Calcined tetrabutylammonium kaolinite and montmorillonite and adsorption of Fe(II), Co(II) and Ni(II) from solution

Kaolinite and montmorillonite were modified with tetrabutylammonium (TBA) bromide, followed by calcination. The structural changes were monitored with XRD, FTIR, surface area and cation exchange capacity measurements. The modified clay minerals were used for adsorption of Fe(III), Co(II) and Ni(II) ions from aqueous solution under different conditions of pH, time and temperature. The uptake of the metal ions took place by a second order kinetics. The modified montmorillonite had a higher adsorption capacity than the corresponding kaolinite. The Langmuir monolayer capacities for the modified kaolinite and montmorillonite were Fe(III): 9.3 mg g^− 1 and 22.6 mg g^− 1; Co(II): 9.0 mg g^− 1 and 22.3 mg g^− 1; and Ni(II): 8.4 mg g^− 1 and 19.7 mg g^− 1. The modified kaolinite interacted with Co(II) in an endothermic manner, but all the other interactions were exothermic. The decrease of the Gibbs energy in all the cases indicated spontaneous adsorption.     

Preparation and characterization of magnetic polymethylmethacrylate microbeads carrying ethylene diamine for removal of Cu(II), Cd(II), Pb(II), and Hg(II) from aqueous solutions

Magnetic polymethylmethacrylate (mPMMA) microbeads carrying ethylene diamine (EDA) were prepared for the removal of heavy metal ions (i.e., copper, lead, cadmium, and mercury) from aqueous solutions containing different amount of these ions (5–700 mg/L) and at different pH values (2.0–8.0). Adsorption of heavy metal ions on the unmodified mPMMA microbeads was very low (3.6 μmol/g for Cu(II), 4.2 μmol/g for Pb(II), 4.6 μmol/g for Cd(II), and 2.9 μmol/g for Hg(II)). EDA‐incorporation significantly increased the heavy metal adsorption (201 μmol/g for Cu(II), 186 μmol/g for Pb(II), 162 μmol/g for Cd(II), and 150 μmol/g for Hg(II)). Competitive adsorption capacities (in the case of adsorption from mixture) were determined to be 79.8 μmol/g for Cu(II), 58.7 μmol/g for Pb(II), 52.4 μmol/g for Cd(II), and 45.3 μmol/g for Hg(II). The observed affinity order in adsorption was found to be Cu(II) > Pb(II) > Cd(II) > Hg(II) for both under noncompetitive and competitive conditions. The adsorption of heavy metal ions increased with increasing pH and reached a plateau value at around pH 5.0. The optimal pH range for heavy‐metal removal was shown to be from 5.0 to 8.0. Desorption of heavy‐metal ions was achieved using 0.1 M HNO₃. The maximum elution value was as high as 98%. These microbeads are suitable for repeated use for more than five adsorption‐desorption cycles without considerable loss of adsorption capacity. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 81–89, 2000     

Kinetic and Equilibrium Modeling of Pb(II) and Co(II) Sorption onto Rose Waste Biomass

Abstract

An attempt was made to assess the biosorption potential of rose waste biomass for the removal of Pb(II) and Co(II) ions from synthetic effluents. Biosorption of heavy metal ions (>90%) reached equilibrium in 30 min. Maximum removal of Pb(II) and Co(II) occurred at pH 5 and 6 respectively. The biosorbent dose for efficient uptake of Pb(II) and Co(II) was 0.5 g/L for both metals. The biosorbent size affected the Pb(II) and Co(II) biosorption rate and capacity. Rose waste biomass was found effective for Pb(II) and Co(II) removal from synthetic effluents in the concentration range 10–640 mg/L. Equilibrium sorption studies showed that the extent of Pb(II) and Co(II) uptake by the rose waste biomass was better described by the Langmuir isotherm in comparison to the Freundlich model. The uptake capacities of the two metal ions were 156 and 27.15 mg/g for Pb(II) and Co(II) respectively.     

