Reduction of Cr(VI) to Cr(III) and removal of total chromium from wastewater using scrap iron in the form of zerovalent iron(ZVI): Batch and column studies

This work experimentally investigates Cr(VI) reduction to Cr(III) using waste scrap iron in the form of zerovalent iron (ZVI) collected from the mechanical workshop of the Institute, both in batch and continuous operation. The reduction of Cr(VI) to Cr(III) was found to be complete (～100%) depending on the experimental conditions. Lower pH values favour Cr(VI) reduction. Two concurrent reactions take place, that is reduction of Cr(VI) by Fe⁰ (ZVI) and by Fe²⁺ generated due to H⁺ corrosion of iron. Maximum around 22%, 11% and 2% Cr(III) remained dissolved in solution while the experiments were carried out at initial pH of 2, 4.67 and 7. Higher ZVI loading increases Cr(VI) reduction rate, however, consumption of iron is noted to be higher. The results indicate that the bed is exhausted rapidly at higher pH, initial Cr(VI) concentration and flow rate. This is attributable to predominance passivation of ZVI surface forming Cr(III)–Fe(III)‐oxide layer. SEM analysis of ZVI before and after the experiments confirms formation of passive oxide on iron surface is responsible for deterioration of Cr(VI) reduction efficiency due to its blanketing effect.     

Capacity of Cr(VI) reduction in an aqueous solution using different sources of zerovalent irons

Zerovalent iron (ZVI) has drawn intense interest as an effective and inexpensive tool to enhance degradation of various environmental contaminants. Reduction of Cr(VI) to Cr(III) by ZVI merits environmental concern as a hazardous species is transformed into a non-hazardous one. Objectives of this research were to assess kinetics and capacity of Cr(VI) reduction by different sources of ZVIs, of which chemical parameters can base in situ application of ZVI to treat Cr(VI) contaminated water. Reduction kinetics were first-order and rapid showing that 50% of the initial Cr(VI) was reduced within 7.0 to 347 min depending on Cr(VI) concentration, temperature and ZVI source. The reduction rates were increased with decreasing the initial Cr(VI) concentrations and increasing the reaction temperatures. The J ZVI (Shinyo Pure Chemical Co., Japan) was more effective in Cr(VI) reduction than PU (Peerless Metal Powders, USA). The maximum reduction capacities of J and PU ZVIs at 25°C were 0.045 and 0.042 mmol g⁻¹ Fe⁰, respectively. A relatively higher value of the net reaction energy (E _a ) indicated that Cr(VI) reduction by ZVI was temperature dependent and controlled by surface properties of ZVI. Chemical parameters involved in the Cr(VI) reduction by ZVI such as temperature quotient, kinetic rates, and stoichiometry indicated that the ZVI might be effective for in situ treatment of the Cr(VI) containing wastewater.     

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.     

Electrospinning of polyacrylonitrile nanofibers embedded with zerovalent iron and cerium oxide nanoparticles,as Cr(VI) adsorbents for water treatment

Zerovalent iron (ZVI) and cerium oxide (CeO₂) nanoparticles (NPs) embedded in polyacrylonitrile nanofibers (NFs) were obtained via electrospinning. Each NF was characterized using Fourier transform infrared spectroscopy and X-ray diffraction. The scaffold morphology and average diameter of the NFs were determined using scanning electron microscopy (SEM). Energy dispersive X-ray spectroscopy (EDS) mapping and Raman spectroscopy were used to characterize the NPs dispersion in the NFs. The Cr(VI) removal efficiency (%E) of ZVI and CeO₂ NPs was compared with the efficiency of their corresponding NFs. CeO₂ NPs showed 79% Cr(VI) removal; the efficiency was better for their NFs (96%). Regeneration of ZVI NFs was 98 %E. ZVI NPs were the best adsorbent with 99.9% efficiency. An adsorption mechanism was proposed using Langmuir, Freundlich, and Temkin isotherm models. SEM–EDS analyses revealed that Cr adsorbed on the NP and NF surfaces. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 137, 48663.     

