零价铁、铜改性生物炭及其对Cr(Ⅵ)吸附性能的影响

针对纳米零价铁（nanoscale zero valent iron,nZVI）易团聚的特性,本文用鸡骨生物炭（BC）作载体,制备出生物炭-零价铁（Fe-BC）去除Cr(Ⅵ),并与铜改性的生物炭-零价铁（Fe-Cu-BC）和BC对Cr(Ⅵ)的吸附性能进行了对比。通过扫描电镜（SEM）和能谱仪（EDS）、X射线衍射（XRD）、N₂吸脱附等温线和傅里叶红外光谱（FTIR）对材料表面形貌及结构性质进行分析,同时考察了溶液pH、接触时间等条件对吸附剂吸附容量的影响,通过吸附动力学和吸附等温线分析了吸附特性。结果表明,在pH=2的条件下去除Cr(Ⅵ)效果较好;吸附平衡遵从Langmuir吸附等温式;吸附动力学符合准二级动力学方程。Fe-BC材料吸附水体污染物后可用磁分离技术加以回收。Fe-Cu-BC缩短了对Cr(Ⅵ)的吸附平衡时间。制备出的吸附剂对Cr(Ⅵ)的理论最大吸附量顺序为 Fe-BC>Fe-Cu-BC>BC;同时, Fe-BC吸附量为153.60mg/g,对比于先前报道的nZVI对Cr(Ⅵ)的吸附容量85mg/g左右,有了很大的提升,说明BC作载体成功解决了nZVI易团聚的缺点,拓展了实际应用。     

虾壳生物炭/纳米零价铁同步去除水体中Se(Ⅳ)和环丙沙星

针对富硒养殖业中潜在的硒与抗生素共存废水,以虾壳制备的氮掺杂多孔生物炭(NBC)为骨架,原位合成纳米零价铁(nZVI),构建具有NBC和nZVI活性功能成分的复合材料(NBC-nZVI),采用扫描电镜(SEM)、氮气吸附、X射线衍射(XRD)、傅里叶红外光谱(FTIR)和X射线光电子能谱(XPS)表征样品。考察NBC-nZVI对Se(Ⅳ)和环丙沙星(CIP)的同步吸附行为。结果表明,NBC-nZVI对CIP和Se(Ⅳ)的去除性能优于NBC和nZVI;Se(Ⅳ)优先于CIP被吸附于NBC-nZVI表面,并介导CIP的吸附,提高NBC-nZVI对CIP的去除性能;CIP对NBC-nZVI吸附Se(Ⅳ)无明显影响;双组分体系中NBC-nZVI对CIP和Se(Ⅳ)的吸附行为符合准二级动力学和Sips等温模型,对CIP与Se(Ⅳ)的最大理论吸附量分别为130.6,335.7 mg/g。     

生物炭负载纳米零价铁去除硝酸盐作用的研究

为探究生物炭负载纳米零价铁（nZVI/BC）去除水中硝酸盐的机制及其影响因素,采用小麦秸秆为载体制备吸附材料。通过XRD和SEM的表征分析知：铁被成功的负载在生物炭表面,生物炭作为载体分散了纳米零价铁颗粒,并减少了它们的团聚。吸附材料对硝酸盐去除效果的实验研究表明：负载纳米零价铁的小麦秸秆生物炭对硝酸盐的去除效果可达到100%,nZVI/BC氮气选择性为21%;铁炭比（w）为1:2时硝酸盐的去除效果最佳;在偏酸性条件下,氨氮选择性更高,对硝酸盐的去除效果更好;硝酸盐和氨氮去除率会随着硝酸盐初始浓度的升高而逐渐下降。     

Fe浸渍污泥生物炭对含Cd(Ⅱ)废水的吸附性能研究

通过城市污泥热解制备污泥生物炭(BC),采用FeCl_3溶液浸渍污泥生物炭后制备出磁性污泥生物炭(MBC),对比了BC与MBC去除水溶液中Cd(Ⅱ)的能力。考察溶液初始pH、吸附时间、吸附温度以及Cd(Ⅱ)初始浓度对BC和MBC去除Cd(Ⅱ)效果的影响。结果表明,BC和MBC均符合拟二级动力学吸附模型;Langmuir吸附等温模型能够更好地描述BC和MBC去除Cd(Ⅱ)的过程。在溶液初始pH为6.0,生物炭投加量为10 mg,Cd(Ⅱ)质量浓度为10～150 mg/L的溶液25 mL,吸附时间为360 min,温度为25℃的最佳条件下,BC和MBC对Cd(Ⅱ)最大的吸附量分别为76.93 mg/g和167.42 mg/g。经过5次吸附解吸试验,MBC的Cd(Ⅱ)去除率保持在90%以上,BC的Cd(Ⅱ)去除率在55%左右,说明MBC具有更好应用于去除含Cd(Ⅱ)废水的能力。     

