4A分子筛去除水中Pb2+、Cd2+、Zn2+、Cu2+性能和机理

文章通过采用SEM、XRD、FTIR分析4A分子筛吸附重金属离子Pb~(2+)、Cd~(2+)、Zn~(2+)、Cu~(2+)前后形貌和结构的变化,探讨了这4种重金属离子在4A分子筛上的吸附性能和机制。研究结果表明:4A分子筛吸附Pb~(2+)和Cd~(2+)后,分子筛的形貌和结构未发生改变,吸附Zn~(2+)和Cu~(2+)后,4A分子筛表面有氢氧化物沉淀附着;吸附Cu~(2+)后,4A分子筛的XRD特征衍射峰消失,表明其晶相结构发生了改变,转化为无定形,此外,属于4A分子筛骨架的部分红外特征吸收峰减弱至几乎消失;Pb~(2+)、Cd~(2+)、Zn~(2+)、Cu~(2+)在4A分子筛上的吸附符合Langmuir等温吸附模型,最大吸附量分别为2.818、2.514、2.317、1.877 mmol/g,而拟二级动力学吸附速率常数Pb~(2+)Cd~(2+)Cu~(2+)Zn~(2+)。4A分子筛对Pb~(2+)和Cd~(2+)的去除机理主要为离子交换吸附和表面沉淀,对Cu~(2+)和Zn~(2+)的去除则既有离子交换吸附和表面沉淀作用,又有化学沉淀作用。     

纳米二氧化锆吸附Pb~(2+)的研究

采用沉淀法合成了纳米级二氧化锆,利用SEM、XRD技术,对纳米ZrO_2进行微观形貌和粒径分析,探讨了吸附时间、吸附温度、pH值以及Pb~(2+)初始浓度对吸附的影响,分析了吸附热力学性质和动力学特性,初步探讨了吸附机理。研究结果表明:在吸附温度为40℃,Pb~(2+)初始浓度为10 mg/L,pH为4.5时,吸附反应40 min后,最大吸附量为17.8 mg/g;纳米ZrO_2对Pb~(2+)吸附等温线符合Langmuir模型,其吸附动力学过程以准二级动力学方程拟合效果最好;温度在303~323 K时,纳米ZrO_2吸附Pb~(2+)的吉布斯自由能ΔG~o<0、焓变ΔH~o<0、熵变ΔS~o<0,表明纳米ZrO_2对Pb~(2+)的吸附是一个自发放热过程。     

碱法提取的混合海洋硅藻粗多糖对铅离子的吸附特性研究

采用浓碱法(40 mg·mL~(-1)NaOH)辅助冻融、加热方法提取混合海洋硅藻粗多糖,通过比较粗多糖得率、总糖、蛋白质及硫酸基含量筛选提取方法,并利用最佳方法提取的粗多糖作为生物吸附剂对Pb~(2+)进行吸附.提取实验结果表明,最优的提取方法为浓碱(40 mg·mL~(-1)NaOH)-冻融法,其粗多糖得率为33.14%,总糖含量为31.65%(480 nm)和27.27%(490 nm),蛋白质含量为6.44%、硫酸基含量为3.23%.吸附结果表明,该粗多糖对Pb~(2+)的吸附在2 h左右达到平衡,在180 r·min-1、25℃、pH=4~6时吸附效果最佳;在初始浓度为600 mg·L-1混合重金属溶液条件下,粗多糖对Cd~(2+)、Pb~(2+)、Cu~(2+)和Ni~(2+)的吸附容量大小顺序为:Ni~(2+)Cu~(2+)Cd~(2+)Pb~(2+)(以物质的量浓度为单位进行评价);粗多糖中含有的小分子糖类杂质对Pb~(2+)吸附的贡献远远大于蛋白质杂质.吸附动力学拟合结果表明,此硅藻粗多糖对Pb~(2+)的吸附过程更符合伪二级动力学模型,且Langmuir方程拟合的可决系数R2大于0.9,说明粗多糖对Pb~(2+)的吸附为单层吸附.     

