Magnetic chitosan nanoparticles for removal of Cr(VI) from aqueous solution

A simple method was introduced to prepare magnetic chitosan nanoparticles by co-precipitation via epichlorohydrin cross-linking reaction. The average size of magnetic chitosan nanoparticles is estimated at ca. 30 nm. It was found that the adsorption of Cr(VI) was highly pH-dependent and its kinetics follows the pseudo-second-order model. Maximum adsorption capacity (at pH 3, room temperature) was calculated as 55.80 mg·g^? 1, according to Langmuir isotherm model. The nanoparticles were thoroughly characterized before and after Cr(VI) adsorption. From this result, it can be suggested that magnetic chitosan nanoparticles could serve as a promising adsorbent for Cr(VI) in wastewater treatment technology.     

Enhanced removal of Cr(VI) from aqueous solution using polypyrrole/Fe3O4 magnetic nanocomposite

Fe(3)O(4) coated polypyrrole (PPy) magnetic nanocomposite was prepared via in situ polymerization of pyrrole monomer for the removal of highly toxic Cr(VI). Structure and morphology of the prepared nanocomposite were characterized by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), X-ray diffraction pattern, Field emission scanning electron microscopy (FE-SEM) and high resolution transmission electron microscopy (HR-TEM). Electron spin resonance (ESR) studies confirmed that the nanocomposite is magnetic in nature. Up to 100% adsorption was found with 200mg/L Cr(VI) aqueous solution at pH 2. Adsorption of Cr(VI) on the surface of the adsorbent was confirmed by the ATR-FTIR and X-ray photoelectron spectroscopy (XPS). XPS studies also suggested that ion exchange and reduction on the surface of the nanocomposite may be the possible mechanism for Cr(VI) removal by the PPy/Fe(3)O(4) nanocomposite. Adsorption results showed that Cr(VI) removal efficiency by the nanocomposite decreased with an increase in pH. Adsorption kinetics was best described by the pseudo-second-order rate model. Isotherm data fitted well to the Langmuir isotherm model. Thermodynamic study revealed that the adsorption process is endothermic and spontaneous in nature. Desorption experiment showed that in spite of the very poor recovery of the adsorbed Cr(VI); the regenerated adsorbent can be reused successfully for two successive adsorption-desorption cycles without appreciable loss of its original capacity.     

Effective removal and fixation of Cr(VI) from aqueous solution with Friedel's salt

Friedel's salt (3CaO·Al₂O₃·CaCl₂·10H₂O or Ca₄Al₂(OH)₁₂Cl₂(H₂O)₄) is a calcium aluminate hydrate formed by hydrating cement or concrete in seawater at a low cost. In the current study, we carefully examined the adsorption behaviors of Friedel's salt for Cr(VI) from aqueous solution at different concentrations and various initial pHs. The adsorption kinetic data are well fitted with the pseudo-first-order Lageren equation at the initial Cr(VI) concentration from 0.10 to 8.00 mM. Both the experimental and modeled data indicate that Friedel's salt can adsorb a large amount of Cr(VI) (up to 1.4 mmol Cr(VI)/g) very quickly (t_1/2 = 2–3 min) with a very high efficiency (>99% Cr(VI) removal at [Cr] < 4.00 mM with 4.00 g/L of adsorbent) in the pH range of 4–10. In particular, the competitive adsorption tests show that the Cr(VI) removal efficiency is only slightly affected by the co-existence of Cl⁻ and HCO₃⁻. The Cr(VI)-fixation stability tests show that only less than 0.2% adsorbed Cr(VI) is leaching out in water at pH 4–10 for 24 h because the adsorption/exchange of Cr(VI) with Friedel's salt leads to the formation of a new stable phase (3CaO·Al₂O₃·CaCrO₄·10H₂O). This research thus suggests that Friedel's salt is a potential cost-effective adsorbent for Cr(VI) removal in wastewater treatment.     

