Removal of perfluorinated surfactants from wastewater by adsorption and ion exchange——Influence of material properties,sorption mechanism and modeling

Perfluorooctane sulfonate(PFOS) has attracted increasing concern in recent years due to its world-wide distribution, persistence, bioaccumulation and potential toxicity. The influence of sorbent properties on the adsorptive elimination of PFOS from wastewater by activated carbons, polymer adsorbents and anion exchange resins was investigated with regard to their isotherms and kinetics. The batch and column tests were combined with physicochemical characterization methods, e.g., N_2 physisorption, mercury porosimetry, infrared spectroscopy, differential scanning calorimetry, titrations, as well as modeling. Sorption kinetics was successfully modelled applying the linear driving force(LDF) approach for surface diffusion after introducing a load dependency of the mass transfer coefficient βs.The big difference in the initial mass transfer coefficient βs,0, when non-functionalized adsorbents and ion-exchange resins are compared, suggests that the presence of functional groups impedes the intraparticle mass transport. The more functional groups a resin possesses and the longer the alkyl moieties are the bigger is the decrease in sorption rate.But the selectivity for PFOS sorption is increasing when the character of the functional groups becomes more hydrophobic. Accordingly, ion exchange and hydrophobic interaction were found to be involved in the sorption processes on resins, while PFOS is only physisorptively bound to activated carbons and polymer adsorbents. In agreement with the different adsorption mechanisms, resins possess higher total sorption capacities than adsorbents. Hence, the latter ones are rendered more effective in PFOS elimination at concentrations in the low μg/L range, due to a less pronounced convex curvature of the sorption isotherm in this concentration range.     

地下水循环井技术处理土壤和地下水中甲基叔丁基醚研究

研究了MTBE在砂土中的静态吸附以及采用地下水循环井技术(GCW)去除砂土和地下水中MTBE的衰减规律。结果表明:MTBE在砂土中的吸附动力学符合准二级动力学方程,相关系数R2为0.99618,在砂土中的吸附平衡时间为24 h;吸附热力学符合Linear平衡吸附,吸附系数为0.00306 m3/kg。GCW运行30 h后,地下水饱和含水层中MTBE浓度由500 mg/L降至72.5 mg/L,去除率为85.5%;砂土中MTBE的吸附量由0.93 mg/g降至0.03 mg/g,去除率达96.4%。水平方向距GCW越近,MTBE的去除效率越快,垂直方向位于GCW上部的MTBE优先会被去除,最佳修复时间为运行15 h。GCW对砂土和地下水中高浓度MTBE具有良好的修复效果。     

污泥生物炭制备吸附陶粒

以城市污泥热解产生的生物炭(BC)与高岭土(KL)为原料制备吸附陶粒(SKC),研究其对环丙沙星(CIP)的吸脱附性能,开展吸附动力学和等温吸附特性研究,结合形貌、孔结构、物相组成、表面电位探讨其吸附机制,利用TCLP法研究重金属浸出特征.结果表明BC与KL以6∶4的质量比混合造粒,经1 050℃烧结5 min得到的SKC对CIP有明显的吸附效果,去除率达65.34%;SKC对CIP的吸附符合二级动力学模型,在不同质量浓度下的吸附特性适用于Freundlich等温吸附模型,吸附过程同时存在物理和化学吸附.SKC具有良好的孔隙结构,物相组成以硅铝氧化物、铁氧化物和金属磷酸盐为主,既能降低重金属的浸出毒性又具有良好的CIP吸附去除效果,有望为处理废水中高浓度CIP提供一种低成本可回收的吸附材料,也为BC的规模化安全利用提供了新思路.     

