Sorption of uranyl ions on TiO2: Effects of pH, contact time, ionic strength, temperature and HA

Sorption of U(VI) onto TiO₂ as functions of pH, ionic strength, contact time, soil humic acid (SHA), solid-to-liquid ratio and temperature was studied under ambient conditions using batch and spectroscopic approaches. The sorption of U(VI) on TiO₂ was significantly dependent on pH and ionic strength. The presence of SHA slightly enhanced the sorption of U(VI) on TiO₂ below pH 4.0, while it inhibited U(VI) sorption in the higher pH range. U(VI) sorption on TiO₂ was favored at high temperatures, and the sorption process was estimated to be endothermic and spontaneous. Reduction of U(VI) to lower valent species was confirmed by X-ray photo-electron spectroscopy analysis. It is very interesting to find that U(VI) sorption on TiO₂ was promoted in solutions with higher back-ground electrolyte concentrations. In the presence of U(VI), higher back-ground electrolyte made more TiO₂ particles aggregate through (001) facets, leading more (101) facets to be exposed. Therefore, the reduction of U(VI) was enhanced by the exposed (101) facets and more U(VI) removal was observed.     

新型高效改性材料在重金属废水处理中的应用

使用原始吸附材料,如微生物、有机或无机材料等吸附废水中的重金属时,通常呈现较低的吸附性能,其吸附量通常都低于30mg/g。因此,研究者更多地关注提高各种吸附材料的吸附能力。国内外一些研究者采用新型、高效的物理或化学改性技术对吸附材料进行表面改造,如将高聚物接枝融合到菌体表面、表面分子印迹吸附剂、固定化微生物、酸改性处理有机或无机材料等,与常规材料相比,改性后材料对重金属的最大吸附容量一般可提高到100mg/g以上。随着各种改性技术的不断成熟,利用改性材料吸附重金属废水将成为今后研究重金属废水处理的主流方向。     

Adsorption and mechanistic study of the invasive plant-derived biochar functionalized with CaAl-LDH for Eu(III) in water

Herein, we developed the invasive plant-derived biochar (IPB) functionalized with CaAl-LDH at five mass ratios using a physical mixture method, assessed their adsorption perform for Eu(III), and explored the relative mechanisms. Results show that the IPB successfully loaded CaAl-LDH in five composites and their Eu(III) sorption affinities were strongly affected by solution pH, contact time, temperature, and the mass ratio of LDH and IPB. All the sorpiton process for Eu(III) occurred on the heterogeneous surface of five composites and the boundary layer diffusion limited the chemical sorption rate. Interestingly, the CaAl-LDH/IPB composite with high ratio of IPB had higher sorption capacity than the one with high ratio of LDH due to larger porosity of the former. Three mechanisms containing ion exchange between Al and Eu ions, surface complexation with carboxyl- and oxygen-containing functional groups, and precipitation were involved in the Eu(III) sorption, but the dominant sorption mechanism for each CaAl-LDH/IPB composite differed with different mass ratio of CaAl-LDH and IPB. In composite with more IPB (e.g., CaAl-LDH/IPB-13), both ion exchange and surface complexes dominated the sorption process and the intensity of Eu³⁺ was identified with the one of Eu₂O_3. Whereas in composites with high LDH, ion exchange dominated the sorption and the intensity of Eu³⁺ was obviously higher than the one of Eu₂O₃. This research will provide a new perspective for the application of the LDH/biochar materials.     

铀尾矿库渗漏地下含水层中六价铀的几种吸附反应运移模型对比

在铀尾矿地区,溶解态U(Ⅵ)渗漏到含水层中会对周围环境造成严重的威胁.使用反应运移软件PHT3D对U(Ⅵ)在含水层中的迁移和吸附过程进行模拟.结果表明,相比于不考虑吸附情形,考虑吸附的U(Ⅵ)反应迁移阻滞现象明显.线性和Langmuir吸附等温线模型在水动力条件复杂、地球化学条件多变时的模拟效果与表面络合模型相比较差,甚至有时得到与实际相反的结果,这说明了传统Kd吸附经验模型的局限性.由表面络合模型计算得出的分配系数Kd值是时空变化的,其更能反映实际中多变水化学条件下的吸附过程,适合描述复杂的不同水文地球化学条件.     

