γ-Al2O3催化二异丁烯脱氢环化.pdf

石油化
500
PETROCHEMICAL TECHNOLOGY
2013年第42卷第5期
Cr2O-A2O催化二异丁烯脱氢环化
李品红22,朱刚利,宋焕玲3,夏春谷
(1.中国科学院兰州化学物理研究所羰基合成与选择氧化国家重点实验室,甘肃兰州
2.中国科学院大学,北京100049;3.中国科学院苏州纳米技术与纳米仿生研究所,苏州江苏215123)
[摘要]采用等体积浸渍法制备CnOY-Al2O3催化剂,并在固定床反应器中进行了二异丁烯(DIB)脱氢环化反应的实验,考察
了Cr2O.负载量、反应温度、原料LHSV以及n(DIB):n(N2)对脱氢环化反应的影响。采用BET,XRD,UV-MVis,1H1-TPR
DSC等手段对催化剂进行了表征。实验结果表明,Cr2OyY-A1O催化剂具有较好的脱氧环化制对二甲苯的性能,Cr:O,的分散
性对催化剂活性影响较大,负载量低于6.8%(w)时分散性较好;当催化剂中Cr4O2负载量为4.2%~6.8%(w)时,催化剂表现出
较优的催化性能;采月6.8%(w)Cr2O2yY-A2O2催化剂时,较优的反应条件为:n(DIB):n(N2)=1:1、LHSV=2h'、500℃、
0.1MPa,此时转化率可达到83.0%,收率可达到2.8%
关键词]氧化铬催化剂;对二甲苯;脱氢环化;生物质;二异丁烯
文章编号]1000~8144(2013)05-0500-06
中图分类号TQ241.13
文献标志码]A
Diisobutylene Dehydrocyclization over Cr2 O /Y-A120 Catalysts
Li Pinhong, Zhu Gangli, Song Huanling, Xia Chung
(1. State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of
Sciences, Lanzhou Gansu 730000, China; 2. University of Chinese Academy of Sciences, Beijing 100049, China
3. Suzhou Institute of Nano-tech and Nano-bionics, Chinese Academy of Sciences, Suzhou Jiangsu 215123, China
I Abstract Cr O /Y-A120 catalysts for the dehydrocyclization of diisobutylene(DIB)to para-xylene
were prepared by incipient wetness impregnation and characterized by means of BET, XRD, UV-
Vis, H2-TPR and DSC. The dehydrocyclization was studied in a fixed bed reactor and the influences
of Cr2 O; loading, reaction temperature, LHSV and n(DIB): n(N2)on the dehydrocyclization were
investigated. The results show that Cr species can be dispersed well when the Cr,O, loading is less
than 6. 8%(w )and that the activity of the catalyst with the Cr O loading in the range of4.2%-68%(w)
is high. The conversion of DIB and the yield of para-xylene can reach 83.0%and 22.8% respectivel
under the optimized reaction conditions of 6.8%(w)Cr O /Y-AL2O as the catalyst, 500 C, LHSV 2 h
and n(DIB) n(N2)1 1. In addition, it was revealed that the amorphous carbon deposition led to the
inactivation of the catalysts at high temperature
I Keywords chromium oxide catalyst; para-xylene; dehydrocyclization; biomass; isobutylene
对二甲苯是重要的有机化工.原料,主要用于基生产路线得到关注,却以生物基丁醇经异丁烯二
生产对苯二甲酸。对苯二甲酸在化纤、树脂、农药聚和脱氢环化获得对二甲笨3,这将为对二甲苯
和塑料等诸多化工领域也有着极其广泛的应用。随的合成提供一条由生物质开始的新工艺路线。在这
着我国聚酯工业的飞速发展,对二甲苯的产量已不条合成路线中,二异丁烯(DIB)转化为对二甲苯的
能完全满足需求,供应缺口越来越大
过程是重要的环节。
长期以来,对二甲苯的生产一直依赖于石化
路线-2,生产工艺主要有:从邻位和对位二甲苯收日期」2012-10-19;、修改稿日期2013-02-17
异构体混合物中进行抽提分离;甲苯歧化与烷基转
作者简介]李品红(1987~),男,湖北省恩施市人,硕土生,
电话18862105856,电邮pinhongl@licp.cas.cn。联系人:夏春谷,
移,苯为联产品;芳烃异构化;烷烃芳构化。在大
电邮dexia(@lip.cas.cn
力发展可再生资源的国际背景下,对二甲苯的生物[基金项目]苏州市科技局应用基础研究计划项目(SYG201219)