The effect of alkyl chain length on the degradation of alkylimidazolium- and pyridinium-type ionic liquids in a Fenton-like system

Background, aim, and scope  Ionic liquids are regarded as essentially “green” chemicals because of their insignificant vapor pressure and, hence, are a good alternative to the emissions of toxic conventional volatile solvents. Not only because of their attractive industrial applications, but also due to their very high stability, ionic liquids could soon become persistent contaminants of technological wastewaters and, moreover, break through into natural waters following classical treatment systems. The removal of harmful organic pollutants has forced the development of new methodologies known as advanced oxidation processes (AOPs). Among them, the Fenton and Fenton-like reactions are usually modified by the use of a higher hydrogen peroxide concentration and through different catalysts. The aim of this study was to assess the effect of hydrogen peroxide concentration on degradation rates in a Fenton-like system of alkylimidazolium ionic liquids with alkyl chains of varying length and 3-methyl-N-butylpyridinium chloride. Materials and methods  The ionic liquids were oxidized in dilute aqueous solution in the presence of two different concentrations of hydrogen peroxide. All reactions were performed in the dark to prevent photoreduction of Fe(III). The concentrations of ionic liquids during the process were monitored with high-performance liquid chromatography. Preliminary degradation pathways were studied with the aid of ¹H NMR. Results  Degradation of ionic liquids in this system was quite effective. Increasing the H₂O₂ concentration from 100 to 400 mM improved ionic liquid degradation from 57–84% to 87–100% after 60 min reaction time. Resistance to degradation was weaker, the shorter the alkyl chain. Discussion  The compound omimCl was more resistant to oxidation then other compounds, which suggests that the oxidation rates of imidazolium ionic liquids by OH· are structure-dependent and are correlated with the n-alkyl chain length substituted at the N-1-position. The level of degradation was dependent on the type of head group. Replacing the imidazolium head group with pyridinium increased resistance to degradation. Nonetheless, lengthening the alkyl chain from four to eight carbons lowered the rate of ionic liquid degradation to a greater extent than changing the head group from imidazolium to pyridinium. 1H-NMR spectra show, in the first stage of degradation, that it is likely that radical attack is nonspecific, with any one of the carbon atoms in the ring and the n-alkyl chain being susceptible to attack. Conclusions  The proposed method has proven to be an efficient and reliable method for the degradation of imidazolium ionic liquids by a Fenton-like reagent deteriorated with lengthening n-alkyl substituents and by replacing the imidazolium head group with pyridinium. The enhanced resistance of 1-butyl-3-methylpyridinium chloride when the resistance of imidazolium ionic liquids decreases with increasing H₂O₂ concentration is probably indicative of a change in the degradation mechanism in a vigorous Fenton-like system. H-NMR spectra showed, in the first stage of degradation, that radical attack is nonspecific, with any one of the carbon atoms in the ring and the n-alkyl chain being susceptible to attack. Recommendations and perspectives  Since ionic liquids are now one of the most promising alternative chemicals of the future, the degradation and waste management studies should be integrated into a general development research of these chemicals. In the case of imidazolium and pyridinium ionic liquids that are known to be resistant to bio- or thermal degradation, studies in the field of AOPs should assist the future structural design as well as tailor the technological process of these chemicals     

Removal of PAHs with surfactant-enhanced soil washing: influencing factors and removal effectiveness

PAH removal with surfactant enhanced washing was investigated through a series of laboratory tests to examine the effect of stirring speed, washing time, surfactant concentration, liquid/solid ratio, temperature, and on-and-off mode. The first four factors show significant influence on the PAH removal while the latter two do not. Total removal ratio and a new proposed parameter, solubilization percentage, are used to evaluate the effectiveness quantitatively.     

