Comparative Study of Zn2+, Cd2+, and Pb2+ Removal From Water Solution Using Natural Clinoptilolitic Zeolite and Commercial Granulated Activated Carbon. Equilibrium of Adsorption

Abstract

The aim of this work is to study the effectiveness of regional, low-cost natural clinoptilolitic zeolite tuff in heavy metal ions removal from aqueous solution, through comparative study with commercial granulated activated carbon. The equilibrium of adsorption of Cd²⁺, Pb²⁺, and Zn²⁺ on both adsorbents have been determined at 25, 35, and 45°C in batch mode. The granulated activated carbon has shown around three times higher adsorption capacity for Cd²⁺ and Zn²⁺ than natural zeolite, and almost the same adsorption capacity for Pb²⁺ as the natural zeolite. The metal ion selectivity series Pb²⁺ > Cd²⁺ > Zn²⁺, on a mass basis, has been obtained on both adsorbents. The Langmuir and Freundlich model have been used to describe the adsorption equilibrium. The thermodynamic parameters were calculated from the adsorption isotherm data obtained at different temperatures. The study of the influence of the acidity of the metal ion aqueous solution has shown an increase of metal ion uptake with increase of the pH. The sorption mechanism of Cd²⁺, Pb²⁺, and Zn²⁺ on natural zeolite changes from ion-exchange to ion-exchange and adsorption of metal-hydroxide with increase of the pH from 2 to 6 (and 7 for Zn²⁺). The preliminary cost calculation, based on adsorbents maximum adsorption capacity and their price, have revealed the potential of natural zeolite as an economic alternative to the granulated activated carbon in the treatment of heavy metal polluted wastewater.     

Synthesis of magnetic Fe3O4@SiO2-(-NH2/-COOH) nanoparticles and their application for the removal of heavy metals from wastewater

In this work, Fe₃O₄@SiO₂-(-NH₂/-COOH) nanoparticles were synthesized for the removal of Cd²⁺, Pb²⁺ and Zn²⁺ ions from wastewater. The results of characterization showed that Fe₃O₄@SiO₂-(-NH₂/-COOH) was superparamagnetic with a core–shell structure. The surface of Fe3O4 was successfully coated with silica and modified with amino groups and carboxyl groups through the use of a silane coupling agent, polyacrylamide and polyacrylic acid. The dispersion of the particles was improved, and the surface area of the Fe3O4@SiO2-(-NH2/-COOH) nanoparticles was 67.8 m²/g. The capacity of Fe₃O₄@SiO₂-(-NH₂/-COOH) to adsorb the three heavy metals was in the order Pb²⁺ > Cd²⁺ > Zn²⁺, and the optimal adsorption conditions were an adsorption dose of 0.8 g/L, a temperature of 30°C and concentrations of Pb²⁺, Cd²⁺ and Zn²⁺ below 120, 80 and 20 mg/L, respectively. The maximum adsorption capacities for Pb²⁺, Cd²⁺ and Zn²⁺ were 166.67, 84.03 and 80.43 mg/g. The adsorption kinetics followed a pseudo-second-order model and Langmuir isotherm model adequately depicted the isotherm adsorption process. Thermodynamic analysis showed that the adsorption of the three metal ions was an endothermic process and that increasing the temperature was conducive to this adsorption.     

Adsorption capacity and removal efficiency of heavy metal ions by Moso and Ma bamboo activated carbons

In order to understand the adsorption capacity and removal efficiency of heavy metal ions by Moso and Ma bamboo activated carbons, the carbon yield, specific surface area, micropore area, zeta potential, and the effects of pH value, soaking time and dosage of bamboo activated carbon were investigated in this study. In comparison with once-activated bamboo carbons, lower carbon yields, larger specific surface area and micropore volume were found for the twice-activated bamboo carbons. The optimum pH values for adsorption capacity and removal efficiency of heavy metal ions were 5.81–7.86 and 7.10–9.82 by Moso and Ma bamboo activated carbons, respectively. The optimum soaking time was 2–4 h for Pb²⁺, 4–8 h for Cu²⁺ and Cd²⁺, and 4 h for Cr³⁺ by Moso bamboo activated carbons, and 1 h for the tested heavy metal ions by Ma bamboo activated carbons. The adsorption capacity and removal efficiency of heavy metal ions of the various bamboo activated carbons decreased in the order: twice-activated Ma bamboo carbons > once-activated Ma bamboo carbons > twice-activated Moso bamboo carbons > once-activated Moso bamboo carbons. The Ma bamboo activated carbons had a lower zeta potential and effectively attracted positively charged metal ions. The removal efficiency of heavy metal ions by the various bamboo activated carbons decreased in the order: Pb²⁺ > Cu²⁺ > Cr³⁺ > Cd²⁺.     

