Analytical Investigations on a Releasing Agent Application in Aluminium Diecasting (6 pp)

Background, Aims and Scope Releasing agents, applied in the aluminium diecasting process, usually consist of water, oils, waxes, polysiloxanes, as well as of a set of additives like emulsifiers, corrosion inhibitors, and biocides. During spray application and part release, gases and aerosols are emitted into workplace air. The chemical compositions of these emissions are determined by the components of the releasing agents and their reaction products formed during thermal stress of more than 700 °C. In the frame of the joint project, the analytical tasks were to develop an appropriate sampling strategy for this production environment, to draw conclusions about the occurrence of hazardous chemicals from production plant studies and from laboratory-scale thermolysis experiments, and to determine the biodegradability of customary releasing agents. Methods During realistic test production, active air sampling was performed in a production hall using different adsorption materials. Cotton fabric sheets were positioned in the production area as passive samplers. Thermolysis experiments were performed at 600 °C with sealed quartz ampoules. The biodegradability of different releasing agents was determined according to German industry standard DIN 51828 (2000). For analyses, GC/MS (headspace), FTIR, HPLC, IC, and ICP-OES techniques were applied. Results and Discussion The substance spectrum, which was found in workplace air, was dominated by saturated and non-saturated aliphatic hydrocarbons. Besides these, alcohols, alkyl phenols, xylenes and other benzene derivatives, aldehydes, glycols, carboxylic acid esters, and amides were present. The German limiting value of 40 mg/m3 of complex hydrocarbon mixtures in a diecasting workplace atmosphere was clearly under-run. Total hydrocarbon contents ranged between 2.7 and 6.3 mg/m3. Five different PAH were found in the air close to the diecasting machine, with maximum concentrations between 0.05 and 3.06 μg/m3. Concentrations of nonylphenols ranged from 10 to 200 μg/m3, and those of triethanolamine from 20 to 30 μg/m3. From 17 elements analyzed, only B, Fe, P, S, Si, and Ti were emitted in small amounts. It was striking that the PAH patterns resulting from thermolysis experiments were quite the same compared to those determined during the diecasting process. An influence of water and of Fe/Al on the composition of the thermolysis products could mostly be shown. The degrees of biodegradation of three releasing agent extracts after 21 days were 21%, 29%, and 55%, respectively. Conclusion A sampling strategy was developed, which allows an emission assessment for the industrial process of aluminium diecasting. It enabled one to control limiting values, to characterise a wide variety of compounds emitted, and to identify and quantify relevant pollutants. Only a few hazardous substances could be detected during the exemplary use of one releasing agent within the compounds emitted into workplace air. Indications were found, that the prediction of the formation of harmful substances from releasing agent components should be possible via thermolysis experiments. The biodegradability test can serve to assess the expenditure of disposal of the usual leakage run-off of excess agent during production. Recommendation and Outlook Investigations on further differently composed releasing agents, e.g. powders, would be desirable. A substitution of nonylphenol ethoxylates by less harmful components would surely be an improvement of a releasing agent with regard to work safety and health care, because of avoiding the emission of toxic and endocrine active nonylphenols. The surprisingly wide range of biodegradability of the investigated releasing agents points to an optimization potential, that has obviously not yet been considered.     

室内甲醛污染治理技术研究

鉴于室内空气甲醛污染的危害,使用市售的"家丁"牌甲醛消除剂,对其去除甲醛性能进行了测试研究.研究结果表明,甲醛消除剂可以快速、有效地消除室内空气中的甲醛,又可以减少室内装修材料中游离甲醛的释放,是治理室内空气甲醛污染的有效手段之一.     

