硝基胍炸药废水处理的密度泛函理论研究

发布时间：2018-04-12 13:52

本文选题：硝基胍 + B3LYP　；参考：《中北大学》2017年硕士论文

【摘要】：近年来,硝基胍炸药需求量的激增和工业生产的扩张,造成了严重的的硝基胍炸药废水,已引起人们广泛的关注。炸药废水中各物质的存在形态以及它们之间的相互作用对于炸药废水的处理至关重要,而量子化学方法在研究物质的存在形态、各物质分子之间的协同效应及其动力学过程方面具有优势。鉴于目前仍然没有能够有效去除硝基胍炸药废水的废水处理剂,本课题拟进行四氟乙烯/四氟化碳作用下硝基胍存在形态及其动力学密度泛函理论研究,探索聚四氟乙烯废水处理剂作用机理。同时,考虑到火炸药废水处理的安全性问题,本文对感度进行了预估。首先,为了探索硝基胍炸药感度的计算方法,我们以实验上已经合成并且有实验感度的八类化合物作为研究对象,从这些化合物的实验感度和理论方法入手,探索一种行之有效的、简单的、可预估炸药感度的理论方法。我们进行了硝基环丁烷炸药及其衍生物表面静电势与感度理论研究。在DFT-B3LYP/6-311++G**水平上,研究了硝基环丁烷及其衍生物和硝基环己烷N-NO2和C-NO2键的中点、环上方分子表面静电势及其统计量,建立了三种标题化合物实验撞击感度h50与分子表面静电势及其统计量之间的定量关系。其次,借助于B3LYP/6-311++G(2df,2p)方法分别对α型硝基胍???C2F4/CF4???H2O和β型硝基胍???C2F4/CF4???H2O中所有单体及复合物结构进行优化,并得到了稳定的结构。对复合物结构进行分析,研究了氢键键长、分子间相互作用能的变化,以及协同效应或反协同效应的发生。为了验证上述结论,我们对各种复合物结构进行AIM分析,通过分析键长、电子密度的变化,进一步证明了关于协同效应的结论。最后,借助于MP2/6-311++g(d,p)方法对β型硝基胍单体、β型硝基胍???C2F4以及β型硝基胍???H2O进行了动力学研究,分析了反应物、过渡态以及生成物的结构变化,对反应焓变进行了计算。利用Multiwfn软件,对β型硝基胍???C2F4/CF4???H2O三聚体复合物的静电势统计量进行分析,找出了静电势的相关统计量与三聚体相互作用能的关系。选取前文线性关系较好的感度公式对β型NQ???C2F4/CF4???H2O三聚体复合物进行了感度预估。研究发现,硝基胍分子、四氟乙烯/四氟化碳分子以及水分子之间可以形成较强的分子间相互作用和协同效应,在硝基胍废水当中放入聚四氟乙烯,它有可能将硝基胍废水当中的硝基胍萃取、富集,从而达到硝基胍废水处理的目的。同时通过感度的计算,研究了炸药废水处理的安全性,这些都为炸药废水的实验研究提供了理论依据和技术支持。
[Abstract]:In recent years, explosive nitroguanidine demand surge and the expansion of industrial production, causing serious nitroguanidine explosive wastewater, has aroused widespread concern. Critical treatment interactions between species of the different substances in wastewater and their explosive for explosive wastewater, and quantum chemical methods in forms of substance the advantages of synergy and dynamic processes among molecules. Since there is still no waste water can effectively remove the nitroguanidine explosive wastewater treatment agent, this thesis intends to make a tetrafluoroethylene / four carbon fluoride under the action of nitroguanidine morphology and dynamic density functional theory study, to explore the mechanism of wastewater treatment agent of PTFE. At the same time and considering the explosive safety problems of wastewater treatment, this paper estimates of sensitivity. First of all, in order to explore the explosive nitroguanidine Sense degree calculation method, we have to experiment and experimental synthesis of eight compounds of sense as the research object, sensitivity and theoretical methods of these compounds from the experiment starting, to explore an effective, simple, can be used to estimate sensitivity theory. We have studied the theory of sense nitro explosives and cyclobutane derivatives of surface electrostatic potential. At the level of DFT-B3LYP/6-311++G**, the midpoint of nitro cyclobutane derivatives and Nitrocyclohexane N-NO2 and C-NO2 key ring, above the molecular surface electrostatic potential and statistics, set up three kinds of the title compound experiment the quantitative relationship between the impact sensitivity of H50 with a molecular surface electrostatic potential and statistics. Secondly, with the help of B3LYP/6-311++G (2DF, 2P) methods were used to alpha nitroguanicline??? C2F4/CF4??? H2O and beta type nitroguanicline??? C2F4/CF4??? All the monomers and composites H2O The structure optimization, and obtain a stable structure. The complex structure analysis of hydrogen bond length, intermolecular interaction energy changes and synergistic effect or antagonistic effects. In order to verify the above conclusions, we conducted AIM analysis on various kinds of complex structure, through the analysis of the bond length, the change of electron the density, further proof of the synergy conclusion. Finally, with the help of MP2/6-311++g (D, P) method of beta type nitroguanidine monomer, beta type nitroguanicline??? C2F4 and betaammonium nitroguanicline??? H2O studied dynamics analysis of reactants, transition states and structure generation the changes of reaction enthalpies were calculated. By using Multiwfn software, the beta type nitroguanicline??? C2F4/CF4??? Electrostatic potential statistics H2O trimer complex analysis, find out the relationship between the electrostatic potential measurement system and trimer interaction energy of the selection. This linear relationship between the sensitivity formula of beta NQ better??? C2F4/CF4??? H2O trimer complex sensitivity were estimated. The study found that nitroguanidine molecules can form strong intermolecular interactions and synergies between tetrafluoroethylene / four fluorinated carbon molecules and water molecules in nitroguanidine from waste water in the PTFE, it is possible to make nitroguanidine extraction, the enrichment of nitroguanidine wastewater, so as to achieve the purpose of nitroguanidine wastewater treatment. At the same time by calculating the sensitivity, on the safety of explosive wastewater treatment, the experimental study on explosive wastewater to provide a theoretical basis and technical support.

【学位授予单位】：中北大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：X789

【参考文献】