The role of ferrous ion in Fenton and photo-Fenton processes for the degradation of phenol

The efficiency of different Fenton-related oxidative processes such as Fenton, solar-Fenton and UV-Fenton were examined using phenol as a model compound in simulated and industrial wastewater. A batch study was conducted to optimize parameters like pH, hydrogen peroxide concentration and ferrous ion concentration governing the Fenton process. At optimum conditions, different Fenton-related processes were compared for the degradation of phenol. Increased degradation and mineralisation efficiency were observed in photo-Fenton processes as compared to conventional Fenton process. The maximum mineralising efficiency for phenol with Fenton, solar and UV-Fenton processes were 41%, 96% and 97% respectively. In Fenton process, carboxylic acids like acetic acid and oxalic acid were formed as end products during the degradation of phenol while in photo-Fenton processes, both these ions were identified during the early stages of phenol degradation and were oxidized almost completely at 120 min of the reaction time. In photo-Fenton processes (solar and UV light) complete degradation were observed with 0.4 mM of Fe2+ catalyst as compared to 0.8 mM of Fe2+ in conventional Fenton process. In Fenton and solar-Fenton processes, an iron reusability study was performed to minimize the amount of iron used in treatment process. The efficacy of Fenton and solar-Fenton processes was applied to effluent from phenol resin-manufacturing unit for the removal and mineralisation of phenol.     

Influence of oxalic acid formed on the degradation of phenol by Fenton reagent

The objective of this work is to examine the influence of oxalic acid formed on the degradation of phenol by Fenton reagent. Oxalic acid formed at initial stage within 30 min significantly suppresses the reduction of ferric ion, thus terminating degradation reaction. The yield of oxalic acid is dependent on the amount of ferrous ion dosed since the minimal amount of oxalic acid is formed after the degradation reaction terminates. Mineralization of phenol by Fenton reagent stagnates after 120 min under the conditions used in this study. The reason why the mineralization stagnated can be assumed to be following two mechanisms other than the depletion of H₂O₂. In the case where a small amount of ferrous ions is dosed, the reduction of ferric ions is minimal by oxalic acid formed. In the case where a large amount of ferrous ions is dosed, the amount of degradable organic compounds is insufficient owing to preferential conversion to oxalic acid. The mineralization can be enhanced by the intermittent dosing of ferrous ions, which facilitates the suppression of oxalic acid formation during the degradation by Fenton reagent.     

Photoelectro-Fenton mineralization of phenol through optimization of ferrous regeneration

The degradation of phenol in acidic solution at pH 3 has been investigated under various photo- and electrochemical conditions. A laboratory-scale reactor on which were mounted net electrodes (RuO₂/IrO₂-coated Ti anodes (DSA) and stainless steel cathodes) and 254 nm UV lamps was established to effectively reduce ferric reagents. The experimental results of the photoelectron-chemical reaction suggested that the current efficiency of reducing ferric ion was improved by increasing the number of electrodes used, and the UV lamps were important to inducing the reduction of ferric carboxylates, which were the major intermediates that were formed upon a particular degree of phenol oxidation. Accordingly, the addition of an initial concentration of 400 ppm ferrous salt and 10,200 ppm hydrogen peroxide (in a continuous mode) resulted in the removal of over 92 % of TOC (initial phenol?=?2,000 ppm, TOC?=?1,532 ppm) by 4 h of the photoelectro-Fenton and the sequential 2 h of the photo-Fenton processes. HPLC was utilized to monitor the formation of aromatic and carboxylate byproducts, and revealed that the aid of photo irradiation eliminated most of the oxalate residue from the final solution, which would have contributed to the 25 % of the TOC that was inactive in the electrolytic system.     

