Removal of ofloxacin antibiotic using heterogeneous Fenton process over modified alginate beads

The aim of this work is to study the heterogeneous oxidative degradation of ofloxacin antibiotic using a composite material prepared from sodium alginate and cyclohexane dinitrilo tetraacetic acid(CDTA). The characterization tests indicated the successful incorporation of metal chelator and iron. It was also demonstrated that the synthesized beads are mesoporous. The influence of several experimental parameters(i.e.: H2O2 dose,working temperature, beads loading and initial drug concentration) on the process performances was evaluated. The reaction temperature significantly affects the drug conversion efficiency. It was also observed that the synthesized material was efficient toward the target antibiotic degradation in the presence of small quantities of hydrogen peroxide. Under optimum conditions(0.05 g of granules, initial drug concentration = 10 mg/L,25 μL of 10 mmol/L H2O2), conducted in a batch reaction, 94% degradation of ofloxacin was reached. The results also indicate that the composite material showed a reasonable stability;a relatively low decrease of activity after four successive runs(only 9%) and a negligible iron leaching(0.8%) have been observed. The synthesized composite material offered interesting advantages in terms of simplicity, good stability, ease of recovery from the liquid medium after use and its efficiency in the presence of low quantities of oxidant. It constitutes a good candidate in the water treatment area.     

Interfacial mechanisms of heterogeneous Fenton reactions catalyzed by iron-based materials: A review

The heterogeneous Fenton reaction can generate highly reactive hydroxyl radicals(·OH)from reactions between recyclable solid catalysts and H_2O_2 at acidic or even circumneutral pH.Hence,it can effectively oxidize refractory organics in water or soils and has become a promising environmentally friendly treatment technology.Due to the complex reaction system,the mechanism behind heterogeneous Fenton reactions remains unresolved but fascinating,and is crucial for understanding Fenton chemistry and the development and application of efficient heterogeneous Fenton technologies.Iron-based materials usually possess high catalytic activity,low cost,negligible toxicity and easy recovery,and are a superior type of heterogeneous Fenton catalysts.Therefore,this article reviews the fundamental but important interfacial mechanisms of heterogeneous Fenton reactions catalyzed by iron-based materials..OH,hydroperoxyl radicals/superoxide anions(HO_2./O_2~-.)and high-valent iron are the three main types of reactive oxygen species(ROS),with different oxidation reactivity and selectivity.Based on the mechanisms of ROS generation,the interfacial mechanisms of heterogeneous Fenton systems can be classified as the homogeneous Fenton mechanism induced by surface-leached iron,the heterogeneous catalysis mechanism,and the heterogeneous reaction-induced homogeneous mechanism.Different heterogeneous Fenton systems catalyzed by characteristic iron-based materials are comprehensively reviewed.Finally,related future research directions are also suggested.     

Advanced treatment of biologically pretreated coal gasification wastewater by a novel heterogeneous Fenton oxidation process

Sewage sludge from a biological wastewater treatment plant was converted into sewage sludge based activated carbon(SBAC) with Zn Cl2 as activation agent, which was used as a support for ferric oxides to form a catalyst(Fe Ox/SBAC) by a simple impregnation method.The new material was then used to improve the performance of Fenton oxidation of real biologically pretreated coal gasification wastewater(CGW). The results indicated that the prepared Fe Ox/SBAC significantly enhanced the pollutant removal performance in the Fenton process, so that the treated wastewater was more biodegradable and less toxic. The best performance was obtained over a wide p H range from 2 to 7, temperature 30°C, 15 mg/L of H2O2 and 1 g/L of catalyst, and the treated effluent concentrations of COD, total phenols,BOD5 and TOC all met the discharge limits in China. Meanwhile, on the basis of significant inhibition by a radical scavenger in the heterogeneous Fenton process as well as the evolution of FT-IR spectra of pollutant-saturated Fe Ox/BAC with and without H2O2, it was deduced that the catalytic activity was responsible for generating hydroxyl radicals, and a possible reaction pathway and interface mechanism were proposed. Moreover, Fe Ox/SBAC showed superior stability over five successive oxidation runs. Thus, heterogeneous Fenton oxidation of biologically pretreated CGW by Fe Ox/SBAC, with the advantages of being economical, efficient and sustainable, holds promise for engineering application.     

