壳聚糖基印迹水凝微球对Cr (VI)的选择性吸附研究

目前水环境污染物成分复杂,常用的化学沉淀法已很难将重金属污染物分类去除并资源化利用,由此产生了大范围的危废污染环境,需要进行二次处理。利用离子印迹技术对壳聚糖基水凝微球进行改性,制备具有对Cr (VI)特异识别性能的吸附材料(CTS-IGB）,对其在单一Cr (VI)溶液和模拟电镀废水中的吸附行为特征进行研究。研究结果表明:在20 ℃、pH值为3时,CTS-IGB在单一Cr (VI)溶液和模拟电镀废水中Cr (VI)的吸附量在180 min内分别达到37.4 和44.3 mg/g,半饱和吸附时间仅分别为5.8和23.5 min;吸附行为符合准二级动力学。吸附等温线拟合表明吸附过程符合Freundlich模型;热力学参数表明吸附过程是放热反应,且吸附后无序度减小;相比于未改性壳聚糖水凝微球,CTS-IGB在共存离子（模拟电镀废液及其他双组份溶液）工况下对Cr (VI)的选择性提高32%~74%。该材料可作为潜在的吸附材料用于污染水环境中Cr (VI)的分离及回收。     

Removal of hexavalent chromium from wastewater by Fe0-nanoparticles-chitosan composite beads: characterization, kinetics and thermodynamics

Fe0-nanoparticles-chitosan composite beads (CS-NZVI beads) were prepared and used to remove hexavalent chromium (Cr (VI)) from wastewater. Characterization with a scanning electron microscopy (SEM) demonstrated that with the increase of the concentration of CS from 5.0 to 20.0 g/L and NaOH from 0.5 to 2.0 mol/L, the average aperture size of the CS-NZVI beads decreased from 26.8 to 10.6 μm and 42.6 to 0.8 μm, respectively. Batch experiments revealed that the removal of Cr (VI) using CS-NZVI beads was consistent with pseudo first-order reaction kinetics. The rate constant increased with increasing NZVI dosage but decreased with the increase in pH values. The Freundlich isotherm described the adsorption process better, suggesting that the CS-NZVI beads were heterogeneous in the surface properties. At equilibrium qmax was 35.97 mg/g. The thermodynamics study suggested that Cr (VI) removal by CS-NZVI beads was an endothermic and spontaneous process, reflecting good affinity of the sorbent for Cr (VI) ions and increasing randomness at the solid-solution interface during the adsorption process. This result will be very useful to understand the effects of NZVI on heavy metal Cr (VI) removal from wastewater in the successful application.     

Removal of hexavalent chromium in soil and groundwater by supported nano zero-valent iron on silica fume

Silica fume supported-Fe(0) nanoparticles (SF-Fe(0)) were prepared using commercial silica fume as a support. The feasibility of using this SF-Fe(0) for reductive immobilization of Cr(VI) was investigated through batch tests. Compared with unsupported Fe(0), SF-Fe(0) was significantly more active in Cr(VI) removal especially in 84 wt% silica fume loading. Silica fume had also been found to inhibit the formation of Fe(III)/Cr(III) precipitation on Fe nanoparticles' surface, which was increasing the deactivation resistance of iron. Cr(VI) was removed through physical adsorption of Cr(VI) onto the SF-Fe(0) surface and subsequent reduction of Cr(VI) to Cr(III). The rate of reduction of Cr(VI) could be expressed by pseudo first-order reaction kinetics. The rate constant increased with the increase in iron loading but decreased with the increase in initial Cr(VI) concentration. Furthermore, column tests showed that the SF-Fe(0) could be readily transported in model soil.     

Removal of hexavalent chromium in aquatic solutions by pomelo peel

This study investigated the removal of hexavalent chromium(Cr(VI)) in aqueous solutions using pomelo peel(PP) and FeCl_3-modified pomelo peel(FPP) as novel biomass adsorbents.Batch adsorption experiments were performed to evaluate the effects of pH,time,temperature,initial concentration,and adsorbent dose on Cr(VI) removal by PP and FPP.The results show that the maximum adsorption capacity of Cr(VI)was 21.55 mg/g for FPP and 0.57 mg/g for PP at a pH of 2.0 and a temperature of 40℃.The surface shape,microstructure,and chemical composition of FPP were analyzed with scanning electron microscopy(SEM),Fourier transform infrared spectroscopy(FTIR),and energy dispersive spectroscopy(EDS),and compared with those of PP.The results show that the adsorption performance of FPP was much better than that of PP,indicating that FPP can be an alternative high-efficiency adsorbent for Cr(VI) removal.     