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).     

Enhanced Removal of Cu(II) by Photocatalytic Reduction Using Maghemite PVA-Alginate Separable Beads: Kinetic and Equilibrium Studies

The feasibility of Cu(II) removal by photoreduction using maghemite polyvinylalcohol-alginate beads was investigated. Photoreduction experiments were performed to investigate the influence of initial concentration and pH on the removal of copper(II) metallic ions. The fate of Cu(II) during the photoreduction process was investigated using the X-ray photoelectron spectroscopy. It was observed that the Cu(II) removal rate was faster under sunlight than without sunlight due to the reduction process of Cu(II) to Cu(I). The photoreduction results showed that the adsorption of Cu(II) ions followed a Langmuir Hinshelwood model with the photoreduction rate constant and adsorption coefficient values of 24.1 ppm/min and 0.0098 ppm^?1, respectively.     

Chromium (VI) removal from water using starch coated nanoscale zerovalent iron particles supported on activated carbon

Starch coated nanoscale zerovalent iron (S-nZVI) was immobilized in activated carbon (AC) and its Cr (VI) removal characteristics were studied. Macroscopic evidence and mechanism analysis proved that S-nZVI and AC were closely linked and mutual complementary. Different factors including pH of the original solution, reaction time, and mass ratio (S-nZVI@AC/Cr =10:1, 20:1, 30:1, 50:1, 60:1, 70:1) were studied to analyze the removal rate. Results showed that the removal rate of Cr (Ⅵ) could reach 99.96% under the condition of pH of 5, and temperature =25?°C, when the mass ratio of S-nZVI@AC/Cr was 60:1. The removal of Cr(Ⅵ) by S-nZVI@AC followed pseudo-second-order kinetics. X-ray diffraction (XRD) resulted demonstrate that S-nZVI@AC existed in a Fe₃C state before reaction and in a Fe(III) state after reaction. XPS (X-ray photoelectrons spectroscopy) analysis suggested that the mechanism of Cr (VI) removal by S-nZVI@AC is adsorption and reduction. S-nZVI@AC might be a potential composite material for the purification and detoxification of Cr (VI) in water because of its efficiency and stability.     

光催化法处理含Cr(VI)废水的研究

采用P 25 TiO2作为光催化剂,研究了废水的pH值、Cr(VI)的初始浓度、气氛及有机物等因素对含铬废水中Cr(VI)去解率的影响。结果表明,在pH值为3.0时,光催化反应速率最大;反应气氛对该体系中Cr(VI)的光催化还原无明显影响;苯酚、葡萄糖等有机物的存在能有效地促进Cr(VI)的光催化还原,当加入与Cr(VI)等物质的量的苯酚或葡萄糖时,150 mL反应液[Cr(VI)浓度为0.96 mmol/L],0.15 g光催化剂,经12 W紫外灯照射反应120 m in,Cr(VI)完全被去除,相对于在反应体系中不加有机物时,Cr(VI)光催化还原效率提高了近100%;Cr(VI)的光催化还原符合L-H动力学规律。     

Heterocyclic modification of chitosan for the adsorption of Cu (II) and Cr (VI) ions

A heterocyclic modification of chitosan has been attempted for development of an effective adsorbent material for removal of metal ions. The modified polymer was characterized using infrared (IR) spectroscopy, thermogravimetric analysis (TGA), scanning electron microscopy (SEM), energy dispersive x-ray spectroscopy (EDS) and x-ray diffraction (XRD) techniques. The adsorption capacity exhibited for Cu (II) and Cr (VI) were 83.75 and 85.0 mgg^?1, respectively, which is a significant improvement over chitosan. The adsorption on the modified polymer was a second-order kinetic process and followed Langmuir isotherm model. The thermodynamic analysis indicated exothermic and spontaneous nature of adsorption. About 80% of the adsorbed metal ions were desorbed in appropriate stripping solutions indicating reusability.     