柠檬酸盐强化UV/Fenton-生物法处理乳化油废水

以乳化油配水为对象, 研究了柠檬酸盐扩大UV/Fenton工艺的适用pH值范围与强化出水可生化性及与活性污泥法联用的效果.结果表明,柠檬酸盐可将UV/Fenton法的适用pH值范围扩大至4~8,且能提高UV/Fenton处理出水的可生化性.UV/Fenton处理后,原水BOD5/COD由0.02提高到0.32,投加1.0mmol/L柠檬酸钠后提高至0.53. UV/Fenton处理与经1.0mmol/L柠檬酸钠强化UV/Fenton处理出水经8h生物处理,COD去除率分别为78.7%,96.0%.柠檬酸钠浓度从0增加至1.0mmol/L时,经UV/Fenton处理过的出水再经生物处理出水的COD由293mg/L降低至48mg/L;继续增大时,COD基本保持不变.柠檬酸钠强化UV/Fenton处理可扩大pH值范围,改善废水的可生化性.     

零价铁与过硫酸盐异相芬顿降解活性艳橙X-GN

采用零价铁(Fe~0)与过硫酸盐构建异相类芬顿体系,由Fe0腐蚀释放Fe~(2+)催化S_2 O_8~(2-)产生硫酸根自由基快速降解偶氮染料活性艳橙,考察了初始p H值、Fe~0投加量、过硫酸盐投加量和温度对降解过程的影响。结果表明,当活性艳橙初始浓度为100 mg/L、pH值为7、Fe~0投加量为0.5 g/L、过硫酸盐投加量为1 mmol/L和反应温度为30℃时,反应60 min后活性艳橙降解率达到92.6%。酸性条件和提高反应温度均有利反应的进行,而且活性艳橙的降解率在初始pH值为9时也高于90%。反应过程符合准一级动力学,表观反应速率常数k为0.0513 min~(-1)(30℃)。UV-Vis扫描显示,活性艳橙的发色基团在反应过程中被破坏。由Fe~0与S_2O_8~(2-)构成的异相Fenton体系可作为一种高效手段用于染料废水的处理。     

Fenton法去除微囊藻毒素及有机污染物的研究

利用Fenton法处理含有微囊藻毒素的湖水,经处理后的水样中微囊藻毒素去除率达到97．33％,CODMn、UV254、叶绿素a的去除率分别达到54．32％、32．22％和98．90％。在水样中投加10mg／L的聚合氯化铝,搅拌沉淀后水中残留总Fe低于GB5749--2006（生活饮用水卫生标准》限值。     

Novel Al-doped carbon nanotubes with adsorption and coagulation promotion for organic pollutant removal

Al-doped carbon nanotubes (Al-doped CNTs) were prepared as a multifunctional integrated material of adsorbent and coagulant aid for organic pollutant removal from aqueous solution. It was observed that aluminum species were dispersed homogeneously on the surface of CNTs, and mainly anchored onto defect structures of the CNTs. The introduction of aluminium efficiently improved adsorption ability for methyl orange (MO) onto the CNTs, and maximum adsorption capacity calculated from the Langmuir isotherm model can reach 69.7 mg/g. The MO adsorption kinetics can be better described by the pseudo-second-order and pore diffusion kinetic models, and the diffusion of MO anions into pores of the Al-doped CNT adsorbent should be the rate-determining step. Thermodynamic analyses indicated that the adsorption of MO onto Al-CNTs-2.0 was endothermic and spontaneous. Moreover, adsorption capacity for MO on the Al-doped CNTs was evidently dependent on the CNT dose, solution pH and adsorbent dose. From the perspective of low-cost and multifunctional, suspension obtained during the Al-doped CNT adsorbent preparation, was tested as coagulant to remove humic acid (HA). A significant observation is that the suspension exhibited an excellent coagulation performance for HA, because abundant aluminous polymer and Al-doped CNTs existed in the suspension.     