粉末活性炭粒径对水中菲吸附动力学的影响效应研究

以菲为目标污染物,研究了粉末活性炭(PAC)在微尺度(1～ 100.Μm)下的粒径效应对多环芳烃吸附性能的影响.实验中按照中值粒径将研磨后得到的粉末活性炭划分为:PAC-1 (19 μm)、PAC-2(46μm)、PAC-3(76 μm).通过比表面积及孔隙度自动分析仪、原位拉曼光谱、扫描电镜等手段对PAC物化性质进行表征,发现粒径减小使PAC的BET比表面积和总孔容增加了10％ ～20％左右,而对PAC表面化学性质的影响较小.PAC的粒径分布对其吸附性能有显著影响,这种影响主要体现为吸附速率成倍的增加,其次是吸附容量有30％ ～36％的增幅.分别用3种动力学模型对吸附过程进行拟合,结果表明,伪二级动力学方程的拟合程度最高,PAC-1有最大的吸附速率常数k,并且随着粒径的减小,k值逐渐增大.     

铜铈复合氧化物上石化行业典型VOCs的氧化行为与动力学

采用共沉淀法和等体积浸渍法制备了CuCeO x复合催化剂,对材料的物化性质进行了XRD、低温N2吸脱附、H2-TPR和O2-TPD表征.以石化行业典型VOCs(苯、甲苯和正己烷)为探针污染物,研究了污染物组成与浓度、反应空速、O2浓度、H2O浓度和催化剂种类对其氧化行为的影响,并对反应动力学参数进行了模型拟合.共沉淀得到的催化剂具有均匀的活性相、好的低温可还原性能和较多的活性表面氧物种.甲苯氧化率随着污染物浓度升高而降低,高转化率下苯浓度与其氧化率无相关性,正己烷的氧化率与入口浓度呈正比.苯能够显著抑制甲苯的氧化,而甲苯加入有利于苯的氧化.正己烷对苯氧化的影响较小,但能够促进甲苯的转化,苯系物对正己烷氧化有明显的抑制作用.低空速和高氧浓度都有利于污染物的氧化,氧浓度的变化对正己烷和苯的氧化影响较小.水汽对甲苯的氧化有明显的抑制作用,而对苯和正己烷氧化有明显的促进作用.共沉淀催化剂具有更好的甲苯和苯氧化性能,而无水条件下浸渍催化剂具有更好的正己烷氧化性能.拟一级动力学模型能够很好地模拟不同条件下污染物的氧化行为.     

发酵液作为EBPR碳源的动力学模拟

发酵液是一种优质的碳源,能够提高生物除磷系统(EBPR)的除磷效果.采用基于碳源代谢的修正ASM2模型,能够较好地模拟发酵液作为EBPR碳源的动力学变化规律.发酵液作为EBPR唯一碳源时,系统中的异养菌不仅不对聚磷菌(PAO)的生长构成竞争关系,反而促进PAO的生长.发酵液作为实际污水的补充碳源时,优化了污水中的碳源组成,创造了有利于聚磷菌生长的环境,使EBPR中聚磷菌达到微生物总量的40%以上,比实际污水作为碳源的EBPR中的PAO含量提高了3.3倍.     

基于废陶瓷的多孔陶瓷研制及其对Ni2+的吸附性能

通过SEM、XRD、FT-IR表征及多孔陶瓷对废水中镍的去除能力,确定多孔陶瓷的制备条件:原料中田菁粉掺杂质量分数为4%,焙烧温度为800℃.SEM和孔结构表征说明,焙烧使多孔陶瓷形貌、结构发生变化;随着焙烧温度的升高,多孔陶瓷的比表面积和孔容呈现降低的趋势,而孔径呈现增大的趋势;EDS分析能表明,原废瓷粉和多孔陶瓷的主要元素组成均为Si、Al、O.SEM、XRD和FT-IR分析表明,多孔陶瓷吸附前后结构稳定.吸附Ni2+的系列实验表明,多孔陶瓷用量为10 g·L-1,吸附时间为60 min,进水pH值为6.32,进水Ni2+浓度在100 mg.L-1以内.在此条件下废水的Ni2+去除率可达89.7%,多孔陶瓷对废水中镍有较好的去除效果.以制备的多孔陶瓷处理含镍废水,考察多孔陶瓷对废水中Ni2+的吸附动力学和吸附等温线,结果表明,多孔陶瓷对Ni2+的吸附过程符合准二阶动力学模型(R2=0.999 9),Qe为9.09 mg·g-1;吸附过程可用Freundlich方程和Langmuir方程来描述,温度由20℃升高至40℃,最大吸附量Qm由14.49 mg·g-1上升至15.38 mg·g-1.     

