Removal of copper (II) from aqueous solution by adsorption onto low-cost adsorbents

The use of low-cost adsorbents was investigated as a replacement for current costly methods of removing metals from aqueous solution. Removal of copper (II) from aqueous solution by different adsorbents such as shells of lentil (LS), wheat (WS), and rice (RS) was investigated. The equilibrium adsorption level was determined as a function of the solution pH, temperature, contact time, initial adsorbate concentration and adsorbent doses. Adsorption isotherms of Cu (II) on adsorbents were determined and correlated with common isotherm equations such as Langmuir and Freundlich models. The maximum adsorption capacities for Cu (II) on LS, WS and RS adsorbents at 293, 313 and 333 K temperature were found to be 8.977, 9.510, and 9.588; 7.391, 16.077, and 17.422; 1.854, 2.314, and 2.954 mg g(-1), respectively. The thermodynamic parameters such as free energy (delta G0), enthalpy (delta H0) and entropy changes (delta S0) for the adsorption of Cu (II) were computed to predict the nature of adsorption process. The kinetics and the factors controlling the adsorption process were also studied. Locally available adsorbents were found to be low-cost and promising for the removal of Cu (II) from aqueous solution.     

Sorption of styrene from aqueous solutions with oil absorptive resin

We demonstrated the utility of oil-absorbing 4-tert-butylstyrene-divinylbenzene-ethylene/propylene/diene resins in the removal of environmental hormones such as styrene from water. A maximum treatment efficiency of 99.47% was observed when using a static process, while the dynamic process yielded a maximum efficiency of 96.25%. The sorption efficiency was greater for solutions containing higher initial concentrations of styrene and for extended static contact times, but decreased with increasing hydraulic retention time. The influences of styrene concentration, sorption time, and hydraulic retention time on sorption efficiency were successfully predicted using a polynomial equation, sigmoidal function and exponential decay equation, respectively. It was found that the sorption process was well described by a first-order kinetic model.     

Pre-treating biosorbents for purification of bioethanol from aqueous solution

Cost-effective biosorbents made from the byproducts of agriculture, forest, and related industries, such as barley straw, canola meal, and wood sawdust, have significant water adsorption capacity, showing a great potential for selective water removal from bioalcohols to produce fuel grade products. However, there is a challenge that the biosorbents are not stable when they come in contact with aqueous solution. There are organic carbons released from biosorbents to liquid phase, which needs to be addressed before this technology is applied in the industrial purification of bioalcohols. In this work, raw barley straw representing an abundant group of cellulosic materials in the above-mentioned industries was used as a model material. A methodology of chemical and physical treatment was developed to treat barley straw which successfully enhanced the stability and reduced the total organic carbon release from the material into the aqueous solution. In addition, the pre-treated barley straw biosorbent had significantly increased micropores, and the Brunauer--Emmett--Teller surface area favored by water adsorption compared with raw barley straw. It also had higher water uptake and dynamic water adsorption selectivity. The pre-treated barley straw was able to selectively remove water and generate concentrated ethanol.     

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.     

Adsorption of Cu(II) ions from aqueous solutions on biochars prepared from agricultural by-products

In this study, the adsorption of Cu(II) from aqueous solutions by agricultural by-products, such as rice husks, olive pomace and orange waste, as well as compost, was evaluated. The aim was to obtain sorbent materials (biochars) through hydrothermal treatment (300?°C) and pyrolysis (300?°C and 600?°C). The effect of adsorbent dose, pH, contact time and initial Cu(II) concentration in batch-mode experiments was investigated. The optimum Cu(II) adsorption conditions was found to occur at 5-12?g/L adsorbent dose, initial pH 5-6, and reaction time 2-4?h. Furthermore, the adsorption kinetics were best described by the pseudo-second order model for all the tested materials, while the adsorption equilibrium best fitted by the linear and Freundlich isotherms. Comparing rice husks and olive pomace, the higher adsorption capacity resulted after pyrolysis at 300?°C. With respect to the orange waste and compost, the highest adsorption capacity was observed using biochars obtained after hydrothermal treatment and pyrolysis at 300?°C.     

