Transport of chromium(VI) through a Cyanex 921‐supported liquid membrane from HCl solutions

The transport of chromium(VI) through a flat‐sheet supported liquid membrane containing Cyanex 921 as a carrier has been investigated. The permeation of the metal is investigated as a function of various experimental variables: hydrodynamic conditions, concentration of chromium(VI) and HCl in the feed phase, carrier concentration and diluent in the membrane and strippant concentration in the stripping phase. The mass transfer coefficient and the thickness of the aqueous boundary layer were calculated from the experimental data. Furthermore, the selectivity of Cyanex 921‐based flat‐sheet supported liquid membrane towards different metal ions and the behaviour of the system against other carriers are presented. Copyright © 2003 Society of Chemical Industry     

3,5‐Dimethylpyrazolium Fluorochromate(VI)‐Catalysed Oxidation of Organic Substrates by Hydrogen Peroxide under Solvent‐Free Conditions

3,5‐Dimethylpyrazolium fluorochromate (VI), C₅H₈N₂H[CrO₃F], DmpzHFC , serves as an efficient catalyst for oxidation of primary, secondary and allylic alcohols to the corresponding carbonyl compounds using H₂O₂ at room temperature under solvent‐free conditions. Oxidation of methyl phenyl sulfides and triphenylphosphine were also carried out successfully.     

Photoredox processes in the Cr(VI)–Cr(III)–oxalate system and their environmental relevance

Irradiation of the [Cr(C₂O₄)₃]³⁻ complex or the chromate(VI)–oxalate mixture, or the ternary system composed of Cr(III), Cr(VI) and oxalate, leads to chromium photoreductions in consequence of the ligand to metal charge transfer (LMCT) excitations induced by artificial solar radiation. In the case of the Cr(III) complex, the photoreduction involves the innersphere electron transfer leading to the formation of the Cr(II) species and the C₂O₄⁻ radicals. On reacting with molecular oxygen, Cr(II) is oxidised to Cr(III) catalysing thereby the oxalate substitution reaction. Moreover, under specific conditions, Cr(II) can be also oxidised to Cr(VI). Chromate(VI) is not photoreducible, but in the presence of oxalate, or other sacrificial electron donor, the outersphere photoinduced electron transfer (PET) produces Cr(V) species and the C₂O₄⁻ radicals. This initiates a series of thermal reactions leading to the formation of Cr(III) and oxidized oxalate (CO₂). In the system composed of [Cr(C₂O₄)₃]³⁻ and chromate(VI), the acidic medium and anoxic conditions favour the Cr(VI) photoreduction, whereas alkaline oxygenated solutions assist the Cr(VI) photoproduction. When an approximately neutral solution equilibrated with the ambient air is irradiated intermittently, Cr(VI) is consumed and/or produced, accordingly to the time sequence of exposure and dark periods. The oscillations of Cr(VI) concentrations are accompanied by continuous oxidation of oxalate, playing the role of the sacrificial electron donor. The effects of solution pH, molecular oxygen, concentrations of reagents and cations on the reaction rates were investigated. The results of this paper revealed that the Cr(III)/Cr(VI) system under environmental conditions behaves as the photocatalytic one catalysing the oxidation of oxalate or other organic matter by molecular oxygen, contributing thereby to the abatement of pollution.     

Photo‐reduction and adsorption in aqueous Cr(VI) solution by titanium dioxide,carbon nanotubes and their composite

BACKGROUND: This study compared the removal of aqueous Cr(VI) by multi‐walled carbon nanotubes (CNTs) modified by sulfuric acid, titanium dioxide (TiO₂) and composite of CNTs and TiO₂. RESULTS: More than 360 h contact time was needed to completely adsorb 3 mg L^?1 of Cr(VI) by CNTs, indicating that the rate of adsorption by CNTs alone was slow. The reaction time approaching equilibrium depended on the Cr(VI) concentration. XPS analysis of CNTs after adsorbing Cr(VI) showed that the Cr(VI) on the surface of CNTs was partially reduced to Cr(III). A 3 mg L^?1 solution of Cr(VI) was fully photocatalyzed by commercial TiO₂ (Degussa P25) in less than 0.5 h under UV irradiation. Unlike P25, reduction by another commercial TiO₂ (Hombikat UV100) took 4 h and more than 2 h were necessary for reduction by the composite. Thus the efficiency of Cr(VI) photo‐reduction by the composite was lower than by TiO₂, but higher than that by CNTs. XPS analysis of TiO₂ and composite showed the existence of both Cr(VI) and Cr(III) on their surfaces. CONCLUSION: In contrast to TiO₂, the reduction rate of aqueous Cr(VI) using CNTs as adsorbent was slow. P25 had a markedly higher photocatalytic efficiency than the composite or UV100 alone. Using P25 to reduce aqueous Cr(VI) has a higher potential for practical application. The diameters of TiO₂ and CNTs and the ratio of TiO₂/CNTs are key problems in the preparation of TiO₂/CNTs composite. Copyright © 2011 Society of Chemical Industry     