The adsorption behavior of Cu(II), Pb(II), and Co(II) of ethylene vinyl acetate‐clinoptilolite nanocomposites

In this study, ethylene vinyl acetate (EVA) was mixed with clinoptilolite (C), a natural zeolite, to prepare EVA‐C nanocomposites. The films were characterized by SEM‐EDS, XRD, and FT‐IR, and heavy metal removal was studied using the batch technique. The effects of the initial pH value and concentration of solutions, contact time, and filler dosage on the adsorption capacity of the composites were investigated. To study the influence of pretreatment on the filler, clinoptilolite was activated using KCl, NaCl, and HCl. Adsorption results show that equilibrium was reached after 24 h, and that sorption reached its maximum at pH values between 5 and 7. The selectivity trend was observed to be Pb > Cu > Co, which was consistent for both single and mixed metal‐ion solutions. Pretreatment significantly increased adsorption capacity of the composite, but was dependent on the conditioning reagent. Nanocomposites filled with HCl‐activated particles demonstrated a high adsorption capacity of between 70 and 80% for all three metals, while KCl‐activated particles were the least efficient with a maximum adsorption capacity of 69% for Pb(II), 54% for Cu(II) and 48% for Co(II). The adsorption data were then fitted to both Langmuir and Freundlich isotherms over the entire concentration range, and the Langmuir isotherm showed a better fit of the experimental sorption data than the Freundlich isotherm. The results obtained show that this simple methodology which can be up‐scaled has great potential for the preparation of a wide variety of similar particle‐filled adsorbent nanocomposites in other environmental remediation applications. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Sorption of Pb(II), Cd(II) and Zn(II) by iminodiacetate chelating resins in non-competitive and competitive conditions

Two chelating resins (CRs) bearing iminodiacetate (IDA) groups derived from acrylonitrile - divinylbenzene (AN-DVB) copolymers having 10 and 15 wt.% nominal cross-linking degrees and a high mobility of the functional groups caused by the presence of a longer spacer between the matrix and the IDA groups were synthesized and tested as sorbents for heavy metal ions like: Pb(II), Cd(II) and Zn(II) from aqueous solutions by batch and column techniques. Experimental data obtained from batch equilibrium tests have been analyzed by two isotherm models: Freundlich and Langmuir. The overall adsorption tendency of CRs toward Pb(II), Cd(II) and Zn(II), under non-competitive conditions, followed the order: Cd(II) > Pb(II) > Zn(II). Selectivity studies were performed in ternary mixture of Pb(II), Cd(II) and Zn(II) to check if the synthesized CRs can be useful for selective separation of heavy metal cations. The results revealed that the CRs with IDA groups exhibited high selectivity toward Pb(II), both in batch and column techniques. Regeneration of the resins was achieved using 0.1 M HCl solution.     

Kinetic and equilibrium studies of Pb(II) and Cd(II) removal from aqueous solution onto colemanite ore waste

The adsorption characteristics of Pb(II) and Cd(II) onto colemanite ore waste (CW) from aqueous solution were investigated as a function of pH, adsorbent dosage, contact time, and temperature. Langmuir, Freundlich and Dubinin-Radushkevich (D-R) models were applied to describe the adsorption isotherms. Langmuir model fitted the equilibrium data better than the Freundlich isotherm. The adsorption capacity of CW was found to be 33.6 mg/g and 29.7 mg/g for Pb(II) and Cd(II) ions, respectively. Analyte ions were desorbed from CW using both 1 M HCl and 1 M HNO₃. The recovery for both metal ions was found to be higher than 95%. The mean adsorption energies evaluated using the D-R model indicated that the adsorption of Pb(II) and Cd(II) onto CW were taken place by chemisorption. The thermodynamic parameters (ΔG^o, ΔH^o and ΔS^o) showed that the adsorption of both metal ions was feasible, spontaneous and exothermic at 20-50 °C. Adsorption mechanisms were also investigated using the pseudo-first-order and pseudo-second-order kinetic models. The kinetic results showed that the adsorption of Pb(II) and Cd(II) onto CW followed well pseudo-second order kinetics.     

