Kinetics of photocatalytic VOCs abatement in a standardized reactor

A standardized micro-pilot scale continuous flow apparatus has been built up, using two types of differential photoreactors, and equipped with a refined control of the working conditions in order to study the photocatalytic degradation as a way to abate VOCs in air. Kinetic measurements have been carried out on trichloroethylene (TCE), methanol and benzene as model pollutants. The absence of diffusional limitation and of reaction product effect on the kinetics have both been demonstrated under our working conditions. The influences of concentration, light flux and temperature on the initial degradation rate have been studied. A simple Langmuir-Hinshelwood kinetic model has been verified for TCE and methanol, whereas benzene degradation was more complex and did not follow this simple mechanism. The determined experimental data aim at being useful in the scaling-up of photocatalytic reactors.     

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.     

光催化降解模拟室内挥发性有机污染物研究

用浸渍-提拉法制备玻璃弹簧负载型TiO2薄膜催化剂,在自制的反应器中进行光催化降解由丙酮、甲苯、对二甲苯组成的模拟室内挥发性有机污染物VOCs研究.研究发现:催化剂中掺杂金属离子能影响催化剂的降解效果,降解效果依次为掺铈TiO2＞纯TiO2＞掺银TiO2;气体流量显著影响降解效果,丙酮、甲苯和对二甲苯的最佳降解流量分别为3、5、7 L/min;混合气体中非对称性的极性分子的降解效率高于对称性分子,导致丙酮、对二甲苯组分降解率降低,甲苯降解率增高.     

TiO2薄膜气相光催化氧化低浓度三氯甲烷和三氯乙烯的研究

自行设计了气固相光催化实验系统,以铝材为担载体,TCM和TCE为模拟污染物,在常温、常压下,对辐射光源、气体相对湿度、污染物反应浓度等因素对TCM和TCE的光催化降解反应的影响进行了研究.结果表明,在研究所采用的实验条件下,辐射光源采用254 nm时的降解效率要比采用365 nm时高10%左右;气体相对湿度为40%时光催化降解效率最高;随着污染物反应浓度的增加,TCM的降解效率降低,而TCE的降解效率增加.初步的反应动力学研究结果表明,TCM和TCE在二氧化钛表面的光催化降解反应可采用Langmuir-Hinshelwood动力学方程来表征.     

Chemical absorption process for degradation of VOC gas using heterogeneous gas-liquid photocatalytic oxidation: toluene degradation by photo-Fenton reaction

A novel process for degradation of toluene in the gas-phase using heterogeneous gas-liquid photocatalytic oxidation has been developed. The degradation of toluene gas by photo-Fenton reaction in the liquid-phase has experimentally examined. The photo-Fenton reaction in the liquid-phase could improve the overall toluene absorption rate by increasing the driving force for mass transfer and as a result enhance the removal of toluene in the exhaust gas. The toluene concentrations in the inlet gas were varied in the range from 0.0968 to 8.69gm(-3) with initial hydrogen peroxide concentration of 400mgl(-1) and Fe dose of 5.0mgl(-1). It was found that toluene in the inlet gas was almost completely dissolved into water and degraded in the liquid-phase for the inlet toluene gas concentration of less than 0.42gm(-3). The dynamic process of toluene gas degradation by the photo-Fenton reaction providing information for reaction kinetics and mass transfer rate was examined. Toluene removal kinetic analysis indicated that photo-Fenton degradation was significantly affected by H(2)O(2) concentration. The experimental results were satisfactorily described by the predictions simulated using the simplified tanks-in-series model combined with toluene removal kinetic analysis. The present results showed that the proposed chemical absorption process using the photo-Fenton heterogeneous gas-liquid photocatalytic oxidation is very effective for degradation of volatile organic gases.     

Photocatalytic oxidation of gaseous chlorinated organics over titanium dioxide

The photocatalytic oxidation of high levels of volatile chlorinated organic compounds in gas phase has been studied using a specially designed photoreactor. The influence of light intensity, initial water vapour concentration, temperature, inlet contaminant concentration and flow rate on destruction efficiency has been investigated. The performance of the titanium catalyst was strongly affected by the presence of water in the air stream. Experiments have been most successfully conducted at room temperature, low initial contaminant concentrations, low flow rates and high light intensities. Several by-products have been detected performing photocatalytic degradation of trichloroethylene (TCE) and tetrachloroethylene (PCE). No catalyst deactivation was observed.     

