Uptake of Ni(II) Ions from Aqueous Solution by Kaolinite and Montmorillonite: Influence of Acid Activation of the Clays

Abstract

Kaolinite and montmorillonite were treated with 0.25 M H₂SO₄ and the acid activated clays along with the parent clays were tested for their uptake capacity for Ni(II) ions from aqueous solution. The batch adsorption experiments were conducted under a set of variables (concentration of Ni(II) ion, amount of clay, pH, time and temperature of interaction). Increasing pH favored Ni(II) uptake till the ions were precipitated as the insoluble hydroxides at pH > 8.0. The uptake was rapid up to 40 min and equilibrium was obtained within 180 min. The kinetics of the process was evaluated by subjecting the results to a number of models like the pseudo-first order, second order, Elovich equation, liquid film diffusion, and intra-particle diffusion and it was found that the data more closely resembled a second order process. The experimental data conformed to both Langmuir and Freundlich isotherms showing that the interactions were mostly chemical in nature. The clays had reasonable monolayer adsorption capacity of 10.4, 11.9, 28.4, and 29.5 mg g^?1 for kaolinite, acid activated kaolinite, montmorillonite, and acid-activated montmorillonite respectively. Montmorillonite had much better adsorption capacity than kaolinite and the acid activation boosted the adsorption capacity of both kaolinite and montmorillonite. The interactions were exothermic in nature, accompanied by decrease in both entropy and Gibbs energy. The results have established good potentiality for kaolinite, montmorillonite and their acid-activated forms to take up and separate Ni(II) from aqueous medium through adsorption-mediated immobilization.     

Removal of Orange II by Phosphonium-modified Algerian Bentonites

An Algerian montmorillonite was modified with two organic surfactants, methyltriphenyl phosphonium bromide and n-hexyltriphenyl phosphonium bromide. The solids obtained were used as adsorbents to remove Orange II, an anionic dye from aqueous solutions. Batch experiments were conducted to study the effects of temperature (20–60°C), initial concentration of adsorbate (50–150 mg L^?1) and pH of solution 6.5 on dye adsorption. Due to their organophilic nature, exchanged montmorillonites were able to adsorb Orange II at a very high level. Adsorption of Orange II for B-NHTPB and B-MTPB at different pH show that the adsorption capacity clearly decreases with an increase in pH of the initial solution from 2 to 8, this decrease being dramatic for pH > 8. This may be due to hydrophobic interactions of the organic dye with both phosphonium molecules and the remaining non-covered portion of siloxane surface. The kinetics of the adsorption was discussed on the basis of three kinetic models, i.e., the pseudo-first-order, the pseudo-second-order, and the intraparticle diffusion models. Equilibrium is reached after 30 min and 60 min for B-MTPB and B-NHTPB, respectively; the pseudo-second-order kinetic model described very well the adsorption of Orange II on modified bentonites. The non-linear Langmuir model provided the best correlation of experimental data, maximum adsorption of Orange II is 53.78 mg g^?1 for B-NHTPB and 33.79 mg g^?1 for B-MTPB. The thermodynamic parameters, such as free energy of adsorption (ΔG°), enthalpy change (ΔH°), and entropy change (ΔS°) were also determined and evaluated. From thermodynamic studies, it was deduced that the adsorption was spontaneous and exothermic.     

Starch/rice husk ash based superabsorbent composite: high methylene blue removal efficiency

