Adsorption of Cr (VI) Oxyanions onto Modified Wood Pulp

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

EQUILIBRIUM,KINETICS, AND BREAKTHROUGH STUDIES FOR ADSORPTION OF Cr(VI) ON CHITOSAN

Wastewater containing low levels of pollutants can be effectively treated by the adsorption technique. In the present work, an adsorption study was carried out using chitosan as adsorbent in a fixed-bed column for the removal of Cr(VI) from wastewater solutions. The column performance of Cr(VI) adsorption onto chitosan was studied at different bed heights (3–9 cm), flow rates (50–200 mL/min), initial metal concentrations (2–10 mg/L), pH values (2–7), and temperatures (30°–60°C). The equilibrium data for the batch adsorption of Cr(VI) on chitosan were tested using the Langmuir, Freundlich, and BET isotherm models. The Langmuir model was found to be the most suitable, with a maximum adsorption capacity of 35.7 mg/g and a correlation coefficient (R ²) = 0.952. The experimental data were found to fit well with the pseudo-second-order kinetic model, with R ² = 0.999. The dynamics of the adsorption process was modeled using the Adams-Bohart, Thomas, and mass transfer models. The models were used to predict the breakthrough curves of adsorption systems and to determine the characteristic design parameters of the column. The adsorption data were observed to fit well with all three models. The model parameters were derived using MATLAB software. In order to compare quantitatively the applicability of adsorption dynamic models in fitting to experimental data, the percentage relative deviation (P) was calculated and found to be less than 5, confirming that the fit is good for all three models.     

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.     

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

Abstract

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

Removal of Chromium(VI) Using Surface Modified Superparamagnetic Iron Oxide Nanoparticles

This study describes the removal of Chromium(VI) from aqueous solutions using surface tailored superparamagnetic iron oxide nanoparticles (SPION) coated with bis(2,4,4-trimethylpentyl)dithiophosphinic acid (Cyanex-301). The synthesized Cyanex-301 coated SPION has been characterized by Transmission Electron Microscopy (TEM), Fourier-Transfer Infrared Spectroscopy (FT-IR), X-ray Photonic Spectroscopy (XPS), and Thermogravimetric Analysis (TGA). The adsorption mechanism was proposed to be via complexation between the thiol group on Cyanex-301 and Cr(VI) ions based on the XPS and FTIR analysis. It has been found that the equilibrium can be attained in less than 2 hr. The adsorption behavior of Cr(VI) on the Cyanex-301 coated SPION can be well described by the Langmuir model and the maximum adsorption capacity for Cr(VI) was estimated to be 30.8 mg/g. The selectivity of the Cyanex-301 coated SPION adsorbent towards Cr(VI) ions was found to be high and the maximum loading capacity obtained is up to an order of magnitude higher than that of other adsorbents reported in the literature. The desorption studies showed that more than 70% of Cr(VI) can be recovered using HNO₃ as eluting solution. Our findings suggest a high potential of the designed adsorbent material for the treatment of industrial wastewater containing Cr(VI).     

Solution combustion synthesis of CeO2 powders and its application in water treatment

CeO₂ powders were synthesized via a solution combustion method. The product was characterized by X-ray diffraction scanning electron microscope, and BET surface area analysis. The results indicated that the CeO₂ powders present a foaming state with a surface area of 28.17 m² g^–1. The adsorption performance of the CeO₂ powders was tested toward the removal of typical pollutants of Cr(VI) and Congo red (CR). The results showed that the adsorption of Cr(VI) and CR onto CeO₂ powders followed the Langmuir isotherm model and pseudo-second-order kinetics, with an adsorption capacity of 5.69 mg g^–1 and 35.51 mg g^–1, respectively.     