Application of cupuassu shell as biosorbent for the removal of textile dyes from aqueous solution

The cupuassu shell (Theobroma grandiflorum) which is a food residue was used in its natural form as biosorbent for the removal of C.I. Reactive Red 194 and C.I. Direct Blue 53 dyes from aqueous solutions. This biosorbent was characterized by infrared spectroscopy, scanning electron microscopy, and nitrogen adsorption/desorption curves. The effects of pH, biosorbent dosage and shaking time on biosorption capacities were studied. In acidic pH region (pH 2.0) the biosorption of the dyes were favorable. The contact time required to obtain the equilibrium was 8 and 18 h at 298 K, for Reactive Red 194 and Direct Blue 53, respectively. The Avrami fractionary-order kinetic model provided the best fit to experimental data compared with pseudo-first-order, pseudo-second-order and chemisorption kinetic adsorption models. The equilibrium data were fitted to Langmuir, Freundlich, Sips and Radke-Prausnitz isotherm models. For both dyes the equilibrium data were best fitted to the Sips isotherm model.     

Adsorptive removal of Cd(II) and Pb(II) ions from aqueous solutions by using Turkish illitic clay

The ability of Turkish illitic clay (TIC) in removal of Cd(II) and Pb(II) ions from aqueous solutions has been examined in a batch adsorption process with respect to several experimental conditions including initial solution pH, contact time, initial metal ions concentration, temperature, ionic strength, and TIC concentration, etc. The characterization of TIC was performed by using FTIR, XRD and XRF techniques. The maximum uptake of Cd(II) (11.25 mg g⁻¹) and Pb(II) (238.98 mg g⁻¹) was observed when used 1.0 g L⁻¹ of TIC suspension, 50 mg L⁻¹ of initial Cd(II) and 250 mg L⁻¹ of initial Pb(II) concentration at initial pH 4.0 and contact time of 240 min at room temperature. The experimental data were analyzed by the Langmuir, Freundlich, Temkin and Dubinin Radushkevich (D-R) isotherm models. The monolayer adsorption capacity of TIC was found to be 13.09 mg g⁻¹ and 53.76 mg g⁻¹ for Cd(II) and Pb(II) ions, respectively. The kinetics of the adsorption was tested using pseudo-first-order, pseudo-second-order, Elovich and intraparticle diffusion models. The results showed that the adsorption of Cd(II) and Pb(II) ions onto TIC proceeds according to the pseudo-second-order model. Thermodynamic parameters including the Gibbs free energy (ΔG), enthalpy (ΔH), and entropy (ΔS) changes indicated that the present adsorption process was feasible, spontaneous and endothermic in the temperature range of 5–40 °C.     

Batch sorption dynamics and equilibrium for the removal of lead ions from aqueous phase using activated carbon developed from coffee residue activated with zinc chloride

Lignocellulosic materials are good precursors for the production of activated carbon. In this work, coffee residue has been used as raw material in the preparation of powder activated carbon by the method of chemical activation with zinc chloride for the sorption of Pb(II) from dilute aqueous solutions.The influence of impregnation ratio (ZnCl₂/coffee residue) on the physical and chemical properties of the prepared carbons was studied in order to optimize this parameter. The optimum experimental condition for preparing predominantly microporous activated carbons with high pore surface area (890 m²/g) and micropore volume (0.772 cm³/g) is an impregnation ratio of 100%. The developed activated carbon shows substantial capability to sorb lead(II) ions from aqueous solutions and for relative impregnation ratios of 75 and 100%, the maximum uptake is practically the same. Thus, 75% represents the optimal impregnation ratio.Batch experiments were conducted to study the effects of the main parameters such as contact time, initial concentration of Pb(II), solution pH, ionic strength and temperature. The maximum uptake of lead(II) at 25 °C was about 63 mg/g of adsorbent at pH 5.8, initial Pb(II) concentration of 10 mg/L, agitation speed of 200 rpm and ionic strength of 0.005 M. The kinetic data were fitted to the models of pseudo-first order and pseudo-second order, and follow closely the pseudo-second order model. Equilibrium sorption isotherms of Pb(II) were analyzed by the Langmuir, Freundlich and Temkin isotherm models. The Freundlich model gives a better fit than the others.Results from this study suggest that activated carbon produced from coffee residue is an effective adsorbent for the removal of lead from aqueous solutions and that ZnCl₂ is a suitable activating agent for the preparation of high-porosity carbons.     

