固相膜萃取-气相色谱法测定地表水中有机氯农药研究

研究了固相膜萃取对地表水中有机氯农药(OCPs)物质的提取效果,并与液液提取法(LLE)进行比较.建立了固相膜萃取/气相色谱法检测地表水中20种有机氯农药的方法.结果表明:当萃取膜为HLB膜,洗脱液溶剂为丙酮和正己烷,萃取效果最理想,20种OCPs的回收率稳定在74.1%~94.3%之间,固相膜萃取法与传统液液提取法相比,既提高了萃取效率同时又减少了有机萃取溶剂的用量.该法检测实际样品时,同时加入2种内标指示剂对方法的性能进行了验证,2种内标示踪剂的回收率分别为71.6%~94.8%和69.9%~109.5%,样品中20种OCPs均未检出.     

中和-络合萃取-双极膜电渗析处理金刚烷胺制药废水

采用中和沉淀-络合萃取-双极膜电渗析组合工艺协同处理金刚烷胺制药胺化废水与溴化废水.结果表明,通过胺化废水与溴化废水的中和反应,可以大幅消减废水中溶解性固体和有机污染物,避免后续萃取过程中的乳化现象.在pH值为8.0、油/水相比为1∶1的条件下,P204∶正辛醇=3∶2的复配萃取剂对废水中TOC和TN的萃取效率分别为56.9%和20.6%,金刚烷胺及其衍生物几乎被完全萃取.以2.0 mol·L-1的HCl溶液为反萃取剂,可以将47.5%的金刚烷胺从负载有机相中反萃分离,再生后的萃取剂可以多次重复使用.对萃余液采用双极膜电渗析进行处理,可以去除64.2%的无机盐和部分有机物,同时还能回收到较高浓度的酸,但由于氢离子的渗漏难以回收高浓度的碱.     

Application of a hydroxylamine nitrate stability model to plutonium purification process equipment

A mathematical model that predicts hydroxylamine nitrate (HAN) (NH₂OH·HNO₃) stability is applied to aqueous solutions containing HAN, nitric acid and plutonium that are used in plutonium purification processes. The model estimates the stability of these solutions with respect to the rapid, hazardous, autocatalytic reaction of HAN with nitric acid that generates heat and gas. It also accounts for reaction kinetics, temperature changes, gas generation rates, solution volumes and flow rates, and distribution of plutonium and nitric acid between aqueous and organic phases. The model is applied to three typical process vessels used in solvent extraction purification of plutonium – a countercurrent aqueous/organic plutonium stripping column, an oxidation column used for HAN and hydrazine destruction, and a plutonium rework tank. Both normal and off-normal process scenarios are modeled. Two of the off-normal scenarios lead to the rapid autocatalytic reaction of HAN with nitric acid where heat and gas are generated and that could lead to damage of the process equipment and/or release of hazardous plutonium solution from the vessel. In these two cases, stationary aqueous solutions containing HAN, Pu(III), and nitric acid were allowed to slowly react until conditions for the autocatalytic reaction were reached.     

铬渣中铬的浸出行为

采用BCR法连续浸提研究铬渣中铬的存在形态,结果表明:铬渣中总铬和六价铬主要以残渣态和可氧化态形式存在;通过铬渣动态连续浸提实验与静态浸提实验研究了浸提剂和活性炭对铬渣中铬浸出行为的影响,研究发现p H值为3.1的醋酸浸提剂浸出液中铬浓度最低,且添加活性炭后的静态浸出液中铬的浓度有不同程度降低。     

本煤层瓦斯抽采渗流模型及数值模拟

在研究煤层瓦斯抽采时,假定煤岩为具有孔隙裂隙的双重介质,在运动方程、连续性方程和辅助方程基础上,以煤岩体应变为耦合媒介建立了考虑裂隙瓦斯渗流、微孔隙吸附瓦斯解吸扩散和煤岩变形的渗流模型.借助多物理场分析软件COMSOL Multiphysics,将模型转化为偏微分方程组,结合沙曲矿24305工作面瓦斯赋存条件进行分析求解.结果表明,进行煤层瓦斯预抽时,抽采初期瓦斯压力下降较快,抽采孔间距对抽采效果影响比较显著,距离抽采孔越远瓦斯压力下降越慢,抽采时瓦斯渗流速度变化可分3个阶段.参考模拟结果现场布置孔距为6m的顺层钻孔,抽采稳定时瓦斯纯量达5～7 m3/min,抽采效果比较理想.     

