Column dynamic studies and breakthrough curve analysis for Cd(II) and Cu(II) ions adsorption onto palm oil boiler mill fly ash (POFA)

This paper investigates the adsorption characteristics of palm oil boiler mill fly ash (POFA) derived from an agricultural waste material in removing Cd(II) and Cu(II) from aqueous solution via column studies. The performance of the study is described through the breakthrough curves concept under relevant operating conditions such as column bed depths (1, 1.5, and 2 cm) and influent metal concentrations (5, 10, and 20 mg/L). The Cd(II) and Cu(II) uptake mechanism is particularly bed depth- and concentration-dependant, favoring higher bed depth and lower influent metal concentration. The highest bed capacity of 34.91 mg Cd(II)/g and 21.93 mg Cu(II)/g of POFA was achieved at 20 mg/L of influent metal concentrations, column bed depth of 2 cm, and flow rate of 5 mL/min. The whole breakthrough curve simulation for both metal ions were best described using the Thomas and Yoon–Nelson models, but it is apparent that the initial region of the breakthrough for Cd(II) was better described using the BDST model. The results illustrate that POFA could be utilized effectively for the removal of Cd(II) and Cu(II) ions from aqueous solution in a fixed-bed column system.     

Biosorption of copper, cobalt and nickel by marine green alga Ulva reticulata in a packed column

Biosorption of copper, cobalt and nickel by marine green alga Ulva reticulata were investigated in a packed bed up-flow column. The experiments were conducted to study the effect of important design parameters such as bed height and flow rate. At a bed height of 25 cm, the metal-uptake capacity of U. reticulata for copper, cobalt and nickel was found to be 56.3+/-0.24, 46.1+/-0.07 and 46.5+/-0.08 mgg(-1), respectively. The Bed Depth Service Time (BDST) model was used to analyze the experimental data. The computed sorption capacity per unit bed volume (N0) was 2580, 2245 and 1911 mgl(-1) for copper, cobalt and nickel, respectively. The rate constant (K(a)) was recorded as 0.063, 0.081 and 0.275 lmg(-1)h(-1) for copper, cobalt and nickel, respectively. In flow rate experiments, the results confirmed that the metal uptake capacity and the metal removal efficiency of U. reticulata decreased with increasing flow rate. The Thomas model was used to fit the column biosorption data at different flow rates and model constants were evaluated. The column regeneration studies were carried out for three sorption-desorption cycles. The elutant used for the regeneration of the biosorbent was 0.1 M CaCl2 at pH 3 adjusted using HCl. For all the metal ions, a decreased breakthrough time and an increased exhaustion time were observed as the regeneration cycles progressed, which also resulted in a broadened mass transfer zone. The pH variations during both sorption and desorption process have been reported.     

Fixed-bed study for lanthanide (La, Eu, Yb) ions removal from aqueous solutions by immobilized Pseudomonas aeruginosa: experimental data and modelization

A fixed-bed study was carried out by using cells of Pseudomonas aeruginosa immobilized in polyacrylamide gel as a biosorbent for the removal of lanthanide (La, Eu, Yb) ions from aqueous solutions. The effects of superficial liquid velocity based on empty column, particle size, influent concentration and bed depth on the lanthanum breakthrough curves were investigated. Immobilized biomass effectively removed lanthanum from a 6 mM solution with a maximum adsorption capacity of 342 micromolg(-1) (+/-10%) corresponding closely to that observed in earlier batch studies with free bacterial cells. The Bohart and Adams sorption model was employed to determine characteristic parameters useful for process design. Results indicated that the immobilized cells of P. aeruginosa enable removal of lanthanum, europium and ytterbium ions from aqueous effluents with significant and similar maximum adsorption capacities. Experiments with a mixed cation solution showed that the sequence of preferential biosorption was Eu3+ > or = Yb3+ > La3+. Around 96+/-4% of the bound lanthanum was desorbed from the column and concentrated by eluting with a 0.1 M EDTA solution. The feasibility of regenerating and reusing the biomass through three adsorption/desorption cycles was suggested. Neural networks were used to model breakthrough curves performed in the dynamic process. The ability of this statistical tool to predict the breakthrough times was discussed.     

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.     