生物炭零价铁去除水中硝酸盐氮影响因素探究

本文以小麦秸秆制备的生物炭和零价铁为原材料,考察了生物炭投加量、硝酸盐氮初始浓度、溶液初始pH对硝酸盐氮去除效果和产物选择性的影响,结果如下：生物炭投加量为1g时,硝酸盐氮去除率最高为83.6%,加入生物炭后可以抑制氨氮的生成。硝酸盐氮去除率随着硝酸盐氮初始浓度的升高而降低;酸性条件下更有利于硝酸盐氮的去除。     

生物炭负载纳米铁绿色制备及去除水溶液中Cr(Ⅵ)研究

以污水处理厂剩余污泥和花生衣提取液为原料,制备污泥基生物炭（SBC）、纳米零价铁（nZVI）和污泥基生物炭负载纳米零价铁（nZVI@SBC）,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nZVI@SBC对Cr(Ⅵ)处理效果最好,反应50 min后,Cr(Ⅵ)去除率达100%。SEM和BET表征结果表明污泥基生物炭作为载体可明显减少纳米零价铁颗粒的团聚,增加了比表面积,提高了Cr(Ⅵ)的去除率。     

生物炭负载纳米零价铁对水体典型污染物去除效果的研究进展

生物炭负载纳米零价铁(nZVI@BC)作为一种绿色环保的新型纳米零价铁改性材料,因其对水体污染物具有良好的修复效果而被广泛应用.本文总结了近年来生物炭负载纳米零价铁在水体环境中的应用研究进展,综述了其制备过程和吸附机理,重点阐述了生物炭负载纳米零价铁对水体中的重金属污染、有机污染以及氮、磷污染的修复效果,并对该领域今后...     

响应面法优化纳米零价铁改性棕榈生物炭的制备工艺

利用响应面法对纳米零价铁修饰棕榈生物炭(nZVI-PB)的制备工艺进行优化,以磷吸附量为考察指标,选取碱活化KOH浓度(CKOH)、热解温度(T)和复合材料中C/Fe质量比为考察因子作为因素进行Box-Behnken试验设计。结果表明,nZVI-PB制备的最佳条件:KOH浓度为3.6 mol·L~(-1),热解温度为486.79℃,材料中C/Fe质量比为0.73,该条件下nZVI-PB的磷吸附量为61.31 mg·g~(-1)。     

抗坏血酸稳定纳米零价铁的制备及其在含Cd(Ⅱ)废水处理中的应用

利用液相还原法制备抗坏血酸稳定纳米零价铁（AAS-nZVI）并将其应用于含Cd（Ⅱ）废水的处理。在确定最佳AAS/Fe²⁺（摩尔比）的基础上,研究了AAS-nZVI投加量、反应时间和溶液初始pH对Cd（Ⅱ）处理效果的影响,通过L₉（3⁴）正交试验优化AAS-nZVI处理含Cd（Ⅱ）废水的工艺条件;考察了AAS-nZVI的空气稳定性及其处理含Cd（Ⅱ）废水的动力学特性;通过SEM和XRD对处理Cd（Ⅱ）前后的AAS-nZVI进行形貌观测和表征分析。结果表明,AAS/Fe²⁺（摩尔比）为1∶3时,AAS-nZVI对Cd（Ⅱ）去除的去除效果最佳。AAS-nZVI投加量、反应时间和溶液初始pH对Cd（Ⅱ）去除率的影响均达到显著水平（p < 0.05）,其中AAS-nZVI投加量的影响达到极显著水平（p < 0.01）;其显著性大小依次为：AAS-nZVI投加量 > 反应时间 > 溶液初始pH。在AAS-nZVI投加量为2.0g/L、反应40min、溶液初始pH=6的最佳工艺条件下,含Cd（Ⅱ）废水（初始浓度20mg/L,溶液体积100mL）的去除率可达92.62%。AAS-nZVI具有很好的空气稳定性,空气中放置15d的AAS-nZVI对Cd（Ⅱ）的去除率仅下降1.99%。AAS-nZVI对Cd（Ⅱ）的去除较好地符合准一级动力学模型,可用L-H动力学模型描述;AAS-nZVI对Cd（Ⅱ）的去除是吸附和还原共同作用的结果。     