污泥-稻壳混烧灰对Pb(Ⅱ)吸附性能的研究

稻壳与污泥协同焚烧是一种富有前景的污泥能源化措施,污泥稻壳混烧灰是一种被忽视的资源。该文旨在探究污泥稻壳混烧灰在高浓度含铅废水处理中的应用潜力,分析了不同污泥和稻壳配比混烧灰的基本理化性质,研究了不同p H和不同Pb~(2+)初始浓度下混烧灰对Pb~(2+)的吸附特性,并初步探究该吸附过程的动力学和吸附机理。结果表明混烧灰对Pb~(2+)的吸附容量可媲美其它经过复杂改性处理的灰渣;在燃烧温度900℃时,污泥掺量60%、稻壳掺量40%制备的混烧灰吸附性能最好,在p H为5,初始Pb~(2+)浓度低于400 mg/L时混烧灰对Pb~(2+)的去除率高于90%;相较于Freundlich等温吸附模型,Langmuir等温吸附模型的拟合结果更好,拟合最大吸附量为108.7mg/g;动力学研究发现混烧灰对Pb~(2+)的吸附行为主要发生在5 h以内。混烧灰对Pb~(2+)去除的主要原因是混烧灰中无定形二氧化硅微水解形成硅醇对Pb~(2+)的作用,无定形二氧化硅表面存在孤立羟基和成对羟基导致了2种吸附产物Pb_2SiO_4和PbSiO_3·xH_2O存在。     

胡敏素对Pb~(2+)吸附的响应面优化及机理

采用Box-Behnken响应面优化实验设计对胡敏素吸附去除水中Pb~(2+)的过程进行了优化,设定吸附时间、吸附剂用量、pH值、温度和Pb~(2+)初始浓度5个影响因素,建立了吸附率与上述因素之间的二次多项式模型,确定了最优吸附条件,对吸附过程的等温模型、热力学特性及吸附机理进行了研究.研究表明吸附剂用量、pH值、温度和Pb~(2+)初始浓度为显著因素.胡敏素对Pb~(2+)吸附的最优条件为:吸附时间85min、投加量1.2g/L、pH=4.7、温度44.5℃、Pb~(2+)初始浓度202mg/L.最优条件下,实测Pb~(2+)吸附率可达92.59%.胡敏素对Pb~(2+)的吸附符合Langmuir等温线方程,最大吸附量为170.28mg/g;计算得知胡敏素吸附Pb~(2+)的热力学状态函数ΔG~0、ΔS~0和ΔH~0分别为-29.30~-24.21k J/mol、126.70J/(mol·K)和13.59k J/mol,吸附过程为吸热过程.胡敏素表面的羰基、羟基、氨基和羧基等活性基团可以和Pb~(2+)发生配位络合作用,Ca、Na和Mg等离子与Pb~(2+)发生离子交换作用.研究结果表明,胡敏素作为一种极具潜力的绿色廉价吸附剂,可用于处理含Pb~(2+)废水.     

土壤芽孢杆菌产胞外聚合物对Pb~(2+)吸附特性研究

根据与细菌菌体结合的紧密程度,胞外聚合物(EPS)可以分为粘液层EPS(S-EPS)、松散附着EPS(LB-EPS)、紧密附着EPS(TB-EPS),以土壤芽孢杆菌作为实验菌株,研究了各层EPS在不同温度、pH值条件下对Pb~(2+)的吸附特性,建立了EPS的吸附动力学模型和吸附等温线模型,并采用扫描电子显微镜(SEM)观察各层EPS吸附Pb~(2+)前后的表观形态的变化.当吸附温度为35℃、pH值为5.5时,S-EPS、LB-EPS、TB-EPS对Pb~(2+)的吸附量分别为91.35、100.61和90.28mg/g,表明LB-EPS对Pb~(2+)的吸附能力更强.各层EPS吸附Pb~(2+)的吸附动力学模型和吸附等温线模型均符合准二级动力学模型和Langmuir等温吸附模型,表明吸附过程分别受化学吸附机理控制和单分子层吸附控制,并通过Langmuir模型计算得到,S-EPS、LB-EPS、TB-EPS对Pb~(2+)的最大吸附量分别为124.224、127.389和119.760mg/g.同时,扫描电镜结果表明吸附前后各层EPS表观形态均差异明显,其中LB-EPS呈肺泡状,具有更大的比表面积,因此更多的Pb~(2+)吸附在其表面.     