Cr(VI) removal from aqueous solution using chemically reduced and functionalized graphene oxide

Chemically reduced and functionalized graphene oxide (GO) was prepared by refluxing of GO with ethylenediamine (ED) using dimethyl formamide (DMF) as solvent. It was confirmed that both ED and DMF contributed to the reduction and functionalization of GO. The resulting adsorbent (ED–DMF–RGO) with amine groups was highly efficient in removing Cr(VI) from its aqueous solution and could be easily separated by filtration. The optimum pH for total Cr removal was observed at pH 2.0 and the Cr(VI) removal capacity of ED–DMF–RGO at this pH was 92.15 mg g^?1, which was about 27 times higher than that of activated carbon, even nearly 4–8 times higher than that of various modified activated carbons. The presence of other ions such as Na⁺, K⁺, Ca²⁺, Cl^?, and Br^? had little effect on the removal of Cr(VI). Interestingly, Cr(VI) was reduced to low-toxic Cr(III) during the adsorption process, which followed an indirect reduction mechanism. Both the Cr(VI) adsorption and subsequent reduction of adsorbed Cr(VI) to Cr(III) contributed to the Cr(VI) removal. The obtained ED–DMF–RGO may be applicable in Cr(VI) removal if they are produced on a large scale and at low price in near future.     

Adsorption of Cr(VI) from aqueous solution by hydrous zirconium oxide

A type of ZrO₂·nH₂O was synthesized and its Cr(VI) removal potential was investigated in this study. The kinetic study, adsorption isotherm, pH effect, thermodynamic study and desorption were examined in batch experiments. The kinetic process was described by a pseudo-second-order rate model very well. The Cr(VI) adsorption tended to increase with a decrease of pH. The adsorption data fitted well to the Langmuir model. The adsorption capacity increased from 61 to 66 mg g^?1 when the temperature was increased from 298 to 338 K. 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 obtained were negative indicating a spontaneous adsorption process. The effective desorption of Cr(VI) on ZrO₂·nH₂O could be achieved using distilled water at pH 12.     

Preparation of flake-like polyaniline/montmorillonite nanocomposites and their application for removal of Cr(VI) ions in aqueous solution

In this study, flake-like polyaniline/montmorillonite (PANI/MMT) nanocomposites with rough surface were successfully prepared by in situ chemical oxidation polymerization during which poly(2-acrylamido-2-methylpropanesulfonic acid), a polymer acid, on the surface of clay platelets was used as dopant of PANI and played a ‘bridge’ role to combine PANI with clay. Flake thickness and surface roughness of PANI/MMT composites decreased with the increase of montmorillonite/aniline feeding ratio. The effects of operating parameters including pH, contact time, Cr(VI) concentration, and adsorbent dose were studied. The pseudo-second-order equation and three adsorption isotherms including Langmuir, Freundlich, and Temkin equations were applied to determine the adsorption rate and capacity. The results show that the flake-like PANI/MMT nanocomposites exhibited a high adsorption capacity (167.5 mg/g). The excellent adsorption characteristic of flake-like PANI/MMT nanocomposites will render it a highly efficient and economically viable adsorbent for Cr(VI) removal.     

Characterization of Cr(VI) removal from aqueous solutions by a surplus agricultural waste--rice straw

The removal of Cr(VI) from aqueous solution by rice straw, a surplus agricultural byproduct was investigated. The optimal pH was 2.0 and Cr(VI) removal rate increased with decreased Cr(VI) concentration and with increased temperature. Decrease in straw particle size led to an increase in Cr(VI) removal. Equilibrium was achieved in about 48 h under standard conditions, and Cr(III), which appeared in the solution and remained stable thereafter, indicating that both reduction and adsorption played a part in the Cr(VI) removal. The increase of the solution pH suggested that protons were needed for the Cr(VI) removal. A relatively high level of NO(3)(-) notably restrained the reduction of Cr(VI) to Cr(III), while high level of SO(4)(2-) supported it. The promotion of the tartaric acid modified rice straw (TARS) and the slight inhibition of the esterified rice straw (ERS) on Cr(VI) removal indicated that carboxyl groups present on the biomass played an important role in chromium remediation even though were not fully responsible for it. Isotherm tests showed that equilibrium sorption data were better represented by Langmuir model and the sorption capacity of rice straw was found to be 3.15 mg/g.     