Removal of metal ions from the complexed solutions in fixed bed using a strong-acid ion exchange resin

Fixed bed removal of equimolar metal ions (Co²⁺, Ni²⁺, Mn²⁺, Sr²⁺) from aqueous solutions using a strong-acid resin was examined. The solution contained a water-soluble complexing agent including ethylenediaminetetraacetic acid, nitrilotriacetic acid, and citric acid. Experiments were performed under different solution pH and molar concentration ratios of complexing agent to the total metals. It was shown from batch studies that the equilibrium exchange of metals and the resin mainly depended on solution pH, and partly on the type of complexing agent used. A mass transfer model was proposed to describe the breakthrough curves of the resin bed, which contained two parameters (τ and k) estimated from the observed breakthrough data. The calculated breakthrough curves agreed well with the measured ones (standard deviation <6%). In fixed bed tests at low pH (=2), the type of complexing agent had little effect on the breakthrough data. For a given complexing agent, the metal with a larger overall formation constant (K_f) showed a smaller exchange capacity. For a given metal ion, the complexing agent with a larger K_f also revealed a smaller exchange capacity.     

Artificial neural network (ANN) modeling of adsorption of methylene blue by NaOH-modified rice husk in a fixed-bed column system

In this study, rice husk was modified with NaOH and used as adsorbent for dynamic adsorption of methylene blue (MB) from aqueous solutions. Continuous removal of MB from aqueous solutions was studied in a laboratory scale fixed-bed column packed with NaOH-modified rice husk (NMRH). Effect of different flow rates and bed heights on the column breakthrough performance was investigated. In order to determine the most suitable model for describing the adsorption kinetics of MB in the fixed-bed column system, the bed depth service time (BDST) model as well as the Thomas model was fitted to the experimental data. An artificial neural network (ANN)-based model was also developed for describing the dynamic dye adsorption process. An extensive error analysis was carried out between experimental data and data predicted by the models by using the following error functions: correlation coefficient (R ²), average relative error, sum of the absolute error and Chi-square statistic test (χ ²). Results show that with increasing bed height and decreasing flow rate, the breakthrough time was delayed. All the error functions yielded minimum values for the ANN model than the traditional models (BDST and Thomas), suggesting that the ANN model is the most suitable model to describe the fixed-bed adsorption of MB by NMRH. It is also more rational and reliable to interpret dynamic dye adsorption data through a process of ANN architecture.     

锆负载型树脂用于含氟废水深度处理的研究

本文研制了一种以火力发电厂废树脂为载体的锆负载型氟离子吸附剂 ,并在评价了该树脂对氟离子的吸附性能之后探讨了该树脂用于火力发电厂含氟废水深度处理的可能性。研究结果表明 ,锆的最佳负载的最佳浓度为0 .5mol/L ,该负载树脂的最佳吸附pH为 3.0— 4 .0 ,用填充柱进行的动态实验结果表明 ,pH =3时的吸附容量显著高于 pH=4时的值。利用该树脂对火力发电厂模拟含氟废水进行了双柱串联吸附工艺处理 ,当柱流量为 35mL/min(SV10 )、第二柱穿透时 ,第一柱的吸附容量为 10 2 2 8mg/L湿树脂 ;用 0 .1mol/L的NaOH溶液进行再生 ,柱流量选择为 35mL/min(SV10 )时 ,脱附率在 95 %以上。     

Simultaneous heavy metal removal mechanism by dead macrophytes

The use of dead, dried aquatic plants, for water removal of metals derived from industrial activities as a simple biosorbent material has been increasing in the last years. The mechanism of simultaneous metal removal (Cd2+, Ni2+, Cu2+, Zn2+ and Pb2+) by 3 macrophytes biomass (Spirodela intermedia, Lemna minor and Pistia stratiotes) was investigated. L. minor biomass presented the highest mean removal percentage and P. stratiotes the lowest for all metals tested. Pb2+ and Cd2+ were more efficiently removed by the three of them. The simultaneous metal sorption data were analysed according to Langmuir and Freundlich isotherms. Data fitted the Langmuir model only for Ni and Cd, but Freundlich isotherm for all metals tested, as it was expected. The K(F) values showed that Pb was the metal more efficiently removed from water solution. The adsorption process for the three species studied followed first order kinetics. The mechanism involved in biosorption resulted ion exchange between monovalent metals as counter ions present in the macrophytes biomass and heavy metal ions and protons taken up from water. No significant differences were observed in the metal exchange amounts while using multi-metal or individual metal solutions.     

