Adsorption performance of suitable nanostructured novel composite adsorbent of poly(N-methylaniline) for removal of heavy metal from aqueous solutions

Poly(N-methylaniline) (PNMA) composite composed of N-methylaniline and poly(ethanol) was prepared by in situ polymerization technique and characterized using FTIR, SEM-EDS and XRD instruments. Characterization of product revealed that this composite is crystalline in nature and the particles size is less than100 nm. The potential of this composite in removal of Cr(VI) ions from synthetic aqueous effluents was investigated by batch sorption system. The experimental results confirmed that this adsorbent has the potential application for removal of Cr(VI) ions from aqueous solution with the sorption capacity of 125 mg/g of Cr(VI)/0.1 g of adsorbent.     

Adsorption of hexavalent chromium from aqueous solutions by bio-chars obtained during biomass pyrolysis

In this study, bio-chars were evaluated as a potential adsorbent for the removal of Cr (VI) ions from aqueous solutions. The effects of some important parameters including initial pH (1.5–7), adsorbent dose (0.2–5 g/L), contact time (5–900 min) and initial Cr (VI) ion concentration (5–75 mg/L) were tested on the removal of Cr (VI) ions from aqueous solution in batch experiments. Maximum adsorption capacities of the tested bio-chars under the certain experimental conditions determined as optimal were 3.53 mg/g for NCBC, 3.97 mg/g for NZCBC and 6.08 mg/g for ACBC, respectively. Results of the kinetic and isotherm modeling studies revealed that the adsorption data fitted well with a pseudo-second order and Langmuir model. In among the tested bio-chars, the bio-char (ACBC) was largely equivalent to activated carbon: AC (9.97 mg/g) in terms of adsorption capacity. All results indicated that the bio-chars had higher adsorption capacity than some chars and activated carbons reported previously, and also that these bio-chars could be used successfully as low-cost adsorbents for the removal of chromium ions from aqueous solutions under the tested experimental conditions.     

Influence of regeneration conditions on the cyclic performance of amine-grafted mesoporous silica for CO2 capture: An experimental and statistical study

This work deals with the behavior of amine-grafted mesoporous silica (referred to as TRI-PE-MCM-41) throughout adsorption–desorption cycles in the presence of 5% CO₂/N₂ using various regeneration conditions in batch experiments. The criteria proposed to determine the optimum regeneration conditions are the working adsorption capacity, the rate of desorption and the change of adsorption capacity between consecutive cycles. Using a 2³ factorial design of experiments, the impact on the performance of the adsorbent of different levels of temperature, pressure, and flow rate of purge gas during desorption was determined. It was found that all the parameters under study have a statistically significant influence on the working adsorption capacity, but only temperature is influential with respect to desorption rate. Regeneration using temperature swing was found to be attractive, as the highest CO₂ adsorption capacity (1.95 mmol g^?1) and the fastest desorption rate (9.82×10^?4 mmol g^?1 s^?1) occurred when desorption was carried out at 150 °C. However, if vacuum is applied, regeneration can be achieved at a temperature as low as 70 °C with only a 13% penalty in terms of working adsorption capacity. It was also demonstrated that under the proper regeneration conditions, TRI-PE-MCM-41 is stable over 100 adsorption–desorption cycles.     

Poly(N,N-dimethylaminoethyl methacrylate)/graphene oxide hybrid hydrogels: pH and temperature sensitivities and Cr(VI) adsorption