Selective removal of Cr(VI) ions from aqueous solutions including Cr(VI), Cu(II) and Cd(II) ions by 4-vinly pyridine/2-hydroxyethylmethacrylate monomer mixture grafted poly(ethylene terephthalate) fiber

In this study, a new reactively fibrous adsorbent was prepared by grafting 4-vinly pyridine (4-VP) and 2-hydroxyethylmethacrylate (HEMA) monomer mixture onto poly(ethylene terephthalate) (PET) fibers for removal of Cr(VI), Cu(II) and Cd(II) metal ions from aqueous solution by using batch adsorption method. The influence of various parameters such as graft yield (GY), pH, adsorption time, initial ion concentration and adsorption temperature was investigated. The selectivity of the reactive fiber was also examined. The results show that the adsorbed amount of metal ions followed as given in the order Cr(VI) > Cd(II) > Cu(II). At pH 3, Cr(VI) was removed by 99% while the initial concentration of ions was at 5 mg L⁻¹ and by 94% at 400 mg L⁻¹. It was found that the grafted fiber is more selective for Cr(VI) ions in the mixed solution of Cr(VI)–Cu(II), Cr(VI)–Cd(II) and Cr(VI)–Cu(II)–Cd(II) at pH 3 and it was observed that the grafted fibers are stable and regenerable by acid and base without losing their activity.     

Enhancing the electrochemical Cr(VI) reduction in aqueous solution

In this study we present the cathodic Cr(VI) reduction using electrodissolution of iron anode. In batch experiments we tested four different cathodic materials; the best conditions were found when copper was used. It is observed that when more current is applied into the electrochemical cell faster reduction rates are achieved. Continuous experiments also reveal that Cr(VI) reduction could be done in a very efficient way. To confirm the experimental data, cyclic voltammetry was used and it was found that the cathodic Cr(VI) reduction is taking place.     

Grape waste as a biosorbent for removing Cr(VI) from aqueous solution

Grape waste generated in wine production is a cellulosic material rich in polyphenolic compounds which exhibits a high affinity for heavy metal ions. An adsorption gel was prepared from grape waste by cross-linking with concentrated sulfuric acid. It was characterized and utilized for the removal of Cr(VI) from synthetic aqueous solution. Adsorption tests were conducted in batch mode to study the effects of pH, contact time and adsorption isotherm of Cr(VI), which followed the Langmuir type adsorption and exhibited a maximum loading capacity of 1.91 mol/kg at pH 4. The adsorption of different metal ions like Cr(VI), Cr(III), Fe(III), Zn(II), Cd(II) and Pb(II) from aqueous solution at different pH values 1-5 has also been investigated. The cross-linked grape waste gel was found to selectively adsorb Cr(VI) over other metal ions tested. The results suggest that cross-linked grape waste gel has high possibility to be used as effective adsorbent for Cr(VI) removal.     

Efficient removal of Cr(VI) from aqueous solution by natural pyrite/rhodochrosite derived materials: Performance,kinetic and mechanism

In this work, pyrite/rhodochrosite (Py_xRh_y) composite synthesized from natural pyrite and rhodochrosite to remediate Cr(VI) containing wastewater was systematically investigated and evaluated. Results show that pyrite/rhodochrosite (1:1) showed the best Cr(VI) removal performance. XRD showed that emergence of MnS and pyrrhotite contributed to a significant increasing Cr(VI) reduction rate. The estimated maximum adsorption capacity was 95.58 mg/g at pH value of 6, temperature of 303.15 k, which was larger than other iron and manganese-based materials. Additionally, thermodynamic study illuminated that Cr(VI) removal by Py₁Rh₁ was a spontaneous and endothermic process. Taffel curve and EIS result presented higher corrosion current and lower electrical resistance for Py₁Rh₁, respectively, which was more favorable for the electron transfer. The surface cyclic regeneration of Fe(II) and Mn(II) provided long-term electron transfer to the Cr(VI) reduction. Our results demonstrated the great potentials of natural pyrite and rhodochrosite synthetic materials in the remediation of Cr(VI) polluted water.     

