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.     

光反应器中UV/Fenton光降解湖水中微囊藻毒素的研究

在光催化反应器中,采用UV/Fenton光催化氧化技术,对湖水中微囊藻毒素的光催化降解过程中各影响因子分析表明:微囊藻毒素光催化氧化降解率受光照强度、氧化剂种类及浓度、溶液pH和不同光催化体系等多因素的影响.光促催化氧化体系对MC-LR藻毒素降解具有显著的作用,在紫外光与氧化剂的协同作用下,紫外光照强度越高,越易于促进MC-LR藻毒素快速降解,降解率可到达80%以上.     

Kinetic modeling on photooxidative degradation of C.I. Acid Orange 7 in a tubular continuous-flow photoreactor

The decolorization of C.I. Acid Orange 7 (AO7), an anionic monoazo dye of acid class, was investigated using UV radiation in the presence of H2O2 in a tubular continuous-flow photoreactor as a function of oxidant and dye concentrations, reactor length and volumetric flow rate. The removal efficiency of AO7 depends on the operational parameters and increases as the initial concentration of H2O2 is increased but it decreases when the flow rate and initial concentration of AO7 are increased. The decolorization rate follows pseudo-first order kinetic with respect to the dye concentration. A rate equation for decolorization of AO7 was achieved by kinetic modeling. This model allows predicting concentration of AO7 in different photoreactor lengths for different volumetric flow rates and initial concentrations of H2O2 and AO7. The calculated results obtained from kinetic model were in good agreement with experimental data.     

Photodestruction of Acid Orange 7 (AO7) in aqueous solutions by UV/H2O2: influence of operational parameters

The photodestruction of Acid Orange 7 (AO7), an anionic acidic dye, was studied in the UV/H2O2 process. H2O2 and UV light have a negligible effect when they were used on their own. Removal efficiency of AO7 was sensitive to the operational parameters such as initial H2O2 concentration, initial AO7 concentration, pH and different light sources. The photodestruction of AO7 was inhibited by addition of EtOH as an electron scavenger. The semi-logarithmic graphs of the concentration of AO7 versus time (t<30 min) were linear, suggesting pseudo-first order reactions (k(optimum)=0.105 min(-1)). A simple kinetic model is proposed which is in agreement with experimental results.     

喷射环流三相光催化反应器可见光下降解酸性湖兰A的研究

设计了一种喷射环流三相光催化反应器。用该反应器在可见光下,对染料酸性湖兰A在不同初始浓度、催化剂浓度、pH、光照时间下光催化降解脱色率的影响进行了研究。实验结果表明,反应最佳pH为6,反应最佳时间为20min,催化剂最佳投加量为8g／L。在最优条件下,染料脱色率达90％以上。     

Effect of fatty acids and oils on photodegradation of azadirachtin‐A

Abstract

Azadirachtin‐A on exposure to UV‐light (254 nm) as a thin film on glass surface gave a isomerised (Z)‐2‐ methylbut‐2‐enoate product. Half‐life of azadirachtin‐A as thin film under UV light was found to be 48 min. Azadirachtin ‐A was irradiated along with saturated and unsaturated fatty acids, and fatty oils under ultra‐violet light as thin film. Saturated fatty acid increased the rate of photodegradation of azadirachtin‐A, whereas unsaturated fatty acids such as oleic, linoleic and elaidic acid reduced the rate of degradation. Castor, linseed and olive oil accelerated the rate of degradation, whereas neem oil showed no or little change in the rate of degradation of azadirachtin‐A. None of these fatty acids and fatty oils were effective in controlling the rate of degradation of azadirachtin‐A under UV‐light as thin film.     

