高氯酸胺盐的制备、性能及含高氯酸根废液的处理研究

发布时间：2018-03-16 03:37

本文选题：理论计算　切入点：高氯酸胺盐　出处：《南京理工大学》2015年硕士论文　论文类型：学位论文

【摘要】：本文介绍了两种高氯酸胺盐类含能材料,包括了它们的理论计算、制备工艺、结构表征和基本性能的研究。制备高氯酸胺盐的过程中,会产生含C104-的废液,为此文章给出了一种简单而行之有效的废液处理方法。通过Gaussian03软件计算了高氯酸、胍、三聚氰胺和高氯酸胍的键长、键角。利用分子动力学模拟技术,计算了两种模型下高氯酸和胍之间的分子间作用力,初步估算了它们形成共价键的可能性。运用Molekel软件计算了高氯酸、胍、三聚氰胺的电子密度,还生成了静电势能表面图,推测了容易形成新的价键的原子或者基团。常温下以水作为溶剂,碳酸胍和高氯酸发生中和反应,经过冰水浴冷却结晶制得高氯酸胍。由于胍中有2个-NH2,如果高氯酸与胍的-NH2发生反应成键,可能会生成胍的高氯酸一盐和二盐,因此设计了碳酸胍和HClO4投料比为1：2或1：4的反应。两种反应的产物经XRD、红外光谱、元素分析、核磁共振’H谱和质谱分析测试,结果表明为同一物质,均为[C(NH2)3]+[ClO4]-。利用TGA和DSC对产物进行了热分解性和热安定性研究,升降法测试了撞击感度,结果表明,高氯酸胍是一种比较钝感的炸药,它的感度明显低于SY和PETN。纯品的高氯酸胍流散性很差,加入Al粉后高氯酸胍流散性显著增加。不同密度下的纯品和加入A1粉的高氯酸胍的爆速均为5500m/s左右,’加入5%A1粉对爆速的影响较小。三聚氰胺中含有三个-NH2,六元环上也含有三个低静电势的N原子。高氯酸可能分别与三聚氰胺生成一盐、二盐、三盐或者它们的混合物。所以,设计了反应物投料比分别为1：1、1：2和1：3的三个反应。对三种产物进行了XRD、元素分析、红外光谱分析、液相色谱分析、核磁共振1H谱等测试,证明三种不同投料比下反应均生成三聚氰胺的一高氯酸盐。对产物进行了TG、DSC等性能测试,还用扫描电子显微镜观察了产物形貌。在DMF和乙醇的混合溶液中,培养出了三聚氰胺一高氯酸盐和DMF的单晶,进行了晶胞参数测试。高氯酸盐在水中的溶解度极大、扩散速度快、化学性质稳定且具有一定的毒性,它的环境污染问题是分析化学和环境科学研究的新热点。针对高浓度(30g/L)的C104-含能材料废水,用大量KCl处理。针对低浓度(5g/L)的C104-,采用强碱性大孔阴离子树脂(D201)处理,进行了静态吸附、动态吸附以及树脂再生实验。结果表明,无论针对高浓度还是低浓度的C1O4-废水,处理效果都较好。
[Abstract]:In this paper, two kinds of perchlorate energetic materials are introduced, including their theoretical calculation, preparation process, structure characterization and basic properties. In this paper, a simple and effective method for treating waste liquid is presented. The bond length and angle of perchloric acid, guanidine, melamine and guanidine perchlorate are calculated by Gaussian03 software. The intermolecular forces between perchloric acid and guanidine were calculated and the possibility of covalent bonding between perchloric acid and guanidine was preliminarily estimated. The electron densities of perchloric acid, guanidine and melamine were calculated by Molekel software. The neutralization reaction between guanidine carbonate and perchloric acid was carried out at room temperature using water as solvent. Guanidine perchlorate was prepared by cooling crystallization in an ice bath. Since there are two -NH _ 2 in guanidine, if perchloric acid reacts with -NH _ 2 of guanidine, it may produce mono- and disalt of guanidine. Therefore, the reaction of guanidine carbonate and HClO4 feed ratio of 1: 2 or 1: 4 was designed. The products of the two reactions were tested by XRD, IR, elemental analysis, nuclear magnetic resonance spectroscopy and mass spectrometry, and the results showed that the products were the same substance. The thermal decomposition and thermal stability of the products were studied by TGA and DSC. The impact sensitivity of the products was measured by means of lifting method. The results show that guanidine perchlorate is a relatively blunt explosive. Its sensitivity was significantly lower than that of sy and PETN.The pure guanidine perchlorate had poor fluidity. The dispersity of guanidine perchlorate increased significantly after adding Al powder. The detonation velocity of guanidine perchlorate at different densities and that of guanidine perchlorate added with A1 powder was about 5500 m / s or so. The effect of addition of 5 powders on detonation velocity was small. Melamine contained three -NH _ 2 and six components. The ring also contains three low-potential N atoms. Perchloric acid may form a salt with melamine, Two salts, three salts, or their mixtures. Therefore, three reactions with reactant feed ratios of 1: 1: 1: 2 and 1: 3 were designed. The three products were tested by XRD, elemental analysis, infrared spectroscopy, liquid chromatography, 1H NMR, etc. It was proved that three kinds of reaction under different feed ratio gave rise to a perchlorate of melamine. The properties of the product were tested by TG-DSC, and the morphology of the product was observed by scanning electron microscope. In the mixed solution of DMF and ethanol, the morphology of the product was observed by scanning electron microscope (SEM). The single crystals of melamine perchlorate and DMF were cultured, and the unit cell parameters were tested. The problem of environmental pollution is a new focus in analytical chemistry and environmental science. C104- containing material wastewater with high concentration of 30g / L is treated with a large amount of KCl. For C104-with low concentration of 5g / L, it is treated with strong alkaline macroporous anion resin D201. Static adsorption, dynamic adsorption and resin regeneration experiments were carried out. The results showed that the treatment effect of C1O4- wastewater with high concentration or low concentration was better.
【学位授予单位】：南京理工大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：X789;TB34

【参考文献】