Superabsorbent hydrogels composites based on the biopolymer starch (ST) and rice husk ash (RHA) were successfully developed and tested towards the removal of methylene blue (MB), a cationic dye. RHA content hit the morphology, mechanical and water uptake properties of the composite. Batch adsorption experiments, carried out under pH 5 at 33 °C and with 2000 mg L^?1 as the initial concentration of MB, showed that at 5 wt% RHA the composite exhibited a remarkable adsorption capacity reaching up to 1906.3 mg g^?1 within 60 min. The adsorption kinetics followed the pseudo-second-order model and intraparticle diffusion was involved in this process. The Langmuir adsorption isotherm suggested a monolayer formation and spontaneous process. Thermodynamic parameters confirmed the spontaneity of the adsorption and suggested electrostatic interaction among the cationic dye molecules and the anionic adsorption sites on the adsorbent surface. FTIR analysis confirmed the adsorption process occurs via electrostatic mechanism associated with hydrophobic interactions. The adsorbents showed reusability with slight loss of adsorption capacity in five consecutive adsorption/desorption cycles. These results demonstrate ST/RHA superabsorbent composite as a low-cost, eco-friendly, robust and powerful adsorbent material for wastewater remediation.     

ADSORPTION OF A LEATHER DYE ON MESOPOROUS STRUVITE OBTAINED FROM SWINE WASTEWATER

Struvite powder obtained from swine wastewater was used as adsorbent to remove an azo leather dye from aqueous solution. The material was characterized by X-ray diffraction, surface area, and atomic force microscopy. The sample presented a single phase having a mesoporous structure and surface area of 35.63 m² g^?1. Langmuir and Freundlich isotherm models were fitted to the adsorption data and both satisfactorily represented the process. The maximum adsorption capacity was 38.14 mg g^?1. From the analysis of thermodynamic parameters such as free energy of adsorption (ΔG°), enthalpy (ΔH°), and entropy (ΔS°) it was verified that the adsorption process is very fast, spontaneous, and exothermic in nature, with weak forces acting.     

Modeling of Adsorptive Filtration of a Leather Dye in a Fixed Bed Column

Abstract

Activated carbons offer an efficient option for the removal of organic and inorganic contaminants from water. However, due to its high costs and difficulty in the regeneration, other low cost adsorbents have been used. In this work, the adsorption capacity of an adsorbent carbon with high iron oxides concentration was compared with that of a commercial activated carbon in the removal of a leather dye from an aqueous solution. The adsorbents were characterized using SEM/EDAX analysis and BET surface area. The capacity of adsorption of the adsorbents was evaluated through the static method at 25°C. The results showed that the color removal was due to the adsorption and precipitation of the dye on the surface of the solids. The adsorption equilibrium was described according to the linear model for the adsorbent carbon and the equilibrium constant was 0.02 L g^?1. The equilibrium of adsorption on activated carbon exhibited a behavior typical of the Langmuir isotherm and the monolayer coverage was 24.33 mg g^?1. A mathematical model was proposed to describe the dynamics of the color removal using a fixed bed considering that the color removal is due to the adsorption and the precipitation of the dye on the adsorbent.     

Performance of Unmodified Paper Solid Waste for Cadmium Removal From Aqueous Phase: Equilibrium and Kinetic Studies

The reuse of paper solid waste (PSW) as a low-cost sorbent for Cd removal from aqueous phase was investigated. Batch experiments were conducted to study the effects of pH (3.5, 5.5, 7.5), contact time (10–360 min), PSW dose (2.5–20 g L^?1), and Cd concentration (5–50 mg L^?1) at an ionic strength of 0.01 M NaNO₃ on adsorption efficiency and capacity. Cd removal of ～96% occurred in 20 mg L^?1 Cd solution at pH 5.5 containing 20 g L^?1 PSW. Equilibrium was attained after 120 min and the equilibrium adsorption capacity of PSW increased with increasing Cd concentration from 5 to 50 mg L^?1. The kinetic process of Cd adsorption obeyed the pseudo-second-order kinetic model. Langmuir and Freundlich models described equally well the experimental data and the maximum adsorption capacity was 4.89 mg g^?1. PSW can be used for reducing Cd concentration in Cd-contaminated water systems.     

