Removal of Cu(II), Fe(III), and Cr(III) from Aqueous Solution by Aniline Grafted Silica Gel

Abstract

The aniline moiety was covalently grafted onto silica gel surface. The modified silica gel with aniline groups (SiAn) was used for removal of Cu(II), Fe(III), and Cr(III) ions from aqueous solution and industrial effluents using a batch adsorption procedure. The maximum adsorption of the transition metal ions took place at pH 4.5. The adsorption kinetics for all the adsorbates fitted better the pseudo second‐order kinetic model, obtaining the following adsorption rate constants (k₂): 1.233 · 10^?2, 1.902 · 10^?2, and 8.320 · 10^?3 g · mg^?1 min^?1 for Cr(III), Cu(II), and Fe(III), respectively. The adsorption of these transition metal ions were fitted to Langmuir, Freundlich, Sips, and Redlich‐Peterson isotherm models; however, the best isotherm model fitting which presented a lower difference of the q (amount adsorbed per gram of adsorbent) calculated by the model from the experimentally measured, was achieved by using the Sips model for all adsorbates chosen. The SiAn adsorbent was also employed for the removal of the transition metal ions Cr(III) (95%), Cu(II) (95%), and Fe(III) (94%) from industrial effluents, using the batch adsorption procedure.     

Adsorption performance and physicochemical mechanism of MnO2-polyethylenimine-tannic acid composites for the removal of Cu(II) and Cr(VI) from aqueous solution

In this work, an adsorbent, which we call MnPT, was prepared by combining MnO₂, polyethylenimine and tannic acid, and exhibited efficient performance for Cu(II) and Cr(VI) removal from aqueous solution. The oxygen/nitrogen-containing functional groups on the surface of MnPT might increase the enrichment of metal ions by complexation. The maximum adsorption capacities of MnPT for Cu(II) and Cr(VI) were 121.5 and 790.2 mg·g⁻¹, respectively. The surface complexation formation model was used to elucidate the physicochemical interplay in the process of Cu(II) and Cr(VI) co-adsorption on MnPT. Electrostatic force, solvation action, adsorbate–adsorbate lateral interaction, and complexation were involved in the spontaneous adsorption process. Physical electrostatic action was dominant in the initial stage, whereas chemical action was the driving force leading to adsorption equilibrium. It should be noted that after adsorption on the surface of MnPT, Cr(VI) reacted with some reducing functional groups (hydroxylamine-NH₂) and was converted into Cr(III). The adsorption capacity declined by 12% after recycling five times. Understanding the adsorption mechanism might provide a technical basis for the procedural design of heavy metal adsorbents. This MnPT nanocomposite has been proven to be a low-cost, efficient, and promising adsorbent for removing heavy metal ions from wastewater.     

Adsorption of Cr(III), Ni(II), Zn(II), Co(II) ions onto phenolated wood resin

In this study, phenolated wood resin was used an adsorbent for the removal of Cr(III), Ni(II), Zn(II), Co(II) ions by adsorption from aqueous solution. The adsorption of metal ions from solution was carried at different contact times, concentrations and pHs at room temperature (25°C). For individual metal ion, the amount of metal ions adsorbed per unit weight of phenolated wood resin at equilibrium time increased with increasing concentration and pH. Also, when the amounts of metal ions adsorbed are compared to each other, it was seen that this increase was order of Cr(III) > Ni(II) > Zn(II) > Co(II). This increase was order of Cr(III) > Ni(II) > Co(II) > Zn(II) for commercial phenol–formaldehyde resin. Kinetic studies showed that the adsorption process obeyed the intraparticle diffusion model. It was also determined that adsorption isotherm followed Langmuir and Freundlich models. Adsorption isotherm obtained for commercial phenol–formaldehyde resin was consistent with Freundlich model well. Adsorption capacities from Langmuir isotherm for commercial phenol–formaldehyde resin were higher than those of phenolated wood resin, in the case of individual metal ions. Original adsorption isotherm demonstrated the monolayer coverage of the surface of phenolated wood resin. Adsorption kinetic followed the intraparticle diffusion model. The positive values of ΔG° determined using the equilibrium constants showed that the adsorption was not of spontaneous nature. It was seen that values of distribution coefficient (K_D) decreasing with metal ion concentration in solution at equilibrium (C_e) indicated that the occupation of active surface sites of adsorbent increased with metal ions. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2838–2846, 2006     