Influence of pH on persulfate oxidation of TCE at ambient temperatures

In situ chemical oxidation (ISCO) is a technology used for groundwater remediation. This laboratory study investigated the use of the oxidant sodium persulfate for the chemical oxidation of trichloroethylene (TCE) at near ambient temperatures (10, 20 and 30 degrees C) to determine the influence of pH (pH=4, 7 and 9) on the reaction rate (i.e., pseudo-first-order rate constants) over the range of temperatures utilized. TCE solutions (60 mg l(-1); 0.46 mM) were prepared in phosphate buffered RO water and a fixed persulfate/TCE molar ratio of 50/1 was employed in all tests. Half-lives of TCE degradation at 10, 20 and 30 degrees C (pH 7) were 115.5, 35.0 and 5.5h, respectively. Maximum TCE degradation occurred at pH 7. Lowering system pH resulted in a greater decrease in TCE degradation rates than increasing system pH. Radical scavenging tests used to identify predominant radical species suggested that the sulfate radical (SO(4)(.-)) predominates under acidic conditions and the hydroxyl radical (.OH) predominates under basic conditions. In a side by side comparison of TCE degradation in a groundwater vs. unbuffered RO water it was demonstrated that when the system pH is buffered to near neutral pH conditions due to the presence of natural occurring groundwater constituents that the TCE degradation rate is higher than in unbuffered RO water where the system pH dropped from 5.9 to 2.8. The results of this study suggest that in a field application of ISCO, pH should be monitored and adjusted to near neutral if necessary.     

Trichloroethylene degradation by photocatalysis in annular flow and annulus fluidized bed photoreactors

The effects of trichloroethylene (TCE) gas flow rate, relative humidity, TiO(2) film thickness, and UV light intensity on photodegradation of TCE have been determined in an annular flow type photoreactor. Phosgene and dichloroacetyl chloride formation could be controlled as a function of TCE gas flow rate and photodegradation of TCE decreased with increasing relative humidity. The optimum thickness of TiO(2) film was found to be approximately 5 mum and the photocatalytic reaction rate of TCE increased with square root of UV light intensity. In addition, the effects of the initial TCE concentration, phase holdup ratio of gas and solid phases (epsilon(g)/epsilon(s)), CuO loading on the photodegradation of TCE have been determined in an annulus fluidized bed photoreactor. The TCE photodegradation decreased with increasing the initial TCE concentration. The optimum conditions of the phase holdup ratio (epsilon(g)/epsilon(s)) and CuO wt.% for the maximum photodegradation of TCE was found to be 2.1 and 1.1 wt.%, respectively. Therefore, an annulus fluidized bed photoreactor is an effective tool for TCE degradation over TiO(2)/silica gel with efficient utilization of photon energy.     

Natural attenuation of trichloroethene and its degradation products at a lake-shore site

Subsurface contamination by trichloroethene (TCE) was detected at a Michigan National Priorities List (NPL) site in 1982. The TCE plume resulted from the disposal of spent solvent and other chemicals at an industrial facility located in the eastern shore of Lake Michigan. TCE degradation products of three dichloroethene (DCE) isomers, vinyl chloride (VC) and ethene were present. The plume was depleted of oxygen and methanogenic at certain depths. Transects of the plume were sampled by slotted auger borings the year after the TCE plume was first discovered. Water samples were also taken from lake sediments to a depth of 12 m about 100 m offshore. Later samples were taken along the shoreline of the lake with a hand-driven probe. Later in 1998 water was taken from sediments about 3-m from the shoreline. The average concentration of each chemical and net apparent base coefficient between appropriate pairs of transects between the lower site and lakeshore were calculated. Loss rates were then calculated from an analytical solution of the two-dimensional advective-dispersive-reactive transport equation. Net apparent rate coefficients and a set of coupled reaction rate equations were used to extract the apparent loss coefficients. This study showed the field evidence for natural attenuation of TCE.     

