ZrO2催化苯胺和CO2合成二苯基脲反应.pdf

石油学报(石油加工)
2014年10月
ACTA PETROLEI SINICA (PETROLEUM PROCESSING SECTION)
第30卷第5期
文章编号:1001-8719(2014)05-0817-06
Cu-Fe/ZrO2催化荞胺和CO2合成二恭基脲反应
张丽丽,安华良,赵新强,王延吉
(河北工业大学绿色化工与高效节能河北省重点实验室,天津300130)
摘要:以Cu-Fe/ZrO2为催化剂、乙腈为溶剂,进行苯胺与CO2合成二苯基脲(DPU)反应,考察了反应条件对该反
应的影响和催化剂的重复使用性能,推测了Cu-Fe/Zr()2对该反应的催化作用机理。结果表明,苯胺与CO2合成
DPU反应的适宜条件为催化剂与苯胺质量比0.10、乙腈/苯胺体积比1.0、反应温度160℃、CO2初始压力1MPa
反应时间7h;在此条件下,苯胺转化率、DPU产率及其选择性分别为5.5%、5.3%和96.9%。CuFe/Zr(2催化剂表
面存在3类活性中心,即CuFe金属位M、 Lewis酸位Zr和 Lewis碱位Zr-O,在它们的协同作用下实现了苯胺与
CO2合成DPU的反应。催化剂重复使用4次后失活,活性组分Cu的流失是其失活的主要原因
关鍵词:苯胺;二氧化碳;二苯基脲;负载双金属催化剂
中图分类号:TQ246.3文献标识码:Adoi:10.3969/j.issn.1001-8719.2014.05.009
Synthesis of Diphenyl Urea From Aniline and CO2 Catalyzed by Cu-fe/Zro
ZHANG Lili, AN Hualiang, ZHAO Xinqiang, WANG Yanj
Hebei Provincial Key Laboratory of Green Chemical Technology and Efficient Energy Saving, Hebei University of Technology
Tianjin 300130, Chine
Abstract: The synthesis of diphenyl urea (DPU) was carried out with Cu-fe/Zro2 as heterogenous
catalyst, starting from aniline and CO, with acetonitrile as solvent. The effects of reaction
conditions and the reusability of Cu-fe/Zro, catalyst in the reaction of aniline and CO, to DPU were
investigated. Then the catalytic mechanism of Cu-fe/Zro2 in the reaction was proposed. The
results showed that the suitable reaction conditions were as follows, catalyst to aniline mass ratio of
O 10, acetonitrile to aniline volume ratio of 1.0, reaction temperature of 160C, O2 initial pressure o
1 Mpa and reaction time of 7 h, under which the conversion of aniline, the yield and selectivity of DPU
were 5.5%, 5.3% and 96.9%, respectively. There existed three kinds of active sites on the surface of Cu-
Fe/Zro catalyst, which were the metal site M, Lewis acid site Zrand Lewis basic site Zr-o. The
cooperative catalysis of the three active sites favored the process of DPU synthesis. Cu-fe/Zro was
deactivated after reused in DPU synthesis for 4 cycles due to the loss of Cu active species.
Key words: aniline; carbon dioxide; diphenyl urea; supported bimetallic catalyst
二苯基脲(DPU)是一种重要的有机合成中间要大量碱液中和处理。非光气法合成DPU路线中,
体,应用广泛。DPU传统的合成方法为光气法,其苯胺氧化羰基化法、硝基苯还原羰基化法及硝基苯
原料光气剧毒,安全间题严重,并且副产物HCI需与苯胺酸位氧化还原羰化法均以CO为原料,需使
收稿日期;2013-08-06
基金项目:国家自然科学基金项目(21076059)、天津市自然科学基金项目(12 JCYBJC12800)和河北省应用基础研究计划重点基础研究项目
(12965642D)资助
第一作者:张丽丽,女,硕士研究生,从事绿色过程工程与工艺研究;Tel:022-60202426;F-mail: zlltinghua(@163,com
通讯联系人:赵新强,男,教授,从事绿色过程工程与工艺研究;Tel:022-60202427;E-mail:zhaoxu(@hebut.edu.cn