Review on heterogeneous oxidation and adsorption for arsenic removal from drinking water

The long term exposure of arsenic via drinking water has resulted in wide occurrence of arsenisim globally, and the oxidation of the non-ionic arsenite (As(III)) to negatively-charged arsenate (As(V)) is of crucial importance for the promising removal of arsenic. The chemical oxidants of ozone, chlorine, chlorine dioxide, and potassium permanganate may achieve this goal; however, their application in developing countries is sometimes restricted by the complicate operation and high cost. This review paper focuses on the heterogeneous oxidation of As(III) by solid oxidants such as manganese oxide, and the adsorption of As(V) accordingly. Manganese oxide may be prepared by both chemical and biological methods to achieve good oxidation performance towards As(III). Additionally, manganese oxide may be combined with other metal oxides, e.g., iron oxide, to improve the adsorption capability towards As(V). Furthermore, manganese oxide may be coated onto porous materials of metal organic frameworks to develop novel adsorbents for arsenic removal. To achieve the application in engineering works, the adsorbents granulation may be achieved by drying and calcination, agglomeration, and the active components may also be in situ coated onto the porous materials to maintain the oxidation and adsorption activities as much as possible. The novel adsorbents with heterogeneous oxidation and adsorption capability may be carefully designed for the removal of arsenic in household purifiers, community-level decentralized small systems, and the large-scale drinking water treatment plants (DWTPs). This review provides insight into the fundamental studies on novel adsorbents, the development of innovative technologies, and the demonstration engineering works involved in the heterogeneous oxidation and adsorption, and may be practically valuable for the arsenic pollution control globally.     

Formation and transformation of schwertmannite in the classic Fenton process

The massive amount of sludge generated by the classic Fenton process, which has often been hypothesized to consist of ferric hydroxide, remains a major obstacle to its large-scale application. Therefore, reutilization of Fenton sludge has recently gained more attention.Understanding the formation, transformation, and properties of Fenton sludge combined with the stages of the Fenton reaction is pivotal, but not well illustrated yet. In this study,SEM-EDS, FT-IR, XRD, and XPS were applied to study the morphology, crystallinity,elemental composition, and valence state of Fenton sludge. The authors report that schwertmannite and 2-line ferrihydrite were generated and transformed in the oxidation phase and the neutralization phase of the Fenton process. SO_4~(2-) in the solution decreased by8.7%–26.0% at different molar ratios of Fe(II) to H_2 O_2; meanwhile, iron ion precipitated completely at pH 3.70 with the formation of schwertmannite containing sulfate groups in the Fenton sludge. The structural sulfate(Fe-SO_4) in schwertmannite was released from the precipitate with the addition of OH-, and the production of Fenton sludge decreased with increasing pH when pH 3.70. Goethite was found to form when the final p H was adjusted to 12 or at a reaction temperature of 80°C. Moreover, the possible thermal transformation to goethite and hematite indicated that Fenton sludge can be reused as a raw material for synthesizing more stable iron(hydro)oxides. The results provide useful insights into the formation and transformation of Fenton sludge, with implications for regulating the crystal type of Fenton sludge for further reuse.     

