污泥基活性炭去除水中重金属离子效能与动力学研究

以城市污泥为主要原料制备了污泥基活性炭(SAC),考察了其对重金属离子的吸附去除效能和吸附动力学规律.并选择了2种商品活性炭(煤质炭,MAC和椰壳炭,YAC)作为对比,以初始浓度为50mg/L的Cu(II),Pb(II),Cd(II),Cr(VI)4种重金属离子为去除对象,分别进行了3种活性炭的表面理化性质分析及其对4种重金属离子的吸附试验.结果表明,SAC的比表面积和微孔容积仅为YAC和MAC的1/3~1/2,吸附速率也相对较慢,但其对Cu(II),Pb(II),Cr(VI),Cd(II)的平衡吸附量却远大于2种商品活性炭,分别为9.9,8.9,8.2,5.4mg/g,说明SAC表面的高酸性基团含量对重金属离子的吸附起到了关键作用;Langmuir与Freundlich吸附等温模型均能较好地拟合SAC对Cu(II)和Pb(II)的吸附,SAC对Cr(VI)的吸附过程更符合Langmuir模型,而SAC对于Cd(II)的吸附过程用Langmuir与Freundlich两个模型均不能较好地拟合,说明SAC表面缺少能够与Cd(II)发生反应的结合位点.     

高分散氮化碳溶胶在重金属离子吸附去除中的应用

吸附材料在水中的分散性对于增加其与吸附质间相互作用,实现污染物的高效去除尤为重要.本文基于分子形态易于调控的石墨相氮化碳二维材料,通过简单的化学处理方法制备成高度分散于水中的溶胶吸附剂（M-C₃N₄-sol、U-C₃N₄-sol）,通过透射电镜（TEM）、X射线衍射（XRD）、傅里叶变换红外光谱（FTIR）、X射线光电子能谱仪（XPS）、Zeta电位仪（Zeta Potential Analyzer）、比表面积及孔径分布仪（BET）等对其形貌、组成、结构进行了表征.结果表明,氮化碳溶胶呈现纳米级纤维状结构,在水中有着极佳的分散性.相较于原始氮化碳（g-C₃N₄）,溶胶吸附剂对多种重金属离子的吸附去除能力得到大幅度提升,尤其是对Pb²⁺具有较高的吸附选择性.在298 K时,对Pb²⁺的吸附在1 min内即可达到平衡,快速吸附过程符合准二级动力学模型和Freundlich等温模型.吸附机理的研究表明,M-C₃N₄-sol对Pb²⁺的吸附是在静电引力、离子交换、氨基的表面络合和阳离子-π键的协同作用下完成的.吸附金属离子后,M-C₃N₄-sol发生脱稳形成易于实现固液分离的沉淀产物,对其进行稀硝酸脱附再生,吸附容量没有明显降低,表明其良好的循环使用性能.     

生物吸附法去除重金属离子的研究进展

本文对生物吸附去除重金属污染的研究和应用现状进行了综合评述.首先,介绍了细菌、真菌、藻类这3类研究较多的生物吸附剂,比较了它们对重金属离子的吸附容量,并简要介绍了一些新型的吸附剂.然后,讨论了生物吸附的影响因素、吸附机理、吸附剂的预处理和固定化、吸附等温式和吸附动力学模型等.最后,介绍了生物吸附法的应用情况.本文还展望了生物吸附法研究和应用的两个可能发展方向,一是利用包括生物吸附在内的多种工艺的综合技术,特别是利用活细胞来处理实际废水.二是开发出类似于离子交换树脂的商业化生物吸附剂,并努力开拓商业市场.     

