羟基铝柱撑膨润土负载纳米铁还原Cr(Ⅵ)

用具有良好吸附能力的羟基铝柱撑膨润土作载体,通过FeSO₄与NaBH₄反应制得羟基铝柱撑膨润土负载的纳米铁(nanoscale zero-valent iron supported on Al-pillared bentonite,NZVI/Al-PILC).用X射线衍射(X-ray diffraction, XRD)、(Brunauer-Emmett-Teller,BET)法对NZVI/Al-PILC进行了结构表征.以Cr(Ⅵ)为目标污染物,考察了NZVI/Al-PILC与Cr(Ⅵ)反应过程中,介质pH、不同起始浓度的Cr(Ⅵ)对其去除率的影响,并与相同铁含量的纳米铁(nanoscale zero-valent iron,NZVI)进行了比较.结果表明,在相同实验条件下,Cr(Ⅵ)与NZVI/Al-PILC反应120　min后去除率接近100%,不仅高于相同铁含量NZVI对Cr(Ⅵ)去除率(63.0%),而且也明显优于相同铁含量的NZVI和相同含土量的羟基铝柱撑膨润土对Cr(Ⅵ)去除率的加和(75.4%).     

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%.     

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      

膨润土负载纳米铁的改性及对水中As(Ⅴ)的吸附

用十六烷基三甲基溴化铵(CTMAB)对膨润土负载纳米零价铁(Bent-n ZVI)进行表面改性,得到表面改性膨润土负载纳米铁(Bent-n ZVI)/CTMAB。通过SEM、Zeta电位和中位径d(50)分析,与膨润土(Bent)、改性膨润土(CTMAB-Bent)、Bent-n ZVI进行了对比,结果表明:相比Bent-n ZVI,(Bent-n ZVI)/CTMAB中的纳米铁颗粒更为分散且呈链状分布,d(50)仅为5.21μm,并且Zeta电位为+0.65 m V,更易静电吸引和吸附阴离子As O43-。4种材料的除砷结果亦表明其中(Bent-n ZVI)/CTMAB去除率最高,达到了93.9%。光电子能谱(XPS)分析表明(Bent-n ZVI)/CTMAB的除砷产物中只有As(Ⅴ),并不存在其还原态As(Ⅲ),说明(Bent-n ZVI)/CTMAB是通过吸附作用去除As(Ⅴ)。     

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...     

CTMAB/CPAM复合改性膨润土吸附水中苯酚和硝基苯

用十六烷基三甲基溴化铵(CTMAB)和阳离子型聚丙烯酰胺(CPAM)改性膨润土,制得系列CTMAB-膨润土(C-Bt)、CPAM-膨润土(P-Bt)和复合改性膨润土(C/P-Bt).采用XRD分析了各类有机膨润土的底面间距,并比较了它们吸附水中苯酚和硝基苯的性能.结果显示,C/P-Bt的底面间距大于相应的C-Bt和P-Bt,表明CTMAB与CPAM能同时层插到膨润土层间.C/P-Bt吸附性能优于C-Bt及C-Bt加P-Bt,在相同平衡浓度下(苯酚为7 045 mg/L,硝基苯为409 mg/L),60C/4%P-Bt对苯酚和硝基苯的吸附量分别为150 mg/g和69 mg/g,吸附量比60C-Bt分别提高了26%和28%,比60C-Bt加4%P-Bt分别提高了22%和26%,表现出明显协同吸附效应.这说明CTMAB在C/P-Bt层间的排列模式受CPAM的影响,形成了对有机物亲和能力更强的吸附介质.该新型有机膨润土在有机污染控制中有良好的应用前景.     

阳-非离子有机膨润土对水中硝基苯的吸附作用

分别用阳离子表面活性剂CTMAB、非离子表面活性剂Triton X-100及其混合物改性膨润土制得一系列的单阳离子、单非离子、阳-非离子有机膨润土.比较了它们对水中硝基苯的吸附性能及机理.结果表明,有机膨润土吸附水中硝基苯的等温吸附曲线呈线性,主要为分配作用所致,分配作用的大小由有机膨润土有机碳含量决定,并与改性时表面活性剂的种类、组成及配比有关;阳-非离子混合表面活性剂改性的有机膨润土有机碳含量(foc)高于相应的单阳离子和单非离子有机膨润土有机碳含量的和,因此,阳-非离子有机膨润土对水中硝基苯的吸附能力显著增强.     