Diuron Multilayer Adsorption on Activated Carbon from CO2 Activation of Grape Seeds

Granular activated carbons were obtained from grape seeds by pyrolysis at 600°C and subsequent physical activation with CO₂ (750–900°C, 1–3 h, 25–74% burn-off). The carbon and ash content increased during the activation, reaching values of 79.0% and 11.4%, respectively. Essentially microporous materials with BET surface areas between 380 and 714 m²/g were obtained. The performance of the activated carbon in the adsorption of diuron in aqueous phase was studied within the 15–45°C temperature range. Equilibrium data showed that the maximum uptake increased with temperature from 120 to 470 µmol/g, also evidencing some dependence of the adsorption mechanism on temperature. Data were fitted to five isotherm models [Langmuir, Freundlich, Dubinin–Radushkevich, BET, and GAB (Guggenheim, Anderson, and de Boer)]. Kinetic data were analyzed using first- and second-order rate equations and intraparticle diffusion model. The second-order rate constant values obtained (2.8–13.5 × 10^?3 g/µmol min) showed that the hollow core morphology of the material favors the adsorption kinetics.     

Synthesis and characterization of carbon/AlOOH composite for adsorption of chromium(VI) from synthetic wastewater

In this work, flake like carbon/AlOOH composite has been synthesized and evaluated as a new adsorbent for the removal of Cr(VI) from synthetic wastewater. Different characterization tools such as, SEM, EDAX, XRD and XPS were performed to characterize the composite material. Batch adsorption studies for Cr(VI) removal were performed under the influence of various operational parameters such as solution pH, contact time, initial solution concentration and temperature. Results obtained revealed that adsorption of Cr(VI) onto carbon/AlOOH composite followed the pseudo-second order kinetics and Freundlich isotherm model. Thermodynamic results suggests that adsorption of Cr(VI) onto carbon/AlOOH composite was spontaneous and endothermic in nature.     

Synthesis of functionalized PET fibers by grafting and modification and their application for Cr(VI) ion removal

A new fiber adsorbent for removing Cr(VI) ions from aqueous solution was prepared by grafting and modification. The grafted fiber and modified fiber were characterized by SEM, FTIR, and TGA. FTIR analysis indicated that acrylonitrile monomer was grafted onto the PET surface and that new groups were present on the surface after the modification. Scanning electron microscopy showed that the PET fiber was wider after grafting and especially modification. The TGA results showed that the degradation steps and the thermal behavior of the PET fiber changed after modification. The effects of the pH, ion concentration, and temperature on the amount of Cr(VI) adsorbed were investigated. The fiber showed its maximum adsorption capacity in acidic medium. Isotherm studies indicated that the experimental results were best fitted to the Langmuir isotherm. The adsorption capacity of the modified fiber was found to be 25.77, 38.17, and 44.84 mg/g fiber at 25, 35, and 45 °C, respectively. Kinetic results indicated that the adsorption of Cr(VI) onto the modified fiber followed a pseudo-second-order kinetic model. Calculated thermodynamic parameters demonstrated that the adsorption of Cr(VI) ions on the modified fiber is an endothermic, feasible, and spontaneous process.     

Removal of chromium(VI) from aqueous solutions using polypyrrole-based magnetic composites

PPy/Fe₃O₄/AgCl composites were prepared via in situ polymerization for the removal of highly toxic Cr(VI). The structure and morphology of the prepared composites were characterized by the XRD, SEM, TEM, and VSM examinations. Up to 100 % removal was found with 1000 mg/L Cr(VI) aqueous solution at pH 2.0. The process of Cr(VI) ions’ adsorption was easy to reach equilibrium at higher temperatures. Adsorption results showed that Cr(VI) removal efficiency by the composites decreased with an increase in pH. Adsorption kinetics was described by the pseudo-second-order rate model. Isotherm data fitted well to the Langmuir isotherm model. Desorption experiment showed that the regenerated adsorption of PPy/Fe₃O₄/AgCl can be reused successfully for three times successive adsorption–desorption cycles without appreciable loss of its original capacity.     