Chelation of Cu(II), Zn(II), and Fe(II) by Tannin Constituents of Selected Edible Nuts

The tannin fractions isolated from hazelnuts, walnuts and almonds were characterised by colorimetric assays and by an SE-HPLC technique. The complexation of Cu(II) and Zn(II) was determined by the reaction with tetramethylmurexide, whereas for Fe(II), ferrozine was employed. The walnut tannins exhibited a significantly weaker reaction with the vanillin/HCl reagent than hazelnut and almond tannins, but the protein precipitation capacity of the walnut fraction was high. The SE-HPLC chromatogram of the tannin fraction from hazelnuts revealed the presence of oligomers with higher molecular weights compared to that of almonds. Copper ions were most effectively chelated by the constituents of the tannin fractions of hazelnuts, walnuts and almonds. At a 0.2 mg/assay addition level, the walnut tannins complexed almost 100% Cu(II). The Fe(II) complexation capacities of the tannin fractions of walnuts and hazelnuts were weaker in comparison to that of the almond tannin fraction, which at a 2.5 mg/assay addition level, bound Fe(II) by ~90%. The capacity to chelate Zn(II) was quite varied for the different nut tannin fractions: almond tannins bound as much as 84% Zn(II), whereas the value for walnut tannins was only 8.7%; and for hazelnut tannins, no Zn(II) chelation took place at the levels tested.     

Arsenic adsorption using copper (II) oxide nanoparticles

Arsenic poisoning is a major problem in today's life. To reduce its concentration in drinking water, different metal based compounds were explored as arsenic adsorbents. In the present study, copper (II) oxide nanoparticles were prepared by thermal refluxing technique and used as an adsorbent for arsenic removal from water. Characterization of the adsorbent using TEM, BET, XRD and FTIR implied that the prepared adsorbent was in nano size and had excellent adsorption behavior with surface area of 52.11 m²/g. Systematic adsorption experiments were carried out with different process parameters such as contact time, adsorbent mass, pH, temperature and stirring speed and found that copper (II) oxide had very good efficiency towards arsenic adsorption. Thermodynamic parameters and adsorption kinetics were studied in detailed to know the nature and mechanism of adsorption. Results showed that the adsorption process followed pseudo second order kinetic and endothermic behavior. Adsorption equilibrium was studied with Langmuir and Freundlich isotherm models. The adsorption process followed Langmuir isotherm with an adsorption capacity of 1086.2 μg/g. A regeneration study was proposed in order to reuse the adsorbent for better economy of the process. Finally, a process design calculation is reported to know the amount of adsorbent required for efficient removal of arsenic from aqueous medium.     

Pb(II) biosorption using DAP/EDTA-modified biopolymer (Chitosan)

Abstract

In this study, chitosan was chemically modified with only diammonium phosphate (DAP) and DAP/EDTA (ethylenediaminetetraacetic acid) mixture for the removal of Pb(II) ions from aqueous solution. Modified chitosan forms were analyzed using thermo-gravimetric analyzer (TGA), Fourier transform infrared (FTIR) spectroscopy, and scanning electron microscopy (SEM) to investigate the thermal degradation behavior, structural modifications, and the surface texture of the cross-linked chitosan adsorbents, respectively. The adsorption results were analyzed by well-known kinetic and isotherm models. The kinetics of metal adsorption followed the pseudo-second-order model. The maximum sorption capacities obtained from the Langmuir isotherm model were 126?mg/g for diammonium phosphate-modified Chitosan (DMC) and 137?mg/g for DAP/EDTA-modified chitosan (EDMC). The thermodynamic analysis showed that the metal removal process was endothermic in nature.     

Removal Characteristics of Cd(II), Cu(II), Pb(II), and Zn(II) by Natural Mongolian Zeolite through Batch and Column Experiments

The removal characteristics of Cd(II), Cu(II), Pb(II), and Zn(II) from model aqueous solutions by 5 natural Mongolian zeolites were investigated. The adsorption of metals on zeolites reached a plateau value within 6 h. The adsorption kinetic data were fitted with adsorption kinetic models. The equilibrium adsorption capacity of the zeolites was measured and fitted using Langmuir and Freundlich isotherm models. The order of adsorption capacity of zeolite was Pb(II) > Zn(II) > Cu(II) > Cd(II). The maximum adsorption capacity of natural zeolite depends on its cation exchange capacity and pH. The leaching properties of metals were simulated using four leaching solutions. The results show that natural zeolite can be used as an adsorbent for metal ions from aqueous solutions or as a stabilizer for metal-contaminated soils.     

