摘要
采用柠檬酸为络合剂,溶胶-凝胶法制备系列CeO_2-CuO/ZnO/Al_2O_3,在3.0 MPa压力和220~230℃反应条件下,甲苯二胺(TDA)和乙烯催化合成二乙基甲苯二胺(DETDA)为探针反应,考察其催化性能,其中CeO_2掺杂量为3%,催化活性最高。通过X射线衍射(XRD)、傅里叶红外光谱(FT-IR)、差热重量分析法(DTG-DTA)、核磁氢谱1 H NMR对CeO_2-CuO/ZnO/Al_2O_3、DETDA、TDA进行检测和表征,揭示了它们的微观结构和内在规律性。XRD检测发现CeO_2掺杂量增多,CeO_2-CuO/ZnO/Al_2O_3衍射峰强度增强,提高了晶化程度,金属原子存在协同效应,增多了活性中心。FT-IR揭示了DETDA内部化学键键型,拥有甲基、亚甲基的多取代芳胺。DTG-DTA检测出的质量变化与热效应两种信息,DETDA的DTG-DTA曲线在66.0、271.0℃存在二个吸热峰,分别为氨基脱离苯环、DETDA的分解产生。通过1 H NMR对DETDA、TDA检测,得到DETDA、TDA的氢原子的数目分别为18和10,分子中各个氢核对应所归属的吸收峰,分别和它们分子式中的氢原子数目吻合。CeO_2-CuO/ZnO/Al_2O_3催化合成DETDA,反应条件温和,工艺流程简单,容易实现高效率和连续化工业生产,因此具有广阔的发展前景。
A series of CeO2-CuO/ZnO/A1203 were prepared by sol-gel method with citric acid as complex agent. The properties of CeO2-CuO/ZnO/A1203 were investigated with the synthesis of diethyltoluenediamine （DETDA） catalyzed by toluenediamine （TDA） and ethylene catalytic as the probe reaction under 3.0 MPa pressure at 220~230 ℃. As the doping amount of CeO2 is up to 3%, CeO2-CuO/ ZnO/A1203 shows the highest catalytic activity. CeO2-CuO/ZnO/A1203, DETDA and TDA were characterized by X-ray diffraction, Fourier transform infrared spectroscopy （FT-IR）, derivative thermogravimetric analysis and differential thermal analysis and 1 H NMR so as to reveal the microstructure and intrinsic regularity. Intensity of CeO2-CuO/ZnO/A12O3 diffraction peaks was strengthened, meanwhile the crystallization degree was improved with the increasing of CeO2 doping content. There are more active centers as the metal atoms show synergistic effect. The chemical bond types in DETDA and TDA were revealed by FT-IR. DETDA is a multi-substituted aromatic amine with methyl and ethyl. Quality change and thermal effect were detected by differential thermal analysis （DTG-DTA）. There were two peaks at 66. 0 and 271.0 ℃ respectively, as amino was broken away from benzene ring and DETDA decomposed. There are 18 and 10 hydrogen atoms in DETDA and FDA molecules, respectively, consistent with their formulas detected by 1 H NMR. There is a wide development prospect in catalytic synthesis of DETDA over CeO2- CuO/ZnO/Al2O3 due to its mild reaction conditions, simple technological process, high efficiency and easily implemented industrial production.
作者
贾太轩
丁炳伟
冯世宏
张震斌
吴红梅
郭宇
JIA Taixuan;DING Bingwei;FENG Shihonga;ZHANG Zhenbina;WU Hongmei;GUO Yu(College of Chemistry ＆ Environmental Engineering,Anyang Institute of Technology,Anyang,Hanan 455000,China;Hebi Uhoo Chemical Company Limited,Hebi,Henan 458000,China;College of Chemistry ＆ Environmental Engineering,Liaoning University of Technology,Jinzhou,Liaoning 121004,China)
出处
《化学世界》
CAS
CSCD
2018年第6期365-370,共6页
Chemical World
基金
国家自然科学基金(Nos.U1404217
21601075)
河南省高等学校重点科研(No.16B53001)资助项目
