Fe (III) supported on resin as effective catalyst for the heterogeneous oxidation of phenol in aqueous solution

FeIII supported on resin as an effective catalyst for oxidation was prepared and applied for the degradation of aqueous phenol. Phenol was selected as a model pollutant and the catalytic oxidation was carried out in a batch reactor using hydrogen peroxide as the oxidant. The influent factors on oxidation, such as catalyst dosage, H2O2 concentration, pH, and phenol concentration were examined by considering both phenol conversion and chemical oxygen demand (COD) removal. The FeIII-resin catalyst possesses a high oxidation activity for phenol degradation in aqueous solution. The experimental results of this study show that almost 100% phenol conversion and over 80% COD removal can be achieved with the FeIII-resin catalyst catalytic oxidation system. A series of prepared resin were investigated for improving the oxidation efficiency. It was found that the reaction temperature and initial pH in solution significantly affected both of phenol conversion and COD removal efficiency. The activity of the catalyst significantly decreased at high pH, which was similar to the Fenton-like reaction mechanism. Results in this study indicate that the FeIII-resin catalytic oxidation process is an efficient method for the treatment of phenolic wastewater.     

Application of Brassica napus hairy root cultures for phenol removal from aqueous solutions

Phenolic compounds present in the drainage from several industries are harmful pollutants and represent a potential danger to human health. In this work we have studied the removal of phenol from water using Brassica napus hairy roots as a source of enzymes, such as peroxidases, which were able to oxidise phenol. These hairy roots were investigated for their tolerance to highly toxic concentrations of phenol and for the involvement of their peroxidase isoenzymes in the removal of phenol. Roots grew normally in medium containing phenol in concentrations not exceeding 100 mg l(-1), without the addition of H(2)O(2). However, roots were able to remove phenol concentrations up to 500 mg l(-1), in the presence of H(2)O(2), reaching high removal efficiency, within 1h of treatment and over a wide range of pH (4-9). Hairy roots could be re-used, at least, for three to four consecutive cycles. Peroxidase activity gradually decreased to approximately 20% of the control, at the fifth cycle. Basic and near neutral isoenzymes (BNP) decreased along time of recycling while acidic isoenzymes (AP) remained without changes. Although both group of isoenzymes would be involved in phenol removal, AP showed higher affinity and catalytic efficiency for phenol as substrate than BNP. In addition, AP retained more activity than BNP after phenol treatment. Thus, AP appears to be a promising isoenzyme for phenol removal and for application in continuous treatments. Furthermore, enzyme isolation might not be necessary and the entire hairy roots, might constitute less expensive enzymatic systems for decontamination processes.     

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。     

Mineralization of phenol by Ce(IV)-mediated electrochemical oxidation in methanesulphonic acid medium: a preliminary study

The mediated electrochemical oxidation (MEO) process using cerium(IV) in methanesulphonic acid (MSA) as the oxidizing medium was employed for the mineralization of phenol in batch and continuous feeding modes. Although nitric acid was an extensively studied electrolyte for organic mineralization reactions in MEO processes it does possess the problem of NO(x) gas production during the reduction of nitric acid in the cathode compartment of the electrochemical cell. This problem could be circumvented by proper choice of the electrolyte medium such as MSA. The mediator cerium in MSA solution was first oxidized to higher oxidation state using an electrochemical cell. The produced Ce(IV) oxidant was then used for the destruction of phenol. It was found that phenol could be mineralized to CO2 by Ce(IV) in MSA. The evolved CO2 was continuously measured and used for the calculation of destruction efficiency. The destruction efficiency was observed to be 85% based on CO2 evolution for 1000 ppm phenol solution at 80 degrees C in continuous feed mode.     

NiO/AC催化臭氧氧化去除水中的苯酚

采用低温湿式浸渍法制备了负载氧化镍/活性炭(简称NiO/AC)催化剂。在不同pH、叔丁醇浓度等条件下,对NiO/AC与臭氧联合催化臭氧氧化苯酚的降解效果等进行了研究。用XRD、SEM及BET技术分析了活性炭与催化剂的组成、形貌及结构变化。结果表明,镍以棒状氧化镍的形式负载在活性炭表面,与AC相比,NiO/AC比表面积减少了47.9%。在O3/NiO/AC与苯酚的反应体系中,反应遵循羟基自由基(HO.)机理,苯酚的去除率比单独臭氧氧化提高了29%,且与溶液pH呈正相关。NiO/AC催化性能较稳定,镍离子最大析出浓度仅为7 mg/L,可重复使用。     

