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.     

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.     

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 urea,creatinine, and uric acid from three solution types using spherical activated carbon and its recyclability

In this paper, we propose that the urinary toxins from the wastewater be adsorbed on an adsorbent such as spherical activated carbon and the latter be regenerated by subjecting it to high temperatures to recycle activated carbon and also to recycle the water used in dialysis. We studied the adsorption of artificial waste dialysate, which is a mixed solution of urea, creatinine, and uric acid, and the separate solutions for each of these and found that their extents of adsorption onto the spherical activated carbon material were nearly identical. The amount of adsorption was approximately 1.4 mg·g⁻¹ for urea, 18 mg·g⁻¹ for creatinine, and 20 mg·g⁻¹ for uric acid. The urea, creatinine, and uric acid adsorbed onto the spherical activated carbon decomposed on heat treatment at 500 °C, and the adsorption capacity of the spherical activated carbon was regenerated. Our study successfully demonstrated that the spherical activated carbon can be recycled in the waste dialysate treatment process.     

Enhanced adsorptive removal of Cr(VI) in aqueous solution by polyethyleneimine modified palygorskite

Polyethyleneimine (PEI) modified palygorskite (Pal) was used for the adsorption of Cr(VI) in aqueous solution. The absorbent was characterized by Fourier transform infrared spectroscopy (FT-IR) and thermogravimetric analysis (TGA). Characterized results confirmed that the Pal has been successfully modified by PEI. The modification of PEI increased the Cr(VI) adsorption performance of the Pal by the adsorption combined reduction mechanism, and amino groups of the adsorbent play the main role in the enhanced Cr(VI) adsorption. The maximum adsorption capacity was 51.10 mg·g⁻¹ at pH 4.0 and 25 °C. The adsorption kinetics of Cr(VI) on the adsorbent conforms to the Langmuir isotherm model. The maximum adsorption occurs at pH 3, and then the adsorption capacity of PEI-Pal was decreased with the increase of pH values. The adsorption kinetics of Cr(VI) on PEI-Pal was modeled with pseudo-second-order model. The addition of Cl⁻, SO₄²⁻ and PO₄³⁻ reduced the Cr(VI) adsorption by competition with Cr(VI) for the active sites of PEI-Pal. The Cr(VI) saturated PEI-Pal can be regenerated in alkaline solution, and the adsorption capacity can still be maintained at 30.44 mg·g⁻¹ after 4 cycles. The results demonstrate that PEI-Pal can be used as a potential adsorbent of Cr(VI) in aqueous solutions.     

Multiwalled CNTs for Cr(VI) removal from industrial wastewater: An advanced study on adsorption,kinetics, thermodynamics for the comparison between the embedded and non‐embedded carboxyl group

The adsorption capabilities of multiwalled carbon nanotubes (MWCNTs) with and without the embedded carboxyl group for the removal of parts per million levels of hexavalent chromium were examined as a function of several parameters, namely contact time, pH of initial solution, initial concentration of Cr(VI), adsorbent dosage as well as temperature of solution. Adsorption isotherms have been utilized to explain the adsorption mechanism. Ion exchange, intra‐particle diffusion, and electrostatic interactions are found to be the fundamental mechanisms describing the adsorption of Cr(VI). The maximum adsorption capacities of Cr(VI) ion by raw MWCNTs and functionalized MWCNTs were found to be 84.75 and 78.13 mg · g^?1, respectively, as calculated by the Langmuir adsorption isotherm model. This is with regard to the electron‐rich atoms inside the functional group which repels the negatively charged dichromate ions. Kinetic studies were performed, and the data was found in good agreement with the pseudo‐second‐order.     