Removal of Se(IV) from aqueous solution using sulphuric acid-treated peanut shell

A carbonaceous sorbent was prepared from peanut shell via sulphuric acid treatment. Se(IV) removal from aqueous solution on the sorbent was studied varying time, pH, Se(IV) concentration, temperature and sorbent status (wet and dry). Se(IV) removal was faster using the wet sorbent than the dry sorbent following a pseudo-first-order model. Se(IV) removal increases at low pH values, and decreases as pH increases until pH 7. Sorption was found to fit the Langmuir equation and sorption capacity for the wet sorbent was higher than that for the dry one. Both sorbents showed an increased selenium sorption by rising the temperature. Redox processes between Se(IV) and the carbon sorbent are involved. Analysis by scanning electron microscope and X-ray powder diffraction for the sorbent after the reaction with acidified Se(IV) confirmed the availability of elemental selenium as particles on the sorbent surface as a result of Se(IV) reduction. Physicochemical tests showed an increase in sorbent acidity, cation exchange capacity (CEC) and surface functionality after the reaction with acidified Se(IV), indicating the oxidation processes occurring on the sorbent surface. Due to its reduction properties, the sorbent seems efficient for Se(IV) removal from aqueous solution.     

Sorption of cadmium and zinc from aqueous solutions by zeolite 4A, zeolite 13X and bentonite

The sorption and desorption of cadmium and zinc on zeolite 4A, zeolite 13X and bentonite has been studied using batch sorption studies. Parameters such as equilibrium time, effect of pH and sorbent dose were studied. The sorbents exhibited good sorption potential for cadmium and zinc with a peak value at pH 6.0 and 6.5, respectively. The sorption followed the Freundlich sorption model. More than 70% sorption occurred within 20 min and equilibrium was attained at around 90 min for the three sorbents. The metals sorption by zeolite 4A was higher than that by zeolite 13X and bentonite. The desorption studies were carried out using NaCl solution and the effect of NaCl concentration on desorption was also studied. Maximum desorption of 76% for cadmium and 80% for zinc occurred with 10% NaCl.     

Experimental investigation of adsorption capacity of anthill in the removal of heavy metals from aqueous solution

In the present work, the adsorption capacity of anthill was investigated as a low‐cost adsorbent to remove the heavy metal ions, lead (II) ion (Pb²⁺), and zinc (II) ion (Zn²⁺) from an aqueous solution. The equilibrium adsorption isotherms of the heavy metal ions were investigated under batch process. For the study we examined the effect of the solution's pH and the initial cations concentrations on the adsorption process under a fixed contact time and temperature. The anthill sample was characterized using a scanning electron microscope (SEM), X‐ray fluorescence (XRF), and Fourier transform infrared (FTIR) techniques. From the SEM analysis, structural change in the adsorbent was a result of heavy metals adsorption. Based on the XRF analysis, the main composition of the anthill sample was silica (SiO₂), alumina (Al₂O₃), and zirconia (ZrO₂). The change in the peaks of the spectra before and after adsorption indicated that there was active participation of surface functional groups during the adsorption process. The experimental data obtained were analyzed using 2‐ and 3‐parameter isotherm models. The isotherm data fitted very well to the 3‐parameter Radke–Prausnitz model. It was noted that Pb²⁺ and Zn²⁺ can be effectively removed from aqueous solution using anthill as an adsorbent.     