CuO / 过硫酸氢钾体系催化氧化苯酚简

本论文通过直接沉淀法制备了CuO催化剂,结合过硫酸氢钾,在常温常压下催化氧化处理苯酚模拟废水。采用电子显微镜（SEM）、X射线粉末衍射（XRD）对催化剂进行了表征,并研究了反应过程中各影响因素对降解效率的影响。实验结果表明,在催化剂用量为0.2 g/L,氧化剂浓度为0.25 g/L,pH值为7,反应时间为60 min的条件下,浓度为50 mg/L的苯酚降解率可达100%,TOC去除率达84%。进一步实验表明,催化剂具有良好的重复使用能力。最后,通过自由基捕捉实验,考察了体系中的自由基种类,并根据实验结果,讨论了CuO/过硫酸氢钾体系的催化降解机理。     

Synergetic effects of anodic-cathodic electrocatalysis for phenol degradation in the presence of iron(II)

A novel electrocatalysis method for phenol degradation was described using a β-PbO₂ anode modified with fluorine resin and a Ni–Cr–Ti alloy cathode. In case of air sparging at the cathodic zone, the techniques of anodic–cathodic electrocatalysis (ACEC) and ferrous ion catalyzed anodic–cathodic electrocatalysis (FACEC) in the presence of iron(II) were developed. Both of ACEC and FACEC were more effective than anodic electrocatalysis (AEC). The percentage of phenol eliminated by FACEC could increase by nearly 30% compared with that of AEC, and the current efficiency could reach to 70%. Important operating factors such as ferrous ion concentration, air-sparging rate and applied current were investigated and it was found that such beneficial effects could be achieved at a suitable current and ratio of the concentration of ferrous ion to the air sparged. The mechanism of phenol degradation is proposed to be the generation of hydroxyl radicals concerned with the two electrodes. Results also indicated that the process provided an efficient way to regenerate ferrous ion compared with the conventional Fenton's system.     

Isolation and characterization of a Rhodococcus strain with phenol-degrading ability and its potential use for tannery effluent biotreatment

Introduction

Wastewater derived from leather production may contain phenols, which are highly toxic, and their degradation could be possible through bioremediation technologies.

Materials, methods and results

In the present work, microbial degradation of phenol was studied using a tolerant bacterial strain, named CS1, isolated from tannery sediments. This strain was able to survive in the presence of phenol at concentrations of up to 1,000?mg/L. On the basis of morphological and biochemical properties, 16S rRNA gene sequencing, and phylogenetic analysis, the isolated strain was identified as Rhodococcus sp. Phenol removal was evaluated at a lab-scale in Erlenmeyer flasks and at a bioreactor scale in a stirred tank reactor. Rhodococcus sp. CS1 was able to completely remove phenol in a range of 200 to 1,000?mg/L in mineral medium at 30 ± 2?°C and pH 7 as optimal conditions. In the stirred tank bioreactor, we studied the effect of some parameters, such as agitation (200?C600 rpm) and aeration (1?C3?vvm), on growth and phenol removal efficiency. Faster phenol biodegradation was obtained in the bioreactor than in Erlenmeyer flasks, and maximum phenol removal was achieved at 400?rpm and 1 vvm in only 12?h. Furthermore, Rhodococcus sp. CS1 strain was able to grow and completely degrade phenols from tannery effluents after 9?h of incubation.

Conclusion

Based on these results, Rhodococcus sp. CS1 could be an appropriate microorganism for bioremediation of tannery effluents or other phenol-containing wastewaters.     

纳米四氧化三铁同步去除水中的Pb（Ⅱ）和Cr（Ⅲ）离子

采用共沉淀方法制备纳米四氧化三铁颗粒（MNPs）,通过扫描电镜（SEM）、X射线衍射（XRD）和光电子能谱分析（XPS）等表征手段对材料进行分析。同时考察了不同MNPs投加量、pH值、温度和初始浓度条件下对纳米四氧化三铁同步去除水中Pb（Ⅱ）和Cr（Ⅲ）离子的影响。结果表明,在pH为6.0、温度为25℃、纳米四氧化三铁的投加量为4.0 g/L下,吸附3 h后,Pb（Ⅱ）-Cr（Ⅲ）复合溶液中Pb的去除率为70.5%,Cr的去除率可达77.4%。pH和温度对去除过程影响较大。SEM和XRD分析证实成功制备了纳米级四氧化三铁,XPS结果表明,复合溶液中Pb（Ⅱ）和Cr（Ⅲ）离子的去除过程为同步吸附。吸附等温线研究说明,Pb（Ⅱ）的吸附是放热过程且为单相吸附;相反Cr（Ⅲ）的吸附是吸热过程且为多相吸附。重复利用实验表明,MNPs利用3次后对Pb和Cr的去除率几乎未受影响。因此,MNPs可用于实际工程中多种重金属离子共存废水的原位处理。     

