Analysis of reaction pathways for n-pentane cracking over zeolites to produce light olefins

被引:81
作者
Hou, Xu [1 ]
Qiu, Yuan [1 ]
Zhang, Xiangwen [1 ]
Liu, Guozhu [1 ]
机构
[1] Tianjin Univ, Collaborat Innovat Ctr Chem Sci & Engn, Sch Chem Engn & Technol, Key Lab Green Chem Technol,Minist Educ, Tianjin 300072, Peoples R China
关键词
n-Pentane cracking; Zeolites; Reaction pathways; Light olefins; Metal-incorporation; CATALYTIC CRACKING; HEXANE CRACKING; REACTION-MECHANISMS; ZSM-5; ZEOLITES; THERMAL/CATALYTIC CRACKING; MONOMOLECULAR CRACKING; PROPYLENE PRODUCTION; NAPHTHA CRACKING; HYDRIDE TRANSFER; CRYSTAL SIZE;
D O I
10.1016/j.cej.2016.08.047
中图分类号
X [环境科学、安全科学];
学科分类号
08 ; 0830 ;
摘要
Reaction pathways including monomolecular protolytic cracking, hydride transfer, beta-scission, and certain side reactions of n-pentane cracking over zeolites have been systematically investigated. Monomolecular protolytic cracking routes were mainly initiated by attack of acid sites on C-H or C-2-C-3 bonds. Operating conditions or zeolite pore caliber can tailor not only the first scission, but also the balance among carbenium ions related routes, e.g. hydride transfer, deprotonation, side reactions, etc. Increasing reaction temperature or zeolite pore caliber promoted the cleavage of C-H bond, and large pore caliber and high conversion were beneficial to the hydride transfer and side reactions. Compared to HZSM-35 and H-Beta, HZSM-5 zeolite with middle pore caliber exhibited the highest selectivity to light olefins, and Agincorporation can further promoted selectivity to light olefins at a little cost of P/E (propylene to ethylene) ratio. Promotion of Ag-incorporation on light olefins formation was probably due to the active sites generated by silver species acting as dehydrogenation sites, and enhancing the cleavage of C-H bond. (C) 2016 Elsevier B.V. All rights reserved.
引用
收藏
页码:372 / 381
页数:10
相关论文
共 41 条
[1]   Heterogeneous oligomerization of ethylene over highly active and stable Ni-AlSBA-15 mesoporous catalysts [J].
Andrei, Radu Dorin ;
Popa, Marcel Lone ;
Fajula, Francois ;
Hulea, Vasile .
JOURNAL OF CATALYSIS, 2015, 323 :76-84
[2]  
[Anonymous], 1984, 8 INT C CAT
[3]   Monomolecular cracking of n-hexane on Y, MOR, and ZSM-5 zeolites [J].
Babitz, SM ;
Williams, BA ;
Miller, JT ;
Snurr, RQ ;
Haag, WO ;
Kung, HH .
APPLIED CATALYSIS A-GENERAL, 1999, 179 (1-2) :71-86
[4]   Microkinetic modeling of propane aromatization over HZSM-5 [J].
Bhan, A ;
Hsu, SH ;
Blau, G ;
Caruthers, JM ;
Venkatasubramanian, V ;
Delgass, WN .
JOURNAL OF CATALYSIS, 2005, 235 (01) :35-51
[5]   Mechanistic considerations in acid-catalyzed cracking of olefins [J].
Buchanan, JS ;
Santiesteban, JG ;
Haag, WO .
JOURNAL OF CATALYSIS, 1996, 158 (01) :279-287
[6]   Current views on the mechanism of catalytic cracking [J].
Corma, A ;
Orchillés, AV .
MICROPOROUS AND MESOPOROUS MATERIALS, 2000, 35-6 :21-30
[7]   The role of pore topology on the behaviour of FCC zeolite additives [J].
Corma, A ;
González-Alfaro, V ;
Orchillés, AV .
APPLIED CATALYSIS A-GENERAL, 1999, 187 (02) :245-254
[8]   Modified HZSM-5 zeolites for intensifying propylene production in the transformation of 1-butene [J].
Epelde, Eva ;
Gayubo, Ana G. ;
Olazar, Martin ;
Bilbao, Javier ;
Aguayo, Andres T. .
CHEMICAL ENGINEERING JOURNAL, 2014, 251 :80-91
[9]   A geometric solution to the largest-free-sphere problem in zeolite frameworks [J].
Foster, MD ;
Rivin, I ;
Treacy, MMJ ;
Friedrichs, OD .
MICROPOROUS AND MESOPOROUS MATERIALS, 2006, 90 (1-3) :32-38
[10]   A quantum-chemical study of hydride transfer from alkanes to carbenium cations in the gas phase: A comparison with liquid- and solid-acid catalytic systems [J].
Frash, MV ;
Solkan, VN ;
Kazansky, VB .
JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS, 1997, 93 (04) :515-520