A new functionalized reduced graphene oxide adsorbent for removing heavy metal ions in water via coordination and ion exchange

ABSTRACT

Heavy metal ion pollution has become a serious problem. In this paper, a new type of adsorbent, reduced graphene oxide grafted by 4-sulfophenylazo groups (RGOS), was synthesized to adsorb heavy metal ions in an aqueous solution via two kinds of adsorption modes, ion exchange and coordination. The maximum adsorption capacities of the RGOS for Pb(II), Cu(II), Ni(II), Cd(II) and Cr(III) were 689, 59, 66, 267 and 191 mg/g, respectively. Adsorption equilibrium time of RGOS for heavy metal ions is no more than 10 min. Adsorption mechanism was supposed based on elemental analyses, adsorption data, and Fourier transform infrared spectra.     

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.     

Metal ion adsorption behavior of lignocellulosic fiber–ethylene vinyl acetate composites

This study describes the applicability of lignocellulosic fiber dispersed in ethylene vinyl acetate (EVA) to adsorb Pb(II), Cr(III), and Cr(VI) ions in aqueous solutions. Water absorption studies revealed that metal‐ion uptake does not only take place on the surface of the adsorbent but ions can also diffuse into the composite. The adsorption of the metal ions under different experimental conditions was studied. Solute concentration, pH, and contact time were used to assess the adsorption capacity and efficiency. The amount of metal adsorbed increased to 7 mg/g with an increase in solute concentration but compromising the efficiency. Adsorption equilibrium was reached after 3 h, when the maximum lead adsorption was above 80%. The optimum pH for the adsorption of Pb(II) and Cr(III) was 6.5, and pH 2.5 was used for the adsorption of Cr(VI). Competitive adsorption revealed the order of adsorption to be: Pb(II) > Cr(VI) > Cr(III). POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Heterocyclic modification of chitosan for the adsorption of Cu (II) and Cr (VI) ions

A heterocyclic modification of chitosan has been attempted for development of an effective adsorbent material for removal of metal ions. The modified polymer was characterized using infrared (IR) spectroscopy, thermogravimetric analysis (TGA), scanning electron microscopy (SEM), energy dispersive x-ray spectroscopy (EDS) and x-ray diffraction (XRD) techniques. The adsorption capacity exhibited for Cu (II) and Cr (VI) were 83.75 and 85.0 mgg^?1, respectively, which is a significant improvement over chitosan. The adsorption on the modified polymer was a second-order kinetic process and followed Langmuir isotherm model. The thermodynamic analysis indicated exothermic and spontaneous nature of adsorption. About 80% of the adsorbed metal ions were desorbed in appropriate stripping solutions indicating reusability.     

Implications of the structure of cementitious wastes containing Pb(II), Cd(II), As(V), and Cr(VI) on the leaching of metals

Cement stabilisation has been widely applied for the immobilisation of heavy metal ions before their disposal in landfills. This paper investigated the microstructure of cementitious wastes containing Pb, Cd, As, and Cr using an electron probe microanalyser and examined the implications of the microstructure on the leaching of the metal ions. From the microstructure analysis, it was proposed that Pb, As, and Cr ions were homogeneously dispersed in the calcium silicate hydrate (C-S-H) matrix by adsorption or precipitation with calcium or silicate compounds present in the cement. However, Cd formed discrete Cd(OH)₂ precipitates believed to be contained within the cement pores or adsorbed on the C-S-H matrix. The leaching of metals in the pH region of 6 to 8 decreased in the following order: Cr(VI)>Cd(II)>Pb(II)>As(V). This leaching trend was found to be influenced by the manner in which the metal ions were incorporated into the cement matrix.     

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     

Selective Adsorption of Mo(VI) From Re(VII) Containing Effluent on Orange Waste Gel Modified by Ethylenediamine,Diethylamine, and Triethylamine

New adsorption gels were prepared by chemically immobilizing functional groups of ethylenediamine, diethylamine and/or triethylamine on orange waste, named OW-en, OW-DEA, and OW-TEA, respectively. By comparing with the adsorption of other coexisting metals, such as Re(VII), Pb(II), Fe(III), Zn(II), Mn(VII), Ca(II), and Cu(II), the novel gels exhibited selectivity only for Mo(VI) and the adsorption behavior obeys the Langmuir model. The maximum adsorption capacity for molybdenum was in the order, OW-en (2.17 mol/kg) > OW-TEA (1.26 mol/kg) > OW-DEA (0.88 mol/kg). A kinetic study for the adsorption of molybdenum at various temperatures confirmed that the endothermic adsorption process followed pseudo-second order kinetics. In addition, its excellent adsorption characteristics for Mo(VI) were confirmed by the adsorption and elution tests using a column packed with the OW-en gel, especially by separation of Mo(VI) from Mo-Re containing industrial effluent.     

