Kinetics and thermodynamic studies of Cr(VI) adsorption using environmental friendly multifunctional zeolites synthesized from coal fly ash under mild conditions

Abstract

The Na-P1 zeolite was produced from coal fly ash and modified with different environmental friendly surfactants. The potential of these green modified zeolites was investigated as adsorbents for Cr(VI) ions in a batch system. XRD, SEM, XRF, and ICP-AES analyses were used for the characterization of raw materials and zeolite samples. The environmental friendly modified zeolites successfully immobilized different toxic elements in their framework inhibiting the transfer of these toxic elements to the surrounding liquid phase. The effects of various operational parameters on Cr(VI) removal were studied. The Hexamethylenediamine (HDTMA) and Ammonyx KP (KP) modified zeolites had larger chromium removal potential than the other samples at all temperatures. The effectiveness of Cr(VI) ions elimination became greater as the pH decreased and the adsorbent dose increased. The Freundlich, Langmuir, and Dubinin–Radushkevich isotherms were fitted to the equilibrium data. The Dubinin–Radushkevich and Langmuir models gave a better fitness to equilibrium data of HDTMA-Na-P1 and KP-Na-P1, respectively. The positive and high ΔH° values showed the endothermic nature of the total Cr(VI) sorption procedure and indicated that Cr(VI) adsorption onto HDTMA-Na-P1 and KP-Na-P1 is a chemisorption. The negative ΔS° values also showed that chromium ions were stable on the surface of adsorbents. The adsorption potential of the developed eco-friendly KP-Na-P1 was higher than those of other adsorbents reported in the literature.     

Adsorption studies of Cr(VI) and Cu(II) metal ions from aqueous solutions by synthesized Ag and Mg co-doped TiO2 nanoparticles

ABSTRACT

This communication provides the eliminating of heavy metals from water resources using Ag-Mg/TiO₂ nanoparticles. The nanoparticles with a size of 15 nm were prepared using sol-gel technique and used for the removal of Cr(VI) and Cu(II) from waste waters. Batch sorption studies were carried out to investigate the adsorption of the above metal ions for a concentration range of 0.1–10 mg/L. The maximum sorption capacity values were found to be 2.42 mg/g for Cr(VI) and 2.03 mg/g for Cu(II) at a concentration of 0.1 ppm. The mechanism of adsorption was also investigated. The results showed that both Freundlich and Dubinin–Radushkevitch isotherms were found to be the best fit for the adsorption of metals. The results from kinetic data reveal that the pseudo-second-order and Reichenberg film diffusion models were found to be well fit for the experimental data. The value of the thermodynamic parameter ΔH° revealed the endothermic adsorption process and negative value of ΔG° shows the feasibility and spontaneity of material–anion interaction. In addition, the method is considered to be simple and cost-effective, and shows excellent adsorption removal properties on heavy metals for industrial applications.     

Kinetic,equilibrium and thermodynamic studies on removal of Cr(VI) by activated carbon prepared from Ricinus communis seed shell

A study on the removal of hexavalent chromium ions from aqueous solution by using activated carbon prepared from Ricinus communis has been done. In this process, it was carbonised and activated by treating with concentrated sulphuric acid followed by heating for 5 h at 500°C. Batch adsorption experiments are also carried out as a function of pH, contact time, initial concentration of the adsorbate, adsorbent dosage and temperature. The experimental data are fitted well to the Freundlich adsorption isotherm. Thermodynamic parameters such as ΔH°, ΔS° and ΔG° are calculated, which indicated that the adsorption is spontaneous and endothermic in nature. Adsorbent used in this study is characterised by FT‐IR and SEM before and after the adsorption of Cr(VI). © 2011 Canadian Society for Chemical Engineering     

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.     

Synthesis of polyaniline nanocomposite and its application for chromium removal from aqueous solution

The aim of this research was to investigate the sorption characteristics of polyaniline coated on sawdust (PAn/SD) for the removal of Cr(VI) ions from aqueous solutions. The sorption of Cr(VI) ions was carried out by the batch method. Characterization of PAn/SD was done by FTIR and SEM. The optimum conditions of sorption were found to be a PAn/SD dose of 0.6 g in 100 mL of Cr(VI) solution (50 mg/L), a contact time of 20 min, pH 2, and a temperature of 20°C, Increased temperature had a negative effect on the removal efficiency. Three equations, that is Morris–Weber, Lagergren, and pseudo‐second‐order, were tested to track the kinetics of the removal process. The kinetic data indicated that the adsorption process was described by the Morris–Weber equation. The Langmuir, Freundlich, and Dubinin–Radushkevick models were used with sorption data to estimate sorption capacity, intensity, and energy. The data were fitted with the Freundlich model. The thermodynamic parameters ΔH, ΔS, and ΔG were evaluated. They showed that the adsorption of Cr(VI) onto PAn/SD was feasible, spontaneous, and exothermic under the studied conditions. For desorption of Cr(VI) adsorbed onto PAn/SD, aqueous NaOH was used; with it, 85% of the adsorbed Cr(VI) could be desorbed. J. VINYL ADDIT. TECHNOL., 2012. © 2012 Society of Plastics Engineers     

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.     

