电场净化法制备精制黄磷的试验研究

【作者】 钟忠；

【导师】 沈强华；

【作者基本信息】 昆明理工大学 ， 冶金物理化学， 2007， 硕士

【摘要】 黄磷是一种极重要的基础工业原料，主要用作制赤磷、磷酸及磷化合物原料，还用于化工、农药等多个领域。将黄磷精制处理后的高纯黄磷或赤磷，还用于电子化学、半导体材料、医药工业以及军工等领域。云南有丰富的磷资源，已探明磷矿储量近80亿吨，黄磷、磷酸等生产精细化工产品的母体原材料产量在全国占据重要地位，黄磷和湿法磷酸产量均居全国首位，其中黄磷产量占全国总产量的55％以上，精细磷化工已成为云南省工业第四大支柱产业。本文介绍了我国磷资源的分布及储量，列举了云南省黄磷的生产及利用状况。对目前工业黄磷生产技术现状作了简要概述，分析了目前黄磷生产方法及原理，对其流程及生产工艺作了论述。文中对目前精制黄磷现状及利用作了详细的论述，在黄磷精制方法上可以分为化学法和物理法，其中化学法主要有碘化物法、含氯化合物法、酸处理法和三价铁离子法、水相氧化法，物理法主要有蒸馏法和吸附法。本文对微观电荷极化原理进行了阐述，同时介绍了几种荷电电荷的运动状态、静电力引起的静力学、动力学现象以及均匀电场和非均匀电场粒子的运动现象。通过比较计算，我们知道元素磷与砷等其它杂质的电阻率、电负性、电离势等物理性质的显著差异，我们采用高压电场方式使杂质极化，再利用电泳力使其分离。根据实验原理我们设计了一套黄磷除砷设备，并设计了多种试验工艺。试验过程中我们根据所收集资料及理论分析，认为此试验影响因素主要由电场强度、作用时间、电极间距、放料流速比等决定。为此，我们围绕这些因素做了大量的试验，最后确认最佳试验条件为：温度55℃，电压20kV，时间90min，精制黄磷出口与高砷黄磷出口流速比为10∶1，电极Φ90mm时，进行试验砷去除率可达到58％以上，试验以上一级的产品作为下一级原料，经三次处理砷含量在20ppm以下。其它杂质的去除效果也很好，经过三次处理后砷去除率为94％，回收率高于99.9％，处理前后黄磷颜色由混浊变为透明。利用电场作用可对液态或熔融态的物料进行净化除杂，其中有原油的脱水、冶金领域能将金属中的非金属夹杂物去除、工业循环水中的高压静电离子水处理，此外还用于高压静电除尘、食品的高压静电场杀菌及保鲜等。这种在电场作用下脱除杂质的技术正在被众多的行业研究应用。在世界普遍重视环保的今天，只有在产品发展初期就将清洁生产纳入规划，才能实现真正意义上的环境保护。本试验研究探索利用高压静电场的方法精制黄磷，不使用化学添加剂，能耗低，工业黄磷中的杂质富集在副产品中，磷回收率高，不产生废弃物，从根本上解决了“三废”处理问题。更多还原

【Abstract】 The yellow phosphorus is a kind of very important foundation material for industry, it mainly makes the red phosphorus, the phosphoric acid and it is also phosphorous material compound , in addition it also uses in the chemical industry, the agricultural chemicals and so on. The high pure yellow phosphorus which is purified from yellow phosphorus or red phosphorus will be used in electronic chemistry, semi-conducting material industry, pharmaceutical industry and martial industry and so on.This paper introduced phosphorus resources distribution and the reserves of our country , has enumerated the yellow phosphorus production and the using condition in YunNan province. It has made a brief outline on the present industrial yellow phosphorus production technology situation and it has analyzed the present yellow phosphorus production method and the principle , it also has made the elaboration to its flow and the production craft.The paper has made a detailed discussion on the yellow phosphorus present purification situation and the Using status, the yellow phosphorus purification method main include the chemical method and the physical method, in which chemical method mainly includes the iodide method, chloric compound method, the acid treatment method and the ferric method, the aqueous phase oxo-process, then the physical method mainly includes the distillation and the adsorption method.This paper has expatiated the microscopic electric polarization principle and has analyzed several kinds of locomotor state to the electric charge, the statics and dynamics phenomenon caused by the electrostatic force and the phenomenon of uniform electric field and inhomogeneous electric field granule movement. Through the comparative computation, we discovered that the yellow phosphorus and impurities (As, Fe, etc) has remarkable different properties (resistivity, negativity, ionization potential, etc) , based on these properties we can make impurities polarized by different charges in high voltage electric field ,then using the electrophoretic force to separate it.According to the experimental principle we have designed a yellow phosphorus purifier equipment, and designed many kinds of experimental technics, according to the data collected and the theoretical analysis, we know that the experimental influence factor is the electric-field intensity, the response time, the electrode spacing, the flux proportion on material’s discharge relative velocity. Therefore, we have done large numbers of experiments based on these factors, finally we confirmed the best experimental conditions are: temperature 55℃, voltage 20kV, time 90 minutes, purification yellow phosphorus exportation and high arsenic yellow phosphorus exportation relative velocity proportion at 10:1, electrodeΦ90mm. in that condition the arsenic elimination rate can be achieved 58%. The experiment takes the former product as material, after thrice processing the arsenic content is below 20ppm, at the same time the ratio of eliminated arsenic is 94% ,and the impurity elimination effect is also very good, the phosphorus’ returns-ratio more than 99.9% after that processing the yellow phosphorus color becomes transparent.Using the electric field purification method we may carry on the liquid state or the molten material disposing impurity, including the crude oil dehydration, non-metallic inclusions eliminating in the metallurgy domain, high-pressured static electricity ion water disposal in circulating water industry. In addition it also uses in the high-pressured static electricity dust removal, food high-pressured electrostatic field sterilizing and maintaining fresh .This technology of removing the impurity under the electric field function is being researched and applied in multitudinous industries.In the day which the world generally takes environmental protection in mind, in order to realize the true environmental protection we need to bring cleaning production to layout ,only by that we can realized the real cleaning production .This experimental study exploration uses high pressure electrostatic field method to purify yellow phosphorus, doesn’t use the chemical additive, the energy consumed in this method is low, the impurity in industry yellow phosphorus is concentrate in the sideline product, the phosphorus’ returns-ratio is high, it doesn’t produce rejectamenta . It has fundamentally solved the "three-waste-processing" problem.更多还原