F-127改性纳米零价铁及对水中2,4-DCP的去除

为了增强纳米零价铁的分散性,本研究采用环境友好型材料Pluronic F-127对纳米零价铁(NZVI)进行表面改性,形成分散型纳米零价铁(F-NZVI),并用于水中2,4-DCP的去除.通过不同质量比的F-NZVI颗粒沉降试验和对2,4-DCP的去除试验,发现存在沉降去除和悬浮去除两个阶段,确定F-127与NZVI颗粒的最佳质量比为2∶1,2,4-DCP最大去除率为72.32%.通过SEM、FTIR、XRD、XPS对样品进行表面形貌、组成和晶体结构分析,发现F-127对提高NZVI分散性和抗氧化性有显著作用.通过控制不同因素研究F-NZVI去除水中2,4-DCP的最优条件,实验结果表明,当2,4-DCP初始浓度为20 mg·L~(-1)时,F-NZVI去除2,4-DCP的最佳pH值为5,F-NZVI最佳投加量为3 g·L~(-1).     

稳定型纳米零价铁去除地下水中2,4-二氯苯酚

为改善纳米零价铁(NZVI)在水溶液中容易发生团聚和易被氧化的缺点.本文研究利用廉价易得的环境友好型材料羧甲基淀粉钠(CMS)对NZVI进行包覆改性,利用空间位阻效应提高其分散悬浮性.利用透射电镜和X射线衍射研究了改性后的纳米铁微观结构及物相组成,通过化学实验研究其对2,4-二氯苯酚(2,4-DCP)的去除效果.结果表明,改性后的NZVI直径大约在80~100 nm,呈链状或分散颗粒分布,主要物质组成为零价铁,具有强还原性.当CMS的比例为80.00%时,悬浮性最佳;经过CMS包覆改性后,NZVI还保留原有的活性,在不同包覆比例对于2,4-DCP的去除效果的实验中发现,同样CMS比例为80%时去除效果最好,达到83.69%,且有明显的脱氯降解过程.     

三氧化二铝球负载纳米零价铁去除硝基苯研究

本文以三氧化二铝小球为载体,成功制备出负载型纳米零价铁(Fe@Al_2O_3)。利用复合材料还原水相中的硝基苯,研究了铁投加量和硝基苯初始浓度对硝基苯去除率的影响,并借助GC-MS分析硝基苯可能的降解途径。结果表明:负载后零价铁颗粒平均粒径在100nm左右,均匀分散在Al_2O_3表面及内部孔道上;Fe@Al_2O_3在空气/水条件保存后,硝基苯去除率仍达到90.44%,抗氧化能力明显优于未负载的NZVI;零价铁还原硝基苯生成苯胺是主要反应,伴随着氧化副反应生成微量的无机氮。     

有机蒙脱石负载纳米铁去除4-氯酚的研究

采用离子交换法制备了有机改性蒙脱石（CMt）,以此为载体和分散剂,通过液相还原过程成功制备出负载型纳米零价铁颗粒（NZVI-CMt）,并对其结构利用XRD、SEM等手段进行表征.同时,借助高效液相色谱法（HPLC）分析研究了不同条件下合成材料对4-氯酚（4-CP）的去除情况,并对降解机理进行了探讨.结果表明：制备出的负...     