Magnetite/graphene/polyaniline composite for removal of aqueous hexavalent chromium

Here, we report the synthesis of Fe₃O₄/G/PANI composite containing magnetite nanoparticles (Fe₃O₄), graphene sheets (G), and polyaniline (PANI) via chemical route for removal of toxic Cr (VI) from water. TEM image shows the formation of uniformly distributed magnetite nanoparticles on graphene/PANI composite. HRTEM images shows the formation of crystalline magnetite nanoparticles showing lattice fringes with inter‐planner distance 0.21 nm. The magnetic measurement shows magnetization 22 emu/g and ferromagnetic property of the adsorbent. The equilibrium adsorptions were well‐described by the Langmuir isotherm model and shows maximum adsorption capacity 153.54 mg/g at pH 6.5 and temperature 30 °C. The kinetics data well fitted by pseudo‐second‐order model and around 86% Cr (VI) removal completed within 20 min. The Cr (VI) removal capacitive decreases with increase in pH and ionic strength. The adsorbent shows leaching of iron nanoparticles at pH 1 whereas stable in solution having pH 2 and more. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44002.     

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.     

Removal of hexavalent chromium in wastewater by polyacrylamide modified iron oxide nanoparticle

Iron oxide nanoparticle has been successfully modified by polyacrylamide and the polyacrylamide modified magnetic nanoparticles (PMMNs) were applied to remove Cr(VI) in wastewater. The vibrating sample magnetometer (VSM) spectra indicated the large saturation magnetization and superparamagnetic property of the PMMNs. This made the polyacrylamide modified iron oxide easily separate with liquid phase. Scanning electron microscope (SEM) results showed that both the synthesized iron oxide and the PMMNs were nanoscale. Batch adsorption studies had been carried out to determine the effect of pH, contact time, Cr(VI) initial concentration, and coexisting salts on the adsorption of Cr(VI). Maximum removal (98.30%) was observed from an initial concentration of 100 mg L^?1 Cr(VI) at pH 3.0, 30°C. This process followed pseudo‐second‐order kinetics model and the equilibrium time was 40 min. The experimental data fitted the Langmuir isotherm better than Freundlich. Maximum adsorption amount of Cr(VI) by PMMN was 35.186 mg g^?1. The effect of coexisting salts on Cr(VI) removal was not apparent even the concentration of salt was 10 times as big as the low concentration, 0.01M. It had been proposed that the mechanism of Cr(VI) uptake onto PMMN was adsorption‐coupled reduction. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40945.     

Removal of Cr(VI) from Aqueous Solution: Electrocoagulation vs Chemical Coagulation

Abstract

Hydrolyzed products of Al(III) have affinity below pH_zpc for oppositely charged mono and bi‐nuclear species of hexavalent chromium. This study investigates the comparative performance of electrocoagulation (EC) and chemical coagulation (CC) for the removal of Cr(VI) from aqueous solution. The highest removal of Cr(VI) achieved with EC was about 42% with 4.36 mA/cm² current density. Cathodic adsorption of chromium boosted up Cr(VI) removal during EC. Simultaneous electro‐ and chemical‐dissolution lead to high current efficiency of about 178%. Both the pH and the coagulant dosage have a significant impact on Cr(VI) removal in the pH ranges from 4.9 to 7.0. CC with alum and aluminum sulfate (AS) removed about 11% and 12% of Cr(VI). Co‐adsorption of divalent SO₄ ^2? ions with Cr(VI) is responsible for the lower removal observed with chemical coagulants. About 0.061 and 0.099 mole of SO₄ ^2? was adsorbed per mole Al in the precipitate in the pH range 4.9 to 7.0 with AS and alum. A higher coagulant dosage increases the removal of Cr(VI) but adversely affects the removal efficiency (Cr(VI) removed per unit of Al dosing). Cell current density (CD) has shown little effect on Cr(VI) removal and the pH elevation at the same charge density. Higher initial Cr(VI) concentration improves the removal efficiency as the species of Cr(VI) is acidic in solution and decreases the pH elevation rate.     