Composite nanofibers of polyacrylonitrile/natural clay for decontamination of water containing Pb(II), Cu(II), Zn(II) and pesticides

Composite nanofibers containing polyacrylonitrile and natural clay particles were fabricated and investigated for the removal of Pb(II), Cu(II) and Zn(II) from aqueous solutions. The adsorption behavior of Pb(II), Cu(II) and Zn(II) can be well described by the Langmuir adsorption model and high loading capacities at pH 7 were obtained. The kinetics of the adsorption process showed that equilibrium was attained after 60 min and the experimental data followed a pseudo-first-order model. The nanocomposites were also tested for photocatalytic degradation of Monocrotophos pesticides in which high degradation efficiency (>90%) was obtained in less than 60 min.     

Separation and concentration processes of solutions of Co(II), Ni(II), Cr(III), Fe(III) and Mn(II) by extraction with toluene-dissolved rosin

The extraction and stripping of Co(II), Ni(II), Cr(III) and Fe(III) from aqueous solutions by rosin dissolved in toluene has been investigated. Results obtained show that rosin is better extractant than abietic or n-lauric acids under comparable conditions. From these results, and the data of Mn(II) solvent extraction studied previously under the same conditions, a separation and concentration process for these five cations in aqueous solutions has been designed. Saturated solutions of Fe(III), Cr(III), Mn(II) and finally Co(II) and Ni(II) have been obtained successively by extraction and stripping, by addition of ammonium hydroxide to obtain the appropriate pH value, and by modifying adequately the organic phase/aqueous phase volume ratio.     

Synergistic Solvent Extraction and Transport of Zn(II) and Cu(II) across Polymer Inclusion Membranes with a Mixture of TOPO and Aliquat 336

Separation of zinc(II) and copper(II) ions from aqueous solutions by synergistic extraction and transport through polymer inclusion membranes (PIMs) has been investigated. A mixture of trioctylphosphine oxide (TOPO) and trioctymethylammonium chloride (Aliquat 336) was used as a selective extractant as well as an ion carrier in polymer membranes. The effects of hydrochloric acid concentration in the aqueous phase and extractants concentration in the organic phase on the separation process of zinc(II) and copper(II) ions have been studied. Zn(II) ions were successfully separated from Cu(II) ions in solvent extraction process using 0.025 M TOPO and 0.06 M Aliquat 336 in kerosene. Polymer inclusion membranes (PIMs) containing a mixture of TOPO and Aliquat 336 as the ion carrier have been prepared and the facilitated transport of Zn(II) and Cu(II) ions has been studied. The influence of membrane composition on the transport kinetic of Zn(II) and Cu(II) has been evaluated. Zn(II) ions were preferably transported from the aqueous solutions containing Cu(II) and above 87% of Zn(II) ions were effectively recovered from the 0.5 M HCl solution as the source phase through PIM into 0.5 M H₂SO₄ as the stripping phase.     

Equilibrium and kinetic studies of chromium ions adsorption on Co (II)-based phosphonate metal organic frameworks

Chromium is present in wastewaters resulted from a lot of industrial processes such as electroplating, dye, cement, leather tanning, and paint. Its presence at values higher than maximum admitted value of 0.05 mg/L can affect the human health and the environment. Therefore, it is essential to remove chromium from wastewaters before discharge. In this study, the adsorption potential of three types of Co (II)-based phosphonate metal organic frameworks, obtained by the reaction of CoSO₄.7H₂O with phosphonoacetic acid (CP), N,N-bis(phosphonomethyl)glycine (Gly), or vinyl phosphonic acid (VP) in hydrothermal conditions, has been investigated. The study involves batch types experiments investigating the effects of the solution pH, solid:liquid ratio, initial concentration of Cr(VI), and contact time upon the adsorption efficiency of the studied materials. Langmuir, Freundlich, Temkin, and Dubinin–Radushkevich were applied to adsorption equilibrium data to find the best among these models. The kinetics of adsorption was found to follow the pseudo-second-order model. It was found that the adsorption efficiency of the studied materials in the removal process of Cr(VI) ions from aqueous solutions is in the following order: Co-CP<Co-Gly< Co-VP.     

