Kinetic analysis and energy efficiency of phenol degradation in a plasma-photocatalysis system

Combination of two kinds of advanced oxidation processes (AOPs) is an effective approach to control wastewater pollution. In this research, a pulsed discharge plasma system with multi-point-to-plate electrode and an immobilized TiO(2) photocatalysis system is coupled to oxidize target pollutant in aqueous solution. Kinetic analysis (pseudo-first order kinetic constant, k) and energy efficiency (energy yield value at 50% phenol conversion, G(50)) of phenol oxidation in different reaction systems (plasma alone and plasma-photocatalysis) are reviewed to account for the synergistic mechanism of plasma and photocatalysis. The experimental results show that higher k and G(50) of phenol oxidation can be obtained in the plasma-photocatalysis system under the conditions of different gas bubbling varieties, initial solution pH and radical scavenger addition. Moreover, the investigation tested hydroxyl radical (OH) is the most important species for phenol removal in the synergistic system of plasma-photocatalysis as well as in the plasma alone system.     

Degradation of 4-chlorophenol by a microwave assisted photocatalysis method

In this work, the degradation of 4-chlorophenol (4CP) under simultaneous microwave assisted UV (electrodeless discharge lamp) photocatalysis technique (MW/UV/TiO2) was investigated. Several factors affecting the degradation of 4CP by MW/UV/TiO2 method, such as the dosage of photocatalysts, the initial pH value of the solutions, gas bubbling, light intensity and addition of H2O2 oxidant, were studied in detail. The synergistic effects between microwave irradiation and TiO2 photocatalysis were also studied. The major intermediates were found to be chlorobenzene, phenol, hydroquinone, benzoquinone and 4-chlorocatechol. Based on the results, a general reaction pathway for the degradation of 4CP was proposed.     

Degradation of phenol in water using a gas-liquid phase pulsed discharge plasma reactor

In this paper, a gas-liquid phase pulsed discharge plasma reactor was used to dispose phenol in aqueous solutions. The effect of pulsed peak voltage and energy, solution conductivity, solution pH, and additive gas varieties on degradation efficiency of phenol was reviewed in the research. The observed results showed that degradation efficiency of phenol increased with the increase of pulsed peak voltage, discharge energy and treatment time. The degradation efficiency of phenol with the oxygen additive was higher than that with the argon additive. The degradation efficiency was higher in the basic solution.     

Effect of various gases and chemical catalysts on phenol degradation pathways by pulsed electrical discharges

The processes of phenol degradation by pulsed electrical discharges were investigated under several kinds of discharge atmospheres (oxygen, argon, nitrogen and ozone) and chemical catalysts (ferrous ion and hydrogen peroxide). The temporal variations of the concentrations of phenol and the intermediate products were monitored by HPLC and GC–MS, respectively. It has been found that the effect of various gases bubbling on phenol degradation rate ranked in the following order: oxygen-containing ozone > oxygen > argon > nitrogen. The high gas bubbling flow rate was beneficial to the removal of phenol. It was found that the degradation proceeded differently when in the presence and absence of catalysts. The phenol removal rate was increased when ferrous ion was added. This considerable enhancement may be due to the Fenton's reaction. What's more, putting the chemical additives hydrogen peroxide into the reactor led to a dramatic increase in phenol degradation rate. The mechanism was due to the direct or indirect photolysis and pyrolysis destruction in plasma channel. Furthermore, the intermediate products were monitored by GC–MS under three degradation conditions. More THBs were generated under degradation conditions without gases bubbling or adding any catalyst, and more DHBs under the condition of adding ferrous ion, and more carboxylic acids under the condition of oxygen-containing ozone gas bubbling. Consequently, three distinct degradation pathways based on different conditions were proposed.     