Removal of Cr(VI) From Aqueous Solution by Turkish Vermiculite: Equilibrium,Thermodynamic and Kinetic Studies

Abstract

The adsorption of Cr(VI) from aqueous solution by Turkish vermiculite were investigated in terms of equilibrium, kinetics, and thermodynamics. Experimental parameters affecting the removal process such as pH of solution, adsorbent dosage, contact time, and temperature were studied. Equilibrium adsorption data were evaluated by Langmuir, Freundlich and Dubinin–Radushkevich (D–R) isotherm models. Langmuir model fitted the equilibrium data better than the Freundlich model. The monolayer adsorption capacity of Turkish vermiculite for Cr(VI) was found to be 87.7 mg/g at pH 1.5, 10 g/L adsorbent dosage and 20°C. The mean free energy of adsorption (5.9 kJ/mol) obtained from the D–R isotherm indicated that the type of sorption was essentially physical. The calculated thermodynamic parameters (ΔG ^o , ΔH ^o and ΔS ^o ) showed that the removal of Cr(VI) ions from aqueous solution by the vermiculite was feasible, spontaneous and exothermic at 20–50°C. Equilibrium data were also tested using the adsorption kinetic models and the results showed that the adsorption processes of Cr(VI) onto Turkish vermiculite followed well pseudo-second order kinetics.     

Adsorption Characteristics of Chromium(VI) Ions onto Fe(III)-Coordinated Amino-Functionalized Poly(glycidylmethacrylate)-Grafted TiO2-Densified Cellulose

An investigation was conducted with a newly developed adsorbent, iron(III)- coordinated amino-functionalized poly(glycidylmethacrylate)-grafted TiO₂-densified cellulose (Fe(III)-AM-PGDC) on the removal of chromium(VI) from aqueous solution. Batch experiments were performed under various conditions of time, pH, concentration, dose, ionic strength, and temperature. Adsorption of Cr(VI) on Fe(III)-AM-PGDC was dominated by ion exchange or outer-sphere complexation. The maximum adsorption capacity was found to be 109.76 mg g^?1. Thermodynamic study showed that adsorption of Cr(VI) onto Fe(III)-AM-PGDC is more favored. The complete removal of Cr(VI) from electroplating wastewater was achieved by the adsorbent. The adsorbent did not lose its adsorption capacity even after the fourth regeneration.     

Equilibrium Modeling of Ternary Adsorption of Phenols onto Modified Activated Carbon

The prediction of adsorption equilibria in multicomponent systems is of prime importance. Therefore, the equilibrium adsorption data for the following multicomponent systems have been studied. The present paper deals with the simultaneous removal phenol (P), 4-chlorophenol (CP), 4-nitrophenol (NP) and catechol (C), resorcinol (R), hydroquinone (HQ) onto modified activated carbon (MAC) from ternary mixtures. The BET surface area of SC was found to be 934 m²/g, whereas BJH adsorption/desorption surface area of pores is 53.03/58.15 m²/g. The equilibrium adsorption data were obtained at different initial concentrations (C₀ = 50–1000 mg/L), 12 h contact time, 30°C temperature, MAC dosage of 10 mg/L at solution pH. Equilibrium isotherms for the ternary adsorption of P–CP–NP and C–R–HQ onto MAC have been analyzed by using non-modified Langmuir, modified Langmuir, extended Langmuir, extended Freundlich and Sheindorf–Rebuhn–Sheintuch (SRS) models. The competitive Sheindorf–Rebuhn–Sheintuch (SRS) model fits for both ternary adsorption equilibrium data satisfactorily and adequately.     

