铝钛柱撑系列改性膨润土处理含铬废水的应用研究

以钠基膨润土为原料,制备了铝钛无机柱撑、铝钛有机柱撑系列改性膨润土,比较了膨润土原土及铝钛无机有机柱撑改性膨润土处理含铬废水的性能,探讨了改性膨润土用量、pH值、搅拌时间等因素对膨润土吸附Cr(Ⅵ)实验的影响。结果表明:有机柱撑改性膨润土、无机柱撑改性膨润土对废水的处理效果明显好于原土;膨润土用量、废水的pH对Cr(Ⅵ)的吸附效率影响很大;在无机柱撑改性中,当pH为4,投加量为6g L,搅拌时间为30min,Cr(Ⅵ)质量浓度为30mg L时,Cr(Ⅵ)去除率达到66 5%;在有机柱撑改性中,当pH为5,投加量为6g L,搅拌时间为30min,Cr(Ⅵ)质量浓度为30mg L时,Cr(Ⅵ)去除率达到94 6%;铝钛无机、有机柱撑改性膨润土对铬离子水样处理的吸附等温线均符合Langmuir吸附等温方程,饱和吸附量和Langmuir常数分别为9 823,8 790mg g和4 5167,4 327。      

海藻酸钠改性纳米零价铁还原土壤中Cr(Ⅵ)

采用液相还原法合成纳米零价铁（NZVI）及海藻酸钠改性纳米零价铁（SA-NZVI）去除土壤中的水溶性Cr（VI）.X射线衍射图谱（XRD）、傅里叶红外变换图谱（FTIR）表征结果显示,利用海藻酸钠（SA）对NZVI改性能有效抑制NZVI的氧化;扫描电镜（SEM）表征结果显示,SA对NZVI有较好的分散性.实验结果表明,当海藻酸钠的添加量≤0.2%时,制备得到的SA-NZVI对Cr（VI）的去除率随着SA负载量的增加而递增;SA添加量>0.2%时,去除率随着SA负载量的增加而下降;SA添加量为0.2%时制备得到的SA_0.2-NZVI对Cr（VI）的去除效果最优.随着材料投加量的增加和反应时间的延长,SA_0.2-NZVI对土壤中水溶性Cr（VI）的去除率也随之提高.酸性条件更有利于SA_0.2-NZVI去除土壤中水溶性Cr（VI）.NZVI、SA_0.2-NZVI、SA均对土壤中水溶性Cr（VI）有去除效果,去除率依次为SA_0.2-NZVI > NZVI > SA.当土壤中初始Cr（VI）含量为288.11 mg·kg^-1,pH=8,投加量为0.4 g·L^-1时,反应2 h后SA_0.2-NZVI对Cr（VI）的去除率可达到98.78%.     

有机膨润土负载纳米铁去除废水中硝基苯

用具有良好吸附能力的有机膨润土作载体,通过FeSO4与NaBH4反应制得负载型的纳米铁(NZVL/CTMAB-Bent),用XRD、BET对其性能进行了表征.以硝基苯为目标污染物,试验了 -NZVI/CTMAB-Bent对不同起始浓度硝基苯的去除作用,考察了介质PH对其去除效率的影响,并与相同铁含量的纳米铁(NZVI)进行了比较.此外.还对NZVI/CTMAB-Bent还原硝基苯的机理进行了探讨.结果表明,NZVI/CTMAB-Bent对硝基苯的去除能力远高于相同铁含量的NZVI.也明显优于相同含量的有机膨润土和相同铁含量的NZVI对硝基苯去除率的加和.     

负载纳米零价铁铜藻基活性炭的制备及其去除水中Cr(Ⅵ)的研究

以铜藻为原料,采用氯化锌活化法、初湿含浸法制备了负载纳米零价铁铜藻基活性炭(NZVI/SAC),并采用X射线衍射、扫描电镜和X射线光电子能谱等方法对材料进行了分析.结果表明,纳米零价铁颗粒以50~150 nm粒径的球形形态负载在铜藻基活性炭上,且NZVI/SAC表面具有一层以铁的氧化物形态存在的核壳结构.对水中Cr(Ⅵ)的去除实验表明,NZVI/SAC是一种适用于高浓度Cr(Ⅵ)废水的处理材料;NZVI/SAC去除水中Cr(Ⅵ)的机制是还原反应与吸附共同作用,p H4时NZVI/SAC对Cr(Ⅵ)的去除以还原作用为主,p H4时材料对Cr(Ⅵ)的去除主要以NZVI和SAC的吸附作用决定;当载铁量为30%、p H=2、温度为30℃时,2 g·L-1的NZVI/SAC能将100 mg·L-1Cr(Ⅵ)在10 min内快速降解,此时以还原反应为主,最终去除率达100%.     