Adsorption of Cr(VI) in wastewater using magnetic multi-wall carbon nanotubes

Magnetic multi-wall carbon nanotubes were prepared with wet chemical treatments and characterized by a transmission electron microscope (TEM) and X-ray diffraction (XRD). They were used as adsorbents for the removal of Cr(VI) in aqueous solutions. The effects of adsorbent dosage, the concentration of Cr(VI) in aqueous solution, temperature, and pH value on the removal efficiency were studied. Results showed that the adsorption capacity of the magnetic multi-wall carbon nanotubes increased with the initial Cr(VI) concentration, but decreased with the increase of adsorbent dosage. The adsorption amount increased with contact time. The adsorption kinetics were best represented by the pseudo second-order kinetic model, and the adsorption isotherms indicated that the Langmuir model better reflected the adsorption process. The obtained calculation results for the Gibbs free energy revealed that the adsorption was a spontaneous and endothermic process. The enthalpy deviation was 3.835 kJ·mol⁻¹. The magnetic multi-wall carbon nanotubes showed significant potential for application in adsorption of heavy metal ions.     

Characterization of cobalt ferrite-supported activated carbon for removal of chromium and lead ions from tannery wastewater via adsorption equilibrium

In this experiment, cobalt ferrite-supported activated carbon (CF-AC) was developed and characterized via the wet impregnation method for the removal of Cr and Pb(II) ions from tannery wastewater. Batch adsorption was carried out to evaluate the effect of experimental operating conditions (pH of solution, contact time, adsorbent dose, and temperature), and the removal efficiencies of Cr and Pb(II) ions by the developed adsorbents were calculated and recorded for all experimental conditions. These variables were estimated and reported as removal efficiencies of 98.2% for Cr and 96.4% for Pb(II) ions at the optimal conditions of 5, 0.8 g, 80 min, and 333 K for pH, adsorbent dose, contact time, and temperature, respectively. The equilibrium for the sorption of Cr and Pb(II) ions was studied using four widely used isotherm models (the Langmuir, Freundlich, Dubinin-Radushkevich, and Temkin isotherm models). It was found that the Freundlich isotherm model fit better with the coefficient of determination (R²) of 0.948 4 and a small sum of square error of 0.000 6. The maximum adsorption capacities (Q_m) of Pb(II) and Cr adsorbed onto CF-AC were determined to be 6.27 and 23.6 mg/g, respectively. The adsorption process conformed well to pseudo-second order kinetics as revealed by the high R² values obtained for both metals. The thermodynamic parameters showed that adsorption of Cr and Pb(II) ions onto CF-AC was spontaneous, feasible, and endothermic under the studied conditions. The mean adsorption energy (E) values revealed that the adsorption mechanism of Cr and Pb(II) by CF-AC is physical in nature. The results of the study showed that adsorbent developed from CF-AC can be efficiently used as an environmentally friendly alternative adsorbent, for removal of Cr and Pb(II) ions in tannery wastewater.     

改性活性炭对饮用水中铬酸盐的去除特性研究

研究了阳离子聚合物十六烷基三甲基氯化铵(CTAC)、癸基三甲基溴化铵(MTAB)以及三甲基正十四烷溴化铵(DTAB)对颗粒活性炭的改性特点以及改性后活性炭对饮用水中六价铬的去除效果。目的在于开发一种能有效去除饮用水中铬盐离子的吸附材料。研究中首先利用吸附平衡实验比较了未改性活性炭以及三种阳离子聚合物改性后活性炭对铬的吸附能力。结果表明:阳离子聚合物改性能有效提高活性炭对铬的吸附,同时CTAC改性后活性炭对铬盐的吸附效果要好于MTAB和DTAB。另外,活性炭对六价铬的吸附过程符合Langm iur吸附平衡模型以及二级动力学模型。阳离子聚合物在活性炭上的稳定性也是个重要的问题。对其检测的结果表明聚合物和活性炭的结合非常稳定,改性活性炭吸附六价铬的过程中阳离子聚合物的脱附量少于3%。     

Efficient removal of Cr(VI) by tannic acid-modified FeS nanoparticles: Performance and mechanisms

