Improved selectivity in the toluene alkylation reaction through understanding and optimising the process variables

被引:55
作者
Breen, J. P.
Burch, R.
Kulkarni, M.
McLaughlin, D.
Collier, P. J.
Golunski, S. E.
机构
[1] Queens Univ Belfast, Sch Chem & Chem Engn, CenTACat, Belfast BT9 5AG, Antrim, North Ireland
[2] Johnson Matthey Technol Ctr, Reading RG4 9NH, Berks, England
基金
英国工程与自然科学研究理事会;
关键词
toluene alkylation; ZSM-5 zeolite catalyst; boron; magnesium; methanol; p-xylene;
D O I
10.1016/j.apcata.2006.09.017
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
It has been demonstrated that it is possible to produce p-xylene with near-perfect selectivity by optimising the process variables of the toluene alkylation reaction over a B/ZSM-5 catalyst. This has been achieved specifically by minimising the undesirable isomerisation of p-xylene on the external acid sites of the catalyst by controlling the contact time. This offers a superior route to high selectivity compared to multiple pre-treatments of the catalyst to eliminate external acid sites (for example, by silanisation). Additionally, a high toluene: methanol feed ratio is beneficial because it minimises the methanol dehydration reaction. A further benefit is that the maximum theoretical conversion of toluene is limited, which diminishes p-xylene product inhibition. These findings confirm that toluene alkylation is best operated in a multistage reactor, but also highlight the need for removal of p-xylene as well as addition of methanol between stages. The method of catalyst preparation is not critical, provided that there is sufficient boron present (> 6.5 wt%) and any boron lost through sublimation during the reaction is replenished. It has been found that an active catalyst can be produced in situ by either loading a physical mixture of hydroboric acid and HZSM-5 into the reactor prior to reaction or even placing a bed of hydroboric acid upstream from a bed of HZSM-5. The in situ-formed catalyst readily achieves > 99.9% selectivity to the desired pxylene isomer, under optimised conditions. (c) 2006 Elsevier B.V. All rights reserved.
引用
收藏
页码:53 / 60
页数:8
相关论文
共 28 条
[1]   MECHANISM OF SOME CONVERSIONS OVER ZSM5 CATALYST [J].
ANDERSON, JR ;
MOLE, T ;
CHRISTOV, V .
JOURNAL OF CATALYSIS, 1980, 61 (02) :477-484
[2]   KINETICS OF TOLUENE ALKYLATION WITH METHANOL ON HZSM-8 ZEOLITE CATALYST [J].
BHAT, YS ;
HALGERI, AB ;
RAO, TSRP .
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH, 1989, 28 (07) :890-894
[3]   The mechanism of dimethyl ether formation from methanol catalyzed by zeolitic protons [J].
Blaszkowski, SR ;
vanSanten, RA .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (21) :5152-5153
[4]   Enhanced para-xylene selectivity in the toluene alkylation reaction at ultralow contact time [J].
Breen, J ;
Burch, R ;
Kulkarni, M ;
Collier, P ;
Golunski, S .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (14) :5020-5021
[5]  
BREEN JP, 2004, Patent No. 2004074219
[6]   ALKYLATION OF TOLUENE WITH METHANOL-III - PARA-SELECTIVITY ON MODIFIED ZSM-5 ZEOLITES [J].
CAVALLARO, S ;
PINO, L ;
TSIAKARAS, P ;
GIORDANO, N ;
RAO, BS .
ZEOLITES, 1987, 7 (05) :408-411
[7]   Decisive role of transport rate of products for zeolite para-selectivity: Effect of coke deposition and external surface silylation on activity and selectivity of HZSM-5 in alkylation of toluene [J].
Cejka, J ;
Zilkova, N ;
Wichterlova, B ;
EderMirth, G ;
Lercher, JA .
ZEOLITES, 1996, 17 (03) :265-271
[8]   Acid-catalyzed synthesis of mono- and dialkyl benzenes over zeolites:: Active sites, zeolite topology, and reaction mechanisms [J].
Cejka, J ;
Wichterlová, B .
CATALYSIS REVIEWS-SCIENCE AND ENGINEERING, 2002, 44 (03) :375-421
[9]   The conversion of methanol to olefins: a transient kinetic study [J].
Dewaele, O ;
Geers, VL ;
Froment, GF ;
Marin, GB .
CHEMICAL ENGINEERING SCIENCE, 1999, 54 (20) :4385-4395
[10]   ROLE OF EXTERNAL SURFACE SITES IN SHAPE-SELECTIVE CATALYSIS OVER ZEOLITES [J].
FRAENKEL, D .
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH, 1990, 29 (09) :1814-1821