Removal of phenol from aqueous solution by coupling alternating current with biosorption

Environmental Science and Pollution Research - The present research was devoted to water decontamination through the valorization of cellulosic fibers for the preparation of performing biosorbent,...     

Degradation of nitrogen-heterocyclic compounds by anodic oxidation and electro-Fenton methods.

This study describes the degradation of nitrogen-heterocyclic compounds (NHCs) by anodic oxidation and electro-Fenton. Using indole as a model nitrogen-heterocyclic compound, the removal of indole reached 68% and 97% by anodic oxidation and electro-Fenton, respectively, while the decay of TOC was 15% and 38% correspondingly. By the analysis of ultraviolet-visible spectra and liquid chromatography/mass spectrum, the degradation mechanism of indole by electro-Fenton was proposed as hydroxyl oxidation and anodic oxidation. The degradation of other NHCs including quinoline, isoquinoline and pyridine by anodic oxidation and electro-Fenton revealed the same sequence: quinoline approximately equal isoquinoline > indole > pyridine. A significant correlation between ln k (natural logarithm of rate constants) and E(LUMO) (the energy of the lowest unoccupied molecular orbit) was obtained by quantitative structure-activity relationship analysis. Degradation of coking plant wastewater showed the removal of COD and TOC were 42% and 22% respectively after 180 min treatment by electro-Fenton.     

Degradation of paracetamol by advance oxidation processes using modified reticulated vitreous carbon electrodes with TiO2 and CuO/TiO2/Al2O3

The degradation of paracetamol in aqueous solutions in the presence of hydrogen peroxide was carried out by photochemistry, electrolysis and photoelectrolysis using modified 100 pores per inch reticulated vitreous carbon electrodes. The electrodes were coated with catalysts such as TiO₂ and CuO/TiO₂/Al₂O₃ by electrophoresis followed by heat treatment. The results of the electrolysis with bare reticulated vitreous carbon electrodes show that 90% paracetamol degradation occurs in 4 h at 1.3 V vs. SCE, forming intermediates such as benzoquinone and carboxylic acids followed by their complete mineralisation. When the electrolysis was carried out with the modified electrodes such as TiO₂/RVC, 90% degradation was achieved in 2 h while with CuO/TiO₂/Al₂O₃/RVC, 98% degradation took only 1 h. The degradation was also carried out in the presence of UV reaching 95% degradation with TiO₂/RVC/UV and 99% with CuO/TiO₂/Al₂O₃/RVC/UV in 1 h. The reactions were followed by spectroscopy UV-Vis, HPLC and total organic carbon analysis. These studies show that the degradation of paracetamol follows a pseudo-first order reaction kinetics.     

Mineralization of paracetamol in aqueous medium by anodic oxidation with a boron-doped diamond electrode

The degradation of 100ml of solutions with paracetamol (N-(4-hydroxyphenyl)acetamide) up to 1 g l(-1) in the pH range 2.0-12.0 has been studied by anodic oxidation in a cell with a boron-doped diamond (BDD) anode and a graphite cathode, both of 3-cm2 area, by applying a current of 100, 300 and 450 mA between 25 and 45 degrees C. Complete mineralization is always achieved due to the great concentration of hydroxyl radical (*OH) generated at the BDD surface, with release of NH4+ and NO3- ions. The mineralization rate is pH-independent, increases with increasing applied current and temperature, but decreases when drug concentration raises from 315 mg l(-1). Reversed-phase chromatography revealed a similar complex paracetamol decay in acid and alkaline media. Ion-exclusion chromatography allowed the detection of oxalic and oxamic acids as ultimate carboxylic acids. When the same solutions have been comparatively treated with a Pt anode, a quite poor mineralization is found because of the production of much lower *OH concentration. Under these conditions, the degradation rate is enhanced in alkaline medium and polymerization of intermediates is favored in concentrated solutions. Paracetamol can be completely destroyed with Pt and its kinetics follows a pseudo-first-order reaction with a constant rate independent of pH.     

臭氧/高锰酸盐预氧化对生物过滤净水效能的影响

比较了臭氧(O3)和高锰酸盐复合药剂(PPC)对水源水预氧化的助凝效果及其对后续陶粒生物过滤净水效能的影响.结果表明,两种预氧化剂投加量均为2 mg/L时,PPC的助凝效果较为明显,浊度和溶解性有机碳(DOC)的去除率分别由未投加氧化剂时的85.7%和24.2%提高到88.3Z和35.2%;O3能够增加沉淀后水的可生化性,使特征紫外吸光度(SUVA)由0.97L/(m·mg)降至0.89 L/(m·mg).PPC预氧化有助于生物过滤对浊度的稳定去除,而O3预氧化则有助于生物过滤对DOC的去除.与O3预氧化相比,PPC预氧化有利于后续生物过滤运行初期对NH4 -N的去除,二者后续生物过滤在前3个月对NH4 -N的平均去除率分别为26.6%和73.1%,运行后期二者NH4 -N去除率接近.当进水NH4 -N大于2.0 mg/L时,DO是其去除的主要限制因素.     