Adsorption of copper(II), cobalt(II), and iron(III) ions from aqueous solutions on poly(ethylene terephthalate) fibers

The adsorption behavior of poly(ethylene terephthalate) (PET) fibers towards copper(II), cobalt(II), and iron(III) ions in aqueous solutions was studied by a batch equilibriation technique. Influence of treatment time, temperature, pH of the solution, and metal ion concentration on the adsorption were investigated. Adsorption values for metal ion intake followed the following order: Co(II) > Cu(II) > Fe(III). One hour of adsorption time was found sufficient to reach adsorption equilibrium for all the ions. The rate of adsorption was found to decrease with the increase in the temperature. Langmuir adsorption isoterm curves were found to be significant for all the ions studied. The heat of adsorption values were calculated as −5, −2.8, and −3.6 kcal/mol for Cu(II), Co(II), and Fe(III) ions, respectively. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1935–1939, 1998     

Uptake of Pb2+ Using N-Vinyl Imidazole Based Uniform Porous Hydrogels

The uniform porous and continuous phase lead (II) adsorbent hydrogel, was prepared by copolymerizing 2-hydroxyethyl methacrylate (HEMA), acrylic acid (AAc), and N,N′-methylenebisacrylamide (MBAAm), with n-vinyl imidazole (VIM). A series of hydrogels, including different ratios of VIM, were prepared by photopolymerization and characterized. The influence of the uptake conditions such as pH, functional monomer percent, contact time, initial feed concentration, and foreign metal ions on the metal ion binding capacity of hydrogel, were also tested. The selective chelation of heavy metal ions from synthetic wastewater was also studied. The affinity order on molar basis was observed as follows: Pb (II) > Zn (II) > Cd (II). Chelation behavior of heavy metal ions could be modelled using both the Langmuir and Freundlich isotherms and it was seen that the Langmuir isotherm model was the best fit for the adsorption of Pb (II) ions in P(VIM/AAc/HEMA) hydrogel. Moreover, the limits of detection and the quantification values were determined. Regeneration of the hydrogels was easily performed with 1 M HCl and the same hydrogel can be reused five times almost without any loss of adsorption capacity. All these features make P(VIM/AAc/HEMA) hydrogels potential candidate adsorbent for heavy metal removal.     

Removal of Heavy Metal Ions using New Chelating Material Containing N,O, and S Donor Sites

Abstract

A new chelating material (AT‐PHE‐HCHO) was synthesized by reacting 2‐aminothiazole‐phenol (AT‐PHE) azodye and formaldehyde (HCHO) in an alkaline medium. The materials were characterized by elemental analysis, FT‐IR and ¹H‐NMR spectroscopic studies. The chelating material was used for the adsorption of Cu(II), Zn(II), Mn(II), and Cr(III) from dilute aqueous solutions with variation of adsorption parameters. The adsorption was described quantitatively by fitting the equilibrium data to the Freundlich isotherm. The thermodynamic parameters ΔS and ΔH were calculated to be 86.02 J mol^?1 K^?1 and ?126.9 KJ mol^?1, respectively. The metal adsorption followed the sequence Cu(II)>Zn(II)～Cr(III)>Mn(II). The material was used for the removal of metal ions from synthetic as well as real samples.     

Adsorption of Cr (VI) Oxyanions onto Modified Wood Pulp

A new adsorbent was prepared from wood pulp (WP) after reaction with epichlorohydrin and dimethylamine in the presence of pyridine and N,N-dimethylformamide (DMF). The adsorption of Cr (VI) from aqueous solutions by the so-prepared wood pulp adsorbent (WP-A) was investigated. Various factors affecting adsorption, such as pH, adsorbent concentration (1–5 g/L), agitation time (5–60 min), and Cr (VI) concentration (50–700), were taken into consideration. The adsorption of Cr (VI) onto (WP-A) was found to be pH-dependent and maximum adsorption was obtained at pH 3. The adsorption data obeyed Langmuir and Freundlich adsorption isotherms. The Langmuir adsorption capacity (Q_max) was found to be 588.24 mg/g. Freundlich constants, K_F and n, were found to be 55.03 and 2.835, respectively.     