TiO2-Al2O3复合光催化剂的制备及光催化性能

以Ti（SO4）2、Al2（SO4）3·18H2O为原料,采用乙醇助水热法制备了Al2O3-TiO2复合光催化剂,并通过改变A1／Ti物质的量之比、乙醇的体积分数、水热反应温度和反应时间等得到材料制备的最佳条件。XRD分析表明样品中的TiO2以锐钛矿晶相存在,SEM显示样品粒径范围在30-50nm之间。用最佳条件制备的复合光催化剂降解甲基橙溶液,反应30min后降解率这91％,降解过程符合一级动力学方程。     

Role of oxygen active species in the photocatalytic degradation of phenol using polymer sensitized TiO2 under visible light irradiation

The role of dissolved oxygen, and of active species generated by photo-induced reactions with oxygen, in the photocatalytic degradation of phenol was investigated using polymer [poly-(fluorene-co-thiophene) with thiophene content of 30%, so-called PFT30] sensitized TiO2 (PFT30/TiO2) under visible light irradiation. The photoluminescent (PL) quantum yield of PFT30/TiO2 was about 30% of that of PFT30/Al(2)O(3), proving that electron transfer took place between the polymer and TiO2. The result that photocatalytic degradation of phenol was almost stopped when the solution was saturated with N(2) proved the importance of O(2). Addition of NaN(3), an effective quencher of singlet oxygen ((1)O(2)), caused about a 40% decrease in the phenol degradation ratio. Addition of alcohols caused about a 60% decrease in the phenol photodegradation ratio, indicating that the hydroxyl radicals (OH), whose presence was confirmed by electron spin resonance (ESR) spectroscopy, was the predominant active species in aqueous solution. In anhydrous solution, singlet oxygen ((1)O(2)) was the predominant species. These results indicate that oxygen plays a very important role in the photocatalytic degradation of phenol.     

The effect of solution pH and peroxide in the TiO2-induced photocatalysis of chlorinated aniline

Chlorinated anilines are frequently used in the industry as starting materials for chemical synthesis. This type of compounds can end up as pollutants in wastewater. 2-Chloroaniline (2-ClA) was selected irradiating under monochromatic UV light at 300nm. The reaction rate could be enhanced by introducing low level of H(2)O(2) into the UV/TiO(2) system. Excess H(2)O(2) could not increase the HO* generation but retarded the reaction rate. The pH effect was also investigated in UV/TiO(2) and UV/TiO(2)/H(2)O(2) systems. All the experimental results show that pH is a sensitive parameter to the rate of degradation. Low reaction rate at acidic pH could be accounted by the dark adsorption test which has also proven the photocatalysis of TiO(2) may contribute to a two-step process: (1) 2-ClA pre-adsorbed onto TiO(2) and (2) photoexcitation of TiO(2). At high pH, rate enhancement could be observed at UV/TiO(2) system because of the increase generation of HO*. However, the introduction of H(2)O(2) slowdown the decay rate at such alkaline medium.     

Non-thermal plasma-induced photocatalytic degradation of 4-chlorophenol in water

TiO(2) photocatalyst (P-25) (50mgL(-1)) was tentatively introduced into pulsed high-voltage discharge process for non-thermal plasma-induced photocatalytic degradation of the representative mode organic pollutant parachlorophenol (4-CP), including other compounds phenol and methyl red in water. The experimental results showed that rate constant of 4-CP degradation, energy efficiency for 4-CP removal and TOC removal with TiO(2) were obviously increased. Pulsed high-voltage discharge process with TiO(2) had a promoted effect for the degradation of these pollutants under a broad range of liquid conductivity. Furthermore, the apparent formation rates of chemically active species (e.g., ozone and hydrogen peroxide) were increased, the hydrogen peroxide formation rate from 1.10x10(-6) to 1.50x10(-6)Ms(-1), the ozone formation rate from 1.99x10(-8) to 2.35x10(-8)Ms(-1), respectively. In addition, this process had no influence on the photocatalytic properties of TiO(2). The introduction of TiO(2) photocatalyst into pulsed discharge plasma process in the utilizing of ultraviolet radiation and electric field in pulsed discharge plasma process enhanced the yields of chemically active species, which were available for highly efficient removal and mineralization of organic pollutants.     