粉煤灰合成NaA型沸石对重金属离子的吸附动力学

以粉煤灰为原料,采用两步法合成了单一沸石矿物种的NaA型沸石,对合成产物的结构和性能进行了表征.通过静态吸附实验,研究了NaA型沸石对水溶液中Cu(ΙΙ)、Cr(Ⅵ)和Zn(ΙΙ)离子的吸附特性,从动力学角度探讨了吸附机理.结果表明,在所研究的浓度和pH值条件下,NaA型沸石对3种重金属的吸附符合Langmuir等温吸附方程,静态饱和吸附量(Qm)分别为82.30,65.96,47.78mg/g;3种金属离子在水溶液中的存在方式和大小是影响它们吸附行为的主要因素,通过动边界模型推算表明:NaA型沸石对Cu(ΙΙ)和Zn(ΙΙ)离子的吸附过程的速度控制步骤为液膜扩散,对Cr(Ⅵ)离子的吸附过程的速度控制步骤为颗粒扩散,3种金属离子的吸附过程符合伪二级方程.     

酿酒酵母吸附Zn2+、Pb(2+)、Ag+、Cu2+的动力学特性研究

利用静态摇瓶实验方法,研究了工业废弃酿酒酵母无缓冲溶液体系吸附Zn2 、Pb2 、Ag 、Cu2 的动力学特性.结果表明,酵母吸附Zn2 、Pb2 、Ag 、Cu2 的动力学过程可以用准二级动力学方程进行描述.金属离子初始浓度在0.08～3.0 mmol·L-1范围内,Langmuir方程可以较好地描述Zn、Pb、Ag的等温吸附行为,Zn、Pb、Ag的理论饱和吸附量分别为0.522 mmol·g-1(34.11 mg·g-1)、0.577 mmol·g-1(119.50mg·g-1)和0.329 mmol·g-1(35.50 mg·g-1).以mol为基础的金属离子吸附量顺序是:Pb＞Zn＞Ag;以mg为基础的金属离子吸附量顺序是:Pb＞Ag＞Zn.Freundlich方程对整个浓度范围内的平衡数据拟合效果较差,但是它可以较好地描述低浓度Zn2 (初始浓度0.08～0.5mmol·L-1)、低浓度Pb2 (0.08～1.0 mmol·L-1)以及高浓度Ag (1.5～3.0 mmol·L-1)的等温吸附行为.酵母吸附Zn2 、Pb2 、Ag 、Cu2 过程中,溶液pH值有不同程度的增加,增加幅度大小顺序是Zn＞Pb＞Ag＞Cu,这间接反映出Zn2 、Pb2 、Ag 、Cu2 与水溶液中H 的竞争力逐步减弱.吸附过程中酵母释放大量的K ,其次是Mg2 ,而Ca2 、Na 的释放量较低,数量级一般可分别达到几百μmol·g-1 、几十μmol·g-1、几到几十μmol·g-1、十几μmol·g-1.     

Immobilization study of biosorption of heavy metal ions onto activated sludge

Activated sludge was immobilized into Ca-alginate beads via entrapment, and biosorption of three heavy metal ions, copper(Ⅱ), zinc(Ⅱ), and chromimum(Ⅱ), from aqueous solution in the concentration range of 10-100 mg/L was studied by using both entrapped activated sludge and inactivated free biomass at pH≤5. A biphasic metal adsorption pattern was observed in all immobilized biomass experiments. The biosorption of metal ions by the biosorbents increased with the initial concentration increased in the medium. The adsorption rate of immobilized pre-treated activated sludge(PAS) was much lower than that of free PAS due to the increase in mass transfer resistance resulting from the polymeric matrix. Biosorption equilibrium of beads was established in about 20 h and the adsorbed heavy metal ions did not change further with time. No significant effect of temperature was observed in the test for free biomass while immobilized PAS appeared to be strong temperature dependent in the test range of 10 and 40℃.Besides, the content of activated sludge in the calcium alginate bead has an influence on the uptake of heavy metals. The sorption equilibrium was well modeled by Langmuir isotherm, implying monomolecular adsorption mechanism. Carboxyl group in cell wall played an important role in surface adsorption of heavy metal ions on PAS.     