An improved UV/Fe3+ process by combination with electrocatalysis for p-nitrophenol degradation

p-nitrophenol (PNP) was investigated as a model pollutant under the improved UV/Fe3+ process by combination with electrocatalysis. In the individual UV/Fe3+ process, PNP degradation rate was dependent on Fe(III) concentration and decreased during degradation due to the depletion of ferric ion and thus it was very difficult to reach the quick mineralization of organics. These drawbacks could be significantly overcome in the modified UV/Fe3+ process, and synergetic effects for PNP and COD removal were observed at two investigated Fe(III) concentrations. The enhancements on the degree of conversion for PNP and COD in presence of 0.5 mM Fe(III) were 184% and 242%, respectively, and PNP of initial concentration of 1.0 mM could be completely removed within 1 h. Thus such a process would be very attractive to the rapid mineralization of the biorefractory compounds for wastewater treatment. The possible reasons for the synergetic effects were the electrochemical regeneration of ferric ion and the role of the oxygen that formed on the anode. Based on degradation intermediates identification and synergetic effect probe, a general reaction pathway for PNP degradation in the improved process was proposed.     

组合阳极联合气体扩散阴极电催化降解苯胺

采用气体扩散电极为阴极，钛基氧化物（Ti／SnO2-Sb2O5-IrO2）和金属铁构成组合阳极，构建了新型电化学氧化体系用于降解有机污染物。利用该氧化体系，在不同实验条件下考察了苯胺降解的效果与降解过程的相关规律。结果表明，阴极电位、铁阳极通电时间以及苯胺初始浓度均显著影响苯胺的降解效果。当阴极电位为-0．7V，pH3．0，铁阳极通电时间20min时，电化学处理200mg／L苯胺480min，TOC的去除效率达到80．4％，矿化电流效率（MCE）为8．6％，显示了该氧化体系具有良好的有机物降解能力。此外，苯胺降解过程中氨氮和硝态氮浓度的变化表明，苯胺分子中的氮主要转化为NH4和NO3^-。     

Titania-supported silver-based bimetallic nanoparticles as photocatalysts

Photocatalytic process has shown recently a great potential as an environmental friendly and clean remediation technology for organic pollutants in wastewater. This work described the synthesis of silver-based bimetallic nanoparticles using colloid chemistry and the subsequent immobilization onto titania to form composite photocatalytic materials (titania-supported Ag–Pt nanoparticles). The photocatalysts were characterized by X-ray diffraction, electron microscopy, and nitrogen physisorption. The catalytic activity of the photocatalysts was evaluated by photocatalytic degradation of phenol and 2-chlorophenol (2-CP) in synthetic wastewater solutions. The photocatalytic processes were conducted in a batch photoreactor containing appropriate solutions of phenol and 2-CP with UV irradiation of 450 W. UV-visible spectrophotometer was used for analyzing the concentration of phenol and 2-CP in solutions. Parameters affecting the photocatalytic process such as the solution pH, phenol and 2-CP concentrations, and catalyst concentration were investigated. The results obtained revealed that TiO₂-supported Ag/Pt nanoparticles showed a higher activity for UV-photocatalytic degradation of both phenol and 2-CP pollutants in the solution (as compared to the plain rutile TiO₂). The photodegradation processes were optimized by the 0.5-g/L catalyst with a pollutant concentration of 50 mg/L for all the samples. Complete degradation for both phenol and 2-CP was achieved after 120 min.     

三维电极/电-Fenton法降解苯酚

采用电-Fenton耦合三维电极法处理苯酚模拟废水，研究了活性炭作为第三电极的三维电极体系中苯酚的去除效果，重点考察了常温下初始pH值、电流强度、Fe²⁺浓度等因素对苯酚降解的影响。结果表明：在常温下，曝气速率20 L/min，初始pH=3，电流强度为0.3 A/m²，Fe²⁺浓度为0.1 mmol/L，反应时间60 min时，废水的苯酚的氧化降解率为91%，COD去除率为64%。在此条件下，三维电极/电-Fenton表现出较强的氧化能力，具有较好的去除效果，可应用于含苯酚废水的处理。     