Modeling of the production of OH and O radicals in a positive pulsed corona discharge plasma

A mathematical model was applied to describe the behavior of OH and O radicals in positive pulsed corona discharge of N₂-H₂O mixture gas. The model takes into account the generation and disappearance of radials in a pulsed corona discharge reactor by a single pulse or continuous pulses. Their concentrations were derived by considering direct electron effect on the dissociation of gaseous molecules (O₂, N₂, H₂O) and subsequent excitation transfer reaction of excited oxygen atoms to produce OH radicals. The equations promoted could be solved numerically with the FORTRAN subroutine Treanor. So as to establish the validity of the model simulation, the calculated results were compared with the experimental data. Although there is some discrepancy between the calculation and experiment, the total trend is coincident.     

Immobilization of TiO2 and Fe-C-TiO2 photocatalysts on the cotton material for application in a flow photocatalytic reactor for decomposition of phenol in water

TiO2 and Fe-C-TiO2 photocatalysts have been immobilized on the cotton material and used in a flow photocatalytic reactor for phenol decomposition. The cotton material has been applied as a support for photocatalyst, because can be easily removed and replaced in a reactor, what facilitates the performance of the photocatalytic process. Fe-C-TiO2 photocatalyst has been prepared by modification of TiO2 fine particles of anatase structure with FeC2O4 through heating in Ar at 500 degrees C. The immobilized photocatalysts could efficiently decompose phenol in multiple use, Fe-C-TiO2 showed higher photocatalytic activity than TiO2, around 15-18 mg and 15-16 mg of phenol have been decomposed after 5 h of UV irradiation on Fe-C-TiO2 and TiO2, respectively. After addition of H2O2 the phenol decomposition and the mineralization degree have been accelerated, especially with immobilized Fe-C-TiO2 photocatalyst, in case of that the photo-Fenton reaction occurred. In the presence of H2O2 around 26-28 mg and 21-24 mg of phenol have been decomposed on Fe-C-TiO2 and TiO2 respectively, after 5 h of UV irradiation.     

Degradation of C.I. Reactive Red 2 through photocatalysis coupled with water jet cavitation

The decolorization of an azo dye, C.I. Reactive Red 2 was investigated using TiO(2) photocatalysis coupled with water jet cavitation. Experiments were performed in a 4.0 L solution under ultraviolet power of 9 W. The effects of TiO(2) loading, initial dye concentration, solution pH, geometry of cavitation tube, and the addition of anions on the degradation of the dye were evaluated. Degradation of the dye followed a pseudo-first order reaction. The photocatalysis coupled with water jet cavitation elevated degradation of the dye by about 136%, showing a synergistic effect compared to the individual photocatalysis and water jet cavitation. The enhancement of photocatalysis by water jet cavitation could be due to the deagglomeration of catalyst particles as well as the better contact between the catalyst surfaces and the reactants. Venturi tube with smaller diameter and shorter length of throat tube favored the dye decolorization. The degradation efficiency was found to increase with decreasing initial concentration and pH. The presence of NO(3)(-) and SO(4)(2-) enhanced the degradation of RR2, while Cl(-), and especially HCO(3)(-) significantly reduced dye decolorization. The results of this study indicated that the coupled photocatalysis and water jet cavitation is effective in degrading dye in wastewater and provides a promising alternative for treatment of dye wastewater at a large scale.     

Decomposition of benzene in the RF plasma environment. Part I. Formation of gaseous products and carbon depositions

This study employed radio-frequency (RF) plasma for decomposing benzene (C6H6) gas, and examined both gaseous products and solid depositions after reaction. The reactants and products were analyzed mainly by using both an on-line Fourier transform infrared (FT-IR) spectrometer and a gas chromatography. The analyses for solid deposition included electron spectroscopy for chemical analysis (ESCA), element analysis and heat value analysis. The C2H2, C2H4, C2H6, CH4, CO2 and CO were detected and discussed. The analytical results demonstrate that in the C6H6/Ar plasma, C2H2 is the sole gaseous product being detected. The fraction of total carbon input converted into C2H2 YC2H2 increased with increasing C6H6 feed concentration, but decreased with increasing input power. In the C6H6/H2/Ar system, besides C2H2, CH4, C2H4 and C2H6 were also detected, and their yields increased with increasing H2/C6H6 ratio. The above results indicated that the addition of H2 (auxiliary gas) achieves the benefit of creating hydrogen-rich species like CH4, C2H4 and C2H6. In the C6H6/O2/Ar system, C6H6 could be totally oxidized into CO2, CO and H2O, and no measurable phenol was found. Analyses of solid depositions revealed that the carbon depositions were similar to those of Anthracite. The carbon deposition has a heat value of 7000 kcal/kg. Additionally, the possible reaction pathways were also built up and discussed.     

