Ozonation catalyzed by homogeneous and heterogeneous catalysts for degradation of DEHP in aqueous phase

Di-(2-ethyl hexyl) phthalate (DEHP), a recalcitrant and an endocrine disrupting chemical, was studied for its removal from wastewater by advanced oxidation process. The effects of pH, transition metal ions, and granular activated carbon (GAC) were investigated. Removal of DEHP increased with increase in pH and among metal ions Cr(III) was found to be the most active catalyst to remove DEHP. In the case of GAC, original carbon (G0) and GAC pre-ozonated in gas phase for 10 min (G10) were tested as catalysts in catalytic ozonation and found G0 to be more active than G10. This is because, during pre-ozonation, basic groups like chromene, pyrones and also graphene layers were oxidized to acidic surface oxygen groups. These basic surface groups are reported to be active catalytic centres for ozone decomposition into .OH which is a strong oxidant. According to kinetic manipulations, DEHP degradation rate constant due to .OH was affected by the catalyst while that due to direct ozonation is same in all cases with or without catalyst. G0 was doped with chromia gels (G0/CrA) to combine the benefits of homogeneous and heterogeneous catalysis. G0/CrA showed lower catalytic efficiency than that of only G0. This might be because of changes in surface structure of GAC caused by doping of chromia gel and changes in chemical nature of Cr(III) during formation of gel. A good correlation was found between the rate constants of ozone decay and DEHP degradation (R2=0.96). This correlation confirms that ozone decomposition into .OH is a critical factor for the activity of a catalyst during ozonation.     

CuFe2O4/activated carbon composite: a novel magnetic adsorbent for the removal of acid orange II and catalytic regeneration

CuFe2O4/activated carbon magnetic adsorbents, which combined the adsorption features of activated carbon with the magnetic and the excellent catalytic properties of powdered CuFe2O4, were developed using a simple chemical coprecipitation procedure. The prepared magnetic composites can be used to adsorb acid orange II (AO7) in water and subsequently, easily be separated from the medium by a magnetic technique. CuFe2O4/activated carbon magnetic adsorbents with mass ratio of 1:1, 1:1.5 and 1:2 were prepared. Magnetization measurements, BET surface area measurements, powder XRD and SEM were used to characterize the prepared adsorbents. The results indicate that the magnetic phase present is spinel copper ferrite and the presence of CuFe2O4 did not significantly affect the surface area and pore structure of the activated carbon. The adsorption kinetics and adsorption isotherm of acid orange II (AO7) onto the composites at pH 5.2 also showed that the presence of CuFe2O4 did not affect the adsorption capacity of the activated carbon. The thermal decomposition of AO7 adsorbed on the activated carbon and the composite was investigated by in situ FTIR, respectively. The results suggest that the composite has much higher catalytic activity than that of activated carbon, attributed to the presence of CuFe2O4. The variation of the adsorption capacity of the composites after several adsorption-regeneration cycles has also been studied.     

Effect of operational factors on bioregeneration of binary phenol and 4-chlorophenol-loaded granular activated carbon using PVA-immobilized biomass cryogels

The effects of dry biomass density in cryogel beads, shaking speed and initial concentration ratio of phenol to 4-chlorophenol (4-CP) on the bioregeneration efficiencies of binary phenol and 4-CP-loaded granular activated carbon (GAC) for phenol and 4-CP, respectively, were investigated under the simultaneous adsorption and biodegradation approach. The results revealed higher bioregeneration efficiencies of binary-loaded GAC for phenol and 4-CP at higher dry biomass density but moderate shaking speed. The optimum dry biomass density in cryogel beads and shaking speed for use in bioregeneration were found to be 0.01 g/mL and 250 rpm, respectively. With respect to the initial phenol to 4-CP concentration ratio, the bioregeneration efficiencies were lower under increasing phenol and 4-CP initial concentrations, respectively, with the effect being more conspicuous under increasing 4-CP concentration. Higher bioregeneration efficiencies were achieved with the use of immobilized rather than suspended biomasses.     