牛粪源蚓粪及其生物炭对Pb2+、Cd2+的吸附特性

以牛粪源蚓粪(CV)为原料,于350℃下热解制备蚓粪生物炭(标记为CVC350)并表征其物理化学性质,进一步就CV和CVC350对Pb~(2+)和Cd~(2+)的吸附性能进行了研究,结果表明:与CV相比,CVC350的比表面积增大,孔径变小,芳香性和非极性增强.CV和CVC350对Pb~(2+)和Cd~(2+)的等温吸附曲线均符合Langmuir方程,两者对Pb~(2+)的最大吸附量表现为CVC350CV,而两者对Cd~(2+)的最大吸附量间差异不明显.解吸特性研究表明,CV和CVC350对Pb~(2+)的吸附率明显高于其对Cd~(2+)的吸附率,且两者的吸附态Cd~(2+)与其吸附态Pb~(2+)相比均相对更易解吸.CV和CVC350对Pb~(2+)的吸附动力学均为快速吸附过程,而CV和CVC350对Cd~(2+)的吸附动力学则均表现为快速吸附和慢速吸附两个阶段.当溶液初始pH较低时,CV和CVC350对Pb~(2+)和Cd~(2+)吸附量受pH影响明显,且CV和CVC350对Cd~(2+)的吸附受pH变化的影响相对更大.FTIR分析表明,CV对Pb~(2+)和Cd~(2+)的吸附位点主要集中在脂肪醇或脂肪酸、碳酸盐和磷酸盐,而CVC350对Pb~(2+)和Cd~(2+)的吸附位点主要为芳香醇或芳香酸和碳酸盐.     

一株低温真菌的筛选及其对重金属离子的吸附研究

从排污口废水中筛选到一株能耐受一定浓度Pb~(2+)和Zn~(2+)的低温真菌,将其作为吸附剂,研究了其吸附动力学及吸附方式、温度和pH值对其吸附Pb~(2+)和Zn~(2+)的影响,绘制、拟合吸附等温线,并在模拟废水环境中进行逐级吸附试验。结果表明:Pb~(2+)和Zn~(2+)初始浓度接近100 mg/L时,可在20℃吸附15 min时达到平衡,吸附曲线符合Langmuir等温吸附模型,静态吸附的吸附量偏高。当pH值为4~6,温度在4~15℃时吸附量最大,这正是低温真菌的优势所在。人工配制了含Pb~(2+)和Zn~(2+)的模拟废水,分别经过5级和6级吸附后,出水可达到GB 25466—2010《铅、锌工业污染物排放标准》要求。     

絮凝快速分离水处理技术简介及发展趋势

从排污口废水中筛选到一株能耐受一定浓度Pb~(2+)和Zn~(2+)的低温真菌,将其作为吸附剂,研究了其吸附动力学及吸附方式、温度和pH值对其吸附Pb~(2+)和Zn~(2+)的影响,绘制、拟合吸附等温线,并在模拟废水环境中进行逐级吸附试验。结果表明:Pb~(2+)和Zn~(2+)初始浓度接近100 mg/L时,可在20℃吸附15 min时达到平衡,吸附曲线符合Langmuir等温吸附模型,静态吸附的吸附量偏高。当pH值为4~6,温度在4~15℃时吸附量最大,这正是低温真菌的优势所在。人工配制了含Pb~(2+)和Zn~(2+)的模拟废水,分别经过5级和6级吸附后,出水可达到GB 25466—2010《铅、锌工业污染物排放标准》要求。     

