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.     

ADSORPTION,KINETICS, AND EQUILIBRIUM STUDIES ON REMOVAL OF 4,4-DDT FROM AQUEOUS SOLUTIONS USING LOW-COST ADSORBENTS

The removal of a chlorinated pesticide (4,4-DDT) from aqueous solutions by a batch adsorption technique using different low-cost adsorbents was investigated. Two adsorbents, wood sawdust (A) and cork wastes (B), were used to determine adsorption efficiency. The influence of the adsorbent particle size and the organic matter of water (humic acids) on the removal process was studied. The obtained results were compared to those obtained with a commercial powdered activated carbon (PAC, F400, Chemviron) (C). Kinetic studies were performed to understand the mechanistic steps of the adsorption process. The rate of the adsorption kinetics of 4,4-DDT on the low-cost adsorbents was found best fitted with a pseudo-second-order kinetic model. This is in contrast to the rate of the adsorption kinetics of the PAC F400, which was best fitted with the Lagergren model. The application of the Morris-Weber equation showed that the adsorption process of 4,4-DDT on these adsorbents was complex. Both the adsorption on the surface and the intraparticle diffusion were the rate-controlling mechanisms. Langmuir and Freundlich adsorption isotherms were applicable to the adsorption process and their constants were evaluated. The adsorption capacity (q_m) calculated from the Langmuir isotherm (69.44 mg·g^?1, 19.08 mg·g^?1, and 163.90 mg·g^?1, respectively, for A, B, and C) showed that the process is highly particle size dependent, that the organic matter influenced the adsorption process negatively, and that wood sawdust is the most effective adsorbent for the removal of 4,4-DDT from aqueous solutions. The adsorbents studied exhibited a possible application in water decontamination, as well as in treatment of industrial and agricultural waste waters.     

Removal of Copper(II) and Zinc(II) from Aqueous Solutions Using a Lignocellulosic-Based Polymeric Adsorbent Containing Amidoxime Chelating Functional Groups

In this study, the adsorption of Cu(II) and Zn(II) ions from aqueous solutions onto amidoximated polymerized banana stem (APBS) has been investigated. Infrared spectroscopy was used to confirm graft copolymer formation and amidoxime functionalization. The different variables affecting the sorption capacity such as pH of the solution, adsorption time, initial metal ion concentration, and temperature have been investigated. The optimum pH for maximum adsorption was 10.5 (99.99%) for Zn²⁺ and 6.0 (99.0%) for Cu²⁺ at an initial concentration of 10 mg L^?1. Equilibrium was achieved approximately within 3 h. The experimental kinetic data were analyzed using pseudo-first-order and pseudo-second-order kinetic models and are well fitted with pseudo- second-order kinetics. The thermodynamic activation parameters such as ΔG^o, ΔH^o, and ΔS^o were determined to predict the nature of adsorption. The temperature dependence indicates an exothermic process. The experimental isotherm data were well fitted to the Langmuir model with maximum adsorption capacities of 42.32 and 85.89 mg g^?1 for Cu(II) and Zn(II), respectively, at 20°C. The adsorption efficiency was tested using industrial effluents. Repeated adsorption/regeneration cycles show the feasibility of the APBS for the removal of Cu(II) and Zn(II) ions from water and industrial effluents.     

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.     

Sodic and Acidic Crystalline Lamellar Magadiite Adsorbents for the Removal of Methylene Blue from Aqueous Solutions: Kinetic and Equilibrium Studies

The present study reports the feasibility of two synthetic crystalline lamellar nano-silicates, sodic magadiite (Na-mag) and its converted acidic form (H-mag), as alternative adsorbents for the removal of the dye methylene blue (MB) from aqueous solutions. The ability of these adsorbents for removing the dye was explored through the batch adsorption procedure. Effects such as the pH and the adsorbent dosage on the adsorption capacities were explored. Four kinetic models were applied, the adsorption being best fitted to a fractionary-order kinetic model. The kinetic data were also adjusted to an intra-particle diffusion model to give two linear regions, indicating that the kinetics of adsorption follows multiple sorption rates. The equilibrium data were fitted to Langmuir, Freundlich, Sips, and Redlich-Peterson isotherm models. The maxima adsorption capacities for MB of Na-mag and H-mag were 331 and 173 mg g^?1, respectively.     

