【作者】 王菲；

【导师】 王连军；

【作者基本信息】 南京理工大学 ， 环境工程， 2010， 博士

【摘要】 起爆药在我国的军工领域中发挥着重要的作用,相当一部分起爆药为有机或无机酸的重金属盐,在起爆药的生产过程中将会产生重金属废水。重金属废水是对生态环境和人类健康危害最大的工业废水之一,随着我国的工业化不断深入,重金属废水所带来的污染日趋严重,直接威胁到人民的身心健康。近几年来,我国的重金属废水污染事件频繁发生,再次给我们敲响了警钟。K·D复盐起爆药为我国自主知识产权产品,国外并没有对该废水问题进行研究报道。现在针对K·D复盐起爆药重金属废水的处理工艺虽然能使出水达到国家相应的排放标准,但是处理工艺选择性差,有可能造成二次污染,并不是最佳的选择。由于重金属废水污染的严重性,其所带来的环境污染问题也得到越来越多的重视,加之当今不可再生资源短缺,因此,研发出更加环保有效的起爆药生产废水处理技术以及新型离子交换树脂不仅可以有效的治理重金属废水、保护环境,同时可以减轻企业的经济负担。相比于其他常规的重金属废水处理方法和吸附剂,离子交换树脂吸附法具有处理效率高、操作简便、成本低等优点而受到广泛的关注。本文在此基础上,主要研究了2个方面的内容。一是,针对K·D复盐与GTG起爆药生产废水中含有的铅、镉两种主要的重金属污染物,考察了D418和001×7两种离子交换树脂处理工艺在K-D复盐起爆药生产废水中的应用研究以及对铅、镉离子的吸附行为。通过对两种离子交换树脂的筛选,采用较好的001×7离子交换树脂作为处理K·D复盐起爆药生产废水中金属离子的吸附剂进行进一步的工程化与资源化研究。二是,为了进一步提高离子交换树脂的吸附性能,探讨了离子交换树脂的改性研究,并研究了改性离子交换树脂对金属离子的吸附性能。本研究在促进离子交换树脂处理工艺在起爆药重金属废水中的进一步应用以及为实际工程应用提供一定的理论依据和技术支持、缓解重金属废水所带来的环境危害等方面具有一定的现实意义。本文首先探讨了离子交换树脂的改性研究,以D401离子交换树脂为母体对其进行进一步功能化修饰,制备出一种改性D401离子交换树脂,并用红外光谱、扫描电镜对其进行了表征,对比了D401离子交换树脂改性前后对铅离子的吸附性能,并从吸附等温线、吸附热力学、吸附动力学、脱附性能以及吸附机理等方面考察了改性D401树脂对铅离子的吸附性能。扫描电镜、红外光谱、能谱分析等表征手段表明改性D401树脂表面具有孔结构,含有-N(CH2COOH)2、-SO3H两种功能基团；改性D401树脂对铅离子的吸附量较改性前有了明显的提高；吸附过程符合Freundlich和Langmuir等温吸附方程,液膜扩散为铅离子在改性D401树脂上吸附速率的主要控制步骤；改性D401树脂具有较快的吸附速率,且脱附性能稳定、重复使用性好；改性D401树脂对铅离子的吸附有两种途径：功能基团-N(CH2COOH)2中的N、O原子与pb2+形成配位键,而功能基团电离出的H+与pb2+发生了离子交换。其次研究了D418、001×7离子交换树脂对K·D复盐与GTG起爆药生产废水中存在的铅、镉离子的吸附行为,并研究了对K·D复盐起爆药实际生产废水的动态吸附。结果表明,Freundlich和Langmuir等温方程均适合描述铅离子在D418树脂上的等温吸附过程,Freundlich等温方程更适合描述镉离子在D418树脂上的等温吸附过程；而铅离子在001×7树脂上的吸附过程符合Langmuir等温吸附方程,Freundlich等温方程更适合描述镉离子在001×7树脂上的等温吸附过程。液膜扩散与颗粒内扩散共同影响着铅离子、镉离子在D418、001×7离子交换树脂上吸附速率。D418离子交换树脂对K·D复盐起爆药生产废水中铅离子的动态吸附实验确立的适宜工艺条件为：吸附流速,6 BV/h；吸附温度,313 K；脱附流速,3 BV/h；脱附温度,室温；脱附剂,3mol/L的硝酸；脱附剂用量,5 BV。001×7离子交换树脂对K·D复盐起爆药生产废水中铅离子的动态吸附实验确立的适宜工艺条件为：吸附流速,6 BV/h；吸附温度,室温；脱附流速,3 BV/h；脱附温度,室温；脱附剂,3mol/L的硝酸；脱附剂用量,4 BV。最后考察了离子交换树脂吸附工艺在K·D复盐起爆药生产废水处理中的应用研究。通过对D418、001×7两种离子交换树脂的筛选,采用001×7离子交换树脂作为处理K·D复盐起爆药生产废水中金属离子的吸附剂,进行进一步的工程化与资源化研究,为K·D复盐起爆药生产废水除铅段提供了一种处理效率高、操作简便、能够避免二次污染的新工艺,并提供了一种可以对金属离子进行回收的综合处理方法。稳定性放大实验结果证明,采用所选定的适宜的吸附和脱附条件进行实验,001×7树脂用于处理K·D起爆药生产废水中的铅,其吸附、脱附性能稳定,可使出水达到相应标准排放,单位体积树脂对该废水的处理量达到84倍树脂体积,对铅的处理效果良好,去除率接近100%,脱附率达到94%以上。同时稳定性实验也表明,上批次2 BV低浓度的脱附液套用于下批次的树脂脱附,树脂的脱附率保持稳定,不影响下批次的吸附效果。采用离子交换树脂工艺处理起爆药生产废水中的金属离子,不仅具有较高的处理效率,同时可以避免二次污染的产生,对铅进行回收利用,因此是一种较好处理起爆药生产废水中金属离子的方法。更多还原