含氮大分子吸附剂的制备及其对Cd(II)的吸附

利用三聚氯氰的温度梯度反应活性,在较低温度下,用多乙烯多胺与三聚氯氰进行亲核取代反应,合成出一种以三嗪环为连接点的不溶含氮大分子颗粒吸附剂(N-MGA),并将其用于去除水体中的Cd(Ⅱ).通过元素分析、FTIR和SEM对N-MGA进行表征,同时对Cd(Ⅱ)的吸附进行吸附动力学、等温吸附模型拟合和吸附机理进行研究,考察了溶液pH对Cd(Ⅱ)吸附性能的影响、吸附剂的吸附-解吸再生循环性能及结构稳定性.结果表明,该吸附剂对Cd(Ⅱ)的吸附机理是利用吸附剂氨基上氮的孤对电子与Cd(Ⅱ)的配位络合作用进行吸附,且吸附过程符合准二级动力学模型和Langmuir吸附等温线模型,最大吸附量可达539.1 mg/g,且对Cd(Ⅱ)的吸附较为容易,吸附能力较强;在Cd(Ⅱ)初始质量浓度为3636.5和70.0 mg/L时,对Cd(Ⅱ)的吸附率分别可达97.5％和99.9％,且10次吸附-解吸再生循环中吸附率维持在97.0％～98.2％,解吸率均在97.6％以上,吸附剂回收率均在92.0％以上.     

Sorption of Pb(II), Cd(II) and Zn(II) by iminodiacetate chelating resins in non-competitive and competitive conditions

Two chelating resins (CRs) bearing iminodiacetate (IDA) groups derived from acrylonitrile - divinylbenzene (AN-DVB) copolymers having 10 and 15 wt.% nominal cross-linking degrees and a high mobility of the functional groups caused by the presence of a longer spacer between the matrix and the IDA groups were synthesized and tested as sorbents for heavy metal ions like: Pb(II), Cd(II) and Zn(II) from aqueous solutions by batch and column techniques. Experimental data obtained from batch equilibrium tests have been analyzed by two isotherm models: Freundlich and Langmuir. The overall adsorption tendency of CRs toward Pb(II), Cd(II) and Zn(II), under non-competitive conditions, followed the order: Cd(II) > Pb(II) > Zn(II). Selectivity studies were performed in ternary mixture of Pb(II), Cd(II) and Zn(II) to check if the synthesized CRs can be useful for selective separation of heavy metal cations. The results revealed that the CRs with IDA groups exhibited high selectivity toward Pb(II), both in batch and column techniques. Regeneration of the resins was achieved using 0.1 M HCl solution.     

Kinetic and equilibrium studies of Pb(II) and Cd(II) removal from aqueous solution onto colemanite ore waste

The adsorption characteristics of Pb(II) and Cd(II) onto colemanite ore waste (CW) from aqueous solution were investigated as a function of pH, adsorbent dosage, contact time, and temperature. Langmuir, Freundlich and Dubinin-Radushkevich (D-R) models were applied to describe the adsorption isotherms. Langmuir model fitted the equilibrium data better than the Freundlich isotherm. The adsorption capacity of CW was found to be 33.6 mg/g and 29.7 mg/g for Pb(II) and Cd(II) ions, respectively. Analyte ions were desorbed from CW using both 1 M HCl and 1 M HNO₃. The recovery for both metal ions was found to be higher than 95%. The mean adsorption energies evaluated using the D-R model indicated that the adsorption of Pb(II) and Cd(II) onto CW were taken place by chemisorption. The thermodynamic parameters (ΔG^o, ΔH^o and ΔS^o) showed that the adsorption of both metal ions was feasible, spontaneous and exothermic at 20-50 °C. Adsorption mechanisms were also investigated using the pseudo-first-order and pseudo-second-order kinetic models. The kinetic results showed that the adsorption of Pb(II) and Cd(II) onto CW followed well pseudo-second order kinetics.     

Synthesis,adsorption and selectivity of inverse emulsion Cd(Ⅱ) imprinted polymers

Inverse emulsion polymerization was employed to synthesize inverse emulsion Cd(II) imprinted polymers(IEII P). The morphology and functional groups of IEIIP were characterized by SEM,FTIR and TG. Static adsorption experiments and competitive adsorption test were used to evaluate the adsorption ability of IEIIP. The adsorption capacity of polymers could reach 86.7 mg·g~(-1) under the optimal adsorption conditions. The pseudo second order kinetic model and Langmuir isotherm model could be used to analyze the experimental data well. The adsorption process of IEIIP was chemical adsorption process and monomolecular type. Thermodynamic parameters showed that the adsorption process was endothermic and could occur spontaneously. The selectivity coefficients k of Cd~(2+)/Pb~(2+), Cd~(2+)/Zn~(2+) and Cd~(2+)/Cu~(2+) were 2.4998, 1.2437 and 4.6882, respectively. The proposed method provides a new thought for removing Cd(II) in water samples.     