Adsorption of different dyes from aqueous solution using Si-MCM-41 having very high surface area

Adsorption characteristics of four different dyes Safranin O (cationic), Neutral Red (neutral), Congo Red (anionic) and Reactive Red 2 (anionic) on Si-MCM-41 material having very high surface area are reported. The surface morphology of Si-MCM-41 material before and after adsorbing dye molecules are characterised by FTIR, HRXRD, nitrogen adsorption–desorption isotherms, FESEM, and HRTEM. The adsorption capacities of Si-MCM-41 for the dyes followed a decreasing order of NR > SF > CR > RR2. The adsorption kinetics, isotherm and thermodynamic parameters are investigated in detail for these dyes using calcined Si-MCM-41. The kinetics and isotherm data showed that both SF and NR adsorb more rapidly than CR and RR2, in accordance with pseudo-second-order kinetics model as well as intraparticle diffusion kinetics model and Langmuir adsorption isotherm model respectively. The thermodynamic data suggest that the dye uptake process is spontaneous. The high adsorption capacities of dyes on Si-MCM-41 (q_m = 275.5 mg g^?1 for SF, q_m = 288.2 mg g^?1 for NR) is explained on the basis of electrostatic interactions as well as H-bonding interactions between adsorbent and adsorbate molecules. Good regeneration capacity is another important aspect of the material that makes it potent for the uptake of dyes from aqueous solution.     

Competitive Separation of Lead,Cadmium, and Nickel from Aqueous Solutions Using Activated Carbon: Response Surface Modeling,Equilibrium, and Thermodynamic Studies

In this study, the competitive separation of lead, cadmium, and nickel ions from aqueous solutions using a commercial activated carbon (AC) has been investigated and optimized using response surface methodology (RSM). The optimal conditions to reach the highest adsorption capacity for these metals were found as follows: initial pH = 6.3, temperature = 56.8°C, and shaking speed = 308 rpm. Under these conditions, the sequence of adsorption capacity toward the metal ions was as follows: Pb (II): 9.44 mg g^?1 > Cd (II): 9.37 mg g^?1 > Ni (II): 4.52 mg g^?1. The effect of shaking speed on the adsorption capacity of AC was higher than the effects of the initial pH and temperature, indicating the more important role of physisorption than chemisorption in the adsorption of these metal ions. This was confirmed by the results of thermodynamic studies. The equilibrium adsorption data were fitted to the Freundlich, Langmuir adsorption isotherm models and the Dubinin–Radushkevich model parameters were evaluated. All the models were tested and all were shown to represent the experimental data satisfactorily. The thermodynamic parameters such as ΔH, ΔS, and ΔG were computed from the experimental data. These values show that the adsorption is endothermic and spontaneous. The positive value of ΔS° indicates increasing of randomness at the solid/liquid interface during the adsorption of metal ions on AC.     

Highly Efficient Removal of Congo red from Wastewater by Nano-Cao

Nano-CaO with high surface area of 120 m² · g^?1 has been used as adsorbents for Congo red adsorption from wastewater. The maximum adsorption capability of Congo red on nano-CaO reached 357.14 mg · g^?1 in 10 min, while the maximum capability on commercial CaO was only 238.66 mg · g^?1 in 30 min. In comparison with commercial CaO, some published metal oxides for Congo red adsorption such as Fe₂O₃, NiO, MgO, and Mn₂O₃, etc., the Nano-CaO exhibited much more favorable adsorptive property. In addition, the effects of pH, salt concentration, and temperature were also investigated, and these factors played significant roles for Congo red adsorption on Nano-CaO.     

Adsorptive removal of cationic dye from aqueous solutions by ZnO/ZnMn2O4 nanocomposite

The ZnO/ZnMn₂O₄ nanocomposite (ZnMn) was used as adsorbent for the removal of cationic dye Basic Yellow 28 (BY28) from aqueous solutions. The adsorbent was characterized by X-ray diffraction, scanning electron microscope, TEM, Fourier transform infrared ray, BET, particle size distribution and zeta potential measurements. The adsorption parameters, such as temperature, pH and initial dye concentration, were studied. Kinetic adsorption data were analyzed using the pseudo-first-order, pseudo-second-order and intraparticle diffusion kinetic models. The Langmuir and Freundlich isotherm models were applied to fit the equilibrium data. The maximum adsorption capacity of BY28 was 48.8 mg g^?1. Various thermodynamic parameters, such as ΔG°, ΔH° and ΔS°, were calculated.     