Optimal Synergistic Extraction of Cr(VI) from Aqueous Acidic Media Using Alamine 300/Aliquat 336 and Di-n-octyl Amine/Tributyl Phosphate Mixed Reagents

Data for the extraction of chromium(VI) from aqueous sulfate solutions by Alamine 300/Aliquat 336 and di–n–octyl amine/tributyl phosphate (DOA/TBP) have been subjected to formulation of an optimization structure for an effective Cr(VI) separation based on the derivative variation method. Both experimentally and analytically defined optimum Cr(VI) removal efficiencies are ranging about 83–99%, 71–93%, and 60–73% for Alamine 300/Aliquat 336, DOA/TBP, and DOA, respectively. Modeling efforts based on mass-action law methodology and non-homogeneous differential approach have shown considerable success yielding a 10% mean error, and satisfies established limiting behavior of the physical event.     

Preparation and characterization of higher degree‐deacetylated chitosan‐coated magnetic adsorbent for the removal of chromium(VI) from its aqueous mixture

Chitosan (90% deacetylated) coated magnetic adsorbent prepared by coprecipitation method to remove Cr(VI) from its aqueous solution. The experimental studies depicts that the predominant option for removal of Chromium by adsorption from its aqueous phase using Magnetic‐Chitosan (MC). The subsequent physical, chemical, and magnetic properties of MC were characterized by X‐ray powder diffraction, scanning electron microscopy, Fourier transform infrared spectrometer, vibrating sample magnetometer. The influence of batch process parameters such as contact time, initial concentration, pH, and coexisting anions were investigated. The Box‐Behnken experimental design in response surface methodology was performed to design the experiment optimal operating conditions. The maximum percentage reduction of Cr(VI) is 96.3 that was obtained by magnetic chitosan with the optimal operating conditions of 149.53 mg/L at pH of 5.32 at the contact time of 80 min and at the temperature of 303 K. The average diameter of the magnetic chitosan was calculated from X‐ray diffractometer analysis as 24.5 nm. The equilibrium adsorption isotherm models such as Langmuir and Freundlich and the adsorption kinetics such as pseudo first order, pseudo second order and intra‐particle diffusion kinetic model were analyzed. The experimental data's suited for the best fit with the Langmuir isotherm model and pseudo first order kinetic model. It also revealed that Cr(VI) adsorption on MC is intrinsically exothermic and spontaneous. The magnetic chitosan was also used to investigate for the removal of Cr(VI) from the real water sources such as surface, underground, and tannery wastewater. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45878.     

Cr(VI) reduction by bio and bioinorganic catalysis via use of bio‐H2: a sustainable approach for remediation of wastes

Use of biologically‐produced hydrogen (bio‐H₂) as an electron donor for Cr(VI) reduction by native and palladized cells of Desulfovibrio vulgaris NCIMB 8303 was demonstrated. The bio‐H₂ was produced fermentatively by Escherichia coli HD701 (a strain upregulated with respect to formate hydrogenlyase expression) using glucose solution or two industrial confectionery wastes as fermentable substrates. Maximum Cr(VI) reduction occurred at the expense of bio‐H₂ using palladized biomass (bio‐Pd(0)), with negligible residual Cr(VI) remaining from a 0.5 mmol dm^?3 solution after 2.5 h. Use of bio‐H₂ as the electron donor for Cr(VI) reduction by agar‐immobilized bio‐Pd(0) in a continuous‐flow system gave 90% reduction efficiency at a flow residence time of 0.7 h, which was maintained for the duration of bio‐H₂ evolution by E. coli HD701. This study shows the potential to remediate toxic metal waste at the expense of food processing waste, as a sustainable alternative to landfilling. Copyright © 2007 Society of Chemical Industry     

Rapid removal of Cr(VI) ions from aqueous solutions by the macroporous poly(N,N′‐dimethylamino ethyl methacrylate) hydrogels

To improve the adsorption ability of hexavalent chromium [Cr(VI)], the macroporous poly(N, N′‐dimethylamino ethyl methacrylate) [poly(DMAEMA)] hydrogels were successfully fabricated by free‐radical copolymerization in ethanol/water mixture using N, N′‐dimethylamino ethyl methacrylate (DMAEMA) as the monomer, N, N′‐methylenebisacrylamide (MBAA) as the cross‐linker, and Na₂SO₄ solution as the porogen. The effects of various parameters, such as the concentration of Na₂SO₄ solutions, the dosage of MBAA, pH values, adsorption kinetic, and isotherm curves, were all investigated through systematic experiments. Scanning electron microscope (SEM) was employed to characterize the various pore structures. The experimental results showed that the influence of Na₂SO₄ solution to the pore morphology in the matrix was significant. The poly(DMAEMA) hydrogels can effectively adsorb Cr(VI) ions in aqueous media, and the macroporous structures could obvious improve the response rate and adsorption capacity. These results prove that the macroporous poly(DMAEMA) gels can be treated as a potential material for environmental pollution control. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis of zeolite Na-P1 from coal fly ash produced by gasification and its application as adsorbent for removal of Cr(VI) from water

