Copper and cadmium removal from synthetic industrial wastewater using chitosan and nylon 6

Purpose

Chitosan with nylon 6 membranes was evaluated as adsorbents to remove copper and cadmium ions from synthetic industrial wastewater.

Methods

Chitosan and nylon 6 with glutaraldehyde blend ratio with (1:1+Glu, 1:2+Glu, and 2:1+Glu) have been prepared and these were used as membranes to remove copper and cadmium ions from synthetic industrial wastewater. Characterization of the synthesized membrane has been done with FTIR, XRD, TGA/DTA, DSC, and SEM. Chemical parameters for quantities of adsorption of heavy metal contamination have been done and the kinetics of adsorption has also been carried out.

Results

The optimal pH for the removal of Cd(II) and Cu(II) using chitosan with nylon 6. Maximum removal of the metals was observed at pH 5 for both the metals. The effect of adsorbent dose also has a pronounced effect on the percentage of removal of the metals. Maximum removal of both the metals was observed at 5 g/100 ml of the adsorbent.

Conclusion

Copper and cadmium recovery is parallel at all time. The percentage of removal of copper increased with increase in the pH from 3 to 5. In the case of cadmium containing wastewater, the maximum removal of metal occurred at pH 5. The uptake amount of Cu²⁺ ions on chitosan increased rapidly with increasing contact time from 0 to 360 min and then reaches equilibrium after 360 min; the equilibrium constant for copper and cadmium ions is more or less the same for the adsorption reaction.     

共存物质对重金属絮凝齐MCC除镉性能的影响

为进一步拓展天然高分子絮凝剂壳聚糖的应用范围,以壳聚糖、L-半胱氨酸为原料,通过酰胺化反应制备一种具有重金属捕集功能的高分子重金属絮凝剂-2-氨基-3-巯基丙酰壳聚糖（MCC）,研究了水体中常见的阴阳离子、有机配位剂及浊度对MCC除镉性能的影响,探讨了絮体形貌与絮体分形维数及絮凝除镉效果间的关系。结果表明,Na＋、Cl-、N03、F-、SO4 2-的存在对MCC除Cd2＋均有促进作用,Ca2＋表现为明显的抑制作用;低浓度的EDTA对除镉有促进作用,随着EDTA浓度的增大,逐渐转为抑制作用;低浓度的腐殖酸对MCC去除Cd2＋有显著的促进作用;在一定范围内,浊度可促进MCC对Cd2＋的去除;絮体间空隙越多,絮体分形维数越小,除镉效果越好。     

共存物质对重金属絮凝剂 MCC 除镉性能的影响简

为进一步拓展天然高分子絮凝剂壳聚糖的应用范围,以壳聚糖、L-半胱氨酸为原料,通过酰胺化反应制备一种具有重金属捕集功能的高分子重金属絮凝剂-2-氨基-3-巯基丙酰壳聚糖（MCC）,研究了水体中常见的阴阳离子、有机配位剂及浊度对MCC除镉性能的影响,探讨了絮体形貌与絮体分形维数及絮凝除镉效果间的关系。结果表明,Na⁺、Cl^-、NO₃^-、F^-、SO₄^2-的存在对MCC除Cd²⁺均有促进作用,Ca²⁺表现为明显的抑制作用;低浓度的EDTA对除镉有促进作用,随着EDTA浓度的增大,逐渐转为抑制作用;低浓度的腐殖酸对MCC去除Cd²⁺有显著的促进作用;在一定范围内,浊度可促进 MCC对Cd²⁺的去除;絮体间空隙越多,絮体分形维数越小,除镉效果越好。     

巯基酯化壳聚糖的合成及对Cd2＋的去除性能研究

采用化学方法,研究了以巯基甲壳质制备巯基酯化壳聚糖的最佳合成方案。研究表明,巯基甲壳质的脱乙酰条件（包括时间、温度、氢氧化钠浓度）影响其产物巯基酯化壳聚糖对重金属镉离子的吸附效果。当脱乙酰时间为2h,温度为160℃,氢氧化钠浓度为20％时,20mg的合成产物对30mLCd2＋浓度为20mg／L水样的去除率最高,达到85．46％,其对镉离子的吸附量达到28．5mg／g。通过对产物进行红外分析发现,巯基甲壳质中出现脂基特征峰值,脱乙酰后脂基并没有消失,证明最后的产物为巯基酯化壳聚糖。     