纳米TiO2光催化氧化去除水中痕量双氯芬酸的研究

以TiCl4为前驱体,采用水解法经不同温度煅烧制备了具有不同理化性能的纳米TiO2光催化剂。利用X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、物理吸附仪、紫外—可见光漫反射吸收光谱(UV-Vis DRS)等手段对纳米TiO2的晶相结构、粒径、孔径分布以及禁带宽度等进行了表征。以蒸馏水配制的双氯芬酸溶液为目标物,进行了纳米TiO2光催化氧化去除双氯芬酸的活性测试,研究了纳米TiO2的理化性能与光催化氧化活性之间的关系。结果表明,经400℃煅烧制得的纳米TiO2样品具有最高的光催化氧化活性,其在紫外光照射60min下对双氯芬酸的去除率为98%左右,比单独紫外光照射高出85百分点。纳米TiO2光催化氧化去除双氯芬酸的反应近似一级反应动力学模型,其中经400℃煅烧制得的纳米TiO2光催化氧化去除双氯芬酸的表观反应速率常数为0.054 54min-1,是普通商用TiO2的2倍左右,与德国Degussa P-25TiO2的光催化氧化活性最相近。     

掺杂锰矿粉的PbO2复合电极的制备与应用

采用高压塑片法制备了纯PbO2电极及掺杂锰矿粉的PbO2复合电极,通过扫描电镜、加速寿命测试对电极性能进行了考察,并探讨了用PbO2复合电极对弱酸性桃红BS溶液进行的电催化降解机制和工艺条件.结果表明.PbO2复合电极的使用寿命是纯PbO2电极的3.3倍;在所考察的范围内,随着电流密度的增大,染料转化率和COD去除率均随之增加-当电流密度由70mA/cm2增加到90 mA/cm2时,染料转化率和COD去除率增加趋势减缓;溶液pH对染料降解有影响,弱酸性桃红BS溶液在强酸和强碱条件下的降解效果较好,pH在3.98～7.99时,染料转化率和COD去除率变化不大;染料转化率和COD去除率均随着电解时间呈递增关系,3.0 h后上升趋势逐渐减缓;支持电解质为NaCl时,能使染料转化率迅速提高,但其COD去除率不是很高;支持电解质为KNO3时,能显著提高弱酸性桃红BS溶液的COD去除率,0.5 h时COD去除率达到83%以上.另外,通过加入羟自由基清除剂叔丁醇的研究表明,在弱酸性桃红BS的降解过程中,有羟自由基产生并参与了催化降解反应.     

Degradation of anti-inflammatory drug ketoprofen by electro-oxidation: comparison of electro-Fenton and anodic oxidation processes

The electrochemical degradation of the nonsteroidal anti-inflammatory drug ketoprofen in tap water has been studied using electro-Fenton (EF) and anodic oxidation (AO) processes with platinium (Pt) and boron-doped diamond (BDD) anodes and carbon felt cathode. Fast degradation of the parent drug molecule and its degradation intermediates leading to complete mineralization was achieved by BDD/carbon felt, Pt/carbon felt, and AO with BDD anode. The obtained results showed that oxidative degradation rate of ketoprofen and mineralization of its aqueous solution increased by increasing applied current. Degradation kinetics fitted well to a pseudo-first-order reaction. Absolute rate constant of the oxidation of ketoprofen by electrochemically generated hydroxyl radicals was determined to be (2.8?±?0.1)?×?10⁹ M^?1 s^?1 by using competition kinetic method. Several reaction intermediates such as 3-hydroxybenzoic acid, pyrogallol, catechol, benzophenone, benzoic acid, and hydroquinone were identified by high-performance liquid chromatography (HPLC) analyses. The formation, identification, and evolution of short-chain aliphatic carboxylic acids like formic, acetic, oxalic, glycolic, and glyoxylic acids were monitored with ion exclusion chromatography. Based on the identified aromatic/cyclic intermediates and carboxylic acids as end products before mineralization, a plausible mineralization pathway was proposed. The evolution of the toxicity during treatments was also monitored using Microtox method, showing a faster detoxification with higher applied current values.     