Ferrioxalate-mediated photodegradation and mineralization of 4-Chlorophenol

INTENTION, GOAL, SCOPE, BACKGROUND: Advanced oxidation processes are powerful methods which are capable of transforming refractory, nonbiodegradable and/or toxic organic compounds into harmless end products such as carbon dioxide and water. However, one commen problem of all advanced oxidation processes is the high demand of electrical energy for ultraviolet lamps, which causes high operational costs. Minimization of the required irradiation time, and therefore the energy consumption, by optimization of other reaction conditions such as catalyst-oxidant type and concentration, pH, temperature, pollutant/oxidant ratio etc., therefore continues to gain importance. OBJECTIVE: The main objective of this study was the minimization of the required irradiation time through optimization of the use of a newly patented catalyst, ferrioxalate, and also to compare the performance of this catalyst with the performance of other AOPs. METHODS: Oxidation of 4-chlorophenol by photo-Fenton process using potassium ferrioxalate as a mediator was studied in a lab scale photoreactor. The influence of parameters such as hydrogen peroxide and ferrioxalate concentrations, initial pH, power-output, oxalate/iron ratio and different iron sources was evaluated. An upflow photoreactor equipped with a 1000 Watt high-pressure mercury vapour lamp and operating in a recirculation mode was used during photodegradation experiments. The extent of the reduction of 4-chlorophenol, Total Organic Carbon and Chemical Oxygen Demand was used to evaluate the photodegradation reaction. RESULTS AND DISCUSSION: The optimum pH range observed was found to be 2.7-3. The efficiency of 4-chlorophenol oxidation increased with increasing concentrations of hydrogen peroxide and ferrioxalate, reaching a plateau after the addition of 10 and 0.072 mM of those reagents, respectively. Using an Oxalate/iron ratio of 12 was 18% less efficient than using a ratio of 3:1. The efficiency increased with increasing radiation power. However, this increase was not linear. The UV/ferrioxalate/H2O2 process, by which complete mineralization of 100 mg l(-1) 4-chlorophenol was achieved in 20 min of total reaction time, was the most efficient process among the alternatives applied. CONCLUSIONS: The use of ferrioxalate as the catalyst was found to be more efficient than the use of Fe(II) and Fe(III) iron species. It was possible to completely mineralize 4-chlorophenol. RECOMMENDATION AND OUTLOOK: The results of this study demonstrate that the ferrioxalate-mediated degradation of 4-chlorophenol requires less irradiation times than other advanced oxidation processes. There are mainly 19 phenol isomers and other toxic and nonbiodegradable organic compounds. We recommend that similar studies should be performed on many such compounds in order to attain a clear understanding of the performance of this catalyst. Because of its light sensitivity, this catalyst should be used immediately after its preparation. The use of low pressure mercury vapour lamps in this process should also be considered, since low power outputs may be enough for the process.     

Homogeneous degradation of 1,2,9,10-tetrachlorodecane in aqueous solutions using hydrogen peroxide, iron and UV light

The homogeneous degradation of the polychlorinated n-alkane, 1,2,9,10-tetrachlorodecane (T4C10), was studied in aqueous solutions of hydrogen peroxide, including Fenton and photo-Fenton reaction conditions. All solutions were adjusted to a pH of 2.8 and an ionic strength of 0.1 M NaClO4 prior to photolysis. T4C10 (2 x 10(-6) M) was substantially degraded by the H2O2/UV system (1.0 x 10(-2) M H2O2), with 60% disappearance in 20 min of irradiation in a photoreactor equipped with 300 nm lamps of light intensity 3.6 x 10(-5) Ein L(-1) min(-1) (established by ferrioxalate actinometry). The reaction produced stoichiometric amounts of chloride ion indicating complete dechlorination of the chlorinated n-alkane. T4C10 degraded very slowly under Fenton (Fe2+/H2O2/dark) and Fenton-like (Fe3+/H2O2/dark) conditions. However, when the same solutions were irradiated, T4C10 degraded more rapidly than in the H2O2/UV system, with 61% disappearance in 10 min of exposure. The rapid degradation is related to the enhanced degradation of hydrogen peroxide to oxidizing *OH radicals under photo-Fenton conditions. Degradation was inhibited in both the H2O2/UV and photo-Fenton systems by the addition of KI and tert-butyl alcohol due to *OH scavenging.     