PCDD/DF formations by the heterogeneous thermal reactions of phenols and their TiO2 photocatalytic degradation by batch-recycle system

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/DFs) formation by the thermal reactions of phenols with CuCl2 under oxygen flux were carried out in relation to their formation mechanisms. To evaluate the effect of photocatalytic degradation of titanium dioxide (TiO2) thin film prepared by the sol-gel method, the photocatalysis of PCDD/DFs in acetonitrile/water solution by batch-recycle system was conducted. For the thermal reaction system of powder mixtures of 2,4,5-trichlorophenol (2,4,5-TCP) and CuCl2, the formation rates were 8.1 microg/g-2,4,5-TCP/min for total PCDD/DFs and 6.9 microg/g-2,4,5-TCP/min for PCDDs, and total PCDD/DF rate was higher by approximately 40 fold compared to phenol vapor/oxygen/CuCl2 powder system. For the system of 2,4,5-TCP, PCDDs were mainly formed via ortho-phenoxyphenols (POP) intermediate by the condensation of 2,4,5-trichlorophenate. For PCDD/DF photocatalytic degradations, most PCDD congeners photodecomposed rapidly and the rates presented more than 70% (as dechlorination rates of 76% for PCDDs) at 24 h after irradiation, using PCDD/DFs formed with 2,4,5-TCP. The rate constants were in the order of 4.8-6.1 x 10(-3) min(-1), assuming the pseudo-first-order reactions for their low levels.     

Effect of temperature and dissolved oxygen on the growth kinetics of Pseudomonas putida F1 growing on benzene and toluene

Batch experiments were conducted to determine the effect of temperature and dissolved oxygen concentration on the rates of growth and substrate (benzene and toluene) degradation by the toluene degrading strain, Pseudomonas putida F1. Over a range of temperature from 15 to 35 degrees C the maximum specific growth rate followed the Topiwala-Sinclair relationship when either benzene or toluene served as the sole carbon and energy source. Oxygen limited growth followed Monod saturation kinetics with the specific growth rate given as a function of the dissolved oxygen concentration. The oxygen half-saturation coefficient was found to be approximately 1 mg/l regardless of whether benzene or toluene was the substrate. Similar experiments with Burkholderia (Ralstonia) pickettii PKO1 for grown on toluene revealed an oxygen half-saturation coefficient of 0.7 mg/l.     

以汽油为底物好氧共代谢三氯乙烯

三氯乙烯(trichloroethylene,TCE)是土壤和地下水中广泛存在的有机污染物,好氧生物降解因可将污染物彻底转化成无毒的终产物,一直受到广泛关注,但是TCE好氧降解需要共代谢底物。首次提出以汽油为底物,选取真养产碱杆菌作为活性降解菌株,对地下水中三氯乙烯的好氧共代谢降解进行了初步研究。分别优化了共代谢底物、底物与TCE浓度比、培养基、pH值、盐度、溶解氧等条件,确定了最佳降解条件。当水中TCE的浓度为1 mg/L时,通过对体系预曝氧气,调节汽油浓度为10 mg/L,pH值为5,降解24 h,TCE的降解率可达66.8%。为修复同时被汽油和TCE污染的场地提供了一个新的研究方向。     

Real-time reverse transcription PCR analysis of trichloroethylene-regulated toluene dioxygenase expression in Pseudomonas putida F1

Toluene dioxygenase (tod) is a multicomponent enzyme system in Pseudomonas putida F1. Tod can mediate the degradation of Trichloroethylene (TCE), a widespread pollutant. In this study, we try to explore the TCE-regulated tod expression by using real-time qRT-PCR. The minimal culture media were supplemented with glucose, toluene, or a mixture of glucose/toluene respectively as carbon and energy sources. The TCE was injected into each medium after a 12-hour incubation period. The TCE injection severely affected bacterial growth when cultured with toluene or toluene/glucose mixtures. The cell density dropped 61 % for bacteria growing in toluene and 36 % for bacteria in the glucose/toluene mixture after TCE injection, but the TCE treatment had little effect on bacteria supplied with glucose alone. The decrease in cell number was caused by the cytotoxicity of the TCE metabolized by tod. The results from the real-time qRT-PCR revealed that TCE was capable of inducing tod expression in a toluene-dependent manner and that the tod expression level increased 50 times in toluene and 3 times in the toluene/glucose mixture after 6 hours of TCE treatment. Furthermore, validation of the rpoD gene as a reference gene for P. putida F1 was performed in this study, providing a valuable foundation for future studies to use real-time qRT-PCR in the analysis of the P. putida F1 strain.     