Correlation between cell surface physicochemical properties of bacterial strains and their chromium removal potential

Physicochemical characterization of microbes has gained recently a great interest by scientific community. It is proved of extreme importance in several fields of science and technology applications such as bioremediation. In this work, we investigated the establishment of a possible correlation between chromium removal capacity of seven bacterial strains isolated from contaminated sites with industrial wastes including tanning processing and their cell surface physicochemical properties. Thus, hydrophobicity and donor/acceptor electrons character were obtained using contact angle measurements. Statistical analysis showed a high significant positive correlation between hexavalent chromium (Cr(VI)) removal by the strains and their acceptor electron character γ⁺(r = 0.90). While significant negative correlation between the Cr(VI) removal potential and the ΔGiwi value (r = ?0.844) and also with their donor electron character γ^? (r = ?0.746) were observed. These results may contribute to determine a selectrion criteria of bacteria that can be operated in bioremediation applications.     

Uptake of Cr (VI) by Sphingomonas paucimobilis Biomass from Aqueous Solutions

The Sphingomonas paucimobilis biomass has been successfully utilized to degrade several persistent organic pollutants (POPs). However, few studies have been conducted to use it to remove heavy metals from aqueous solutions. In the present study, biosorption experiments for Cr (VI) were investigated using nonliving biomass of S. paucimobilis isolated from activated sludge, Lianyungang Dapu sewage treatment plant, China. The effects of several parameters including solution pH, contact time, and ionic strength, etc. on Cr (VI) uptake were studied. The biomass was characterized by scanning electron microscopy and energy dispersive X-ray spectroscopy (SEM-EDS) and Fourier transform infrared spectrometer (FTIR). The applicability of the Langmuir and Freundlich models was tested. The correlation coefficients (R) of both models were greater than 0.95. The maximum adsorption capacities were found to be 28.5 mg/g for Cr (VI) at 20°C. The adsorption process was quick and found to follow the pseudo-second-order equation. The optimum adsorption was achieved at pH 2. The adsorption was also NaCl concentrations dependent.     

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.     

Selective sorption of Fe(III) using modified forms of chitosan beads

Modified chitosan beads (CB) were prepared and used for the removal of Fe(III) ions from aqueous solution. The advantages of modified CB than raw CB have been explored. The sorption capacity (SC) of the modified forms of CB namely, protonated CB, carboxylated CB, and grafted CB were found to be 3533, 3905, and 4203 mg kg^?1, respectively, while the raw CB showed the SC of 2913 mg kg^?1 only. Batch adsorption studies were conducted to optimize various equilibrating conditions like contact time, pH, and coions. The sorbents were characterized by FTIR, WDXRF, and SEM with EDAX analysis. The sorption process has been explained with Freundlich and Langmuir isotherms. Thermodynamic parameters such as ΔG°, ΔH°, and ΔS° were calculated to understand the nature of sorption. Modified CB are more selective for Fe(III) than Cu(II), which inturn higher than Cr(VI). A suitable mechanism for iron sorption onto modified CB was established. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Tuning the Properties of Ba-M Hexaferrite BaFe11.5Co0.5O19: A Road Towards Diverse Applications

The development of hexaferrite nanoparticles is scrutinized as potential sorbents for the removal of chromium (Cr) ions from aqueous chromium-containing solutions in a batch adsorption experiment. The transition metal Co doped BaFe₁₂O₁₉ hexaferrite compounds (BHF) have been synthesized successfully via citrate auto combustion technique. The structure, surface morphology and magnetic properties of the samples were studied. X-ray diffraction pattern ratifies the existence of hexagonal phase as a main phase for the prepared samples. The average crystallite sizes are found in the range of 47–49 nm. The high-resolution transmission electron microscopy (HRTEM), as well as the Fourier, transform infrared spectrophotometry results confirm an M-type hexagonal structure existing. The χ-T indicates the temperature-dependent ferromagnetic behavior of BHF nanoparticles. The derivative shows a single transition temperature Tc at 698 °C, and 710 °C for BHF and BCHF respectively. The prepared samples are utilized as an adsorbent for the removal of Cr (VI) from the aqueous solution. The maximum adsorption capacity (qm) of Cr (VI) on the nano hexaferrite is higher than that of various other adsorbents testified in the literature. The pseudo-second-order kinetic model gives a better fit to the experimental data.