一种新型环境矿物材料在废水治理中的应用研究--硅质磷块岩吸附水溶液中镉离子的研究

硅质磷块岩对水溶液中镉离子的吸附实验结果表明,硅质磷块岩对水溶性镉离子具有良好的去除效果,主要影响因素有介质的酸度、作用时间、镉离子的初始浓度和样品用量.在pH=6,作用时间为15 min,初始Cd2+浓度为30mg/L的实验条件下,硅质磷块岩对镉离子的去除率可达98%,有可能利用动态法进行工业废水的连续处理.初步研究结果显示,磷块岩对水溶性镉离子的吸附作用符合Langmuir等温吸附模型,不同产地的硅质磷块岩S1和S2对镉离子的最大吸附容量分别为4.43 mg/g和3.88 mg/g.     

Sub-lethal effects of heavy metals on activated sludge microorganisms

The effects of heavy metals, at sub-lethal concentrations, on activated sludge microbial ecosystem were investigated. Adsorption capacity and rate of copper, chromium, lead and zinc on microbial flocs were much faster than that of organic matters. Metals affected not only the adsorption rate of organic matters but also the COD adsorption capacity of the activated sludge. Effects of heavy metals. on wastewater treatment performance of a sequencing batch reactor were also studied. Metal-laden wastewater at sub-lethal levels affected the performance to different extents, depending on the hydraulic retention time. Metal ions acted as a strong competitor against the organic compounds for active sites on the bioflocs instead of acting as a toxic microbial inhibitor, thus hampering organic adsorption and affecting the COD removal efficiency under shorter HRTs.     

聚合物强化超滤处理含铜废水

聚合物强化超滤工艺（PEUF）是一种将高分子聚合物和超滤技术结合的新型、高效的重金属废水治理方法。以壳聚糖（CTS）为聚合物去除水中的铜离子。考察了吸附络合和超滤过程中影响铜去除率的多种因素。结果表明,溶液pH值为6.0、CTS浓度为0.15 g/L和反应时间为60 min时,通过超滤系统后效果最佳。装载比一定时,铜初始浓度的变化对铜的去除率没有明显影响。CTS对铜的吸附过程符合Langmuir吸附等温方程。还研究了超滤膜的污染情况和膜清洗方法,结果表明,酸清洗效果较好,可使膜通量恢复达87%左右。     

Biosorption of copper(II) from aqueous solutions by pre-treated biomass of marine algae Padina sp

Biosorption of heavy metals can be an effective process for the removal and recovery of heavy metal ions from aqueous solutions. The biomass of marine algae has been reported to have high uptake capacities for a number of heavy metal ions. In this paper, the adsorption properties of a pre-treated biomass of marine algae Padina sp. for copper(II) were investigated. Equilibrium isotherms and kinetics were obtained from batch adsorption experiments. The biosorption capacities were solution pH dependent and the maximum capacity obtained was 0.80 mmol/g at a solution pH of about 5. The biosorption kinetics was found to be fast, with 90% of adsorption within 15 min and equilibrium reached at 30 min. The effects of light metal ions on copper(II) uptake were studied and the presence of light metal ions did not affect copper(II) uptake significantly. Fixed-bed breakthrough curves for copper(II) removal were also obtained. This study demonstrated that the pre-treated biomass of Padina sp. could be used as an effective biosorbent for the treatment of copper(II) containing wastewater streams.     

Preparation of macromolecular heavy metal coagulant and treatment of wastewater containing copper.

Many treatment technologies for wastewater containing heavy metals have been developed in recent years, but these technologies have some disadvantages, such as poor removing efficiency and complex operation. For this reason, a macromolecular heavy metal coagulant polyethyleneimine-sodium xanthogenate (PEX) was prepared by grafting a xanthogenate group to polyethyleneimine. It was determined that PEX has the function of removing both turbidity and copper ions. It was also determined that copper ions and turbidity have a cooperative removal effect with each other in the process of treating wastewater containing both turbidity and copper ions by PEX. The investigation showed that PEX is an amphoteric polyelectrolyte. At lower pH values, the amino groups of the macromolecule are electrically positive; therefore, turbidity is removed because of electroneutralization coagulation; at higher pH values, both amino groups and xanthogenic radical groups contribute to the removal of heavy metals, as a result of chelation. Compared with traditional chemical precipitation by calcium oxide and coagulation by an ordinary inorganic coagulant, PEX showed obvious advantages, for example, removing both turbidity and copper ions, higher removal efficiency, lower suitable pH value, and higher floc settlement velocity.     