Different amounts of graphene oxide (GO) were incorporated to N,N-dimethylaminoethyl methacrylate (DMAEMA), fabricating a series of pH and temperature dual sensitive PDMAEMA/GO hybrid hydrogels by in situ polymerization. Their microscopic network structures as well as swelling properties and Cr(VI) adsorption were characterized. The equilibrium swelling ratios (ESR) of hydrogels increased significantly with 0.5 wt% GO feeding of DMAEMA amount, and then decreased with further GO loading increasing. All hydrogels showed obvious deswelling when pH value of swelling mediums increased from 5 to 10 gradually. At pH 7, hydrogels revealed slight ESR increment with temperature up to 50 °C, above which obvious deswelling occurred. In pH 8 buffer, 0.5 wt% of GO loading triggered lower critical solution temperature (LCST) to decrease by 3 °C, and 2–7 °C increment was observed when 1–6 wt% of GO was loaded, as compared with that of GO-free PDMAEMA hydrogel. Cr(VI) adsorption of hydrogels was also improved by the introduction of GO to some extent, and the maximum Cr(VI) adsorption of 180 mg/g was realized, indicating that the obtained PDMAEMA/GO hybrid hydrogels possess excellent adsorption performance.     

Adsorption thermodynamics and kinetics of Cr(VI) on KIP210 resin

Series of resin selection experiments were carried out and the KIP210 strong base anion exchange resin was confirmed to have the maximum equilibrium adsorption capacity to remove Cr(VI) from wastewater. The adsorption thermodynamics and kinetics of Cr(VI) on KIP210 resin were investigated completely and systematically. The static experiments were performed to study the effects of various parameters, such as shaking speed, resin dosage and pH during the adsorption process. The results indicate that the effect of external diffusion is eliminated at 160 rpm, the best pH value is 3.0 and the removal percentage of Cr(VI) increases with the increase of the resin dosage. The adsorption of Cr(VI) on KIP210 agrees well with the Langmuir isotherm and the adsorption parameters of thermodynamics are ΔH = 26.5 kJ mol⁻¹, ΔS = 126.7 J mol⁻¹ K⁻¹ and ΔG < 0. It demonstrates that the adsorption of Cr(VI) on KIP210 is a spontaneously endothermic physisorption process. Moreover, the adsorption process can be described well by a pseudo-second-order kinetic model and the activation energy is 30.9 kJ mol⁻¹. The kinetic analysis showed that the adsorption rate is controlled by intraparticle diffusion. The resin is successfully regenerated using the NaOH solutions.     

Chromium (VI) removal by methylated biomass of Spirulina platensis: The effect of methylation process

Biosorption of heavy metals is an interesting approach to treat industrial wastewaters by an environmentally friendly system. Spirulina platensis biomass, an effective biosorbent for cations, cannot be used to adsorb chromate due to its negatively charged surface close to neutral conditions; therefore, methylation of biomass was performed to increase its adsorption capacity under these conditions. Batch adsorption tests carried out varying both Cr(VI) and methylated biomass concentrations showed that 2–4 g l^?1 of biosorbent were able to remove Cr(VI) with efficiency ≥80%, while higher Cr(VI) levels (43–50 mg l^?1) showed low removal efficiency. The model of Langmuir was shown to describe the adsorption phenomenon better than the Freundlich one. The values of the overall adsorption capacity of methylated biomass suggested that increased biosorbent availability does not necessarily correspond to larger amount of adsorbed metal. FT-IR spectra of dried and methylated biomass of S. platensis allowed us monitoring the efficiency of the methylation process through the analysis of CH and COO^? vibrational stretching modes, taken as diagnostic of this process.     

Removal of Cr(VI) from aqueous solution by surfactant-modified kaolinite

Removal of Cr(VI) from aqueous solution by hexadecyltrimethylammonium chloride (HDTMA) modified kaolinite (HMK) was investigated, where the maximum adsorptive capacity reached 27.8 mg/g Cr(VI) using HMK compared with only 0.7 mg/g using unmodified natural kaolinite (NK). The adsorption of Cr(VI) on HMK can be well described by the Langmuir isotherm, and the kinetic adsorption of Cr(VI) on both HMK and NK fitted a pseudo-second-order model. FTIR analysis showed that surface modified HDTMA was responsible for the high adsorptive capacity of Cr(VI). HMK was used to remove Cr(VI) from an electroplating wastewater.     