Kinetic,isotherm, and thermodynamic studies of Cr(VI) removal from aqueous solution using mesoporous silica materials prepared by fly ash

A series of mesoporous silica materials (FMD, FMT, and FMC were synthesized with DTAB, TTAB, and CTAB as template, respectively) have been prepared using fly ash as a silica resource. The as-synthesized materials were characterized by BET, XRF, FTIR, and XPS. The results confirmed the mesoporous structure and nitrogen content to act as potential adsorbents. The adsorption properties of these materials were also investigated by batch adsorption experiments. The FMC exhibited the highest effective removal of Cr(VI) (99%). The Cr(VI) adsorption process over FMC follows the pseudo-second-order kinetic and Langmuir model. Thermodynamic studies revealed that the Cr(VI) adsorption by FMC was spontaneous and endothermic. The study of the adsorption mechanism showed that the removal of Cr (VI) by FMC is through electrostatic attraction and chemical reduction. The coexisting ions experiment showed that FMC had high selectivity for Cr(VI). After three regeneration cycles, the Cr(VI) removal rate of FMC adsorbent still remained about 80%. Thus, this inexpensive adsorbent (FMC) is suitable for removing Cr(VI) from discharged industrial water.     

Electrocatalytic reduction of chromium by poly(aniline-co-o-aminophenol): An efficient and recyclable way to remove Cr(VI) in wastewater

Poly(aniline-co-o-aminophenol) (PANOA)-modified glassy carbon electrode (GCE) was first used to investigate the electrocatalytic reduction of dichromate in a NaCl solution of pH 5.0. The results of cyclic voltammograms and UV–vis spectra demonstrated that the reduction of Cr(VI) occurred at PANOA-modified GCE. The FT-IR, ESR and XPS results showed that the Cr(VI) can be doped in the PANOA films and can convert to less-toxic Cr(III). The doping level Cr/N was 78.2% and trace amount of Cl (0.42%) was detected in the doped PANOA, which indicated that the doping process is effective and PANOA had rather good ion selectivity in the 0.10 M NaCl supporting electrolyte. The factors influenced the reduction were also considered. Various initial concentrations of Cr(VI) had different removal rates. The maximum removal rate of Cr(VI) at 20 mg L⁻¹ (32.3%) was better than that of at 5 mg L⁻¹ (22.9%). The solution pH had little effect on Cr(VI) reduction and doping process of the PANOA because PANOA had good electrochemical activity and stability in a wide range of pHs (from pH 4 to pH 8).     

Insights into Supported Copper(II)‐Catalyzed Azide‐Alkyne Cycloaddition in Water

Cross‐linked polymeric ionic liquid material‐supported copper (Cu‐CPSIL), imidazolium‐loaded Merrifield resin‐supported copper (Cu‐PSIL) and silica dispersed CuO (CuO/SiO₂), were prepared and proved to be efficient catalysts for the one‐pot synthesis of 1,4‐disubsituted‐1,2,3‐triazoles by the reaction of alkyl halides with sodium azide and terminal alkynes in water at room temperature. Moreover, these supported copper catalysts were recovered quantitatively from the reaction mixture by simple filtration and reused for five consecutive recycles without significant loss of catalytic activity. Among the three immobilized copper catalysts, Cu‐CPSIL exhibited excellent catalytic activity for the reaction of aliphatic bromides, sodium azide and terminal alkynes. The differences in the catalytic performances of the catalysts could be ascribed to the copper dispersion and the interaction between copper and the supports. In addition, water was used as the reaction media and the proton provider, the latter was found to be very important for the reaction. The XPS results suggested that the supported Cu(II) catalysts were reduced to catalytic Cu(I) species via alkynes homocoupling reaction. By means of IR and ESI‐MS studies, a possible mechanism of cycloaddition based on the reduction of Cu(II) to Cu(I) species was proposed.     