The treatment of waste air containing phenol vapors in biotrickling filter

This research aimed at investigating the biodegradation of phenol contaminated-air streams in biotrickling filter. The effect of inlet concentration (200-1000 ppmv) and empty bed contact time (EBCT) (15-60 s) were investigated under steady state, transient and shock loading, and shutdown periods. Upon rapid start up operation, inlet phenol concentrations of up to 1000 ppmv did not significantly affect the performance of the biotrickling filter at EBCT of 60 s, so that removal efficiency was well greater than 99%. In addition, the EBCT as low as 30 s did not have detrimental effects on the efficiency of the bioreactor and phenol removal was greater than 99%. Decreasing the EBCT to 15s reduced the removal efficiency to around 92%. The maximum elimination capacity obtained in the biotrickling filter was 642 g(phenol) m(-3) h(-1), where the removal efficiency was only 57%. Results from the transient loading experiments revealed that the biotrickling filter could effectively handle the variations of the inlet loads without the phenol removal capacity being significantly affected.     

SO2-4/TiO2光催化降解苯酚

以工业硫酸氧钛为原料水解制得SO42-/TiO2光催化剂,并以苯酚为目标降解物,考察了SO24-/TiO2的光催化性能。结果表明:随着SO42-/TiO2制备过程中焙烧温度的升高,其光催化活性逐渐增加,650℃焙烧获得的SO24-/TiO2的光催化活性最好,此后再升高温度会因催化剂中硫的挥发而下降;在确定苯酚原液初始浓度为50 mg/L条件下,SO42-/TiO2的光催化降解苯酚的最佳工艺条件为反应时间2 h、苯酚pH为7、催化剂用量1 g/L。XRD、SEM和FTIR的分析结果显示实验温度下制得的SO42-/TiO2均为锐钛型TiO2;其间掺杂的SO24-在TiO2表面分散性较好,没有聚集成大的颗粒;红外分析的结果初步判定低温(<550℃)焙烧制得的催化剂SO42-在TiO2表面是螯合双配位吸附,高温焙烧时(>550℃)SO42-在TiO2表面是桥式配位吸附。     

高铁酸盐氧化降解水中苯酚的动力学及机理研究

以自制高铁酸钾(K₂FeO₄)为原料,探讨了影响高铁酸盐氧化降解苯酚的主要因素,并研究了苯酚降解的动力学特征和反应机理。结果表明,高铁酸盐加入量、pH值、持续搅拌、反应温度、反应时间都影响苯酚去除效果。其中高铁酸盐加入量是影响苯酚去除效果的关键因素,高铁酸盐氧化降解苯酚的最佳pH值范围为9～10,持续搅拌和提高反应温度只影响苯酚降解速率而不影响苯酚降解率。苯酚的降解过程遵循一级反应动力学模型。苯酚被高铁酸盐氧化生成CO₂、H₂O以及一部分难矿化的有机物。     

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.     

Metal-mediated chlorinated dibenzo-p-dioxin (CDD) and dibenzofuran (CDF) formation from phenols

Heterogeneous formation of chlorinated dibenzo-p-dioxins (CDDs) and dibenzofurans (CDFs) on CuCl2 from three phenols without ortho chlorine and one phenol with two ortho chlorines was studied in a flow reactor over a temperature range of 325-450 degrees C. Heated nitrogen gas streams containing 8% oxygen, 1.5% benzene vapor, and equal amounts of phenol, 3-chlorophenol, 3,4-dichlorophenol and 2,4,6-trichlorophenol vapor (700 ppmv, each) were passed through a 1 g particle bed of silica and 0.5% (Cu mass) CuCl2. Maximum product yields of greater than 1.4% phenol conversion to CDD and 5.7% phenol conversion to CDF were observed between 400 and 450 degrees C. CDDs formed with loss of one chlorine atom were favored. While total CDD/F yield varied with temperature, CDD/F homologue and isomer distributions did not vary significantly with temperature. Based on the results of experiments with single phenol precursors, phenol precursors could be assigned to all PCDD/F products. Of the chlorinated phenols without ortho chlorine that were studied, 3,4-dichlorophenol was found to have the greatest propensity to form CDFs.     