温和水热法合成钛酸盐纳米管及其对水中重金属离子的吸附研究

采用温和水热法一步快速合成了钛酸盐纳米管(TNTs),并应用于对水中重金属离子Pb(Ⅱ)、Cd(Ⅱ)和Cr(Ⅲ)的吸附.通过选择纳米级锐钛矿替代P25型二氧化钛作为反应原材料,成功将水热反应时间从72 h缩短至6 h.TEM,XRD和FT-IR等表征证实了新合成材料的为管状钛酸盐结构.TNTs对3种重金属离子的吸附动力学均符合准二级动力学方程,吸附等温线均符合Langmuir模型,且对Pb(Ⅱ)、Cd(Ⅱ)和Cr(Ⅲ)的理论最大吸附量分别高达525.58、214.41和69.65 mg·g~(-1).p H=5时,吸附动力学实验表明对于初始浓度分别为200、100和50 mg·L~(-1)的Pb(Ⅱ)、Cd(Ⅱ)和Cr(Ⅲ),在TNTs上的平衡吸附量分别为513.04、212.46和66.35 mg·g~(-1),吸附性能优于传统吸附材料.合成的TNTs结构为三联的[Ti O6]八面体骨架和层间H+/Na+,其吸附机理为金属阳离子与TNTs层间Na+的离子交换.同时,共存离子对吸附的影响实验表明TNTs对重金属离子的吸附存在选择性,即使在较高的共存离子浓度下(10 mmol·L~(-1))TNTs对目标重金属离子的吸附性能依然优异.该研究提供了一种应用钛酸纳米材料高效去除水体重金属离子的方法.     

介孔氮化碳对水中全氟辛烷磺酸的吸附去除研究

以SBA-15为模板、四氯化碳和乙二胺为前驱体,通过聚合反应制备了介孔氮化碳(Mesoporous Carbon Nitride,MCN).同时,采用X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、傅里叶红外光谱(FT-IR)、X射线光电子能谱(XPS)和元素分析等手段对MCN进行了表征分析,并考察了MCN对水中全氟辛烷磺酸(PFOS)的吸附性能.结果表明,MCN吸附PFOS的过程符合准二级动力学模型,其吸附行为遵循Langmuir等温线模型;MCN吸附去除PFOS的效率受溶液pH值、溶液温度及共存离子等因素的影响,其中,溶液pH值的影响最为显著,当溶液pH值分别为2.2和10.6时,MCN对PFOS的去除率分别为98.15%和5.59%;吸附PFOS饱和后的MCN可以用0.1 mol·L-1NaOH溶液进行解吸,经5次循环/再生后的MCN对PFOS的去除率仍在95%以上.与介孔碳(CMK-3)和活性炭(AC)相比,MCN对PFOS显示出更优越的吸附能力.     

Removal of heavy metal ions from aqueous solution using red loess as an adsorbent

The adsorption behaviors of heavy metals onto novel low-cost adsorbent, red loess, were investigated. Red loess was characterized by X-ray diffraction, scanning electron microscopy and Fourier transform infrared spectra. The results indicated that red loess mainly consisted of silicate, ferric and aluminum oxides. Solution pH, adsorbent dosage, initial metal concentration, contact time and temperature significantly influenced the efficiency of heavy metals removal. The adsorption reached equilibrium at 4 hr, and the experimental equilibrium data were fitted to Langmuir monolayer adsorption model. The adsorption of Cu(II) and Zn(II) onto red loess was endothermic, while the adsorption of Pb(II) was exothermic. The maximum adsorption capacities of red loess for Pb(II), Cu(II) and Zn(II) were estimated to be 113.6, 34.2 and 17.5 mg/g, respectively at 25°C and pH 6. The maximum removal efficiencies were 100% for Pb(II) at pH 7, 100% for Cu(II) at pH 8, and 80% for Zn(II) at pH 8. The used adsorbents were readily regenerated using dilute HC1 solution, indicating that red loess has a high reusability. All the above results demonstrated that red loess could be used as a possible alternative low-cost adsorbent for the removal of heavy metals from aqueous solution.     