Microwave assisted rapid and complete degradation of atrazine using TiO(2) nanotube photocatalyst suspensions

A technology, microwave-assisted photocatalysis on TiO(2) nanotubes, which can be applied to degrade atrazine rapidly and completely, was investigated. TiO(2) nanotubes were prepared, and confirmed by XRD, TEM and ESR. Microwave-assisted photocatalytic degradation of atrazine in aqueous solution was investigated. The result indicates that atrazine is completely degraded in 5min and the mineralization efficiency is 98.5% in 20min, which is obviously more efficient than that by the traditional photocatalytic degradation methods. It may be attributed to the intense UV radiation generated by electrodeless discharge lamps under microwave irradiation, the increased number of OH, additional defect sites on TiO(2) under the irradiation of microwave and larger specific surface area of TiO(2) nanotubes which could adsorb more organic substances to degrade than TiO(2) nanoparticles. Along with the degradation of atrazine, the concentrations of Cl(-) and NO(3)(-) increase gradually. In 20min [Cl(-)] and [NO(3)(-)] are 3, 27.8mg/L, respectively, which are close to their stoichiometric values. The major intermediates of atrazine were identified by HPLC/MS and possible degradation pathways of atrazine in microwave-assisted photocatalysis on TiO(2) nanotubes were proposed.     

Treatment of gasoline-contaminated waters by advanced oxidation processes

In this study, the efficiency of advanced oxidative processes (AOPs) was investigated toward the degradation of aqueous solutions containing benzene, toluene and xylenes (BTX) and gasoline-contaminated waters. The results indicated that BTX can be effectively oxidized by near UV-assisted photo-Fenton process. The treatment permits almost total degradation of BTX and removal of more than 80% of the phenolic intermediates at reaction times of about 30 min. Preliminary investigations using water contaminated by gasoline suggest a good potentiality of the process for the treatment of large volumes of aqueous samples containing these polluting species. Heterogeneous photocatalysis and H2O2/UV system show lower degradation efficiency, probably due to the heterogeneous character of the TiO2-mediated system and lost of photonic efficiency of the H2O2/UV system in the presence of highly colored intermediated.     

共掺杂Cu-Ce/TiO_2光催化性能研究

采用溶胶-凝胶法,以钛酸丁酯为前驱体制备了不同Cu-Ce掺杂量的纳米TiO2光催化材料。通过模拟环境室内甲醛气体的降解实验,探讨了不同样品在日光灯和纯可见光下的光催化效果,并采用X射线衍射仪和紫外-可见分光光谱仪对其晶相结构与光学特性进行表征分析。结果表明,Cu-Ce掺杂能明显提高二氧化钛在可见光下的光催化活性,当Cu-Ce掺杂浓度为2.5%时,对甲醛气体的光催化降解效果最佳。     

Advanced oxidation processes applied to tannery wastewater containing Direct Black 38--elimination and degradation kinetics

The application of advanced oxidation processes (H(2)O(2)/UV, TiO(2)/H(2)O(2)/UV and TiO(2)/UV) to treat tannery wastewater was investigated. The experiments were performed in batch and continuous UV reactors, using TiO(2) as a catalyst. The effect of the hydrogen peroxide concentration on the degradation kinetics was evaluated in the concentration range 0-1800 mg L(-1). We observed that the degradation rate increased as the hydrogen peroxide increased, but excessive H(2)O(2) concentration was detrimental because it acted as a hydroxyl radical scavenger since it can compete for the active sites of the TiO(2). In the H(2)O(2)/UV treatment, the COD removal reached around 60% in 4 h of reaction, indicating that the principal pollutants were chemically degraded as demonstrated by the results for BOD, COD, nitrate, ammonium and analysis of the absorbance at 254 nm. Artemia salina toxicity testing performed in parallel showed an increase in toxicity after AOP treatment of the tannery wastewater.     