改性沸石去除地下水中铁锰实验研究

测定了2种改性沸石的基本特性，并选取0.6 m层高的交换柱，通过动态试验，研究其分别用于除铁和除锰的工艺性能。实验结果表明，2种沸石质量全交换容量分别为578.2 mmol/kg和722.2 mmol/kg；产水水质均能达到饮用水标准：含铁量≤0.3 mg/L，含锰量≤0.1 mg/L；减少进水中铁锰含量（≤2 mg/L）和降低运行流速（≤20 m/h），都有利于提高工作交换容量，但流速对除铁沸石影响较小；再生剂为1 mol/L的NaCl，再生速率1 m/h条件下，每升除铁沸石再生剂用量为1.2 L，洗脱率（再生废液中目标离子含量与原水中过滤时的去除量之比）达0.95，比耗（再生剂用量与工作交换容量之比）为16，每升除锰沸石再生剂用量为1.6 L，洗脱率达0.8，比耗为16。     

序批式工艺制备生物聚合硫酸铁混凝剂

本实验研究了序批式工艺(SBR)制备生物聚合铁混凝剂过程中主要影响因素(接种微生物浓度、起始亚铁离子浓度)对亚铁离子氧化速率的影响。研究结果显示,在受试实验条件内,较高的接种微生物浓度和较低的起始Fe2+浓度有利于Fe2+氧化,Fe2+浓度变化与反应时间呈线性关系;当起始Fe2+浓度为20 g/L,接种细菌浓度约为8×108个/mL时,Fe2+氧化速率最大,最大值可达到0.375 g/(L.h)。在反应过程中生成了少量黄色沉淀,经傅里叶变换红外光谱分析后确定其主要成分为黄钾铁矾。合成的生物聚合硫酸铁经过干化后各项指标均符合《水处理剂聚合硫酸铁》(GB 14591-2006)之规定。对比实验表明,自制生物聚合硫酸铁海水混凝时性能优于实验所选品牌的商业产品。     

The role of activated carbon on the removal of p-nitrophenol in an integrated three-phase electrochemical reactor

Three-phase electrochemical reactor is still far from concerned in wastewater treatment in order to improve electrochemical treatment efficiency especially when the concentrations of organic pollutants are relatively low. This paper presents a novel process integrated electrocatalysis and activated carbon (AC) adsorption in a fluidization mode for p-nitrophenol (PNP) abatement, with special attention on probing the role of AC. Sparged by external gas (e.g., O(2)), the electrochemical reactor is actually a three-phase (gas, liquid, solid) reactor. By this one-step integrated process, the treatment efficiency was significantly promoted where PNP of initial concentration 150 mg l(-1) could be completely removed in no more than 30 min and it kept good performance for five consecutive runs, showing potential application for environmental remediation. In the integrated process, AC is in a dynamic state of adsorption and in situ electrochemical regeneration by the attack of electrogenerated hydroxyl radical on organic pollutants. When oxygen is sparged into the process, hydrogen peroxide can be formed by cathodic reduction and then decomposed by catalytic reaction on AC, which further promotes organic pollutants degradation.     

负载TiO2/Fe^3＋的玻璃纤维反应器光催化苯酚

以玻璃纤维为载体,将TiO2负载到其表面形成了空间玻璃纤维反应器,引入Fe3＋作为掺杂改性离子,形成了负载TiO2/Fe^3＋的空间玻璃纤维光催化反应器,并以高压汞灯为光源进行了光催化降解水中苯酚的实验研究,考察了影响苯酚光催化降解的因素,确定了在UV365-250 W光源照射下,pH为3-5,O2通入量1.0 L/（min.L）,反应器内上升流速为0.7 m/min等实验条件下,初始浓度为30 mg/L的苯酚废水经120 min光催化反应后,降解率可达到85%,矿化率可达80%。     

负载TiO2/Fe3+的玻璃纤维反应器光催化苯酚

以玻璃纤维为载体,将TiO2负载到其表面形成了空间玻璃纤维反应器,引入Fe3+作为掺杂改性离子,形成了负载TiO2/Fe3+的空间玻璃纤维光催化反应器,并以高压汞灯为光源进行了光催化降解水中苯酚的实验研究,考察了影响苯酚光催化降解的因素,确定了在UV365～250 W光源照射下,pH为3～5,O2通入量1.0 L/(min.L),反应器内上升流速为0.7 m/min等实验条件下,初始浓度为30 mg/L的苯酚废水经120 min光催化反应后,降解率可达到85%,矿化率可达80%。     