Removal of Hexavalent Chromium by Different Modified Spruce Bark Adsorbents

In this work, spruce bark was used as a raw material to remove Cr(VI) ions from aqueous solutions. Three kinds of chemically modified bark adsorbents were prepared by treatment with formaldehyde (FB), dilute sulfuric acid (AB), and concentrated sulfuric acid (CB), respectively. The chemical modifications mainly changed the relative lignin content in the bark. Lower pH facilitated the adsorption of Cr(VI) ions because reduction of Cr(VI) ions to Cr(III) ions occurred during the adsorption process which consumed a large amount of H⁺ ions. Higher temperature accelerated the adsorption process, owing to the endothermic nature of the redox reaction. At initial solution pH around 1, the adsorption capacities of Cr(VI) ions on FB, AB, and CB were as high as 423, 503, and 759 mg/g, respectively, which were much higher than the reported adsorption capacities by other agricultural and forest biosorbents in the literatures. XPS analysis revealed the adsorption mechanism was adsorption-coupled reduction involving the electron-donor groups of lignin moieties.     

Preparation and characterization of hydrophilicity fibers based on 2-(dimethyamino)ethyl mathacrylate grafted polypropylene by UV- irradiation for removal of Cr(VI) and as(V)

The hydrophilic fibers based on 2-(dimethylamino)ethyl methacrylate (DMAEMA) which could remove Cr(VI) ions rapidly were prepared by UV-irradiation induced grafting of DMAEMA through pre-coating photoinitiator on the fibers and modifying with bromoethane(BE). The FTIR, FESEM, XPS, TG-DTG and contact angle spectra manifested that DMAEMA was grafted onto the surface of PP fibers and subsequently was quaternized. The maximum grafting degree (22.9 %) and exchange capacity of DMAEMA (1.2 mmol g^?1) was obtained when PP fibers was immersed in BP concentration of 0.3 % for 4 h, irradiated with the DMAEMA concentration of 100 % and irradiation time of 20 min, and then was modified with BE. The modified fibers of PP-g-DMAEMA with bromoethane were proved to remove Cr(VI) and As(V) with removal rate of 97.3 % and 96.2 % within 10 min, respectively. The prepared fibers have potential application for the removal of Cr(VI) and As(V) from wastewater highly and rapidly.     

Fe2+-modified Vermiculite for the Removal of Chromium (VI) from Aqueous Solution

A novel adsorbent: Fe²⁺-modified vermiculite was prepared in a two-step reaction. Adsorption experiments were carried out as a function of pH, contact time, and concentration of Cr(VI). It was found that Fe²⁺-modified vermiculite was particularly effective for the removal of Cr(VI) at pH 1.0. The adsorption of Cr(VI) reached equilibrium within 60 min, and the pseudo-second-order kinetic model best described the adsorption kinetics. The adsorption data follow the Langmuir model more than the Freundlich model. At pH 1.0, the maximum Cr(VI) sorption capacity (Q _max ) was 87.72 mg · g^?1. Desorption of Cr(VI) from Fe²⁺-modified vermiculite using NaOH treatment exhibited a higher desorption efficiency by more than 80%. The sorption mechanisms including electrostatic interaction and reduction were involved in the Cr (VI) removal. The results showed that Fe²⁺-modified vermiculite can be used as a new adsorbent for Cr(VI) removal which has a higher adsorption capacity and a faster adsorption rate.     

Adsorption of Cr (VI) on synthetic hematite (α-Fe2O3) nanoparticles of different morphologies

The adsorption of Cr (VI) from aqueous solution onto nanoparticles hematite (α-Fe₂O₃) of different morphologies synthesized by acid hydrolysis, transformation of ferrihydrite, sol gel methods has been investigated. The hematite particle sizes were in the range 15.69-85.84 nm and exhibiting different morphologies such as hexagonal, plate-like, nano-cubes, sub-rounded and spherical. The maximum adsorption capacity of Cr (VI) was found to be in the range 6.33–200 mgg^?1 for all hematite samples. The kinetics of sorption was rapid, reaching equilibrium at 45–240 minutes. Sorption kinetics and equilibria followed pseudo-second order and Langmuir adsorption isotherm models. The rate constants were in the range 0.996–2.37×10^?2 g/mg/min for all samples. The maximum adsorption was attained at pH 3.0, while adsorption decreased as the pH increased from pH 3.0 to 10.0. The study revealed that the hematite with plate-like morphology has the highest adsorption capacity. The sorption process has been found to be feasible following a chemisorption process, and adsorption of Cr (VI) onto hematite nanoparticles was by inner sphere surface complexation due to low desorption efficiency in the range 9.54–53.4%. However, the result of ionic strength revealed that the reaction was by outer sphere complexation. This study showed that morphologies play a vital role in the adsorption capacities of samples of hematite in the removal of Cr (VI) from aqueous solution.     