Investigation of acetylated kapok fibers on the sorption of oil in water

Kapok fibers have been acetylated for oil spill cleanup in the aqueous environment. The structures of raw and acetylated kapok fiber were characterized using Fourier transform infrared (FT-IR) spectroscopy and scanning electron microscopy (SEM). Without severe damage to the lumen structures, the kapok fibers were successfully acetylated and the resulting fibers exhibited a better oil sorption capacity than raw fibers for diesel and soybean oil. Compared with high viscosity soybean oil, low viscosity diesel shows a better affinity to the surface of acetylated fibers. Sorption kinetics is fitted well by the pseudo second-order model, and the equilibrium data can be described by the Freundlich isotherm model. The results implied that acetylated kapok fiber can be used as the substitute for non-biodegradable oil sorption materials.     

Pb(II) removal from water using Fe-coated bamboo charcoal with the assistance of microwaves

Bamboo charcoal(BC) was used as starting material to prepare iron-modified bamboo charcoal(Fe-MBC) by its impregnation in FeCl 3 and HNO 3 solutions simultaneously,followed by microwave heating.The material can be used as an adsorbent for Pb(Ⅱ) contaminants removal in water.The composites were prepared with Fe molar concentration of 0.5,1.0 and 2.0 mol/L and characterized by means of N 2 adsorption-desorption isotherms,X-ray diffraction spectroscopy(XRD),scanning electron microscopy coupled with energy dispersive X-ray spectrometry(SEM-EDS),Fourier transform infrared(FT-IR) and point of zero charge(pH pzc) measurements.Nitrogen adsorption analyses showed that the BET specific surface area and total pore volume increased with iron impregnation.The adsorbent with Fe molar concentration of 2 mol/L(2Fe-MBC) exhibited the highest surface area and produced the best pore structure.The Pb(Ⅱ) adsorption process of 2Fe-MBC and BC were evaluated in batch experiments and 2Fe-MBC showed an excellent adsorption capability for removal Pb(Ⅱ).The adsorption of Pb(Ⅱ) strongly depended on solution pH,with maximum values at pH 5.0.The ionic strength had a significant effect on the adsorption at pH < 6.0.The adsorption isotherms followed the Langmuir isotherm model well,and the maximum adsorption capacity for Pb(Ⅱ) was 200.38 mg/g for 2Fe-MBC.The adsorption processes were well fitted by a pseudo second-order kinetic model.Thermodynamic parameters showed that the adsorption of Pb(Ⅱ) onto Fe-MBC was feasible,spontaneous,and exothermic under the studied conditions,and the ion exchange mechanism played an significant role.These results have important implications for the design of low-cost and effective adsorbents in the removal of Pb(Ⅱ) from wastewater.     

Photocatalytic degradation of carbofuran in TiO2 aqueous solution：Kinetics using design of experiments and mechanism by HPLC/MS/MS

The photocatalytic degradation kinetics of carbofuran was optimized by central composite design based on response surface methodology for the first time. Three variables, TiO2 concentration, initial pH value and the concentration of carbofuran, were selected to determine the dependence of degradation efficiencies on independent variables. Response surface methodology modeling results indicated that the degradation efficiency of carbofuran was highly affected by the initial pH value and the concentration of carbofuran. Then nine degradation intermediates were detected by HPLC/MS/MS. The Frontier Electron Densities of carbofuran were calculated to predict the active sites on carbofuran attacked by hydroxyl radicals and photoholes. Point charges were used to elucidate the chemisorption pattern on TiO2 catalysts during the photocatalytic process. By combining the experimental results and calculation data, the photocatalytic degradation pathways of carbofuran were proposed, including the addition of hydroxyl radicals and the cleavage of the carbamate side chain.