零价纳米铁处理水中Cr(Ⅵ)的实验研究

采用NaBH4还原Fe3+制备纳米级零价铁(NZVI).运用X射线衍射(XRD)、扫描电镜(SEM)对样品进行表征.以Cr(Ⅵ)为研究对象,批实验考察了初始浓度、纳米铁投加量、温度对去除效果的影响,研究NZVI对Cr(Ⅵ)离子的吸附动力学.结果表明,NZVI加入量0.15 gL,水体中20 mg/L的Cr(Ⅵ)的去除率...     

钛柱撑膨润土吸附水溶液中微量Cr(Ⅵ)研究

针对水中微量Cr(Ⅵ)的吸附脱除问题,以河北灵寿县膨润土制备的钛柱撑膨润土为吸附剂,进行了25℃条件下对水溶液中微量Cr(Ⅵ)脱除的试验,测得了被吸附物浓度、吸附时间,吸附剂用量对吸附过程的影响,得出钛柱撑膨润土具有优越的吸附性能.此外还测定了钛柱撑膨润土对Cr(Ⅵ)吸附的等温线,探讨了Cr(Ⅵ)的吸附机理,钛柱撑膨润土对Cr(Ⅵ)的吸附包括表面物理吸附和层间离子化学吸附.     

膨润土负载纳米铁去除水溶液中Cr(Ⅵ)

采用硼氢化钠液相还原法制备纳米铁(nZVI)和多种负载型纳米铁,将其分别用于处理初质量浓度50 mg/L的Cr(Ⅵ)溶液,结果显示膨润土负载纳米铁(B-nZVI)效果最好,去除率可达100%。ESEM和BET表征结果表明:膨润土作为载体可以有效地减弱纳米铁颗粒的团聚,增大纳米铁的比表面积。XRD显示新制备的B-nZVI谱图中出现了明显的Fe0特征峰,而反应后的谱图则证明了Fe(Ⅲ)和Cr(Ⅲ)的存在。动力学研究表明:B-nZVI对水溶液中的Cr(Ⅵ)的还原遵循伪一级反应动力学。     

投加聚合铝铁对A2O系统脱氮除磷效能的影响及机制

为研究A²O污水处理系统聚合铝铁投加对污水中TP的强化去除及对其他污染物的协同去除,通过小试试验对比研究了聚合铝铁分别在A²O系统曝气池前端和末端投加时各污染物的去除特征. 结果表明,与前端投加相比,聚合铝铁在曝气池末端的投加能够显著提升系统对污水中TP和NH₄⁺-N的去除率,但聚合铝铁末端投加时系统出水中ρ(NO₃--N)高于前端投加. 结果表明,聚合铝铁投加量〔以ρ(Al)计〕为4 mg/L时去除效果最好,此时系统对CODCr、TN、NH₄⁺-N、TP的去除率分别为93.3%、64.6%、83.6%和97.6%,出水中ρ(CODCr)、ρ(TN)、ρ(NH₄⁺-N) 和ρ(TP)分别为19.8、15.3、6.1和0.2 mg/L. 另外,在10 ℃下运行时,聚合铝铁对生活污水中TP及NH₄⁺-N的去除更为有效.     

A collaborative strategy for enhanced reduction of Cr(VI) by Fe(0) in the presence of oxalate under sunlight: Performance and mechanism