Construction of Ag2CO3/BiOBr/CdS ternary composite photocatalyst with improved visible-light photocatalytic activity on tetracycline molecule degradation

Photocatalytic degradation was considered as a best strategy for the removal of antibiotic drug pollutants from wastewater. The photocatalyst of ABC (Ag₂CO₃/BiOBr/CdS) composite synthesized by hydrothermal and precipitation method. The ABC composite used to investigate the degradation activity of tetracycline (TC) under visible light irradiation. The physicochemical characterization methods (e.g. scanning electron microscopy (SEM), transmission electron microscopy (TEM), high resolution-transmission electron microscopy (HR-TEM), ultraviolet visible spectroscopy (UV), photoluminescence (PL) and time resolved photoluminescence (TRPL) clearly indicate that the composite has been construct successfully that enhances the widened visible light absorption, induces charge transfer and separation efficiency of electron – hole pairs. The photocatalytic activity of all samples was examined through photodegradation of tetracycline in aqueous medium. The photocatalytic degradation rate of ABC catalyst could eliminate 98.79% of TC in 70 min, which is about 1.5 times that of Ag₂CO_3, 1.28 times that of BiOBr and 1.1 times that of BC catalyst, respectively. The role of operation parameters like, TC concentration, catalyst dosage and initial pH on TC degradation activity were studied. Quenching experiment was demonstrated that ·OH and O₂^·− were played a key role during the photocatalysis process that was evidently proved in electron paramagnetic resonance (EPR) experiment. In addition, the catalyst showed good activity perceived in reusability and stability test due to the synergistic effect between its components. The mechanism of degradation of TC in ABC composite was proposed based on the detailed analysis. The current study will give an efficient and recyclable photocatalyst for antibiotic aqueous pollutant removal.     

芬顿氧化技术在废水处理中的进展研究

随着中国水环境形势的日益严峻以及造纸、印染、制药等行业废水排放标准的提高,传统的废水深度处理工艺已经很难满足污染物去除的要求。在查阅大量国内外最新相关技术文献的基础上,介绍了芬顿氧化技术降解废水中污染物的机理,对比了芬顿氧化试剂的浓度、投加量以及反映时间等因素对COD、色度、总磷等水质指标去除率的影响因素,综述了芬顿氧化法在处理焦化废水、印染废水、农药废水、制药废水、造纸废水等难降解工业废水中的应用研究进展。     

蒽醌类溶解有机质和模拟太阳光耦合驱动下的Fenton法对罗丹明B脱色特征的影响因素研究

考察了光照/无光照条件、体系中不同种类的蒽醌、Fe(Ⅲ)、自由基淬灭剂、H2O2及其含量变化等对罗丹明B降解特征的影响.结果表明:含氧化敏感官能团结构的蒽醌类有机质在光照作用下,促进了Fenton反应的进行,使得罗丹明B脱色程度得到加强.这主要是因为蒽醌类有机质和模拟太阳光耦合作用过程驱动了体系中铁不同形态[Fe(Ⅲ)/Fe(Ⅱ)]之间的持续循环,为Fenton反应过程中关键活性物种羟基自由基的生成提供所了所必须的Fe(Ⅱ).     

Effects of iron (hydr)oxides on the degradation of diethyl phthalate ester in heterogeneous (photo)-Fenton reactions

This work studied the structural effects of hematite(α-Fe2 O3), 2-line ferrihydrite(HFO) and goethite(α-FeOOH) on diethyl phthalate ester(DEP) degradation. The results showed that the degradation of DEP was faster under 365 nm light irradiation than in the dark in the presence of iron(hydr)oxides. The apparent kinetic rates of DEP degradation followed the order HFO goethite ≈ hematite in the dark and HFO hematite goethite under 365 nm light irradiation. Two pathways governed H2 O2 decomposition efficiency on iron(hydr)oxide surfaces:(1) forming UOH on inherent surface hydroxyl groups(Fe-OH) and(2) producing O2 and H2 O on the surface oxygen vacancies. X-ray photoelectron spectroscopy(XPS) analyses indicated that HFO not only has high Fe-OH content but also has high Vo content, resulting in its low H2 O2 utilization efficiency(η). DEP was degraded through hydrogen abstraction and deesterification, and the major products were(OH)2-DEP, mono-ethyl phthalate(MEP), OH-MEP,and phthalate acid(PA). The study is important in understanding the transformation of phthalate esters in top surface soils and surface waters under ultraviolet light.     