Cadmium adsorption on modified chitosan‐coated bentonite: batch experimental studies

BACKGROUND: Several researchers have investigated the use of chitosan as an adsorbent for removal of heavy metals from aqueous streams. Chitosan flake or powder swells and crumbles making it unsuitable for use in an adsorption column. Chitosan also has a tendency to agglomerate or form a gel in aqueous media. The adsorption capacity can be enhanced by spreading chitosan on physical supports that can increase the accessibility of the metal binding sites. Although several attempts have been made to enhance the adsorption capacity of chitosan, using various chemicals, the sorption capacity for metal ions decreased after cross‐linking of chitosan. RESULTS: Bentonite was coated with chitosan (Chi) and its derivative, 3,4‐dimethoxy‐benzaldehyde (Chi/DMB). The product was then used as adsorbent for the removal of Cd²⁺ from aqueous solutions. The presence of imine groups resulting from chemical modification was confirmed using IR, DRS and SEM. The adsorption followed the Langmuir isotherm and could be described by pseudo‐second order kinetics. CONCLUSION: Chi/DMB coated on bentonite increased the accessibility of metal binding sites. The Chi/DMB/bentonite showed no significant pH dependence in the pH range 2–9, but bentonite coated with chitosan revealed very intensive pH dependence, which had a considerable effect on cadmium removal. As expected adsorption of Cd²⁺ by Chi/bentonite and Chi/DMB/bentonite is dependent on contact time and adsorbent dose. In addition, an EDTA solution is suitable for desorption of cadmium ions, and the reusability of Chi/DMB/bentonite is quite good. © 2012 Society of Chemical Industry     

Removal of Cd(II), Pb(II), Cu(II) and Ni(II) from water using modified pine bark

This paper describes the removal of Cd(II), Pb(II), Cu(II), and Ni(II) ions from aqueous solutions using chemically modified pine barks (Pinus nigra). In this article, effects of chemical modification methods on the adsorption capacity have been investigated. Changes of the surface properties were examined by the FTIR, SEM and zeta potential analyses. HCl, NaOH, Fenton reactive, polymerization, acetone, ethanol, chloroform, tetra ethylene glycol, diethyl ether and glycol were used for modification processes. Maximum adsorption capacities were obtained by modification with NaOH (13-20 mg/g), Fenton (12-17 mg/g) and polymerization (12-16.5 mg/g). These modification processes also decreased Chemical Oxygen Demand of water from 1820 mg/L for raw pine barks to 35 mg/L for NaOH modified barks. Adsorption capacities of adsorbents increased from 2 mg/g to 20 mg/g as a result of modification that accordingly increase adsorbent surface activity.     

Selective Transport of Cu(II) across a Polymer Inclusion Membrane with 1-Alkylimidazole from Nitrate Solutions

The selective transport of copper(II), zinc(II), cobalt(II), and nickel(II) ions from nitrate solutions across polymer inclusion membranes (PIMs), which consist of cellulose triacetate as polymeric support, o-nitrophenyl pentyl ether as plasticizer, and 1-alkylimidazole (alkyl from hexyl- to decyl) as ion carrier was reported. PIM was characterized by using atomic force microscopy (AFM) technique. The results show that Cu(II) can be separated very effectively from other transition metal cations as Zn(II), Co(II), and Ni(II) (at a concentration of 10^?3 mol/dm³ each). Alkyl substituents at position 1 of the imidazole ring have been found to affect the hydrophobic properties and initial flux of the transported metal ions. The efficiency of separation of metal ions by 1-alkylimidazole followed the sequence: Cu(II) > Zn(II) > Co(II) > Ni(II). The highest selectivity coefficient for Cu(II) was found with 1-hexylimidazole and its 1 mol/dm³ solution in PIM. Separation of the ions was more effective for the nitrates(V) than for chlorides.     