Nanometer-size zero-valent iron (NZVI) is an efficient reducing agent, but its surface is easily passivated with an oxide layer, leading to reaction inefficiency. In our study, oxalate (OA) was introduced into this heterogeneous system of NZVI, which could form ferrioxalate complexes with the NZVI surface-bound Fe³⁺ and dissolved Fe³⁺ in the solution. Photolysis of ferrioxalate complexes can facilitate the generation of Fe²⁺ from Fe³⁺ and CO₂^?- radical, both species have strong reduction capacity. Hence, a “photo-oxalate-Fe(0)” system through sunlight induction was established, which not only prohibited the formation of a surface passivation layer, but also displayed a synergetic mechanism of ferrioxalate photolysis to enhance reduction, exhibiting remarkably higher degradation activity (several times faster) toward the model pollutant Cr(VI) than the mechanism with NZVI alone. Factor tests suggested that both NZVI dosage and OA content markedly affected the reduction rate. Low pH was beneficial to the reduction efficiency. Moreover, recyclability experiment showed that the reduction rate decreased from 0.21706 to 0.03977 min^?1 after three cycles of reuse due to the NZVI losing reaction activity generally, but the system still maintained considerable reduction capacity. Finally, a mechanism was revealed whereby NZVI would transform to Fe oxides after the exhaustion of its reductive power, and the photolysis of ferrioxalate to promote the cycling of iron species played the predominant role in providing extra reduction ability. These features confirm that introduction of OA into Cr(VI) reduction by NZVI through sunlight induction is advantageous and promising.     

Debromination of decabromodiphenyl ether by organo-montmorillonite-supported nanoscale zero-valent iron：Preparation, characterization and influence factors

An organo-montmorillonite-supported nanoscale zero-valent iron material(M-NZVI) was synthesized to degrade decabromodiphenyl ether(BDE-209). The results showed that nanoscale zero-valent iron had good dispersion on organo-montmorillonite and was present as a core-shell structure with a particle size range of nanoscale iron between 30–90 nm, characterized by XRD, SEM, TEM, XRF, ICP-AES, and XPS. The results of the degradation of BDE-209 by M-NZVI showed that the efficiency of M-NZVI in removing BDE-209 was much higher than that of NZVI. The efficiency of M-NZVI in removing BDE-209 decreased as the pH and the initial dissolved oxygen content of the reaction solution increased, but increased as the proportion of water in the reaction solution increased.     

羟基铁柱撑膨润土处理含磷废水的研究

以羟基铁为柱化剂对天然膨润土进行柱撑改性制备了羟基铁柱撑膨润土,研究了其对废水中磷的吸附性能和影响因素。结果表明:羟基铁能够进入到膨润土的层间,使其层间距增大,表面积增加;羟基铁柱撑膨润土对废水中的磷有很好的去除效果,在常温下,当改性膨润土投加量为4 mg/L,溶液pH值为5,反应时间为60 min,处理质量浓度为20 mg/L的含磷废水时,磷的去除率达到93.9%。平衡吸附量与平衡质量浓度之间的关系更好地符合Langmuir等温吸附方程所描述的规律。     

嗜水气单胞菌强化老化纳米零价铁去除水中Cr(VI)

基于老化对纳米零价铁（NZVI）去除水中Cr（VI）的不利影响,本研究考察了接种嗜水气单胞菌（Aeromonas hydrophila）强化老化NZVI对水中Cr（VI）的去除,并分析了溶解氧、温度、pH、Cr（VI）初始浓度对其去除Cr（VI）的影响,同时利用扫描电镜（SEM）、X射线光电子能谱（XPS）等分析了反应前后材料的形貌特征及Cr的价态变化.结果表明,接种嗜水气单胞菌能显著提高无氧条件下老化NZVI对Cr（VI）的去除效果,且在酸性条件和30~40 ℃条件下去除效果较好,可能是因为该条件下更有利于老化NZVI的腐蚀和微生物的生长,此外,Cr（VI）去除效率随Cr（VI）初始浓度升高而降低.在pH=6,温度为30 ℃,老化nZVI投加量为0.1 g·L^-1,Cr（VI）初始浓度为50 mg·L^-1的条件下反应24 h后,Cr（VI）的去除率可达到100%.XPS分析表明,反应后NZVI表面沉积的Cr主要以Cr（III）的形式存在,可能为Cr（OH）₃沉淀或Fe_xCr_1-x（OH）₃共沉淀物.动力学研究发现,Cr（VI）去除过程符合准二级动力学,去除机制为Cr（VI）的吸附、还原与共沉淀,其中以还原作用为主.     

Removal of Cr(Ⅵ) by glutaraldehyde-crosslinked chitosan encapsulating microscale zero-valent iron: Synthesis,mechanism, and longevity

Microscale zero-valent iron(mZVI) has shown great potential for groundwater Cr(Ⅵ) remediation. However, low Cr(Ⅵ) removal capacity caused by passivation restricted the wide use of mZVI. We prepared mZVI/GCS by encapsulating mZVI in a porous glutaraldehydecrosslinked chitosan matrix, and the formation of the passivation layer was alleviated by reducing the contact between zero-valent iron particles. The average pore diameter of mZVI/GCS was 8.775 nm, which confirmed the mesoporous characteristic ...     