不同运行模式下改良型CAST工艺处理生活污水的除磷性能

实验采用改良型CAST工艺,以生活污水为研究对象,考察了C/P、回流比及温度等不同运行模式对系统除磷性能的影响.结果表明,常温条件下进水C/P由50升至100,系统除磷率均值从15%迅速升至95.6%,除磷性能显著提高;继而降低C/P至75,除磷性能因进水碳源不足再度下降,除磷率均值为51.4%,且长期投加易降解碳源引发系统污泥膨胀并导致污泥大量流失.C/P较低情况下,回流比由25%降低至12.5%,除磷性能提高2.3倍,继续降低回流比至0,除磷性能反而下降;温度实验研究则表明,低温系统(14℃±1℃),除磷率稳定维持在90%以上,而高温短程硝化系统(27℃±1℃)除磷率仅为14.1%,可见低温更有利于系统磷的去除.吸磷小试发现,常温系统污泥以O_2、NO_3~-和NO_2~-为电子受体均能进行吸磷,而低温系统污泥能以O_2、NO_3~-为电子受体进行吸磷,高温系统污泥则仅能以O_2为电子受体进行少量吸磷.此外,实验还发现,系统短期闲置导致的污泥"饥饿"有利于系统除磷率的提高.     

生活垃圾焚烧飞灰固化体力学及重金属浸出特性

以苏州七子山生活垃圾焚烧厂产生的飞灰为研究对象,采用水泥作为固化剂,研究水泥飞灰固化体的应力应变特征及重金属浸出特性,并探讨了水泥飞灰配合比、养护时间等关键性因素对这些特性的影响。实验结果表明:较养护3 d的样品,其余养护时间的样品强度平均增长了约96.2%,而其破坏应变平均减小了56%。随着水泥含量和养护时间的增加,飞灰固化体的强度上升,而其破坏应变减小,该趋势主要归因于钙矾石(AFt)的形成促进了飞灰固化体强度的发展。较飞灰原样,飞灰固化体的重金属浸出浓度随着水泥含量、养护时间的增加而降低了38%~99%,重金属的迁移被限制,主要归因于水化硅酸钙(C—S—H)和钙矾石(AFt)的形成,以及飞灰和水泥水化反应创造的强碱性环境。     

厌氧发酵处理庆大霉素菌渣的可行性及条件优化

采用厌氧发酵处理庆大霉素菌渣,考察了含固率、接种比、接种污泥、发酵底物等因素对庆大霉素菌渣厌氧发酵的影响,并用累积净甲烷产量衡量庆大霉素菌渣进行厌氧发酵的可行性及发酵程度。试验结果证实了庆大霉素菌渣进行厌氧发酵的可行性,其中含固率和接种比对发酵的影响较大,最佳条件为含固率5%,接种比1/3;对比试验所用3种接种污泥,发现接种某造纸厂污水处理IC反应器的厌氧颗粒污泥效果最优,在最优含固率和接种比的条件下,累积净产甲烷量为28.21 m3/t;此外,试验还证实,采用不同菌渣的联合发酵表现出了明显的协同作用,在最优条件下,庆大霉素菌渣与林可霉素菌渣按1∶2的比例联合发酵的产甲烷量可达到37.5 m3/t。     

Study of cyanide removal from contaminated water using zinc peroxide nanomaterial

The present study highlights the potential application of zinc peroxide(ZnO_2)nanomaterial as an efficient material for the decontamination of cyanide from contaminated water. A process patent for ZnO_2 synthesis has been granted in United States of America(US Patent number 8,715,612; May 2014),South Africa,Bangladesh,and India. The ZnO_2 nanomaterial was capped with polyvinylpyrrolidone(PVP)to control the particle size. The PVP capped ZnO_2nanomaterial(PVP-ZnO_2)before and after adsorption of cyanide was characterized by scanning electron microscope,transmission electron microscope,X-ray diffractometer,Fourier transform infrared spectroscopy and time of flight-secondary ion mass spectrometry. The remaining concentration of cyanide after adsorption by PVP-ZnO_2 was determined using ion chromatograph. The adsorption of cyanide over PVP-ZnO_2 was also studied as a function of p H,adsorbent dose,time and concentration of cyanide. The maximum removal of cyanide was observed in p H range 5.8–7.8 within 15 min. The adsorption data was fitted to Langmuir and Fruendlich isotherm and it has been observed that data follows both the isotherms and also follows second order kinetics.     