改性羧甲基纤维素对铀吸附机理的试验研究

对羧甲基纤维素(CMC)进行改性,并将其用于吸附废水中的铀.研究结果表明:在温度为70℃~80℃、单体质量浓度为30%~35%、羧甲基纤维素:丙烯酸(质量比)为10:2.5、反应时间为3.5~4h条件下,CMC改性效果最好;在改性CMC质量浓度为0.10g/L,温度为25℃, pH值为5.0,反应时间60min的条件下,对废水中铀去除率达到了97.1%;改性CMC对溶液中U(VI)的吸附过程符合Freundlich方程,其吸附动力学数据符合准一级方程(R2=0.9618),表明改性CMC的吸附主要是表面吸附;热力学研究表明,改性CMC对铀的吸附吉布斯自由能(ΔG0)0,吸附过程是自发的吸热反应、以物理吸附为主的过程.     

Cr(VI) removal from aqueous solution with bamboo charcoal chemically modified by iron and cobalt with the assistance of microwave

Bamboo charcoal (BC) was used as starting material to prepare Co-Fe binary oxideloaded adsorbent (Co-Fe-MBC) through its impregnation in Co(NO3)2 , FeCl3 and HNO3 solutions simultaneously, followed by microwave heating. The low-cost composite was characterized and used as an adsorbent for Cr(VI) removal from water. The results showed that a cobalt and iron binary oxide (CoFe2O4 ) was uniformly formed on the BC through redox reactions. The composite exhibited higher surface area (331 m2/g) than that of BC or BC loaded with Fe alone (Fe-MBC). The adsorption of Cr(VI) strongly depended on solution pH, temperature and ionic strength. The adsorption isotherms followed the Langmuir isotherm model well, and the maximum adsorption capacities for Cr(VI) at 288 K and pH 5.0 were 35.7 and 51.7 mg/g for Fe-MBC and Co-Fe-MBC, respectively. The adsorption processes were well fitted by the pseudo second-order kinetic model. Thermodynamic parameters showed that the adsorption of Cr(VI) onto both adsorbents was feasible, spontaneous, and exothermic under the studied conditions. The spent Co-Fe-MBC could be readily regenerated for reuse.     

磁性核壳CoFe2O4@SiO2@PIL-AO复合材料的制备及其吸附U (VI)性能研究

通过化学合成法制备了磁性核壳CoFe₂O₄@SiO₂@PIL-AO复合材料,采用傅立叶变换红外光谱（FTIR）、扫描电镜（SEM）和X射线光电子能谱（XPS）对其进行了表征,研究了溶液pH、吸附时间、U （VI）初始浓度和温度等参数对U （VI）吸附性能的影响.实验结果表明：在c₀=0.2 mg·L^-1、pH=6.00±0.05、T=298.15 K、m=0.02 g和t=8 h的条件下,CoFe₂O₄@SiO₂@PIL-AO对U （VI）的吸附作用最强,吸附率达到了97.54%;CoFe₂O₄@SiO₂@PIL-AO吸附U （VI）是一个自发进行的吸热反应,U （VI）吸附动力学符合准二级动力学模型,吸附等温线符合Freundlich模型;CoFe₂O₄@SiO₂@PIL-AO复合材料具有良好的可循环使用性,循环使用5次后它对U （VI）的吸附容量没有明显下降,可重复使用.     

改性明矾浆吸附剂的制备及其除镉性能研究

以明矾生产中产生的废弃物明矾浆为原材料,采用热酸改性、热碱改性、焙烧改性和巯基化改性4种方法进行活化处理,得到新型除镉(Cd)吸附剂.同时,考察了Cd2+初始浓度、pH值和吸附剂投加量对改性明矾浆吸附去除Cd2+的影响,并采用扫描电镜(SEM)、比表面积(BET)、用红外光谱(IR)等仪器对吸附剂进行表征.结果表明,热碱改性明矾浆具有较好的吸附Cd2+的性能,其饱和吸附量为5.41mg·g-1,而原明矾浆的饱和吸附量仅为0.40mg·g-1;热酸改性、焙烧改性和巯基化改性3种明矾浆对Cd2+的吸附性能与原明矾浆相比没有显著差异.改性明矾浆对Cd2+的吸附规律符合Langmuir等温方程式,其吸附机制主要为表面吸附.溶液pH值会显著影响改性明矾浆对Cd2+的吸附量和吸附率.综合而言,在pH≥7时,热碱改性明矾浆具有较好的去除Cd2+能力.     