The coal fly ash produced by gasification is estimated to be over 80 million ton per year in China by 2021. It has mainly been disposed as solid waste by landfill. There is lack of study focused on its utilization. In this paper, the coal fly ash produced by gasification was at first analyzed and then applied to synthesize zeolite as an adsorbent. The effects of synthesis conditions on the cation exchange capacity (CEC) of zeolite were investigated. The results from X-ray diffraction and scanning electron microscope indicated that the crystallinity of the synthesized zeolite is the most important factor to affect the CEC. When the synthesized zeolite with the highest CEC (275.5 meq/100 g) was used for the adsorption of Cr(VI) from aqueous solution, the maximum adsorption capacity for Cr(VI) was found to be 17.924 mg/g. The effects of pH, contact time and initial concentration on the adsorption of Cr(VI) were also investigated. The adsorption kinetics and isotherms can be well described by the pseudo-second-order model and Langmuir isotherm model, respectively.     

Preparation and characterization of iron(III) complex of an amino‐functionalized polyacrylamide‐grafted lignocellulosics and its application as adsorbent for chromium(VI) removal from aqueous media

The growth and decay processes of optically induced birefringence in two novel azobenzene compounds [one was a hyperbranched poly(aryl ether) containing azobenzene groups, and the other was a hydrogen‐bonded complex] were studied. The temperature dependence of the birefringence signal was investigated. The curves for the buildup and decay of birefringence fit well to biexponential functions. The dependence of the fitting parameters on the temperature is also discussed. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

A simple mathematical analysis on the effect of sand in Cr(VI) reduction using zero valent iron

A simple mathematical model was proposed to analyze the enhancement of Cr(VI) reduction when sand materials are added to the zero valent iron (ZVI). Natural decay of Cr(VI) in a control experiment was analyzed by using a zero-order decay reaction. Adsorption kinetics of Cr(VI) to sand was modeled as a first-order reversible process, and the reduction rate by ZVI was treated as a first-order reaction. Natural decay of Cr(VI) was also included in other experiments, i.e., the adsorption to sand, the reduction by ZVI, and both adsorption and reduction when sand and ZVI are present together. The model parameters were estimated by fitting the solution of each model to the corresponding experimental data. To observe the effect of sand addition to ZVI, both adsorption and reduction rate models were considered simultaneously including the natural decay. The solution of the combined model was fitted to the experimental data to determine the first-order adsorption and reduction rate constants when sand as well as ZVI is present. The first-order reduction rate constant in the presence of sand was about 35 times higher than that with ZVI only.     

Simultaneous degradation of RhB and reduction of Cr(VI) by MIL-53(Fe)/Polyaniline (PANI) with the mediation of organic acid

MIL-53(Fe)/polyaniline (PANI) composite was prepared by in situ depositing PANI on the surface of MIL-53(Fe) and their catalytic performances on the simultaneous removal of RhB and Cr(VI) were investigated. The elimination efficiency of both RhB and Cr(VI) reached more than 98% under pH=2 where hydrochloric acid and citric acid were used to adjust the pH. The results indicated that MIL-53(Fe)/PANI revealed an obvious pH response to the degradation of RhB, while citric acid promoted the Cr(VI) photoreduction. UV-Vis spectra, EIS, and photocurrent response experiments showed that MIL-53(Fe)/PANI had a better light response and carrier migration ability than MIL-53(Fe). The transient absorption spectra also exhibited that the lifetimes of photo-generated carriers were prolonged after the conductive polymer deposition on the MIL-53(Fe) surface. Scavenger experiments demonstrated that the main active species were ·O₂^- and OH. Combined with activity evaluation results, and the possible photocatalytic mechanism of MIL-53(Fe)/PANI on RhB oxidation and Cr(VI) reduction was proposed. The addition of conductive polymer can effectively improve the light response of the catalyst under acidic conditions, and meanwhile citric acid also provided a new mediation for the synergistic degradation of multiple pollutants. Good activity and stability of the catalysts made the scale-up purification of acid water feasible under UV-Vis light.     

钢渣颗粒对水中Cr(VI)的吸附与还原作用

以钢渣颗粒为水处理剂,分析了其组成和结构,研究了钢渣颗粒直接吸附去除水中Cr(VI)的工艺过程及机理. 结果表明,钢渣颗粒在适当的粒度与用量下,经10 min搅拌处理,水中Cr(VI)浓度由200 mg/L降低到0.5 mg/L,达到《污水综合排放标准》(GB8978-1996)的要求. 钢渣颗粒对水中Cr(VI)的吸附符合Langmuir等温吸附过程,对Cr(VI)的饱和吸附量达6.878 mg/g. 化学分析和XPS分析均表明,钢渣颗粒对水中Cr(VI)具有吸附与还原的联合作用,吸附后钢渣颗粒中Cr(III)含量由0.0985%提高到0.39%,而FeO含量由9.20%下降到8.35%. 吸附后钢渣颗粒表面形成了Cr(OH)3,说明钢渣颗粒中FeO充当了还原剂,将水中Cr(VI)吸附于钢渣颗粒表面并还原成了低毒的Cr(OH)3随钢渣颗粒沉降直接从水中去除.