Electrochemical degradation of Acid Blue and Basic Brown dyes on Pb/PbO2 electrode in the presence of different conductive electrolyte and effect of various operating factors

Electrocatalytic degradation of Acid Blue and Basic Brown dyes from simulated wastewater on lead dioxide anode was investigated in different conductive electrolytes. It was shown that complete degradation of these dyes is dependent primarily on type and concentration of the conductive electrolyte. The highest electrocatalytic activity was achieved in the presence of NaCl (2g/l) and could be attributed to indirect oxidation of the investigated dyes by the electrogenerated hypochlorite ions formed from the chloride oxidation. In addition, contribution from direct oxidation could also be possible via reaction of these organic compounds with the electrogenerated hydroxyl radicals adsorbed on the lead dioxide surface. In the presence of NaOH, the electrocatalytic activity of the employed anode was not comparable to that in NaCl due primarily to the absence of chloride. This indicates that dyes degradation in NaOH occurs exclusively via direct electrochemical process. However, in H2SO4, the electrode performance was poor due partially to the absence of chloride from the conductive solution. The possibility of electrode poisoning as a result of growth of adherent film on the anode surface or production of stable intermediates not easily further oxidized by direct electrolysis in H2SO4 might also be accountable for the poor performance observed in this conductive electrolyte. Optimizing the conditions that ensure effective electrochemical degradation of Acid Blue and Basic Brown dyes on lead dioxide electrode necessitates the control of all the operating factors.     

Photocatalytic oxidation of xenobiotics in water with immobilized TIO2 on agitator

Abstract

A novel photocatalytic oxidation reactor, using Degussa P‐25 T_iO₂ as a stationary phase with a thickness of 1.5–2.0 um on the blades of agitator, was developed to study the photocatalytic oxidation of xenobiotics. Particularly in this device, separation of photocatalyst from the purified water after oxidation reaction was not necessary, and no other aeration equipment was required to supply oxygen. To examine the efficiency of this device, photocatalytic degradation of xenobiotic organics such as carbofuran was studied as an example. Results indicated that carbofuran could be degraded completely with mineralization efficiency of 20 % after 6 hours of oxidation under the imposed conditions. The mineralization rate of carbofuran was found to follow the pseudo‐first order reaction kinetics. Moreover, the rate constant of mineralization was found to be proportional to T_iO₂ film area and the square root of UV light intensity. These results implied the mineralization efficiency of carbofuran could be improved through increasing T_iO₂ film area and UV light intensity. Accordingly, this novel device showed potential application for degrading xenobiotics in water.     

Photocatalytic oxidation of xenobiotics in water with immobilized TiO2 on agitator

A novel photocatalytic oxidation reactor, using Degussa P-25 TiO2 as a stationary phase with a thickness of 1.5-2.0 um on the blades of agitator, was developed to study the photocatalytic oxidation of xenobiotics. Particularly in this device, separation of photocatalyst from the purified water after oxidation reaction was not necessary, and no other aeration equipment was required to supply oxygen. To examine the efficiency of this device, photocatalytic degradation of xenobiotic organics such as carbofuran was studied as an example. Results indicated that carbofuran could be degraded completely with mineralization efficiency of 20% after 6 hours of oxidation under the imposed conditions. The mineralization rate of carbofuran was found to follow the pseudo-first order reaction kinetics. Moreover, the rate constant of mineralization was found to be proportional to TiO2 film area and the square root of UV light intensity. These results implied the mineralization efficiency of carbofuran could be improved through increasing TiO2 film area and UV light intensity. Accordingly, this novel device showed potential application for degrading xenobiotics in water.     

On the performance of Fe and Fe,F doped Ti-Pt/PbO2 electrodes in the electrooxidation of the Blue Reactive 19 dye in simulated textile wastewater

The electrochemical performance of pure Ti–Pt/β-PbO₂ electrodes, or doped with Fe and F (together or separately), in the oxidation of simulated wastewaters containing the Blue Reactive 19 dye (BR-19), using a filter-press reactor, was investigated and then compared with that of a boron-doped diamond electrode supported on a niobium substrate (Nb/BDD). The electrooxidation of the dye simulated wastewater (volume of 0.1 l, with a BR-19 initial concentration of 25 mg l⁻¹) was carried out under the following conditions: current density of 50 mA cm⁻², volume flow rate of 2.4 l h⁻¹, temperature of 25 °C and electrode area of 5 cm². The performances of the electrodes in the dye decolorization were quite similar, achieving 100% decolorization, and in some cases 90% decolorization was achieved by applying only ca. 0.3 A h l⁻¹ (8 min of electrolysis). The reduction of the simulated wastewater organic load, monitored by its total organic carbon content (TOC), was greater for the Ti–Pt/β-PbO₂–Fe,F electrode obtained from an electrodeposition bath containing 1 mM Fe³⁺ and 30 mM F⁻. In this case, after 2 h of electrolysis the obtained TOC reduction was 95%, while for the pure β-PbO₂ and the Nb/BDD electrodes the reductions were 84% and 82%, respectively.     