含油污泥石油烃在生物强化堆肥处理中降解特性研究

为提高含油污泥的生物降解效率,通过混合菌剂强化堆肥法处理含油污泥的小试试验,采用GC-MS图谱分析技术对石油烃中正构烷烃、藿烷、甾烷的降解规律进行分析.结果表明:7%的油泥经微生物强化堆肥处理49 d后降解率在85%以上.石油烃中3种系列的降解难易顺序为正构烷烃>藿烷>甾烷,从降解规律来看,微生物降油复合菌剂对高碳数正构烷烃的平均降解率（75.55%）大于对低碳数正构烷烃的平均降解率（62.98%）,说明总石油烃中降解率最大的是正构烷烃.微生物降油复合菌剂对藿烷的降解率在90%以上,其对22S-31,32,33,34-四升藿烷的降解率最高.微生物降油复合菌剂能够促进孕甾烷的转化,且对重排甾烷的降解效果较明显,对甾烷类化合物中4-甲基-24-乙基-胆甾烷的降解效果最好.微生物降油复合菌剂对正构烷烃的奇偶碳降解优势不明显;藿烷的立体构型转化参数大于甾烷的立体构型转化参数,这也解释了藿烷的降解易于甾烷的原因.研究显示,微生物降油复合菌剂对石油烃中正构烷烃、藿烷、甾烷的降解效果均较好.      

普鲁士蓝@酵母菌催化剂的合成及其Fenton性能

自组装合成普鲁士蓝@酵母菌(PB@yeast)非均相Fenton催化剂,场发射扫描电镜(FE-SEM)、能量色谱(EDS)、X射线衍射(XRD)、傅里叶红外光谱(FT-IR)等表征结果表明PB纳米颗粒成功负载于酵母菌表面,形成稳定且高度分散的核壳结构复合微球;荧光增白剂CXT降解实验结果证明该复合微球兼备吸附与Fenton催化性能,酵母菌载体的吸附作用加快了废水中荧光增白剂CXT向催化剂活性位点的转移,促进FeⅢ-FeⅡ电子传递,显著提高了Fenton反应催化活性,酵母载体增强了PB纳米粒子的分散度与稳定性,有效解决PB纳米催化剂易团聚、易溶解的问题.PB@yeast催化剂经循环使用4次后对荧光增白剂CXT的去除效率无明显下降,表现出较好的催化效果和稳定性能.     

组合液膜对自配淋洗液中Cd的提取回收效果

淋洗法是解决土壤重金属污染的有效方法之一,其对土壤Cd污染的治理效果较好,但需对Cd污染土壤进行淋洗后的含Cd淋洗废液进行再生和回收利用.为了克服传统液膜分离技术不稳定、膜溶液易流失等缺陷.采用P204（磷酸二异辛酯）为络合剂的组合液膜提取技术对自配土壤淋洗液中Cd2+进行提取,考察水相pH、w（P204）、接受相酸浓度、膜相与接受相体积比、接收相不同酸、水相初始c（Cd2+）对Cd2+提取率的影响,并提出动力学方程,进一步研究Cd2+在多金属离子分离条件.结果表明:①络合剂与Cd2+形成络合物在液膜系统中传输,最佳提取条件为pH 4.2、w（P204）5.0%、接受相酸浓度4.0 mol/L、膜相与接受相体积比1:3,接收相酸种类对提取率影响不明显;②水相c（Cd2+）越低,提取率越高;③基于传质动力学模型,建立了回收系数与水相pH和w（P204）的关系方程,分别为P_c=（3.20×104+2.03×1010[H+]2）-1和P_c-1=3.208×104+1.742[C0]-2,得到Cd2+通过料液和膜边界层的厚度（d_w）为17.8 μm,络合物通过膜的扩散系数（D_m0）为7.61×10-8 m2/s.研究显示,在最佳提取条件下,初始c（Cd2+）为5.0×10-3 mol/L时,240 min内提取率可达93%,通过调节多金属离子体系中Cd2+的提取条件与参数,或调节每种金属提取条件与参数,进行反复提取,Cd2+可以与其他重金属成功分离.      