Exploitation of Trichoderma harzianum mycelial waste for the removal of rhodamine 6G from aqueous solution

The harvested mycelial waste of Trichoderma harzianum was used as an adsorbent for the removal of rhodamine 6G and was studied in batch mode. The effects of agitation time and initial dye concentration, adsorbent dosage and pH were examined. The study revealed that the amount of dye adsorbed (mgg(-1)) increased with increase in agitation time and reached equilibrium after 120 min, for dye concentrations of 10-50 mg L(-1). The adsorbent dosage of 1.0 g/50 mL and pH of 8.0 were found to be optimum for maximum dye removal. The batch mode adsorption data followed both the Langmuir and Freundlich isotherms. The pseudo first- and second-order rate kinetics were applied to the adsorbent system. The adsorption kinetics of rhodamine 6G showed that the pseudo-second-order kinetic model provided the best correlation of the equilibrium data. The study implies that it is possible to develop a dye removal system by using T. harzianum biomass, which occurs as sludge in waste stream of fermentation industries.     

Removal and recycling of copper from aqueous solutions using treated Indian barks

Removal of copper from aqueous solutions containing 100–1000 ppm, using different Indian bark species, was performed on laboratory scale. The percentage removal of metal ions depends on the solution pH, bark species and time. The efficiency of copper removal by the used raw barks increases with a rise of solution pH and reaches a maximum of about 65–78% around pH 4–5. However, the decontaminated aqueous solutions were colored due to the dissolution of soluble organic compounds contained in the raw bark. This increases the biological and chemical oxygen demand (BOD and COD) of the solutions as well as the total organic carbon content (TOC). For this reason, raw bark should be treated either by chemical or biological means. Such treatment will allow the extraction of the soluble organic compounds and increase the chelating capacity and efficiency of the treated bark. Depending on the pH value, the chelating efficiency of treated barks is about 1.2–2.2 times that of the raw ones. Moreover, the retention capacity of the Indian treated bark varies from about 42–51 mg/g of dry bark. It is equal to or higher than that of common European species. About 1.8 mols of H₃O⁺ are released, by the treated barks, for every mol of chelated copper ions. Moreover, scanning electron microscopy (SEM) observations show uniform distribution of metal ions throughout the copper saturated bark. Infra red (IR) spectra suggest that the copper ions are chelated to hydroxyl and/or carboxyl functional groups of organic compounds contained in the treated bark. It seems that the interaction of the copper ions with the bark follows a cation exchange mechanism. This hypothesis is supported by elution experiments that allow recovery of about 99% of the contained copper. The retention capacity of the treated bark is almost constant after five cycles of chelation–elution, suggesting that the ‘life time cycle' is sufficiently long for continuous industrial application. The spent copper loaded barks can either be incinerated or pyrolysed. It generates solids containing either ≈80% of CuO or ≈14% of Cu°, respectively. Such materials can be used either in the secondary or primary copper production, thus offering a friendly environmental solution of effluents' treatment. The suggested process can be used as an alternative to the classical technologies for effluent decontamination. It is also efficient for polishing effluents treated by other methods.     

Kinetic and equilibrium characterization of uranium(VI) adsorption onto carboxylate-functionalized poly(hydroxyethylmethacrylate)-grafted lignocellulosics

