The thermal transformation mechanism of chlorinated paraffins: An experimental and density functional theory study

The increasing production and usage of chlorinated paraffins(CPs) correspondently increase the amount of CPs that experience thermal processes. Our previous study revealed that a significant amount of medium-chain chlorinated paraffins(MCCPs), short-chain chlorinated paraffins(SCCPs) as well as aromatic and chlorinated polycyclic aromatic hydrocarbons(Cl-PAHs) were formed synergistically during the thermal decomposition of CP-52(a class of CP products).However, the transformation mechanisms of CP-52 to these compounds are still not very clear.This article presents a mechanistic analysis on the decomposition of CP-52 experimentally and theoretically. It was found that CP-52 initially undergoes dehydrochlorination and carbon chain cleavage and it transformed into chlorinated and unsaturated hydrocarbons. Cyclization and aromatization were the most accessible pathways at low temperatures(200–400°C), both of which produce mostly aromatic hydrocarbons. As the temperature exceeds 400°C, the hydrocarbons could decompose into small molecules, and the subsequent radical-induced reactions become the predominant pathways, leading to the formation of Cl-PAHs. The decomposition of CP-52 was investigated by using density functional theory and calculations demonstrating the feasibility and rationality of PCB and PCN formation from chlorobenzene. The results improve the understanding of the transformation processes from CP-52 to SCCPs and Cl-PAHs as well as provide data for reducing their emissions during thermal-related processes.     

济南秋季大气PM_(2.5)中水溶性离子的在线观测

2008年9月29日—10月15日使用大气细颗粒物快速捕集系统实时、在线分析了济南秋季PM2.5中水溶性离子的质量浓度,并结合气象资料和部分前体物(SO2,NOx和O3)浓度进行了相关分析.结果表明:济南秋季燃煤污染严重,SO42-,NO3-和NH4+是大气PM2.5中水溶性离子的主要组分,三者质量浓度之和占总水溶性离子(TW SI)质量浓度的90%以上;SO42-污染物主要受远距离传输的影响,NO3-和NH4+污染物主要受局地源的影响;SO42-和NO3-的昼夜形成机理不同,它们的形成过程主要受相对湿度、温度和O3浓度的影响.周边地区生物质燃烧导致了济南重污染天气的产生,降水对污染物的清除作用较强.对比土壤和海盐中各种离子的质量浓度比可知,济南秋季PM2.5中的K+受生物质燃烧的影响较大,C l-主要来源于海盐和生物质燃烧,Na+主要来源于海盐.     

添加小麦秸秆生物炭对黄土吸附苯甲腈的影响

选择苯甲腈为目标污染物,研究添加不同热解温度制备小麦秸秆生物碳对黄土吸附苯甲腈的影响. 研究表明:不加生物炭黄土对苯甲腈的吸附约8h达到平衡,而加入生物炭后,黄土对苯甲腈的吸附时间缩短,并随着加入生物炭热解温度的升高,吸附平衡时间缩短越明显,同时,黄土对苯甲腈的饱和吸附量也显著增加;添加生物炭黄土对苯甲腈的动力学吸附数据显示较好的符合了准二级动力学方程;无论是否添加生物炭,苯甲腈在黄土上的吸附都符合Freundlich吸附的等温模型,随系统温度升高,添加生物炭黄土对苯甲腈的饱和吸附量也显著增加,表明该吸附过程为吸热反应;苯甲腈在黄土上的吸附等温线符合C-型吸附等温模式. 计算结果显示,平均吸附自由能E介于1.865~3.171kJ/mol,表明苯甲腈在黄土上的吸附,无论是否添加生物炭,都以物理吸附为主;热力学参数计算结果显示,无论是否添加生物炭,黄土对苯甲腈的吸附过程中吉布斯自由能ΔG^θ均小于0、熵变ΔS^θ和焓变ΔH^θ均大于0,表明土壤对苯甲腈的吸附为自发进行的吸热过程. 研究结果说明,添加生物炭黄土对苯甲腈的吸附过程包含表面吸附和颗粒内部扩散、外部液膜扩散等机制.     

大气污染物排放总量控制管理机制的探讨

阐述实施大气污染物总量控制的特点及作用，分析研究现行的总量控制管理模式，进行总量控制监控机制设计，提出总量控制政策体系的改进建议。     

微生物絮凝剂促进厌氧污泥颗粒化及其机制的研究

以市政污水消化污泥为种泥,一组投加微生物絮凝剂MBF21,另一组不投加MBF21作为对照,研究了微生物絮凝剂MBF21在低浓度下UASB反应器启动过程中厌氧污泥颗粒化的作用机理．在为期102d的实验中,对厌氧污泥颗粒的形成期、成长期、成熟期进行了系统的考察．至实验结束时,投加微生物絮凝剂组的厌氧颗粒污泥平均直径比对照组大0．3mm,产甲烷活性比对照组高31％以上．对厌氧颗粒污泥的扫描电镜及荧光显微照片观察中均发现了大量产甲烷菌．对微生物絮凝剂的红外光谱分析及污泥性能的测定结果确定了微生物絮凝剂促进厌氧污泥颗粒化的作用主要是吸附架桥．     