Adsorption studies of Cr(VI) and Cu(II) metal ions from aqueous solutions by synthesized Ag and Mg co-doped TiO2 nanoparticles

ABSTRACT

This communication provides the eliminating of heavy metals from water resources using Ag-Mg/TiO₂ nanoparticles. The nanoparticles with a size of 15 nm were prepared using sol-gel technique and used for the removal of Cr(VI) and Cu(II) from waste waters. Batch sorption studies were carried out to investigate the adsorption of the above metal ions for a concentration range of 0.1–10 mg/L. The maximum sorption capacity values were found to be 2.42 mg/g for Cr(VI) and 2.03 mg/g for Cu(II) at a concentration of 0.1 ppm. The mechanism of adsorption was also investigated. The results showed that both Freundlich and Dubinin–Radushkevitch isotherms were found to be the best fit for the adsorption of metals. The results from kinetic data reveal that the pseudo-second-order and Reichenberg film diffusion models were found to be well fit for the experimental data. The value of the thermodynamic parameter ΔH° revealed the endothermic adsorption process and negative value of ΔG° shows the feasibility and spontaneity of material–anion interaction. In addition, the method is considered to be simple and cost-effective, and shows excellent adsorption removal properties on heavy metals for industrial applications.     

Adsorption of Cu(II) and Cr(VI) onto Treated Shorea dasyphylla Bark: Isotherm,Kinetics, and Thermodynamic Studies

The efficacy of treated Shorea dasyphylla bark for Cu(II) and Cr(VI) adsorption was assessed in a batch adsorption system as a function of pH, agitation period, and initial metal concentration. The equilibrium nature of Cu(II) and Cr(VI) adsorption was described by the Freundlich, Langmuir, and Dubinin-Radushkevich isotherms. The maximum monolayer capacities of treated Shorea dasyphylla bark, estimated from the Langmuir equation were 184.66 and 42.72 mg/g for Cu(II) and Cr(VI), respectively. The experimental results were fitted using pseudo-first order, pseudo-second order and intraparticle diffusion kinetic models; the pseudo-second order showed the best conformity to the kinetic data. Thermodynamic parameters such as enthalpy change (ΔH°), free energy change (ΔG°) and entropy change (ΔS°) were determined by applying the Van't Hoff equation. The adsorption of Cu(II) and Cr(VI) onto treated Shorea dasyphylla bark was found to be spontaneous and exothermic. The adsorption mechanism was confirmed by means of Fourier transform infrared (FTIR) and Energy dispersive X-ray (EDX) spectroscopy. The dimensionless constant separation factor (R _L), indicated that treated Shorea dasyphylla bark was favorable for Cu(II) and Cr(VI) adsorption.     

Study on adsorption of Cu(II)–Cr(VI) binary system by carbonized Eupatorium adenophorum

We first report a mechanism study on the adsorption of Cu(II)-Cr(VI) binary mixture by a novel low-cost adsorbent, carbonized Eupatorium adenophorum. The influences by pH value, dosage, initial concentration, temperature, and adsorption time on its performance to absorb copper and chromium were investigated. The experimental data were fitted according to the Langmuir and Freundlich adsorption isotherm models, the pseudo-first-order kinetics, the pseudo-second-order kinetics, and the intra-particle diffusion model. The results indicated that when the reaction system was with its pH = 5, the dosage of carbonized Eupatorium adenophorum was 0.1 g, the adsorption time was 30 min, and the temperature was 25°C; the adsorption capacities for Cu(II) and Cr(VI) reached 27.62 mg/g and 9.68 mg/g, respectively. The process of carbonized Eupatorium adenophorum to absorb Cr(VI) is also accompanied by redox reactions. The Langmuir model and the pseudo-second-order model can better ?t the experimental data. Observation by fourier transform infrared spectroscopy (FTIR) and scanning electron microscope (SEM) found no significant change of functional groups before and after the adsorption by carbonized Eupatorium adenophorum, and this adsorption process is mainly a physical adsorption.     