镍网负载纳米TiO2光催化反应器对酸性品红脱色效果实验研究

采用负载纳米TiO2的三维镍网装配了光催化反应器,就其对酸性品红溶液进行脱色效果进行了实验研究。考察了反应器的3种装配条件、品红初始浓度、pH值、H2O2投加量、紫外光剂量等因素对酸性品红脱色效果的影响。结果表明：UV灯＋镍网＋TiO2模式组合的反应器脱色效果最好;在相同的处理时间内酸性品红溶液的脱色率随起始浓度的增大而减小;将酸性品红溶液pH值调至5时脱色效果最明显,70 min的脱色率可高达94.8%。脱色效果还可以通过溶液中添加H2O2和控制紫外线剂量来调节。当溶液中H2O2投加量为0.5 g/L时,处理70 min后的脱色率可高达98.3%;到达反应界面紫外光剂量越多则能够获得越高的酸性品红脱色率。     

镍网负载纳米TiO_2光催化反应器对酸性品红脱色效果实验研究

采用负载纳米TiO2的三维镍网装配了光催化反应器,就其对酸性品红溶液进行脱色效果进行了实验研究。考察了反应器的3种装配条件、品红初始浓度、pH值、H2O2投加量、紫外光剂量等因素对酸性品红脱色效果的影响。结果表明:UV灯+镍网+TiO2模式组合的反应器脱色效果最好;在相同的处理时间内酸性品红溶液的脱色率随起始浓度的增大而减小;将酸性品红溶液pH值调至5时脱色效果最明显,70 min的脱色率可高达94.8%。脱色效果还可以通过溶液中添加H2O2和控制紫外线剂量来调节。当溶液中H2O2投加量为0.5 g/L时,处理70 min后的脱色率可高达98.3%;到达反应界面紫外光剂量越多则能够获得越高的酸性品红脱色率。     

Effect of photosensitizer diethylamine on the photodegradation of polychlorinated biphenyls

The objective of this study was to investigate the effect of diethylamine and xenon simulated sunlight on the photodegradation of two forms of PCBs including PCBs in transformer oil and PCB congener 138. The result of GC chromatograms illustrated the shifting pattern of higher chlorinated biphenyls in transformer oil degraded to lower chlorinated biphenyls with the extension of exposure time. The effect of diethylamine and xenon simulated sunlight was significant on the photodegradation of both PCBs in transformer oil and congener 138. The initial degradation rates of congener 138 (1.14 x 10(-9) to 4.47 x 10(-9) mol l(-1) h(-1)) were in direct proportion to the initial concentrations of congener 138 which confirmed the pseudo-first-order reaction of PCB photodegradation. The apparent quantum yields (phi) of congener 138 using diethylamine in xenon photoreactor were ranged between 2.08 x 10(-2) and 9.8 x 10(-4). PCB congeners 123, 97, 70, 67, 33, 29, 17, 12, and 9 were detected as the descendants of the photodegradation of congener 138 through dechlorination. The major pathway of congener 138 photodegradation in this study was via para-dechlorination.     

Effect of fatty acids and oils on photodegradation of azadirachtin-A

Azadirachtin-A on exposure to UV-light (254 nm) as a thin film on glass surface gave a isomerised (Z)-2-methylbut-2-enoate product. Half-life of azadirachtin-A as thin film under UV light was found to be 48 min. Azadirachtin-A was irradiated along with saturated and unsaturated fatty acids, and fatty oils under ultra-violet light as thin film. Saturated fatty acid increased the rate of photodegradation of azadirachtin-A, whereas unsaturated fatty acids such as oleic, linoleic and elaidic acid reduced the rate of degradation. Castor, linseed and olive oil accelerated the rate of degradation, whereas neem oil showed no or little change in the rate of degradation of azadirachtin-A. None of these fatty acids and fatty oils were effective in controlling the rate of degradation of azadirachtin-A under UV-light as thin film.     