Application of natural and modified hectorite clays as adsorbents to removal of Cr(VI) from aqueous solution–Thermodynamic and equilibrium study

A hectorite (H) clay sample has been modified with 2-mercaptobenzimidazole (MBI) using homogeneous and heterogeneous routes. Both modification methodologies resulted in similar products, named H_HOM and H_HET, respectively. These materials were characterized by CO₂ gas adsorption, elemental analysis, nuclear magnetic nuclei of carbon-13 and silicon-29. The effect of two variables (contact time and metal concentration) has been studied using batch technique at room temperature and pH 2.0. After achieving the best conditions for Cr(VI) adsorption, isotherms of this adsorbate on using the chosen adsorbents were obtained, which were fitted to non-linear Sips isotherm model. The maximum number of moles adsorbed was determined to be 11.63, 12.85 and 14.01 mmol g⁻¹ for H, H_HOM and H_HET, respectively, reflecting the maximum adsorption order of H_HET > H_HOM > H. The energetic effects (Δ_intH°, Δ_intG° and Δ_intS°) caused by chromium ion adsorption were determined through calorimetric titrations.     

减压膜蒸馏分离含Cr(VI)水溶液的实验研究

采用标称孔径为 0 .2 2 μm的聚偏氟乙烯微孔膜 ,对减压膜蒸馏法分离Cr(VI)水溶液进行了实验研究 ,探讨了进料浓度和pH值对膜分离性能的影响 .得到的最佳工艺条件为 :冷侧真空度 0 .0 96MPa、进料温度 6 0℃、进料流速 6 0L/h .在该工艺条件下膜具有良好的分离性能 ,此时 ,膜通量为 34.52kg/ (m2 ·h) ,截留率为 99.2 5% .结果表明 ,Cr(VI)水溶液经减压膜蒸馏技术处理后 ,能达到 0 .5mg/L的国家Cr(VI)控制浓度排放标准 .     

Efficient removal of Cr (VI) from aqueous solution by halloysite/poly(amidoamine) dendritic nano-hybrid materials: kinetic,isotherm and thermodynamic studies

This paper demonstrates functionalization of a new hybrid nanoclay for effective adsorption of chromium(VI) ions from wastewater. Halloysite nanotubes (HNTs) were functionalized by poly(amidoamine) dendritic polymers (HNTs-(DEN-NH₂)) via a convergent synthetic route by carboxylic acid as a linkage. Various characterization methods confirm that poly(amidoamine) dendritic groups were effectively grafted onto the surface of HNTs that found a high specific surface area of 75 m²/g, as measured by micrometric BET analyzer. Moreover, the adsorption activity of HNTs-(DEN-NH₂) for Cr(VI) was systematically investigated using a batch solution that reveals the removal efficiency of 98% for HNTs-(DEN-NH₂) comparing to 23% for pristine HNTs, at optimum conditions. The enhancement of Cr(VI) removal for HNTs-(DEN-NH₂) comparing to HNTs was mainly ascribed to be due to the electrostatic interaction, that was confirmed by the results of Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS). Moreover, regeneration studies display that HNTs-(DEN-NH₂) can maintain removal Cr(VI) with high efficiency after four consecutive cycles.     

Adsorption of Cr(VI) from aqueous solutions by spent activated clay

Adsorption of Cr(VI) onto spent activated clay (SAC), a waste produced from an edible oil refinery company, was investigated for its beneficial use in wastewater treatment. After pressure steam treatment, SAC was used as an adsorbent. The adsorption kinetic data were analyzed and fitted well in a pseudo-first-order equation and the rate of removal was found to speed up with decreasing pH and increasing temperature. Activation energy for the adsorption process was found to be 4.01–5.47 kcal/K mol. The Langmuir adsorption isotherm was used to fit the equilibrium data and the effect of pH, temperature and ionic strength were studied. The maximum adsorption capacities for Cr(VI) ranged from 0.743 to 1.422 mg/g for temperature between 4 and 40 °C under a condition of pH 2.0. The studies conducted show the process of Cr(VI) removal to be spontaneous at high temperature and endothermic in nature. From the waste utilization and environment point of view, the work carried out is important and useful. Results obtained can serve as baseline data for designing a treatment process using this low-cost adsorbent for the treatment of wastewater rich in Cr(VI).     