Ferrous sulfide (FeS) nanoparticles constitute an effective hexavalent chromium (Cr(VI)) treatment reagent. However, FeS nanoparticles aggregate easily, significantly limiting their engineering applicability. To overcome this shortcoming and further improve Cr(VI) removal efficiency, this study used tannic acid (TA) to modify FeS nanoparticles. The results demonstrated that TA-modified FeS nanoparticles, TA-nano-FeS, had a significantly reduced tendency to agglomerate, and maintained particle diameters of 10–100 nm, which were much shorter than diameters of FeS nanoparticles. In addition, TA-nano-FeS could combine the surface-active functional groups of TA. The maximum removal capacity of TA-nano-FeS was 381.04 mg/g, which was 2.92 and 1.83 times higher than those of TA and nano-FeS, respectively. Furthermore, the acidic condition was more beneficial for Cr(VI) removal, and the coexisting cations (Ca²⁺ and Mg²⁺) slightly decreased the removal efficiency of Cr(VI). Adsorption, reduction, and co-precipitation were the removal mechanisms, and the reaction products included FeCr₂O₄, Cr₂O₃, Fe₂O₃, Cr(OH)₃, and S₈. The results provided valuable information for the practical application of TA-nano-FeS in Cr(VI) removal.     

Biosorption and bioreduction of Cr(VI) by locally isolated Cr-resistant bacteria.

Cr(VI) biosorption and bioreduction ability of locally isolated Cr-resistant bacteria was investigated using the shake-flask technique. A mixture of S. epidermidis and B. cereus showed the highest minimum inhibitory concentration (MIC) level at 750 mg/L Cr(VI) followed by S. aureus and Bacillus sp. of 250 mg/L, and A. haemolyticus of 70 mg/L. From the Langmuir adsorption isotherm, the treatment of cells with heat-acid resulted in the highest amount of Cr(VI) adsorped (78.25 mg/g dry wt. for S. epidermidis) compared to heat-acetone (67.93 mg/g dry wt. Bacillus sp.), heat only (36.05 mg/g dry wt. S. epidermidis) or untreated cells (45.40 mg/g dry wt. S. epidermidis and B. cereus). FTIR analysis showed the involvement of amine groups in Cr(VI) adsorption. In the bioreduction study, A. haemolyticus was able to completely reduce Cr(VI) up to 50 mg/L.     

砂样钢渣对酸性Cr(Ⅵ)的吸附动力学与机理研究

以砂样钢渣作为吸附剂,研究了去除废水中Cr6+的工艺条件和机理。结果表明,最佳工艺条件分别为：pH值0.8~1.5,温度为20℃~25℃,钢渣投放量为5 g,废水初始体积以150~200 mL为宜。铬去除量与钢渣水溶液静置时间呈线性关系,且颗粒内扩散模型、准一级和二级速率方程、Langmuir和Freundlich吸附等温模型拟合曲线的相关系数较大,属于单分子层的吸附方式并具有较好的吸附性。通过机理分析可知,砂样钢渣对Cr6+的吸附过程分为还原（降毒）、水化、沉淀、吸附等4个阶段,钢渣最大吸附量为45.872 mg/g,占砂样钢渣的比例较小。钢渣完成吸附铬后,仍可用来配制砂浆、混凝土等。     

HDTMA改性沸石吸附水中Cr（VI）研究

摘要：研究以阳离子表面活性剂HDTMA改性天然斜发沸石,制得HDTMA改性沸石,进而研究HDTMA改性沸石对废水中Cr（VI）的吸附特征。结果表明：HDTMAL改性沸石对cr（VI）吸附符合Langmuir等温式和拟二级动力学方程,饱和吸附量为10．99mg／g,吸附主要为化学吸附,但温度、pH值和干扰离-~HDTMA沸石吸附cr（VI）具有明显影响。     

Co-removal of hexavalent chromium through adsorption during copper precipitation.