Photodecomposition of o-cresol by UV-LED/TiO2 process with controlled periodic illumination

This study investigated the effect of controlled periodic illumination on the photonic efficiency and temporal decomposition behavior of o-cresol by UV/TiO2 process in a slurry reactor using light emitting diodes as the light source. Based on the same UV light intensity of 6.7 W m(-2), the calculated photonic efficiencies increased from 1.5% to 6.3% with the decreasing duty cycle from 1.0 to 0.1 possibly ascribed to the decreasing electron-hole recombination. Actually, the calculated photonic efficiency under periodic illumination at sufficiently intermittence was inferior to, but approached, those under continuous illumination at equivalent average UV light intensity. The calculated electric energy per order increased from 32 to 37 k W h m(-3)order(-1) for experiments conducted with the increasing duty cycle from 0.1 to 1.0, and the electric energy consumption decreased significantly due to the lower duty cycle and average UV light intensity. The photocatalytic decomposition of o-cresol with the UV-light emitting diodes light could be well modeled by the Langmuir-Hinshelwood kinetic equation.     

Reduction of photoreactivation with the combined UV/peracetic acid process or by delayed exposure to visible light.

Photoreactivation of microorganisms following UV inactivation is a well-known, but complex, phenomenon. It is affected by several factors, including UV fluence, wavelength, light intensity, and exposure time to photoreactivating light. The effect on photoreactivation of a combined peracetic acid (PAA)/UV process has not been investigated. Accordingly, this study compared the degree of photoreactivation, under both sunlight and artificial lights, following UV and combined PAA/UV inactivation of fecal coliforms. Effluent samples from the Montreal Wastewater Treatment Plant (MWTP) (Quebec, Canada) were exposed, for 3 hours, to both low- and high-intensity artificial lights and sunlight. All resulted in similar photoreactivation levels. However, average photoreactivation for UV-treated wastewater samples was 1.2 logs, compared with 0.1 log for the combined PAA/UV treatment. Hence, the use of PAA in combination with UV can significantly reduce the potential for photoreactivation. To simulate the photoreactivation conditions of the MWTP effluent (which passes through a 4-km outfall tunnel with approximately 3 hours detention time), UV-treated samples were kept in the dark for 3 hours before photoreactivating light exposure. After this period, photoreactivation levels were close to zero. Hence, the effects of photoreactivation may be diminished by use of a combined disinfection scheme and/or by delaying exposure of the disinfected wastewater to light.     

Photodegradation of humic acids in the presence of hydrogen peroxide

A batch photoreactor was used to evaluate the UV/H2O2 oxidation process for the removal of humic acids in water. A 450-W UV lamp with high-pressure mercury vapor was employed as the light source. The residues of humic acids and hydrogen peroxide were measured for assessment of process performance and understanding of process reaction behavior. The UV photolysis alone can play an important role in the degradation of humic acids. The presence of hydrogen peroxide was found to promote the degradation efficiency. However, excessive dosage of H2O2 does not further improve the degradation of humic acids. On the contrary, the lower the H2O2 dosage the higher the amount of humic acids which can be removed. Aeration with air does not favor the removal efficiency of humic acids as the oxidation lasts for a sufficiently long time. The presence of carbonate species deteriorates the humic acids' removal, whereas it results in a larger amount of H2O2 decomposition.     