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.     

Photocatalytic oxidation of gaseous DMF using thin film TiO2 photocatalyst

The heterogeneous photocatalytic oxidation of gaseous N,N'-dimethylformamide (DMF) widely used in the manufacture of synthetic leather and synthetic textile was investigated. The experiments were carried out in a plug flow annular photoreactor coated with Degussa P-25 TiO2. The oxidation rate was dependent on DMF concentration, reaction temperature, water vapor, and oxygen content. Photocatalytic deactivation was observed in these reactions. The Levenspiel deactivation kinetic model was used to describe the decay of catalyst activity. Fourier transform infrared (FTIR) was used to characterize the surface and the deactivation mechanism of the photocatalyst. Results revealed that carbonylic acids, aldehydes, amines, carbonate and nitrate were adsorbed on the TiO2 surface during the photocatalytic reaction. The ions, NH4+ and NO3-, causing the deactivation of catalysts were detected on the TiO2 surface. Several treatment processes were applied to find a suitable procedure for the regeneration of catalytic activity. Among these procedures, the best one was found to be the H2O2/UV process.     

固定化催化剂TiO2膜光催化降解三氯乙醛的研究

研究了负载于玻璃上的固定化催化剂TiO2膜光催化降解水中三氯乙醛的效果,探讨了TiO2膜光催化降解三氯乙醛的机理,考察了溶液pH值和三氯乙醛初始浓度埘TiO2膜光催化降解三氯乙醛的影响,并研究了固定化催化剂TiO2膜光催化降解三氯乙醛的动力学.结果表明,固定化催化剂TiO2膜光催化降解水中三氯乙醛的效果良好,当三氯乙醛初始浓度为2.25 mg/L时,在紫外光照时间3 h下,三氯乙醛的降解率高达100%.在相司紫外光照时间下,三氯乙醛的光催化降解率随着三氯乙醛初始浓度的增大而下降.在溶液pH=6.5时,三氯乙醛的降解效率最高.固定化催化剂TiO2膜光催化降解三氯乙醛的反应遵循一级反应动力学,反应速率常数随三氯乙醛初始浓度的增大而减小.     

Real-time reverse transcription PCR analysis of trichloroethylene-regulated toluene dioxygenase expression in Pseudomonas putida F1

Toluene dioxygenase (tod) is a multicomponent enzyme system in Pseudomonas putida F1. Tod can mediate the degradation of Trichloroethylene (TCE), a widespread pollutant. In this study, we try to explore the TCE-regulated tod expression by using real-time qRT-PCR. The minimal culture media were supplemented with glucose, toluene, or a mixture of glucose/toluene respectively as carbon and energy sources. The TCE was injected into each medium after a 12-hour incubation period. The TCE injection severely affected bacterial growth when cultured with toluene or toluene/glucose mixtures. The cell density dropped 61 % for bacteria growing in toluene and 36 % for bacteria in the glucose/toluene mixture after TCE injection, but the TCE treatment had little effect on bacteria supplied with glucose alone. The decrease in cell number was caused by the cytotoxicity of the TCE metabolized by tod. The results from the real-time qRT-PCR revealed that TCE was capable of inducing tod expression in a toluene-dependent manner and that the tod expression level increased 50 times in toluene and 3 times in the toluene/glucose mixture after 6 hours of TCE treatment. Furthermore, validation of the rpoD gene as a reference gene for P. putida F1 was performed in this study, providing a valuable foundation for future studies to use real-time qRT-PCR in the analysis of the P. putida F1 strain.     

