Yi Yanhui, Zhang Rui, Wang Li, Yan Jinhui, Zhang Jialiang, Guo Hongchen
State Key Laboratory of Fine Chemicals, School of Chemical Engineering, and School of Physics and Optoelectronic Engineering, Dalian University of Technology, Dalian 116024, Liaoning, China.
ACS Omega. 2017 Dec 27;2(12):9199-9210. doi: 10.1021/acsomega.7b01060. eCollection 2017 Dec 31.
Nitrogen-containing organic chemicals such as amines, amides, nitriles, and hydrazones are crucial in chemical and medical industries. This paper reports a direct synthesis of ,-dimethyl cyanamide [(CH)NCN] and amino acetonitrile (NHCHCN) through a methane/ammonia (CH/NH) coupling reaction triggered by dielectric barrier discharge plasma, with by-products of hydrazine, amines, and hydrazones. The influence of CH/NH molar ratio, feedstock residence time, and specific energy input on the CH/NH plasma coupling reaction has been investigated and discussed. Under the optimized conditions, the productivities of (CH)NCN and NHCHCN reached 0.46 and 0.82 g·L·h, respectively, with 8.83% CH conversion. In addition, through combining the optical emission spectra diagnosis and the reaction results, a possible CH/NH plasma coupling reaction mechanism has been proposed. This paper provides a potential fine application of CH and NH in green synthesis of liquid nitrogen-containing organic chemicals, such as nitriles, amines, amides, and hydrazones.
含氮有机化学品，如胺类、酰胺类、腈类和腙类，在化学和医药工业中至关重要。本文报道了通过介质阻挡放电等离子体引发的甲烷/氨（CH₄/NH₃）耦合反应直接合成α,α-二甲基氰胺[(CH₃)₂NCN]和氨基乙腈（NH₂CH₂CN），同时伴有肼、胺类和腙类副产物。研究并讨论了CH₄/NH₃摩尔比、原料停留时间和比能量输入对CH₄/NH₃等离子体耦合反应的影响。在优化条件下，(CH₃)₂NCN和NH₂CH₂CN的产率分别达到0.46和0.82 g·L⁻¹·h⁻¹，CH₄转化率为8.83%。此外，通过结合发射光谱诊断和反应结果，提出了一种可能的CH₄/NH₃等离子体耦合反应机理。本文为CH₄和NH₃在绿色合成含氮有机化学品（如腈类、胺类、酰胺类和腙类）中的潜在精细应用提供了依据。