Competitive adsorption of Pb, Cu and Cd ions from aqueous solutions by multiwalled carbon nanotubes

The individual and competitive adsorption capacities of Pb²⁺, Cu²⁺ and Cd²⁺ by nitric acid treated multiwalled carbon nanotubes (CNTs) were studied. The maximum sorption capacities calculated by applying the Langmuir equation to single ion adsorption isotherms were 97.08 mg/g for Pb²⁺, 24.49 mg/g for Cu²⁺ and 10.86 mg/g for Cd²⁺ at an equilibrium concentration of 10 mg/l. The competitive adsorption studies showed that the affinity order of three metal ions adsorbed by CNTs is Pb²⁺>Cu²⁺>Cd²⁺. The Langmuir adsorption model can represent experimental data of Pb²⁺ and Cu²⁺ well, but does not provide a good fit for Cd²⁺ adsorption data. The effects of solution pH, ionic strength and CNT dosage on the competitive adsorption of Pb²⁺, Cu²⁺ and Cd²⁺ ions were investigated. The comparison of CNTs with other adsorbents suggests that CNTs have great potential applications in environmental protection regardless of their higher cost at present.     

Removal of metal ions using lignite in aqueous solution—Low cost biosorbents

Turkish lignite can be used as a new adsorption material for removing some toxic metals from aqueous solution. The adsorption of lignite (brown young coals) to remove copper (Cu²⁺), lead (Pb²⁺), and nickel (Ni²⁺) from aqueous solutions was studied as a function of pH, contact time, metal concentration and temperature. Adsorption equilibrium was achieved between 40 and 70 min for all studied cations except Pb²⁺, which is between 10 and 30 min. The adsorption capacities are 17.8 mg/g for Cu²⁺, 56.7 mg/g for Pb²⁺, 13.0 mg/g for Ni²⁺ for BC₁ (Ilg?n lignite) and 18.9 mg/g for Cu²⁺, 68.5 mg/g for Pb²⁺, 12.0 mg/g for Ni²⁺ for BC₂ (Beysehir lignite) and 7.2 mg/g for Cu²⁺, 62.3 mg/g for Pb²⁺, 5.4 mg/g for Ni²⁺ for AC (activated carbon). More than 67% of studied cations were removed by BC₁ and 60% BC₂, respectively from aqueous solution in single step. Whereas about 30% of studied cations except Pb²⁺, which is 90%, were removed by activated carbon. Effective removal of metal ions was demonstrated at pH values of 3.8–5.5. The adsorption isotherms were measured at 20 °C, using adsorptive solutions at the optimum pH value to determine the adsorption capacity. The Langmuir adsorption isotherm was used to describe observed sorption phenomena. The rise in temperature caused a slight decrease in the value of the equilibrium constant (K_c) for the sorption of metal ions. The mechanism for cations removal by the lignite includes ion exchange, complexation and sorption. The process is very efficient especially in the case of low concentrations of pollutants in aqueous solution, where common methods are either economically unfavorable or technically complicated.     

Toxic metal ion removal by terpolymer ion-exchanger from aqueous environments: synthesis,thermal degradation,batch separation,kinetic and isotherm studies

A novel chelating resin was synthesized and characterized by elemental, physico-chemical, GPC, NMR, and SEM analyses. Batch separation was adopted to study the recovery of selected metal ions with respect to the pH, time, concentrations, and electrolytes. From the results, it was observed that the order of the rate of metal ion uptake by the resin was Fe³⁺ > Cu²⁺ > Zn²⁺ > Ni²⁺ > Co²⁺ > Pb²⁺ ions. The adsorption kinetics follows first order, and isotherm models were also found to fit each other. The resin showed three-step thermal degradation, and its kinetic and thermodynamic parameters were also evaluated.     