Synthesis of NIPAAm-based polymer-grafted silica beads by surface-initiated ATRP using Me4Cyclam ligands and the thermo-responsive behaviors for lanthanide(III) ions

The applicability of atom transfer radical polymerization (ATRP) to the copolymerization of N-isopropylacrylamide (NIPAAm) with N-vinyl-2-pyrrolidone (NVP) was examined in CuCl/CuCl₂-catalyst system using tris[2-(dimethylamino)ethyl]amine (Me₆TREN) and 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane (Me₄Cyclam) as ligands. In the Me₆TREN system, less reactive NVP not only does not quantitatively copolymerize but also interferes with homopolymerization of NIPAAm units. In contrast, the Me₄Cyclam system under heating was more active, although the controllability for polymer homogeneity is lower than Me₆TREN system. The application of active Me₄Cyclam system to surface-initiated ATRP has successfully prepared silica beads surface-modified with NIPAAm copolymers of NVP and 4-vinylpyridine (VPy). The thermo-responsive behavior of surface-grafted NIPAAm-based polymers was investigated for lanthanide trivalent ions (Ln(III)) in different pH solutions. In the weak acidic solutions of pH = 5.4–5.6, all the surface-grafted polymers including poly(NIPAAm) exhibited only adsorption behavior with regular selectivity (Eu³⁺ > Sm³⁺ > Nd³⁺ > Ce³⁺ > La³⁺) below the phase-transition temperatures. In the more acidic solution of pH = 2.9, the surface-grafted poly(NIPAAm) and NVP copolymers exhibited adsorption and desorption behaviors below and above the phase-transition temperatures, while VPy copolymers exhibited only adsorption independent of temperature change. Furthermore, the adsorption capacity of all the surface-grafted polymers was deteriorated by the lowering of pH. The observed desorption and the deterioration of adsorption capacity suggest the weakening of adsorption strength for Ln(III) in low pH solutions. In this study, a possible adsorption/desorption mechanism of Ln(III) on surface-grafted NIPAAm-based polymers is discussed.     

Fabrication of copper coated polymer foam and their application for hexavalent chromium removal

The polymer foam coated with zero-valent copper (Cu⁰) was designed and prepared for the removal of hexavalent chromium (Cr(VI)) in water. Firstly, porous poly(tert-butyl acrylate) was fabricated by concentrated emulsion polymerization and then acrylic acid groups were generated on the surface of foam by hydrolysis reaction. Secondly, with the help of the large amount reactive carboxylic acid groups, polyethyleneimine (PEI) were chemically grafted onto the surface by the reaction between amine group and acrylic acid group. Finally, zero-valent copper was reduced by sodium borohydride (NaBH₄) and coated on the surface of polymer foam. Thus the copper functionalized porous adsorbent (Cu⁰–PEI–PAA) was constructed, and then applied for removing Cr(VI) from aqueous solution. The removal mechanism of Cr(VI) involved redox reaction by zero-valent copper and adsorption by amine groups, simultaneously. As a result, 99.5% of Cr(VI) could be removed within 2 h, and the maximum removal capacity for Cr(VI) of Cu⁰–PEI(1800)–PAA was 9.16 mg/g. Furthermore, the effect of initial concentration of Cr(VI), pH value, and temperature on the Cr(VI) removal was investigated. Therefore, the as-prepared zero-valent copper-loaded polymer foam could be an efficient and promising remediation material to remove Cr(VI) from wastewater.     

Spectroscopic characterization of the reduction and removal of chromium (VI) by tropical peat and humin

The reduction of Cr(VI) to Cr(III) in aqueous solution, and the subsequent removal of Cr(III) using in natura peat or its humin fraction, was characterized by electron paramagnetic resonance (EPR), ultraviolet–visible (UV–Vis) spectroscopy and X-ray photoelectron (XPS) spectroscopy. EPR spectroscopy g-factors ranging from 2.0029 to 2.0030 indicated the presence of organic free radicals (OFR) associated with carbon atoms. The spin densities of the samples increased with pH in the range pH 2.0–pH 6.0. An XPS spectroscopy peak at 579.0 eV was attributed to Cr(VI), and peaks at 576.8 eV and 677.3 eV to two different chemical forms of Cr(III). Removal of chromium increased with the reduction of Cr(VI) to Cr(III), and removal rates after 50 h were 13% (peat) and 15% (humin) at pH 6.0, and 70% (peat) and 80% (humin) at pH 2.0. The greater efficiency of the humin fraction in the reduction/removal process is discussed in terms of the chemical structures of these materials.     