Modified activated carbon for the removal of copper,zinc, chromium and cyanide from wastewater

Modified activated carbon are carbonaceous adsorbents which have tetrabutyl ammonium iodide (TBAI) and sodium diethyl dithiocarbamate (SDDC) immobilised at their surface. This study investigates the adsorption of toxic ions, copper, zinc, chromium and cyanide on these adsorbents that have undergone surface modification with tetrabutyl ammonium (TBA) and SDDC in wastewater applications. The modification technique enhance the removal capacity of carbon and therefore decreases cost-effective removal of Cu(II), Zn(II), Cr(VI) and CN⁻ from metal finishing (electroplating unit) wastewater. Two separate fixed bed modified activated carbon columns were used; TBA-carbon column for cyanide removal and SDDC-carbon column for multi-species metal ions (Cu, Zn, Cr) removal. Wastewater from electroplating unit containing 37 mg l⁻¹ Cu, 27 mg l⁻¹ Zn, 9.5 mg l⁻¹ Cr and 40 mg l⁻¹ CN⁻ was treated through the modified columns. A total CN⁻ removal was achieved when using the TBA-carbon column with a removal capacity of 29.2 mg g⁻¹ carbon. The TBA-carbon adsorbent was found to have an effective removal capacity of approximately five times that of plain carbon. Using SDDC-carbon column, Cu, Zn and Cr metal ions were eliminated with a removal capacity of 38, 9.9 and 6.84 mg g⁻¹, respectively. The SDDC-carbon column has an effective removal capacity for Cu (four times), Zn (four times) and Cr (two times) greater than plain carbon.     

Hexavalent chromium adsorption on superparamagnetic multi-wall carbon nanotubes and activated carbon composites

Hexavalent chromium (Cr(VI)) adsorption from aqueous solutions on magnetically modified multi-wall carbon nanotubes (M-MWCNT) and activated carbon (M-AC) was investigated. M-MWCNT and M-AC were prepared by co-precipitation method with Fe²⁺:Fe³⁺ salts as precursors. The magnetic adsorbents were characterized by X-ray diffraction (XRD), thermogravimetric analysis (TGA) and scanning electron microscope (SEM). The effects of amount of adsorbents, contact time, initial pH, temperature and the initial concentration of Cr(VI) solution were determined. The adsorption equilibrium, kinetics, thermodynamics and desorption of Cr(VI) were investigated. Equilibrium data fitted well with the Langmuir isotherm for both of the adsorbents. The theoretical adsorption capacities are 14.28 mg/g of M-MWCNT and 2.84 mg/g of M-AC. Cr(VI) adsorption kinetics was modeled with pseudo-second order model, intra-particle diffusion model and Bangham model. Thermodynamic parameters were calculated and ΔG°, ΔH° and ΔS° indicate that the adsorption of Cr(VI) onto M-MWCNT and M-AC was exothermic and spontaneous in nature. Results revealed that M-MWCNT is an easily separated effective adsorbent for Cr(VI) adsorption from aqueous solution.     

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.     

Palladium,silver, and zinc oxide nanoparticles loaded on activated carbon as adsorbent for removal of bromophenol red from aqueous solution

The adsorption of bromophenol red (BPR) onto three adsorbents including palladium, silver and zinc oxide nanoparticles loaded on activated carbon (Pd-NP-AC, Ag-NP-AC and ZnO-NP-AC) in a batch system has been studied and the influence of various parameters has been optimized. The influence of time on removal of BPR on all adsorbent was investigated and experimental data were analyzed by four kinetic models including pseudo first and second-order, Elovich and the intraparticle diffusion equations. Following fitting the experimental data to these models, the respective parameters of each model such as rate constants, equilibrium adsorption capacities and correlation coefficients for each model were investigated and based on well known criterion their applicability was judged. It was seen that the adsorption of BPR onto all adsorbents sufficiently described by the pseudo second-order equation in addition to interparticle diffusion model. The adsorption of BPR on all adsorbent was investigated at various concentration of dye and the experimental equilibrium data were analyzed and fitted to the Langmuir, Freundlich, Tempkin, Dubinin, and Radushkevich equations. A single stage in batch process was efficient and suitable for all adsorbents using the Langmuir isotherm with maximum adsorption of 143 mg g^?1 for Pd-NP-AC, 250 mg g^?1 for Ag-NP-AC and 200 mg g^?1 for ZnO-NR-AC. Thermodynamic parameters such as ΔG°, ΔH°, and ΔS° for Pd-NP-AC adsorbent were calculated.     