Removal of lead,copper, nickel,cobalt, and zinc from water by a cancrinite-type zeolite synthesized from fly ash

As a low Si/Al ratio zeolite, cancrinite received very scant study in previous studies on the adsorption removal of heavy metals from water. In this study, a cancrinite-type zeolite (ZFA) was synthesized from Class C fly ash via the molten-salt method. Adsorption equilibriums of Pb²⁺, Cu²⁺, Ni²⁺, Co²⁺, and Zn²⁺ on ZFA were studied in aqueous solutions and were well represented by Langmuir isotherms. The increase of pH levels during the adsorption process suggests that the uptake of heavy metals on ZFA was subjected to an ion exchange mechanism. It is found that the maximum exchange level (MEL) follows the order: Pb²⁺ (2.530 mmol g^?1) > Cu²⁺ (2.081 mmol g^?1) > Zn²⁺ (1.532 mmol g^?1) > Co²⁺ (1.242 mmol g^?1) > Zn²⁺ (1.154 mmol g^?1). Comparison with previous studies shows that the MEL of ZFA is higher than the commonly used natural zeolites; and it is also comparable to (or higher than) several synthetic zeolites and ion exchange resins. The high MEL of heavy metals on ZFA is attributed to the high cation exchange capacity (CEC) and proper pore size of cancrinite. The pseudo-first-order kinetics suggests that the ion exchange processes were diffusion-controlled.     

Utilization of some starch derivatives in heavy metal ions removal

Three types of starch derivatives containing amide groups were used in removal of heavy metal ions from their solutions. These starch derivatives were poly(acrylamide)–starch graft copolymer, carbamoylethylated starch, and starch carbamate. The different factors affecting metal ion adsorption on these substrates, such as pH, metal ion concentration, type of starch derivatives, treatment time, and temperature, were studied. Results obtained indicate that the poly(acrylamide)–starch graft copolymer was a selective adsorbant for Hg²⁺ at pH 0.5–1. The adsorption values ofdifferent metal ions on these starch derivatives follow the order of Hg²⁺ > Cu²⁺ > Zn²⁺ > Ni²⁺ > Co²⁺ > Cd²⁺ > Pb²⁺. The adsorption values depend upon pH, type of starch derivative, treatment duration, and temperature. The adsorption efficiency percentage of metal ions on the three substrates follows the order of carbamoylethylated starch > poly(acrylamide) − starch graft copolymer > starch carbamate. © 1998 John Wiley & Sons, Inc. J Appl Polm Sci 69: 45–50, 1998     

Removal of Heavy Metal Ions from Water by Cross-Linked Potato Di-Starch Phosphate Polymer

Potato di-starch phosphate polymer was synthesized by cross-linking potato starch with phosphorus oxy-chloride in basic medium and was then dispersed (0.2-1%) in aqueous solutions of divalent heavy metal ions (Cu²⁺, Ni²⁺, Zn²⁺, and Pb²⁺), to investigate their removal efficiency by the starch and was found to increase with increase in the polymeric starch content and increase in the heavy metal ion concentration. The removal order was found to be Pb²⁺ (78.1%) > Cu²⁺ (58.5%) > Zn²⁺ (20.5%) > Ni²⁺ (17.3%) against the constant polymeric starch content. UV-Visible, Fluorescence, FT-IR, SEM, and CHN techniques were used for characterization of different complexes formed.     