Phosphate removal from water using an iron oxide impregnated strong base anion exchange resin

Removing phosphate from water is important as it causes eutrophication, which in turn has a harmful effect on aquatic life, resulting in a reduction in biodiversity. On the other hand, recovery of phosphate from phosphorus containing wastewater is essential for developing an alternative source of phosphorus to overcome the global challenge of phosphorus scarcity. Phosphate removal from aqueous solutions was studied using an iron oxide impregnated strong base anion exchange resin, Purolite FerrIX A33E in batch and fixed-bed column experiments. Phosphate adsorption in the batch study satisfactorily fitted to the Langmuir isotherm with a maximum adsorption capacity of 48 mg P/g. In the column study, increase in inlet phosphate concentration (5–30 mg P/L), and filtration velocity (2.5–10 m/h) resulted in faster breakthrough times and increase in breakthrough adsorption capacities. Increase in bed height (3–19 cm) also increased adsorption capacity but the breakthrough time was slower. The breakthrough data were reasonably well described using the empirical models of Bohart–Adams, Thomas, and Yoon–Nelson, except for high bed heights. Phosphate adsorbed was effectively desorbed using 1 M NaOH and the adsorbent was regenerated after each of three adsorption/desorption cycles by maintaining the adsorption capacity at >90% of the original value. Greater than 99.5% of the desorbed P was recovered by precipitation using CaCl₂.     

Artificial neural network optimization for removal of hazardous dye Eosin Y from aqueous solution using Co2O3-NP-AC: Isotherm and kinetics study

The present research is focused on the synthesis and characterization of cobalt (III) oxide (Co₂O₃) nanoparticle loaded on activated carbon to prepare an outstanding sorbent for the removal of eosin Y (EY) as hazardous dye from aqueous solution. The sorbent was identified by SEM and XRD analysis. The effect of solution pH, adsorbent dosage (0.005–0.02 g), contact time (0.5–30 min) and initial eosin Y concentration (30–80 mg L⁻¹) on the adsorption process was investigated and modeled by artificial neural network. Following optimization of variables, the experimental equilibrium data was analysis by Langmuir, Freundlich, Tempkin and D–R isothermal models and explored that the data well presented by Langmuir model with a maximum adsorption capacity of 555.56 mg g⁻¹ at 25 °C. Kinetic studies at various adsorbent dosage and initial EY concentrations show that high removal percentage (>90%) was achieved within 15 min of the start of every experiment at most conditions. The adsorption of EY follows the pseudo-second-order rate equation in addition to intraparticle diffusion model. The experimental data were applied to train the multilayer feed forward neural network with three inputs and one output with different algorithms and different numbers of neurons in the hidden layer. The minimum mean squared error (MSE) of 1.49e − 04 and determination coefficient of (R²) 0.9991.     

Synthesis,characterization of Fe3O4@glycine doped polypyrrole magnetic nanocomposites and their potential performance to remove toxic Cr(VI)

Fe₃O₄ coated glycine doped polypyrrole magnetic nanocomposite (Fe₃O₄@gly-PPy NC) was prepared via coating of suspended Fe₃O₄ nanoparticles with gly-PPy. FE-SEM and HR-TEM images indicated that Fe₃O₄ nanoparticles were encapsulated by precipitating gly-PPy moieties. Chromium(VI) adsorption followed a Langmuir isotherm with maximum capacity of 238–303 mg/g for a temperature range of 25–45 °C at pH 2. The adsorption process was governed by the ionic interaction and the reduction of Cr(VI) to Cr(III) by the PPy moiety. Results showed that NCs are effective adsorbents for the removal of Cr(VI) from wastewater and can be separated by external magnetic field from the reactor.     