Visible light photoreduction of Cr(VI) in aqueous solution using iron-containing zeolite tubes

In this study, a novel visible light photocatalyst consisting of iron-loaded zeolite tubes was designed to reduce Cr(VI) to Cr(III) in aqueous solution. Iron was incorporated into hollow, porous ZSM-5 tubes using two different methods. In the first method, the iron-encapsulated ZSM-5 tubes were prepared by introducing iron into the mesoporous silica template prior to the formation of the hollow ZSM-5 tubes resulting in an encapsulated iron species. In the second method, iron was ion-exchanged into the ZSM-5 shell during a post-synthesis treatment. The iron-loaded ZSM-5 structures were extensively characterized by powder X-ray diffraction (XRD), elemental analysis, solid-state ²⁷Al magic angle spinning nuclear magnetic resonance (MAS NMR), electron paramagnetic resonance (EPR), electron microscopy with energy dispersive X-ray analysis, and X-ray photoelectron spectroscopy (XPS). The iron in the iron-exchanged ZSM-5 tubes tended to aggregate compared to the iron in the iron-encapsulated ZSM-5 tubes. Both the iron encapsulated and iron-exchanged ZSM-5 hollow tubes were active for the visible light photoreduction of Cr(VI) to Cr(III) in aqueous solution. The iron-exchanged ZSM-5 tubes were very active initially but suffered from substantial iron leaching after the first use in aqueous Cr(VI) photoreduction relative to the iron-encapsulated ZSM-5 tubes which showed very little leaching of the iron.     

Removal of Hexavalent Chromium from Aqueous Solutions by Sodium Dodecyl Sulfate Stabilized Nano Zero-Valent Iron: A Kinetics,Equilibrium, Thermodynamics Study

Sodium dodecyl sulfate stable nanoscale zero-valent iron (SDS-nZVI) was synthesized by the sodium borohydride reduction method, characterized with SEM and XRD. SDS-nZVI was used for the removal of Cr (VI) from aqueous solutions at different conditions in a batch process. XRD analysis indicated the presence of iron oxide and iron-chromium hydroxide coprecipitation on the surface of SDS-nZVI after reaction some time. The reaction kinetics, mechanism, isotherms, and thermodynamics for Cr (VI) removal of aqueous solution via SDS-nZVI were investigated. The pseudo-second-order model was relatively suitable for describing the reaction process. Intraparticle diffusion model was used to analysis the mechanism, the results indicated that there were two processes (bulk diffusion and surface diffusion) controlling the reaction rate, while only one was rate limiting in any particular time range. The fitted Temkin and D-R model satisfactorily explanted the experimental data in the range of 303–343 K. The maximum removal capacity of SDS-nZVI for Cr (VI) was obtained for 336.7 mg g^?1 at 303 K. The overall removal process was endothermic. These results demonstrated that SDS-nZVI could potentially be used as an effective material for environmental remediation.     

颗粒活性炭载纳米零价铁去除水中的Cr(Ⅵ)

以Fe2+溶液为原料、NaBH4为还原剂,采用传统液相还原技术合成了颗粒活性炭(GAC)载纳米零价铁(nZVI)复合材料GAC-nZVI,用扫描电镜对GAC-nZVI进行表征,通过间歇实验考察了其对去除Cr(VI)的影响。结果表明,GAC能阻止nZVI颗粒聚集,合成的GAC-nZVI能有效去除水中的Cr(VI)。在Cr(VI)初始浓度50 mg/L、温度40℃和pH=2.0、投加GAC-nZVI 3.0 g/L的条件下反应5 min,Cr(VI)去除率为99.4%。pH=2.0?4.0时,处理后水中总铬浓度均低于1 mg/L,表明残留少量Cr(III)。随pH值和Cr(VI)浓度增加,Cr(VI)去除率降低;随反应温度和GAC-nZVI投加量增加,Cr(VI)去除率增加。准一级动力学模型可用于描述Cr(VI)的去除过程。相同条件下,GAC-nZVI去除Cr(VI)的反应速率常数达0.19797 min?1,为原颗粒活性炭反应速率常数0.0023 min?1的86倍。随pH值降低或反应温度和GAC-nZVI投加量增加,反应速率常数增加。     