碳基吸附剂原位吸附底泥重金属离子研究进展

本文综述了碳基吸附剂去除湖泊底泥中重金属离子的研究进展,具体介绍了生物炭基吸附剂、碳纳米管基吸附剂以及氧化石墨烯基吸附剂在修复湖泊重金属污染底泥中的应用,分析了影响重金属污染底泥修复的影响因素.结果表明,生物炭基吸附剂,碳纳米管基吸附剂,氧化石墨烯基吸附剂以及改性碳基吸附剂均能够有效修复底泥重金属,抑制重金属的生物有效性,同时上覆水pH值、氧化还原电位、有机质和水体扰动会影响重金属修复效果.最后针对碳基吸附剂在修复底泥重金属方面的局限性,展望了未来碳基吸附剂修复湖泊重金属污染底泥的发展方向.     

Mg (OH)2@粉煤灰复合材料对重金属离子的去除研究

根据“粒子设计”思想，以粉煤灰为载体，采用非均匀形核法制备了一种核壳结构粉煤灰负载纳米氢氧化镁复合材料，并对其吸附废水中Cu （II）、Ni （II）和Pb （II）性能进行研究.采用扫描电子显微镜（SEM）、EDS能谱、比表面积分析仪（BET）、X射线衍射（XRD）、红外光谱（FTIR）等技术对包覆前后的复合粉体进行了表征.结果表明，复合粉体表面均匀包覆了大量纳米氢氧化镁和少量水合碳酸镁，比表面积增大到原来（粉煤灰1.79m²/g）的30多倍，平均孔径由11nm增加至14.7nm.平均孔隙宽度从12.8nm增加至15.4nm.粉煤灰表面的Si-O-Si、Si-O-C与氢氧化镁之间形成Si-O-C-O-Mg和Si-O-Mg-OH.复合粉体材料去除重金属的效率明显高于原粉煤灰和氢氧化镁，其单位饱和吸附量分别达到了216.30、116.50、160.96mg/g.根据Zeta电位、FTIR及模拟方程分析了复合粉体吸附重金属离子机理，结果表明复合粉体材料对重金属离子通过沉淀反应、静电吸引、离子交换等方式进行吸附，吸附过程等温线符合Langmuir等温模型，动力学符合颗粒内扩散模型，热力学符合自发吸热反应.通过解吸再生试验发现，经过5次循环再生利用后，复合粉体对重金属离子的去除率达到50%以上，这说明复合粉体在吸附过程中具有良好的再生性能.     

五种重金属离子对黑褐新糠虾的急性毒性试验

通过Cu、Hg、Cd、Zn、Pb等5种重金属离子对黑褐新糠虾的急性毒性试验,分别得出了5种重金属离子对黑褐新糠虾的24、48、72、96 h半致死浓度及安全浓度,依次为:Cu2 0.625、0.161、0.161、0.125、0.013 mg/L;Zn2 4.028、1.083、0.917、0.583、0.058mg/L;Cd2 2.679、0.625、0.250、0.161、0.016mg/L;Pd2 13.750、13.750、9.583、1.917、0.192mg/L;Hg2 0.161、0.150、0.150、0.150、0.015 mg/L。研究结果表明:黑褐新糠虾对5种金属离子的敏感性为Cu2 >Hg2 >Cd2 >Zn2 >Pb2 ,黑褐新糠虾作为水域重金属离子的监测生物具有较明显的优势。     

Batch studies of adsorption of copper and lead on activated carbon from Eucalyptus camaldulensis Dehn. Bark

Powdered activated carbon (PAC) prepared from Eucalyptus camaldulensis Dehn. bark was tested for its adsorption capacity for Cu(Ⅱ) and Pb(Ⅱ). The experiment was conducted to investigate the effects of pH, contact time, initial metal concentration, and temperature. The best adsorption of both Cu(Ⅱ) and Pb(Ⅱ) occurred at pH 5, where the adsorption reached equilibrium within 45 min for the whole range of initial heavy metal concentrations (0.1-10 mmol/L). The adsorption kinetics was found to follow the pseudo-...     