超高“Z型”中庭高度对自燃排烟特性影响的数值模拟研究

超过12m的超高中庭发生火灾时,常规排烟方法不能完全满足实际需求。通过FDS软件对某超高"Z型"中庭进行数值模拟,研究中庭高度对自然排烟特性的影响。该"Z型"中庭底层南面是自然进风口,顶层北面是自然排烟口,以烟气最先到达指定楼层人员危险时间值为到达危险时间。实验条件下模拟结果表明:无风情况下,中庭高度增加,到达危险时间增加,自然排烟效果增强。到达危险时间t与中庭高度h之间满足一定指数增长关系:t=y0+Aexp(h/α),中庭火源位置和中庭宽度对y0、A和α有一定影响。有风情况下,外界风向与进风口方向一致时,中庭自然排烟效果优于无风状况,中庭越高效果越强。在外界风向与排烟口方向相反时,烟气倒灌进中庭,自然排烟效果较弱。     

基于探采对比的煤层瓦斯含量分析及预测

针对新建矿井地勘瓦斯含量测值偏低和井下实测瓦斯含量较少的特点,结合工程和科研实践,提出了利用大量的工作面瓦斯涌出量反演煤层原始瓦斯含量技术和基于探采对比的煤层瓦斯含量预测方法。以邹庄井田32煤层为研究对象,在考虑瓦斯抽采情况下计算3204工作面瓦斯涌出量,并反演该工作面煤层原始瓦斯含量。通过对比采掘过程中获得的瓦斯含量和地勘瓦斯含量,得到不同钻孔深度时的地勘瓦斯含量修正系数,并采用瓦斯地质研究方法对32煤层分3个单元进行瓦斯含量预测。结果表明:32煤层瓦斯含量整体呈现"东部大于西部,北部大于南部"的规律,与临近矿井具有相似的瓦斯赋存规律。这表明利用探采对比的方法预测煤层瓦斯含量是可靠的。     

突发事件情景演化及关键要素提取方法

针对突发事件应急处置难度大的特点,突发事件应急管理模式必须向"情景-应对"转变。从系统复杂性、开放式预先设想以及序贯性三个主要原则的角度理解突发事件情景演化的机理,构建了突发事件情景演化系统模型,并以此为基础设计了突发事件情景网络关键要素的提取方法。该方法以危险源形成、突发事件演化以及应急响应三方面主要内容为情景网络的主体,以三方面主要内容所涉及的影响因素为分支,适当的选取情景网络关键要素并将关键要素分为四类。该方法的提出弥补了情景网络关键要素提取方法理论的空白,为突发事件情景构建提供了理论支持。     

Analysis of trace dicyandiamide in stream water using solid phase extraction and liquid chromatography UV spectrometry

An improved method for trace level quantification of dicyandiamide in stream water has been developed. This method includes sample pretreatment using solid phase extraction. The extraction procedure (including loading, washing, and eluting) used a flow rate of 1.0 mL/min, and dicyandiamide was eluted with 20 mL of a methanol/acetonitrile mixture (V/V = 2:3), followed by pre-concentration using nitrogen evaporation and analysis with high performance liquid chromatography–ultraviolet spectroscopy (HPLC–UV). Sample extraction was carried out using a Waters Sep-Pak AC-2 Cartridge (with activated carbon). Separation was achieved on a ZIC^®-Hydrophilic Interaction Liquid Chromatography (ZIC-HILIC) (50 mm × 2.1 mm, 3.5 μm) chromatography column and quantification was accomplished based on UV absorbance. A reliable linear relationship was obtained for the calibration curve using standard solutions (R² > 0.999). Recoveries for dicyandiamide ranged from 84.6% to 96.8%, and the relative standard deviations (RSDs, n = 3) were below 6.1% with a detection limit of 5.0 ng/mL for stream water samples.     

Determination of 27 pharmaceuticals and personal care products (PPCPs) in water: The benefit of isotope dilution

• Isotope dilution method was developed for the determination of 27 PPCPs in water. • The established method was successfully applied to different types of water samples. • The correction effect of corresponding 27 ILSs over 70 d was investigated. • Benefit of isotopic dilution method was illustrated for three examples. Pharmaceuticals and personal care products (PPCPs) are a unique group of emerging and non-persistent contaminants. In this study, 27 PPCPs in various water samples were extracted by solid phase extraction (SPE), and determined by isotope dilution method using liquid chromatography coupled to tandem triple quadruple mass spectrometer (LC-MS/MS). A total of 27 isotopically labeled standards (ILSs) were applied to correct the concentration of PPCPs in spiked ultrapure water, drinking water, river, effluent and influent sewage. The corrected recoveries were 73%–122% with the relative standard deviation (RSD)<16%, except for acetaminophen. The matrix effect for all kinds of water samples was<22% and the method quantitation limits (MQLs) were 0.45–8.6 ng/L. The developed method was successfully applied on environmental water samples. The SPE extracts of spiked ultrapure water, drinking water, river and wastewater effluent were stored for 70 days, and the ILSs-corrected recoveries of 27 PPCPs were obtained to evaluate the correction ability of ILSs in the presence of variety interferences. The recoveries of 27 PPCPs over 70 days were within the scope of 72%–140% with the recovery variation<37% in all cases. The isotope dilution method seems to be of benefit when the extract has to be stored for long time before the instrument analysis.