High adsorption of Cd (II) by modification of synthetic zeolites Y,A and mordenite with thiourea

Zeolites Y, A and mordenite (ZY, ZA and ZM) were obtained from diatomite in a template-free system, and the products were modified by thiourea (TU). Characterization studies results indicated that the TU molecules were loaded onto the exterior surfaces of the synthetic zeolites as well as the channels. Elemental analysis and energy-dispersive X-ray spectrometer proved that the TU molecules loaded on to ZA were more than ZY and ZM. Removal of Cd(II) was investigated, and it was found that the modified zeolites have higher removal capacity, modified ZA is especially noticeable. In the adsorption experiments, the effects of various parameters such as sorbent content, contact time, concentration of cadmium solution, pH, selectivity and regeneration were discussed. At the best removal efficiency by modified zeolites, the maximum adsorption capacity is 94.3 mg·g⁻¹, 103.2 mg·g⁻¹ and 89.7 mg·g⁻¹ at 25 °C, respectively. The sorbents show good efficiency for the removal of Cd(II) in the presence of different multivalent cations and have good regeneration effect. For the modified samples, removal experiments take place via ion exchange and complexation processes.     

海藻酸钙固定化零价铁抗团聚及堵塞的作用机制

以海藻酸钠(SA)、氯化钙、微米零价铁(MZVI)为原料,制备了海藻酸钙(CA)固定化MZVI填料(CAZ),通过静态烧杯实验和动态PRB模型实验,探讨了CA运用对Cr(Ⅵ)的去除性能的影响,并通过电镜扫描分析了CA避免团聚、堵塞机制。实验结果表明,CA凝胶颗粒的运用能显著提升MZVI的除Cr(Ⅵ)性能,CAZ相比MZVI对Cr(Ⅵ)的去除率和反应速率分别提升7.1倍、23.0倍;MZVI利用率的提高是CAZ反应器处理Cr(Ⅵ)水量显著大于MZVI反应器的主要原因,MZVI反应速率的提高是CAZ反应器出水Cr(Ⅵ)浓度显著低于MZVI反应器的主要原因。电镜扫描结果表明,SA与氯化钙交联形成的CA具有丰富的骨架孔道结构,具有骨架支撑作用,能有效克服MZVI颗粒因重力作用导致团聚、降低比表面积的缺陷。CA表层固定的MZVI颗粒与Cr(Ⅵ)反应生成的(Fe_xCr_1-x)(OH)₃络合沉淀会冲破CA表层外壳,释放到零价铁-渗透反应墙(Fe⁰-PRB)系统中,导致PRB反应初期出现堵塞现象;大部分MZVI颗粒...     

Removal of Cd（II） by Nanometer AIO（OH） Loaded on Fiberglass with Activated Carbon Fiber Felt as Carrier

A new nanometer material, nanometer AlO（OH） loaded on the fiberglass with activated carbon fibers felt（ACF） as the carrier, was prepared by hydrolytic reaction for the removal of Cd（II） from aqueous solution using column adsorption experiment. As was confirmed by XRD determination, the hydrolysis production loaded on fiberglass was similar to the orthorhombic phase AlO（OH）. SEM images showed that AlO（OH） particles were in the form of small aggregated clusters. The Thomas model was applied for estimating the kinetic parameters and the saturated adsorption ability of Cd（II） adsorption on the new adsorbent. The results showed that the maximum adsorption capacity of Cd（II） was 128.50 mg·g^-1 and 117.86 mg·g^-1 for the adsorbent mass of 0.3289 g and the adsorbent mass of 0.2867 g, respectively. The elution experiment result indicated that the adsorbed Cd ions was easily desorbed from the material with 0.1 mol·L^-1 HCl solution. Adsorption-desorption cycles showed the feasibility of repealed uses of the composited material. The adsorption capacities were influenced by pH and the initial Cd（II） concentration. The amount adsorbed was greatest at pH 6.5 and the initial Cd（II） concentration of 0.07 mg·L^-1, respectively. Nanometer AlO（OH） played a major role in the adsorption process, whereas the fiberglass and ACF were assistants in the process of removing Cd（II）. In addition, the adsorption capacities for Cd（II） were obviously reduced from 128.50 mg·L^-1 to 64.28 mg·L^-1 when Pb ions were present because Pb ions took up more adsorption sites.     

