Removal of Cr(VI) from aqueous solutions using modified red pine sawdust

The adsorption of Cr(VI) from aqueous solutions on sawdust (SD), base extracted sawdust (BESD) and tartaric acid modified sawdust (TASD) of Turkish red pine tree (Pinus nigra), a timber industry waste, was studied at varying Cr(VI) concentrations, adsorbent dose, modifier concentration and pH. Batch adsorption studies have been carried out. Sawdust was collected from waste timber industry and modified with various amount of tartaric acid (TA) (0.1-1.5M). The batch sorption kinetics has been tested and the applicability of the Langmuir and Freundlich adsorption isotherms for the present system has been tested at 25+/-2 degrees C. Under observed test conditions, the equilibrium adsorption data fits the linear Freundlich isotherms. An initial pH of 3.0 was most favorable for Cr(VI) removal by all adsorbents. Maximum Cr(VI) was sequestered from the solution within 120 min after the beginning for every experiment. The experimental result inferred that chelation and ion exchange is one of the major adsorption mechanisms for binding metal ions to the SD. Percentage removal of Cr(VI) was maximum at the initial pH of 3.0 (87.7, 70.6 and 55.2% by TASD, BESD, and SD, respectively). Adsorption capacities range from 8.3 to 22.6 mg/g for SD samples.     

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 .     

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.     

Modeling of kinetics of Cr(VI) sorption onto grape stalk waste in a stirred batch reactor

Recently, Cr(VI) removal by grape stalks has been postulated to follow two mechanisms, adsorption and reduction to trivalent chromium. Nevertheless, the rate at which both processes take place and the possible simultaneity of both processes has not been investigated. In this work, kinetics of Cr(VI) sorption onto grape stalk waste has been studied. Experiments were carried out at different temperatures but at a constant pH (3 ± 0.1) in a stirred batch reactor. Results showed that three steps take place in the process of Cr(VI) sorption onto grape stalk waste: Cr(VI) sorption, Cr(VI) reduction to Cr(III) and the adsorption of the formed Cr(III). Taking into account the evidences above mentioned, a model has been developed to predict Cr(VI) sorption on grape stalks on the basis of (i) irreversible reduction of Cr(VI) to Cr(III) reaction, whose reaction rate is assumed to be proportional to the Cr(VI) concentration in solution and (ii) adsorption and desorption of Cr(VI) and formed Cr(III) assuming that all the processes follow Langmuir type kinetics. The proposed model fits successfully the kinetic data obtained at different temperatures and describes the kinetics profile of total, hexavalent and trivalent chromium.The proposed model would be helpful for researchers in the field of Cr(VI) biosorption to design and predict the performance of sorption processes.     

Stripping of copper coatings from steel in Cr(VI)-free commercial bath

In this work the electrochemical characteristics of copper and steel in chromate, cyanide, and phosphate baths as well as in a commercial bath (ENSTRIP S-180), in the absence of chromium and cyanides were determined. Average rates of copper coatings stripping from steel in the above mentioned baths and the baths influence on the morphology of steel surfaces were described. It was found that the commercial bath ENSTRIP S-180 could be successfully used for stripping of copper coatings from steel elements.     

Controllable preparation and efficient visible-light-driven photocatalytic removal of Cr(VI) using optimized Cd0.5Zn0.5S nanoparticles decorated H-Titanate nanotubes

Based on one-dimensional (1D) H-titanate nanotubes (H-TNTs: TNTs with loosely distributed H⁺ across the interlayers), a novel series of Cd_0.5Zn_0.5S loaded H-TNTs (Cd_0.5Zn_0.5S/TNTs) composites with varied ratios have been achieved by the in-situ growth method. The as-prepared samples were characterized by (high-resolution) transmission electron microscopy (HR/TEM), XRD, FT-IR, XPS, UV–vis diffuse reflectance spectroscopy (UV–vis DRS), fluorescence spectroscopy (FL), photocurrent, electron spin resonance (ESR) spectroscopy, etc. These studies concurrently revealed a successful formation of Cd_0.5Zn_0.5S/TNTs heterojunction, and a homogeneous distribution of Cd_0.5Zn_0.5S nanoparticles over the surface of 1D H-TNTs. The incorporation of the appropriate amount of Cd_0.5Zn_0.5S nanoparticles (10%) significantly improves the efficiency of photogenerated electron-hole pairs separation. The photocatalytic reduction efficiency of the Cd_0.5Zn_0.5S/TNTs for Cr(VI) and degradation efficiency for organic molecules increased initially and then decreased with the amount of loaded Cd_0.5Zn_0.5S nanoparticles. The optimal photocatalytic efficiency was observed at 10 %Cd_0.5Zn_0.5S/TNTs, which were 2.71-fold and 4.8-fold than that of pure H-TNTs for the removal of the Cr(VI) and the degradation of the organic molecules, respectively. The ESR test signified that the holes (h⁺) and superoxide radicals (∙O₂^–) played an essential role in the degradation process of organic molecules. Finally, a reasonable explanation for enhanced photocatalysis performance was proposed.     