Facile fabrication of graphene oxide-polyethylenimine composite and its application for the Cr(VI) removal

A binary composite consisting of graphene oxide (GO) and polyethylenimine (PEI) was fabricated by a facile physical mixing. Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscope (FE-SEM), thermo-gravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) and Zeta potential were used to characterize the prepared graphene oxide-polyethylenimine composite (GOPC). A series of experiments were carried out to investigate the effects of some important parameters, such as molecular weight of PEI, pH, time and temperature, on the adsorption efficiency of GOPC. Due to the high amine density of GOPC, its adsorption for Cr(VI) occurred more easily at lower pH mainly via electrostatic interaction. The adsorption process matched well with the Langmuir isotherm model and the pseudo-second-order kinetic model. The maximum adsorption capacity from the Langmuir model was 370.37 mg/g at pH 2.0 and 45°C for GOPC. Thermodynamic parameters revealed spontaneous and endothermic nature of the Cr(VI) adsorption onto GOPC. The main adsorption mechanism of GOPC toward Cr(VI) was electrostatic interaction. The adsorption-desorption experiments suggested GOPC was easily recycled and its stable adsorption capacity endowed it great potential as an adsorbent of Cr(VI) from wastewater.     

Solvothermal polycondensation of novolacs phenolic-resin to nanopowders and their derived activated nanocarbons as efficient adsorbents for water cleaning

Novolacs phenolic-resin (PF) was easily polycondensed into polymeric powders with sizes and morphologies ranging from microspheres to nanoparticles by a simple solvothermal process without adding any crosslinking agent. Activating the highly divided PF powders by CO₂ resulted in nanosize activated carbons with high specific surface area (2092 m² g^?1) and large pore volume (1.33 cm³ g^?1) while preserving a high carbon yield of about 38 wt%. As for adsorption tests, the micropore-dominated activated nanocarbons exhibited fast and high adsorption capabilities towards both Cr(VI) ions and bulky rhodamine B molecules due to their much improved external surface area and the greatly shortened intra-particle diffusion distance. The equilibrium adsorption amounts of Cr(VI) and RB on the activated nanocarbons as estimated by the Langmuir model were 200 and 990 mg g^?1, achieved within an adsorption time of 30 and 360 min, respectively.     

Column adsorption of Cr (VI) from dilute aqueous solution on tailored micro-mesoporous low-cost activated carbon: performance indicators and breakthrough modeling

Abstract

The adsorption technology based on low-cost adsorbents is of great interest for alternative sustainable abatement of toxic heavy metals from dilute industrial wastewaters. In this study, the performance of tailored low-cost activated carbon (AC) in column adsorption of Cr (VI) from dilute aqueous solution is evaluated using the rapid small scale column tests procedure. At solutions pH 2, the response of column performance indicators such as number of bed volumes, carbon usage rate, breakthrough capacity and column utilization for achieving effluent discharge limit of 0.5?mg L^?1 Cr (VI) to changes in flow rate and bed height are studied. At breakpoints, the low-cost AC showed number of bed volumes (38–259) and column utilization (10–72%) for empty bed contact time (0.8–6.13?min). The bed regeneration efficiency was low at 48%. Also, the low-cost AC exhibited total dynamic selectivity for Cr (VI) from simulated electroplating wastewater. The breakthrough data were correlated using a mass transfer model of Michael’s constant-pattern behavior. The results of this study demonstrate the possible application of the tailored low-cost AC for efficient column adsorption of Cr (VI) from dilute wastewaters.