Wastewater degradation by iron/copper nanoparticles and the microorganism growth rate

Nowadays, trends in wastewater treatment by zero-valent iron (ZVI) were turned to use bimetallic NZVI particles by planting another metal onto the ZVI surface to increase its reactivity. Nano size zero-valent iron/copper (NZVI/Cu⁰) bimetallic particles were synthesized in order to examine its toxicity effects on the wastewater microbial life, kinetics of phosphorus, ammonia stripping and the reduction of chemical oxygen demand (COD). Various concentrations of NZVI/Cu⁰ and operation conditions both aerobic and anaerobic were investigated and compared with pure NZVI experiment. The results showed that addition 10 mg/L of NZVI/Cu⁰ significantly increased the numbers of bacteria colonies under anaerobic condition, conversely it inhibited bacteria activity with the presence of oxygen. Furthermore, the impact of nanoparticles on ammonia stripping and phosphorus removal was also linked to the emitted iron ions electrons. It was found that dosing high concentration of bimetallic NZVI/Cu⁰ has a negative effect on ammonia stripping regardless of the aeration condition. In comparison to control, dosing only 10 mg/L NZVI/Cu⁰, the phosphorus removal increased sharply both under aerobic and anaerobic conditions, these outcomes were obtained as a result of complete dissolution of bimetallic nanoparticles which formed copper-iron oxides components that are attributed to increasing the phosphorus adsorption rate.     

Simultaneous elution of polycyclic aromatic hydrocarbons and heavy metals from contaminated soil by two amino acids derived from β-cyclodextrins

Two highly water-soluble amino acids, which derived from -CDs, i.e., glutamic acid- -cyclodextrin (GluCD) and ethylene-diamine- -cyclodextrin (EDCD), were synthesized and were examined for their e ect on solubilization of anthracene (ANT), complexation of cadmium (Cd2+), and elution removal of ANT and Cd2+ in soil. The results showed that GluCD and EDCD were powerful complexant for ANT and Cd2+. In the presence of 10 g/L GluCD and EDCD, the solubilization of ANT increased by 47.04 and 23.85 times compared to the control, respectively. GluCD resulted in approximately 90% complexation of Cd2+ while 70% complexation was observed for EDCD. Simultaneously, GluCD and EDCD could greatly enhance the elution removal of ANT and Cd2+ from soil. GluCD resulted in the highest elution e ciency of ANT and Cd2+.With the addition of 10 g/L GluCD, 53.5% of ANT and 85.6% of Cd2+ were eluted, respectively. The ANT had a negligible e ect on the Cd2+ removal due to di erent complexing sites of ANT and Cd2+, while Cd2+ enhanced the ANT removal under the addition of GluCD because Cd2+ neutralized the –COOH group of GluCD. Adversely, the removal of ANT was decreased with Cd2+ under the addition of EDCD, this was due to the fact that Cd2+ enhanced the polarity of EDCD molecule and inhibited the complexation between ANT and EDCD. The study suggested that GluCD could be preferred and be successfully applied to remediation of heavy metals or organic compounds in contaminated soil.     

氧化石墨烯负载零价纳米铁吸附水中环丙沙星的研究

通过溶液还原法制备了氧化石墨烯负载零价纳米铁NZVI16-GO1(F16G1),并将其用于水中环丙沙星的去除.同时,采用X射线衍射仪(XRD)、场发射扫描电镜(FE-SEM)、能谱仪(EDS)和热重分析仪(TG)等手段表征了F16G1的结构、化学组成和微观形貌.结果发现,F16G1对水中环丙沙星具有良好的吸附性能;氧化石墨烯的引入可以有效降低零价纳米铁的自身团聚;F16G1与环丙沙星的吸附作用很大程度上受静电引力的影响.实验同时考察了p H值、反应时间、初始浓度、投加量等因素对F16G1吸附环丙沙星的影响.结果表明,在p H=4~5之间,溶液的p H值对吸附量没有明显影响;F16G1对环丙沙星的最大吸附量是656.66 mg·g-1;Langmuir等温吸附模型可以用来描述吸附平衡过程.零价纳米铁的磁性使复合材料便于回收.     