This study investigated the feasibility of using a new adsorbent prepared from coconut coir pith, CP (a coir industry-based lignocellulosic residue), for the removal of uranium [U(VI)] from aqueous solutions. The adsorbent (PGCP-COOH) having a carboxylate functional group at the chain end was synthesized by grafting poly(hydroxyethylmethacrylate) onto CP using potassium peroxydisulphate-sodium thiosulphite as a redox initiator and in the presence of N,N'-methylenebisacrylamide as a crosslinking agent. IR spectroscopy results confirm the graft copolymer formation and carboxylate functionalization. XRD studies confirm the decrease of crystallinity in PGCP-COOH compared to CP, and it favors the protrusion of the functional group into the aqueous medium. The thermal stability of the samples was studied using thermogravimetry (TG). Surface charge density of the samples as a function of pH was determined using potentiometric titration. The ability of PGCP-COOH to remove U(VI) from aqueous solutions was assessed using a batch adsorption technique. The maximum adsorption capacity was observed at the pH range 4.0-6.0. Maximum removal of 99.2% was observed for an initial concentration of 25mg/L at pH 6.0 and an adsorbent dose of 2g/L. Equilibrium was achieved in approximately 3h. The experimental kinetic data were analyzed using a first-order kinetic model. The temperature dependence indicates an endothermic process. U(VI) adsorption was found to decrease with an increase in ionic strength due to the formation of outer-sphere surface complexes on PGCP-COOH. Equilibrium data were best modeled by the Langmuir isotherm. The thermodynamic parameters such as DeltaG(0), DeltaH(0) and DeltaS(0) were derived to predict the nature of adsorption. Adsorption experiments were also conducted using a commercial cation exchanger, Ceralite IRC-50, with carboxylate functionality for comparison. Utility of the adsorbent was tested by removing U(VI) from simulated nuclear industry wastewater. Adsorbed U(VI) ions were desorbed effectively (about 96.2+/-3.3%) by 0.1M HCl. The adsorbent was suitable for repeated use (more than four cycles) without any noticeable loss of capacity.     

Biosorption of copper (II) from chemical mechanical planarization wastewaters

Copper Chemical Mechanical Planarization (Cu-CMP) is a critical step in integrated circuit (IC) device manufacturing. CMP and post-CMP cleaning processes are projected to account for 30-40% of the water consumed by IC manufacturers in 2003. CMP wastewater is expected to contain increasing amounts of copper as the industry switches from Al-CMP to Cu-CMP causing some IC manufacturers to run the risk of violating discharge regulations. There are a variety of treatment schemes currently available for the removal of heavy metals from CMP wastewater, however, many introduce additional chemicals to the wastewater, have large space requirements, or are expensive. This work explores the use of microorganisms for waste treatment. A Staphylococcus sp. of bacteria was isolated and studied to determine the feasibility for use in removing copper from Cu-CMP wastewater. A model Cu-CMP wastewater was developed and tested, as well as actual Cu-CMP wastes. Continuous-flow packed column experiments were performed to obtain adsorption data and show copper recovery from the waste. A predictive, empirical model was used to accurately describe Cu removal. Additionally, the immobilized cells were regenerated, allowing for the concentration and potential recovery of copper from the wastewater.     

A comparative study for the sorption of Cd(II) by K-feldspar and sepiolite as soil components, and the recovery of Cd(II) using rhamnolipid biosurfactant

This study investigated the sorption characteristics and recovery of selected heavy metal Cd(II) from K-feldspar and sepiolite, representative soil components, using rhamnolipid biosurfactant. Although the proposed technique was classified as a soil bioremediation process, it can also be applied to treatment of waste waters containing Cd(II) ions with minor modifications. The effect of initial Cd(II) concentration on sorption capacity was characterized by determining the sorption isotherms. Of the four models examined, the Freundlich model showed the best fit for the sorption of Cd(II) on K-feldspar, whereas the Langmuir-model was used successfully to characterize the sorption of Cd(II) on sepiolite. Although a high Cd(II) uptake of 7.49 mmol/kg by K-feldspar was obtained, sepiolite was a superior Cd(II) accumulater, with a maximum Cd(II) uptake of 24.66 mmol Cd(II)/kg. The presence of Cd(II) in the sepiolite or K-feldspar prior to addition of the rhamnolipid generally resulted in less rhamnolipid sorption to sepiolite or K-feldspar. The maximum Cd(II) desorption efficiency by rhamnolipid from K-feldspar was substantially higher than that of sepiolite and determined to be 96% of the sorbed Cd(II), whereas only 10.1% of the sorbed Cd(II) from sepiolite was recovered by rhamnolipid solution.     