Reduction and removal of Cr(VI) from aqueous solutions using modified byproducts of beer production

Biosorption, as an effective and low-cost technology treating industrial wastewaters containing Cr(VI), has become a significant concern worldwide. In this work, acid-modified byproducts of beer production (BBP) were used to remove Cr(VI) from aqueous solutions. Removal of Cr(VI) increases as the pH is decreased from 4.0 to 1.5, but the maximum of total Cr removal is obtained in a pH range from 2.0 to 2.5. Nearly 60% of the initial Cr(VI) (100 mg L(-1)) was adsorbed or reduced to Cr(III) within the first 10 min at pH 2.0. The Cr(VI) removal capability of acid-modified BBP materials was almost completely retained after regenerating with acid. FT-IR and XPS spectra revealed that carboxylate and carboxyl groups on the surface of modified BBP materials play a major role in Cr(VI) binding and reduction, whereas amide and other groups play a minor role in the Cr(VI) removal process.     

Removal of Ni(II), Zn(II) and Cr(VI) from aqueous solution by Alternanthera philoxeroides biomass

Alternanthera philoxeroides biomass, a type of freshwater macrophyte, was used for the sorptive removal of Ni(II), Zn(II) and Cr(VI) from aqueous solutions. Variables of the batch experiments include solution pH, contact time, particle size and temperature. The biosorption capacities are significantly affected by solution pH. Higher pH favors higher Ni(II), Zn(II) removal, whereas higher uptake of Cr(VI) is observed as the pH is decreased. A two-stage kinetic behavior is observed in the biosorption of Ni(II), Zn(II) and Cr(VI): very rapid initial biosorption in a few minutes, followed by a long period of a slower uptake. It is noted that an increase in temperature results in a higher Ni(II), Zn(II) and Cr(VI) loading per unit weight of the sorbent. Decreasing the particle sizes of the Alternanthera philoxeroides biomass leads to an increase in the Ni(II), Zn(II) and Cr(VI) uptake per unit weight of the sorbent. All isothermal data are fairly well fitted with Langmuir equations. The thermodynamic parameter, DeltaG degrees, were calculated. The negative DeltaG degrees values of Cr(VI), Ni(II) and Zn(II) at various temperatures confirm the adsorption processes are spontaneous.     

Enhanced removal of p-chloroaniline from aqueous solution by a carboxylated polymeric sorbent

In the present study a carboxylated styrene-divinylbenzene (St-DVB) polymeric sorbent (CSPS) was prepared for enhanced removal of p-chloroaniline from aqueous solution. A commercial styrene-divinylbenzene polymeric sorbent Amberlite XAD-4 was selected as the reference sorbent to evaluate the performance of CSPS. Characterization of CSPS was determined by infrared spectroscopy and pore size distribution. A p-chloroaniline sorption enhancement on CSPS at capacity about twice of Amberlite XAD-4 was observed, which was mainly attributed to the carboxyl group added on the polymeric matrix. Different pH-dependent sorption property of p-chloroaniline onto XAD-4 and CSPS was observed partly due to the role of carboxyl group. Sorption isotherm of p-chloroaniline on CSPS could be represented by Freundlich model reasonably, and that on XAD-4 was more suitable for Langmuir model. Kinetic studies demonstrated that the uptake of p-chloroaniline on CSPS and XAD-4 followed the pseudo-second order model. Moreover, breakthrough curves on CSPS further demonstrated its better performance towards p-chloroaniline removal from aqueous solution. Complete regeneration of the spent sorbent CSPS was achieved by dilute hydrochloric acid for its repeated use, implying its potential application in associated chemical wastewater treatments.     

Cr(VI) reduction in aqueous solutions by siderite

Hexavalent chromium is a common and toxic pollutant in soils and wastewaters. Reduction of the mobile Cr(VI) to less mobile and less toxic Cr(III) is a solution for decontamination of industrial effluents. In this study, the reduction of hexavalent chromium in aqueous solutions by siderite was investigated. The influences of amount of acid, contact time, siderite dosage, initial Cr(VI) concentration, temperature and particle size of siderite have been tested in batch runs. The process was found to be acid, temperature and concentration dependent. The amount of acid is the most effective parameter affecting the Cr(VI) reduction since carbonaceous gangue minerals consume acid by side reactions. The highest Cr(VI) reduction efficiency (100%) occurred in the 50 mg/l Cr(VI) solution containing two times acid with respect to stoichiometric amount of Cr(VI) and at the conditions of siderite dosage 20 g/l, contact time 120 min and temperature 25 degrees C. Reduction efficiency increased with increase in temperature and decrease in particle size. The reduction capacity of siderite was found to be 17 mg-Cr(VI)/g.