Photoelectrochemical behaviour of uniform growth TiO2 nanotubes via bubble blowing synthesised in ethylene glycol with hydrogen peroxide

Uniformly sized TiO2 nanotubes with high aspect ratios were synthesised on a large substrate (100 mm x 100 mm) via the bubbling system through anodisation of Ti in ethylene glycol containing 5 wt% NH4F and 5 wt% H2O2. The benefits of bubbling system in producing uniformly sized TiO2 nanotubes throughout the Ti foil are illustrated. Moreover, the effects of applied voltage and fluoride content on the resulting nanotubes were also considered. Such uniform sized TiO2 nanotubes are a key to produce hydrogen efficiently using PEC cell. The results show higher photocurrent responses for the high aspect ratio, uniform TiO2 nanotubes because of excellent interfacial electron transfer.     

Decomposition of phenol by hybrid gas/liquid electrical discharge reactors with zeolite catalysts

Application of hybrid gas/liquid electrical discharge reactors and a liquid phase direct electrical discharge reactor for degradation of phenol in the presence and absence of zeolites have been investigated. Hybrid gas/liquid electrical discharges involve simultaneous high voltage electrical discharges in water and in the gas phase above the water surface leading to the additional OH radicals in the liquid phase and ozone formation in the gas phase with subsequent dissolution into the liquid. The role of applied zeolites, namely NH4ZSM5, FeZSM5 and HY, were also studied. Phenol degradation and production of primary phenol by-products, catechol and hydroquinone, during the treatment were monitored by HPLC measurements. The highest phenol removal results, 89.4-93.6%, were achieved by electrical discharge in combination with FeZSM5 in all three configurations of corona reactors. These results indicate that the Fenton reaction has significant influence on overall phenol removal efficiency in the electrical discharge/FeZSM5 system due to the additional OH radical formation from hydrogen peroxide generated by the water phase discharge.     

超临界流体干燥法制备TiO2/ Fe2O3 和TiO2/ Fe2O3/ SiO2 复合纳米粒子及光催化性能

以TiCl₄ 、Fe (NO₃ )₃·9H₂O 和Na₂SiO₃19H₂O 为原料, 采用溶胶凝胶法结合超临界流体干燥法(SCFD)制备了纳米级TiO₂/ Fe₂O₃ 和TiO₂/ Fe₂O₃/ SiO₂ 复合光催化剂。以光催化降解苯酚对所得催化剂的催化活性进行了评价。结果表明, 纳米TiO₂/ Fe₂O₃ 复合粒子与单组分TiO₂ 比较, 复合粒子光催化活性高于单组分的TiO₂, 6h 苯酚降解率高达95.9 %。SiO₂ 的加入可以抑制纳米粒子粒径的长大和晶相的转变, 增强TiO₂ 纳米粒子的热稳定性。复合光催化剂中Fe₂O₃ 最佳掺入量为0.06 %, SiO₂ 最佳掺入量为10 %(摩尔分数) 。并用XRD、TEM 和FTIR 等手段进行了表征。TiO₂ 以锐钛矿型形式存在, SiO₂ 以无定性形式存在。比较了不同制备方法制得的TiO₂/ Fe₂O₃ 复合光催化剂, 得出超临界干燥法制备的光催化剂具有粒径小、比表面积大、分散性好、光催化活性高等特点。采用超临界流体干燥可直接得锐钛型纳米复合光催化剂。     

Processes of carbon disulfide degradation under the action of a pulsed corona discharge

Experiments on decomposition of carbon disulfide CS₂ in air under the action of a pulsed nanosecond corona discharge have been carried out. The energetic efficiency of the degradation amounted to 290–340 g (kW h)^–1, which is significantly higher than with the use of a corona discharge at a constant voltage. The main degradation products are sulfur dioxide SO₂, carbonyl sulfide COS, sulfuric acid, and carbon dioxide. Processes occurring in pulsed corona discharge plasma and leading to carbon disulfide degradation are considered. Different methods of air purification from carbon disulfide are compared.