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.     

Equilibrium modeling,kinetic and thermodynamic studies on the adsorption of Cr(VI) using activated carbon derived from matured tea leaves

A new porous carbon with high surface area of 1,313.41 m² g^?1 with pore volume 1.359 cm³ g^?1 has been synthesized from matured tea leaves by chemical activation method using phosphoric acid. The carbon was found to be highly efficient for removal of Cr(VI) from aqueous solution. The effects of various parameters such as contact time, initial metal ion concentration, pH, temperature and amount of adsorbent on the extent of adsorption were studied. Langmuir, Freundlich and Temkin adsorption models were used to interpret the experimental data. The adsorption data were best fitted with Langmuir isotherm model. The adsorption capacity of Cr(VI) onto the activated carbon calculated from Langmuir isotherm was found to be 30.8 mg g^?1 at pH 4.8 and temperature 303 K. The adsorption capacity increases from 25.36 to 32.04 mg g^?1 with an increase in temperature from 303 to 323 K at initial Cr(VI) concentration of 60 mg L^?1. The adsorption process followed a pseudo second order kinetic model. Thermodynamic parameters ΔH⁰ (28.6 KJ mol^?1), ΔG⁰ at three different temperatures [(?0.145, ?1.09, ?2.04) KJ mol^?1] and ΔS⁰ (94.87 J mol^?1 K^?1) were calculated. These values confirm the adsorption process to be endothermic and spontaneous in nature.     

Mechanistic,Kinetic, and Thermodynamic Evaluation of Adsorption of Hazardous Malachite Green onto Conch Shell Powder

The present study explores the ability of a new adsorbent—conch shell powder (CSP) in removing Malachite Green from aqueous solutions. The effect of various process parameters, namely initial solution pH, temperature, initial dye concentration, adsorbent dose, and contact time was investigated. Adsorption equilibrium data were well described by the Langmuir isotherm with maximum adsorption capacity of 92.25 mg g^?1 at 303 K. The kinetic data conformed to the pseudo-second-order kinetic model. A thermodynamic study showed the spontaneous nature and feasibility of the adsorption process. The results provide strong evidence to support the hypothesis of adsorption mechanism.     

Adsorption of Rhodamine B onto O-Carboxymethylchitosan-N-Lauryl

The adsorption of a cationic dye (rhodamine B; RB) on O-carboximethyl-N-acetylated (L-CMCh) in aqueous solution was investigated. The effect of the process parameters such as the contact time, pH, and temperature are reported. Both temperature and pH influence dye adsorption. To determine the adsorption capacity, the equilibrium adsorption data were analyzed by the Langmuir, Langmuir-Freundlich, and Redlich-Peterson isotherm models. The results showed better agreement with the Langmuir-Freundlich model than the other models. The maximum adsorption capacity of RB for L-CMCh was determined as 38.5 mg g^?1 at pH 8.5 and 25°C. The kinetic results follow a pseudo-second-order rate equation. The activation energy value for adsorption of RB on L-CMCh was found to be 52.0 kJ mol^?1. The negative values of Gibbs free energy and enthalpy show the adsorption to be spontaneous and exothermic. The negative value of the enthalpy for adsorption of RB onto L-CMCh shows the adsorption to be exothermic.     

