Extended geometric method: a simple approach to derive adsorption rate constants of Langmuir-Freundlich kinetics

A new and simple equation has been presented here for calculation of adsorption and desorption rate constants of Langmuir-Freundlich kinetic equation. The derivation of new equation is on the basis of extension and correction to the geometric method which has been presented by Kuan et al. [Kuan, W.-H., Lo, S.-L., Chang, C.M., Wang, M.K., 2000. A geometric approach to determine adsorption and desorption kinetic constants. Chemosphere 41, 1741-1747] for the kinetics of adsorption/desorption in aqueous solutions. The correction is to consider that the concentration of solute is not constant and changes as adsorption proceeds. The extension is that we applied Langmuir-Freundlich kinetic model instead of Langmuir kinetic model to consider the heterogeneity and therefore it is more applicable to the real systems. For solving Langmuir-Freundlich kinetic model, some geometric methods and also Taylor expansion were used and finally a simple and novel equation was derived (Eq. (20)) for calculation of adsorption rate constant. This new method was named "extended geometric method". The input data of the obtained equation can be simply derived from initial data of adsorption kinetics. Finally the adsorption of methyl orange onto granular activated carbon was carried out at dynamic and equilibrium conditions and the capabilities of extended geometric method were examined by the experimental data.     

Toluene removal biofilter modeling: Optimization and case study

Based on the model proposed by De Visscher and Van Cleemput for methane oxidation in landfill cover soils, a simulation model for biofiltration of toluene-contaminated air has been developed for biofilters with substrate inhibition. A convenient way to optimize biofilter performance was developed assuming Haldane kinetics. It was calculated that for a typical oilsands operation emitting 200 ton of toluene annually, 90% of the toluene can be removed by a 740 m³ biofilter, if the waste gas sent to the biofilter has a toluene concentration of 2.25 g m⁻³. The optimal initial concentration increases with increasing target efficiency.     

Immobilization of Pb(II), Cd(II) and Ni(II) ions on kaolinite and montmorillonite surfaces from aqueous medium

The present study investigates the immobilization of Pb(II), Cd(II) and Ni(II) on clays (kaolinite and montmorillonite) in aqueous medium through the process of adsorption under a set of variables (concentration of metal ion, amount of clay, pH, time and temperature of interaction). Increasing pH favours the removal of metal ions till they are precipitated as the insoluble hydroxides. The uptake is rapid with maximum adsorption being observed within 180 min for Pb(II) and Ni(II) and 240 min for Cd(II). A number of available models like the Lagergren pseudo first-order kinetics, second-order kinetics, Elovich equation, liquid film diffusion and intra-particle diffusion are utilized to evaluate the kinetics and the mechanism of the immobilization interactions. Two isotherm equations due to Langmuir and Freundlich showed good fits with the experimental data. Kaolinite and montmorillonite have considerable Langmuir monolayer capacity with respect to Pb(II), Cd(II) and Ni(II), the values being in the range of 6.8-11.5mg/g (kaolinite) and 21.1-31.1mg/g (montmorillonite). The Freundlich adsorption capacity follows a similar order. The thermodynamics of the immobilization process indicates the same to be exothermic with Pb(II) and Ni(II), but endothermic with Cd(II). The interactions with Pb(II) and Ni(II) are accompanied by decrease in entropy and Gibbs energy while the endothermic immobilization of Cd(II) is supported by an increase in entropy and an appreciable decrease in Gibbs energy. The results have established good potentiality for kaolinite and montmorillonite to remove heavy metals like Pb(II), Cd(II) and Ni(II) from aqueous medium through adsorption-mediated immobilization.     

山梨酸废水在ABR中的基质降解行为

稳态条件下,采用厌氧折流板反应器(anaerobic baffled reactor,ABR)处理山梨酸废水并进行基质降解动力学研究.实验表明,在污泥负荷为0.54～1.63 kg COD/(kg VSS·d)的范围内,COD去除率随着负荷的增加从85%降到55%.各隔室出水COD沿程递减,前3个隔室承担了去除COD的重要作用,但随着污泥负荷的增加,后部承担的COD去除率比例增大.基于各串联隔室完全混合的假定,推导ABR中山梨酸废水的基质降解动力学方程,并通过实验确定相关动力学参数及相应的动力学方程.实测值与预测值基本吻合.     

海洋巨藻(Durvilaea potatorum)生物吸附剂对Hg~(2 )的吸附动力学研究

对经特殊的稳定化预处理所得的海洋巨藻 (Durvillaeapotatorum)生物吸附剂对Hg2 的吸附动力学进行了研究 ,报导了不同Hg2 初始浓度、温度以及生物吸附剂平均粒径下动态吸附量与时间的关系 .结果显示 ,各吸附动力学曲线呈优惠型 ;当生物吸附剂平均粒径为 0 .45mm时 ,Hg2 的半饱和时间tS均不超过 6 0min ;Hg2 初始浓度和生物吸附剂粒径越小 ,吸附温度越大 ,达到吸附平衡所需的时间越短 .在测试范围内 ,生物吸附剂的平衡吸附容量与粒径和温度无关 .同时考察了吸附过程中的传质效应并对液膜传质系数kL进行了关联 ,结果表明 :当吸附时间t≤tS时 ,Hg2 的吸附速率为液膜传质控制 ;在测试范围内 ,kL为 0 .0 40 7～ 0 .112cm/s.本研究结果为利用海洋巨藻 (Durvillaeapotatorum)生物吸附剂处理含汞废水的规模化应用提供了一定的依据 .图 5表 2参 11     