Anaerobic biodegradation of alkylbenzenes and trichloroethylene in aquifer sediment down gradient of a sanitary landfill

The objective of this investigation was to evaluate the anaerobic biodegradability of benzene, toluene, ethylbenzene, ortho-, meta- and para-xylene (BTEX) and trichloroethylene (TCE) in aquifer sediment down gradient of an unlined landfill. The major organic contaminants identified in the shallow unconfined aquifer are cis-dichloroethylene (c-DCE) and toluene. The biodegradative potential of the contaminated aquifer was measured in three sets of microcosms constructed using anaerobic aquifer sediment from three boreholes down gradient of the landfill. The degradability of BTEX and TCE was examined under ambient and amended conditions. TCE was degraded in microcosms with aquifer material from all three boreholes. Toluene biodegradation was inconsistent, exhibiting biodegradation with no lag in one set of microcosms but more limited biodegradation in two additional sets of microcosms. TCE exhibited an inhibitory effect on toluene degradation at one location. The addition of calcium carbonate stimulated TCE biodegradation which was not further stimulated by nutrient addition. TCE was converted to ethylene, a harmless byproduct, in all tests. Benzene, ethylbenzene and xylene isomers were recalcitrant in both ambient and amendment experiments. Biodegradation occurred under methanogenic conditions as methane was produced in all experiments. Bromoethane sulfonic acid (BES), a methanogenic inhibitor, inhibited methane and ethylene production and TCE biodegradation. The results indicate the potential for intrinsic bioremediation of TCE and toluene down gradient of the Wilder's Grove, North Carolina, landfill. The low concentrations of TCE in monitoring wells was consistent with its biodegradation in laboratory microcosms.     

The study of lag phase and rate improvement of TCE decay in UV/surfactant systems

The photodegradation of trichloroethene (TCE) in surfactant micelles was investigated. The decay of TCE was studied in the Rayonet RPR-200 merry-go-round photoreactor, at 253.7 nm monochromatic ultraviolet (UV) lamps, in the presence of surfactants. Surfactants are used as additional hydrogen sources to improve the photodegradation rates of TCE. About three times the rate increment is observed in the presence of Brij 35 surfactant micelles than in water alone. The increasing concentrations of H+ and Cl- indicate that they are the final products of TCE photodegradation (i.e. photodechlorination is the dominant mechanism in this system). A lag phase is observed at the beginning of the degradation, but the duration of the lag phase is apparently reduced as the initial pH increases. Because the overall decay of TCE is also found faster at higher pH levels, it is suggested that the free radical reaction is dominant at high pH levels, and the formation of lag phases is mainly due to the deficiency of free radicals at lower pH levels. The photodecomposition of TCE in surfactant micelles is also proven to be a clean and effective process. It generates no chlorinated by-products or intermediates during the process, and TCE is fully decomposed within a reasonable time.     

Electrolytic trichloroethene degradation using mixed metal oxide coated titanium mesh electrodes

Electrochemical systems provide a low cost, versatile, and controllable platform to potentially treat contaminants in water, including chlorinated solvents. Relative to bare metal or noble metal amended materials, dimensionally stable electrode materials such as mixed metal oxide coated titanium (Ti/MMO) have advantages in terms of stability and cost, important factors for sustainable remediation solutions. Here, we report the use of Ti/MMO as an effective cathode substrate for treatment of trichloroethene (TCE). TCE degradation in a batch reactor was measured as the decrease of TCE concentration over time and the corresponding evolution of chloride; notably, this occurred without the formation of commonly encountered chlorinated intermediates. The reaction was initiated when Ti/MMO cathode potentials were less than -0.8 V vs. the standard hydrogen electrode, and the rate of TCE degradation increased linearly with progressively more negative potentials. The maximum pseudo-first-order heterogeneous rate constant was approximately 0.05 cm min(-1), which is comparable to more commonly used cathode materials such as nickel. In laboratory-scale flow-though column reactors designed to simulate permeable reactive barriers (PRBs), TCE concentrations were reduced by 80-90%. The extent of TCE flux reduction increased with the applied potential difference across the electrodes and was largely insensitive to the spacing distance between the electrodes. This is the first report of the electrochemical reduction of a chlorinated organic contaminant at a Ti/MMO cathode, and these results support the use of this material in PRBs as a possible approach to manage TCE plume migration.