涂铁多孔陶瓷对水中亚甲基蓝的动态吸附

研究了涂铁多孔陶瓷填料柱对水中亚甲基蓝（MB）的动态吸附性能。探讨了填料高度、MB初始质量浓度和流速对穿透曲线的影响;分别用BDST模型、Thomas模型和线性回归对动态吸附实验数据拟合,获得了相关参数,并研究了填料的再生性能。结果表明,涂铁多孔陶瓷（IOCPC）能有效去除水中MB,填料层升高,穿透曲线上的穿透点向右移动,穿透时间延长;而随流速、MB初始质量浓度的增大,穿透曲线上的穿透点向左移动,穿透时间缩短。用BDST模型能准确预测穿透时间,误差＜5%;用Thomas模型可较好地描述了MB浓度为10和50 mg/L、初速为2 mL/min时IOCPC对MB的吸附动力学,相关系数分别为0.99和0.93,平衡吸附容量分别为0.078和0.13 mg/g。对吸附饱和后的涂铁多孔陶瓷可用pH=3的硝酸再生,重复使用3次穿透曲线上的穿透点基本不变。     

A comparative investigation on the biosorption of lead by filamentous fungal biomass

The removal of lead from aqueous solutions by adsorption on filamentous fungal biomass was studied. Batch biosorption experiments were performed to screen a series of selected fungal strains for effective lead removal at different metal and biomass concentrations. Biosorption of the Pb²⁺ ions was strongly affected by pH. The fungal biomass exhibited the highest lead adsorption capacity at pH 6. Isotherms for the biosorption of lead on fungal biomass were developed and the equilibrium data fitted well to the Langmuir isotherm model. At pH 6, the maximum lead biosorption capacity of Mucor rouxii estimated with the Langmuir model was 769 mg/g dry biomass, significantly higher than that of most microorganisms. Biomass of Mucor rouxii showed specific selectivity for Pb²⁺ over other metals ions such as Zn²⁺. Ni²⁺ and Cu²⁺. This fungal strain may be applied to develop potentially cost-effective biosorbent for removing lead from effluents. The technique of scanning electron microscopy coupled with X-ray dispersion analysis shows that Pb²⁺ has exchanged with K⁺ and Ca²⁺ on the cell wall of Mucor rouxii, thereby suggesting ion exchange as one of the dominant mechanisms of metal biosorption for this fungal strain.     

Lead removal in fixed-bed columns by zeolite and sepiolite

The removal efficiency of zeolite (clinoptilolite) and sepiolite from lead containing aqueous solutions was investigated. A series of experiments were conducted in batch-wise and fixed-bed columns. Synthetic wastewaters containing lead (50 mg l (-1)) and acetic acid (0.001 N) along with untreated and regenerated clinoptilolites and sepiolites were used in the adsorption studies. Batch tests were mainly conducted to isolate the magnitude of lead precipitation from real adsorption. Adsorption isotherms for both abstraction and adsorption were constructed. The removal of lead is found to be a sum of adsorption induced by ion exchange and precipitation of lead hydroxide. The breakthrough curves were obtained under different conditions by plotting the normalized effluent lead concentration (C/C0) versus bed volume (BV). The ion exchange capacity of sepiolite and clinoptilolite for lead removal showed good performance up to approximately 100 and 120 BV where the C/C0 remained below 0.1, respectively. The lead removal capacity of clinoptilolite bed from wastewater containing only lead yielded 45% higher performance compared to that of acetic acid partly due to a decrease in the effluent pH and consequently in precipitation. Also, the presence of acetic acid in the sepiolite column decreased the bed volumes treated by about 40%. Removal efficiency of lead-acetic system both in untreated clinoptilolite and sepiolite columns was found higher than that in regenerated columns.     