A systematic study was conducted to assess the mechanisms involved in the co-removal of hexavalent chromium during chemical precipitation of divalent copper. Batch tests were used to assess the precipitation phenomena in both pure copper solutions and also mixed copper-Cr(VI) solutions with progressive addition of sodium carbonate to increase pH and induce precipitation. It was found that the co-removal of Cr(VI) was caused by two distinct mechanisms: coprecipitation of copper with Cr(VI) at pH 5.0 to 5.2, leading to the formation of CuCrO4 precipitates. Once the fine crystallites of CuCrO4 were formed, the test solution became heterogeneous and this accelerated the production of copper-carbonate precipitates, mainly in the form of CuCO3 Cu(OH)2, at pH 5.2 to 6.2. The latter precipitates were negatively charged at pH below 7.5, and thus they were able to adsorb a considerable amount of the remaining chromate ions [HCrO4- and CrO4(2-)]. The extent of adsorption depended on both pH and surface loading. Besides electrostatic attraction, ligand exchange was also found to play some role. Maximum adsorption occurred at pH 6.5. When pH was raised to 10.0, approximately 25-30% of the adsorbed chromium could become desorbed due to a surface charge reversal on the adsorbent.     

煤质活性炭对Cr(Ⅵ)和As(Ⅲ)的吸附及其影响因素

以煤质活性炭(CAC)为吸附剂,吸附水溶液中Cr(Ⅵ)和As(Ⅲ)。研究了pH值、温度、吸附时间和活性炭投加量等因素对活性炭去除Cr(Ⅵ)和As(Ⅲ)效果的影响。结果表明,Cr(Ⅵ)和As(Ⅲ)最佳吸附的pH值分别为2和5,且pH值对吸附率的影响较大。Cr(Ⅵ)的吸附受温度影响较大,当温度从20℃增加到40℃,吸附率由70%提高到了95%;As(Ⅲ)的吸附随温度的升高先增加后减少,其最佳吸附温度为30℃。Langmuir吸附等温式能够很好地拟合Cr(Ⅵ)和As(Ⅲ)的实验数据,而Pseudo second order模型则较好描述了Cr(Ⅵ)和As(Ⅲ)的吸附动力学。Cr(Ⅵ)和As(Ⅲ)吸附的热力学研究表明,该吸附是一个自发进行的自然吸热过程。     

微生物吸附低温水体中Cr(Ⅵ)、Cd(Ⅱ)离子研究

利用从活性污泥中分离、纯化、筛选得到的霉菌,进行吸附水体中Cr(Ⅵ)、Cd(Ⅱ)离子研究。结果表明:在Cr(Ⅵ)、Cd(Ⅱ)质量浓度分别为300mg/L时,菌种生长良好。吸附水体中Cr(Ⅵ)、Cd(Ⅱ)的最佳条件:pH值5.0,时间1h,温度10℃。吸附规律符合Langmuir等温吸附模型,由回归方程得到Cr(Ⅵ)的表观最大吸附量为14mg/g;Cd(Ⅱ)的表观最大吸附量为52mg/g。对菌种吸附低温水体中两种重金属离子时pH值变化影响及其吸附动力学进行了研究。证明该菌可以有效地去除低温水体中Cr(Ⅵ)、Cd(Ⅱ)离子。     

Chromate sorption and reduction kinetics onto an aminated biosorbent.

A novel biosorbent was prepared by chemically grafting of polyethylenimine (PEI) onto the fungal biomass of Penicillium chrysogenum through a two-step reaction. The modified biosorbent is favorable for the removal of anionic Cr(VI) species from aqueous solution due to the protonation of amine groups on the biomass surface. The sorption capacity for Cr(VI) increased by 7.2-fold after surface modification. Sorption kinetics results show that the pseudo-second-order kinetic model described the experimental data well. During the sorption process, X-ray photoelectron spectroscopy (XPS) was used to analyze the chromium species on the biosorbent surface and the results indicate that part of the Cr(VI) ions were reduced to Cr(III) ions which can be chelated with the amine groups on the biomass surface. The reduced Cr(III) ions formed some aggregates on the surface at higher solution pHs.     

Adsorptive performance of penta-bismuth hepta-oxide nitrate, Bi?O?NO?, for removal of methyl orange dye

The adsorption of methyl orange dye from aqueous solution onto penta-bismuth hepta-oxide nitrate, Bi(5)O(7)NO(3), synthesized by precipitation method, was studied in a batch adsorption system. The effects of operation parameters such as adsorbent dose, initial dye concentration, pH and temperature were investigated. The adsorption equilibrium and mechanism of adsorption was evaluated by Langmuir and Freundlich isotherm and different kinetic models, respectively. The results indicate that adsorption is highly dependent on all operation parameters. At optimum conditions, the adsorption capacity was found to be 18.9 mg/g. The adsorption data fits well with the Langmuir isotherm model indicating monolayer coverage of adsorbate molecules on the surface of Bi(5)O(7)NO(3). The kinetic studies show that the adsorption process is a second-order kinetic reaction. Although intra-particle diffusion limits the rate of adsorption, the multi-linearity plot of intra-particle model shows the importance of both film and intra-particle diffusion as the rate-limiting steps of the dye removal. Thermodynamic parameters show that the adsorption process is endothermic, spontaneous and favourable at high temperature.     