Effects of humic substances on the decomposition of 2,4-dichlorophenol by ozone after extraction from water into acetic acid through activated carbon

The objectives of this study are to clarify the behavior of humic substances throughout the processes of 2,4-dichlorophenol (2,4-DCP) adsorption on granular activated carbon (GAC) from water and extraction into acetic acid, and the influence of the extracted humic substances on the decomposition of 2,4-DCP by ozone in the acetic acid. The adsorption capacity of GAC for 2,4-DCP was not influenced by the humic substances preloaded to have equilibrium concentration of 24.9mg Cl(-1) (14.5mg Cg(-1)). The adsorption capacity of GAC for 2,4-DCP decreased to one tenth of new GAC after the first adsorption-extraction step because of only 16% desorption in the first step. However, 2,4-DCP adsorbed on GAC was completely extracted after the second step suggesting that GAC can be used as adsorbent to transfer 2,4-DCP from water to acetic acid. The concentration ratio of 2,4-DCP from water into acetic acid was around 2x10(5), whereas the concentration ratio of humic substances was about 3.5, indicating that 2,4-DCP was selectively adsorbed and extracted by this system. The first order degradation rate constant for 2,4-DCP by ozone in acetic acid increased with the addition of humic substances. The rate constant with 16mg Cl(-1) of humic substances was 2.6 times as high as that without humic substances. Humic substances behaved as a promoter for the degradation of 2,4-DCP by ozone.     

Degradation of 4-chlorophenol by microwave irradiation enhanced advanced oxidation processes

In this work the synergistic effects of several microwave assisted advanced oxidation processes (MW/AOPs) were studied for the degradation of 4-chlorophenol (4-CP). The efficiencies of the degradation of 4-CP in dilute aqueous solution for a variety of AOPs with or without MW irradiation were compared. The results showed that the synergistic effects between MW and H2O2, UV/H2O2, TiO2 photocatalytic oxidation (PCO) resulted in a high degradation efficiency for 4-CP. The potential of MW/AOPs for treatment of industrial wastewater is discussed.     

吸附-电化学氧化耦合处理对氯苯酚废水及动力学

以毡状活性炭纤维为阳极,不锈钢为阴极,吸附-电化学氧化耦合降解对氯苯酚废水进行了研究。考察了吸附或耦合电化学氧化过程、电流密度、支持电解质硫酸钠浓度和活性炭纤维重复使用对废水COD去除率的影响,结果表明,采用吸附-电化学氧化耦合方法,当电流密度7.6 mA/cm2支持电解质（硫酸钠）浓度为1 g/L,处理时间为180 min,4-CP废水COD去除率可达97.09%。毡状活性炭纤维对4-CP的静态吸附过程符合Langmiu吸附等温方程。建立了吸附-电化学氧化COD去除动力学模型,动力学模型参数表明,对于COD的去除,电化学氧化作用比吸附作用大。     

Effect of adsorbents coated with titanium dioxide on the photocatalytic degradation of propoxur

Photocatalytic oxidation of pesticides in aqueous media irradiated by UV light is a rapidly growing field of research. Therefore, the treatment technology for degradation of propoxur (an insecticide) using titanium dioxide coated on the supports such as activated carbon, zeolite, brick, quartz and glass beads, was performed in this research. Results show that GAC/TiO2 is the best complexing agent for oxidizing propoxur because of its adsorption properities. The others follow the sequence: plain TiO2 > glass beads > zeolite > brick > quartz. The degradation rate of propoxur with plain TiO2 is higher than that with TiO2/GAC complexing agent. But the mineralization rate of propoxur with plain TiO2 is lower than that with TiO2/GAC complexing agent. However, it can be concluded that using GAC as the support can improve the photocatalytic efficiency.     