Heterogeneous photocatalytic oxidation of organics for air purification by near UV irradiated titanium dioxide

The photocatalytic degradation of high concentrations of various organic pollutants (acetone, 2-propanol and toluene) in dry and humid air streams was carried out using a specially designed photoreactor based on the UV-TiO2 principle. The influence of several parameters which control the destruction efficiency (flow rate, initial contaminant and water vapour concentration, temperature and light intensity) has been studied. The conversion was maximal at room temperature, low flow rates and low initial contaminant concentrations. The presence of water in the inlet stream strongly affected the performance of the catalyst. The primary oxidation product of 2-propanol was acetone.     

La掺杂SnO2/Ti电极电催化降解邻硝基苯酚

采用凝胶一溶胶法制备了La掺杂SnO2/Ti电极并用于邻硝基苯酚废水的电解研究.分析了电流密度、电极距离、溶液初始pH对邻硝基苯酚电解效果的影响,确定了最佳电解条件.结果表明,La/Sn(摩尔比)为0.03,热处理温度为450℃下制备的La掺杂SnO2/Ti电极对邻硝基苯酚的降解效果最好.当电流密度为20 mA/cm2,电极距离为2 cm,溶液初始pH为6～7时,电解180 min后的邻硝基苯酚的降解率可达95.1%.利用液相色谱和离子色谱检测了邻硝基苯酚电解产物,并初步分析了邻硝基苯酚的降解途径.     

Degradation of 1,4-dioxane in water with heat- and Fe2+-activated persulfate oxidation

This research investigated the 1,4-dioxane (1,4-D) degradation efficiency and rate during persulfate oxidation at different temperatures, with and without Fe²⁺ addition, also considering the effect of pH and persulfate concentration on the oxidation of 1,4-D. Degradation pathways for 1,4-D have also been proposed based on the decomposition intermediates and by-products. The results indicate that 1,4-D was completely degraded with heat-activated persulfate oxidation within 3–80 h. The kinetics of the 1,4-D degradation process fitted well to a pseudo-first-order reaction model. Temperature was identified as the most important factor influencing the 1,4-D degradation rate during the oxidation process. As the temperature increased from 40 to 60 °C, the degradation rate improved significantly. At 40 °C, the addition of Fe²⁺ also increased the 1,4-D degradation rate. Interestingly, at 50 and 60 °C, the 1,4-D degradation rate decreased slightly with the addition of Fe²⁺. This reduced degradation rate may be attributed to the rapid conversion of Fe²⁺ to Fe³⁺ and the production of an Fe(OH)₃ precipitate which limited the ultimate oxidizing capability of persulfate with Fe²⁺ under higher temperatures. Higher persulfate concentrations led to higher 1,4-D degradation rates, but pH adjustment had no significant effect on the 1,4-D degradation rate. The identification of intermediates and by-products in the aqueous and gas phases showed that acetaldehyde, acetic acid, glycolaldehyde, glycolic acid, carbon dioxide, and hydrogen ion were generated during the persulfate oxidation process. A carbon balance analysis showed that 96 and 93 % of the carbon from the 1,4-D degradation were recovered as by-products with and without Fe²⁺ addition, respectively. Overall, persulfate oxidation of 1,4-D is promising as an economical and highly efficient technology for treatment of 1,4-D-contaminated water.     

New TiO2/C sol-gel electrodes for photoelectrocatalytic degradation of sodium oxalate

This paper reports the preparation of carbon doped TiO2 electrodes by a modification of a sol-gel route. The electrodes have been characterized by measuring their photocurrent, as a function of applied potential. Their photoelectrocatalytic activity, relative to similar sol-gel electrodes without carbon, has been assessed by measuring the decomposition of a 10 mM sodium oxalate solution. Measurements have been made on electrodes prepared with 2%, 5% and 10% of active carbon. The highest photocurrents and the highest photoelectrocatalytic activity were both obtained with electrodes prepared by heating, at 600 degrees C, electrodes prepared with 5% of active carbon. All the electrodes showed evidence of enhanced photocatalytic activity at 1.2 V. Five percent addition of C double the measured rates of photodegradation, even though, in these preliminary studies, no attempt has been made to optimize the type of carbon or the details of the electrode preparation.     