Simultaneous photocatalytic reduction of Cr(VI) and oxidation of bisphenol A induced by Fe(III)-OH complexes in water

Simultaneously photocatalytic reduction of Cr(VI) and oxidation of bisphenol A (BPA) in aqueous solution in the presence of Fe(III)-OH complexes were investigated under a 250 W metal halide lamp (lambda>or=365 nm). Synergy effect of the simultaneous photocatalytic oxidation and reduction of both pollutants was achieved. The effects of initial pH value, initial concentration of BPA, Cr(VI) and Fe(III) were preliminarily investigated. The results showed that both photocatalytic reduction of Cr(VI) and degradation of BPA could occur simultaneously in the Fe(III)/Cr(VI)/BPA ternary system, and the rates of photocatalytic reduction of Cr(VI) and the oxidation of BPA were more rapid at a low pH range of 2.0-3.0. The increase of the initial concentration of Fe(III) was favorable to both photocatalytic reduction of Cr(VI) and oxidation of BPA. The reduction efficiency of Cr(VI) decreased with increasing initial concentrations of Cr(VI) and BPA, but the degradation efficiency of BPA was not changed obviously at different Cr(VI) concentrations.     

Polypyrrole decorated ZnTi hydrotalcite with enhanced adsorption and Cr(VI) photoreduction activity under visible-light

A conjugated polymer polypyrrole (PPy) was used to decorate the ZnTi hydrotalcite (ZnTi-LDH) for constructing an organic–inorganic PPy/ZnTi-LDH composite by a facile in-situ oxidation polymerization. It was found that the as-prepared composite displayed a superior photocatalytic performance and excellent stability under visible light irradiation, which Cr(VI) reduction efficiency (99.72% for 35 min) was around 53 and 12 times higher than those of the pristine ZnTi-LDH and pure PPy, respectively, and still maintained 95.10% even after 5th cycles. The dramatically enhanced photocatalytic performances were attributed to the beneficial combination of the ZnTi-LDH stratified structure and conductive PPy, which effectively facilitated charge transfer, restrained recombination, and increased visible-light absorption. Particularly, PPy as a remarkable conductive polymer, played a crucial role in the Cr(VI) reduction, which not only was a light acceptor to produce photo-generated charge carriers but also provided a good electron transport path to accelerate the separation and migration of electron-hole pairs to improve the photoreduction performances. Finally, possible photocatalytic reaction mechanism of the PPy/ZnTi-LDH was also proposed.     

The comprehensive investigation on removal mechanism of Cr(VI) by humic acid-Fe(II) system structured on V,Ti-bearing magnetite surface

The Cr(VI) could be adsorbed and reduced by the humic acid (HA)-Fe(II) system structured on the V, Ti-magnetite (VTM) surface. The Cr(VI) removal process included adsorption and reduction stages. First, the Cr(VI) was adsorbed on the VTM-HA surface via the ionic bonds between the Ti atoms of VTM core and the O atoms of the HCrO₄^?. The adsorption of Cr(VI) is uniform, monolayer, and controlled by Cr(VI) diffusion. Subsequently, the adsorbed Cr(VI) was reduced by the HA-Fe(II) system on the VTM-HA surface. During the Cr(VI) reduction process, the HA and Fe(II) have a synergistic effect. The Cr(VI) was reduced to the Cr(III) by the HA and Fe(II). Meanwhile, the HA could also reduce Fe(III) to Fe(II), making Fe(II) continue to participate in the Cr(VI) reduction. The olefin, hydroxyl, and aldehyde groups of HA were the primary electron donors during the Cr(VI) reduction. The Fe(II) acted as an electron bridge, transferring the electron from HA to Cr(VI). The reduced Cr(III) was deposited on the VTM-HA surface via the complexation with the carboxyl and hydroxyl groups of HA. The results demonstrated that the Cr(VI) could be adsorbed, reduced and complexed by the HA-Fe(II) system on the VTM-HA surface synchronously.     

