利用蚀刻废液生产碱式氯化铜过程中二英类污染物的去除

针对蚀刻废液及其回收后生产的碱式氯化铜产品中二英(PCDD/Fs)和二英类多氯联苯(dl-PCBs)进行了分析研究,并比较了采用去除工艺前后两类污染物含量水平的变化特征.利用高分辨气相色谱/高分辨质谱对样品中PCDD/Fs和dl-PCBs进行分析,结果表明,氯化铜废液中PCDD/Fs和dl-PCBs的平均总浓度分别为264、139 pg·mL-1,而铜氨液中浓度分别为0.09、0.50 pg·mL-1;碱式氯化铜产品中浓度分别为106 pg·g-1(2.79 pg WHO-TEQ2005·g-1)和27.8 pg·g-1(0.69 pg WHO-TEQ2005·g-1);而经过吸附和过滤等去除工艺后,产品中PCDD/Fs和dl-PCBs的TEQ浓度水平分别降低至0.10—0.25 pg WHO-TEQ2005·g-1和0.05—0.72 pg WHO-TEQ2005·g-1,满足欧盟对于矿物源性饲料添加剂中PCDD/Fs和dl-PCBs的限量标准要求.研究表明该工艺能够有效去除利用蚀刻废液生产碱式氯化铜过程中的二英类污染物.     

Comparative study on the efficiency and environmental impact of two methods of utilizing polyvinyl chloride waste based on life cycle assessments

Two processes of utilizing polyvinyl chloride （PVC） waste, an incineration process and a vacuum pyrolysis process, for energy conversion were compared to determine their efficiency and environmental perfor- mance. We carried out a life cycle assessment with each of the two processes to evaluate their environmental impact and defined the goals and limits of our remit. As well, we established an inventory of PVC waste from incineration and vacuum pyrolysis based on process analysis, data collection and calculations. The results show that electrical power output per unit mass of PVC waste in the incineration process was twice as high as that of the vacuum pyrolysis process. Incineration had a larger total environmental impact potential than vacuum pyrolysis. The total environmental impact potential of PVC waste from incineration was three times higher than that from vacuum pyrolysis. Incineration of PVC disposed 300 ng. 100 kgI of dioxins and vacuum pyrolysis 98.19 ng- 100 kgI of dioxins. As well, we analyzed the data for their uncertainty with results quantified in terms of three uncertainties： basic uncertainty, additional uncertainty, and computational uncertainty. The coefficients of variation of the data were less than 25% and the quality of the inventory data was acceptable with low uncertainty. Both PVC waste disposal processes were of similar quality and their results comparable. The results of our life cycle impact assessment （LCIA） showed considerable reliability of our methodology. Overall, the vacuum pyrolysis process has a number advantages and greater potential for development of PVC disposal than the incineration process.     

Al13形态的凝胶层析分离及分离级分特性对比

采用聚丙烯酰胺凝胶柱层析法分离纯化聚合氯化铝(PAC)中的Al₁₃形态,并采用Al- Ferron逐时络合比色法、透射电镜(TEM)和ZATESIZER测定仪对分离纯化过程中所得3个级分进行了分析表征和电荷特性的研究;采用烧杯实验法对3个级分处理实际和模拟水样的混凝效果进行了对比性研究.Al- Ferron逐时络合比色法和TEM结果表明,在层析法分离中级分随着洗脱时间延长按分子的大小依次洗脱下来,因此截取中间组分即可得到含量95 %左右的纳米Al₁₃形态;电荷特性和混凝效果研究结果表明,第3个级分其他两者具有更好的除浊、除腐殖酸和脱色效果,并且具有更强的电中和能力,因此Al₁₃形态是一种具有较高正电荷和较高的水解稳定性以及宽的pH适用范围,在给水和废水处理中是一种较为有效的Al形态.     

Cu(NO3)2在亚甲蓝湿式氧化处理中的应用

用CWAO技术处理COD为2 000 mg/L的亚甲蓝水溶液.以Cu(NO3)2为催化剂,考察了催化剂投加量、反应温度、压力及进水pH值对亚甲蓝水样COD去除率、脱色率、出水pH值的影响.实验表明,亚甲蓝的氧化效率随催化剂投加量的增加,反应温度及压力的升高而升高.然而,综合考虑亚甲蓝的氧化效率、试剂费用、设备成本及能量消耗,实验确定Cu(NO3)2的投加量以Cu2 计为150 mg/L,反应温度及压力分别为200℃和2.0 MPa.在酸性进水条件下,COD去除率随进水pH值的降低而升高;而在碱性进水条件下,COD去除率随进水pH值的升高而升高.pH值按COD去除率由高到低的排列顺序是:3.87、11.23、5.50、7.25、9.47,实验确定最佳进水pH值是3.87.在以上最佳的操作条件下,反应150 min,水样COD去除率达97.4%,脱色率达99.97%,出水pH值3.63.     

十六烷基三甲基氯化铵与荧蒽对小球藻的联合毒性及其作用机制

以普通小球藻(Chlorella vulgaris)为受试生物,采用批量培养方法研究了阳离子表面活性剂十六烷基三甲基氯化铵(CTAC)与多环芳烃荧蒽(Flu)的联合毒性及其作用机制.结果表明,当CTAC初始浓度固定为100μg/L时,随Flu浓度的升高(0~100.84μg/L), CTAC与Flu的联合毒性由协同效应(0~22.50μg/L)转为拮抗效应(22.50~100.84μg/L).当Flu浓度为1.13μg/L时,协同效应达到最大(RI＝2.01),与对照组相比,生物量抑制率从37.5%增加至80.9%;对氮和铁单位吸收量分别从0.27mg和9.18μg降至0.09mg和2.14μg;藻细胞Zeta电位从-10.0mV提高至-8.3mV;叶绿素a和可溶性蛋白质含量分别从5.00mg/L和80.65μg/mg降为2.57mg/L和50.36μg/mg.根据实验结果分析, CTAC与Flu复合污染体系提高了藻细胞Zeta电位,抑制了小球藻对氮和铁的吸收,降低了藻细胞体内叶绿素和蛋白质的含量.     