Degradation of the herbicide 2,4-DP by anodic oxidation, electro-Fenton and photoelectro-Fenton using platinum and boron-doped diamond anodes

This paper reports the degradation of 2,4-DP (2-(2,4-dichlorophenoxy)-propionic acid) solutions of pH 3.0 by environmentally friendly electrochemical methods such as anodic oxidation, electro-Fenton and photoelectro-Fenton with a Pt or boron-doped diamond (BDD) anode. In the two latter techniques an O(2)-diffusion cathode was used and 1.0mM Fe(2+) was added to the solution to give hydroxyl radical (*OH) from Fenton's reaction between Fe(2+) and H(2)O(2) generated at the cathode. All treatments with BDD are viable to decontaminate acidic wastewaters containing 2,4-DP since they give complete mineralization, with loss of chloride ion, at high current due to the great production of oxidant *OH at the BDD surface favoring the destruction of final carboxylic acids. *OH formed from Fenton's reaction destroys more rapidly aromatic products, making the electro-Fenton and photoelectro-Fenton processes much more efficient than anodic oxidation. UVA light in photoelectro-Fenton with BDD has little effect on the degradation rate of pollutants. The comparative procedures with Pt lead to slower decontamination because of the lower oxidizing power of this anode. The effect of current on the degradation rate and efficiency of all methods is studied. The 2,4-DP decay always follows a pseudo-first-order kinetics. Chlorohydroquinone, chloro-p-benzoquinone and maleic, fumaric, malic, lactic, pyruvic, acetic, formic and oxalic acids are detected as products by chromatographic techniques. A general sequence accounting for by the reaction of all these intermediates with the different oxidizing agents is proposed.     

Highly efficient degradation of ofloxacin by UV/Oxone/Co2+ oxidation process

Introduction

In this study, UV/Oxone/Co²⁺ oxidation process was applied to degradation of ofloxacin (OFL) in the presence of Co²⁺ as the catalytic and Oxone as the oxidant. The operation parameters including pH, temperature, dosages of reagents, and reaction time were studied in detail.

Results

The results showed that the optimum conditions for the UV/Oxone/Co²⁺ processes were determined as follows: temperature?=?25°C, pH?=?5.0, [Oxone]?=?0.6?mmol/L, [Oxone]/[Co²⁺]?=?1,000, and reaction time?=?60?min. Under these conditions, 100% of the OFL degraded. The kinetics was also studied, and degradation of OFL by the UV/Oxone/Co²⁺ process could be described by first-order kinetics.

Conclusions

Mineralization of the process was investigated by measuring the total organic carbon (TOC), and the TOC decreased by 87.0% after 60?min. This process could be used as a pretreatment method for wastewater containing ofloxacin.     

UV/H2O2联合氧化法去除畜禽养殖废水中抗生素

随着畜禽养殖业的迅猛发展,畜禽养殖废水污染问题日益突出,尤其是养殖过程中大量使用抗生素,致使畜禽养殖废水含有抗生素,成为一类新型环境危害污染物.如何有效去除畜禽养殖废水中的抗生素,成为国内外研究热点.采用UV/H2O2联合氧化法去除畜禽养殖废水中抗生素(磺胺甲恶唑、磺胺噻唑、磺胺甲噻二唑、磺胺二甲氧嘧啶、磺胺二甲嘧啶)...     

Fate of citalopram during water treatment with O3, ClO2, UV and Fenton oxidation

In the present study we investigate the fate of citalopram (CIT) at neutral pH using advanced water treatment technologies that include O₃, ClO₂ oxidation, UV irradiation and Fenton oxidation. The ozonation resulted in 80% reduction after 30 min treatment. Oxidation with ClO₂ removed >90% CIT at a dosage of 0.1 mg L⁻¹. During UV irradiation 85% reduction was achieved after 5 min, while Fenton with addition of 14 mg L⁻¹ (Fe²⁺) resulted in 90% reduction of CIT. During these treatment experiments transformation products (TPs) were formed from CIT, where five compounds were identified by using high resolution and tandem mass spectrometry. Among these desmethyl-citalopram and citalopram N-oxide have been previously identified as human metabolites, while three are novel and published here for the first time. The three TPs are a hydroxylated dimethylamino-side chain derivative, a butyrolactone derivative and a defluorinated derivative of CIT.