Porous Carrageenan-<Emphasis Type="Italic">g</Emphasis>-polyacrylamide/bentonite superabsorbent composites: swelling and dye adsorption behavior

A novel superabsorbent composite based on kappa-Carrageenan (κC) was prepared by graft copolymerization of acrylamide (AAm) onto κC in the presence of bentonite powder using methylenebisacrylamide (MBA) as a crosslinking agent, ammonium persulfate (APS) as an initiator, and sodium carbonate as a pore-forming agent. The swelling behavior in distilled water and in solutions with different pH values was investigated. The results indicated that with increasing carrageenan/bentonite weight ratio, the swelling capacity is increased but the gel content is decreased. The swelling rate of the hydrogels was improved by introducing sodium carbonate as pore-forming agent. The prepared superadsorbent composites were used as adsorbent for a cationic dye, methylene blue. Isotherm of adsorption and the effect of pH, adsorption dosage, contact time and initial dye concentration on dye adsorption were also studied. The results showed that maximum adsorption capacity of methylene blue on the prepared adsorbents is 156.25 mg g^?1 and adsorption is well-described by Langmuir isotherm model.     

Methylene Blue Adsorption on Natural and Modified Clays

Toxic methylene blue dye is removed from water by accumulating it on the surface of clay minerals. Clay adsorbents are obtained from kaolinite, montmorillonite, and their acid activated forms. The adsorption experiments are carried out in a batch process in environments of different pH, initial dye concentration, amount of clay, interaction time, and temperature. Adsorption of dye is best described by second order kinetics. In the temperature range of 303 to 333 K, the Langmuir monolayer capacity for three kaolinite species increased from 45.5 to 56.5 mg g^?1, 45.9 to 57.8 mg g^?1, 46.3 to 58.8 mg g^?1, and for three montmorillonites species from 163.9 to 181.8 mg g^?1, 166.7 to 188.8 mg g^?1, and 172.4 to 192.3 mg g^?1. The interaction is an endothermic process driven by entropy increase and spontaneous adsorptive accumulation is ensured by favorable Gibbs energy decrease. It is found that acid activation enhances the adsorption capacity of kaolinite and montmorillonite.     

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.     

Hydrothermal synthesis of mesoporous TiO<Subscript>2</Subscript> nanotubes and their adsorption affinity toward Basic Violet 2

Hydrothermal method was used to synthesize TiO₂ nanotubes (TNTs), which are considered as a novel adsorbent with high surface area and adsorption capacity. Different methods including X-ray diffraction (XRD), transmission electron microscope (TEM) and Brunauer–Emmett–Teller (BET) analysis were used to investigate and identify synthesized TNTs. The adsorption capacity of TNTs was investigated with regard to removing Basic Violet 2 (BV2) as a model organic pollutant from aqueous solution. The mean outer, inner diameter and thickness of the TNTs were found to be approximately 9, 4 and 2.5 nm, respectively. BET–BJH method was used for measuring specific surface area and pore volume of the TNTs which turned out to be 200.38 m² g^?1 and 0.44 cm³ g^?1, respectively. The results of the study indicated synthesized TNTs may be considered as efficient and effective adsorbent for removing BV2 (75.63%) from aqueous solution. The impact of the operational variables, i.e. initial BV2 concentration (2–20 mg L^?1), dosage of adsorbent (0.01–0.6 g), and pH (2–8) in relation to the adsorption capacity of BV2 onto TNTs were investigated. The experimental results of the study were meticulously taken into consideration for discussing and analyzing the adsorption isotherms and kinetics. It was found that the collected experimental data regarding the kinetic and isotherm examinations were compatible and well-matched with the pseudo-first order kinetic model and Langmuir isotherm model (R ²?=?0.9634).     

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.     

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.     

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.     

Dynamics and Thermodynamics Studies on the Lead and Cadmium Removal from Aqueous Solutions by Padina sp. Algae: Studies in Single and Binary Metal Systems

Raw and modified biomasses prepared from Padina sp. algae have been used as sorbent for the removal of lead and cadmium from single and binary aqueous solutions. The effects of chemical pretreatment, exposure time, initial solution pH, initial metal concentration, and temperature on the metal uptake by the algae were investigated. It was observed that initial solution pH considerably influenced Pb and Cd uptake. The maximum removal occurred at initial pH of 5.0 for lead and 6.0 for cadmium. Also, alkali modified biomass has been shown to have a high uptake capacity for both lead and cadmium. The kinetic and equilibrium experimental data fitting tested with various models. The pseudo-first-order kinetic model and Langmuir isotherm provided the best correlation of the kinetic and equilibrium experimental data, respectively. The maximum uptake estimated from the Langmuir isotherm was 264 mg g^?1 for lead and 164 mg g^?1 for cadmium ions. Experimental biosorption data in binary system were well described by the extended Langmuir model. Various thermodynamic parameters, such as ΔG°, ΔH°, and ΔS° were calculated.     

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.     