腐植酸对重金属铅镉的吸附特征

为了揭示腐植酸对单一Pb、单一Cd和Pb、Cd复合污染物的吸附特征,笔者通过吸附模拟实验分析了pH、温度、反应时间和初始浓度等因素变化对风化煤腐植酸吸附重金属离子Pb~(2+)和Cd~(2+)的影响.结果表明,腐植酸对Pb~(2+)的吸附受pH值变化的影响很小,但对Cd~(2+)的吸附随着pH增加而增加;腐植酸对Pb~(2+)和Cd~(2+)吸附饱和的时间均为240 min;对Pb~(2+)和Cd~(2+)的吸附量均随温度的增加而增加;Langmuir吸附模型对腐植酸吸附单一Pb~(2+)、单一Cd~(2+)和铅镉复合态中Pb~(2+)的拟合较好,Freundlich吸附模型则对腐植酸吸附铅镉复合态中Cd~(2+)的拟合较好;准二级动力学模型能较好地拟合腐植酸吸附Pb~(2+)和Cd~(2+)的过程,说明腐植酸对铅镉的吸附为物理吸附和化学吸附的复合吸附过程;铅镉复合态下Pb~(2+)和Cd~(2+)存在竞争吸附,单一Pb~(2+)溶液中加入Cd~(2+)对腐植酸吸附Pb~(2+)基本无影响,但单一Cd~(2+)溶液中加入Pb~(2+)时,Pb~(2+)会与Cd~(2+)产生竞争吸附,从而降低Cd~(2+)的吸附量.本研究结果可为利用腐植酸稳定土壤中Pb~(2+)、Cd~(2+)等重金属离子的技术开发提供参考.     

Distribution and ecological effect of mercury in Laogang landfill, Shanghai, China

Laogang landfill near Shanghai is the largest landfill in China, and receives about 10000 t of daily garbage per day, Samples of topsoil and plants were analyzed to evaluate mercury pollution from the landfill. For topsoil samples, there were significant correlations among total mercury （HgT）, combinative mercury （Hgc） and gaseous mercury （HgG）, and content of total organic carbon （TOC）, but, no significantly relationship was found between Hg content and filling time. Hg content changes in vertical profiles with time showed that the average Hgv of profiles 1992, 1996, and 2000 was similar, but their average HgG was quite different. HgT was significantly correlated with Hgc in profile 1992 and 2000, and Hgv was significantly correlated with Hg6 in profile 1996. HgG/Hgv ratio in profile samples decreased in the order of （HgG,/HgT）1992〉（HgG/HgT）1996〉〉（HgG/HgT）2000. A simple outline of Hg release in landfill could be drawn： with increasing of filling time, degradation undergoes different biodegradation, accordingly, gaseous mercury goes through small, more, and small proportion to total mercury. Distribution of Hg in plants was inhomogeneous, following the order of leaf〉root〉stem. The highest value of leaf may be associated with higher atmospheric Hg from landfill. Ligneous plants （e.g. Phyllostachys glanca, Prunus salicina and Ligustrum lucidum） are capable of enriching more Hg than herbaceous plants.     

EDTA-enhanced phytoremediation of lead contaminated soil by Bidens maximowicziana

Phytoremediation is a potential cleanup technology for the removal of heavy metals from contaminated soils.Bidens maximowicziana is a new Pb hyperaccumulator,which not only has remarkable tolerance to Pb but also extraordinary accumulation capacity for Pb.The maximum Pb concentration was 1509.3 mg/kg in roots and 2164.7 mg/kg in overground tissues.The Pb distribution order in the B. maximowicziana was:leaf>stem>root.The effect of amendments on phytoremediation was also studied.The mobility of soil Pb and the Pb concentrations in plants were both increased by EDTA application.Compared with CK(control check),EDTA application promoted translocation of Pb to overground parts of the plant.The Pb concentrations in overground parts of plants was increased from 24.23-680.56 mg/kg to 29.07-1905.57 mg/kg.This research demonstrated that B.maximowicziana appeared to be suitable for phytoremediation of Pb contaminated soil,especially,combination with EDTA.     