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.     

A novel green synthesis of zero valent iron nanoparticles (NZVI) using three plant extracts and their efficient application for removal of Cr(VI) from aqueous solutions

In the present study, NZVI particles were synthesized from the plant extracts including Rosa damascene (RD), Thymus vulgaris (TV), and Urtica dioica (UD). The FTIR arspectshowed that polyphenols, proteins and organic acids which serve as reducing and stabilizing agents play a significant role in the synthesis of NPs and reduce the possibility of aggregation of NPs compared to chemical techniques of NPs synthesis. The amount and type of compounds in plant extracts affect the structure and also agglomeration of NPs after adsorption process. Based on the results, the highest removal efficiency occurred at pH 2. With increase in contact time and amount of dose, the percentage removal increases. Inversely, increase of initial concentration of Cr(VI) decreases the removal efficiency of the contaminant. These nanoparticles have a high adsorption capacity. Accordingly, by applying a dose of 0.2 g/l and contact time of 10 min, the three NPs yielded >90% removal efficiency. Also, for 1 min contact time, the percentage removal was 94.87%, 83.48% and 86.8% for RD-Fe, UD-Fe and TV-Fe, respectively. By an increase to 25 min, the removal percentage reached to 100% for TV-Fe and UD-Fe. Moreover, 30 min was required to remove Cr(VI) completely by RD-F.     

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.     

Facile synthesis of Ti3C2 MXene-modified Bi2.15WO6 nanosheets with enhanced reactivity for photocatalytic reduction of Cr(VI)

Through a facile hydrothermal method, we have successfully prepared Ti₃C₂/Bi_2.15WO₆ (TC/BWO) composite, and systematically investigated their reactivity for the photocatalytic reduction of Cr(VI) under visible light. X-ray diffraction and Raman analysis confirm the formation of heterostructure between Bi_2.15WO₆ and Ti₃C₂. The resultant 7TC/BWO composite exhibits enhanced photoactivity toward Cr(VI) reduction. After 120 min irradiation, the conversion of Cr(VI) reaches 92.5% with the quasi-first-order kinetic constant of k = 0.0145 min^?1, which is higher than that of pure BWO (30% and k = 0.0005 min^?1). The electrochemical and photoluminescent characterization confirm that the introduction of Ti₃C₂ is conducive to the separation of carriers, thus significantly improves the photocatalytic performance of TC/BWO. Furthermore, the radical capture experiments verify that the electrons are important for enhancing reduction of Cr(VI) to Cr(III). As a result, this research provides a comprehensive understanding of the reduction of Cr(VI) by TC/BWO composite under visible light.     

Formation and mechanism of nanoscale zerovalent iron supported by phosphoric acid modified biochar for highly efficient removal of Cr(VI)

The effect of phosphoric acid modified biochar on activity of nanoscale zero valent iron particles is not clear until now. In this research, Egeria najas powder driven biochar-supported nanoscale zero valent iron was modified by phosphoric acid (P-BC/nZVI) for highly effective removal of Cr(VI) from wastewater. The TEM and XRD of P-BC/nZVI indicated that nZVI particles were successfully immobilized on the P-BC surface. The batch experiment results show that the Cr(VI) removal efficiency by P-BC/nZVI was higher than that of BC/nZVI, nZVI, P-BC and BC. Moreover, the optimal ratio of nZVI to P-BC lies at 3:1 with fixed P-BC/nZVI dosage of 0.75 g/L, initial Cr(VI) concentration of 20 mg/L, solution pH of 2, and reaction temperature of 333 K. Additionally, Cr(VI) removal capacities by nZVI, BC/nZVI and P-BC/nZVI aged for 15 days in water were 12.9 %, 28.55 % and 99.35 %, respectively. Furthermore, corresponding reaction kinetics fitted well with pseudo-second order model, and adsorption isotherm fitted to Sips isothermal model. The SEM-EDS and XPS confirm that Cr(VI) was participated in the reaction, and about 63.43 % of Cr(VI) was reduced to Cr(III), and the rest was adsorbed on the surface of P-BC/nZVI. The removal mechanism of Cr(VI) by P-BC/nZVI was complex, including adsorption, reduction and surface complex formation.     

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.     