Use of an activated carbon from antibiotic waste for the removal of Hg(II) from aqueous solution

Porous carbon has been prepared from waste antibiotic material by a chemical activation method using K(2)CO(3) as an activating reagent. Carbon was studied systematically by the adsorption of nitrogen and iodine. It was found that the process parameters such as activation temperature and activation time are crucial for preparing high-quality activated carbon. The proper choice of the preparation conditions allows to produce microporous activated carbon with a micropore volume up to 0.492 cm(3)/g and a BET surface area of 1260 m(2)/g. Adsorption of mercury(II) from an aqueous solution on antibiotic carbon was investigated under the varying conditions of agitation time, metal ion concentration and pH. The adsorption capacity of the carbon is 129 mg/g.     

Electrochemical remediation of copper (II) from an industrial effluent Part II: three-dimensional foam electrodes

A batch recycle removal of copper ions from an industrial effluent by means of copper foam cathodes was tested. A constant current of 750 A was applied to the cell in order to perform the reduction. Copper depletion was investigated at different solution flow rates and a removal greater than 98% was obtained with a flow rate of 1000 l/h. The influence of initial metal concentration on copper deposition and current efficiency is also discussed.     

Biosorption of Cu and Zn from aqueous solutions by dried marine green macroalga Chaetomorpha linum

The biosorption of the heavy metals Cu²⁺ and Zn²⁺ by dried marine green macroalga (Chaetomorpha linum) was investigated. The biosorption capacities of the dried alga for copper and zinc were studied at different solution pH values (2–6), different algal particle sizes (100–800 μm) and different initial metal solution concentrations (0.5–10 mM). An optimum pH value of 5 was found suitable for both metal ions biosorption for both metal ions. At the optimum particle size (100–315 μm), biosorbent dosage (20 g/l) and initial solution pH (pH 5), the dried alga produced maximum copper and zinc uptakes values (q_max) of 1.46 and 1.97 mmol/g respectively (according to the Langmuir model). The kinetic data obtained at different initial metal concentrations indicated that the biosorption rate was fast and most of the process was completed within 120 min. This study illustrated an alternative technique for the management of unwanted biological materials using processed algal material. C. linum is one of the fast-growing marine algae in the lake of Tunis and could be utilized as a biosorbent for the treatment of Cu²⁺ and Zn²⁺ contaminated wastewater streams.     

Utilization of waste product (tamarind seeds) for the removal of Cr(VI) from aqueous solutions: Equilibrium, kinetics, and regeneration studies

In the present study, an adsorbent was prepared from tamarind seeds and used after activation for the removal of Cr(VI) from aqueous solutions. The tamarind seeds were activated by treating them with concentrated sulfuric acid (98% w/w) at a temperature of 150 °C. The adsorption of Cr(VI) was found to be maximum at low values of initial pH in the range of 1–3. The adsorption process of Cr(VI) was tested with Langmuir, Freundlich, Redlich–Peterson, Koble–Corrigan, Tempkin, Dubinin–Radushkevich and Generalized isotherm models. Application of the Langmuir isotherm to the system yielded a maximum adsorption capacity of 29.7 mg/g at an equilibrium pH value ranging from 1.12 to 1.46. The adsorption process followed second-order kinetics and the corresponding rate constants obtained were 2.605 × 10⁻³, 0.818 × 10⁻³, 0.557 × 10⁻³ and 0.811 × 10⁻³ g/mg min⁻¹ for 50, 200, 300 and 400 mg/L of initial Cr(VI) concentration, respectively. The regenerated activated tamarind seeds showed more than 95% Cr(VI) removal of that obtained using the fresh activated tamarind seeds. A feasible solution is proposed for the disposal of the contaminants (acid and base solutions) containing high concentrations of Cr(VI) obtained during the regeneration (desorption) process.