混凝-Fenton氧化联合处理含丙烯酸化工废水

采用混凝-Fenton氧化联合技术,对可生化性差的含有丙烯酸的化工废水进行处理,考察了不同因素对COD去除率的影响。结果表明,对于COD为150000～160000mg／L的高浓度丙烯酸废水,经过混凝和Fenton氧化的联合处理,废水COD的去除率可高达80％左右,但出于实际生产运用中成本、运行难度和污泥量的考虑,选择其混凝最佳反应条件为：10％PAC投加量为5％,1‰PAM投加量为0．25％,pH为9,反应时间1h;Fenton最佳反应条件：初始pH为3,[Fe^2＋]／[H2O2]的摩尔比为0．05,H2O2与废水的体积比为2％左右,反应时间3h,沉降1h。在这个条件下,COD的去除率可达60％左右,而且可生化性比较好。     

铁炭耦合Fenton试剂-混凝沉淀法预处理DMAC废水

N,N-二甲基乙酰胺(DMAC)危害大,是化纤废水中的主要污染物之一. 采用铁炭微电解-Fenton试剂-混凝沉淀工艺预处理DMAC废水. 结果表明:在海绵铁投加量为30 g/L,铁炭体积比为1,pH为2,微电解反应1 h,H₂O₂投加量为5 mL/L,pH为3,Fenton试剂反应2.0 h,混凝沉淀pH为9.0,沉淀40 min的最佳工艺条件下,COD_Cr的去除率可稳定在70%以上;紫外可见分光光计测定证明,经微电解反应后DMAC的助色基团—CH₃和CO被破坏,经过Fenton 氧化后,—NH—基团才能被破坏,废水中的大分子物质被破坏,最终转变成小分子物质,为后续处理奠定了基础.      

Fenton试剂处理活性艳红印染废水的实验研究

采用Fenton试剂对活性艳红印染废水进行了处理。通过正交实验考察了反应时间、反应温度、双氧水/硫酸亚铁摩尔比以及pH对印染废水的色度及COD去除率的影响,确定了Fenton试剂处理废水的最佳条件。结果表明,随着反应时间的延长,色度及COD去除率增大,最佳反应时间为20 min;色度及COD的去除率随着反应温度的升高而增大,最佳反应温度为50℃。色度及COD的去除率在双氧水(30%)的用量与硫酸亚铁用量之比为1:3.1时,去除效果最好;最佳pH值为4.5。出水达到排放标准。此法具有去除率高,设备简单,占地面小,操作方便,不产生二次污染等优点。     

Fenton氧化技术处理印染废水的试验研究

采用Fenton试剂对含分散红E-4B和活性艳兰KN-R染料组成的模拟印染废水进行氧化处理,考察了H2O2和Fe2＋浓度、pH、反应时间等因素对去除效果的影响。在H2O2投加量为5.0ml/L,Fe-SO4.7H2O投量为1.1g/L,pH为3,反应25min后静置5min的条件下,初始COD为700mg/L,色度为1200倍的废水的COD去除率可达到95%,脱色率达97%。结果表明,Fenton试剂对该废水可以起到很好的处理效果。     

Novel synthesis of aluminum hydroxide gel-coated nano zero-valent iron and studies of its activity in flocculation-enhanced removal of tetracycline

A newly designed aluminum hydroxide gel-coated nanoscale zero-valent iron(AHG@NZVI)with enhanced activity and dispersibility of NZVI was successfully synthesized.The AHG@NZVI composite was synthesized via control of the surface AHG content.AHG@NZVI-1,AHG@NZVI-2 and AHG@NZVI-3 were prepared under centrifugal mixing speeds of 1000,2000 and 4000 r/min,respectively.The activity of AHG@NZVI was evaluated by its tetracycline(TC) removal efficiency.The effects of AHG content,pH value,reaction temperatu...