Xi'an Hi-tech Research Institute, Xi'an, People's Republic of China.
Environ Technol. 2021 Jul;42(17):2709-2720. doi: 10.1080/09593330.2019.1710573. Epub 2020 Jan 27.
Unsymmetrical dimethylhydrazine (UDMH) is a liquid propellant widely used in aviation and aerospace. It produces a large amount of dimethyl hydrazine wastewater during long-term storage, testing, and reinjection. Traditional treatments produce numerous secondary contaminants such as residual high carcinogens, including N-nitrosodimethylamine (NDMA) and formaldehyde dimethylhydrazone (FDMH). In this paper, the dielectric barrier discharge (DBD) low temperature plasma technology is used to degrade the dimethyl hydrazine wastewater. Aiming at the problem of secondary pollutants in the degradation process, we used qualitative and quantitative methods to study the changes of NDMA and FDMH during the degradation of dimethyl hydrazine wastewater by DBD low temperature plasma. The kinetics of these two products showed that the degradation process of NDMA was consistent with the first-order reaction kinetics. Using density functional theory, we established molecular models of UDMH, NDMA and FDMH. According to the molecular orbital theory, the formation mechanism of NDMA and FDMH was calculated from three aspects: reaction structure, reaction path and energy change. We found that during the degradation of dimethyl hydrazine, the dimethyl hydrazine oxidation product was initiated by hydrogen abstraction on methyl (-CH) and amine (-NH). NDMA is produced by the oxidation of -NH, whereas FDMH is mainly produced from dimethyl hydrazine and formaldehyde.
不对称二甲肼(UDMH)是一种广泛应用于航空航天领域的液体推进剂。在长期储存、测试和再注入过程中,它会产生大量的二甲肼废水。传统的处理方法会产生许多二次污染物,包括残留的高致癌物质,如 N-亚硝基二甲胺(NDMA)和甲脒二甲腙(FDMH)。在本文中,我们采用介电阻挡放电(DBD)低温等离子体技术来降解二甲肼废水。针对降解过程中产生的二次污染物问题,我们采用定性和定量方法研究了 DBD 低温等离子体降解二甲肼废水中 NDMA 和 FDMH 的变化。这两种产物的动力学研究表明,NDMA 的降解过程符合一级反应动力学。我们利用密度泛函理论建立了 UDMH、NDMA 和 FDMH 的分子模型。根据分子轨道理论,从反应结构、反应路径和能量变化三个方面计算了 NDMA 和 FDMH 的生成机制。我们发现,在二甲肼的降解过程中,二甲肼的氧化产物是由甲基(-CH)和胺基(-NH)上的氢提取引发的。NDMA 是由 -NH 的氧化产生的,而 FDMH 主要来自二甲肼和甲醛。