有机配体对膨润土负载纳米零价铁还原Cr(Ⅵ)的影响

六价铬〔Cr(Ⅵ)〕因具有剧毒性和致癌性而被广泛关注. 以Fe(Ⅲ)与 NaBH₄反应制得负载型的纳米铁(B-NZVI),并对该材料做了TEM和AAS的表征;深入考察B-NZVI去除Cr(Ⅵ)的动力学规律,以及草酸、柠檬酸、草酸钠、柠檬酸钠等有机配体对膨润土负载纳米零价铁还原Cr(Ⅵ)去除速率的影响,并对其影响机理进行初步探讨. 结果表明,膨润土负载纳米零价铁对Cr(Ⅵ)的去除行为符合Langmuir-Hinshelwood模型,其k_obs为0.011 97 min-1;草酸、柠檬酸、草酸钠和EDTA可促进B-NZVI对Cr(Ⅵ)的还原去除作用;柠檬酸钠则起到抑制作用. a      

羟基Fe、Al柱撑蒙脱石对庆大霉素的吸附行为

以蒙脱石(Mont)为原料,在不同OH/Fe物质的量比(x)和Fe/Al物质的量比(y)柱撑条件下制备出系列羟基铁(xOH/Fe-Mont)、羟基铝(OH/Al-Mont)和羟基铁铝(yFe/Al-Mont)柱撑蒙脱石,采用XRD和FT-IR对柱撑蒙脱石进行表征,并研究了柱撑改性对蒙脱石对庆大霉素(Gen)吸附行为的影响.结果表明:柱撑蒙脱石对Gen吸附量显著提高,且Mont(42.83mg/g) << OH/Al-Mont(63.50mg/g) < 1.5OH/Fe-Mont(70.50mg/g) << 0.025Fe/Al-Mont(87.20mg/g),吸附Gen最佳pH值为9.等温吸附适于采用Freundlich方程拟合,吸附动力学符合伪二级动力学方程,吸附3h可超过平衡吸附量的80%.XRD分析表明,羟基铁和羟基铝主导柱撑(y≤0.5)蒙脱石层间距扩增是吸附量增加的主要原因,而yFe/Al-Mont中y≥1.0时,层间距并不是吸附量变化的的主导机制;FT-IR分析表明阳离子交换是Gen和铝离子进入蒙脱石的主导机制.     

应用纳米零价铁处理模拟含Cr(Ⅵ)无氧地下水

研究了实验室自制的纳米零价铁处理模拟含Cr(Ⅵ)无氧地下水的影响因素、吸附动力学,并结合体系中Fe2+浓度、氧化还原电位、Zeta电位和理论计算得到的pe-pH图对纳米零价铁去除Cr(Ⅵ)的机制进行了探讨.实验结果表明,纳米零价铁对Cr(Ⅵ)的去除率随着初始Cr(Ⅵ)/Fe质量比的升高而降低.当溶液的pH为7.0,初始Cr(Ⅵ)/Fe质量比为0.025、0.050、0.075和0.100时,相应地Cr(Ⅵ)的去除率分别为100.0%、85.6%、72.7%和39.6%.酸性条件更有利于纳米零价铁对Cr(Ⅵ)的去除,当初始Cr(Ⅵ)/Fe质量比为0.100,溶液的pH为3.0、5.0、7.0、9.0和11.0时,体系中Cr(Ⅵ)的去除率分别为73.4%、57.6%、39.6%、44.1%和41.2%.纳米零价铁去除Cr(Ⅵ)的过程符合拟二级动力学方程.当溶液的pH为7.0,初始Cr(Ⅵ)/Fe质量比为0.025时,吸附速率常数(k)最大,为9.76×10-3g.(mg.m in)-1.Cr2O27-吸附到纳米零价铁表面后被迅速地还原为Cr3+,生成的Cr3+与纳米零价铁表面的FeOOH结合生成Cr-Fe膜.而Cr-Fe膜将阻断电子在纳米零价铁与Cr2O27-之间的传输,Cr(Ⅵ)得不到还原,从而纳米零价铁对Cr2O27-的去除以吸附为主.     