Photochemical degradation and mineralization of 4-chlorophenol

INTENTION, GOAL, SCOPE, BACKGROUND: Since the intermediate products of some compounds can be more toxic and/or refractory than the original compund itself, the development of innovative oxidation technologies which are capable of transforming such compounds into harmless end products, is gaining more importance every day. Advanced oxidation processes are one of these technologies. However, it is necessary to optimize the reaction conditions for these technologies in order to be cost-effective. OBJECTIVE: The main objectives of this study were to see if complete mineralization of 4-chlorophenol with AOPs was possible using low pressure mercury vapour lamps, to make a comparison of different AOPs, to observe the effect of the existence of other ions on degradation efficiency and to optimize reaction conditions. METHODS: In this study, photochemical advanced oxidation processes (AOPs) utilizing the combinations of UV, UV/H2O2 and UV/H2O2/Fe2+ (photo-Fenton process) were investigated in labscale experiments for the degradation and mineralization of 4-chlorophenol. Evaluations were based on the reduction of 4-chlorophenol and total organic carbon. The major parameters investigated were the initial 4-chlorophenol concentration, pH, hydrogen peroxide and iron doses and the effect of the presence of radical scavengers. RESULTS AND DISCUSSION: It was observed that the 4-chlorophenol degradation efficiency decreased with increasing concentration and was independent of the initial solution pH in the UV process. 4-chlorophenol oxidation efficiency for an initial concentration of 100 mgl(-1) was around 89% after 300 min of irradiation in the UV process and no mineralization was achieved. The efficiency increased to > 99% with the UV/H2O2 process in 60 min of irradiation, although mineralization efficiency was still around 75% after 300 min of reaction time. Although the H2O2/4-CP molar ratio was kept constant, increasing initial 4-chlorophenol concentration decreased the treatment efficiency. It was observed that basic pHs were favourable in the UV/H2O2 process. The results showed that the photo-Fenton process was the most effective treatment process under acidic conditions. Complete disappearance of 100 mgl(-1) of 4-chlorophenol was achieved in 2.5 min and almost complete mineralization (96%) was also possible after only 45 min of irradiation. The efficiency was negatively affected from H2O2 in the UV/H2O2 process and Fe2+ in the photo-Fenton process over a certain concentration. The highest negative effect was observed with solutions containing PO4 triple ions. Required reaction times for complete disappearance of 100 mgl(-1) 4-chlorophenol increased from 2.5 min for an ion-free solution to 30 min for solutions containing 100 mgl(-1) PO4 triple ion and from 45 min to more than 240 min for complete mineralization. The photodegradation of 4-chlorophenol was found to follow the first-order law. CONCLUSION: The results of this study showed that UV irradiation alone can degrade 4-CP, although at very slow rates, but cannot mineralize the compound. The addition of hydrogen peroxide to the system, the so-called UV/H2O2 process, significantly enhances the 4-CP degradation rate, but still requires relatively long reaction periods for complete mineralization. The photo-Fenton process, the combination of homogeneous systems of UV/H2O2/Fe2+ compounds, produces the highest photochemical elimination rate of 4-CP and complete mineralization is possible to achieve in quite shorter reaction periods when compared with the UV/H2O2 process. RECOMMENDATIONS AND OUTLOOK: It is more cost effective to use these processes for only purposes such as toxicity reduction, enhancement of biodegradability, decolorization and micropollutant removal. However the most important point is the optimization of the reaction conditions for the process of concern. In such a case, AOPs can be used in combination with a biological treatment systems as a pre- or post treatment unit providing the cheapest treatment option. The AOP applied, for instance, can be used for toxicity reduction and the biological unit for chemical oxygen demand (COD) removal.     

Contribution of free radicals to chlorophenols decomposition by several advanced oxidation processes

The chemical decomposition of aqueous solutions of various chlorophenols (4-chlorophenol (4-CP), 2,4-dichlorophenol (2-DCP), 2,4,6-trichlorophenol (2,4,6-TCP) and 2,3,4,6-tetrachlorophenol (2,3,4,6-TeCP)), which are environmental priority pollutants, is studied by means of single oxidants (hydrogen peroxide, UV radiation, Fenton's reagent and ozone at pH 2 and 9), and by the Advanced Oxidation Processes (AOPs) constituted by combinations of these oxidants (UV/H2O2 UV/Fenton's reagent and O3/UV). For all these reactions the degradation rates are evaluated by determining their first-order rate constants and the half-life times. Ozone is more reactive with higher substituted CPs while OH* radicals react faster with those chlorophenols having lower number of chlorine atoms. The improvement in the decomposition levels reached by the combined processes, due to the generation of the very reactive hydroxyl radicals. in relation to the single oxidants is clearly demonstrated and evaluated by kinetic modeling.     

Degradation of 3,3′-iminobis-propanenitrile in aqueous solution by Fe0/GAC micro-electrolysis system

The degradation of 3,3′-iminobis-propanenitrile was investigated using the Fe⁰/GAC micro-electrolysis system. Effects of influent pH value, Fe⁰/GAC ratio and granular activated carbon (GAC) adsorption on the removal efficiency of the pollutant were studied in the Fe⁰/GAC micro-electrolysis system. The degradation of 3,3′-iminobis-propanenitrile was affected by influent pH, and a decrease of the influent pH values from 8.0 to 4.0 led to the increase of degradation efficiency. Granular activated carbon was added as cathode to form macroscopic galvanic cells between Fe⁰ and GAC and enhance the current efficiency of the Fe⁰/GAC micro-electrolysis system. The GAC could only adsorb the pollutant and provide buffer capacity for the Fe⁰/GAC micro-electrolysis system, and the macroscopic galvanic cells of the Fe⁰/GAC micro-electrolysis system played a leading role in degradation of 3,3′-iminobis-propanenitrile. With the analysis of the degradation products with GC–MS, possible reaction pathway for the degradation of 3,3′-iminobis-propanenitrile by the Fe⁰/GAC micro-electrolysis system was suggested.     