棘孢曲霉(Aspergillus aculeatus)对Pb~(2+)和Cd~(2+)的吸附特征

为了研究棘孢曲霉(Aspergillus aculeatus)对溶液中Pb~(2+)和Cd~(2+)吸附过程的特征,分别从动力学、热力学和吸附等温线三方面进行了实验,同时还研究了pH、温度、时间、重金属离子起始浓度和吸附剂用量对吸附过程的影响。等温吸附过程可以用Langmuir方程来描述。在实验设定条件下,棘孢曲霉对Pb~(2+)和Cd~(2+)最大吸附量分别为71.2 mg/g和59.8 mg/g;动力学实验数据很好的符合二级动力学方程,吸附达到平衡的时间为3 h;热力学实验数据显示该吸附过程为自发的、吸热的过程。     

棘孢曲霉（Aspergillus aculeatus）对Pb2＋和Cd2＋的吸附特征

为了研究棘孢曲霉（Aspergillus aculeatus）对溶液中Pb^2＋和Cd^2＋吸附过程的特征,分别从动力学、热力学和吸附等温线三方面进行了实验,同时还研究了pH、温度、时间、重金属离子起始浓度和吸附剂用量对吸附过程的影响。等温吸附过程可以用Langmuir方程来描述。在实验设定条件下,棘孢曲霉对Pb^2＋和Cd^2＋最大吸附量分别为71.2 mg/g和59.8 mg/g;动力学实验数据很好的符合二级     

棘孢曲霉（Aspergillus aculeatus）对Pb^2＋和Cd^2＋的吸附特征

为了研究棘孢曲霉（Aspergillus aculeatus）对溶液中Pb^2＋和Cd^2＋吸附过程的特征,分别从动力学、热力学和吸附等温线三方面进行了实验,同时还研究了pH、温度、时间、重金属离子起始浓度和吸附剂用量对吸附过程的影响。等温吸附过程可以用Langmuir方程来描述。在实验设定条件下,棘孢曲霉对Pb^2＋和Cd^2＋最大吸附量分别为71．2mg／g和59．8mg／g;动力学实验数据很好的符合二级动力学方程,吸附达到平衡的时间为3h;热力学实验数据显示该吸附过程为自发的、吸热的过程。     

Lead biosorption and desorption by intact and pretreated spirulina maxima biomass

In order to search for locally available and untried biomaterials in China with high removal capacity of heavy metals from wastewater, the feasibility of Spirulina maxima as biosorbent for lead removal and recovery from aqueous solution was investigated. The lead biosorption was studied by using intact biomass and pretreated biomass of S. maxima. The effects of operational conditions (e.g. pH, contact time, biomass concentration etc.) on lead biosorption were investigated. The biosorption was solution pH dependent and the maximum adsorption was obtained at a solution pH of about 5.5. The adsorption equilibrium was reached in 60 min. The biosorption followed the Freundlich isotherm model. The maximum removal ratios of lead were about 84% in intact biomass and 92% in pretreated biomass. The lead adsorbed could be desorbed effectively by 0.1 M nitric acid, EDTA and hydrochloric acid. The results in this study indicated that pretreated biomass of S. maxima was a promising candidate for removing lead from wastewater.     

Sorption of Cr(VI) from dilute solutions and wastewater by live and pretreated biomass of Aspergillus flavus

Sorption of Cr(VI) was carried out from dilute solutions using live and pretreated biomass in a batch mode. Effects of agitation time, adsorbent dosage and pH were examined. The autoclaved biomass that showed maximum adsorption capacity (Q(0)=0.335 mg g(-1)) was used as an adsorbent in column studies. The optimized flow rate of 2.5 ml min(-1) and bed height 10 cm were used to determine the effect of metal ion concentration on removal of Cr(VI). Applying the BDST model to calculate the adsorption capacity (N(0)) of column, which showed 4.56 x 10(-5), 7.28 x 10(-5), 6.89 x 10(-5), 3.07 x 10(-5), 2.80 x 10(-5)mg g(-1) for 4, 8, 12, 16 and 20 mg dm(-3) of Cr(VI), respectively. Batch sorption proved to be more efficient than the column sorption and hence batch sorption was used to remove Cr(VI) from a textile dyeing industry wastewater. The phytotoxic effect of treated and untreated wastewater was studied against Zea mays. Toxicity was reduced by 50% in the treated effluent.     