Removal of methylene blue by coupling black carbon adsorption with TiO2 photodegradation

In this study, the removal of methylene blue (MB) by the coupling of black carbon (BC) and TiO₂ was investigated. The effects of different parameters such as catalyst dose, sorbent, initial concentrations of dye, pH of the solutions, recycles on discoloration, and chemical oxidation demand (COD) reduction of MB were monitored to optimize the reaction conditions. The discoloration and COD conversation rate of MB obtained by the coupling process were 100% after 90?min irradiation. The synergistic effect of MB-adsorption on BC followed by degradation through TiO₂ photocatalysis was proved by FT–IR spectrophotometer. The BC as by-product of natural materials is a promising adsorbent for waste water treatment.     

Thermodynamic investigation of the effect of oxygen and hydrogen chloride potential upon generation and decomposition behavior of dioxins

The thermodynamic equilibrium of the C‐H‐O‐Cl system has been calculated to elucidate the generation and decomposition behavior of dioxins, and is discussed from the viewpoint of the oxygen and hydrogen chloride potential. The dioxins behavior is greatly dependent on the oxygen potential, i.e. higher temperature and oxygen potential lead to the complete decomposition of dioxins, while low hydrogen chloride potential under insufficient oxygen condition leads to an increase of multi‐chlorine displacement of dioxins.     

二氧化钛改性油页岩渣对水溶液中亚甲基蓝和六价铬的吸附

以油页岩渣及其二氧化钛改性材料为吸附剂,探究它们去除水溶液中亚甲基蓝和六价铬的能力.通过实验,控制溶液的pH值、温度、初始浓度和接触时间,观察吸附效果变化特征,研究其动力学和热力学性能.实验表明,改性油页岩渣吸附亚甲基蓝和六价铬的吸附率是未改性的2—3倍,且改性油页岩渣对亚甲基蓝的吸附率可达97%,对六价铬的吸附率不到25%.吸附亚甲基蓝时,pH值越大,吸附效果越好;而吸附六价铬时,最适pH值为4.改性油页岩渣吸附亚甲基蓝实验符合准二阶动力学方程,计算得反应活化能为13.29 kJ.mol-1,表明此过程主要是物理吸附.在热力学方面,由范特霍夫方程计算得ΔG〈0、ΔH〉0,表明此过程自发吸热,可见此过程还伴有化学吸附.Langmuir和Freundlich等温模型拟合结果表明,Langmuir模型数据拟合甚佳,R2=0.9999,说明改性油页岩渣吸附亚甲基蓝是单分子层吸附.二氧化钛改性油页岩渣经7次回收利用后,对亚甲基蓝的吸附效果仅减少约1.5%.     

五氟苯甲酰氯衍生色谱法分析水体中痕量羟基多溴联苯醚

以五氟苯甲酰氯(PFBCl)作为衍生化试剂,气相色谱-电子捕获检测器(Gas chromatography-electron capture detector,GC-ECD)为检测手段,建立了水体中痕量羟基多溴联苯醚(Hydroxylated polybrominated diphenyl ethers,简称OH-PBDEs)的酰基化衍生-GC/ECD检测方法.通过实验讨论了衍生化缓冲溶液、衍生化时间以及衍生后萃取溶液异辛烷的用量对检测结果的影响,确定了最佳的衍生化条件.在最佳的衍生化条件下,4-OH-BDE 42、4’-OH-BDE 49、6-OH-BDE 47、2’-OH-BDE 68和6’-OH-BDE 99的衍生化产物均获得了良好的分离度和色谱响应值.本方法的仪器检出限为0.02—0.14 pg,方法检出限为0.61—4.67 pg.L-1,标准曲线线性相关系数的范围为0.9973—0.9996,相对标准偏差均小于10%.3种采自大连市不同地区环境水样的加标回收率检测结果表明,所建立的分析方法适于水体中痕量OH-PBDEs的检测.     

离子液体1-丁基-3-甲基咪唑氯盐对斜生栅藻的毒性效应

按照毒性试验标准方法研究了不同浓度离子液体1-丁基-3-甲基咪唑氯盐([BMIM]Cl)对斜生栅藻的影响,测定了半数抑制浓度(IC50)、叶绿素含量、超氧化物歧化酶(SOD)活性、过氧化氢酶(CAT)活性以及藻细胞通透性的变化,观察了80mg/L[BMIM]Cl处理96h对藻细胞的影响.结果表明:[BMIM]Cl对斜生栅藻生长具有抑制作用,随着浓度的增大抑制率增加,叶绿素含量下降, 48h IC50、72h IC50和96h IC50分别为103.77、76.44和68.49mg/L.藻细胞对[BMIM]Cl有一定的氧化应激反应,CAT和SOD活性随[BMIM]Cl浓度升高而降低.[BMIM]Cl对藻细胞的细胞膜有一定程度的破坏作用,藻细胞通透性随浓度升高而增大,同时藻细胞的超微结构受到了[BMIM]Cl的影响,造成质壁分离,叶绿体片层断裂,线粒体嵴数量减少.