Decomposition of alachlor by ozonation and its mechanism

Decomposition and corresponding mechanism of alachlor, an endocrine disruptor in water by ozonation were investigated. Results showed that alachlor could not be completely mineralized by ozone alone. Many intermediates and final products were formed during the process, including aromatic compounds, aliphatic carboxylic acids, and inorganic ions. In evoluting these products, some of them with weak polarity were qualitatively identified by GC-MS. The information of inorganic ions suggested that the dechlorination was the first and the fastest step in the ozonation of alachlor.     

Enzymatic oxidation of aqueous pentachlorophenol

The influence of the nonionic surfactant Tween 80 on pentachlorophenol （PCP） oxidation catalyzed by horseradish peroxidase was studied. The surfactant was tested at concentrations below and above its critical micelle concentration （CMC）. Enhancement of PCP removal was observed at sub-CMCs. The presence of Tween 80 in the reaction mixture reduced enzyme inactivation which occurred through a combination of free radical attack and sorption by precipitated products. A simple first-order model was able to simulate time profiles for enzyme inactivation in the presence or absence of Tween 80. At supra-CMCs, the surfactant caused noticeable reductions in PCP removal, presumably through micelle partitioning of PCP which precluded the hydrophobic PCP molecule from interacting with the enzyme.     

基于综合水质标识指数和对应分析法的校园河道水质评价

以三峡大学的校园河道求索溪为研究对象,利用综合水质标识指数法确定求索溪水质类别,分析其水质时空变化规律,并利用对应分析法得出求索溪中不同监测点的主要污染因子.研究结果表明:求索溪整体的综合水质标识指数为7.423,整体水质为劣V类(地表水环境质量标准GB 3838-2002)且黑臭.从时间变化来看,求索溪4月份的水质最差,5月份次之,4、5月份所有监测点的水质都劣于V类且黑臭;8月份水质最好,水质为Ⅳ类;从空间分布来看,8个监测点综合水质标识指数均超过6.0,水质为劣V类,其中6号监测点的水质相对最好,监测点3号的水质相对最差;对应分析法得出求索溪的整体水体污染程度受总氮因子的影响最大,其次为总磷.该研究拟为求索溪及类似校园河道的水环境治理研究提供基础依据和参考.     

Effects of chitosan on growth of an aquatic plant (Hydrilla verticillata) in polluted waters with different chemical oxygen demands

Effects of chitosan on a submersed plant, Hydrilla verticillata, were investigated. Results indicated that H. venicillata could prevent ultrastructure phytotoxicities and oxidativereaction from polluted water with high chemical oxygen demand (COD). Superoxide dismutase (SOD) activity and malondialdehyde (MDA) contents in H. verticillata treated with 0.1% chitosan in wastewater increased with high COD (980 mg/L) and decreased with low COD (63 mg/L), respectively. Ultrastructural analysis showed that the stroma and grana of chloroplast basically remained normal. However, plant cells from the control experiment (untreated with chitosan) were vacuolated and the cell interval increased. The relict of protoplast moved to the center, with cells tending to disjoint. Our findings indicate that wastewater with high COD concentration can cause a substantial damage to submersed plant, nevertheless, chitosan probably could alleviate the membrane lipid peroxidization and ultrastructure phytotoxicities, and protect plant cells from stress of high COD concentration polluted water.     