Optimization of kinetic data for two‐stage batch adsorption of Pb(II) ions onto tripolyphosphate‐modified kaolinite clay

BACKGROUND: Most adsorption studies consider only the adsorption of pollutants onto low cost adsorbents without considering how equilibrium and kinetic data can be optimized for the proper design of adsorption systems. This study considers the optimization of kinetic data obtained for the removal of Pb(II) from aqueous solution by a tripolyphosphate modified kaolinite clay adsorbent. RESULTS: Modification of kaolinite clay with pentasodium tripolyphosphate increases its cation adsorption capacity (CEC) and specific surface area (SSA) from 7.81 to 78.9 meq (100 g)^?1 and 10.56 to 13.2 m² g^?1 respectively. X‐ray diffraction patterns for both unmodified and tripolyphosphate‐modified kaolinite clay suggest the modification is effective on the surface of the clay mineral. Kinetic data from the batch adsorption of Pb(II) onto the tripolyphosphate‐modified kaolinite clay adsorbent were optimized to a two‐stage batch adsorption of Pb(II) using the pseudo‐second‐order kinetic model. Mathematical model equations were developed to predict the minimum operating time for the adsorption of Pb(II). Results obtained suggest that increasing temperature and decreasing percentage Pb(II) removal by the adsorbent enhanced operating time of the adsorption process. The use of two‐stage batch adsorption reduces contact time to 6.7 min from 300 min in the single‐stage batch adsorption process for the adsorption of 2.5 m³ of 500 mg L^?1 Pb(II) under the same operating conditions. CONCLUSION: Results show the potential of a tripolyphosphate‐modified kaolinite clay for the adsorption of Pb(II) from aqueous solution and the improved efficiency of a two‐stage batch adsorption process for the adsorption of Pb(II) even at increased temperature. Copyright © 2009 Society of Chemical Industry     

A Novel Pinus Tabulaeformis Based Adsorbent for the Removal of Malachite Green

Pyrolytic char treated with muffle furnace (TPC), a novel adsorbent, were investigated to enhance its adsorption capacity of malachite green (MG) dye. In addition, the dye adsorption behavior of the TPC in aqueous solution was investigated. The treatment temperature, treatment time, and the particle size of PC had a positive effect on the dye adsorption capacity of TPC. Equilibrium data was fitted well with Langmuir and Redlich-Peterson models with maximum adsorption capacity of 91.24, 111.27, and 119.01 mg g^?1 at 293, 303, and 313 K, respectively. The kinetic of adsorption was found to confirm to the Elovich equation with good correlation and the overall rate of MG uptake was found to be controlled by film diffusion, pore diffusion and particle diffusion. The Boyd plot confirmed that the external mass transfer was the rate-limiting step in the adsorption process. Different thermodynamic parameters have also been evaluated and it was found that the adsorption was spontaneous, feasible, and endothermic in nature. Adsorbents could be regenerated using 0.1 mol L^?1 NaOH solution at least three cycles, with up to 90% recovery. The TPC used in this work proved to be an effective material for the treatment of MG bearing aqueous solutions.     

Application of mesoporous magnetic nanosorbent developed from macadamia nut shell residues for the removal of recalcitrant melanoidin and its fractions

ABSTRACT

A novel mesoporous magnetic nanosorbent developed from macadamia nut shell residues was applied as an adsorbent for the removal of dissolved organic carbon (DOC) associated with melanoidin and its fractions in a batch system. The most favored molecular fraction of the melanoidin for adsorption onto the nanosorbent was 1–5 kDa with adsorption capacity of 10.26 mg DOC g^?1 achieving 68.4% removal efficiency. The sorption behaviors were all well fitted to a pseudo-second-order kinetic model and Langmuir isotherm. Optimum operating conditions needed for the maximum uptake of 14.7 mg DOC g^?1 were found to be pH of 6.3, temperature of 41.7°C at the dosage of the magnetic nanosorbent of 877.7 ppm.     