New carbon composite adsorbents for the removal of textile dyes from aqueous solutions: Kinetic,equilibrium, and thermodynamic studies

New carbon composite materials were prepared by pyrolysis of mixture of coffee wastes and red mud at 700 °C with the inorganic: organic ratios of 1.9 (CC-1.9) and 2.2 (CC-2.2). These adsorbents were used to remove reactive orange 16 (RO-16) and reactive red 120 (RR-120) textile dyes from aqueous solution. The CC-1.9 and CC-2.2 materials were characterized using Fourier transform infrared spectroscopy, Nitrogen adsorption/desorption curves, scanning electron Microscopy and X-ray diffraction. The kinetic of adsorption data was fitted by general order kinetic model. A three-parameter isotherm model, Liu isotherm model, gave the best fit of the equilibrium data (298 to 323 K). The maximum amounts of dyes removed at 323 K were 144.8 (CC-1.9) and 139.5 mg g^?1 (CC-2.2) for RO-16 dye and 95.76 (CC-1.9) and 93.80 mg g^?1 (CC-2.2) for RR-120 dye. Two simulated dyehouse effluents were used to investigate the application of the adsorbents for effluent treatment.     

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.     

Equilibrium,Kinetics, and Thermodynamics of Bovine Serum Albumin Adsorption on Single-Walled Carbon Nanotubes

We investigated the equilibrium, kinetics, and thermodynamics of bovine serum albumin (BSA) adsorption on single-walled carbon nanotubes (SWNTs) from aqueous solutions with different pH and temperatures. We analyzed the experimental adsorption equilibrium and kinetic data to evaluate the adsorption characteristics of SWNTs for BSA. The results show that the effects of pH and temperature were important. Moreover, the adsorption isotherm data of BSA on SWNTs are consistent with the Langmuir and Freundlich models, while the kinetics can be expressed by the pseudo-first-order and the intraparticle diffusion rate models. The maximum protein adsorption capacity of SWNTs, which have a surface area of 191.2 m²/g, was found to be 609.8 mg g^?1 at pH 4 and 40°C, and this was the highest value obtained among our previous studies examined with various metal oxides. In addition, the zeta potential measurements were examined to understand the effects of charge density of the surface and the protein on the adsorption process. Thermodynamic analysis results indicate that the nature of adsorption changes with pH. SWNTs were found to be effective for BSA adsorption.     

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.     

Equilibrium Isotherms,Thermodynamics, and Kinetic Studies for the Adsorption of Food Azo Dyes onto Chitosan Films

The adsorption of FD&C red 2 and FD&C yellow 5 onto chitosan films (CFs) was evaluated by equilibrium isotherms, thermodynamics, and kinetic studies. The effects of temperature (298–328 K), initial dye concentration (50–300 mg L^?1), stirring rate (50–350 rpm), and contact time (0–120 min) were investigated at pH of 2.0 and 100 mg L^?1 of CFs. The dye concentration was determined by spectrophotometry. Freundlich and Langmuir models were used to represent the equilibrium data. The Langmuir model was the more adequate to represent the equilibrium data (R² > 0.99 and average relative error <2.50%) and the maximum adsorption capacities were 494.13 and 480.00 mg g^?1 for FD&C red 2 and FD&C yellow 5, respectively, obtained at 298 K. The R_L values ranged from 0.044 to 0.145. The adsorption was exothermic, spontaneous, and favorable. For the FD&C red 2, 90% of saturation was attained at 120 min and the Elovich model was the more appropriate. For the FD&C yellow 5, 95% of saturation was attained at 20 min and the pseudo first-order model was the more adequate to fit the kinetic data. CFs were easily separated from the liquid phase after the adsorption process, providing benefits for industrial applications, and its application range can be extended for azo dyes.     

Pecan Nutshell as Biosorbent to Remove Toxic Metals from Aqueous Solution

Abstract

In the present study we reported for the first time, the feasibility of pecan nutshell (PNS-Carya illinoensis) as an alternative biosorbent to remove Cr(III), Fe(III) and Zn(II) metallic ions from aqueous solutions. The ability of PNS to remove these metallic ions was investigated by using batch biosorption procedure. The effects, such as pH and the biosorbent dosage on the adsorption capacities of PNS were studied. Five kinetic models were tested, the adsorption kinetics being the better fitted one to the fractionary-order kinetic model.

The equilibrium data were fitted to Langmuir, Freundlich, Sips, and Redlich-Peterson isotherm models. Taking into account a statistical error function, the data were best fitted to Sips isotherm models. The maximum biosorption capacity of PNS were 93.01, 76.59, and 107.9 mg g^?1 for Cr(III), Fe(III), and Zn(II), respectively.