超声-Fenton法处理偶氮染料橙黄II的研究

以偶氮染料橙黄II为研究对象 ,考察了Fenton反应在超声辐射条件下 ,pH值、H2 O2 浓度、Fe2 + 离子浓度对COD去除率的影响。实验结果表明 ,超声对Fenton试剂处理偶氮染料橙黄II具有强化作用。超声条件下 ,当染料浓度为10 0mg/L、pH为 3.0、Fe2 + 离子浓度为 10mg/L、H2 O2 浓度为 4 0 0mg/L时 ,反应 90min ,COD去除率最高可达 93%。     

Persulfate oxidation for in situ remediation of TCE. I. Activated by ferrous ion with and without a persulfate-thiosulfate redox couple

The objective of the laboratory study is to examine the conditions under which transition metal ions (e.g., ferrous ion, Fe2+) could activate the persulfate anion (S2O8(2)-) to produce a powerful oxidant known as the sulfate free radical (SO4-*) with a standard redox potential of 2.6 V. The SO4-* is capable of destroying groundwater contaminants in situ such as trichloroethylene (TCE). Experiments using Fe2+ as an activator under various molar ratios of S2O8(2)-/Fe2+/TCE in an aqueous system indicated that partial TCE degradation occurred almost instantaneously and then the reaction stalled. Either destruction of SO4-* in the presence of excess Fe2+ or the rapid conversion of all Fe2+ to Fe3+ limited the ultimate oxidizing capability of the system. Sequential addition of Fe2+ in small increments resulted in an increased TCE removal efficiency. Therefore, it appeared that Fe2+ played an important role in generating SO4-*. An observation of oxidation-reduction potential (ORP) variations revealed that the addition of sodium thiosulfate (Na2S2O3) to the ferrous ion activated persulfate system could significantly decrease the strong oxidizing conditions. It was hypothesized that the thiosulfate induced reducing conditions might convert Fe3+ to a lower valence state of Fe2+, making the Fe2+ available to activate persulfate decomposition. The sequential addition of thiosulfate (S2O3(2)-), after the initial stalling of ferrous ion activated persulfate oxidation of TCE, resulted in an improvement in TCE removal. The ferrous ion activated persulfate-thiosulfate redox couple resulted in fairly complete TCE degradation in aqueous systems in a short time frame. In soil slurry systems, TCE degradation was slower in comparison to aqueous systems.     

Decomposing phenol by the hidden talent of ferromagnetic nanoparticles

Researches on modified Fenton reactions applied in phenol degradation have been focused on reducing secondary pollution and enhancing catalytic efficiency. Newly developed methods utilizing carriers, such as Resin and Nafion, to immobilize Fe(2+) could avoid iron ion leakage. However, the requirement of high temperature and the limited reaction efficiency still restrained them from broad application. Based on a recently discovered "hidden talent" of ferromagnetic nanoparticles (MNPs), we established a MNP-catalyzed phenol removal assay, which could overcome these limitations. Our results showed that the MNPs removed over 85% phenol from aqueous solution within 3h even at 16 °C. The catalytic condition was extensively optimized among a range of pH, temperature as well as initial concentration of phenol and H(2)O(2). TOC and GC/MS analysis revealed that about 30% phenol was mineralized while the rest became small molecular organic acids. Moreover the MNPs were thermo-stable and could be regenerated for at least five rounds. Thus, our findings open up a wide spectrum of environmental friendly applications of MNPs showing several attractive features, such as easy preparation, low cost, thermo-stability and reusability.     