微波再生载苯酚活性炭过程中再生产物分析

研究了载氮气和无载气2种条件下,微波再生载苯酚活性炭过程中再生产物的成分和苯酚随再生过程的去向分布。结果表明,无载气时,微波功率越高,再生反应器内温度越高,吸附质的高温裂解反应越彻底,再生产物以挥发性气体为主,有机质种类很少;而当微波功率较低或载氮气再生时,反应器内温度相对较低,苯酚难以被彻底分解,再生产物中含多种复杂的链状或环状有机物。此外,载氮气时,经气提、挥发而去除的苯酚量约占总吸附量的一半,再生炭上无苯酚残留,活性炭吸附性能可完全恢复乃至优化;无载气时,经挥发而去除的苯酚量只有19.9%,其余大量苯酚则在微波作用下裂解或缩合为其他物质随尾气而去除,且再生炭上仍有少量苯酚未被解吸出来。因此,前者活性炭再生的效果优于后者。     

Kinetics of catalytic oxidation of benzene, n-hexane, and emission gas from a refinery oil/water separator over a chromium oxide catalyst

With the advances made in the past decade, catalytic incineration of volatile organic compounds (VOCs) has become the technology of choice in a wide range of pollution abatement strategies. In this study, a test was undertaken for the catalytic incineration, over a chromium oxide (Cr2O3) catalyst, of n-hexane, benzene, and an emission air/vapor mixture collected from an oil/water separator of a refinery. Reactions were carried out by controlling the feed stream to constant VOC concentrations and temperatures, in the ranges of 1300-14,700 mg/m3 and 240-400 degrees C, respectively. The destruction efficiency for each of the three VOCs as a function of influent gas temperature and empty bed gas residence time was obtained. Results indicate that n-hexane and the oil vapor with a composition of straight- and branch-chain aliphatic hydrocarbons exhibited similar catalytic incineration effects, while benzene required a higher incineration temperature or longer gas retention time to achieve comparable results. In the range of the VOC concentrations studied, at a given gas residence time, increasing the operating temperature of the catalyst bed increased the destruction efficiency. However, the much higher temperatures required for a destruction efficiency of over 99% may be not cost-effective and are not suggested. A first-order kinetics with respect to VOC concentration and an Arrhenius temperature dependence of the kinetic constant appeared to be an adequate representation for the catalytic oxidation of these volatile organics. Activation energy and kinetic constants were estimated for each of the VOCs. Low-temperature destruction of the target volatile organics could be achieved by using the Cr2O3 catalyst.     

An assessment of the suitable operating conditions for the CeO2/gamma-Al2O3 catalyzed wet air oxidation of phenol

It has been shown that the CeO2/gamma-Al2O3 catalyst is a feasible alternative to CeO2 for the catalytic wet air oxidation (CWAO) of phenol because it remains an effective catalyst and yet is cheaper to prepare. In this study, we found that the optimal cerium content in the CeO2/gamma-Al2O3 catalyst was 20 wt.%, regardless of catalyst loading. Furthermore, at 180 degrees C, with a phenol concentration of 1000 mg l(-1), and an O2 partial pressure of 1.0M Pa or 1.5M Pa, the optimal catalyst loading was 3.0 gl (-1). The efficacy of CWAO of phenol improved with O2 partial pressure, although the effects of O2 pressure were more significant between 0.5 MPa and 1.5 MPa than between 1.5 MPa and 2.0 MPa. After 2 h of reaction, approximately 100% phenol conversion and 80% total organic carbon (TOC) removal was recorded at 180 degrees C, 1000 mg l(-1) of phenol and 3.0 g l(-1) of catalyst. Because these percentages subsequently leveled off, it is suggested that 2 h is a suitable time over which to run the reaction. The efficacy of CWAO of phenol decreased as initial phenol concentration was raised (from 400 to 2500 mg l(-1)), with the exception of phenol conversion after about 2 h, for which 400 mg l(-1) produced the lowest phenol conversion figure. Higher phenol concentrations require both catalyst loading and O2 partial pressure to be increased to maintain high performance. For example, for 2000 mg l(-1) and 2500 mg l(-1) phenol, nearly 100% phenol conversion and 90% TOC removal after 4 h of reaction at 180 degrees C required 4.0 g l(-1) of catalyst and 2.0 MPa.     