Biological Cr(VI) reduction in indigenous sludge cultures from Gauteng, South africa.

The Cr(VI) reducing capability of an acclimated indigenous culture cultivated from primary sludge was evaluated in batch and packed-bed bioreactor systems. Performance evaluation was carried out in unmodified cultures, cultures modified by substituting terminal organisms in the consortium by a known Cr(VI)-reducing organism (Escherichia coli ATCC 33456), and pure cultures of Cr(VI)-reducing organisms. A high Cr(VI) reduction rate was observed in modified cultures and in the pure culture of the Cr(VI)-reducing bacteria (Bacillus sp.). Furthermore, the Bacillus sp. pure culture outperformed both the unmodified and modified consortium cultures in reducing Cr(VI). Abiotic Cr(VI) reduction activity was evaluated in heat-killed and azide (N3) inactivated control cultures. No significant Cr(VI) reduction was observed in the controls. This study is part of the continuing research to identify synergistic culture systems for treating toxic compounds from polluted environments.     

复合制剂修复铬污染土的条件优化及微观特性

针对单一还原法和固化/稳定化技术处理铬污染土效果不佳的问题,提出还原-固化/稳定化联用方法,通过单掺试验和L9(34)正交试验,确定了还原剂、吸附剂、固化剂所组成的复合制剂的最佳配比,并采用扫描电镜对固化/稳定化铬污染土进行了微观表征.研究结果表明,复合制剂最佳配比为:CaS5用量是污染土中Cr(Ⅵ)还原为Cr(Ⅲ)所...     

Mechanistic evidence and efficiency of the Cr(VI) reduction in water by different sources of zerovalent irons.

The objective of this research was to assess the mechanism and effectiveness of the zerovalent iron (ZVI) to remediate the Cr(VI) contaminated water. The mechanism of Cr(VI) reduction by ZVI was evaluated by characterising surface properties and chemical compositions of Fe and Cr products using SEM-EDS, XRD and XPS analyses. The effectiveness of ZVI in Cr(VI) reduction was assessed by the luminescent bacteria (Photobacterium Phosphoreum). The Cr(VI) was reduced to Cr(III), when the reactive Fe(o) was oxidised to Fe(II, III), showing the presence of Fe2O3, (Fe-Cr)2O3 and FeOOH. The SEM-EDS analysis showed that ZVI with a higher reducing capacity was more subject to changes of surface and morphological properties due to ionisation of ZVI. The Cr and Fe in precipitates subsisted exclusively in the Cr(III) or Fe(III) states with the respective forms of Cr(OH)3 or Cr2O3 and FeOOH or Fe2O3. Electrons produced from ZVI oxidation reduced Cr(VI) to Cr(III), thus resultantly Cr(III) precipitated or co-precipitated with Fe(III) to form Fe(III)-Cr(III) hydroxide or Fe(III)-Cr(III) oxyhydroxide. Toxicity of water reacted with ZVI was significantly lower than that of the untreated water.     

基于MODFLOW的地下水Cr(VI)污染水动力场模拟预测研究

随着社会和经济的快速发展,我国地下水污染问题已日益突出,地下水中Cr(Ⅵ)的污染已成为危害环境和人类健康的危险物质.由于Cr(Ⅵ)的毒性高、易迁移等特点,给地下水环境带来严重的安全隐患.在对某市城区水文地质及工程地质条件进行分析的基础上,依据2005年的资料用Visual Modflow进行参数率定,确定水文地质参数,建立了第四系地下水系统准三维非稳定流模型;再用2005-2009年的资料验证了模型的可靠性,利用此模型进行地下水流场模拟预测,并将现状条件下(2010年)Cr(Ⅵ)污染晕与预测的地下水流场形态进行叠加来预测Cr(Ⅵ)污染晕的发展趋势,为今后当地政府部门应对Cr(Ⅵ)污染地下水治理提供相关政策建议与决策参考,具有重要意义.