     

Equilibrium,kinetics and thermodynamics study on biosorption of Cr(VI) by fresh biomass of <Emphasis Type="Italic">Saccharomyces cerevisiae</Emphasis>

The low cost fresh biomass of Saccharomyces cerevisiae (S. cerevisiae) was utilized for removal of Chromium ion from aqueous solution. The maximum biosorption was found to occur at pH 1.0. The biosorption capacity of S. cerevisiae was found to be 3.89 mg/g for a solution with initial Cr(VI) concentration of 50 mg/L at 35 °C. Several biosorption isotherms were used to fit the equilibrium data, indicating biosorption relied mainly on physical adsorption onto heterogeneous surface. Kinetic models were evaluated and we found that pseudo-second-order rate kinetic model showed better correlation, and the biosorption of Cr(VI) was governed by film diffusion as well as intraparticle diffusion. Thermodynamic constants indicated that the biosorption was spontaneous and endothermic. Fourier transform infra-red (FTIR) spectroscopy was used to reveal the main function groups of biosorption, which were hydroxyl, amine groups, C-H of the alkanes, C=O and S=O.     

Removal of chromium (VI) from aqueous solutions using quaternized chitosan microspheres

In this study, quaternized chitosan microspheres (QCMS) were prepared and its Cr(VI) removal potential was investigated. Batch experiments were conducted to examine kinetics, adsorption isotherm, pH effect, and thermodynamic parameters. Equilibrium was attained within 50 min and maximum removal of 97.34% was achieved under the optimum conditions at pH 5. Adsorption data for Cr (VI) uptake by the QCMS were analyzed according to Langmuir, Freundlich, and Temkin adsorption models. The maximum uptake of Cr(VI) was 39.1 mg·g^-1. Thermodynamic parameters for the adsorption system were determinated at 293 K, 303 K, 313 K and 323 K. (ΔH°=16.08 kJ·mol^-1;ΔG°=-5.84 to -8.08 kJ·mol^-1 and ΔS°=74.81 J·K^-1·mol^-1). So the positive values of both ΔH° and ΔS° suggest an endothermic reaction and increase in randomness at the solid-liquid interface during the adsorption.ΔG° values obtainedwere negative indicating a spontaneous adsorption process. The kinetic process was described by a pseudo-second-order rate equation very well. The results of the present study indicated that the QCMS could be considered as a potential adsorbent for Cr (VI) in aqueous solutions.     

Reduction of hexavalent chromium by Bacillus sp. isolated from chromite mine soils and characterization of reduced product

BACKGROUND: The reduction of highly mobile and toxic hexavalent chromium by bacterial strains is considered to be a viable alternative to reduce Cr(VI) contamination, in soils and water bodies, emanating from the overburden dumps of chromite ores and mine drainage. The present study reports the isolation of Cr(VI) resistant bacterial strains from an Indian chromite mine soil and their potential use in reduction of hexavalent chromium. RESULTS: Among the isolates, a bacterial strain (CSB‐4) was identified as Bacillus sp. based on standard biochemical tests and partial 16SrRNA gene sequencing, which was tolerant to as high as 2000 mg L^?1 Cr(VI) concentration. The strain was capable of reducing Cr(VI) to Cr(III) in different growth media. Under the optimized conditions pH ～7.0, 100 mg L^?1 Cr(VI), 35 °C temperature and stirring speed 100 rpm, CSB‐4 reduced more than 90% of Cr(VI) in 144 h. The time course reduction data fitted well an exponential rate equation yielding rate constants in the range 3.22 × 10^?2 to 6.5 × 10^?3 h^?1 for Cr(VI) concentration of 10–500 mg L^?1. The activation energy derived from temperature dependence rate constants between 25 and 35 °C was found to be 99 kJ mol^?1. The characterization of reduced product associated with bacterial cells by SEM‐EDS, FT‐IR and XRD was also reported. CONCLUSION: Reasonably high tolerance and reduction ability of indigenous Bacillus sp. (CSB‐4) for Cr(VI) under a wide range of experimental conditions show promise for its possible use in reclamation of chromite ore mine areas including soils and water bodies. Copyright © 2010 Society of Chemical Industry     

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.     

Adsorption of hexavalent chromium by chitosan‐based polymeric surfactants

Chitosan‐based polymeric surfactants (CBPSs) were prepared by the partial N‐acylation of amine groups on chitosan with acid anhydrides. To apply the CBPSs for the removal of Cr(VI) commonly found in wastewater, a batch test was conducted to evaluate the adsorption capacity. The removal efficiency of Cr(VI) by the CBPS depended on several factors, including the solution pH, CBPS dose, and ionic strength. Our results show that the CBPSs exhibited a greater adsorption capacity for Cr(VI) than have other modified chitosans reported in the literature. The maximum adsorption capacity of Cr(VI) was 180 mg/g of CBPS at a final pH of 5.3. From the results of dynamic light scattering, we propose that the removal mechanism of Cr(VI) by the CBPSs was mainly through the adsorption of negatively charged chromium ions by positively charged amine groups on the CBPSs followed by colloidal precipitation because of its lower solubility. Conclusively, we found that the CBPS was significantly effective for the removal of Cr(VI). © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 44–50, 2005