Sorption of heavy metal ions from aqueous solution by a novel cast PVA/TiO2 nanohybrid adsorbent functionalized with amine groups

Sorption of Cd(II), Ni(II) and U(VI) ions onto a novel cast PVA/TiO₂/APTES nanohybrid adsorbent with variations in adsorbent dose, pH, contact time, initial metal concentration and temperature has been investigated. The adsorbent were characterized by SEM and FTIR analysis. BET surface area, pore diameter and pore volume of adsorbent were 35.98 m² g⁻¹, 3.08 nm and 0.059 cm³ g⁻¹, respectively. The kinetic and equilibrium data were accurately described by the double-exponential and Freundlich models for all metals. The maximum sorption capacities were 49.0, 13.1 and 36.1 mg g⁻¹ for Cd(II), Ni(II) and U(VI) ions with pH of 5.5, 5 and 4.5, respectively. Thermodynamic studies showed that the sorption process was favored at higher temperature. The adsorbent can be easily regenerated after 5 cycles of sorption–desorption.     

Capacity of activated carbon in the removal of acid dyes subsequent to its thermal treatment

A commercial activated carbon (Prolabo) was subjected to thermal treatment at 400 and 600 °C for 2 h. Characterization of the parent, and heated products, was carried out by determining the N₂/77 K adsorption isotherms, FTIR spectra, acidic/basic sites, and adsorption of iodine, Acid Blue 74 (AB), Acid Red 73 (AR) and Acid Yellow 23 (AY) from aqueous solution. Thermal treatment resulted in some enhancement in the porosity characteristics (specific area and pore volume) particularly in micropores, although insignificant changes appear in the surface chemical properties. Two liquid-phase adsorption models are applied, the Langmuir and Dubinin–Radushkevich linear equations, which showed satisfactory fit to the adsorption data. Evaluated capacity and affinity parameters demonstrated that the uptake of the acid dyes decrease in the order of AB > AR >> AY, which may be ascribed to chemical structure differences in substituents and side chains leading to unavailable accessibility. Heated carbons exhibit a reduction in uptake of AB, and an increase in case of AY and AR dyes. Changes in surface chemical groups, under action of heat probably influence the adsorbate/adsorbent, adsorbate/liquid and adsorbent/liquid relationships leading to the apparent differences.     

Removal of As(V) and Cr(VI) in aqueous solution by sand media simultaneously coated with Fe and Mn oxides

In this research, sand media simultaneously coated with iron and manganese (iron and manganese coated sand, IMCS) were applied to treat synthetic wastewater contaminated with both Cr(VI) and As(V). Scanning electron microscopy (SEM) and X-ray diffraction spectroscopy (XRD) were used to characterize the surface properties of the coated layer of IMCS. Adsorption of Cr(VI) and As(V) onto IMCS followed a typical anionic type, showing a gradual decrease of adsorption as the solution pH increased. In a single system, IMCS showed a greater adsorption capacity for As(V) than that for Cr(VI) over the entire solution pH range. In a binary system, As(V) preferentially occupied the limited adsorption sites on IMCS and therefore Cr(VI) adsorption was suppressed. This result indicates that As(V) adsorption onto the surface of IMCS occurs through a strong chemical bonding such as an inner-sphere complex. As(V) adsorption onto the IMCS was well described by second-order kinetics. From the adsorption isotherm experiments at pH 4, the maximum adsorbed amount of Cr(VI) and As(V) onto IMCS in a single system was 102 mg/kg and 455 mg/kg, respectively.     

Cr(VI) removal from synthetic and real wastewaters: The use of the invasive biomass Sargassum muticum in batch and column experiments

The macroalgae Sargassum muticum was selected for the treatment of solutions containing Cr(VI). Very acidic pH values were established as optimal for Cr(VI) reduction. Algae chemical modification reduced equilibrium time to 4 h. First order kinetic model was used to describe the reduction kinetic of Cr(VI). A column experiment allowed to distinguish the processes occurring during Cr(VI) elimination: its reduction to Cr(III) and the subsequent adsorption of this species formed. Under the selected conditions the biomass was capable of reducing all the incoming Cr(VI) during 77 h. Industrial wastewaters from chrome plating industry were also tested for chromium removal.     