Adsorption of heavy metal ions from aqueous solution by fly ash

The removal characteristics of lead and copper ions from aqueous solution by fly ash were investigated under various conditions of contact time, pH and temperature. The influence of pH of the metal ion solutions on the uptake levels of the metal ions by fly ash were carried out between pH 4 and 12. The level of uptake of Pb²⁺ and Cu²⁺ ions by the fly ash generally increased, but not in a progressive manner, at higher pH values. The effect of temperature on the uptake of Pb²⁺ and Cu²⁺ ions was investigated between 30 °C and 60 °C, the adsorption of being enhanced at the lowest temperature. Rate constants were evaluated in terms of a first-order kinetics. The rate constant, k for uptake of Pb²⁺ and Cu²⁺ ions were 1.77 × 10⁻² s⁻¹ and 2.11 × 10⁻² s⁻¹, respectively. The experimental results underline the potential of coal fly ash for the recovery of metal ions from waste water. The main mechanisms involved in the removal of heavy metal ions from solution were adsorption at the surface of the fly ash and precipitation.     

Adsorption of Pb2+ and Cd2+ onto a Novel Activated Carbon‐Chitosan Complex

A novel activated carbon‐chitosan complex adsorbent (ACCA) was prepared via the crosslinking of glutaraldehyde and activated carbon‐(NH₂‐protected) chitosan complex under microwave irradiation. The surface morphology of this adsorbent was characterized. The adsorption of ACCA for Pb²⁺ and Cd²⁺ was investigated. The results demonstrate that ACCA has higher adsorption capacity than chitosan. The adsorption follows pseudo first‐order kinetics. The isotherm adsorption equilibria are better described by Freundlich and Dubinin‐Radushkevich isotherms than by the Langmuir isotherm. The adsorbent can be recycled. These results have important implications for the design of low‐cost and effective adsorbents in the removal of heavy metal ions from wastewaters.     

The synthesis of modified alginate flocculants and their properties for removing heavy metal ions of wastewater

A new flocculant was synthesized through the modification of sodium alginate with thiosemicarbazide. In the preparation, amino thiourea groups which had excellent adsorption properties for heavy metal ions were introduced to the flocculant. The structure of the flocculant was confirmed by elemental analysis, Fourier transform infrared, UV spectrophotometry, nuclear magnetic resonance, and thermal analysis. The flocculation behaviors of the flocculant for three heavy metal ions were investigated. The results showed that the removal rates of the flocculant for Pb²⁺, Cd²⁺, and Cu²⁺ reached up to 97.8%, 86.3%, and 80.0%, respectively, and the flocculation capacities were as high as 489, 215, and 160 mg/g, respectively. The excellent adsorption was ascribed to the double effects of electronic interaction and chelation between the flocculant and heavy metal ions. The flocculant had particular flocculation selectivity for Pb²⁺ in the mixed heavy metal ion solutions containing Cd²⁺or Cu²⁺, respectively. The flocculation process corresponded to Langmuir isotherm model, the flocculation kinetics agree with pseudo second order. The flocculant had potential applications for treatment of wastewater. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46577.     

L-cystein modified bentonite-cellulose nanocomposite (cellu/cys-bent) for adsorption of Cu2+, Pb2+, and Cd2+ ions from aqueous solution

In this study, L-cystein modified bentonite-cellulose (cellu/cys-bent) nanocomposite was synthesized and characterized by XRD, FTIR, SEM with EDS, TGA, and TEM techniques. In order to optimize the process the effect of various operational parameters such as pH, adsorbent dosage, contact time, and temperature were also investigated. The adsorption experiments were carried out in initial concentrations range of 20-100 mg L^?1and the adsorbent affinity for metal ions was found to be in order of Cu²⁺ > Pb²⁺ > Cd²⁺. The optimum pH for adsorption of Cu²⁺ and Cd²⁺ was observed at 5 while for Pb²⁺ it was pH 6. Based on the Langmuir model, the maximum adsorption capacity of Cu²⁺, Pb²⁺, and Cd²⁺ at 50^?C was found to be 32.36, 18.52, and 16.12 mg g^?1, respectively. The Langmuir isotherm and pseudo-second order model were found to be better fitted than the other isotherms and kinetic models. The results of thermodynamic parameters confirmed the process to be endothermic and spontaneous in nature.     