【Abstract】 Primary explosive play an important role in our war industry domain, and most of primary explosive are inorganic or organic acid heavy metal salt, can bring heavy metal wastewater in the producing process. Heavy metal wastewater is the most harmful industrial wastewater to the entironment and human health, the pollution of heavy metal wastewater is increasingly fearful with the development of industrialisation and straight threaten the health and mind of people. In recent years, the pollution events of heavy metal wastewater are frequently happen and caution us again. K-D double salt primary explosive is China’s independent intellectual property rights, so the wastewater question of K-D double salt primary explosive is not reported at abroad. Though the wastewater of K-D double salt primary explosive can reach the relevant effluent standard, the selectivity of present treatment technic is low and may bring secondary pollution and is not a optimal choice. Due to the ponderance of heavy metal wastewater pollution, the problem of environment pollution is more and more regarded. Now nonrenewable resource are deficient, so new treatment technics of primary explosive production wastewater with more environment friendly and effective is important to environmental protection and financial burden of corporation. Among familiar technologies, the ion-exchange resin adsorption method seems to be the most suitable method for removing heavy metal ions from aqueous solution because of its low cost, ease of handling and high efficiency, so it gets extensive attention.On the basic of summarize, two aspects content are mainly studied. Firstly, the adsorption performance of Pb2+, Cd2+ in K·D double salt and GTG primary explosive wastewater, and the treatment of K·D double salt primary explosive wastewater are studied by D418,001×7 ion-exchange resin.001×7 resin is selected as the sorbent of treatment of K-D double salt primary explosive wastewater and the feasibility that the treatment technics of K-D double salt primary explosive wastewater by 001×7 resin is ulteriorly studied. Secondly, the resources of the new treatment technics and modification of ion-exchange resin are studied synchronously. The study contributes practical significance to the environment protection, engineering application and academic basis.Modification of ion-exchange resin is studied in the paper, the modified D401 ion-exchange resin is synthesized by chemical modification of D401 resin and characterized by FT-IR and SEM. And the adsorption properties of Pb2+ on the modified D401 is studied by batch adsorption from adsorption isotherm, adsorption thermodynamics, adsorption kinetics, desorption and adsorption mechanism, and the contrast of adsorption performances on the modified D401 and D401 resin are also studied. The modified D401 resin is provided with macroporous structure and two function groups by analyzing FT-IR and SEM. Experimental results show that at the study condition, the adsorption capacity of the modified D401 resin for Pb2+ is obviously increased compare with D401 resin. Freundlich and Langmuir isothermal adsorption models are both suitable for the equilibrium adsorption of the modified D401 resin and the adsorption rate is mainly governed by liquid film diffusion. Adsorption is an endothermic process that runs spontaneously. The modified D401 resin is provided with fast adsorption rate and good desorption capability, and the adsorption capacity remains stable after several consecutive adsorption-desorption cycles. The modified D401 resin is an efficient adsorbent for the removal of Pb2+ from its single-metal ion solution. The adsorption mechanism is concluded that coordinate atoms N and O of function group combine with Pb2+ by coordination bond and H+ ionized by function groups exchanges with Pb2+.The adsorption properties of Pb2+ and Cd2+ on D418,001×7 ion-exchange resin are studied by batch adsorption, dynamic adsorption of Pb2+ of K·D double salt primary explosive wastewater is also studied by column adsorption. At the study condition, Freundlich and Langmuir isothermal adsorption models are both suitable for the adsorption process of Pb2+ on D418 resin, and Freundlich isothermal adsorption model is more suitable for the adsorption process of Cd2+ on D418 resin; And Langmuir isothermal adsorption model is suitable for the adsorption process of Pb2+ on 001×7 resin, Freundlich isothermal adsorption model is suitable for the adsorption process of Cd2+ on 001×7 resin. The adsorption rate is governed by liquid film diffusion and intraparticle diffusion corporately. The feasible technics conditions of dynamic adsorption of D418 resin are:adsorption rate,6 BV/h; adsorption temperature,313 K; desorption rate 3 BV/h; desorption temperature, room temperature; desorbent,3 mol/L nitric acid; desorbent dosage,5 BV. And the feasible technics conditions of dynamic adsorption of 001×7 resin are:adsorption rate,6 BV/h; adsorption temperature, room temperature; desorption rate 3 BV/h; desorption temperature, room temperature; desorbent,3 mol/L nitric acid; desorbent dosage,4 BV.The treatment of K-D double salt primary explosive wastewater by ion-exchange resin is studied.001×7 resin is selected as the sorbent of treatment of K-D double salt primary explosive wastewater and the feasibility that the treatment technics of K-D double salt primary explosive wastewater by 001×7 resin is ulteriorly studied. The study provides a new treatment technics for removing heavy metal ions of K-D double salt primary explosive, the treatment technics is provide with high efficiency, ease of handling and no secondary pollution. The column adsorption experimental results show the adsorption and desorption effect of new treatment technics is well and steady, removal efficiency is close to 100%, desorption efficiency reach 94% and unit volume of resin can dispose 84 times volume actual wastewater. The last time 2 BV low concentration desorption solution can be used for next desorption and desorption efficiency is steady. In conclusion, the ion-exchange resin adsorption method is provide with high efficiency, ease of handling, no secondary pollution and can recovery heavy metals from wastewater, so it is a suitable method for the removal of heavy metal ions from primary explosive production wastewater.更多还原