铁改性赤泥吸附剂的制备及其除砷性能研究

以氧化铝生产废渣--赤泥为原料,采用铁盐改性处理制备了新型羟基铁包覆型赤泥除砷吸附剂.研究考察了吸附剂吸附砷效能、投加量、吸附时间和pH值对吸附除砷效果的影响;采用扫描电镜(SEM)、红外光谱(IR)、比表面积(BET)等仪器对吸附剂进行了表征,并探讨了吸附机制.结果表明,铁盐改性赤泥吸附剂对As(V)具有显著吸附效能,在pH为7,初始砷浓度为1 mg·L-1,铁盐改性赤泥吸附剂饱和吸附容量为50.6mg·g-1时,除砷率高达99.9%,吸附后出水砷含量可达到0.01 mg·L-1以下,吸附规律符合Langmuir等温方程式;溶液pH值显著影响砷去除效果,吸附机制主要为羟基铁的表面吸附机制;吸附后的吸附剂可通过NaOH溶液再生,脱附率达到92.1%.     

多粘类芽孢杆菌GA1所产絮凝剂的絮凝性能研究及机理探讨

采用正交絮凝、粒度检测及电镜扫描考察了多粘类芽孢杆菌GA1所产絮凝剂（MBFGA1）对高岭土溶液、土壤悬浊液、洗煤废水及垃圾渗滤液4种废水的絮凝性能,并利用蒽酮试验和红外光谱对絮凝剂成分进行了初步鉴定.在正交絮凝实验获得的最佳絮凝条件下,絮凝剂对高岭土溶液、土壤悬浊液、洗煤废水和垃圾渗滤液的絮凝率分别高达99.53%、99.50%、98.2%和75.60%,絮体沉降速度分别为0.03 m/s、0.025 m/s、0.025 m/s和0.005 m/s;土壤悬浊液中颗粒絮凝后平均粒径增大且大于10　μm,其余３种废水中颗粒平均粒径减小且小于10　μm;电镜扫描结果显示,絮凝前后废水颗粒的形态均从棱角分明转变为包埋的无棱角;EDTA、HCl以及尿素检验发现4种颗粒与絮凝剂分子间靠离子键结合;蒽酮反应及红外光谱结果显示该絮凝剂为含有较多羟基及羧基等官能团的多糖大分子.实验结果表明絮凝剂对高颗粒物浓度废水有很好的处理效果,其絮凝机理主要是吸附架桥作用.     

Effective adsorption of quadrivalent cerium by synthesized laurylsulfonate green rust in a central composite design

The layered laurylsulfonate intercalated green rust (lauryl-S GR) was synthesized to evaluate the influence of synthesis parameters and aqueous conditions on the adsorption of Ce^IV. The maximum adsorption capacity of 305.58 mg/g by lauryl-S GR was predictably obtained. The pseudo-first-order kinetic model was appropriate in fitting the whole uptake process in a weak acid environment. Three isotherm models including Langmuir, Freundlich, and Tempkin were all reliable in depicting the isotherm adsorption process. The maximum monolayer adsorption capacity of lauryl-S GR towards Ce^IV was 315.46 mg/g. Ce species including CeO and Ce₂O₃ besides CeO₂ were matched in the XPS distribution, directly indicating the reduction reaction brought by Fe^II in the GR occurred to hydrated Ce^IV ions during the adsorption. Nano-sized Ce particles attached to the lauryl-S GRs after the adsorption experiments were observed in the morphological characterization. Flocculated materials were formed on the surface of the lauryl-S GR at a pH of 7, which further reduced the active sites and disrupted the continuous uptake of Ce^IV to the lauryl-S GR. This study expands the application of GRs and supplies an ideal iron-based material for the construction of the affiliated recovery pathway to the traditional separation of Ce.     

仿生腿式地形自适应起落架构型与动力学分析

针对垂直起降飞行器在复杂地形环境下实现平稳着陆的难题,利用仿生学设计理念,以无人直升机为对象,设计了一种基于多连杆机构设计的仿生腿式起落架系统。通过对腿部机构进行运动学分析和动力学分析,建立相关模型,在此基础上,进行仿生腿式起落架的运动控制。首先,从无人直升机的着陆稳定性和承载能力出发,对仿生腿式起落架机械构型进行分析,并介绍了腿部各部分结构。然后,针对仿生腿腿部结构,通过几何法完成对腿部正运动学和逆运动学的求解,建立足端位置与驱动关节角度之间的映射关系。最后,基于运动学模型及四连杆运动学特性,对机体和单腿进行了动力学分析,并建模。通过建立的运动学和动力学模型,结合设计的起落架结构,完成动力学仿真,实现了仿生腿式起落架在复杂地形环境下的平稳着陆,验证了结构的合理性和模型的准确性。     

关于资源再生经济的企业思考（一）——回眸历史 咀嚼个中酸甜苦辣

从市场机制的导入,产业经营的传承,行业模式的变迁,经营方式的选择,资源的集中与对接等方面,回顾了再生资源行业过去30年的发展变化。