Solvothermal synthesis of porous conjugated polymer with high surface area for efficient adsorption of organic and biomolecules

Aimed to prepare high efficient dye sorbent and control water pollution, herein we utilized solvothermal method to synthesize porous polyimide (PI) polymer with a large surface area using DMSO as solvent. Unlike the solid-state thermal polymerized PI with low surface area of 5 m²g^?1, this PI material prepared in DMSO solvent possessed a large surface area of 430 m²g^?1, which was beneficial for adsorption of organic dye in waste water, achieving a max MO adsorption of 200 mg g^?1 three times higher than that of multiwalled carbon nanotube. The adsorption kinetics of dye molecules on PI was investigated in detail and the R² value of 0.99071 for pseudo-second-order model confirms the adsorption was fitted best with Langmuir isotherm.     

Adsorption of Co(II) from Aqueous Medium on Natural and Acid Activated Kaolinite and Montmorillonite

Abstract

Hazardous metal cations enter water through the natural geochemical route or from the industrial wastes. Their separation and removal can be achieved by adsorptive accumulation of the cations on a suitable adsorbent. In the present work, toxic Co(II) ions are removed from water by accumulating them on the surface of clay minerals. Clay adsorbents are obtained from kaolinite, montmorillonite, and their acid activated forms, and are characterized with the measurement of XRD patterns, specific surface area, and cation exchange capacity. The adsorption experiments are carried out in a batch process in environments of different pH, initial Co(II) concentration, amount of clay, interaction time, and temperature. Adsorption of Co(II) on the clays increases continuously from pH 1.0 to 8.0 after which adsorption could not be carried out due to the decreasing solubility of Co(II). Under appropriate conditions, the adsorption of Co(II) is very fast at low coverage approaching equilibrium within 240 min and the interactions are best described by second order kinetics. Langmuir monolayer capacity has been computed in the range of 11.2 to 29.7 mg/g and Co(II) accumulation has the order of acid‐activated montmorillonite>montmorillonite>acid activated kaolinite>kaolinite. Adsorption of Co(II) on kaolinite and acid‐activated kaolinite is endothermic driven by entropy increase but the same process follows exothermically on montmorillonite and acid‐activated montmorillonite supported by entropy decrease. In both cases, spontaneous adsorptive accumulation is ensured by favorable Gibbs energy decrease. It is found that acid activation enhances the adsorption capacity of kaolinite and montmorillonite.     

Polyamine Functionalized Magnetite Nanoparticles as Novel Adsorbents for Cu(II) Removal from Aqueous Solutions

Three novel magnetic adsorbents were synthesized through the immobilization of di-, tri-, and tetraamine onto the surface of silica coated magnetite nanoparticles. The adsorbents were characterized by XRD patterns, FTIR spectroscopy, elemental and thermogravimetric analysis, magnetic measurements, SEM/TEM, EDX spectroscopy, and N₂ adsorption/desorption isotherms. Their capacity to remove copper ions from aqueous solutions was investigated and discussed comparatively. The equilibrium data were analyzed using Langmuir and Freundlich isotherms. The kinetics was evaluated using the pseudo-first-order, pseudo-second-order, and intra-particle diffusion models. The best interpretation for the equilibrium data was given by the Langmuir isotherm for the tri- and tetraamine functionalized adsorbents, while for the diamine functionalized adsorbent the Freundlich model seemed to be better. The kinetic data were well fitted to the pseudo-second-order model. The overall rate of adsorption was significantly influenced by external mass transfer and intraparticle diffusion. It was observed that the adsorption capacity at room temperature decreased as the length of polyamine chain immobilized on the adsorbent surface increased, the maximum adsorption capacities being 52.3 mg g^?1 for 1,3-diaminopropan functionalized adsorbent, 44.2 mg g^?1 for diethylenetriamine functionalized adsorbent, and 39.2 mg g^?1 for triethylenetetramine functionalized adsorbent. The sorption process proved to be highly dependent of pH. The results of the present work recommend these materials as potential candidates for copper removal from aqueous solutions.