Fenton氧化对硝基苯酚过程中Fe2+/Fe3+的氧化还原机制

Fenton降解对硝基苯酚(PNP)过程中,Fe2+经历一个快速氧化后快速还原,最后在高浓度水平上保持稳定的变化过程。通过分析中间产物的变化过程,发现有机中间产物氢醌和苯醌构成一对氧化还原体系催化Fe3+向Fe2+的转化,本研究从Fe2+/3+转化机制的角度进一步明确了Fenton降解PNP的机理。     

Kinetics of acetaminophen degradation by Fenton oxidation in a fluidized-bed reactor

Acetaminophen (ACT), an analgesic and antipyretic substance, is one of the most commonly detected pharmaceutical compound in surface waters and wastewaters. In this study, fluidized-bed Fenton (FB-Fenton) was used to decompose ACT into its final degradation products. The 1.45-L cylindrical glass reactor had inlet, outlet and recirculating sections. SiO₂ carrier particles were supported by glass beads with 2–4 mm in diameter. ACT concentration was determined by high performance liquid chromatography (HPLC). During the first 40 min of reaction, a fast initial ACT removal was observed and the “two-stage” ACT degradation conformed to a pseudo reaction kinetics. The effects of ferrous ion dosage and [Fe²⁺]/[H₂O₂] (FH ratio) were integrated into the derived pseudo second-order kinetic model. A reaction pathway was proposed based on the intermediates detected through SPME/GC–MS. The aromatic intermediates identified were hydroquinone, benzaldehydes and benzoic acids while the non-aromatic substances include alcohols, ketones, aldehydes and carboxylic acids. Rapid initial ACT degradation rate can be accomplished by high initial ferrous ion concentration and/or low FH ratio.     

Photocatalytic degradation of phenol using Ag core-TiO<Subscript>2</Subscript> shell (Ag@TiO<Subscript>2</Subscript>) nanoparticles under UV light irradiation

Ag@TiO₂ nanoparticles were synthesized by one pot synthesis method with postcalcination. These nanoparticles were tested for their photocatalytic efficacies in degradation of phenol both in free and immobilized forms under UV light irradiation through batch experiments. Ag@TiO₂ nanoparticles were found to be the effective photocatalysts for degradation of phenol. The effects of factors such as pH, initial phenol concentration, and catalyst loading on phenol degradation were evaluated, and these factors were found to influence the process efficiency. The optimum values of these factors were determined to maximize the phenol degradation. The efficacy of the nanoparticles immobilized on cellulose acetate film was inferior to that of free nanoparticles in UV photocatalysis due to light penetration problem and diffusional limitations. The performance of fluidized bed photocatalytic reactor operated under batch with recycle mode was evaluated for UV photocatalysis with immobilized Ag@TiO₂ nanoparticles. In the fluidized bed reactor, the percentage degradation of phenol was found to increase with the increase in catalyst loading.     

两相分配式生物反应器处理高盐废水中的苯酚

采用新型两相分配式生物反应器(TPPB)和前期研究得到的高效苯酚降解菌对高盐废水中苯酚的降解进行研究,研究中确定煤油为反应系统的最佳有机溶剂,并考察了废水苯酚含量、废水盐度以及搅拌器搅拌速度对苯酚降解的影响。结果表明,反应系统能正常降解苯酚含量为1 000～2 500 mg/L的高盐苯酚废水;反应系统在含盐量为100 g NaCl/L、搅拌速度为50 r/min的运行工况条件下,降解时间缩短为52 h,总酚去除率为20.58 mg/(L.h)。     

The system design of UV-assisted catalytic oxidation process--degradation of 2,4-D

Unlike the conventional first- or second-order model, a novel approach to design for the removal of 2,4-dichlorophenoxy (2,4-D) by the UV-catalytic oxidation process (UVCOP) was investigated. Two distinctive parameters, initial decay rate and maximum oxidative capacity, were characterized. By using these parameters, the performance of the degradation of 2,4-D by UVCOP regarding to the reagent dosages could be successfully predicted. Low concentrations of ferrous ion was found to be a rate-limiting factor for the process while the dosage of hydrogen peroxide was concluded as a dominant species in determining the maximum oxidation capacities. This information can be used to optimize the treatment process and achieve the expected performance target; an "optimal-dose model" was developed accordingly. The model is an intelligent and useful tool to evaluate the optimal doses of hydrogen peroxide with the minimum dose of ferrous ion, which leads to a better design of the treatment process.