Simultaneous adsorption of aniline and Cr(VI) ion by activated carbon/chitosan composite

Activated carbon/chitosan composite has been used as an adsorbent to remove aniline and Cr(VI) ions from aqueous solutions simultaneously. The effects of preparation conditions such as the ratio of activated carbon to chitosan, crosslinking reagents, crosslinking time, and adsorption conditions including adsorbent dosage, pH value of solution, and contact time on simultaneous adsorption of aniline and Cr(VI) ion were investigated. Experimental results showed that epichlorohydrin was the proper crosslinking reagent, and the ratio of activated carbon to chitosan was kept at 1. When the adsorbent dosage was 4.0 g/L, and the concentrations of aniline and Cr(VI) were lower than 50 and 100 mg/L, respectively, both aniline and Cr(VI) were simultaneously removed at natural pH with high removals (>95%). The presence of Cr(VI) enhanced the adsorption of aniline, while the presence of aniline almost had no influence on the adsorption of Cr(VI). The adsorption processes of both aniline and Cr(VI) followed the pseudo‐second‐order kinetics model, but the sorption of Cr(VI) was preferential to that of aniline by this composite. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39903.     

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.     

Kinetics, thermodynamic and equilibrium study of Cr(VI) adsorption from aqueous solutions by NCL coal dust

The waste material NCL coal dust was used as adsorbent for removal of Cr(VI) from aqueous solutions under batch adsorption experiments. The maximum removal of 99.97% was recorded at pH 2. The time required to attain equilibrium was found to be 60 min. Adsorption kinetics was described by the Lagergren equation. The value of the rate constant of adsorption was found to be 0.0615 min^?1 at 16 mg dm^?3 initial concentration and 298 K. The applicability of the Langmuir and Freundlich equations for the present system was also tested at different temperatures: 298, 313, and 328 K. Both thermodynamic parameters and temperature dependence indicated the endothermic nature of Cr(VI) adsorption on coal dust. The results showed that NCL coal dust is a promising adsorbent for the removal of Cr(VI) from aqueous solutions.     

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.     

Adsorption of cadmium and zinc from aqueous solution on natural and activated bentonite

The adsorption of cadmium and zinc ions on natural bentonite heat-treated at 110°C or at 200°C and on bentonite acid-treated with H₂SO₄ (concentrations: 0·5 mol dm^?3 and 2·5 mol dm^?3), from aqueous solution at 30°C has been studied. The adsorption isotherms corresponding to cadmium and zinc may be classified respectively as H and L types of the Giles classification which suggests the samples have respectively a high and a medium affinity for cadmium and zinc ions. The experimental data points have been fitted to the Langmuir equation in order to calcualte the adsorption capacities (X_m) and the apparent equilibrium constants (K_a) of the samples; X_m and K_a values range respectively for 4·11 mg g^?1 and 1·90 dm³ g^?1 for the sample acid-treated with 2·5 mol dm^?3 H₂SO₄ [(B)-A(2·5)] up to 16·50 mg g^?1 and 30·67 dm³ g^?1 for the natural sample heat-treated at 200°C [B-N-200], for the adsorption process of cadmium, and from 2·39 mg g^?1 and 0·07 dm³ g^?1, also for B-A(2·5), up to 4·54 mg g^?1 and 0·45 dm³ g^?1 [B-N-200], for the adsorption process of zinc. X_m and K_a values for the heat-treated natural samples were higher than those corresponding to the acid-treated ones. The removal efficiency (R) has also been calculated for every sample; R values ranging respectively from 65·9% and 8·2% [B-A(2·5)] up to 100% and 19·9% [B-N-200], for adsorption of cadmium and zinc.     

Isotherms,kinetics, and thermodynamic studies for adsorption of pigments and oxidation products in oil bleaching from catfish waste

Abstract

The aim of this work was to study the bleaching of oil extracted from the heads of the catfish by thermomechanical process through equilibrium, kinetics, and thermodynamics adsorption studies. The condition for the bleaching step was with 1% (w/w) adsorbent composed of 95% activated earth and 5% activated carbon (w/w). The pseudo-first order and pseudo-second order models were the most appropriate to represent the adsorption kinetics. The temperature of 80?°C increased the adsorption capacity of the two adsorbates, and the activation energies values were of 47.47 and 44.82?kJ mol^?1, respectively, for the adsorption of carotenoids and peroxides. The Langmuir model was the most appropriate to describe the bleaching equilibrium curves. The thermodynamic parameters revealed that the processes were endothermic, favorable, and spontaneous and the interaction between adsorbent and adsorbate was physical.     