1,2,4-三氯苯厌氧还原脱氯过程及荧光增白剂PF对脱氯过程影响研究

南京某化工厂生产荧光增白剂PF(1,2-双(5-甲基-2-苯并唑基)-乙烯,调查发现其地下水中存在多种污染物:1,2,4-三氯苯(TCB)、二氯苯同分异构体(DCB)、一氯苯(MCB)、苯和PF.场地多年监测结果显示很可能存在厌氧条件下氯苯类污染物的自然降解.为了探索污染物降解机制并确定荧光增白剂PF对该脱氯过程的影响,笔者通过室内实验发现1,2,4-TCB被脱氯为1,2-DCB、1,3-DCB和1,4-DCB,摩尔比率约为10%、35%、55%.随着1,2,4-TCB投喂次数的增加,降解菌的脱氯速度越来越快,最高可达到7μmol·d~(-1).1,2-DCB和1,3-DCB先脱氯产生MCB,1,4-DCB滞后约两周开始降解,脱氯速度从第14周的0.19μmol·d~(-1)增加到第17周的0.88μmol·d~(-1),并在第108 d左右消耗完全.虽然1,2-DCB和1,3-DCB比1,4-DCB先开始脱氯,但脱氯速度相对缓慢,1,2-DCB的脱氯速度从第12周的0.001μmol·d~(-1)增加到第15周的0.21μmol·d~(-1),1,3-DCB的脱氯速度从第12周的0.06μmol·d~(-1)增加到第17周的0.14μmol·d~(-1).DCBs降解产生的MCB在第160 d左右开始脱氯生成苯,脱氯速度从第23周的0.296μmol·d~(-1)到第25周的1.94μmol·d~(-1)再到第28周的0.007μmol·d~(-1).同时,实验结果表明荧光增白剂PF不会改变1,2,4-TCB的脱氯过程,但在MCB脱氯到苯的过程中具有一定的抑制作用.     

陕西神木大柳塔洗煤厂煤泥水快速沉降剂试验研究

为了解决陕西神木大柳塔洗煤厂煤泥水的快速沉降和洗水循环再利用 ,在深入研究原煤泥水处理工艺技术效能的基础上 ,研究和发展了一种新型高效、经济的煤泥水处理工艺技术 ,合成了一种快速沉降剂。经过反复试验研究 ,使得原煤泥水系统有了极大改善 ,实现了洗水闭路循环和煤泥厂内回收 ,降低了药耗 ,缩短了反应时间 ,达到了快速沉降的目的。     

IMC染色剂的使用对水环境质量影响的安全性评估

依据美国环境保护局工业环境实验室提出的多介质环境目标值(MEG)及其综合排放指数,对IMC-401染色剂在使用过程中一旦泄漏或排放,可能对水环境质量、人体健康和生态系统产生的影响进行了安全性评估。     

本质安全化管理思想及实证研究框架

分析国内本质安全化管理研究现状及存在问题,指出两类系统本质安全化实现路径的差异性:①技术系统本质安全性等于构成要素的本质安全性乘积,只要保证要素本质安全化,系统也趋于本质安全化;②社会技术系统关键要素是智能体,从根本上无法达到本质安全化,但智能体自身具有一定容错性和自组织性,在相对可靠条件下,需要通过和谐交互机制使系统而获得本质安全化。分析和研讨的基础上,提出交互式安全管理理论的本质安全化管理研究基本思路:基于3层次和谐交互机制的本质安全化动态演化机制;并对系统本质安全化进行了量化;给出判定系统能否实现本质安全化条件以及本质安全化管理的基本函数关系;得出了系统本质安全化是系统安全性极限的结论。     

Selective flotation separation of plastics by chemical conditioning with methyl cellulose

The floatability of seven plastics (POM, PVC, PET, PMMA, PC, PS and ABS) in the presence of methyl cellulose (MC) and separation of plastics mixtures were investigated in this paper. It was found that the seven plastics can be separated into three groups by using the wetting agent MC. Group one includes POM and PVC. They are depressed at very low MC concentrations. Group two, including PET, PMMA and PC, has an intermediate floatability. Group three (ABS and PS) has a high floatability. They are almost not depressed within the given MC concentration range. In order to understand the mechanism of selective flotation of plastics and the chemical conditioning process, surface chemical factors, such as wettability of plastics and surface tension of flotation medium, and gravity factors, such as particle density and shape, were studied. It was found that the depressing effect of MC on plastics is ascribed mainly to its adsorption on the plastics surfaces. The MC molecules absorbed on plastics expose some of their polar groups oriented towards the aqueous phase, hence making the plastics surfaces hydrophilic. In addition, flotation selectivity for the plastics is dominated not only by wettability of plastics, but also by particle size, density and shape.