Removal of cadmium using MnO2 loaded D301 resin

MnO2 loaded weak basic anion exchange resin D301 （Anion exchange resin, macroreticular weak basic styrene） as adsorbent has been prepared and applied to the removal of cadmium. The adsorption characteristics have been investigated with respect to effect of pH, equilibrium isotherms, removal kinetic data, and interference of the coexisting ions. The results indicated that the Cd^2＋ could be efficiently removed using MnO2 loaded D301 resin in the pH range of 3-8 from aqueous solutions with the co-existence of high concentration of alkali and alkaline-earth metals ions. The saturate adsorption capacity of the Cd^2＋ was 77.88 mg/g. The adsorption process followed the pseudo first-order kinetics. The equilibrium data obtained in this study accorded excellently with the Langmuir adsorption isotherm.     

Effect of coagulation pretreatment on the fouling of ultrafiltration membrane

The purpose of this study is to understand the effect and mechanism of preventing membrane fouling, by coagulation pretreatment, in terms of fractional component and molecular weight of natural organic matter （NOM）. A relatively higher molecular weight （MW） of hydrophobic compounds was responsible for a rapid decline in the ultrafiltration flux. Coagulation could effectively remove the hydrophobic organics, resulting in the increase of flux. It was found that a lower MW of neutral hydrophilic compounds, which could remove inadequately by coagulation, was responsible for the slow declining flux. The fluxes in the filtration of coagulated water and supernatant water were compared and the results showed that a lower MW of neutral hydrophilic compounds remained in the supernatant water after coagulation could be rejected by a membrane, resulting in fouling. It was also found that the coagulated flocs could absorb neutral hydrophilic compounds effectively. Therefore, with the coagulated flocs formed on the membrane surface, the flux decline could be improved.     

Penetration analysis of elements and bioleaching treatment of spent refractory for recycling

Acidithiobacillus ferrooxidans ATCC23270 and Acidithiobacillus thiooxidans TM-32 were used for bioleaching of spent refractories of aluminium and copper melting furnaces for their recycling.Firstly,penetration of elements into aluminium melting furnace refractory was investigated and it was found that up to 7 cm from surface was contaminated.Comparison on leaching efficiency by the strains ATCC23270 and TM-32 found that the strain ATCC23270 could treat larger amount of the refractories than the strain TM-32 could do.In the experiment of bioleaching of spent refractory aluminium melting furnace by the strain ATCC23270,high leaching efficiency were obtained on Al,Si,and Ca,and extremely low leaching performance was,however,shown on the rest of elements i.e.,Na,Mn,and Zn.Under the strain TM-32 use,relatively high leaching performance was recognized on Al,Si,Ca,Na,Mn,and Zn.In the experiment of bioleaching for spent refractory copper melting furnace,almost the same leaching trends were shown on Cu,Zn,Al,and Si under the strains ACTT23270 and TM-32 uses.     

Simultaneous removal of ammonium and phosphate by zeolite synthesized from coal fly ash as influenced by acid treatment

Zeolite synthesized from fly ash （ZFA） without modification is not efficient for the purification of NH4＋ and phosphate at low concentrations that occur in real effluents, despite the high potential removal capacity. To develop an effective technique to enhance the removal efficiency of ammonium and phosphate at low concentrations, ZFA was modified with acid treatment and the simultaneous removal of ammonium and phosphate in a wide range of concentration was investigated. It was seen that when compared with untreated ZFA, only the treatment by 0.01 mol/L of H2SO4 significantly improved the removal efficiency of ammonium at low initial concentrations. The behavior was well explained by the pH effect. Treatment by more concentrated H2SO4 led to the deterioration of the ZFA structure and a decrease in the cation exchange capacity. Treatment by 0.01 mol/L H2SO4 improved the removal efficiency of phosphate by ZFA at all initial P concentrations, while the treatment by concentrated H2SO4 （≥0.9 mol/L） resulted in a limited maximum phosphate immobilization capacity （PIC）. It was concluded that through a previous mild acid treatment （e.g. 0.01 mol/L of H2SO4）, ZFA can be used in the simultaneous removal of NH4＋ and P at low concentrations simulating real effluent.