纳米Fe3O4负载的浮游球衣菌去除Cr(Ⅵ)的研究

以纳米Fe₃O₄负载浮游球衣菌（Sphaerotilus natans）为复合生物吸附剂,考察了其对Cr(Ⅵ)的吸附性能,并对生物吸附机理进行了初步研究.结果表明,pH值是影响复合生物吸附剂吸附Cr(Ⅵ)的主要因素,吸附的最佳pH为2～3;用此复合生物吸附剂对Cr(Ⅵ)进行吸附,其单位吸附量为0.0217 mmol/g.用HCl对其进行再生,再生率在90％以上;—CONH₂和—NH—是菌体吸附Cr(Ⅵ)的主要活性基团,静电吸引是复合生物吸附剂吸附Cr(Ⅵ)的主要机理之一.     

Performance of bimetallic nanoscale zero-valent iron particles for removal of oxytetracycline

In this study, bimetallic nanoscale zero-valent iron particles(nZVI), including copper/nanoscale zero-valent iron particles(Cu/nZVI) and nickel/nanoscale zero-valent iron particles(Ni/nZVI), were synthesized by one-step liquid-phase reduction and applied for oxytetracycline(OTC) removal. The effects of contact time and initial p H on the removal efficiency were studied. The as-prepared nanoscale particles were characterized by scanning electron microscopy(SEM), energy dispersive spectroscopy(EDS) and X-ray diffraction(XRD). Finally, the degradation mechanisms of OTC utilizing the as-prepared nanoparticles were investigated by using X-ray photoelectron spectroscopy(XPS) and mass spectrometry(MS). Cu/n ZVI presented remarkable ability for OTC degradation and removed71.44% of OTC(100 mg/L) in 4 hr, while only 62.34% and 31.05% of OTC was degraded by Ni/nZVI and nZVI respectively. XPS and MS analysis suggested that OTC was broken down to form small molecules by ·OH radicals generated from the corrosion of Fe0. Cu/nZVI and Ni/n ZVI have been proved to have potential as materials for application in OTC removal because of their significant degradation ability toward OTC.     

Nanoscale zero-valent iron/magnetite carbon composites for highly efficient immobilization of U(Ⅵ)

Nanoscale zerovalent iron/magnetic carbon(NZVI/MC) composites were successfully synthesized by simply calcining yellow pine and iron precursors. NZVI/MC pyrolyzed at 800°C(NZVI/MC800) had a higher percentage of NZVI and displayed better resistance to aggregation and oxidation of NZVI than samples prepared at other temperatures. The NZVI/MC800 material was applied for the elimination of U(Ⅵ) from aqueous solutions. The results suggested that the NZVI/MC800 displayed excellent adsorption capacity(203.94 mg/g)toward U(Ⅵ). The significant adsorption capacity and fast adsorption kinetics were attributed to the presence of well-dispersed NZVI, which could quickly reduce U(Ⅵ) into U(Ⅳ), trapping the guest U(Ⅳ) in the porous biocarbon matrix. The removal of U(Ⅵ) on the NZVI/MC samples was strongly affected by solution pH. The NZVI/MC samples also displayed outstanding reusability for U(Ⅵ) removal after multiple cycles. These findings indicate that NZVI/MC has great potential for remediation of wastewater containing U(Ⅵ).     

Fe0-PRB去除Cr(Ⅵ)反应动力学及影响机制

零价铁渗透式反应墙技术(zero-valent iron permeable reactive barrier,Fe~0-PRB)是近年来兴起的一项高效经济的地下水原位修复技术,被成功应用于地下水Cr(Ⅵ)污染的场地修复中.针对Fe~0-PRB去除Cr(Ⅵ)的反应影响机制开展研究,从动力学角度揭示零价铁去除Cr(Ⅵ)的环境条件响应规律,获得描述零价铁去除Cr(Ⅵ)的反应动力学模型.考察了地下水常见离子对Cr(Ⅵ)去除的影响,发现地下水中氯离子通过影响电子传递影响Cr(Ⅵ)去除,硫酸根、镁离子通过参与反应影响Cr(Ⅵ)去除,碳酸氢根通过参与反应和影响电子传递共同影响Cr(Ⅵ)去除,钙离子对Cr(Ⅵ)去除影响不大.研究结果为Fe~0-PRB去除Cr(Ⅵ)的工艺参数优化提供方法和理论依据.