Biotic and abiotic degradation of pesticide Dufulin in soils

Dufulin is a newly developed antiviral agent (or pesticide) that activates systemic acquired resistance of plants. This pesticide is widely used in China to prevent abroad viral diseases in rice, tobacco and vegetables. In this study, the potential impacts such as soil type, moisture, temperature, and other factors on Dufulin degradation in soil were investigated. Degradation of Dufulin followed the first-order kinetics. The half-life values varied from 2.27 to 150.68 days. The dissipation of Dufulin was greatly affected by soil types, with DT₅₀ (Degradation half time) varying between 17.59, 31.36, and 43.32 days for Eutric Gleysols, Cumulic Anthrosols, and Dystric Regosols, respectively. The elevated moisture accelerated the decay of Dufulin in soil. Degradation of Dufulin increased with temperature and its half-life values ranged from 16.66 to 42.79 days. Sterilization of soils and treatment with H₂O₂ resulted in a 6- and 8-fold decrease in degradation rates compared to the control, suggesting that Dufulin degradation was largely governed by microbial processes. Under different light spectra, the most effective degradation occurred with 100-W UV light (DT₅₀?=?2.27 days), followed by 15-W UV light (DT₅₀?=?8.32 days) and xenon light (DT₅₀?=?14.26 days). Analysis by liquid chromatography-mass spectroscopy (LC-MS) revealed that 2-amino-4-methylbenzothiazole was one of the major decayed products of Dufulin in soils, suggesting that elimination of diethyl phosphate and 2-fluorobenzaldehyde was most like the degradation pathway of Dufulin in Eutric Gleysols.     

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.     

Degradation of chlorophenols in aqueous media using UV XeBr excilamp in a flow-through reactor

2-Chlorophenol (2-CP), 4-chlorophenol (4-CP) and 2,4-dichlorophenol (2,4-DCP) at initial concentrations of 10, 20, 50 and 100mg l(-1) were degraded in aqueous media by direct UV photolysis using dielectric barrier discharge XeBr( *) excilamp (283nm) in a flow-through photoreactor. The pseudo-first order rate constants were highest and half-life times were lowest for 4-CP. The rates of photolysis under the experimental conditions increased in the order: 2-CP<2,4-DCP<4-CP. The intermediates of photolysis were identified by GC-MS and HPLC. The evolution of hydroquinone and p-benzoquinone as major intermediates of 4-CP photolysis was monitored.     

活性炭纤维负载TiO2光催化降解甲醛的影响因素

利用自制光催化气体反应器体系,以活性炭纤维负载TiO2作催化剂,在紫外光照射下模拟降解室内污染气体甲醛,测试了活性炭纤维负载TiO2催化剂的催化活性,探讨了紫外光光强、催化剂的酸度、反应器内湿度及反应时间等控制反应的主要因素对甲醛降解率的影响。结果表明,活性炭纤维与TiO2的协同作用大大提高了对甲醛的降解效果;紫外光强增倍对甲醛降解率有一定提高,但提高幅度仅为11.71%;活性炭纤维用pH=5的TiO2溶胶浸泡做催化剂对甲醛的降解效果最好,60 min内降解率达到68.37%;反应器内的湿度为81%甲醛降解率最高,反应60 min后达82.2%;随着反应时间的延长,甲醛降解率的上升幅度不断减小,最高只能达到94.59%。     

Decomposition of gas-phase trichloroethene by the UV/TiO2 process in the presence of ozone.

The decomposition of gas-phase trichloroethene (TCE) in air streams by direct photolysis, the UV/TiO2 and UV/O3 processes was studied. The experiments were carried out under various UV light intensities and wavelengths, ozone dosages, and initial concentrations of TCE to investigate and compare the removal efficiency of the pollutant. For UV/TiO2 process, the individual contribution to the decomposition of TCE by direct photolysis and hydroxyl radicals destruction was differentiated to discuss the quantum efficiency with 254 and 365 nm UV lamps. The removal of gaseous TCE was found to reduce by UV/TiO2 process in the presence of ozone possibly because of the ozone molecules could scavenge hydroxyl radicals produced from the excitation of TiO2 by UV radiation to inhibit the decomposition of TCE. A photoreactor design equation for the decomposition of gaseous TCE by the UV/TiO2 process in air streams was developed by combining the continuity equation of the pollutant and the surface catalysis reaction rate expression. By the proposed design scheme, the temporal distribution of TCE at various operation conditions by the UV/TiO2 process can be well modeled.