Biosorption of Cu(II) onto agricultural materials from tropical regions

BACKGROUND: In Ghana, the discharge of untreated gold mine wastewater contaminates the aquatic systems with heavy metals such as copper (Cu), threatening ecosystem and human health. The undesirable effects of these pollutants can be avoided by treatment of the mining wastewater prior to discharge. In this work, the sorption properties of agricultural materials, namely coconut shell, coconut husk, sawdust and Moringa oleifera seeds for Cu(II) were investigated. RESULTS: The Freundlich isotherm model described the Cu(II) removal by coconut husk (R² = 0.999) and sawdust (R² = 0.993) very well and the Cu(II) removal by Moringa oleifera seeds (R² = 0.960) well. The model only reasonably described the Cu(II) removal by coconut shell (R² = 0.932). A maximum Cu(II) uptake of 53.9 mg g^?1 was achieved using the coconut shell. The sorption of Cu(II) onto coconut shell followed pseudo‐second‐order kinetics (R² = 0.997). FTIR spectroscopy indicated the presence of functional groups in the biosorbents, some of which were involved in the sorption process. SEM‐EDX analysis confirmed an exchange of Mg(II) and K(I) for Cu(II) on Moringa oleifera seeds and K(I) for Cu(II) on coconut shell. CONCLUSION: This study shows that coconut shell can be an important low‐cost biosorbent for Cu(II) removal. The results indicate that ion exchange, precipitation and electrostatic forces were involved in the Cu(II) removal by the biosorbents investigated. Copyright © 2011 Society of Chemical Industry     

Sorption of Cd(II), Co(II), and Zn(II) Complexes with MGDA on Anion Exchange Resins: A Study of the Influence of Various Parameters

The strongly basic polystyrene gel resins Amberjet 4200, Amberjet 4600, and the macroporous strongly basic polystyrene Purolite A 520E were investigated for their sorption properties towards Cd(II), Co(II), and Zn(II) complexes with MGDA. The object of the study was the sorption behavior of three metal ions on the above-mentioned anion exchangers, depending on the metal ions’ concentration, pH, contact time, and temperature. MGDA is an alternative, environmentally friendly complexing agent. The sorption data were fitted to the Langmuir and Freundlich models. Three different kinetic behaviors: pseudo first order, pseudo second order, and intraparticle diffusion were tested. The variations of thermodynamic functions were also calculated.     

Synergistic extraction and separation of Fe(III) and Zn(II) using TBP and D2EHPA

Waste chloride pickle liquors from hot-dip galvanizing plants, steel plants and flue dust contain reasonable amounts of heavy metals such as Zn, Cr, Ni, etc. Iron is invariably associated with most of these materials and comes into solution during leaching. Thus, the synergistic extraction of zinc(II) and iron(III) from leach solutions in tri-n-butyl phosphate (TBP)–di(2-ethylhexyl) phosphoric acid (D2EHPA) system diluted in kerosene was investigated. The Zn and Fe concentrations in the leach liquor used in the present study were 2 g/L. Experiments were carried out in the pH range of 0.5–4.0, temperature of 25°C, using sole D2EHPA, sole TBP and D2EHPA–TBP mixtures at different ratios. Results showed that the co-extraction of zinc(II) and iron(III) increased with increasing equilibrium pH using D2EHPA. It is demonstrated that the mixtures of TBP and D2EHPA are more efficient and selective than D2EHPA alone. At low pH values, the separation factor is low when pure D2EHPA is used as an extractant; however, using TBP as a synergist, the separation factor increases and results in a better separation of zinc from iron. Increasing TBP to D2EHPA ratios in the organic phase caused a slight shift to the right in the extraction isotherm of iron and a marked shift to the right in the extraction isotherm of zinc, and the maximum separation factor of 13.3 × 10³ was achieved at a TBP to D2EHPA volume ratio of 4:1 (0.58 M TBP: 0.12 M D2EHPA). Furthermore, the effect of equilibrium pH, organic to aqueous phase ratio and Cl^? concentration on the selective extraction was investigated. Using two extraction stages at the O/A ratio of 2:1 and pH_e (equilibrium pH) of 3 and 1 for zinc and iron, respectively, 99% of zinc(II) and 96.25% of iron(III) were extracted.