Enhanced removal of heavy metals in primary treatment using coagulation and flocculation.

The goal of this study was to determine the removal efficiencies of chromium, copper, lead, nickel, and zinc from raw wastewater by chemically enhanced primary treatment (CEPT) and to attain a total suspended solids removal goal of 80%. Operating parameters and chemical doses were optimized by bench-scale tests. Locally obtained raw wastewater samples were spiked with heavy metal solutions to obtain representative concentrations of metals in wastewater. Jar tests were conducted to compare the metals removal efficiencies of the chemical treatment options using ferric chloride, alum, and anionic polymer. The results obtained were compared with those from other studies. It was concluded that CEPT using ferric chloride and anionic polymer is more effective than CEPT using alum for metals removal. The CEPT dosing of 40 mg/L ferric chloride and 0.5 mg/L polymer enhanced heavy metals removal efficiencies by over 200% for chromium, copper, zinc, and nickel and 475% for lead, compared with traditional primary treatment. Efficient metals capture during CEPT can result in increased allowable headworks loadings or lower metal levels in the outfall.     

Cr(VI) removal from synthetic wastewater using coconut shell charcoal and commercial activated carbon modified with oxidizing agents and/or chitosan

In this study, the technical feasibility of coconut shell charcoal (CSC) and commercial activated carbon (CAC) for Cr(VI) removal is investigated in batch studies using synthetic electroplating wastewater. Both granular adsorbents are made up of coconut shell (Cocos nucifera L.), an agricultural waste from local coconut industries. Surface modifications of CSC and CAC with chitosan and/or oxidizing agents, such as sulfuric acid and nitric acid, respectively, are also conducted to improve removal performance. The results of their Cr removal performances are statistically compared. It is evident that adsorbents chemically modified with an oxidizing agent demonstrate better Cr(VI) removal capabilities than as-received adsorbents in terms of adsorption rate. Both CSC and CAC, which have been oxidized with nitric acid, have higher Cr adsorption capacities (CSC: 10.88, CAC: 15.47 mg g(-1)) than those oxidized with sulfuric acid (CSC: 4.05, CAC: 8.94 mg g(-1)) and non-treated CSC coated with chitosan (CSCCC: 3.65 mg g(-1)), respectively, suggesting that surface modification of a carbon adsorbent with a strong oxidizing agent generates more adsorption sites on their solid surface for metal adsorption.     

4A沸石对复合污染水体中Pb2+、Cu2+和Cd2+的去除

采用静态吸附法以4A沸石为吸附剂研究其对复合污染水体中Pb2+、Cu2+和Cd2+的竞争吸附特性,并探讨了影响吸附的环境因素。实验表明,在室温条件下,溶液pH5～6,4A沸石15 mg对10 mL复合污染溶液(Pb2+、Cu2+和Cd2+浓度分别为100 mg/L)吸附20 min时,对溶液中3种重金属的吸附去除率均可达99.8%以上。反应过程中4A沸石对3种重金属的吸附速率大小为Pb2+>Cu2+>Cd2+。复合污染水体中4A沸石对Pb2+、Cu2+和Cd2+的吸附符合Langmuir和Fre-undlich等温吸附方程,相关系数分别为0.9981、0.9901、0.9916和0.9638、0.9194、0.9689。经计算,4A沸石对Pb2+、Cu2+和Cd2+的饱和吸附量分别为129.9 mg/g、107.5 mg/g和99.0 mg/g。4A沸石吸附重金属离子达到吸附平衡的时间较短,对溶液pH值的适应性较好。吸附后的4A沸石可以再生利用,对铅离子洗脱重复利用性较铜离子和镉离子强。     

Cadmium(II) removal from aqueous solutions by pre-treated biomass of marine alga Padina sp

In this study, the adsorption properties of a pre-treated biomass from marine alga Padina sp., a biomass collected from Surin Island, Thailand, for removal of cadmium(II) ions from aqueous solutions was investigated. Batch and column experiments were conducted to determine the adsorption properties of the modified biomass. At a pH of 5, the maximum removal capacity of the biomass is 0.53 mmol/g. The kinetics of cadmium(II) adsorption were fast with 90% of adsorption taking place within 35 min. This study demonstrated that the pre-treated biomass of Padina sp. could be used as an efficient biosorbent for the treatment of cadmium(II)-bearing wastewater streams.     