吸附温度对MgAl金属氧化物微观结构和吸附Cr(VI)性能的影响

研究了MgAl水滑石(LDH)焙烧产物(LDO)对Cr(VI)的吸附性能。考察了吸附温度对LDO吸附性能的影响, 研究了吸附过程的热力学和动力学行为。结合XRD和FT-IR表征, 阐明其吸附机理。结果表明, CrO₄^2–已成功插入水滑石层间, 适当提高吸附温度有利于LDO恢复LDH晶相。在20~60℃范围内, 随吸附温度升高, LDO对Cr(VI)吸附量增大, 50~60℃时, Cr(VI)吸附量为91 mg/g。Cr(VI)的吸附平衡数据符合Langmuir模型方程, ΔG_o为负值说明吸附过程为自发过程, ΔS_o和ΔH_o为正值表明吸附为熵增的吸热过程。吸附动力学符合伪二级动力学模型, LDO 的吸附活化能为20.04 kJ/mol, 表现为扩散控制的活性化学吸附过程。     

Adsorption and mobility of Cr(III)-organic acid complexes in soils

The soluble Cr(III) is likely to be complexed with organic ligands in ligand-rich soil. Cr(VI) chemical reduction by organic acids and bioreduction by microorganisms can produce soluble Cr(III)-organic acids complexes. Thus, it is of great significance to investigate the absorption and mobility of Cr(III)-organic acid complexes in soils. In this study, Cr(III)-EDTA and Cr(III)-cit were prepared and purified, and then were examined for adsorption and mobility. The results demonstrated that Cr(III) was strongly bound to soil, while Cr(III)-organic acid complexes had no or slight interaction with soils since Cr(III)-EDTA and Cr(III)-cit complexes mainly existed as the forms of [Cr(III)-EDTA]⁻ and [Cr(III)-cit], respectively, under the tested conditions with initial pH 4.0-9.0. The adsorption of Cr(III) increased but that of Cr(III)-organic acid complexes decreased with the content of soil organic matter. Compared with Cr(III)-EDTA, the mobility of Cr(III)-cit in soil columns was reduced, due to the specific adsorption between soils and Cr(III)-cit which contained one free hydroxyl group.     

Removal of chromium Cr(VI) by low-cost chemically activated carbon materials from water

Low-cost, chemically activated carbon materials, Pellet-600 and PVA-300, were prepared at relatively low temperatures and show more effective removal efficiency of Cr(VI) from water than commercially available activated carbons tested. The Pellet-600 is a pelletized carbon material with high mesoporous volumes and surface area, and the PVA-300 is composed of a high surface area carbon coating on a fiberglass mat substrate. A much faster adsorption kinetics and a much higher adsorption capacity for Cr(VI) are achieved by the Pellet-600. At very low concentrations of Cr(VI), the PVA-300 displays a strong adsorption ability for Cr(VI). XPS data show an increase in the atomic ratio of Cr/C and oxidation of carbon materials after adsorption of Cr(VI). These results suggest that a high content of mesopores with a high surface area and surface functional groups greatly improve the Cr(VI) removal efficiency from water.     

棓花青褪色光度法测定镀铬液中的铬

在硫酸混酸介质 ,10 0℃恒温水浴中 ,铬 (Ⅵ )能氧化花青 ,使其显著褪色 ,据此建立了测定铬 (Ⅵ )的新方法。铬 (Ⅵ )的浓度在 0～ 1.0 4 μg/mL范围内 ,符合比耳定律 ,表观摩尔吸光系数为 1.90× 10 4 L/ (mol·cm)。此法用于测定镀铬液中铬 (Ⅵ )的含量 ,结果令人满意     

Synthesis of carnation flower-like Bi2O2CO3 photocatalyst and its promising application for photoreduction of Cr(VI)

In this study, we have synthesized high-quality carnation flower-like Bi₂O₂CO₃ hierarchical architectures via a hydrothermal route. The as-synthesized Bi₂O₂CO₃ photocatalyst was systematically characterized and analyzed by various techniques. Its photocatalytic activity was investigated by simulated-sunlight driving photoreduction of Cr(VI), revealing that it exhibits excellent photocatalytic removal of Cr(VI). The effects of various factors (H₂SO₄, NaOH, Cr(VI) concentration, catalyst dosage) on the photoreduction efficiency and involved mechanism were systematically investigated and discussed. In addition, we have also systematically examined the effects of various parameters (H₂SO₄ concentration, 1,5-diphenylcarbazide (DPC) concentration, Cr(VI) concentration, reaction time t and reaction temperature T) on the absorbance of the Cr(VI) solution, with the aim of correctly determining the Cr(VI) concentration according to UV–vis absorption measurements using DPC as the chromogenic agent.