双子型复配增强两性膨润土吸附Cr(VI)的效应

在两性修饰剂十二烷基二甲基甜菜碱（BS）修饰膨润土的基础上,采用双子型阳离子修饰剂乙撑基双十四烷基二甲基氯化铵（EB）对其进行复配修饰,以批处理法研究了不同修饰比例、温度、pH值和离子强度条件下,BS+EB复配修饰膨润土对Cr（VI）的吸附规律和热力学特征,并通过吸附Cr（VI）前后BS+EB复配修饰膨润土的红外光谱和表面电荷探讨了其吸附机制.结果表明,与BS两性修饰膨润土比较,EB复配修饰显著增强了其对Cr（VI）的吸附能力,吸附量增加了2.02~27.25倍,30℃时吸附量呈现BS+150EB（BS和150%比例的EB复配修饰膨润土） > BS+100EB > BS+50EB > BS+25EB > BS > CK（膨润土）的趋势,对Cr（VI）的吸附量随EB修饰比例增加而上升.CK、BS修饰膨润土对Cr（VI）呈现自发、熵增和焓增的特征,而BS+EB复配修饰膨润土对Cr（VI）吸附量随着温度的升高而降低,呈现出增温负效应.随着pH值的升高、离子强度增加,各供试土样对Cr（VI）的吸附量逐渐降低.红外光谱和土壤表面电荷结果证实电荷引力是BS+EB复配修饰土吸附Cr（VI）的主要机制.     

Flower-, wire-, and sheet-like MnO2-deposited diatomites: Highly efficient absorbents for the removal of Cr(VI)

Flower-, wire-, and sheet-like MnO₂-deposited diatomites have been prepared using a hydrothermal method with Mn(Ac)₂, KMnO₄ and/or MnSO₄ as Mn source and diatomite as support. Physical properties of the materials were characterized by means of numerous analytical techniques, and their behaviors in the adsorption of chromium(VI) were evaluated. It is shown that the MnO₂-deposited diatomite samples with different morphologies possessed high surface areas and abundant surface hydroxyl groups (especially the wire-like MnO₂/diatomite sample). Thewire-like MnO₂/diatomite sample showed the best performance in the removal of Cr(VI), giving the maximum Cr(VI) adsorption capacity of 101 mg/g.     

Preparation of MgO/B2O3 coatings by plasma spraying on SUS304 surface and effects of heat-resistant

This study mainly deals with the preparation of MgO/B₂O₃ coatings by plasma spraying on the SUS304 surface and the effects of heat-resistant. The power materials of low thermal conductivity were selected to control the heat divergent performance of high temperature parts. The reticular micro-structure between the cover thermal layer and the substrate was prepared by using the plasma spraying method. The powder mixture of MgO and B₂O₃ were selected as spraying materials and the SUS304 was used as the substrate material. The MgO/B₂O₃ coating was prepared on the surface of the SUS304 to provide better cover thermal performance. The properties of the microstructures and the morphologies were studied by Optical Microscope, Scanning Electron Microscope, Electron Probe Microanalyzer, and X-ray Diffraction. The results showed that the cover thermal performance has been improved.     

Preparation of MgO/B2O3 coatings by plasma spraying on SUS304 surface and effects of heat-resistant

This study mainly deals with the preparation of MgO/B₂O₃ coatings by plasma spraying on the SUS304 surface and the effects of heatresistant. The power materials of low thermal conductivity were selected to control the heat divergent performance of high temperature parts. The reticular micro-structure between the cover thermal layer and the substrate was prepared by using the plasma spraying method. The powder mixture of MgO and B₂O₃ were selected as spraying materials and the SUS304 was used as the substrate material. The MgO/B₂O₃ coating was prepared on the surface of the SUS304 to provide better cover thermal performance. The properties of the microstructures and the morphologies were studied by Optical Microscope, Scanning Electron Microscope, Electron Probe Microanalyzer, and X-ray Diffraction. The results showed that the cover thermal performance has been improved.     

Flower-, wire-, and sheet-like MnO2-deposited diatomites: Highly efficient absorbents for the removal of Cr(VI)

Flower-, wire-, and sheet-like MnO₂-deposited diatomites have been prepared using a hydrothermal method with Mn(Ac)₂, KMnO₄ and/or MnSO₄ as Mn source and diatomite as support. Physical properties of the materials were characterized by means of numerous analytical techniques, and their behaviors in the adsorption of chromium(VI) were evaluated. It is shown that the MnO₂-deposited diatomite samples with different morphologies possessed high surface areas and abundant surface hydroxyl groups (especially the wire-like MnO₂/diatomite sample). The wire-like MnO₂/diatomite sample showed the best performance in the removal of Cr(VI), giving the maximum Cr(VI) adsorption capacity of 101 mg/g.     