Removal of SO2 from O2-containing flue gas by activated carbon fiber (ACF) impregnated with NH3

Adsorption of SO(2) from the O(2)-containing flue gas by granular activated carbons (GACs) and activated carbon fibers (ACFs) impregnated with NH(3) was studied in this technical note. Experimental results showed that the ACFs were high-quality adsorbents due to their unique textural properties. In the presence of moisture, the desulphurization efficiency for the ACFs was improved significantly due to the formation of sulfuric acid. After NH(3) impregnation of ACF samples, nitrogen-containing functional groups (pyridyl C(5)H(4)N- and pyrrolyl C(4)H(4)N-) were detected on the sample surface by using an X-ray photoelectron spectrometer. These functional groups accounted for the enhanced SO(2) adsorption via chemisorption and/or catalytic oxidization.     

Heterogeneous and homogeneous catalytic ozonation of benzothiazole promoted by activated carbon: kinetic approach

Ozone oxidation combined with activated carbon adsorption (O(3)/AC) has recently started to be developed as a single process for water and wastewater treatment. While a number of aspects of aqueous ozone decomposition are well understood, the importance and relationship between aqueous ozone decomposition and organic contaminant degradation in the presence of activated carbon is still not clear. This study focuses on determining the contribution of homogeneous and heterogeneous reactions to organic contaminants removal in O(3)/AC system. Benzothiazole (BT) was selected as a target organic pollutant due to its environmental concern. A reactor system based on a differential circular flow reactor composed by a 19 cm(3) activated carbon fixed bed column and 1 dm(3) storage tank was used. Ozone was produced from pure and dry oxygen using an Ozocav ozone generator rated at 5 g O(3)h(-1). Experimental results show that BT removal rate was proportional to activated carbon dosage. Activated carbon surface contribution to BT oxidation reactions with ozone, increased with pH in absence of radical scavengers. The radical reaction contribution within the pH range 2-11 accounted for 67-83% for BT removal in O(3)/AC simultaneous treatment. Results suggest that at pH higher than the pH of the point of zero charge of the activated carbon dissociated acid groups such as carboxylic acid anhydrides and carboxylic acids present on activated carbon surface could be responsible for the observed increase in the ozone decomposition reaction rate. A simplified mechanism and a kinetic scheme representing the contribution of homogeneous and heterogeneous reactions on BT ozonation in the presence of activated carbon is proposed.     

Microwave process for volatile organic compound abatement

The CHA Corporation has completed the U.S. Air Force Phase II Small Business Innovation Research program to investigate the feasibility of using a novel microwave-based process for the removal and destruction of volatile organic compounds (VOCs) in effluents from noncombustion sources, such as paint booth ventilation streams. Removal of solvents by adsorption, followed by the regeneration of saturated granular activated carbon (GAC) by microwave energy, was achieved in a single fixed-bed reactor. Microwave regeneration of the fixed-bed-saturated carbon restored the original GAC adsorption capacity. After 20 adsorption/regeneration cycles, the adsorption capacity dropped from 13.5 g methyl ethyl ketone (MEK)/100 g GAC to 12.5 g MEK/100 g GAC. During microwave regeneration of the GAC fixed bed, the concentrated desorbed paint solvent was oxidized by passing the solvent mixture through a fixed bed of an oxidation catalyst mixed with silicon carbide in a microwave reactor. A 98% oxidation efficiency was consistently achieved from the oxidation of VOCs in the microwave catalytic reactor.     

Microwave Process for Volatile Organic Compound Abatement

ABSTRACT

The CHA Corporation has completed the U.S. Air Force Phase II Small Business Innovation Research program to investigate the feasibility of using a novel microwave-based process for the removal and destruction of volatile organic compounds (VOCs) in effluents from noncombustion sources, such as paint booth ventilation streams. Removal of solvents by adsorption, followed by the regeneration of saturated granular activated carbon (GAC) by microwave energy, was achieved in a single fixed-bed reactor. Microwave regeneration of the fixed-bed-saturated carbon restored the original GAC adsorption capacity. After 20 adsorption/regeneration cycles, the adsorption capacity dropped from 13.5 g methyl ethyl ketone (MEK)/100 g GAC to 12.5 g MEK/100 g GAC. During microwave regeneration of the GAC fixed bed, the concentrated desorbed paint solvent was oxidized by passing the solvent mixture through a fixed bed of an oxidation catalyst mixed with silicon carbide in a microwave reactor. A 98% oxidation efficiency was consistently achieved from the oxidation of VOCs in the microwave catalytic reactor.     