Increasing the recovery of heavy metal ions using two microbial fuel cells operating in parallel with no power output

The present study aimed to improve the performance of microbial fuel cells (MFCs) by using an intermittent connection period without power output. Connecting two MFCs in parallel improved the voltage output of both MFCs until the voltage stabilized. Electric energy was accumulated in two MFCs containing heavy metal ions copper, zinc, and cadmium as electron acceptors by connection in parallel for several hours. The system was then switched to discharge mode with single MFCs with a 1000-Ω resistor connected between anode and cathode. This method successfully achieved highly efficient removal of heavy metal ions. Even when the anolyte was run in sequencing batch mode, the insufficient voltage and power needed to recover heavy metals from the cathode of MFCs can be complemented by the developed method. The average removal ratio of heavy metal ions in sequencing batch mode was 67 % after 10 h. When the discharge time was 20 h, the removal ratios of zinc, copper, and cadmium were 91.5, 86.7, and 83.57 %, respectively; the average removal ratio of these ions after 20 h was only 52.1 % for the control group. Therefore, the average removal efficiency of heavy metal ions increased by 1.75 times using the electrons stored from the bacteria under the open-circuit conditions in parallel mode. Electrochemical impedance data showed that the anode had lower solution resistance and polarization resistance in the parallel stage than as a single MFC, and capacitance increased with the length of time in parallel.

     

高分子重金属絮凝剂MCC制备及除铜去浊性能

以壳聚糖、L-半胱氨酸为原料,通过酰胺化反应制备了一种具有重金属捕集功能的高分子重金属絮凝剂-2-氨基-3-巯基丙酰壳聚糖(MCC)。以含铜废水为处理对象,通过正交实验研究了MCC的最佳制备条件,对其除铜性能进行了全面探讨,并对絮体形貌进行了观察和分析。结果表明,在最佳条件下制得的MCC具有除浊和捕集重金属离子双重功能,形成的絮体量较大、沉速快,出水水质好,重金属回收率较高,残渣稳定,不易造成二次污染,絮体分形维数越小,空隙越多,除铜效果越好。     

Adsorption of lead onto smectite from aqueous solution

The purpose of this research is to study the effect of a new method of adsorption using membrane filtration to determine the maximum amount of lead adsorbed by clay and investigate the behavior of the clay after adsorption of the said metal. Treatment of wastewater contaminated with heavy metals depends on the characteristics of the effluent, the amount of final discharge, the cost of treatment, and the compatibility of the treatment process. The process of adsorption of heavy metals by clays may be a simple, selective, and economically viable alternative to the conventional physical–chemical treatment. This is justified by the importance of the surface developed by this material, the presence of negative charges on the said surface, the possibility of ion exchange taking place, and its wide availability in nature. The removal of lead from wastewater was studied by using the adsorption technique and using clay as the adsorbent. A method was optimized for adsorption through a membrane approaching natural adsorption. This new method is simple, selective, and the lead adsorption time is about 3 days. The various properties of clay were determined. It was observed that the cation exchange capacity of the clay was 56 meq/100 g of hydrated clay for the raw sample and 82 meq/100 g for the purified sample. The total surface area determined by the methylene blue method was equal to 556 and 783 m²/g for the raw and purified samples, respectively. The adsorption kinetics depends on several parameters. The Pb(II) clay, obeys the Langmuir, Freundlich, and the Elovich adsorption isotherms with high regression coefficients. The use of this adsorbent notably decreases the cost of treatment. It was concluded that clay shows a strong adsorption capacity on Pb(II), the maximum interaction occurring with purified clay treated at high concentration of lead. It is proposed that this adsorption through a membrane be extended for the treatment of effluents containing other metals.     