Enhanced removal of Cr(VI) by biochar with Fe as electron shuttles

Biochar is extensively used as an effective soil amendment for environmental remediation. In addition to its strong contaminant sorption capability, biochar also plays an important role in chemical transformation of contaminant due to its inherent redox-active moieties. However, the transformation efficiency of inorganic contaminants is generally very limited when the direct adsorption of contaminants on biochar is inefficient. The present study demonstrates the role of Fe ion as an electron shuttle to enhance Cr(VI) reduction by biochars. Batch experiments were conducted to examine the effects of Fe(III) levels, pyrolysis temperature of biochar, initial solution pH, and biochar dosage on the efficiency of Cr(VI) removal. Results showed a significant enhancement in Cr(VI) reduction with an increase in Fe(III) concentration and a decrease of initial pH. Biochar produced at higher pyrolysis temperatures (e.g., 700°C) favored Cr(VI) removal, especially in the presence of Fe(III), while a higher biochar dosage proved unfavorable likely due to the agglomeration or precipitation of biochar. Speciation analysis of Fe and Cr elements on the surface of biochar and in the solution further confirmed the role of Fe ion as an electron shuttle between biochar and Cr(VI). The present findings provide a potential strategy for the advanced treatment of Cr(VI) at low concentrations as well as an insight into the environmental fate of Cr(VI) and other micro-pollutants in soil or aqueous compartments containing Fe and natural or engineered carbonaceous materials.     

Removal of Cd2+ from water by Friedel’s salt (FS: 3CaO.Al2O3·CaCl2·10H2O): Sorption characteristics and mechanisms

The development of low-cost and efficient new mineral adsorbents has been a hot topic in recent years. In this study, Friedel’s salt (FS:3CaO·A12O3 ·CaCl2 ·10H2O), a hexagonal layered inorganic absorbent, was synthesized to remove Cd2+ from water. The adsorption process was simulated by Langmuir and Freundlich models. The adsorption mechanism was further analyzed with TEM, XRD, FT-IR analysis and monitoring of metal cations released and solution pH variation. The results indicated the adsorbent FS had an outstanding ability for Cd(Ⅱ) adsorption. The maximum adsorption capacity of the FS for Cd(Ⅱ) removal can reach up to 671.14 mg/g. The nearly equal numbers of Cd2+ adsorbed and Ca2+ released demonstrated that ion-exchange (both surface and inner) of the FS for Cd(Ⅱ) played an important role during the adsorption process. Furthermore, the surface of the FS after adsorption was microscopically disintegrated while the inner lamellar structure was almost unchanged. The behavior of Cd(Ⅱ) adsorption by FS was significantly affected by surface reactions. The mechanisms of Cd2+ adsorption by the FS mainly included surface complexation and surface precipitation. In the present study, the adsorption process was fitted better by the Langmuir isotherm model (R2 = 0.9999) than the Freundlich isotherm model (R2 = 0.8122). Finally, due to the high capacity for ion-exchange on the FS surface, FS is a promising layered inorganic adsorbent for the removal of Cd(Ⅱ) from water.     

Synthesis of a novel illite@carbon nanocomposite adsorbent for removal of Cr(VI) from wastewater

A novel illite@carbon (I@C) nanocomposite adsorbent has been synthesized via a facile hydrothermal carbonization process (HTC) using glucose as carbonaceous source and illite as the carrier. The morphology, microstructure and surface properties of the prepared nanocomposite adsorbent were analyzed by FESEM, TGA, XRD, FT-IR and Zeta potential measurements. Batch experiments were carried out on the adsorption of Cr(VI) to determine the adsorption properties of the composite. The adsorption of Cr(VI) onto the I@C nanocomposite was well described by the pseudo-second-order kinetic model and Langmuir isotherm. Compared with the illite and carbon material (SC) separately, the prepared I@C nanocomposite adsorbent exhibited enhanced adsorption performance for Cr(VI) with a maximum adsorption capacity of 149.25 mg/g, which was higher than that of most reported adsorbents. In addition, the adsorption process was spontaneous and endothermic based on the adsorption thermodynamics study. The adsorption of Cr(VI) by I@C was highly pH-dependent and the optimum adsorption occurred at pH 2.0. The Zeta potential analysis results indicated that the electrostatic interactions between anionic Cr(VI) and the positively charged surface of the adsorbent might be critical to the adsorption mechanism. This study demonstrated that the I@C nanocomposite should be a promising candidate for a low-cost, environmental friendly and highly efficient adsorbent for the removal of toxic Cr(VI) from wastewater.     