改性膨润土对废水中Cd(II)的吸附特征及吸附动力学研究

为探讨改性膨润土对Cd(II)的吸附特征及吸附动力学机制,通过吸附实验探讨了pH值、初始浓度和吸附时间对改性膨润土吸附Cd(II)的影响。结果表明,盐酸改性膨润土对Cd(II)的去除率表现为随溶液pH值升高而升高,而氢氧化钠改性膨润土、膨润土与十二烷基磺酸钠改性膨润土的去除率分别在pH=6和7时达到最大值。膨润土及改性膨润土对Cd(II)的去除率随初始浓度的增加而降低,吸附量随平衡浓度增加而增大,并趋向平稳,吸附符合Langmuir方程,吸附为单分子层吸附。膨润土及改性膨润土的吸附反应在240 min内基本达到平衡,吸附动力学分析表明吸附过程更符合准二级动力学模型,吸附过程以化学吸附为主,膨润土及改性膨润土的吸附速率大小依次为K2HCl-B＞K2NaOH-B＞K2B＞K2SDS-B,液膜扩散与颗粒内扩散过程均为控速步骤。该研究可为改性膨润土处理含镉废水和修复镉污染土壤提供参考。     

Olive leaves extract mediated zero-valent iron nanoparticles: synthesis,characterization, and assessment as adsorbent for nickel (II) ions in aqueous medium

Abstract

Zero-valent iron nanoparticles (NZVI-NPs) possess significantly high surface area and volume ratio, and this unique surface characteristic has enhanced reactivity to their adsorption potential. In this work, a bio-matter (Olive leaves extract) is deployed as a nature-inspired reducing agent for the synthesis of NZVI-NPs. The particle size of NZVI-NPs has been determined using particle sizer. The NZVI-NPs are characterized using analytical and morphological techniques such as ultraviolet???visible spectroscopy (UV???vis), energy dispersive X-ray spectroscopy (EDS), X-ray diffraction spectroscopy (XRD), scanning electron microscope (SEM), Brunauer–Emmett–Teller (BET), and Fourier transform infrared (FTIR) spectroscopy. The average crystalline size of NZVI-NPs are around 30–60?nm while maximum adsorption is at 225?nm. XRD spectrum shows two distinctive diffraction peaks at 25.40° and 42.50° corresponding to lattice plane value indexed at (200) and (222) planes of faced centered cubic (FCC). At optimized experimental conditions, NZVI-NPs show 97% removal efficiency of Ni⁺² ions from aqueous solution. The equilibrium time has been found to be 55?min and the monolayer maximum adsorption capacity is 139.5?mg/g. Kinetically, Ni⁺² ions adsorption has been modelled using various physical isotherms and the data best fitted Freundlich isotherm model and pseudo-first-order kinetic; revealing a maximum adsorption capacity of 139.5?mg/g at 25?±?3?°C and pH of 6.5. Desorption tests affirm the possibility of recovering reasonable amount of NZVI-NPs after used. The specific surface area of the NZVI-NPs sample measured by BET analysis is 21.9967 m²/g indicating a high adsorption capacity.     

Hydrodechlorination of 2,4,6-trichlorophenol for a permeable reactive barrier using zero-valent iron and catalyzed iron

Dehalogenation of toxic organic compounds has been intensively studied during the last decade by using zero-valent iron (ZVI). However, the reactivity of iron is compound specific and very low reactivities were reported for aromatic compounds including chlorophenols. In this study, hydrodechlorination of 2,4,6-trichlorophenol (2,4,6-TCP) was conducted in a batch system by using ZVI and catalyzed iron. No degradation was observed with ZVI over the 40 days experiments. Catalyzed ZVIs removed 2,4,6-TCP and palladium-coated iron (Pd/Fe) and nickel-coated iron (Ni/Fe) showed relatively enhanced reactivity while copper-coated iron (Cu/Fe) and platinum-coated iron (Pt/Fe) showed lower reactivities. The surface area normalized kinetic constants (k _SA ) of Pd/Fe, Ni/Fe, Cu/Fe, Pt/Fe are 2.54×10⁻⁴, 1.01 × 10⁻⁴, 2.24×10⁻⁵, 2.56×10⁻⁵ L m⁻² h⁻¹, respectively. The identification of less chlorinated phenols and phenol confirmed that the removal is dechlorination. Pd/Fe system exerts relatively low pH compared with the ZVI system, and the low pH is favorable for the dechlorination. The reactivity enhancement of catalyzed iron was discussed in terms of catalytic effects and the corrosion potential by the bimetal coupling. Variable Pd content on the Pd/Fe was tested, and the degradation rate of 2,4,6-TCP increased in proportion to the increase of Pd content.