Poly(hydroxamic acid) ligand from palm-based waste materials for removal of heavy metals from electroplating wastewater

Heavy metals pollutants are nonbiodegradable and their bioaccumulation results in detrimental environmental consequences. Therefore, it is important to effectively remove toxic heavy metal waste from industrial sewage. Thus, the main goal of this research is to synthesize an ideal cellulose-based adsorbent from palm-based waste materials (agro waste) in order to be utilized in real-life practical applications with low cost as such removing common toxic heavy metals from industrial effluents. A poly(methyl acrylate) grafted palm cellulose was synthesized via a free-radical initiation process, followed by an oximation reaction to yield poly(hydroxamic acid) ligands. The adsorption capacity (q_e) of poly(hydroxamic acid) ligands for metal ions such as copper (Cu²⁺), iron (Fe³⁺), and lead (Pb²⁺) were 325, 220, and 300 mg g⁻¹, respectively at pH 6. In addition, the X-ray photoelectron spectrometry results are to be proved the binding of metal ions, for instance, Cu(II) ions showed typically significant BEs of 932.7 and 952.0 eV corresponding to the Cu2p3/2 and Cu2p1/2 species. The heavy metal ions adsorption followed a pseudo-first-order kinetic model pathway. The adsorption capacity (q_m) is also derived from the Langmuir isotherm linear plot, which does not showed good correction coefficients. However, the results were correlated to the Freundlich isotherm model, where the R² value showed significance (>0.98), indicating that multiple layer adsorption occurs on the synthesized ligand. The synthesized polymeric ligand is an excellent adsorbent for the removal of heavy metals from the industrial wastewater. In addition, the metal analysis results showed that about 98% removal of copper and iron ions from electroplating wastewater including lead, nickel, and chromium can be removed up to 85–97%.     

Competitive Adsorption of Ag+, Pb2+, Ni2+, and Cd2+ Ions on Vermiculite

Competitive adsorption of Ag⁺, Pb²⁺, Ni²⁺, and Cd² ions on vermiuculite in a binary, ternary, and quaternary mixture was investigated in batch experiments. The effects of the presence of Ag⁺, Ni²⁺, and Cd²⁺ ions on the adsorption of Pb²⁺ ions were investigated in terms of the equilibrium isotherm. Experimental results indicated that Pb²⁺ ions always favorably adsorbed on vermiculite over Ag⁺, Ni²⁺, and Cd²⁺ ions. The adsorption equilibrium data of Pb²⁺ ions better fitted the Langmuir model than the Freundlich model. The results showed that the pseudo-second-order kinetics model was in good agreement with the experimental results for all metal ions, and the adsorption rate among the metal ions followed Ag⁺ > Pb²⁺ > Ni²⁺ > Cd²⁺. The desorption and regenration study indicated that vermiculite can be used repeatedly and be suitable for the design of a continuous process.     

Functionalized nanostructured silica by tetradentate-amine chelating ligand as efficient heavy metals adsorbent : Applications to industrial effluent treatment

Organofunctionalized nanostructured silica SBA-15 with tri(2-aminoethyl)amine tetradentate-amine ligand was synthesized and applied as adsorbent for the removal of Cu²⁺, Pb²⁺, and Cd²⁺ from both synthetic wastewater and real paper mill and electroplating industrial effluents. The prepared materials were characterized by XRD, N₂ adsorption-desorption, TGA, and FT-IR analysis. The Tren-SBA-15 was found to be a fast adsorbent for heavy metal ions from single solution with affinity for Cu²⁺, Pb²⁺, than for Cd²⁺ due to the complicated impacts of metal ion electronegativity. The kinetic rate constant decreased with increasing metal ion concentration due to increasing of ion repulsion force. The equilibrium batch experimental data is well described by the Langmuir isotherm. The maximum adsorption capacity was 1.85 mmol g^?1 for Cu²⁺, 1.34 mmol g^?1 for Pb²⁺, and 1.08 mmol g^?1 for Cd²⁺ at the optimized adsorption conditions (pH=4, T=323 K, t=2 h, C₀=3 mmol L^?1, and adsorbent dose=1 g L^?1). All Gibbs energy was negative as expected for spontaneous interactions, and the positive entropic values from 103.7 to 138.7 J mol^?1 K^?1 also reinforced this favorable adsorption process in heterogeneous system. Experiment with real wastewaters showed that approximately a half fraction of the total amount of studied metal ions was removed within the first cycle of adsorption. Hence, desorption experiments were performed by 0.3M HCl eluent, and Tren-SBA-15 successfully reused for four adsorption/desorption cycles to complete removal of metal ions from real effluents. The regenerated Tren-SBA-15 displayed almost similar adsorption capacity of Cu²⁺, Pb²⁺, and Cd²⁺ even after four recycles. The results suggest that Tren-SBA-15 is a good candidate as an adsorbent in the removal of Cu²⁺, Pb²⁺, and Cd²⁺ from aqueous solutions.     