微生物溶解载铀赤铁矿及再固定铀的试验研究

将载铀赤铁矿、核黄素(RF)和Sphingomonas sanxanigenens(S. sanxanigenens)同时投加到培养基中,监测培养过程中溶液的总铁、亚铁以及U(VI)浓度的变化,表征载铀赤铁矿还原性溶解前后固相产物中铁和铀的化学形态与价态,分析温度、共存离子对RF介导S. sanxanigenens还原性溶解载铀赤铁矿及再固定铀的影响.结果表明:S. sanxanigenens能够还原性溶解载铀赤铁矿,从而导致铀的释放;RF能够促进S. sanxanigenens还原性溶解载铀赤铁矿,且RF浓度越高越有利于这种还原性溶解;在30℃下RF能显著促进载铀赤铁矿的还原性溶解,且产物中稳定态铀的比例较高;添加2mmol/L Ca²⁺或CO₃^2-对RF介导S. sanxanigenens还原性溶解载铀赤铁矿具有促进作用;添加2mmol/L PO₄^3-能提高残渣态铀的比例,促进铀的固定;RF能够促进S. sanxanigenens对Fe(III)和U(VI)的还原,且反应过程伴随着次生铁矿物的生成.这些研究结果为提出RF介导S. sanxanigenens释放及再固定铀的新方法奠定了基础.     

Surface modification of die steel materials by EDM method using tungsten powder-mixed dielectric

Surface modification by material transfer during electrical discharge machining (EDM) has emerged as a key research area in the last decade. Material may be provided to the machined surface of the workpiece by the eroding tool electrode or by using powder-mixed dielectric. Breakdown of the hydrocarbon dielectric contributes carbon to the plasma channel which may also cause surface modification. The present work has investigated the response of three die steel materials to surface modification by EDM method with tungsten powder mixed in the dielectric medium. Taguchi experimental design technique was used to conduct the experiments on each work material independently. Peak current, pulse on-time and pulse off-time were taken as variable factors and micro-hardness of the machined surface was taken as the response parameter. X-ray diffraction (XRD) and spectrometric analysis show substantial transfer of tungsten and carbon to the workpiece surface and an improvement of more than 100% in micro-hardness for all the three die steels. Presence of tungsten carbide (WC and W₂C) indicates that its formation is taking place in the plasma channel. Machining parameters for the best value of micro-hardness for each work material were found to be the same.     

ε-聚赖氨酸生产废菌体对六价铬吸附影响的研究

以ε-聚赖氨酸(ε-PL)发酵生产废菌体小白链霉菌(Streptomyces albulus)PD-1为研究对象,探讨了其对吸附Cr(Ⅵ)的影响.实验过程中,对预处理方式、pH、初始Cr(Ⅵ)浓度、吸附时间和温度等因素进行了考察.结果表明,HCl预处理的菌体具有较好的吸附能力,Cr(Ⅵ)的吸附增加率达到22.7%,最佳pH为2.0左右,温度对Cr(Ⅵ)的吸附影响不大.实验过程中分别采取Langmuir和Freundlich 2种吸附等温模型对实验数据进行了拟合,得到2个模型的线性相关系数R2分别为0.979 4和0.979 8,这表明吸附过程中既存在单层吸附同时也存在复杂的多层吸附,小白链霉菌对Cr(Ⅵ)的最大理论吸附量为23.92mg.g-1.通过傅里叶变换红外光谱分析,酰胺基和羟基等基团在吸附过程中起主要作用.     

表面酸碱2步改性对活性炭吸附Cr(Ⅵ)的影响

研究了酸碱2步改性对活性炭吸附水相中Cr(Ⅵ)的影响.将活性炭(AC₀)在HNO₃溶液中氧化(AC₁),然后在NaOH和NaCl的混合液中处理(AC₂).分别采用平衡和连续吸附试验,测试Cr(Ⅵ)的吸附特征.以Boemh滴定法定量检测活性炭表面酸性官能团数量,结合元素分析结果定量表征活性炭的表面含氧官能团变化;以低温液氮(N₂/77K)吸附法分析活性炭的比表面积和孔径结构.结果表明:活性炭经2步改性后,其Cr(Ⅵ)的吸附容量和吸附速度均显著改变.吸附容量和吸附速度大小依次为AC₂>AC₁>AC₀.改性活性炭表面积下降,表面含氧酸性官能团数量增加.HNO₃液相氧化处理可使活性炭表面生成带正电含氧酸性官能团,第2步改性后活性炭表面酸性官能团H⁺部分被Na⁺取代,使活性炭表面酸性降低.表面较多的含氧酸性官能团(与AC₀相比)、适宜的表面pH(与AC₁相比)是AC₂所表现出较高Cr(Ⅵ)吸附容量的主要原因.