柱状污泥基活性炭制备方法及其除污染效能研究

以城市污水厂剩余污泥为原料,用氯化锌活化法研究一种柱状污泥基活性炭(CSAC)的制备方法及其工艺条件优化,并选择粉末污泥基活性炭(PSAC)和一种商品煤质碳(MAC)作为对照,考察了CSAC对重金属离子Cu(Ⅱ)和Pb(Ⅱ)及有机污染物硝基苯的吸附去除效能.结果表明,CSAC的比表面积及微孔容积分别是306.9 m2·g-1和0.109 cm3·g-1,仅为MAC的36.7%和23.6%,但其对Cu(Ⅱ)和Pb(Ⅱ)的平衡吸附量却远远高于MAC,说明CSAC表面存在的高含量酸性官能团在吸附去除重金属过程中起到了重要的作用.由于制备原料相同及制备工艺相似,CSAC与PSAC的理化性质基本相同,两种炭的表面酸性官能团含量较高,对Cu(Ⅱ)和Pb(Ⅱ)均具有较好的吸附去除效果,优于MAC,只是CSAC的比表面积和微孔容积略低于PSAC;在对硝基苯的吸附实验中,CSAC及PSAC的吸附效率均远远低于MAC,说明在对有机物硝基苯的吸附中,活性炭的比表面积等物理性质起到了较大的作用.同时,所制备的CSAC的稳定度大于95%,易于分离回收,不会造成二次污染,适合废水中重金属离子的吸附去除.     

Comparative evaluation of processes for heavy metal removal from municipal solid waste incineration fly ash

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Heavy metal removal from aqueous solution using carbonaceous K2S-impregnated adsorbent

A novel carbonaceous adsorbent for heavy metal removal was prepared from raw coal by one-step simple sulfur impregnation using K2S. Raw coal was mixed with K2S powder and then heated at 800°C for 30 min in nitrogen to produce K2S char. The sulfur content and form in K2S char were determined, and the ability of K2S char to adsorb Zn2+, Cd2+ and Pb2+ was examined. The K2S impregnation was e ective at impregnating sulfur into coal, especially in the form of elemental, thiophenic and sulfatic sulfur. The sulfur content of K2S char was higher than those of raw coal and pyrolysis char. The Zn2+ removal in 2.4 mmol/L of Zn2+ solution by K2S char was higher than raw coal with the removal rate of 100%. K2S char adsorbed Pb2+ and Cd2+ in 24 mmol/L of Pb2+ and Cd2+ solution with the removal rate of 97% and 35%, respectively. The elution extents of adsorbed Pb2+ and Cd2+ were zero in distilled water and 27% in 0.1 mol/L HCl solution. These results indicated that an e ective adsorbent for heavy metal ions was prepared from coal using K2S sulfur impregnation, and that the adsorbed metals were strongly retained in K2S char.     

Application of activated carbon derived from scrap tires for adsorption of Rhodamine B

Activated carbon derived from solid hazardous waste scrap tires was evaluated as a potential adsorbent for cationic dye removal. The adsorption process with respect to operating parameters was investigated to evaluate the adsorption characteristics of the activated pyrolytic tire char (APTC) for Rhodamine B (RhB). Systematic research including equilibrium, kinetics and thermodynamic studies was performed. The results showed that APTC was a potential adsorbent for RhB with a higher adsorption capacity than most adsorbents. Solution pH and temperature exert significant influence while ionic strength showed little e ect on the adsorption process. The adsorption equilibrium data obey Langmuir isotherm and the kinetic data were well described by the pseudo second-order kinetic model. The adsorption process followed intra-particle di usion model with more than one process a ecting the adsorption process. Thermodynamic study confirmed that the adsorption was a physisorption process with spontaneous, endothermic and random characteristics.     