湖北省PM2.5与PM10比值分析及PM2.5时空分布特征研究

基于2012年-2014年湖北省大气污染物监测数据,通过数据反演方法,得到湖北省17个城市的PM2.5年均浓度.利用ArcGIS绘制出各城市不同年份的颗粒物浓度空间分布图,并对其进行分析.结果表明,2012年-2014年间,湖北省17个城市PM2.5与PM10年均浓度比值为0.66,PM2.5年均浓度超出国家二级标准,整体呈现上升趋势.城市方面,在多数城市PM2.5与PM10浓度上升的同时,仅武汉、黄冈和天门3个城市颗粒物浓度2014年较2013年有所下降,且武汉市PM2.5浓度下降率达12.8%,表明武汉市近两年来采取的政策措施具有较好的可行性和有效性.     

金属铜原子氧效应研究

目的获取金属铜空间原子氧环境适应性数据,提升材料空间环境适应性设计水平。方法将金属铜样品置于射频源原子氧辐照面积内开展原子氧辐照试验,束流密度为2.5×1016/(cm2·s),最长辐照时间为300 min。研究随辐照时间增加样品表面成分、形貌以及性能的变化。结果原子氧辐照后,金属铜表面变得粗糙,300 min辐照样品出现了氧化层脱落现象;随辐照时间增加,样品质量呈增加趋势,300 min辐照样品质量增加0.035 mg;试验后样品太阳吸收比升高最大值达0.07,光谱反射系数下降;原子氧作用导致金属铜表面疏水性能提高,摩擦磨损性能下降。结论得到了金属铜原子氧环境效应数据,可为航天器空间环境效应防护设计提供技术支撑。     

分流比对土壤渗滤系统脱氮效果的影响研究

针对污染物浓度较高的养猪废水,开展了不同分流比条件下土壤渗滤系统处理效果的对比研究,并分析了分流比对系统中脱氮微生物数量及氧化还原电位(ORP)变化的影响.试验结果表明,分流比对土壤渗滤系统的脱氮效果影响较大,而对COD、TSS和TP的去除效果无明显影响,当水力负荷(HLR)为0.01m3·m-2·d-1且分流比为1∶2时,系统对TN的去除效果最好,平均去除率达80.20%,而对其他污染物的平均去除率均可达90%以上;分流比可影响土壤渗滤系统中脱氮微生物的数量,分流比的增大可促进系统中反硝化细菌数量的增加,强化系统的脱氮效果;另外,分流比还可影响系统填料层中ORP的变化.因此,根据系统进水水质选择合适的分流比,是强化土壤渗滤系统脱氮效果的关键因素.     

左氧氟沙星的超声/H2O2联合降解研究

采用超声/H2O2高级氧化技术对喹诺酮类抗生素左氧氟沙星进行降解,考察了H2O2浓度、超声功率、溶液初始pH值对反应过程的影响.结果表明,与单独超声和H2O2氧化相比,超声/H2O2对左氧氟沙星具有明显的协同降解作用. H2O2 添加浓度在3.0~20.0mmol/L范围, 左氧氟沙星的降解率随其添加浓度的增加而增加;超声功率在260W时降解效果最佳;左氧氟沙星初始浓度在10~30mg/L范围内,左氧氟沙星的降解量随其初始浓度的增加而增加;超声/H2O2降解左氧氟沙星在未调节(pH 7.14)效果最佳. HPLC分析发现降解过程主要有2种产物生成, 产物的生成和分布受体系pH的影响较大.