Poly (acrylic acid-co-acryloyl tetrasodium thiacalix[4]arene tetrasulfonate) grafted dextrin: new supper metal ion adsorbing hydrogels

Dextrin as a biodegradable natural polymer has hydrophilic nature that capable to increase the swelling properties and biodegradability of the synthetic hydrogels. This study describes the synthesis of a poly (acrylic acid-co-acryloyl tetrasodium thiacalix[4]arene tetrasulfonate) grafted dextrin superabsorbent hydrogels (ADA) via solution polymerization. The effects of acryloyl tetrasodium thiacalix[4]arene tetrasulfonate (ACSTCA) dose (20–60) on swelling properties of the hydrogels were studied. The synthesized hydrogels were characterized by FTIR, TGA, DMTA and rheometry. The metal ion removal capacity of the gels was investigated by atomic absorption for Cd²⁺, Pb²⁺, and Hg²⁺. The tendency of metal ions adsorption decreased in the order of Pb²⁺>Cd²⁺>Hg²⁺. The effect of key operating parameters including ACSTCA content, contact time, adsorbent dosage, solution pH, and crosslinker density was experimentally studied on Pb²⁺ adsorption from aqueous solution. The equilibrium data was analyzed using Langmuir and Freundlich adsorption isotherms. Our experimental data are in best agreement with Freundlich isotherms, and adsorption of metal cation onto hydrogel followed a pseudo second-order kinetic model. According to the thermodynamic parameters, the adsorption of Pb²⁺ occurred spontaneously. The hydrogels could be regenerated after releasing heavy metal ions, and reused 5 times with less than 7 % loss of adsorption capacity.     

Adsorption of heavy metal cations using coal fly ash modified by hydrothermal method

In this study, the adsorption properties of synthetic zeolite produced from Brazilian coal fly ash were investigated for some heavy metal cations (Zn, Cu, Mn and Pb). The batch method has been employed, using metal concentrations in solution ranging from 100 to 3000 mg/l. Preliminary statistical analysis has indicated that temperature and time of synthesis of zeolites were the most important variables that affect the their adsorption capacity. Results lead to the conclusion that a hydrothermal treatment can increase from 2 to 25 times the adsorption capacity (CA) of the coal ash comparing to its original capacity. The ion-exchange characteristic of the zeolites was determined using Langmuir, Freundlich and Dubinin-Kaganer-Radushkevich isotherms. The adsorption increases as cation concentrations in aqueous solution increases. The preference order observed for adsorption is Pb > Cu > Zn > Mn.     

Removal of Cu2+ and Pb2+ ions from aqueous solutions by starch-graft-acrylic acid/montmorillonite superabsorbent nanocomposite hydrogels

In this study, the removal of copper(II) and lead(II) ions from aqueous solutions by Starch-graft-acrylic acid/montmorillonite (S-g-AA/MMT) nanocomposite hydrogels was investigated. For this purpose, various factors affecting the removal of heavy metal ions, such as treatment time with the solution, initial pH of the solution, initial metal ion concentration, and MMT content were investigated. The metal ion removal capacities of copolymers increased with increasing pH, and pH 4 was found to be the optimal pH value for maximum metal removal capacity. Adsorption data of the nanocomposite hydrogels were modeled by the pseudo-second-order kinetic equation in order to investigate heavy metal ions adsorption mechanism. The observed affinity order in competitive removal of heavy metals was found Cu²⁺ > Pb²⁺. The Freundlich equations were used to fit the equilibrium isotherms. The Freundlich adsorption law was applicable to be adsorption of metal ions onto nanocomposite hydrogel.