模拟土壤淋洗废液中重金属的选择性去除与淋洗液的回收研究

土壤淋洗废液中污染物的选择性去除是实现淋洗液回收的关键.本文以硫化钠（Na₂S）、乙基黄原酸钾（PEX）、二甲基二硫代氨基甲酸钠（DTC）作为重金属沉淀剂处理电子垃圾污染土壤模拟淋洗废液,在筛选出Na₂S作为理想重金属沉淀剂的基础上,研究初始pH值、反应温度、沉淀剂浓度等因素对Na₂S分离络合态重金属的影响,并通过软件模拟和产物表征等方式推测反应机理.结果表明：Na₂S对柠檬酸络合态重金属的分离顺序依次为Cu、Pb、Cd,符合硫化物溶度积原则;反应温度、初始pH值对Na₂S处理络合态重金属无显著影响,重金属去除率均保持在90%以上,柠檬酸的回收率约为95%;Visual MINTEQ模拟结果显示,S^2-投加前液相中重金属主要以H₂CA^-、HCA^2-和CA^3-结合形式存在,S^2-投加后液相中重金属则以HS^-和S^2-结合形式存在;扫描电镜及能谱（SEM-EDS）表明,S^2-与金属阳离子按物质的量比1：1生成硫化物沉淀物,沉淀主要呈团聚、成簇和圆片状存在;X射线衍射（XRD）分析结果表明,沉淀产物中存在CuS、CdS、PbS和CuPbS₂.本研究结果可为化学沉淀法处理重金属污染土壤淋洗废液提供技术参考.     

Adsorptive removal of iron and manganese ions from aqueous solutions with microporous chitosan/polyethylene glycol blend membrane

Microporous chitosan (CS) membranes were directly prepared by extraction of poly(ethylene glycol) (PEG) from CS/PEG blend membrane and were examined for iron and manganese ions removal from aqueous solutions. The different variables affecting the adsorption capacity of the membranes such as contact time, pH of the sorption medium, and initial metal ion concentration in the feed solution were investigated on a batch adsorption basis. The affinity of CS/PEG blend membrane to adsorb Fe(II) ions is higher than that of Mn(II) ions, with adsorption equilibrium achieved after 60 min for Fe(II) and Mn(II) ions. By increasing CS/PEG ratio in the blend membrane the adsorption capacity of metal ions increased. Among all parameters, pH has the most significant effect on the adsorption capacity, particularly in the range of 2.9-5.9. The increase in CS/PEG ratio was found to enhance the adsorption capacity of the membranes. The effects of initial concentration of metal ions on the extent of metal ions removal were investigated in detail. The experimental data were better fitted to Freundlich equation than Langmuir. In addition, it was found that the iron and manganese ions adsorbed on the membranes can be effectively desorbed in 0.1 mol/L HCl solution (up to 98% desorption efficiency) and the blend membranes can be reused almost without loss of the adsorption capacity for iron and manganese ions.     

Zeolite A synthesized from alkaline assisted pre-activated halloysite for efficient heavy metal removal in polluted river water and industrial wastewater

High quality zeolite A was synthesized through a hydrothermal process using alkaline-assisted pre-activated halloysite mineral as the alumina and silica source. The synthesis conditions employed in this study were finely tuned by varying the activating temperature, sodium hydroxide content, water content and Si/Al ratio. The obtained zeolite A showed excellent adsorption properties for both single metal cation solutions and mixed cation solutions when the concentrations of the mixed cations were comparable with those in polluted natural river water and industrial wastewater. High adsorptive capacities for Ag⁺ (123.05 mg/g) and Pb^2 + (227.70 mg/g) were achieved using the synthesized zeolite A. This observation indicates that the zeolite A synthesized from alkaline-assisted pre-activated halloysite can be used as a low-cost and relatively effective adsorbent to purify heavy metal cation polluted natural river water and industrial wastewater.