Experimental Zn(II) retention in a sandy loam soil by very small columns

The use of column experiments, usually performed to better approximate field conditions, may provide information that is not available from batch experiments. In such experiments heavy metals are often adsorbed until saturation followed by desorption experiments. When the affinity of the metal to soil is high, the retention factor (R) could be greater than thousands and the duration of experiments can become impractically long. In order to use reasonable laboratory time, the flow rate should be increased or the column size decreased. The increase in flow rate produces undesirable kinetic and dispersion effects, so we used very small soil columns (pore volume = 0.31–0.70 ml) and relatively high flow rates (0.03–0.12 ml min⁻¹) in studies of Zn(II) adsorption and retention in soils. Conservative tracer flow column experiments under saturation conditions were carried out to determine flow parameters for different flow rates. Column pore volume (V_p), Peclet numbers (Pe) and longitudinal dispersion coefficients (D_L) were determined from breakthrough curves. The effect of type of electrolyte and ionic strength on the Zn(II) retention onto soil was determined. The influence of flow rate and bed height on the retention coefficient and on the mass transfer zone was also studied. The effect of different influent Zn(II) concentrations on the R values obtained was analyzed. Freundlich parameters from column experiments were compared with batch ones. The leaching efficiency of different electrolytes, salts of weak organic acids and EDTA was also studied.     

Competitive biosorption of lead, cadmium, copper, and arsenic ions using algae

The present study aims to evaluate the competitive biosorption of lead, cadmium, copper, and arsenic ions by using native algae. A series of experiments were carried out in a batch reactor to obtain equilibrium data for adsorption of single, binary, ternary, and quaternary metal solutions. The biosorption of these metals is based on ion exchange mechanism accompanied by the release of light metals such as calcium, magnesium, and sodium. Experimental parameters such as pH, initial metal concentrations, and temperature were studied. The optimum pH found for removal were 5 for Cd²⁺ and As³⁺ and 3 and 4 for Pb²⁺ and Cu²⁺, respectively. Fourier transformation infrared spectroscopy analysis was used to find the effects of functional groups of algae in biosorption process. The results showed that Pb²⁺ made a greater change in the functional groups of algal biomass due to high affinity to this metal. An ion exchange model was found suitable for describing the biosorption process. The affinity constants sequence calculated for single system was K _Pb > K _Cu > K _Cd > K _As; these values reduced in binary, ternary, and quaternary systems. In addition, the experimental data showed that the biosorption of the four metals fitted well the pseudo-second-order kinetics model.     

Biosorption of Cr(VI) and Zn(II) ions from aqueous solution onto the solid biodiesel waste residue: mechanistic, kinetic and thermodynamic studies

In this present study, the biosorption of Cr(VI) and Zn(II) ions from synthetic aqueous solution on defatted J atropha oil cake (DJOC) was investigated. The effect of various process parameters such as the initial pH, adsorbent dosage, initial metal ion concentration and contact time has been studied in batch-stirred experiments. Maximum removal of Cr(VI) and Zn(II) ions in aqueous solution was observed at pH 2.0 and pH. 5.0, respectively. The removal efficiency of Cr(VI) and Zn(II) ions from the aqueous solution was found to be 72.56 and 79.81 %, respectively, for initial metal ion concentration of 500 mg/L at 6 g/L dosage concentration. The biosorbent was characterized by Fourier transform infrared, scanning electron microscopy and zero point charge. Equilibrium data were fitted to the Langmuir, Freundlich, Temkin and Dubinin–Radushkevich isotherm models and the best fit is found to be with the Freundlich isotherm for both Cr(VI) and Zn(II) metal ions. The kinetic data obtained at different metal ion concentration have been analysed using the pseudo-first-order, pseudo-second-order and intraparticle diffusion models and were found to follow the pseudo-second-order kinetic model. The values of mass transfer diffusion coefficients (D _e) were determined by Boyd model and compared with literature values. Various thermodynamic parameters, such as ΔG°, ΔH° and ΔS°, were analysed using the equilibrium constant values (K _e) obtained from experimental data at different temperatures. The results showed that biosorption of Cr(VI) and Zn(II) ions onto the DJOC system is more spontaneous and exothermic in nature. The results indicate that DJOC was shown to be a promising adsorbent for the removal of Cr(VI) and Zn(II) ions from aqueous solution.     

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。