苯蒸气在有机膨润土上的吸附动力学

本文研究了苯蒸气在溴化十六烷基三甲基胺（CTMAB）系列单阳离子有机膨润土上的吸附动力学过程。结果表明,苯蒸气在有机膨润土上的吸附符合一级动力学方程,即：r＝KvCo;在12h内,吸附反应均可达到平衡,吸附速率常数（Kv）与温度（T）成正相关,吸附反应的活化能在9．50－17．92kJ.mol^-1之间。     

碱片-离子色谱法测定硫酸盐化速率影响因素

采用碱片-离子色谱法测定空气的硫酸盐化速率,方法在硫酸盐质量浓度为1.00~20.0 mg/L范围内线性良好(r≥0.999 0);碱片剪碎或不剪碎对空白碱片中硫酸根离子质量浓度的测定无明显影响,且高低两种加标浓度的回收率均在80.0%~120%之间;对于碱片实际样品,碱片剪碎更有利于硫酸根离子的快速溶出;随浸泡时间的延长,碱片中溶出的硫酸根离子质量浓度呈上升趋势,7 h硫酸根离子基本溶出完全,从保证结果质量和节省时间的角度考虑,确定最佳浸泡时间为3.5 h,建议碱片全部采取剪碎处理。     

菲和镉单一及复合污染条件下在毛蚶体内的富集动力学研究

采用室内半静态双箱动力学模型实验,研究了菲和镉单一及复合污染条件下在毛蚶(Anadara subcrenata)体内的生物富集,通过对富集与释放过程中毛蚶体内菲和Cd的富集量进行非线性曲线拟合,获得了菲和Cd单一及复合污染条件下在毛蚶体内的吸收速率常数k1、释放速率常数k2、生物富集因子BCF、生物半衰期B1/2和平衡状态下最大富集量CA max等动力学参数。实验结果表明,菲和Cd在实验前期富集速率较高,8 d以后富集速率减缓,释放阶段与富集阶段相似。毛蚶对菲的BCF值为37.80,远大于Cd的BCF值13.12,且生物半衰期时间更长,菲更容易在生物体内富集。菲和Cd联合暴露条件下,在毛蚶体内的CA max和BCF值均大于单一作用,说明二者同时暴露时,毛蚶对菲和镉的吸收富集均有所增强。实验模型拟合度较好,输出值和实测值之间无显著性差异,拟合方程和拟合参数可信。     

臭氧氧化法处理焦化废水生化出水的反应动力学

对臭氧氧化去除焦化废水生化出水COD的反应动力学及其影响因素进行了实验研究,结果表明,在臭氧投加量为8．50mg／min,反应温度为20＇E和初始pH为10．61条件下,对COD的降解符合表观一级反应动力学模型,其相关系数R。=0．9991,表观反应速率常数k。。=1．01×10^-3s-1。该条件下,臭氧氧化对COD的降解主要来源于高活性羟基自由基的强氧化作用。在不同的臭氧投加量（4．25～12．75mg／min）、不同的反应温度（10～40℃）和不同的初始pH（3．76～12．53）下,COD的降解也同样遵循一级反应动力学规律。随着臭氧投加量的增大,COD降解的表观反应速率常数从（0．554×10^-3）s-1增加到（1．06×10＆-3）s-1;随着反应温度的升高,表观反应速率常数从（0．427×10^-3）s-1增加到（1．40×10-3）s-1,温度越高反应速率提高的幅度却越小;在初始pH3．76～10．61范围内,表观反应速率常数从（0．218×10^-3）s-1增加到（1．01×10^-3）s-1,在初始pH为12．53时表观反应速率常数下降到（0．857×10^-3）s-1。     

一株抗Cd~（2＋）菌株的筛选及其吸附性能

Cd2＋为一种毒性金属元素,为了实际解决污水中低浓度重金属污染,实现污水达标排放,通过12C6＋重离子束辐照诱变技术筛选到一株耐受Cd2＋的菌株C2,研究其对Cd2＋的抗性和低浓度Cd2＋的吸附性能表明,Cd2＋浓度≤100 mg/L时,C2菌株可以生长繁殖,但随Cd2＋浓度升高受到抑制;SEM分析表明,受到Cd2＋胁迫时,C2产生大量胞外产物与Cd2＋形成络合物;吸附过程中菌粉表面空隙得到填充,形成凸起;红外光谱分析表明,吸附过程中的主要作用基团为醇羟基O—H键、氨基和酰胺基团;C2菌粉和固定化菌球都对Cd2＋有较好的吸附能力,菌粉吸附效果比固定化菌球稍好;菌粉和固定化吸附剂的最佳吸附初始pH值为5~6.0,最佳投加量分别为1.0 g/L和10 g/L（实际含菌量为1.0 g/L）;Cd2＋浓度在2~20mg/L时,在最佳吸附条件下,菌粉和固定化吸附剂对Cd2＋的吸附率均在90%左右;2种吸附剂吸附过程与Langmuir等温模型和拟二级动力学模型拟合最佳;热力学研究表明吸附反应均能自发进行。以上研究结果表明,C2菌粉和固定化吸附剂均可用于污水中低浓度Cd2＋的去除。