Evaluation of sorption behavior of polymethylene-bis(2-hydroxybenzaldehyde) for Cu(II), Ni(II), Fe(III), Co(II) and Cd(II) ions

Poly[5,5??-methylene-bis(2-hydroxybenzaldehyde)1,2-phenylenediimine] resin was prepared and characterized by employing elemental, thermal analysis, FTIR, and UV?Cvisible spectroscopy. The metal uptake behavior of synthesized polymer towards Cu(II), Co(II), Ni(II), Fe(III) and Cd(II) ions was investigated and optimized with respect to pH, shaking speed, and equilibration time. The sorption data of all these metal ions followed Langmuir, Freundlich, and Dubinin?CRadushkevich isotherms. The Freundlich parameters were computed 1/n?=?0.31?±?0.02, 0.3091?±?0.02, 0.3201?±?0.05, 0.368?±?0.04, and 0.23?±?0.01, A?=?3.4?±?0.03, 4.31?±?0.02, 4.683?±?0.01, 5.43?±?0.03, and 2.8?±?0.05?mmol?g^?1 for Cu(II), Co(II), Ni(II), Fe(III), and Cd(II) ions, respectively. The variation of sorption with temperature gives thermodynamic quantity (??H) in the range of 36.72?C53.21?kJ/mol. Using kinetic equations (Morris?CWeber and Lagergren equations), values of intraparticle transport and the first-order rate constant was computed for all the five metals ions. The sorption procedure is utilized to preconcentrate these ions prior to their determination by atomic absorption spectrometer. It was found that the adsorption capacity values for metal-ion intake followed the following order: Cd(II)?>?Co(II)?>?Fe(III)?>?Ni(II)?>?Cu(II).     

Adsorption of Cr(VI) on Stipa tenacissima L (Alfa): Characteristics,kinetics and thermodynamic studies

This study aims to remove ionic Cr(IV) from aqueous solution using Stipa tenacissima L as a biomass source. The Arabic name for the plant Stipa tenacissima L is HALFA (ALFA) ; it belongs to the category of biosorbents agro-industrial origin. Stipa tenacissima L is from the center of the province of Djelfa Algeria. This biomass was characterized by various analytical techniques such as scanning electron microscopy, energy dispersive spectroscopy and Fourier-transform infrared spectroscopy. In order to optimize the operating conditions for the determination of ions of Cr(VI), the initial concentration of Cr(VI) ions, temperature, pH of the solution and the solid/liquid ratio were individually studied. According to the results, a fix rate of about 90% was recorded. Optimum biosorption conditions were found to be pH ~1, C_o = 50 mg/L, R = 5 g/L and T = 296 K. It was found that biosorption of Cr(VI) ions onto biomass of Stipa tenacissima L was better suitable to Langmuir model. The correlation coefficients for the second-order kinetic model obtained were found to be 0.996 for all concentrations. These indicate that the biosorption system studied belongs to the second-order kinetic model. Thermodynamics parameters as enthalpy, entropy of system and free energy were evaluated, which confirms the feasibility of the process. An empirical modeling was performed by using a 2⁴ full factorial design, and the regression equation for adsorption chromium (VI) was determined from the data. The initial metal ion concentration has the most positive pronounced effect in increasing the chromium (VI) adsorption, whereas the pH and adsorbent dosage have the most negative effect on the process.     

Removal of Chromium(VI) and Chromium(III) from Aqueous Solution by Grainless Stalk of Corn

Abstract

Grainless stalk of corn (GLSC) was tested for removal of Cr(VI) and Cr(III) from aqueous solution at different pH, contact time, temperature, and chromium/adsorbent ratio. The results show that the optimum pH for removal of Cr(VI) is 0.84, while the optimum pH for removal of Cr(III) is 4.6. The adsorption processes of both Cr(VI) and Cr(III) onto GLSC were found to follow first-order kinetics. Values of k _ads of 0.037 and 0.018 min^?1 were obtained for Cr(VI) and Cr(III), respectively. The adsorption capacity of GLSC was calculated from the Langmuir isotherm as 7.1 mg g^?1 at pH 0.84 for Cr(VI), and as 7.3 mg g^?1 at pH 4.6 for Cr(III), at 20°C. At the optimum pH for Cr(VI) removal, Cr(VI) reduces to Cr(III). EPR spectroscopy shows the presence of Cr(V) + Cr(III)-bound-GLSC at short contact times and adsorbed Cr(III) as the final oxidation state of Cr(VI)-treated GLSC. The results indicate that, at pH ≈ 1, GLSC can completely remove Cr(VI) from aqueous solution through an adsorption-coupled reduction mechanism to yield adsorbed Cr(III) and the less toxic aqueous Cr(III), which can be further removed at pH 4.6.