of Ref. []. (Copyright 2006 Wiley)
Tab.1&&Catalytic activities in isomerization of linear paraffins over mesoporous zeolite catalysts
Fig.7&&Dependence of (a) the isomer selectivity, (b) the percentage of di-branched C isomers in total C isomers (denoted as DB), and (c) the cracking selectivity of -octane in -octane-hydroisomerization system on -octane conversion over conventional Pt/H-SAPO-11 and mesoporous Pt/H-SAPO-11-HI catalysts. Reproduced by permission of Ref []. (Copyright 2012 Elsevier)
Fig.8&&Dependence of (a) the 4,6-DMDBT conversion and (b) the remaining sulfur content in 4,6-DMDBT-hydrogenation system on reaction time over Pd/HY-M, Pd/Hbeta-M, Pd/HZSM-5-M, Pd/HY, Pd/NaY-M and Pd/γ-AlO catalysts. Reproduced by permission of Ref. []. (Copyright 2011 American Chemical Society)
Fig.9&&(a) Catalytic performances of mesoporous Mo/HMCM-22-HS and conventional Mo/HMCM-22 catalysts in methane
(b) formation rates of benzene at 700°C on these two catalysts under space velocity of 1500 mL/(g?h). Reproduced by permission of Ref. []. (Copyright 2010 American Chemical Society)
Fig.10&&Stability and selectivity in methanol dehydration over ZSM-5 and ZSM-5/MCM-41 composite alkali-treated by NaOH solution 1.5 mol/L. Reproduced by permission of Ref. []. (Copyright 2012 Elsevier)
Fig.11&&Catalytic conversion of methanol to dimethyl ether (DME) over conventional CaA-0 (a) and mesoporous CaA-2 (b) zeolites at 400°C. Methanol conversion was calculated by considering DME and hydrocarbons as converted products. Reproduced by permission of Ref. []. (Copyright 2009 American Chemical Society)
Fig.12&&Product selectivity of mesoporous HZSM-5 by alkaline treatment as a representative catalyst for MTP reaction as a function of time: CH, CH, CH, aromatics, C1–C4 saturated hydrocarbons, C5 and higher hydrocarbons excluding aromatics. Reaction conditions: = 470°C, WHSV= 1 h, = 0.5 atm, HO: CHOH= 1 ∶ 1. Reproduced by permission of Ref. []. (Copyright 2008 Elsevier)
Fig.13&&(a) and (b) SEM images of the hierarchical mesoporous SAPO-34 zeolite at diff (c) SAED pattern of a horizontal meso (d) nitrogen sorption isotherms and BJH pore size distribution (inset). Reproduced by permission of Ref. []. (Copyright 2009 Royal Soc Chemistry)
Fig.14&&Coke deposition over (a) conventional MFI zeolite and (b) unilamellar MFI zeolite catalysts during MTG conversion. Catalytic conversion over the unilamellar MFI was repeatedly investigated using three different synthesis batches (red circles, black squares, open circles, respectively). The catalytic measurement for conventional zeolite was repeated twice using the same sample (red circles and black squares). The solid black lines and the dotted red and black lines are guides to the eye. Dark blue bars indicate internal (inside the micropores of the zeolite) coke content, and light blue bars indicate external coke content. Reproduced by permission of []. (Copyright 2009 Nature)
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