CWAO of phenol using CeO2/gamma-Al2O3 with promoter--effectiveness of promoter addition and catalyst regeneration

The effect of promoter addition on activity of CeO(2)/gamma-Al(2)O(3) was assessed via the CWAO of phenol. Adding Cu as the promoter rendered the most effective performance, followed by Mn, although the performance of Mn-promoted catalyst was inferior to CeO(2)/gamma-Al(2)O(3). Mineralization of phenol was effectively implemented at 160 degrees C using Cu-promoted catalyst (Ce15Cu5). Furthermore, at 180 degrees C this catalyst produced about 100% conversion of phenol (1h) and 95% removal of chemical oxygen demand (4h), higher than that of CeO(2)/gamma-Al(2)O(3). In contrast, Mn-promoted catalyst (Ce15Mn5) required a temperature above 220 degrees C for acceptable performance. Activity of re-used catalyst declined noticeably, due to deposits of carbonaceous compounds and leaching of metal ions. Regeneration with acetone rinsing after the first run was effective in recovering activity of Ce15Cu5, although after a second run further regeneration with acetone rinsing had only a moderate effect, due to residual carbonaceous deposits and the additive effect of leached metal species in each run. As an alternative to acetone, HCl or HNO(3) solution (0.01 M) was less effective at regenerating activity. In promoted catalysts, leached metal ions accounted for the majority of mineralization of phenol, while the solid catalyst played a dual role of initiator and terminator of free radicals. Despite a superior catalytic performance, leaching of Cu(2+) from the promoted catalyst caused a severe decline in activity and poses the problem of secondary pollution of treated wastewater. Therefore, addition of Cu, as well as other metal species, is unfavorable in promoting the CeO(2)/gamma-Al(2)O(3) catalyst.     

Catalytic destruction of 1,2-dichlorobenzene on V2O5-WO3/Al2O3-TiO2 catalyst

Studies on the catalytic destruction of 1,2-dichlorobenzene were carried out on a specially constructed semi-technical equipment whose most important element was a catalytic reactor with a monolithic catalyst in the form of 150 x 150 x 100 mm cubes. A catalyst made from cordierite with an active layer composed of Al2O3 - 64 wt%, TiO2 - 26 wt%, V2O5 - 6.6 wt% and WO3 - 3.4 wt% was used. The reactor made it possible to carry out the process in the temperature range 150-350 degrees C, at variable catalyst loading and different velocities of gas flow through the reactor. The content of 1,2-dichlorobenzene in the air was analysed by a chromatographic method. A significant effect of catalyst loading and temperature on 1,2-dichlorobenzene destruction efficiency was observed and no effect of the linear flow velocity through the catalyst on o-dichlorobenzene destruction efficiency was reported. The applied vanadium-tungsten catalyst on a monolithic carrier made from TiO2/gamma-Al2O3 revealed very good activity that resulted in an over 80% efficiency of 1,2-dichlorobenzene destruction at the temperature around 250 degrees C at a very high catalyst loading reaching ca. 8200 h(-1). Additionally, in this study the kinetics of 1,2-dichlorobenzene decomposition was determined, specifying the order of reaction and dependence of the decomposition rate constant on temperature, using a simple power-rate law model.     

The effect of γ-Fe2O3 nanoparticles on Escherichia coli genome

Extensive production and application of γ-Fe₂O₃ magnetic nanoparticles (MNPs) has increased their potential risk on environment and human health. This report illustrates a genetic impact of γ-Fe₂O₃ magnetic nanoparticles (MNPs) on Escherichia coli (E. coli). After 3000-generation incubation with MNPs addition, obvious genomic variations were revealed by using repetitive extragenic palindromic PCR (rep-PCR) DNA fingerprint technique. The physicochemical interactions between MNPs and bacteria could be responsible for such genomic responses. It was revealed that Fe³⁺ concentration increased in the medium. Transmission electronic microscopy (TEM) and flow cytometry (FCM) analysis consistently demonstrated the occurrences of adsorption and membranes-internalization of MNPs outside and inside cells. Both increased Fe³⁺ ion and the uptake of MNPs facilitated Fe binding with proteins and DNA strands, resulting in enhancing the mutation frequency of E. coli. Our results would be of great help to assessing the potential impact of MNPs on human and environment.