Biological nitrification/denitrification of high sodium nitrite (navy shipyard) wastewater

In the hydroblasting of ships' boiler tubes, a wastewater high in nitrite (as high as 1200 mg litre(-1)) is produced by the US Navy. This research has evaluated the use of a suspended-growth biological system to treat this wastewater by denitrification. Two biological treatment configurations were evaluated (direct denitrification versus nitrification/denitrification) with nitrification/denitrification producing better nitrite removal efficiencies (54 to 62% versus 40%, respectively). The introduction of metals (cadmium, chromium, lead, copper and iron) in concentrations typical for this wastewater did not inhibit the nitrite removal efficiencies. The influent metal concentrations ranged from 0.02 mg litre(-1) for cadmium to 22 mg litre(-1) for iron and the metal removal efficiencies ranged from 4.8% for cadmium to 50% for copper. Increasing sludge age resulted in improved nitrite removal efficiencies (52%, 57% and 74% for sludge ages of 4, 6 and 8 days, respectively). The resulting biokinetic constants were similar to those reported by others for lower influent concentrations of nitrite or nitrate (Ygs=0.02 mg/mg; Ygn=0.16 mg/mg; Yb=0.8 mg/mg; and b=0.006 h(-1)).     

浮游球衣菌对Pb2+、Cu2+、Zn2+、Cd2+的吸附性能研究

研究了浮游球衣菌（Sphaerotilus natans）在不同吸附条件下对溶液中Pb^2＋、Cu^2＋、Zn^2＋、Cd^2＋的吸附规律。结果表明,Sphaerotilus natans对这4种重金属离子均有一定的吸附作用,并在20min内达到吸附平衡,pH对吸附过程影响较大,pH为5.5时Sphaerotilus natans对这4种金属离子的吸附效果最好,Sphaerotilus natans对它们的吸附选择性为Pb^2＋〉Cu^2＋〉Zn^2＋〉Cd^2＋,Pb^2＋、Cu^2＋能部分置换出已被菌体吸附的Zn^2＋、Cd^2＋。HCI和EDTA溶液可有效地将金属离子从菌体上解吸下来,解吸后的菌体可重复使用。     

Heavy metals removal in fixed-bed column by the macro fungus Pycnoporus sanguineus

The ability of Pycnoporus sanguineus to adsorb heavy metals from aqueous solution was investigated in fixed-bed column studies. The experiments were conducted to study the effect of important design parameters such as column bed height, flow rate and initial concentration of solution. The breakthrough profiles were obtained in these studies. A mathematical model based on external mass transfer and pore diffusion was used for the prediction of mass transfer coefficient and effective diffusivity of metals in macro-fungi bed. Experimental breakthrough profiles were compared with the simulated breakthrough profiles obtained from the mathematical model. Bed Depth Service Time (BDST) model was used to analyse the experimental data and evaluated the performance of biosorption column. The BDST model parameters needed for the design of biosorption columns were evaluated for lead, copper and cadmium removal in the column. The columns were regenerated by eluting the metal ions using 0.1 M hydrochloric acid solution after the adsorption studies. The columns were subjected to repeated cycles of adsorption of same metal ions and desorption to evaluate the removal efficiency after adsorption-desorption.     

Heavy metal removal from synthetic wastewaters in an anaerobic bioreactor using stillage from ethanol distilleries as a carbon source

This work was conducted to investigate the possibility of using stillage from ethanol distilleries as substrate for sulfate reducing bacteria (SRB) growth and to evaluate the removal efficiency of heavy metals present in wastewaters containing sulfates. The experiments were carried out in a continuous bench-scale Upflow Anaerobic Sludge Blanket reactor (13 l) operated with a hydraulic retention time of 18 h. The bioreactor was inoculated with 7 l of anaerobic sludge. Afterwards, an enrichment procedure to increase SRB numbers was started. After this, cadmium and zinc were added to the synthetic wastewater, and their removal as metal sulfide was evaluated. The synthetic wastewater used represented the drainage from a dam of a metallurgical industry to which a carbon source (stillage) was added. The results showed that high percentages of removal (>99%) of Cd and Zn were attained in the bioreactor, and that the removal as sulfide precipitates was not the only form of metal removal occurring in the bioreactor environment.