The effects of the surface oxidation of activated carbon,the solution pH and the temperature on adsorption of ibuprofen

A commercial microporous–mesoporous granular activated carbon was modified by oxidation with either H₂O₂ in the presence or absence of ultrasonic irradiation, or NaOCl or by a thermal treatment under nitrogen flow. Raw and modified materials were characterized by N₂ adsorption–desorption measurements at 77 K, Boehm titrations, pH measurements and X-ray photoelectron spectroscopy. Ibuprofen adsorption kinetic and isotherm studies were carried out at pH 3 and 7 on raw and modified materials. The thermodynamic parameters of adsorption were calculated from the isotherms obtained at 298, 313 and 328 K. The pore size distribution of carbon loaded with ibuprofen brought out that adsorption occurred preferentially into the ultramicropores. The adsorption of ibuprofen on pristine activated carbon was found endothermic, spontaneous (ΔG° = −1.1 kJ mol⁻¹), and promoted at acidic pH through dispersive interactions. All explored oxidative treatments led mainly to the formation of carbonyl groups and in a less extent to lactonic and carboxylic groups. This then helped to enhance the adsorption uptake while decreasing adsorption Gibbs energy (notably −7.3 kJ mol⁻¹ after sonication in H₂O₂). The decrease of the adsorption capacity after bleaching was attributed to the presence of phenolic groups.     

Kinetics,equilibrium and thermodynamic studies on biosorption of hexavalent chromium by dead fungal biomass of marine Aspergillus niger

Quite a number of reports are available on metal binding capacity of different groups of microorganisms. However, reports on the equilibrium studies on biosorption by marine fungi are quite inadequate. The present study was carried out in a batch system using dead biomass of marine Aspergillus niger for the sorption of Cr(VI). The removal rate of Cr(VI) was increased with a decrease in pH and an increase in Cr(VI) and biomass concentration. A. niger exhibited the highest Cr(VI) uptake of 117.33 mg g^?1 of biomass at pH 1.0 in the presence of 400 mg l^?1 Cr at 50 °C. Kinetics studies based on fractional power, zero order, first order, pseudo-first order, Elovich, second order and pseudo-second order rate expressions have also been carried out. The experimental data were analyzed using five, two-parameter isotherms (Langmuir, Freundlich, Dubinin–Radushkevich, Temkin and Halsey). It was observed that Langmuir model exhibited the best fit to experimental data. Thermodynamic parameters of the biosorption (ΔG°, ΔH° and ΔS°) were also determined.     

Temperature swing adsorption of gold(III) ions on poly(N-isopropylacrylamide) gel

The possibility of temperature swing adsorption (TSA) of heavy metals on thermosensitive N-isopropylacrylamide (NIPA) gel has been examined. The NIPA gel has a high degree of affinity for Au(III) ions. The amount of Au(III) ions adsorbed on the NIPA gel is low at 10 °C and high at 50 °C, and the amount adsorbed increases in a stepwise manner with temperature around 32 °C, the lower critical solution temperature (LCST) of poly(NIPA). Au(III) ions tend to be well adsorbed on shrunken gel, but are adsorbed poorly on swollen gel. The adsorption capacity of 0.637 mmol-Au/g-dry gel at 50 °C was obtained from a Langmuir-type isotherm. The NIPA gel adsorbs and desorbs Au(III) ions reversibly by TSA between 50 °C and 10 °C. In addition, the enrichment of Au(III) ions in the diluted solution through TSA was successfully conducted. To discuss the mechanism of adsorption of Au(III) ions on the NIPA gel, the adsorption of Au(III) ions on non-thermosensitive N,N-dimethylacrylamide and thermosensitive N,N-diethylacrylamide gels, which have a structure similar to that of the NIPA gel, was also investigated. These gels adsorb Au(III) ions strongly; however, the amount of Au(III) ions adsorbed is independent of the temperature.