臭氧/沸石工艺处理水中硝基苯的机理探讨

考察了臭氧在H型沸石上吸附与分解情况,发现臭氧在H型沸石上发生了吸附与分解,并且吸附过程与脱附过程是不可逆的,其脱附速率很快.在吸附分解平衡后,臭氧在H型沸石上的吸附分解量与进水臭氧浓度成正比.而在1×10^-3 mol/L Na⁺存在条件下,被Na⁺交换的H型沸石基本不吸附分解臭氧.考察不同阳离子和不同型号沸石对臭氧/沸石工艺去除硝基苯的影响,发现Ca²⁺的影响最大,另外Na型沸石和NH₄型沸石在降解硝基苯的过程中,硝基苯的去除效率逐渐提高,并且Na型沸石中的Na⁺发生溶出,表明盐析效应影响臭氧扩散进入沸石孔道进行自分解和催化分解的能力.脱铝后的H型沸石没有体现降解硝基苯的效果.最后在pH 3.0时,H型沸石也能吸附分解一部分臭氧,说明H⁺的影响不如其它阳离子.     

Perchlorate removal using granular activated carbon supported iron compounds: Synthesis, characterization and reactivity

Synthesis and use of the iron compounds supported on granular activated carbon (ICs/GAC) have shown significant environmental implications for perchlorate (ClO 4 ) removal. ICs/GAC was synthesized via hydrolyzing FeSO 4 ·7H 2 O on GAC, reduced by NaBH 4 solution in polyethylene glycol 6000 and ethanol solution, dried in vacuum condition and exposed to air. Synthesized ICs/GAC was characterized using transmission electron micrograph (TEM), Brunauer-Emmett-Teller, X-ray photoelectron spectroscopy (XPS). ICs/GAC was determined to be containing a large amount of FeOHSO 4 , Fe 2 O 3 and a small amount of zero-valent iron (ZVI) nanoparticles according to TEM and XPS measurements. Batch static kinetic tests showed that 97% of ClO 4 was removed within 10 hr at 90°C and 86% of ClO 4 was removed within 12 hr at 25°C, at ICs/GAC dosage of 20 g/L. The experimental results also showed that FeOHSO 4 and Fe 2 O 3 nanoparticles have the function of perchlorate adsorption and play important roles in ClO 4 removal. The activation energy (E a ) was determined to be 9.56 kJ/mol.     

Cysteine-enhanced reductive degradation of nitrobenzene using nano-sized zero-valent iron by accelerated electron transfer

As an aliphatic amino acid, cysteine (CYS) is diffuse in the living cells of plants and animals. However, little is known of its role in the reactivity of nano-sized zero-valent iron (NZVI) in the degradation of pollutants. This study shows that the introduction of CYS to the NZVI system can help improve the efficiency of reduction, with 30% more efficient degradation and a reaction rate constant nine times higher when nitrobenzene (NB) is used as probe compound. The rates of degradation of NB were positively correlated with the range of concentrations of CYS from 0 to 10 mmol/L. The introduction of CYS increased the maximum concentration of Fe(III) by 12 times and that of Fe(II) by four times in this system. A comparison of systems featuring only CYS or Fe(II) showed that the direct reduction of NB was not the main factor influencing its CYS-stimulated removal. The reduction in the concentration of CYS was accompanied by the generation of cystine (CY, the oxidized form of cysteine), and both eventually became stable. The introduction of CY also enhanced NB degradation due to NZVI, accompanied by the regeneration of CYS. This supports the claim that CYS can accelerate electron transfer from NZVI to NB, thus enhancing the efficiency of degradation of NB.     

纳米零价铁去除水中微量N-亚硝基二甲胺的研究

采用纳米零价铁催化降解水中微量N-亚硝基二甲胺(NDMA),并研究了溶解氧、纳米铁投加量、NDMA初始浓度、初始pH值、温度对纳米铁降解NDMA的影响.结果表明,纳米铁可以在中性厌氧条件下有效降解NDMA,作用效果远胜于普通铁粉;其对NDMA的去除速率随着纳米铁投加量的增加而增大,但与NDMA初始浓度无关;pH值降低或温度升高均有利于NDMA的降解.纳米铁降解NDMA存在一个启动期,启动期的长短与pH值和反应温度有关,提前活化纳米铁能有效提高反应速率.NDMA的降解产物主要是DMA和NH4+,其他产物如UDMH需进一步确认.