活性炭纤维对染料的吸附性能研究

研究了聚丙烯腈活性炭纤维（P－ACF）、粘胶活性炭纤维（R－ACF）和颗粒活性炭（GAC）对5种红色染料的吸附能力,通过简单的模型,算出5种染料在两种活性炭纤维上的吸附速率常数。结果表明,尽管吸附能力随染料种类不同而有一定的差别,但总体上,聚丙烯腈活性炭纤维的吸附能力略低于颗粒活性炭,而粘胶活性炭纤维的吸附能力则远远优于前两种,对染料有着较大的吸附容量和较快的吸附速率。     

Modification of carbon-coated TiO2 by iron to increase adsorptivity and photoactivity for phenol

Carbon-coated TiO(2) modified by iron, were prepared from TiO(2) of anatase structure and PET modified by FeC(2)O(4). Catalysts were prepared by mixing powders of TiO(2) and modified PET and heating at different temperatures, from 400 to 800 degrees C under flow of Ar gas. High adsorption of phenol was observed on the catalyst heated at 400 degrees C, confirmed by FT-IR analysis. On this catalyst, fast rate of phenol decomposition was achieved by addition of small amount of H(2)O(2) to the reaction mixture. Phenol decomposition proceeded mainly through the direct oxidation of phenol species adsorbed on the catalyst surface due to the photo-Fenton reaction. Iron-modified carbon-coated TiO(2) catalysts heated at 500-800 degrees C showed almost no phenol adsorption or oxidation.     

吸附饱和活性炭的Fenton试剂再生

颗粒活性炭吸附有机废水中二异丙基苯等有机物后,采用Fenton试剂对活性炭进行氧化再生。研究H2O2与Fe2＋的摩尔配比及投加量、pH、温度、再生时间等因素对活性炭再生效果的影响。实验结果表明,Fenton体系中Fe2＋和H2O2的摩尔比为1：20,H2O2投加量为120mmol／L,pH为3,再生温度为25℃,再生时间为70min时,为最佳再生条件,再生率可达85．6％,且6次连续再生的平均效率仍能达到84．9％。Fenton试剂再生活性炭的方法表现出较高的经济和环境效益。     

Effects of activated carbon types and service life on removal of endocrine disrupting chemicals: amitrol, nonylphenol, and bisphenol-A

Removal performances of endocrine disrupting chemicals (EDC) such as amitrol, nonylphenol, and bisphenol-A were evaluated in this study using granular activated carbon (GAC) adsorption. This study found that GAC adsorption was effective in removal of EDCs with high K_ow value. Nonylphenol and bisphenol-A were effectively adsorbed onto all carbons (including the used carbons) tested in this study. As indicated by K_ow value, nonylphenol was more effectively adsorbed than bisphenol-A. The coal-based carbon was found more effective than other carbons in the adsorption of nonylphenol and bisphenol-A due to its larger pore volume. The adsorption capacity reduced with the operation year, and the extent of the reduction was different depending upon the carbon type and the operation year. Amitrol was effectively removed by biological degradation, but was poorly adsorbed. Since the microbes residing at the used carbons already accustomed to amitrol, the used carbons removed amitrol better than the virgin carbons. Although the coal-based carbon showed the best removal performance of amitrol, GAC adsorption could not be recommended for amitrol removal because considerable portion of incoming amitrol (9–87%) passed through GAC adsorption column. According to this study, pore volume mainly influenced the adsorption capacity, but the surface charge was also important due to electrical interaction. The adsorption parameters for nonylphenol and bisphenol-A provided by this study could be valuable when GAC adsorption was considered to handle an accidental spill of nonylphenol and bisphenol-A.     

微波辐射回用活性炭对水中亚甲基蓝和Cd~(2+)去除效果的研究

考察了微波-活性炭联合处理技术对模拟染料废水中亚甲基蓝和Cd2+的去除效果。对于100 mL浓度为1 000 mg/L的亚甲基蓝溶液、活性炭用量为10 g时,新活性炭对亚甲基蓝的去除率为99.99%;采用700 W微波对吸附亚甲基蓝的活性炭辐射10 min进行再生并回用,经微波辐射再生10次后活性炭对亚甲基蓝的去除率为99.68%,未经微波作用反复使用10次的活性炭对亚甲基蓝的去除率为85.41%。结果表明:微波处理有效地减缓了活性炭吸附能力的下降速率,实现了活性炭再生和反复使用。在吸附过程中,Cd2+使活性炭对亚甲基蓝的吸附能力略有下降,而共存的亚甲基蓝则促进了活性炭对Cd2+的吸附,对新炭和再生后活性炭物理化学特性的表征证明了活性炭对亚甲基蓝的吸附为物理吸附,对Cd2+的吸附为化学吸附。     

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。