Adsorptive removal of fluoride from water by activated carbon derived from CaCl2-modified Crocus sativus leaves: Equilibrium adsorption isotherms,optimization, and influence of anions

A central composite design using response surface methodology was applied for the experimental design and optimization of fluoride adsorption on an activated carbon derived from calcium chloride-modified Crocus sativus leaves (AC-CMCSL). Fluoride removal efficiency as function of independent variables, such as initial fluoride concentration, pH, adsorbent dose, and time has been investigated. The maximum percentage removal of fluoride at optimum conditions (initial fluoride concentration?=?6.5?mg?L^?1, pH?=?4.5, adsorbent dose?=?15?g?L^?1 and time?=?70?min) was 85.43%. By comparing adsorption isotherm, the Freundlich model provided the best correlation (R²?=?0.99) for the adsorption of fluoride on AC-CMCSL. The maximum adsorption capacity from the Langmuir model (q_max) was 2.01?mg?g^?1. The influence of the co-existing anions on fluoride adsorption was in the following order: PO₄^3??>?SO₄^2??>?Cl^??>?NO₃^?. The results of the present study showed that activated carbon derived from the leaves of calcium chloride-modified Crocus sativus has a good potential for fluoride removal from aqueous solution.     

Development of Green Energy Waste Activated Carbon for Removal of Trivalent Chromium: Equilibrium and Kinetic Modeling

The present work reports on the potential of using a modified activated carbon as an eco-friendly adsorbent (second stage waste), obtained from a bio-diesel waste production plant, for the removal of Cr(III) ions from aqueous solutions. Chemical activation of the green energy waste (GEW), using sulfuric acid as a dehydrating agent, was adapted in this study The effects of pH, contact time, dosage, and initial concentration were evaluated and optimized in a batch processing mode. The modified activated carbon was fully characterized to observe morphological changes using SEM, XRD, and FT-IR techniques. SEM images however, showed significant changes in the carbon morphology before and after the adsorption of Cr(III) ions. The adsorption results indicated that the equilibrium data were in accordance with the Langmuir isotherm, yielding a maximum monolayer adsorption capacity of 171.0 mg g ? 1 at 29° C. Moreover, the kinetic studies indicated that the adsorption process followed a pseudo-second-order model. Assessment of our results revealed that GEW-AC was considered as a prospective adsorbent which could be used as a cost-effective substitute for marketable activated carbons for the removal of Cr(III) ions from wastewater systems.     

A method of thermal and chemical activation of waste bleaching earth for preparation of a low-cost carbon-mineral adsorbent for chromium(VI) removal

ABSTRACT

In this study, the use of a spent bleaching earth for removal of Cr(VI) ions from aqueous solutions was investigated. The waste material derived from the process of vegetable oil purification was subjected to thermal and chemical activation. The so-prepared carbon-mineral adsorbents were characterised by the uptake of chromium(VI) from synthetic solutions. The highest adsorption capacities were obtained for adsorbents carbonised at 400°C (15.9 mg?g^?1) and activated with H₂SO₄ (15.8 mg?g^?1). Based on the equilibrium and kinetic studies, it was concluded that the adsorption mechanism was based on chemisorption only since no correlation with the porous texture was found.     

Removal of Chromium (VI) from Aqueous Solution by Cellulose Modified with D-Glucose

Cellulose powder was grafted with the vinyl monomer glycidyl methacrylate using ceric ammonium nitrate as initiator and was further derived with D-Glucose (D-Glu) to build a adsorbent (Cell-g-GMA-D-Glu). Epoxy cellulose, which was made up of Cell-g-GMA and Cell-hydro-g-GMA, was found to contain 5.48 mmol g^?1 epoxy groups. The adsorption process of the adsorbent was described by the Langmuir model of adsorption well and the maximum adsorption capacity of chromium (VI) reached to 54.59 mg g^?1. The adsorption-desorption tests of the Cell-g-GMA-D-Glu exhibited that the reproducibility of the absorbent was well and the adsorbent could be reused six times at least.