纳米零价铁强化高岭石去除水中Cr(VI)及机制研究

纳米零价铁(nZVI)作为一种治理重金属、核素污染物的环保材料而被广泛关注,而黏土矿物作为常见的重金属吸附材料虽成本低廉、来源广泛,但去除性能又普遍有限。通过液相还原法制备nZVI/高岭石复合材料来强化高岭石去除水中Cr(VI)的性能,利用X射线衍射仪(XRD)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)技术对其结构进行表征,考察了Cr(VI)初始浓度、nZVI/高岭石投加量、温度等条件对Cr(VI)去除率的影响,并探讨了其对水中Cr(VI)的去除能力及机制。结果表明,nZVI/高岭石中的nZVI结晶度低,粒径在50~100 nm,nZVI/高岭石在60 min时对Cr(VI)的去除率达91.7%,分别比nZVI和高岭石提高了2.7倍和18.5倍。nZVI/高岭石对Cr(VI)的去除动力学符合准二级动力学模型,表观反应活化能为27.97 kJ/mol,去除是吸附、还原和共沉淀共同作用的结果。通过nZVI强化可提升高岭土在水处理和环境修复中的应用前景。     

Heterotrophic/autotrophic denitrification (HAD) of drinking water: prospective use for permeable reactive barrier

This work aims to explore the use of an innovative denitrification process developed by our group for groundwater remediation. This process is coupling heterotrophic-autotrophic denitrification processes (HAD) supported by cotton and zero-valent iron (ZVI). In the experimental part, the effect of two amounts of ZVI (150 and 300 g), two nitrate (100 and 220 mg/l) and phosphate (3 and 6 mg/l) inlet concentrations on nitrate removal performance is investigated in two parallel continuous fed plug-flow reactors. The possible in-situ application of the proposed system in permeable reactive barriers (PRB) is further discussed. The HAD showed higher volumetric nitrate removal ratio (VNR) than the cotton supported heterotrophic denitrification one, and VNR increased with the amount of ZVI packed in the reactors. Ammonium production by the reductive action of iron was kept on acceptable level adjusting the contact time between water and ZVI. Iron release from ZVI decreased with time to negligible value (<0.5 mg/l) thanks to the formation of iron green rust compounds (GR). The HAD seems to be adequate for PRB systems, because both cellulose-based material and ZVI have been used in reactive trench for site remediation. Moreover, the proposed process could have the function for removal of nitrate and priority pollutants, such as chlorinated ethenes, simultaneously.     

Boron-Doped Diamond Electrode Performance in Cr(VI) Reduction Using Synthetic and Plating Wastewater

The goal of this work was to evaluate the effectiveness of iron and boron-doped-diamond (BDD) as cathodic electrodes on the reduction of Cr(VI) in synthetic and wastewater samples. The pH and electrolyte composition were varied, and the effect on the Cr(VI) reduction rate was measured. The optimized conditions from the synthetic water Cr(VI) reduction experimental data, were tasted on electroplating wastewater. The results indicated that both a pH of 2 and the use of NaCl as an electrolyte significantly increase the Cr(VI) reduction rate for all synthetic systems, especially the iron-BDD system. The Cr(VI) reduction rate in Fe-BDD systems was also affected by nitrate and sulfate ions. In the case of electroplating wastewater, Cr(VI) reduction by BDD cathodes was faster than with iron cathodes, achieving a complete reduction of 180 mg Cr(VI)/L in 25 min, with 40% less sludge produced. The elemental composition of sludge was analyzed using SEM/EDS and X-ray spectroscopy to confirm that iron and chromium precipitated out of the solution. The sludge had a chemical composition of (31.9%) Fe₂O₃, (29.6%) FeOOH, (21%) FeO, and (17.4%) FeSO₄. Therefore, BDD as an electrode material effectively reduces Cr(VI) in electroplating wastewater, and can be effectively scaled up to industrial applications.     

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.